Technology
for Fossil Power Plants
Proceedings from the Seventh International Conference
October 2225, 2013
Waikoloa, Hawaii, USA
Editors
D. Gandy
J. Shingledecker
Sponsored By
Published By
ASM International
Materials Park, Ohio 44073-0002
www.asminternational.org
Copyright 2014
by
Electric Power Research Institute, Inc.
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ISBN-13: 978-1-62708-060-6
ISBN-10: 1-62708-060-0
SAN: 204-7586
Distributed by ASM International
Materials Park, OH 44073-0002
www.asminternational.org
Printed in the United States of America
Elizabeth Owensby
EPRI, United States
David Gandy
EPRI, United States
Jonathan Parker
EPRI, United States
Jeff Breznak
GE Power & Water, United States
Bruce Pint
Oak Ridge National Laboratory,
United States
Regis Conrad
U.S. Department of Energy, United
States
Dan Purdy
EPRI, United States
Horst Hack
Foster Wheeler, United States
Patricia Rawls
NETL, United States
Jeff Hawk
NETL, United States
Deepak Saha
GE Power & Water, United States
Paul Jablonski
NETL, United States
John Siefert
EPRI, United States
John Marion
Alstom Power, United States
Jim Tanzosh
Babcock & Wilcox Co., United
States
Phil Maziasz
Oak Ridge National Laboratory,
United States
Brian Vitalis
Babcock Power, United States
iii
Fujio Abe
National Institute for Materials
Science, Japan
Giuseppe Cumino
Tenaris-Dalmine, Italy
Fujimitsu Masuyama
Kyushu Institute of Technology,
Japan
Augusto Di Gianfrancesco
Centro Sviluppo Materiali S.p.A, Italy
Alok Mathur
BHEL, India
Jude Foulds
Clarus Consulting, LLC., USA
Peter Mayr
Chemnitz University of Technology,
Germany
Tony Fry
National Physical Laboratory,
United Kingdom
John Oakey
Cranfield University, United
Kingdom
Gerhard Fuchs
University of Florida, USA
Thobeka Pete
ESKOM, South Africa
Masafumi Fukuda
Research Institute for Advanced
Thermal Power Systems, Japan
Ashok Saxena
University of Arkansas, USA
Herbert Heuser
Bhler, Germany
Arthur Stam
DNV Kema, Netherlands
Staf Huysmans
Laborelec GDF Suez, Belgium
Swami Swaminathan
Turbo-Met, USA
Kazuhiro Kimura
National Institute for Materials
Science, Japan
Yasuhiko Tanaka
Japan Steel Works, Japan
Yukio Takahashi
CRIEPI, Japan
Andreas Klenk
MPA Stuttgart, Germany
iv
Rachel Thomson
University of Loughborough, United
Kingdom
Ian Wright
Wright H.T., USA
Xishan Xie
University of Science and Technology
Beijing, China
Christian Ulrich
VGB, Germany
Contents
Preface .................................................................................................................................xix
Section 1: Technology and Program Overviews (Plenary Session)
Progress of China 700C USC Development Program ......................................................... 1
Rui Sun, Zhanzhong Cui, and Ye Tao
ENCIO Project: An European Approach to 700C Power Plant .......................................... 9
A. Di Gianfrancesco, A. Tizzanini, M. Jedamzik, and C. Stolzenberger
Advanced USC Technology Development in Japan ............................................................ 24
Masafumi Fukuda, Eiji Saito, Hiroyuki Semba, Jun Iwasaki, Sakae Izumi, Shinichi
Takano, Takeo Takahashi, and Yasuo Sumiyoshi
Current Status of the U.S. DOE/OCDO A-USC Materials Technology
Research and Development Program .................................................................................. 41
J. Shingledecker, R. Purgert, and P. Rawls
India's National A-USC Mission - Plan and Progress ........................................................ 53
Alok Mathur, O.P Bhutani, T. Jayakumar, D.K. Dubey, and S.C. Chetal
Advantages of A-USC for CO2 Capture in Pulverized Coal Units ...................................... 60
H.L. Hendrix
Section 2: Nickel-Based Alloys for Advanced Ultrasupercritical Power Plants
Nextgenpower Demonstration and Component Fabrication of Nickel Alloys and
Protective Coatings for Steam Temperatures of 750C ...................................................... 74
Arthur F. Stam
A Steam Generator for 700C to 760C Advanced Ultra-Supercritical Design and
Plant Arrangement: What Stays the Same and What Needs to Change .............................. 86
Paul S. Weitzel
An Investigation on Structure Stability of Advanced Austenitic
Heat-Resisting Steels and Ni-Base Superalloys for
600700 C A-USC Power Plant Application ...................................................................... 98
Xishan Xie, Chengyu Chi, Qiuying Yu, Zhihao Yao, Maichang Zhang,
Yaohe Hu, Jianxin Dong, Hongyao Yu, Shuangqun Zhao, Fusheng Lin, Xia Liu,
Linbo Mei, Huachun Yang, and Mingyang Li
vii
viii
ix
Trial Production of Alloy 625 and Alloy 617 Casting Component for
Advanced 700C Class Steam Turbines ............................................................................ 504
Yuichi Hirakawa, Yoshikuni Kadoya, Shin Nishimoto, and Yoshinori Tanaka
xi
The Effect of Post Weld Heat Treatment on the Creep Behaviour and
Microstructural Evolution in Grade 92 Steel Welds for
Steam Pipe Applications .................................................................................................... 615
X. Xu, G.D. West, R.C. Thomson, and J. Parker
Effects of Cr and W Content in High Cr Ferritic Heat-Resistant Steels on
Long-Term Creep Rupture Strength .................................................................................. 627
Yusuke Mito, Kazuhiro Miki, Tsukasa Azuma, and Tohru Ishiguro
Heat-to-Heat Variation in Creep Rupture Ductility of ASME Gr.91 Steels in the
Long-Term-Investigation into Recovery of Microstructure and Void Formation ............. 637
Satoru Kobayashi, Kota Sawada, Toru Hara, Hideaki Kushima, and
Kazuhiro Kimura
Experiences in the Production and Welding of 9-12 % Cr Steels Explained on
Grades 92 and VM12-SHC for USC Power Plants ........................................................... 648
Vida Knezevic, Marko Subanovic, Olivier Hamart, H. Heuser, and K.G. Tak
Creep-Fatigue Interaction in Grade 92 Steel and Its Predictability ................................. 667
Yukio Takahashi, Jonathan Parker, and David Gandy
Creep-Fatigue Properties of Grade 91 Steel ..................................................................... 679
Rami Pohja, Asta Nurmela, Pekka Moilanen, and Stefan Holmstrm
Evaluation of Remaining Life of Gr.91 Welded Elbow Served at
USC Plant for Long-Term ................................................................................................. 690
Seiji Nagai, Masatsugu Yaguchi, Shan Lin, and Souichi Yamazaki
Fracture of Gr. 91 Steel Longitudinal Welded Pipe under
Internal Pressure Creep Condition ................................................................................... 702
Masatsugu Yaguchi, Takayuki Sakai, Takashi Ogata, and Takuaki Matsumura
Creep Cavitation in CSEF Steels ...................................................................................... 714
J. Parker
Evaluation of Long-Term Creep Rupture Life of
Strength Enhanced High Cr Ferritic Steel on the
Basis of Its Temperature Dependence ............................................................................... 732
K. Maruyama, J. Nakamura, and K. Yoshimi
Creep Damage Evaluation of High Cr Ferritic Steel Based on
Change in Hydrogen Desorption Characteristics ............................................................. 744
Shin-ichi Komazaki, Hayato Yamashita, Mitsuharu Yonemura, and Masaaki Igarashi
xii
xiii
xiv
xv
xvi
xvii
xviii
Preface
There were 185 participants representing 18 countries traveling from around the world
to participate in the EPRI 7th International Conference on Advances in Materials
Technology for Fossil Power Plants on the Big Island of Hawaii, USA. This conference
built on the success of the previous 6 conferences originally started by Prof. R. (Vis)
Viswanathan, EPRI (FASM) in 1995 in London, England, and held every three years
since that time in San Sebastian (Spain), Swansea (Wales), Hilton Head Island (USA),
Marco Island (USA), and Santa Fe (USA). This proceeding contains the largest number
of papers ever collected for this conference. Overwhelming response to the 2013
conference (over a 20% increase in number of papers and technical talks) prompted the
organizers to hold the first ever poster session. EPRI and ASM have again partnered to
publish this proceeding which is organized into 9 topical areas: technology overviews,
nickel-based alloys for advanced ultrasupercritical power plants, materials for turbines,
alloys T23/24, Grades 91/92, oxidation and corrosion, welding and weld performance,
new alloys concepts, and creep and general topics.
The high level of interest in the topic of advanced materials for fossil power plants is
being primarily driven by the desire for higher-efficiency advanced ultrasupercritical
(A-USC) steam cycles. The conference brought together, for the first time,
representatives from all the national A-USC projects including the Europe, USA,
Japan, China, and India. Each program is in a different stage of development from
materials fabrication and property studies, operation of test loops and component test
facilities, and planning for a demonstration plant. China appears poised to build and
operate the worlds first coal-fired 700C+ A-USC steam cycle around the year 2020.
Materials, specifically nickel-based alloys and advanced steels and stainless steels, are
the key enabling technology to realize these high efficiency cycles. This proceeding
provides a wealth of information on these alloys as well as new understanding on
advanced steel alloys being used in todays fossil power plants. New alloy concepts
and fundamental understanding on degradation mechanisms (creep, fatigue, oxidation,
corrosion, etc.) were also highlighted in the conference program. Finally, innovative
research into alloys for combustion turbines, a growing area of interest (especially in
countries like the USA where low cost natural gas is changing the focus from coal to
gas), was presented.
The conference award dinner recognized the lifetime achievements of Prof. Fujimitsu
Masuyama, Kyushu Institute of Technology, for his contributions to implementation of
new alloys in fossil power generation. Prof. Masuyama joined past recipients of this
award: Rudolph Blum and Dr. Ian Wright. Attendees were given the opportunity to
rank the 20 posters in the poster session. The best poster award was granted to Shun
Oinuma, Toshiba Corporation, for his poster on Development and Evaluation of Fe/Ni
Dissimilar Metal Weld Turbine Rotor for Advanced USC.
xix
The 7th conference had broadest participation yet for such an event. The chairmen are
indebted to the EPRI conference support staff, members of EPRIs Fossil Materials and
Repair Program (P87), the organizing committee, the international advisory board, and
all the participants who made the conference a huge success.
John Shingledecker and David Gandy
EPRI (2013)
xx
ABSTRACT
This paper presents an overview of Chinas electric power development and the National 700
Ultra-Supercritical (USC) Coal-Fired Power Generation Technology Innovation Consortium.
Besides, the R&D plan and latest progress of China 700 USC coal-fired power generation
technology is also introduced in this paper.
INTRODUCTION
The Status quo of Chinas electric power industry
Chinas power industry has made remarkable achievement with the sustainable development. The
power generation technologies have been improved significantly and the installed capacity has
been growing (Fig. 1). By the end of 2012, the installed capacity of power generation has reached
1145 GW, among which, fossil-fuel power is 796 GW (69.5%), hydropower is 249 GW (21.7%),
nuclear power is 13 GW (1.1%), and wind & other renewable energy power is 64 GW (5.6%),
respectively (Fig. 2).
Due to the efforts of raising the initial parameters and closing down the condensing units smaller
than 100MW, the average coal consumption for power supply by coal-fired units nationwide has
been declining year by year in China. By the end of 2012, the average coal consumption has
decreased to 326 grams/kWh, which is about 20% lower than 2003 (Fig. 4).
Figure 4: Average coal consumption for power supply by coal-fired units nationwide per year
Forecast of Chinas power Generation development
For the future trend of Chinas power generation industry, Fig. 5 indicates the prediction made by
our institute, comparing the capacity in 2012, 2015 and 2020. We can see that Chinas installed
generation capacity will hit 1490 GW and 1800 GW respectively in 2015 and 2020; among
which, the capacity of fossil-fuel power plants will be 1040 GW and 1200 GW respectively.
Additionally, for proportion of fossil fuel units among the total power generation units, fossil fuel
powers share will slowly decline; on the other hand, the renewable energy will be developed
vigorously.
Figure 5: Forecast of Chinas installed power generation capacity in 2015 and 2020
BRIEF INTRODUCTION OF NATIONAL 700 USC CONSORTIUM
Members of the Consortium
On July 23, 2010, the launching ceremony of the National 700 USC Coal-Fired Power
Generation Technology Innovation Consortium was held in the Great Hall of the people by
National Energy Administration (NEA), shown in Fig. 6. The Consortium was lead by NEA, and
3
its 18 members are as follows: Xian Thermal Power Research Institute, Shanghai Power
Equipment Research Institute, Institute of Metal Research (Chinese Academy of Science), China
Iron & Steel Research Institute Group, Electric Power Planning & Engineering Institute, China
Power Engineering Consulting Group, Shanghai Electric Group, Dongfang Electric Corporation,
Harbin Electric Corporation, China First Heavy Industries, China National Erzhong Group,
Baoshan Iron & Steel Co.,LTD, Dongbei Special Steel Group Co.LTD, China Huaneng Group,
China Datang Corporation, China Huadian Corporation, China Guodian Corporation, China
Power Investment Corporation.
formulating the technical roadmap and R&D plans, carrying out project studies, supervising
project execution, and reviewing achievements of the research project at different stages. The
Technical Committee leads the four special working groups.
The research projects related to China 700 USC development are organized and supported by
the Consortium. The Consortium organized members making applications for the national
scientific research funds to the National Energy Administration, the Ministry of Science &
Technology (MOST) and other departments. After approved, the research projects are carried out
according to relevant management regulations or contract. During this process, the Consortium
coordinates the impediment and provide technical support to the projects (Fig. 8).
NEA
Fund
Apply
MOF
R&D Project
Approve
Lead
Consortium
Application
&
Approval
organize
Coordinate Support
Fund
Implementation
Review
Acceptance
MOST
Apply
Approve
Inspect
Appraise
CONTENT
Overall design
Development of heat resistant materials (selecting,
developing, optimizing and assessing )
Development of key components of main equipments and
high temperature pipes
2
3
11
12
13
14
15
16
17
18
19
20
21
1)Boiler tubes
2)Boiler key components
3)Turbine Large Forgings
4)Turbine key Components
5)High temperature pipes and fittings
6)High temperature and high pressure valves
4
system), and layout proposal of each machine shop. Besides, it is also aimed at estimating the
project investment, comparing the cost, and conducting economic evaluation, etc.
This sub-topic is closely related to the construction of the demonstration projects. Currently,
China 700 USC technology R&D focus on some fundamental issues, especially the
development, test, and manufacturing of heat-resistant materials and high temperature
components, so it is premature for the demonstration projects. This sub-topic is still in the
preparation status.
MOST-Initiated National Research Projects in Progress
The Ministry of Science and Technology of china has set up a national program, to develop key
boiler tubes and pipes used for 700 advanced USC power plant. China Iron & Steel Research
Institute Group (CISRI) is the leading member of the project, along with 9 major partners as
follows: Baosteel Group Corporation, Fushun Special Steel Shares Co., Ltd, Yangzhou Chengde
Steel Pipe Co., Ltd, Institute of Mental Research of Chinese Academy of Sciences(IMR CAS),
Xian Thermal Power Research Institute Co., Ltd, Inner Mongolia North Heavy Industries Group
Corporation, Ltd, University of Science and Technology Beijing, Jiangsu University, and Jiangsu
Yinhuan Precision Steel Tube Co., Ltd. The government budget for this project was 29.5 million
RMB and the aforementioned companies, participated in this project, matched up their funding as
required in the course of this great adventure. The duration of the project is from 2012 to 2015.
The research and development of major candidate materials used for 700 USC power plants
were included in this project, such as G115, CCA617 equivalent, Inconel740H equivalent, and
GH2984G. To date, all candidate materials are under industrial trial to make tubes and pipes
according to their proposed application. Hopefully, full-size industrially manufactured tubes and
pipes will be available in china before the end of 2013.
PENDING R&D PROJECTS
China 700 USC R&D is in progress orderly, and there are nine more topics prepared to apply
for support from national scientific research funds, i.e.:
Topic 1: Research on the boiler water wall for 700 USC units
Topic 2: Research on the components of boiler superheater and reheater for 700 USC
units
Topic 4: Research on high temperature steam pipes and fittings for 700 USC units
Topic 5: Research on manufacturing of turbine HP-IP rotor for 700 USC units
Topic 6: Research on manufacturing of high temperature cylinder valve housing for 700
USC units
Topic 7: Research on turbine high temperature blades and fasteners, valve cores wearresisting parts for 700 USC units
Topic 8: Research on turbine high temperature forgings for 700 USC units
Topic 9: Research on turbine high temperature castings for 700 USC units
Abstract
ENCIO (European Network for Component Integration and Optimization) is an European
project aiming at qualifying materials, components, manufacturing processes, as well as
erection and repair concepts, as follow-up of COMTES700 activities and by means of
erecting and operating a new Test Facility.
The 700C technology is a key factor for the increasing efficiency of coal fired power
plants, improving environmental and economic sustainability of coal fired power plants
and achieving successful deployment of carbon capture and storage technologies.
The ENCIO-project is financed by industrial and public funds. The project receives
funding from the European Community's Research Fund for Coal and Steel (RFCS)
under grant agreement n RFCPCT-2011-00003. The ENCIO started on 1 July 2011.
The overall project duration is six years (72 months), to allow enough operating hours,
as well as related data collection, investigations and evaluation of results.
The ENCIO Test Facility will be installed in the Andrea Palladio Power Station which is
owned and operated by ENEL, located in Fusina, very close to Venice (Italy). The Unit 4
was selected for the installation of the Test Facility and the loops are planned for 20.000
hours of operation at 700C.
The present paper summarizes the current status of the overall process design of the
thick-walled components, the test loops and the scheduled operating conditions, the
characterizations program for the base materials and the welded joints, like creep and
microstructural analysis also after service exposure.
Key words: Advanced Ultra Supercritical power plants, Nickel superalloys, welded
joints, test loop, creep behaviour, microstructural stability.
1. Introduction
In the ENCIO-project scientific and technological efforts aim to the successful
deployment of 700C technology in coal fired power plants. The key elements of ENCIO
are the installation and operation of a test facility in Fusina, at an ENEL power plant in
Italy. The project focus is on practical investigations, aiming at proving manufacturing,
welding, repair and life-time concepts for thick-walled components.
Europe is still in the global lead for the 700C technology in the field of fossil-fuel based
power generation. In order to continue with this successful technology development
ENCIO is the next important step to deploy this technology and to remain competitive.
Therefore a group representing the leading European power generators and
equipment suppliers has increased its efforts to speed up the evaluation and
assessment process out of COMTES700.
The 700C technology is a key factor:
9
The strategic importance of these R&D activities is evident for the electricity sector. The
integration of the renewables (RES) is one of the top priorities of European policy. The
consequence for the electricity supply system is that an appropriate balance between
intermitting and dispatchable generation is absolutely necessary. The fossil fuel based
power generation provides the back-up power and grid control function which are
necessary to ensure that the targeted contribution of renewable resources to the
electricity generation portfolio can be achieved.
It is expected that the price of electricity will increase further as soon as the RES share,
the demand for reliable back-up power as well as the global demand for coal will
increase. Different investigations in forecasting the evolution of the electricity sector - in
Europe and worldwide - show that beyond 2025 the commercial viability will be given
which would fit into the time line of the technical maturity of both 700C technology and
carbon capture & storage technologies.
The ENCIO project meets the goal of the RFCS program for coal in terms of efficiency
enhancements and in terms of carbon capture. The scientific and technical approach of
ENCIO consists of the connection in use of new and essentially improved Ni-based
alloys, the development and selection of new manufacturing processes and
consequently to test (under realistic operation condition) new design features of
components needed for the boiler as well as for the turbine.
ENCIO is the perfect transition from pilot towards demonstration, because it contains
elements of both with the goal to have a mature technology available at the end of the
project. In ENCIO the whole European expertise and competence generators and
suppliers are concentrated. This is a clear signal that the proposed work can be done
in a proper manner ensuring that the project objectives can be fully achieved.
Out of the structure and content of the work it is secured that the outcome of ENCIO will
deliver significant progress for the 700C technology, a progress which will be unique in
a global view.
The innovative part can be derived from the fact that new material concepts, new
manufacturing issues and new design features for the components will be demonstrated,
an absolute condition for the successful environmental, technical and sustainable
deployment of the 700C technology and the basis for an efficient carbon capture
process and for saving our coal resources.
The key elements of ENCIO are consequently the use of new and essentially improved
Ni-based alloys, the development and selection of new manufacturing processes and to
test under realistic operation condition new design features of components needed for
the boiler as well as for the turbine. The manufacturing is the key hurdle for a technically
feasible and commercially viable deployment of the 700C technology and consists of
more precise specifications for the ingot, forging, casting, welding including heat
treatment etc. These new process steps will be tested by a smart selection of
component elements required for a successful future operation.
The consequence of the significant progress beyond state of the art is a significant
improvement for the coming generation of fossil fired power plants by the application
and demonstration of their maturity of a complete new type of materials.
The industrial benefit is twofold and can be described as follows: for the European
industry active in the electricity sector the 700C technology provides an urgently
10
needed technology and a clear opportunity for world-wide application of this technology
as a technology leader.
The strategic relevance is given as pointed out before through its role as technology
provider in order to meet the European Councils decisions in mastering the climate
change and to sell this technology worldwide. The competitiveness of both electricity
sector and equipment supplier will be improved. Concerning the generators the
improvement is given by the strategic contribution to a balanced portfolio in lowering the
cost increase due combatting climate change.
For the equipment suppliers their market position will be strengthened in a global sense.
The credibility of the envisaged goals can be derived by the consistency of the working
packages and their deliverables as well as by the integrated responsible experts. The
ENCIO project is targeted for field testing but includes also modelling combined with
simulation. The industrial participation will cover at minimum level about 60% of all
efforts and is relevant in terms of numbers and competence.
The thematic area is an European one: it helps to make the European Council decisions
for decarbonizing the electricity sector reality. The direct link between highly efficient
thermodynamic processes and carbon capture technology is the key for a successful
deployment. The activities of the European Union (EU) in the field of CCS justify this in
addition. The clear need for a European approach is the fact that the partners constitute
themselves European wide and fulfill the specific request for high level skills and
expertise. The successful demonstration of all features of the 700C technology will be
applied all over Europe and globally as a follow-up.
As described previously the strategic importance is evident for the electricity sector. Only
by the back-up and grid control function of the dispatchable generation as nuclear and
fossil the strongly intended major contribution of renewable resources to the electricity
generation portfolio can be achieved. A reduction of the emissions in terms of CO2,
SOx, NOx and dust as well as the saving of resources by less coal consumption will
deliver an essential improvement to the health and safety.
The ENCIO project will contribute to the preservation of natural sources and
environment. This is possible by more efficient processing technologies, reducing
materials and energy consumption.
At the end it will support the use of renewable resources in the electricity sector.
2. PROJECT OBJECTIVES
The key goal of ENCIO is to concentrate all scientific and technological efforts in order to
make the 700C technology ready for deployment. ENCIO is an important step before
the erection of a 700C power plant can start. The ENCIO project consists of the
installation of a Test Facility in the ENEL coal fired power station Andrea Palladio,
based in Fusina (north-east Italy). The rationale behind is that the 700C technology is
the pre-requisite for a successful deployment of the significant technology paths for
carbon capture (i.e. post-combustion and oxyfuel requesting). Both technology lines high efficiency and carbon capture - will converge in a commercially viable power plant:
700C technology combined with carbon capture technology, i.e.
< 100g CO2/kWh and > 40% net efficiency by 2020
The experimental, demonstrational and investigational activities of ENCIO pursue the
following targets:
11
Fusina
Figure 1: Enels power station Andrea Palladio Fusina (Venice Laguna) (Courtesy
of ENEL)
The Fusina power plant is perfectly qualified for installing the TF, as it has previous
experiences in the frame of innovation projects and it was already involved as host
power plant in other EU-funded projects, such as DEBCO (Demonstration of large scale
Biomass Co-firing) and H2-IGCC (Low emission gas turbine for hydrogen rich syngas).
Andrea Palladio station also already hosts a hydrogen fuelled demonstration plant,
including a demonstrative 16 MW GTCC (Gas Turbine Combined Cycle), where hot
component materials (combustor and gas turbine) are tested under long term operation
with hydrogen rich gas mixtures. All DCS (Distributed Control System) data of such a
facility are remotely monitored in real time by ENEL IIN offices based in Pisa. The
12
control, maintenance and operation of the hydrogen fuelled power plant are performed
with the support of personnel of the power station.
3. Structure, timeline, organization and funding
The ENCIO-project is financed by industrial and public funds. The project receives
funding from the European Community's Research Fund for Coal and Steel (RFCS)
under grant agreement n RFCPCT-2011-00003. The ENCIO project started on 1 July
2011. The overall project duration is 6 years (72 months), to allow enough operating
hours, as well as related data collection, investigations and evaluation of results.
The industrial fund consists of contributions of generating companies and of equipment
and materials suppliers. Five partners are contractors to RFCS:
VGB will be responsible for the overall project co-ordination and management including
the relations towards the EC RFCS. VGB is also the coordinator of the COMTES700+
program, that is the overall umbrella also for the other project running in Germany: the
GKM HWT II hosted in Mannheim GKM power plant [5,6]. The structures and the main
targets are summarized in figure 2.
14
4. Project Schedule
The main time milestones are:
late February 2014 start of erection activities outside the boiler
Summer 2014 Fusinas outage for erection activities inside the furnace (i.e.
additional
superheater (SH) bundles, etc.)
early Fall 2014 start of experimental activity
Fall 2017 stop of experimental activity and start of investigation activities after
dismantling
The project structure of the ENCIO project is shown in the chart.
2010
2011
2012
2013
2014
2015
2016
2017
Application to
RFCS Negotiation
Basic Design
EPC
Integrity
Document
Erection &
Commitment
Test Rig
Operations
Investigations
15
16
crack indication will then be selected to produce components to be installed in the test
loop.
Different NDT (Non Destructive Test) methods will be applied and tested to assure high
quality standards.
Non Destructive Surface Tests will be performed frequently during operation for all test
welds. A final repair with orbital TIG (Tungsten Inert Gas) narrow gap and electrode
welding will be executed on additionally aged pieces of A617B (having been in operation
in COMTES700).
5.2 TEST LOOP 2: Hot Isostatic Pressing (HIP) parts + Lifetime monitoring
The HIP technology is interesting for fabrication of T-pieces, valve bodies and turbine
parts. Although this technology is already commercially applied in other fields, it has not
yet been adopted for boiler and turbine pressure parts in power plants (alloy 617B or
alloy 625). The HIP-technology is promising for substituting expensive castings and
consequently a cost reduction may arise from its application to 700C technologies.
NDTs will be performed frequently during operation for all test welds. After the end of
operation final repair welds will be executed on all dismantled pipes of Test Loop 2.
The creep behaviour of alloy 617B is monitored by running tests under respective load
and temperature, as well as by using a thin wall piece designed for ~30000 h (measuring
and monitoring of the creep online).
5.3 TEST LOOP 3: A617 OCC / A263 / HR6W / A625 cast base material and
dissimilar welded joints
The optimized chemical composition of A617B, called A617OCC is applied to explore
possible improvements in weldability, which is due to less formation of chromium
carbides. Additionally, an optimized melting process is implemented to reduce the
amount of impurities in the ingot. Such an optimization has the potential to make welds
more reliable. This is also expected to be an option to reduce relaxation-cracking and
hot-cracking occurrences, which is one of the objectives of ENCIOs tests and
investigations. It can be expected that due to the new melting process the improved
weldability may lead to reduced pre- and post-weld heat treatment requirements. Thus,
A617B OCC has also to be considered as a possible option for reduction of investment
costs of 700C technology.
Furthermore, other Ni-based alloys like A263, HR6W and A625 will be tested. A263
shows a high potential in cost reduction but has not yet been in test operation.
It is also planned to test other material like HR6W for the temperature range 620C to
700C from suppliers such as Sumitomo. These materials will be installed additionally to
the ENCIO test program.
The weldments of the material combinations A617B OCC HR6W and A263 - A625
cast are tested and compared with each other. This is necessary as the combinations
A263 - A625 cast (neither with nor without heat treatment) and A617B OCC HR6W
have not yet been tested and investigated with the required heat treatment.
This aims at an optimized design for the overall plant with regards to competiveness,
costs and performance.
NDTs will be performed frequently during operation for test welds. After the end of
operation final repair welds will be executed on dismantled pipes of Test Loop 3 which
are long enough for this purpose, followed by microstructural investigations, mechanical
and creep testing.
17
18
19
Due to the ENCIO project objectives comprising the implementation of new materials,
new manufacturing processes and new welding and testing features a comprehensive
material qualification procedure is required to comply with obligations of the certified
bodies. As this certification process follows defined rules the preparatory work before
erection cannot be expedited. Nevertheless the feasibility to start qualification tests prior
to the RFCS commencement date has to be explored.
8. Main facts
TF installed - tie-ins installed end of Aug. 2012 (figure 7) [4]
20
This work package is leaded by Centro Sviluppo Materiali S.p.A. (CSM) with the
cooperation of Technische Universitt Darmstadt (TUD) and VGB PowerTech e.V.
(VGB).
The WP4 main objectives are:
The definition of the ranking of manufacturing processes and repair concepts to
reduce the risks in future long-term plant operations,
The identification of life time determinants in particular including main damage
mechanisms in long-term service exposed components (through a
comprehensive characterisation of materials and components), in order to
provide a basis for design, operations and repair methods on future 700C
power plants.
The materials scheduled to be installed in the five test loop are: A617B, A617B OCC,
A625, A263, HR6W. The production processes scheduled for component production
are: forging, casting, extrusion, pilgrim and HIP.
The welding procedures scheduled for the components production are: Orbital TIG
narrow gap welding (cold wire), Electrode welding and TIG narrow gap welding (hot
wire).
This WP will also support WP2, by carrying out laboratory analyses on trial welded joints
devoted to destructive testing (DT) for achieving the proof of weldability and fabricability.
Depending on the case, welded joints will be tested with or without pre weld heat
treatment. Post weld heat treatment will always be applied.
Task 4.1 Base materials: A comprehensive mechanical assessment (hardness, tensile,
indentation, impact tests) and microstructural characterisation (light optical microscopy
(LOM), scanning electron microscopy (SEM), transmission electron microscopy (TEM),
and X-ray diffraction (XRD) analysis) of base components (made by A617B,
A617B OCC, A625, A263), as new material batches or priory exposed in the
COMTES700 loop (without overlapping with the COMTES700 tests), manufactured by
21
different process routes (forging, casting, extrusion, pilgrim, HIP) and with different sizes
and/or wall thicknesses.
Task 4.1 Welded joints: A comprehensive mechanical assessment (hardness, tensile,
impact tests) and microstructural characterisation (LOM, SEM, TEM, XRD analysis) of
welded joints (similar and dissimilar), produced by different welding procedures (Orbital
TIG welding - cold wire, Electrode welding, TIG narrow gap welding - hot wire) and with
or without pre welding heat treatment. Post weld heat treatment will applied be always.
Task 4.3 Simulation of in-service exposure conditions: Specimens from the creep
test program will be adopted for indentation tests to obtain information on mechanical
properties. TEM examinations (head and gauge length) at different times and
temperatures to evaluate on base metals and in weld metals or HAZ (Heat Affected
Zone), for the welded joints, in order to assess and quantify the strain-induced
precipitation effect on overall microstructure evolution (measured in terms of
precipitation evolution and coarsening, formation of new phases).
Task 4.4 Dismantled components: A comprehensive mechanical assessment
(hardness, tensile, indentation, impact tests) and microstructural characterisation (LOM,
SEM, TEM, XRD analysis) of exposed base metals and welded joints (after dismantling)
will be performed.
Task 4.5 Welding repair: A comprehensive mechanical assessment (hardness, tensile,
indentation, impact tests) and microstructural characterisation (LOM, SEM, TEM, XRD
analysis) of the welded joints carried out on in-service exposed pipes taken from
COMTES700, will be performed.
Task 4.6 Creep Assessment program: A creep test program will be carried out to
characterize the long-term behaviour of the different base metals and welded joints
(similar and dissimilar) produced by different WPS (Welding Procedure Specification), as
well as, the effect of pre-/post- weld heat treatments, giving indication on the stress
reduction factor to be applied for the industrial components.
It is foreseen to share the work within all tasks among CSM, VGB and TUD according to
the corresponding resources.
An unique combination of mechanical (instrumented tensile tests or special indentation
procedures from RT to 800C, hardness and micro hardness indentations, etc.) and
metallographic investigation techniques (LOM, SEM with X-ray microanalysis (energydispersive spectroscopy, EDS), EF-TEM incl. scanning transmission electron
microscopy (STEM), XRD) have been selected and applied.
Data generated and metallurgical evidences correlated to the mechanical behaviour of
laboratory samples and full-scale components will be critically analysed and evaluated in
order to identify main damage mechanisms in long-term service exposed components.
This evaluation will be shared with the other partners and results will be made available
to WP 2, WP 5 and WP 6 to provide a basis for design, operations and repair methods
on future 700C power plants.
The key purpose of WP 4 is that all results and findings out of the operation of the TF
will be compiled and evaluated. Based on this assessment the partners will have the
necessary conclusions for engineering, designing, manufacturing and commissioning in
order to start with the erection of a 700C power plant. Therefore, VGB will integrate all
22
Bibliography
1) http://www.vgb.org/en/research_project261.html
2) M. Gazzino: ENCIO project: overview, status up-date and planned fireside
corrosion tests Enel Engineering and Research Division VGB/IEA Workshop
Advanced USC coal-fired power plants; 19-20 September 2012 Vienna, Austria
3) http://www.encio.eu/contact.html
4) http://www.vgb.org/en/research_project355.html
5) http://www.vgb.org/fue_projekt321.html
23
24
operating boiler from 2015 to 2017. The turbine rotor materials which have the same diameter as
commercial rotors will be tested at 700 deg-C and at actual speed.
INTRODUCTION
Figure 1 shows the power generation trend and its fuel share in Japan1). The amount of power
generation increased steadily during 1980s and 1990s. In 2000s, it was maintained around 100
TWh. After the Oil shock in the 70s, coal fired power plants had been steadily replacing oil
fired power plants until the earth quake in 2011, which struck northern Japan and caused tsunami.
Fukushima #1 nuclear power plant was severely damaged by the tsunami. Today, almost all
nuclear power plants have been shut down and natural gas, oil and coal power plants are working
fully to satisfy the market's demand. Natural gas dominates almost half of the power generation
and old oil power plants have returned to the market. Consequently, the cost of fuel which is
imported from abroad increased significantly and turned the countrys international trade into
deficit from surplus.
Coal is expected to become more favorable choice for the newly built power plants in addition to
replacing old coal power plants because of its price and availability. In this situation, the
reduction of CO2 emission from coal power plants is the crucial issue for the country.
25
A-USC
Net Thermal Efficiency 4648%HHV
Boiler
Biomass Co-Firing
CO2 Recovery
Oxyfuel
Exhaust Gas
Steam Turbine
25MPa, 600
USC
Net Thermal Efficiency 42%HHV
Boiler
Steam Turbine
In the case study, we checked existing coal power plants in Japan. There are many older coal
plants in Japan, built in the 70s and early 80s, which will reach the point where they will need
to be rebuilt or retofitted in the near future. Almost all Japanese coal power plants already have
environmental protection equipment like DeNOx, DeSOx, and EP which make up a large part of
the plants. If we can retrofit the old plants with the higher steam temperature technology it is
possible to reduce CO2 at a much lower cost than if we used the other technologies because we
can reuse the expensive environmental protection equipment and some other cold parts from the
existing plants.
We considered Ni-based alloys for the 700 deg-C class turbine rotors. It is necessary to use Ni or
Ni-Fe-based wrought material for rotors of 700 deg-C class steam turbines unless advanced
cooling technology is used. However, it is difficult to make large Ni or Ni-Fe-based wrought
parts and it is assumed that the largest possible size of a part is around 10 tons. Turbine rotors for
large capacity power stations usually weigh 30 to 40 tons. The Welded Rotor concept was
proposed to make large rotors by welding Ni or Ni-Fe-based wrought material and steel. Figure 6
shows a typical welded rotor.
Blades Ni-Based-Alloy
Figure 9 shows the estimated plant thermal efficiency (Net, HHV) of each case after
refurbishment. The thermal efficiency of the original plant is about 40%. Case D is a reference
case, which uses the current technology.
48
46
44
42
40
A
Case
29
30
Long
term reliability
(including Weldment)
Temp. Corrosion
Steam Oxidation
Fatigue
Materials
High
Maintenance
System Design
Piping
(Thermal Exp.)
design
(Thermal Stress)
Basic Engineering
(Boiler Concept)
System
Boiler
Technology
Development
Components
Valves
(SV/CV etc)
DeSH
(including Turbine bypass Spray )
Header
Boiler
Life
Assessment
Welding for
Aged materials
Fabrication
Welding
(including Dissmilar)
Bending
NDT
Figure 13 Boiler Candidate Materials (Courtesy of Nippon Steel & Sumitomo Metal)
Figure 14 HR6W creep rupture strength (Courtesy of Nippon Steel & Sumitomo Metal)
32
Figure 15 Creep rupture strength of HR6W weld (Courtesy of Nippon Steel & Sumitomo Metal
and Babcock-Hitachi)
We have made pipes of HR6W, HR35 and Alloy617 using the Ehrhardt push bench method
(Figure 16). These pipes were prepared in order to conduct material tests, such as welding,
bending and the long term creep test. A large diameter pipe was made for a reheater header
mock-up (Figure 17). The diameter and the wall thickness of the pipe are 675mm and 72mm.
Figure 16 Pipes prepared for material test (Courtesy of Nippon Steel & Sumitomo Metal)
Figure 17 Large diameter pipe prepared for header mock-up (Courtesy of Nippon Steel &
Sumitomo Metal)
Figure 18 shows bended pipes which are made of Alloy617 and HR6W. These pipes were cut into
pieces to check the shape of the cross section and to make test specimens. Pipe welding tests were
carried out. A sample of welded pipes is shown on Figure 19. We put some specimens which
were cut out from the welded portion of pipes into long term creep rupture test.
Some advanced 9Cr steels were also tested. Figure 20 shows the cross section of welded
SAVE12AD pipe and a bended pipe. In the HAZ section of welds, we didnt find any small grain
structure.
33
Some header mock-ups were made to check manufacturability of actual parts of A-USC boiler.
Figure 21 shows a reheater mock-up which uses a pipe shown on Figure 17.
Figure 18 Pipe trial bending (Courtesy of Babcock-Hitachi and Mitsubishi Heavy Industries)
34
Materials
Temperature
Level
Weight
Development Target
FENIX-700
700
>10ton
LTES700R
>700
3040ton
>720
Ni:10ton
+
Steel:20~30ton
Welding
TOS1X
35
Figure 25 Large LTES700R material before forging (Courtesy of Mitsubishi Heavy Industries)
36
37
Figure 31 Concept of 1000MW class double reheat steam turbine (Courtesy of Toshiba)
BOILER COMPONENT TEST AND TURBINE ROTOR TEST
Today, we are preparing for the boiler component test and the turbine rotor test as shown on Fig.
32. In 2015 and 2016 boiler components such as super heaters, pipes, valves, and turbine casing
will be tested by using an actual boiler (Figure 33). Three rotors made of the three candidate rotor
materials will be tested in 700 deg-C atmosphere and at actual speed from 2014 to 2016 (Figure
34). The rotors will be heated by electric heaters in a vacuum chamber, and driven by an electric
motor.
38
2012
2013
2014
2015
2016
Fig. 32 Schedule for boiler component test and turbine rotor test
39
CONCLUSION
The development of the USC technology began in Japan in the 80s, aiming at a cleaner and
more economical use of coal. Today, almost half of the coal power plants have a 600deg-C class
USC steam condition.
A-USC is one of the remarkable technologies being developed to reduce CO2 emissions from
fossil fuel power plants A large scale 9-year project began in 2008 to develop A-USC technology
thoroughly. Major Japanese manufacturers of boilers, steam turbines and valves and some
institutes are cooperating in the project to develop the technology. Five years from the beginning
of the project, we have made some boiler materials and carried out some fundamental tests, such
as tensile, creep, welding, bending etc. Turbine rotor and casing materials have been forged and
casted and are being tested as well.
Today, we are preparing for the boiler component test and turbine rotor test. In 2015 and 2016
boiler components such as superheaters, pipes, and valves will be tested in an actual boiler. Three
rotors made of the three candidate rotor materials will be tested in 700 deg-C atmosphere and at
actual speed from 2014 to 2016.
REFERENCES
[1] http://www.fepc.or.jp/about_us/pr/sonota/__icsFiles/afieldfile/2013/05/17/kouseihi_2012.pdf
[2] Shinya Imano, Jun Sato, Koji Kajikawa and Tatsuya Takahashi,'Mechanical Properties and
Manufacturability of Ni-Fe base Superalloy(FENIX-700) for A-USC Steam Turbine Rotor Large
Forgings', 5th international conference on advances in materials technology for fossilpower plants,
EPRI, 2007
Product names mentioned herein may be trademarks of their respective companies.
40
42
ALLOY SELECTION
The consortium first defined the conditions required for the materials to operate at A-USC
conditions up to 760C (1400F). Based on these preliminary design studies, nickel-based alloys
were selected for detailed evaluation because only these alloys had the requisite strength required
to operate at A-USC conditions. Current USC boilers operate at temperature of approximately
600C which is the limit of the most advanced creep-strength enhanced ferritic (CSEF) steels, but
for temperatures above 700C (1300F), nickel-based alloys are clearly required. Figure 1 shows
the temperature required to produce creep-rupture in 100,000 hours for various alloys. With the
aim of 760C (1400F), age-hardenable alloys (Inconel alloy 740 and Haynes 282) were
considered beyond solution strengthened alloys such as 617. Using the criteria of 100,000 hour
strength at 100MPa (14.5ksi), these temperature limits can be observed from the plot. Although
strength is an important consideration, a number of other critical material properties, must be
considered for materials operating at A-USC conditions. Much of the work highlighted in the
following sections is related to the other important properties needed for boilers and turbines
including: fabricability, weldability, weld performance, tensile and fatigue properties, notch
sensitivity, and steam side oxidation and fireside corrosion resistance. Table 1 provides a list of
some alloys which were studied initially by the consortium and eliminated from future testing.
Table 2 provides a partial list of the key nickel-based alloys selected by the consortia for study
along with comments on their applicability and limitations.
Figure 2: 100,000 hour creep-rupture strength as a function of temperature for alloy/alloy class.
43
Table 1. Ferritic and Iron-based Austentic Alloys Selected for Early Evaluation and Some
Important Findings (Status)
Alloy
Component
Comments
SAVE12
Pipe
Unstable microstructure, welding was challenging [13]
(eliminated from testing)
Super 304H
SH/RH
Met strength projections, may need coatings in some
(CC2328)
environments and shot-peening for oxidation resistance [14]
(only for tubing)
HR6W
SH/RH,
Did not meet strength projections [15] (stopped research, new
Pipe
chemistry now available)
*SH/RH: Superheater and Reheater Tubing
Alloy
Haynes 230
CCA617
Alloy 263
Inconel
740/740H
Haynes 282
Waspalloy
Nimonic
105
PROGRAM SUCESSES
Inconel Alloy 740/740H Development and Code Case Acceptance
Inconel Alloy 740 is an age-hardenable nickel-based alloy developed by Special Metals
Corporation (Huntington, WV USA) for use as superheater and reheater tubing in A-USC power
plants [16]. Due to its excellent high-temperature (creep) strength, see figure 2, and corrosion
resistance, the consortium also evaluated its use for thicker components such as boiler piping and
headers. This involved numerous welding and fabrication trials combined with long-term testing.
Initial challenges were encountered when welding the alloy in sections up to 75mm (3) in
thickness. The consortium worked closely with the alloy designers and other research institutions
to refine the alloy and weld metal composition. Revolutionary progress was made, and the alloy,
Inconel 740H, is now considered weldable as shown in Figure 3 with numerous successful welded
joints produced [17, 18].
44
Figure 3. 75mm (3) weldment in Inconel 740H Pipe (left) and Header mock-up (right) [17]
Materials used in the construction of fired pressure vessels must be designed to ASME B&PV
Code Section I. While there are some materials which are allowed for Section I construction at
760C (1400F), they do not have the requisite strength (allowable stresses) needed to design and
build an A-USC boiler. Thus, the consortium developed a comprehensive data package which
included test data on multiple material heats and product forms containing long-term data [19].
Babcock & Wilcox championed the case with supporting data from the other project members.
ORNL conducted the long-term testing and EPRI conducted the stress analysis. The approved
Section I code case, Code Case 2702, contains fabrication rules, welding specifications (including
weld strength reduction factors), stress allowables, and other key requirements. Users can now
design and specify the alloy for use in Section I construction to a maximum use temperature of
800C (1472F). The alloy has also been adopted by ASME Section B31.1 for power piping.
Creep-rupture testing has surpassed 45,000 hours with no drop-off in rupture strength or ductility.
Research has included studies on notch sensitivity and microstructural development which suggest
the alloy is suitable for long-term service at A-USC conditions [20, 21].
Fireside Corrosion Tests & Oxidation Behavior
Concerns with fireside corrosion at A-USC temperatures and the wide variety of coals burned in
the U.S., necessitated the consortium to do detailed evaluation of all the alloys fireside corrosion
resistance. The aim was to determine the suitability of the alloys over the range of temperatures
expected in superheaters and reheaters (SH./RH) in an A-USC plant and determine if higher
chromium claddings or coatings would be required. Extensive laboratory tests have been
conducted on a wide range of alloys, overlays, and coatings with varying sulfur contents [22], air
cooled probes have been fabricated and testing for up to 16,000 hours in actual boiler
environments [23], a steam-cooled corrosion test loop was operated in a high sulfur coal
environment [24], and the worlds first 760C (1400F) steam cooled loop is now operating in a
U.S. boiler. Figure 3 shows some results from one of the air-cooled probes. In this test, Inconel
740 performed as well as some of the high chromium weld overlays. Figure 4, shows the A-USC
programs steam loop which operates with a steam outlet of 760C (1400F) and contains a
variety of materials and overlays. Current plans are to remove the loop in 2014 for destructive
evaluation and comparison with other field and laboratory data. Work is also ongoing to evaluate
oxycombustion environments. The results show there are alloys and weld overlays which can be
used with confidence to enable an A-USC boiler with acceptable corrosion performance.
45
Figure 4. Cleaned surface of ring samples (identification at the top) from an air cooled probes
after 16,000 hours operation in a utility boiler. Note alloy 740 shows virtually no corrosion
wastage with similar performance to high chromium weld overlays (52 and 72WO). Other
alloys, including HR6W show moderate attack.
bending, welding (pipe and tube), machining, application of overlays, and dissimilar metal
welding applied to A-USC alloys.
Figure 7. ~450kg (1,000 lb) finished weight step casting of Haynes 282
47
Figure 8. Upset and draw operation (left) and worlds first Haynes 282 triple melt ingot (right)
Economy of 760C Materials at 700C
The U.S. programs temperature aim of 760C (1400F) steam is greater than the other programs
worldwide focused on A-USC at 700C (1300F). This has lead to the extensive study of alloys
Inconel 740H and Haynes 282. A critical advantage of these alloys is that they can be used more
cost effectively than solid solution strengthened nickel-based alloys at 700C (1300F) due to
their higher strength at lower temperatures with similar alloy cost. One specific study [32]
compared alloy 617 to 740H for a prototypical A-USC main steam and hot reheat piping system
and showed that by using 740H in lieu of 617, the number of pipes required would decrease, the
length of each individual extruded pipe section would increase, the number of welds for the
piping system would decrease, the pipe thickness would decrease, and the amount of welding
(both filler material and welding time) would decrease. The combined effect of these results
demonstrated that the utilization of 740H over 617 would result in a significant cost savings with
regard to both construction and life management of an A-USC piping system at 700C (1300F).
Figure 9 is a comparison of the piping system in that study. Of interest is that for the main steam
pipe, two 617 pipes were required because the wall thickness of the 617 in a single pipe
arrangement exceeded typical boiler fabrication sizes (thickness was greater than 100mm).
Additionally, the processing characteristics for extrusion (the basis of this study) showed 740H
could be extruded in large diameter thus only one reheat pipe was needed compared to two for the
617 system. Depending on alloy cost, the materials savings alone for using 740H in lieu of 617
was 5 to 20 million USD.
48
Figure 9. Comparison of a 617 and 740H piping system for a 700C (1300F) steam plant. The
617 system requires two main steam and two hot-reheat pipes to avoid wall thickness in excess of
75mm and to allow for extrusion. In contrast only one main steam pipe and one reheat pipe is
needed for the 740H system due to its excellent strength and good fabrication characteristics.
CONCLUSIONS AND NEXT STEPS
Revolutionary progress has been made in advancing the materials technology to enable a 760C
(1400F) A-USC power plant. These successes have only been made possible through a unique
cost-sharing U.S. Consortium of manufacturers and research organizations dedicated achieving to
the aggressive goals set forth by the U.S. DOE. The U.S. DOE/OCDO A-USC Consortium has
had many successes including: demonstration of welding and fabrication of nickel-based alloys
for an A-USC plant, extensive successful fireside corrosion testing including in-plant operation of
the worlds first 760C (1400F) steam cooled corrosion test loop, development of casting
techniques for high-alloy age-hardneable alloys, new materials for rotor forgings, and code
acceptance of Inconel 740H which gives manufacturers, for the first time, an alloy with the
requisite strength for a 760C (1400F) plant. Current research includes scale-up, demonstration,
testing, and weld repair of castings, testing and evaluation of a Haynes 282 forged disc, long-term
creep testing in excess of 45,000 hours to ensure long-term reliability, field corrosion studies, and
economic evaluations. A new project to build a 760C (1400F) component test facility is now
underway. This facility will be unique in that it will test heavy section components 60C (100F)
hotter than any other test facility in the world, will incorporate cyclic operation of welds and
valves, and will include a turbine test. Figure 9 shows a schematic of this planned facility. The
facility plan is an outcome of workshops held with utility stakeholders who desire to see a
demonstration before construction of an A-USC plant. In summary, the materials technology to
design, build, and operate an A-USC power plant now exists or the research is nearing
completion. Current research and development is ongoing and planned to improve the economy of
building such a plant and to ensure its reliable operation.
49
Figure 10. General arrangement of the planned 760C (1400F) component test facility
ACKNOWLEDGMENTS
The authors are greatly indebted the members of the A-USC consortium who have undertaken this
endeavor. First and foremost appreciation is given to Prof. R (Vis) Viswanathan for his
leadership of the project prior to his retirement. Special thanks are given to the many members of
the consortium past and present including but not limited to: H. Hendrix (EPRI), R. Ganta, J.
Pschirer, and J. Marrion (ALSTOM Power), J. Tanzosh (B&W), H. Hack (Foster Wheeler), D.
Saha and J. Breznak (GE), P. Torterelli (ORNL), J. Hawk and P. Jablonski (NETL-Albany), and
B. Vitalis (Riley). The support and guidance of our sponsors is also greatly acknowledged: B.
Romanosky (NETL), R. Conrad (DOE), and Ohio Office of Development.
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[2] International Energy Agency OECD/IEA, 2012. Available at: www.iea.org
[3] B. Diczfalusy. HELE Coal Technology Roadmap. IEA Clean Coal Centre Workshop: on
Advanced ultrasupercritical coal-fired Power Plants, Vienna, Austria 12-20 September
2012.
[4] K. Burnard, O. Ito. HELE Coal Technology Roadmap. IEA Clean Coal Centre Workshop:
on Advanced ultrasupercritical coal-fired Power Plants, Vienna, Austria 12-20 September
2012.
[5] R. Blum, R. Vanstone. Materials Development for Boilers and Steam Turbines Operating at
700C, Proceedings to the 6th International Charles Parsons Materials Conference, Dublin,
Ireland (2003).
[6] R. Viswanathan, R. Purgert, U. Rao: Materials for Advanced Power Engineering 2002,
Proceedings Part II, Forschungszentrum Julich GmbH, 2002. 1109-1129
50
[7] U.S Department of Energy and Ohio Coal Development Office Advanced Ultra-Supercritical
Materials Project for Boiler and Steam Turbines. EPRI, Palo Alto, CA: March 2011.
1022770.Available: http://my.epri.com/portal/server.pt?Abstract_id=000000000001022770
[8] R. Viswananthan, J.F. Henry, J. Tanzosh, G. Stanko, J. Shingledecker, B. Vitalis, R. Purgert.
U.S. Program on Materials Technology for Ultra-Supercritical Coal Power Plants. Journal
of Materials Engineering and Performance. Vol. 14 (3) June 2005. 281-292.
[9] J.P. Shingledecker, I.G. Wright. Evaluation of the Materials Technology Required for a
760C Power Steam Boiler. Proceedings to the 8th Liege Conference on Materials for
Advanced Power Engineering 2006. Forschungszentrum Jlich GmbH (2006) pp. 107-120.
[10] F. Masuyama. R&D Program for A-USC Material Development with Creep
Strength/Degradation Assessment Studies. Proceedings to the 6th International Conference
on Advances in Materials Technology for Fossil Power Plants, Santa Fe, New Mexico,
August 30-September 4, 2010. EPRI, March 2011: 1022300. Distributed by ASM
International. 11-29.
[11] R. Sun. Development of 700C USC Coal-Fired Power Generation Technology in China. IEA
Clean Coal Centre Workshop: on Advanced ultrasupercritical coal-fired Power Plants,
Vienna, Austria 12-20 September 2012.
[12] Personal communication: A. Mathur, O.P. Bhutani, BHEL February 2013.
[13] M. Santella et al. Weld Development for Heavy-Section SAVE12. Presentation at the 5th
International Conference on Advances in Materials Technology for Fossil Power Plants,
Marco Island, FL USA Oct. 3-5, 2007.
[14] R. Viswanathan, J. Sarver, J. Tanzosh. Boiler Materials for Ultra-Supercrtical Coal Power
Plants Steamside Oxidation. Journal of Materials Engineering and Performance. Vol 15
(3), June 2006. 255-274
[15] J.P. Shingledecker. Creep rupture behaviour and recrystallisation in HR6W and Haynes
alloy 230 cold bent boiler tubing for ultrasupercritical steam boiler applications. Energy
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[16] G.D. Smith, H.W. Sizek. Introduction of an Advanced Superheater Alloy for Coal-Fired
Boilers. Corrosion 2000. Paper 00256 2000 NACE International, TX.
[17] B.A. Baker, et al. Welding and Repair Technology for Power Plants, Tenth International
EPRI Conference. June 26-29, 2012 Marco Island, FL USA
[18] J.A. Siefert, J.M. Tanzosh, J.E. Ramirez. Proceedings to the 6th International Conference on
Advances in Materials Technology for Fossil Power Plants, Santa Fe, New Mexico, August
30-September 4, 2010. EPRI, March 2011: 1022300. Distributed by ASM International.
1045-1066.
[19] J.P. Shingledecker, N.D. Evans, G.M. Pharr. Influences of Composition and Grain Size on
Creep-Rupture Behavior of Inconel Alloy 740. Materials Science and Engineering A. 578
(2013) 277-286. 10.1016/j.msea.2013.04.087
[20] J.P. Shingledecker, G.M. Pharr. The Role of Eta Phase Formation on the Creep Strength and
Ductility of INCONEL Alloy 740 at 1023 K (750 C). Metallurgical and Materials
Transactions A., Vol. 43, Issue 6 (2012). 1902-1910. 10.1007/s11661-011-1013-4
[21] J.P. Shingledecker, G.M. Pharr. Testing and Analysis of Full-Scale Creep-Rupture
Experiments on Inconel Alloy 740 Cold-Formed Tubing.Journal of Materials Engineering
and Performance. Volume 22, Issue 2 (2013), Page 454-462. 10.1007/s11665-012-0274-4
[22] H. Hack, G. S. Stanko, Update on Fireside Corrosion Resistance of Advanced Materials for
Ultra-Supercritical Coal-Fired Power Plants, The 31st International Technical Conference
on Coal Utilization & Fuel Systems, May 21-25, 2006, Clearwater, Florida, USA.
[23] M. Gagliano, H. Hack, G. Stanko. Update on the Fireside Corrosion Resistance of Proposed
Advanced Ultrasupercritical Superheater and Reheater Materials: Laboratory and Field Test
51
Results. The 2009 Clearwater Coal Conference, 34th International Technical Conference on
Coal Utilitzation & Fuel Systems. Clearwater, FL May 31-June 4, 2009.
[24] E. Robitz, J. Tanzosh. In Situ Corrosion Testing of Ultrasupercritical Tube and Weld
Overlay Materials. Proceedings to the 6th International Conference on Advances in
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4, 2010. EPRI, March 2011: 1022300. Distributed by ASM International. 288-302.
[25] W.R. Mohn, J.M. Tanzosh. Considerations in Fabricating USC Boiler Components from
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LEGAL NOTICE/DISCLAIMER
This report was prepared by J. Shingledecker (EPRI) pursuant to a Grant partially funded by the
U.S. Department of Energy (DOE) under Instrument Number DE-FG26-0 1 NT 41175 and the
Ohio Coal Development Office/Ohio Department of Development (OCDO) under Grant
Agreement Number CDO/D-OO-20 (now D-05-02A). NO WARRANTY OR
REPRESENTATION, EXPRESS OR IMPLIED, IS MADE WITH RESPECT TO THE
ACCURACY, COMPLETENESS, AND/OR USEFULNESS OF INFORMATION
CONTAINED IN THIS REPORT. FURTHER, NO WARRANTY OR REPRESENTATION,
EXPRESS OR IMPLIED, IS MADE THAT THE USE OF ANY INFORMATION,
APPARATUS, METHOD, OR PROCESS DISCLOSED IN THIS REPORT WILL NOT
INFRINGE UPON PRIVATELY OWNED RIGHTS. FINALLY, NO LIABILITY IS
ASSUMED WITH RESPECT TO THE USE OF, OR FOR DAMAGES RESULTING FROM
THE USE OF, ANY INFORMATION, APPARATUS, METHOD OR PROCESS DISCLOSED
IN THIS REPORT
52
ratings, in addition to older plants of lower ratings. In recent years, supercritical power
plants of 660 MW and 800 MW have been established and are in operation. The steam
2
parameters of the supercritical plants being set up currently in India are 247 kg/cm ,
565 C/ 593 C. Future capacity additions will be mainly in the supercritical range. Ultra
supercritical plants, with steam temperatures over 600 C, are also on the anvil.
In the medium to long term, however, India needs to adopt clean coal technologies that
promise higher efficiencies, reduced coal consumption per unit of power produced and
lower emissions of CO2 and pollutants such as SOx, NOx, etc. Advanced Ultra
Supercritical (A-USC) is one of the most promising of such clean coal technologies,
currently under development in several countries. Among major economies, the drivers
for adopting A-USC technology are perhaps the strongest in India.
With the above backdrop, the Government of India has initiated a National Mission for
Development of Clean Coal (Carbon) Technologies, under which there is a Sub-Mission
for the Development of Advanced Ultra Supercritical Technologies for Thermal Power
Plants. The National Mission is being executed under the overall leadership of the
Principal Scientific Adviser (PSA) to the Government of India. The Mission has a special
focus on achieving a high degree of self reliance in technology apart from economic and
low cost production through indigenization.
The objective of Indias National Mission for the Development of Advanced Ultra
Supercritical Technology for Thermal Power Plants is to develop all the technologies
required for an A-USC plant and to design, manufacture and establish an 800 MW AUSC Demonstration Power Plant. After successful development and demonstration,
there is enormous potential to set up a large number of coal fired power plants based on
the A-USC technology developed.
The development work is being executed by a consortium of three organisations: Bharat
Heavy Electricals Limited (BHEL), the leading power equipment manufacturer of India;
Indira Gandhi Centre for Atomic Research (IGCAR), a premier R&D institution
specializing in the development of high temperature materials; and NTPC Limited
(NTPC), Indias largest power generation utility. Together, the three organizations have
the capabilities required to develop and establish an A-USC power plant. In addition,
wherever necessary, the help of R&D institutions and other organizations is sought.
The time frame for the development is seven years from the date of approval of the
project by the Government of India - comprising 2 years for development and 4
years for setting up the demonstration plant. A comprehensive and detailed roadmap of
the development activities across the entire spectrum, covering materials selection and
development, manufacturing technologies, corrosion test loop, equipment design,
thermal cycle design and overall plant design, has been prepared. Well before the
formal start of the R&D project, several proactive R&D initiatives have been taken to
gain a head start in critical areas of technology and accelerate the pace of development
work and significant progress has been achieved.
DEVELOPMENT AREAS TAKEN UP AND PROGRESS ACHIEVED
The following sections give details of the major developmental activities that have been
completed or are in progress.
54
The specific composition of the materials to be used in the Indian program has been
selected to lie in a narrow zone within the overall material specifications of ASME, in
order to achieve the desired properties and reduce variability.
Development of Processing Technologies
In order to gain experience in processing and using these materials, forged ingots of SS
304HCu and Alloy 617M, starting from the basic ingredients, have been manufactured
on a pilot scale. The materials were characterized at each stage of the production
process and the process was optimized to achieve the specifications and the desired
properties. The manufacturing process has been stabilized and is capable of being
scaled up.
Boiler tubes of SS 304HCu and Alloy 617M have also been manufactured on a pilot
scale, starting from the forged ingots developed earlier. A detailed stage wise
characterisation approach was adopted for the development of tubes of SS 304HCu and
Alloy 617M in order to ensure that the process of manufacture was optimized to obtain
the specified characteristics. This approach helped to overcome problems faced during
the initial trials. The series of heat treatments and characterizations at various stages of
tube manufacture helped in understanding the materials behavior towards mechanical
working and heat treatment. Based on these metallurgical inputs, the process flow
sheets were evolved and optimized.
Materials Testing
A comprehensive materials testing program covering long term creep tests and hot
corrosion for the parent metal, tubes and welded joints, both similar and dis-similar, has
been put in place. The tests being carried out are briefly described below:
Creep Tests
Long term creep tests on Alloy 617M at 650, 700, 750, 800 C, with stress 100 MPa to
360 MPa, and test durations ranging from 100 hours to 10,000 hours are in progress.
Creep tests on Alloy 617M welded with Alloy 617 filler material are being carried out at
650, 700, 750, 800 C, with stress 100 MPa to 360 MPa, and test durations ranging from
100 hours to 1200 hours. Tensile and hot tensile (600-800 C) impact tests are also
being carried out.
Creep tests on Super 304HCu tubes welded with Alloy 617M and Alloy 625 filler material
at 600, 700, 750 C, and stress 125 MPa to 275 MPa, with test durations ranging from
100 hours to 1,500 hours are in progress. Creep tests on parent metal at 600, 650,
55
700C, with stress 100 MPa to 360 MPa, and test durations ranging from 100 hours to
2,000 hours are being carried out.
Creep tests are also being carried out on dissimilar welds of Alloy 617M with SS
304HCu using Alloy 617 filler material welds at 600, 650 and 700 C, and stress 180
MPa to 280 MPa, with test durations ranging from 100 hours to 3,000 hours.
Hot Corrosion Tests
Hot corrosion tests in a simulated flue gas environment have been carried out on Alloy
617M and SS 304HCu tubes in the laboratory at 600, 700, 800 C for up to 1000 hours
duration.
Hot Corrosion Test Loop
The materials chosen have been extensively tested elsewhere for hot corrosion. To
check for hot corrosion with firing of Indian coal, a corrosion test loop is planned to be
installed at an existing power plant in India.
The test loop comprises tubes of T91, SS 304HCu and Alloy 617M. The steam flow is
taken from the main steam line at a temperature of about 540 C. In the test loop, the
steam is heated to a temperature of 720 C. After the test loop, the steam pressure is
reduced to hot reheat pressure in a multistage steam regulation valve, which regulates
the steam quantity to achieve the steam temperature of 720. The steam from the
regulating valve is mixed in a mixing piece with relatively cold steam at about 390 C,
taken from the Low Temperature Superheater (LTSH) outlet link, to get steam at a
temperature of approximately 540 C, in order to return the steam flow into the hot
reheat pipeline. The test loop is likely to be installed in 2014 and is planned to be in
operation for at least two years.
Manufacturing Technologies
To gain hands-on experience in manufacturing with high temperature materials, trials for
all the operations required during the manufacture of boilers, steam turbines and other
power plant equipment, are being carried out. Some of these are briefly mentioned
below.
Welding of Tubes and Plates
Welding was carried out on tubes and plates using various processes like Gas Tungsten
Arc Welding (GTAW), Hot Wire GTAW, semi-automated GTAW on Alloy 617M. The
trials were successful and it was possible to get consistent quality of the butt welds in all
the cases. The process parameters have been finalized for the welding with the
available materials. Some dissimilar welding combinations were also tried out and the
outcome was satisfactory. Figure 1 shows a sample tube to tube butt weld joint.
56
welding and establishment of advanced ultrasonic testing techniques for the detection of
discontinuities in butt and fillet welds.
HP Bypass Valve
Development of valves to suit the pressures and temperatures encountered in A-USC
boilers has been identified as a critical area, due to the complexity of valve design. The
High Pressure Bypass valve for high pressure steam turbine is one such valve, which is
subjected to A-USC steam parameters at the inlet to the HP turbine. The design and
manufacture of an HP Bypass valve for A-USC parameters is therefore being taken up.
Several developmental tasks will be undertaken, including development of materials for
body and other components, stem, hard facing, fasteners, and packings of the valve,
establishment of body spherical and other machining, stem milling, deep hole drilling,
destructive and non-destructive testing procedures, establishment of body-nozzle
welding, seat hard facing, body assembly-seat welding procedures, and establishment
of advanced ultrasonic techniques for detection of discontinuities in welds.
Dis-similar Weld Joint of Turbine Rotor
Development of steam turbine rotor forgings of advanced high temperature nickel base
materials is an important area to be addressed while considering the 710C / 720C
steam cycle. Considering that a monolithic rotor of Alloy 617M would be expensive, a
welded rotor is being considered. The rotor would have an Alloy 617M forging for the
high temperature portion of the HP/IP rotor, with a dis-similar metal weld joint between
the cylindrical forgings of Alloy 617M and 10% Cr steel. Operating experience on dissimilar metal weld joints is not very satisfactory. The joining technique therefore needs to
be developed and tested thoroughly. To address the main issues related to welded
turbine rotor manufacture, laboratory scale studies to demonstrate the weldability of
large size forgings of Alloy 617M to 10% Cr steel and optimization of weld procedures
and welding consumables, while maintaining the properties of the forgings, are being
undertaken.
Technical specifications for the Alloy 617M rotor forgings suitable for use in the 800 MW
A-USC plant, developing the supply base for manufacture of scaled down Alloy 617M
cylindrical forgings, procedure development for narrow-gap tungsten inert gas (NG-TIG)
welding of dissimilar metal weld joints, finalizing the associated non-destructive testing
methodologies, and characterization of the short-term and long-term mechanical
properties of the Alloy 617M/ 10%Cr steel joint are some of the outcomes of the work.
Blade Profiles for HP Turbine
Design of steam flow path and blade profiles for A-USC parameters are important
aspects of steam turbine design as blades using advanced high temperature alloys are
being designed for the first time. A project to develop the blade profiles for A-USC
parameters is under way and is nearing completion. Trial manufacture of steam turbine
blades with Alloy 617M is also being undertaken as part of the project, to ensure that the
manufactured blades satisfy all the specifications. The profile design is also being
verified through Computational Fluid Dynamic (CFD) analysis and also through physical
cascade testing in the laboratory.
58
Thermal Cycle
The target efficiency of the A-USC plant has been set as 46% on HHV basis, under
Indian environmental conditions (cooling water temperature of 33 C), and with Indian
coal firing. This gives a reduction in CO2 emissions of about 11% compared with a
supercritical plant of the same rating. The thermal cycle of the plant has been designed
after a series of techno economic studies to achieve the most economical and efficient
configuration.
Conceptual Design of Boiler
Several techno-economic studies were carried out to decide the optimum configuration
of the boiler. A two pass, single reheat boiler configuration with tilting tangential firing
has been selected.
Tubes of SS304HCu and Alloy 617M are used in the high temperature zones in the
superheater and reheater. Some new features to maximize the utilization of heat are
also included.
CONCLUSION
A National Mission for the development of A-USC technology for thermal power plants
has been initiated by the Government of India, with BHEL, IGCAR and NTPC
constituting the core team. The objective is to establish an 800 MW A-USC
demonstration power plant in a time frame of seven years. A comprehensive plan of
action has been prepared for developing the entire range of technologies necessary.
Several proactive initiatives have been taken to gain a lead time and accelerate the work
before the formal start of the project. There is a strong focus on achieving self reliance in
technology and low cost manufacturing through indigenization.
ACKNOWLEDGEMENTS
The authors wish to acknowledge the help provided by the Office of the Principal
Scientific Adviser to the Government of India and the managements of BHEL, IGCAR
and NTPC in carrying out the work described in this paper and for permitting them to
present this paper. The authors also acknowledge the enormous efforts of the teams in
each organization who carried out the work.
59
feet) deep pile foundations. Available at the site boundary are rail and transmission access, raw
water supplied from Lake Michigan, and natural gas. The fuel delivered by rail is Wyoming
Powder River Basin (PRB) sub-bituminous coal, with characteristics as detailed in Table 1.
The A-USC PC plant is designed with an annual capacity factor of 80%. Annual capacity factor is
defined as the actual annual production divided by the plant rated capacity times 8,760 hours.
The plant design is based on using components suitable for a 30 year life, with provision for
periodic maintenance and replacement of critical parts.
Steam Generator
The boiler island scope and general design basis are summarized below.
The unit is sized to have a gross output of 850 MW before the addition of the PCC system.
Low-NOX axial-swirl burners with over-fired air and SCR is used to achieve emission limits
of 0.03 lb/MBtu (0.013 kg/GJ).
A bottom ash system (submerged chain conveyor) to remove ash from the hopper throat
feeding it into a water-filled trough.
Mercury Removal Halogen injection into the boiler promoting mercury oxidation over SCR
catalyst with co-capture in the FGD. Possible supplemental capture using activated carbon
injection ahead of the ESP, if required.
The PCC technology for this study includes a conventional two column absorber/regenerator
scheme designed for 90% CO2 removal and utilizing 30 wt% MEA as the solvent.
62
Table 1
Coal Analysis for Wyoming Sub-Bituminous Coal
Proximate Analysis Weight Percent As Received
Moisture
30.24
Ash
5.32
Volatile
31.39
Fixed Carbon
33.05
48.18
Hydrogen
3.31
Nitrogen
0.70
Chlorine
0.01
Sulfur
0.37
Oxygen
11.87
Ash
5.32
Moisture
30.24
Heating Value As Received
19,400 (8,340)
17,900 (7,710)
Table 2
Emissions Limitation HHV Basis
Pollutants
Emission Limits
3
PM10
0.01 lb/MBtu
~10 mg/m
PM2.5
0.013 lb/MBtu
~13 mg/m
SO2
0.03 lb/MBtu
~30 mg/m
NOX
0.03 lb/MBtu
~30 mg/m
VOC
Mercury
3
3
3
Carbon Dioxide
Varies
63
The portion of the flue gas exiting the FGD unit and entering the PCC system first enters a flue
gas scrubber where it is contacted with circulating, cooled water. This scrubber cools the flue
gas, which by decreasing volumetric flow and condensing water improves absorber performance.
By adding a dilute caustic solution to the circulating water, residual SO2 in the flue gas can be
removed reducing degradation product formation
From the scrubber, the cooled flue gas enters a blower that provides the head to overcome the
pressure drop of the absorber and piping without increasing the back-pressure on the FGD
system.
The flue gas enters at the bottom of the column and flows upward, and the CO2-lean solvent
enters at the top of the column and flows downward. The CO2-depleted flue gas enters the upper
wash section of the column and is brought in contact with circulating water that cools the flue
gas and scrubs out any amine present. The cleaned flue gas then flows to the stack for discharge
to the atmosphere.
The CO2-rich solvent exits the bottom of the absorber where it is pumped through the rich/lean
solvent exchanger and into the regenerator. The hot rich solvent enters the top of regenerator
where the absorbed CO2 is released by the addition of heat. The heat breaks the chemical bonds
between the CO2 and the solvent, liberating the CO2 and regenerating the solvent so that it can be
returned to the absorber for CO2 removal. The heat is provided by the condensation of low
pressure (~4 bar (60 psi) steam) in the regenerators kettle-type reboilers, the steam being
extracted from the crossover between the IP and LP steam turbines. Heating the rich solvent
before it enters the regenerator decreases the extraction steam required.
The gas leaving the regenerator is cooled before being sent to the reflux drum. The gas exiting
the reflux drum is the product CO2 which is sent to the CO2 compressor system and compressed
to approximately 150 bar (~2200 psia) before entering the pipeline.
The lean solvent exits the bottom of the regenerator and flows through the rich/lean solvent
exchanger where it is cooled. The exiting lean amine is cooled in a trim cooler before returning
to the absorber.
MODELING
PC Cost is a Microsoft Excel based costing tool developed by EPRI that has evolved over a
24 year period of time. Its purpose is to allow engineers and planners to estimate the conceptual
and preliminary costs of PC-fired, subcritical and supercritical power plants [6]. It calculates the
heat and material balance for the unit and the overall plant performance based on the fuel
specification and then determines the cost of the major equipment subsystems by scaling from
reference costs. These reference costs are based on budgetary quotes and/or in-house developed
estimates which have been updated periodically over the life of the costing tool. The goal is to
provide a +/- 30% estimate for the costs for the equipment and materials within the plant
boundary, which includes all the direct and indirect costs for: site preparation, earthwork,
concrete and structural steel, building construction, major equipment, auxiliary equipment,
piping, electrical/instrumentation/control equipment as well as construction labor, bulks, and
subcontractors.
Beginning in 2011, PC Cost was modified to allow it to estimate the performance and cost of AUSC units. As part of that modification, it was decided to use AspenTechs AspenPlus to
perform the majority of the heat and material balance calculations. This would also allow for the
use of the physical properties generated by AspenPlus to be used for heat transfer calculations.
Additional capability was added to allow PC Cost to be able to choose the most cost effective
material for each row of tubes in the boiler backpass, depending on the design pressure and
64
calculated metal temperature. The possible material selections include carbon steel, T91, S304H,
HR3C, HR6W, IN617, HR230 and IN740.
PC Cost assumes a boiler configuration to perform its heat transfer calculations. This
configuration and the corresponding AspenPlus model are shown in Figure 1. Sizing of the PC
furnace is performed using proprietary methods. PC Cost sizes the backpass of the boiler using
conventional heat transfer methods using the flowrates, temperatures, and physical properties
from AspenPlus to determine the heat transfer coefficients and the surface area. The
temperature and pressure of the steam/water are used to determine the wall thickness of the tubes,
tube weights, and then the cost is determined by using unit costs ($/kg) for the boiler components.
One of the main objectives of this project was to produce these studies on a consistent basis as the
pressure and temperature changed. However, one early conclusion from this study is that using
the same boiler geometry for all temperature cases significantly penalizes the higher temperature
cases. PC Cost inherently assumes a long piping run from the top of the boiler to the steam
turbine. As the temperature increases, the material of piping quickly transitions to Inconel 740,
which is roughly 10 times the cost (per kg or lb) than T91. Boiler and turbine manufacturers are
designing plant layouts that minimize the amount of high-nickel alloy required. One option is a
horizontal boiler design proposed by Siemens, [7] which would minimize the length of piping
between the boiler and the turbine. An alternate design would separate the HP and IP turbines
into multiple components [8]. A high temperature HP section would be located near the top of
the boiler, and this would exhaust at a lower temperature and pressure into a conventional HP
steam turbine. After the steam is reheated, the high temperature, hot reheat steam would enter a
similar IP section near the top of the boiler which would exhaust into a conventional IP turbine.
For the remaining equipment, the costs are scaled from reference plant costs using industryaccepted algorithms whose exponents and constants are tailored to each type of equipment.
Additional changes were made to the cost estimate calculation of the steam turbine. Since there
is no commercial A-USC turbine at this time, a method was devised to estimate its cost relative to
a USC turbine. The temperature limit for the steam turbine estimated in PC Cost is 595oC
(1100oF). After discussions with steam turbine consultants, it was decided to apply a
multiplication factor to this estimated steam turbine cost to account for the change in materials
required for the higher operating temperature. At 595oC (1100oF), this multiplication factor was
1.0, and it linearly increased to 1.2 at 760oC (1400oF). Several organizations are currently
working to provide a preliminary design of an A-USC turbine, and a more accurate cost. When
this information becomes available, it will be incorporated into PC Cost.
The steam system heat balance was modeled in Gate/Cycle using Spencer-Cotton-Cannon
algorithms to predict the efficiency of the turbine under the various operating conditions. A
simulation was created for the base plant (no-PCC) and converged on a steam turbine gross
power of 850 MW. This information was used by PC Cost/AspenPlus to calculate the coal flow
rate and the heat and material balance for the boiler systems. The power consumption within the
steam cycle (HP BFW pumps, condensate pumps, etc) was calculated by Gate/Cycle, and the
auxiliary loads for the boiler and AQCS systems were calculated by AspenPlus based on the
calculated flowrates. Values not calculated by AspenPlus for certain plant equipment (mill
power, for example) were estimated from previous EPRI reports.
For the PCC cases, the coal feed and the steam/water flows calculated for the non-PCC cases
were fixed. The LP steam extraction for the PCC system was removed from the IP/LP crossover.
This steam was condensed in the PCC regenerator reboilers and returned to the steam cycle.
However, as expected, the steam extraction resulted in a significant decrease in gross power.
Within the PCC system, there are opportunities to recover useful heat and use this energy to heat
the boiler feed water leaving the condenser. This allows the steam that would normally be
65
extracted from the steam turbine for boiler feedwater heating to be used to generate power. A
heat integration study was carried out for all cases based on the experience gained in previous
reports (References 2-5). This allowed for the increase of gross power and improved the plants
performance as well as reducing load on the cooling tower. Typically 30% of the heat in PCC
system was transferred to the boiler/steam turbine system.
SPRAY2
SPRAY1
MSPIPE
MAINSTM
STM7
FINSH
(HEATER)
STM6
ATT2
(MIXER)
PLATSH
(HEATER)
STM5
ATT1
(MIXER)
STM4
STM3
PSH
(HEATER)
STM2
FGSPLIT
(FSPLIT)
PLATSHQ
FINSHQ
SCR1Q
ROOFWLQ
SCR2Q
RWSTOTQ
PLATSHFG
(HEATER)
FG2
FINSHFG
(HEATER)
FG3
SCR1
(HEATER)
FG4
ROOFWALL
(HEATER)
FG5
SCR2
(HEATER)
PSHQ
FG6
FG7A
FGSPLIT
(FSPLIT)
HRH2TUR
RWSCR
(HEATER)
HRHPIPE
FG7B
HRHOUT
FG1
PSHFG
(HEATER)
REHEATFG
(HEATER)
REHEATQ
REHEAT
(HEATER)
STM1
CRH
FG8A
FG8B
MXFG
(MIXER)
BOILERWA
(HEATER)
BOILERQ
BOILERFG
(HEATER)
BFW2
FG9
FG0
FWECONQ
FWECON
(HEATX)
FWECONW
(HEATER)
BFW1
LOSS
(HEATER
SPL-SPRA
(FSPLIT)
TOSCR
TSPRAY
BFWIN
DRY-COAL
BURNER
(RGIBBS)
HOPPER
(SEP)
AMMONIA
SCR
(RSTOIC)
INGRESS
MXINGRESS
(MIXER)
FROMSCR
BTMASH
AIR
TOAIRHTR
ESPDP
AIRHEAT
(HEATER)
AIRHTOUT
TOESP
FLYASH
AIRHTQ
PASAHEAT
(HEATER)
Figure 1
PC-Cost Boiler Configuration
66
ESP
(SEP)
AMBAIR
TOID
IDFAN
(COMPR)
TOFGD
In addition to the loss of gross power, there is a significant increase in the auxiliary power with
the addition of the PCC system, primarily due to the large CO2 compressors. The decrease in
gross power and increase in auxiliary power creates a substantial decrease in net power,
especially for the 90% CO2 removal cases.
It is intuitive that reducing the percentage of the CO2 removed from the flue gas would have a
significant improvement on the plants performance and economics. To meet the EPAs
Standard of Performance approximately half of the CO2 would have to be removed from the
flue gas compared to 90% CO2 removal. This reduces the LP steam extracted which reduces the
effect on gross power, as well as the auxiliary power load.
BASE PLANT RESULTS (NO PCC CASES)
The results of the Base Plant cases are shown in Table 3. As steam temperature increased, the
overall plant efficiency increased and CO2 emissions decreased. Since the coal flow decreased
with increasing temperature, the power requirements associated with coal feeding and the AQCS
systems decreased. As steam flowrate per MW decreased, the HP BFW pump power also
decreased. These improvements decreased the auxiliary load and increased the net power.
As coal flow decreases, the capital costs for the coal feed system, ash removal, and the AQCS
systems all decrease. As the steam temperature increases, the cost of the boiler increases
primarily for three reasons:
Beyond a certain temperature, the strength is too low and/or corrosion rates too high for
one material and another material must be substituted for the application. Typically,
these upgraded materials are more expensive on a per pound or per kilogram basis.
Even though the steam temperature is increasing, the temperature profile of the flue gas
through the boiler is approximately the same. Therefore, the driving force for heat
transfer is decreasing which requires a larger surface area for a given heat duty.
This can be evidenced in Table 3 which shows the capital cost increasing by 15% between the
595oC (1100oF) case and the 760oC (1400oF) case.
Although the coal feed decreases with increasing steam temperature, the cost of electricity (COE)
increases due to the increasing capital cost. For example in going from 595oC to 760oC (1100 F
to 1400F) the CO2 emissions fall 7.3% but the COE increases 9.1%. One important observation
is that the results in Table 3 reflect conditions in the U.S. market. EPRI has been working with
members in Asia to understand the differences between projects in the U.S. and Asia, and work is
ongoing in this area. The COE in Table 4 shows a comparison between the U.S. market and Asia
based on the following assumptions:
67
Table 3
Preliminary Performance and Economics of 345 bar (5000 psia) units with no PCC.
o
Description
595 C/615 C
1100F/1140F
Gross plant
output, kW
850,000
850,000
850,000 kW
850,000 kW
Auxiliary
load, kW
87,716
82,894
78,925
76,055
Net plant
output, kW
762,284
767,101
771,075
773,945
Net plant
heat rate
8,534 Btu/kWh
9,056 kJ/(kWh)
Net plant
efficiency
(HHV)
39.7%
41.2%
42.4%
43.3%
Plant fuel
consumption
784,500 lb/hr
355,900 kg/hr
761,800 lb/hr
345,500 kg/hr
744,600 lb/hr
337,700 kg/hr
731,700 lb/hr
331,900 kg/hr
CO2
Emission
1,382,000 lb/hr
627,400 kg/hr
CO2
Emission
Capital
Cost, $1000
$1,732,000
$1,766,000
$1,834,000
$2,001,000
Capital
Cost, $/kW
$2,270
$2,300
$2,380
$2,590
$363,000
$365,000
$378,000
$402,000
$67.90
$68.00
$70.00
$74.10
Total
Annual
Costs,
$1000/yr
Cost of
Electricity,
$/MWh
68
EPRI has learned anecdotally that capital costs on a $/kW basis in Asia are 50-70% of
the cost based on U.S. estimates. For this comparison it is assumed that the capital cost
is 60% of what is estimated by PC Cost.
Richardson International Cost Factor Manual [9] estimates the labor index relative to the
U.S. market. The average labor index for Asia given in the manual (Taiwan, Korea, and
India) is 0.4. This was used to adjust the operating and administrative labor rates.
Table 4
Comparison of the COE between the U.S. and Asia
Steam Cycle
U.S. COE
Asia COE
595 C/615 C
(1100F/1140F)
$67.90
$68.70
650oC/671oC
(1200F/1240F)
$68.00
$67.80
705oC/727oC
(1300F/1340F)
$70.00
$68.20
760oC/760oC
(1400F/1400F)
$74.10
$70.20
In the U.S. the COE is largely determined by the capital cost and the coal component is relatively
small. In Asia the reverse is true; the coal cost is a significant portion of the COE. This is
illustrated in Figure 2, which shows the major components of the COE for the 595oC (1100oF)
case. The coal component is about 22% of the COE in the U.S. and about 50% in Asia.
Therefore, operating at higher efficiency is economically important.
As Table 4 shows, the COE is less for the 650oC and 705oC cycles (1200oF and 1300oF) than for
the 595oC (1100oF) cycle. If coal prices increase, this difference becomes more significant.
Because these units all have the same boiler/turbine configuration, the higher temperature cases
are penalized because of the long runs of Inconel 740 main/reheat steam piping. EPRI will
evaluate the cost savings of alternate A-USC plant designs in future work.
69
U.S.
Asia
Capital
Coal
FOM
VOM
Figure 2
1
Cost of Electricity Components in the U.S. and Asia
A-USC AND CO2 CAPTURE
The most significant economic driver for A-USC in the U.S., Europe, and other countries may be
CO2 removal from PC power plants. As previously mentioned, the EPA has released a Standard
of Performance for the removal of CO2 from fossil plants exhaust gas. The Standard proposed a
limit of 1000 lb CO2/MW on a gross basis. Since its release the Standard has been in a comment
and review period, but it is expected that a final limit will be released by the EPA by the end of
2013.
To meet the partial capture limit, slightly less than half of the flue gas enters the PCC absorber.
Because of this, less steam is extracted from the steam turbine and the reduction in gross power
decreases. To meet the EPAs Standard of Performance for the partial CO2 capture cases the
decrease in efficiency was about 4 percentage points as shown in Table 5.
Because of the loss of net power, there is an amplification of the capital cost on a $/kW basis.
For example, in the 595oC (1100oF) case, the overall capital cost increases 14% over the unit with
no PCC. However, on a $/kW basis, the capital cost increased 27% over the case with no PCC
system. On average, the COE increased approximately 30% over the non-PCC cases.
Note: FOM Fixed Operating & Maintenance Costs, VOM Variable Operating &
Maintenance Costs.
70
Table 5
Preliminary Performance and Economics of 345 bar (5000 psia) units with 1000 lb
CO2/MW(g) Emissions Target
Description
815,348
816,484
818,526
821,256
Auxiliary load, kW
130,018
122,143
115,705
110,821
685,330
694,341
702,821
710,435
37.3%
38.6%
39.7%
816,000 lb/hr
370,000 kg/hr
817,000 lb/hr
370,000 kg/hr
819,000 lb/hr
371,000 kg/hr
821,000 lb/hr
373,000 kg/hr
$1,975,000
$2,002,000
$2,063,000
$2,225,000
$2,881
$2,883
$2,936
$3,133
$435,000
$434,000
$440,000
$462,000
Cost of Electricity,
$/MWh
$90.50
$89.20
$89.50
$92.80
The boiler/turbine configuration. One significant conclusion from this study has been that
the cost of the long main and reheat steam lines between the boiler and the steam turbine
significantly increases the capital cost at the higher steam temperatures. Alternate
boiler/steam turbine configurations will be necessary for A-USC designs to be economically
competitive at temperatures higher than 700oC (1300oF).
The alloy costs. Currently Inconel 740 pipe and tubing is estimated to cost 25 times more on
a per pound or kilogram basis than carbon steel. However, Inconel 740 pipe and tubing have
71
not been manufactured in commercial quantities, so this cost is largely speculation. As the
first A-USC units are built, the price for these materials is expected to decrease.
The cost of the turbine. The cost for an A-USC turbine is unknown. As the market
develops, the price for an A-USC turbine will become better understood.
The applicability of A-USC in Asia will largely be driven by coal price. A-USC power
plants will become more economic at higher coal prices.
The plant availability. The Cost of Electricity for these studies is based on a plant
availability of 80%, which is typical of U.S. units in todays market due to increased
renewable energy usage for power generation. Coal fired units in Asia may be operating
closer to 90%, which would decrease the COE.
CO2 capture requirements. If coal is burned in future U.S. power plants, some amount of
CO2 capture will be required. The final regulations for CO2 removal in new fossil power
plants are expected by the end of 2013. The limit set by this regulation will determine to a
large extent the economics of future coal fired units in the U.S.
Finally, significant work is ongoing in many areas of the world related to A-USC:
Both China and India have announced plans to build 700oC A-USC units within the next 5-7
years.
Turbine manufacturers are working to develop A-USC steam turbine designs and estimate
the cost to build an A-USC turbine.
Due to the high cost of the nickel alloys, the cost of the main and reheat steam lines from the
boiler to the turbine will be a significant percentage for the overall power plant capital cost.
Boiler, turbine manufacturers, and EPCs are evaluating plant layout configurations to
minimize the length of these lines, which could change the economic conclusions reached by
this paper
The Materials Consortium continues to work with materials suppliers to understand alloy
prices in commercial quantities.
Because the EPA regulation is based on gross output, there may be advantages to using CO2
removal technologies that do not decrease gross power. EPRI is currently researching the
use of membranes for the removal of CO2. The results of this work are planned for release
later in 2013.
72
REFERENCES
[1] Engineering and Economic Evaluation of 1300F Series Ultra- Supercritical Pulverized
Coal Power Plants: Phase 1, EPRI, Palo Alto, CA 2008, 1015699.
[2] An Engineering and Economic Assessment of Post-Combustion CO2 Capture for 1100oF
Ultra-supercritical Pulverized Coal Power Plant Applications: Phase II Task 3 Final
Report, EPRI, Palo Alto, CA 2010, 1017515.
[3] Engineering and Economic Evaluation of 1300oF Series Ultrasupercritical Plant with PostCombustion Capture: Engineering and Economics, EPRI, Palo Alto, CA 2012, 1026645.
[4] Engineering and Economic Analysis of a 1300F Series USC Demonstration Plant with
Natural Gas Equivalency Post-Combustion Capture. EPRI, Palo Alto, CA, 2013. 1026644.
[5] Minimizing the Derate of Adding Post Combustion Capture to Pulverized Coal Units
EPRI, Palo Alto, CA: 2012. 1023864.
[6] Hoskins, Bill (URS), and Booras, George (EPRI), Assessing the Cost of New Coal-Fired
Power Plants, Power Magazine, October 2005, pg 24-28.
[7] Smith, David, Horizontal Boilers make 700oC Steam Economic, Modern Power Systems,
May 2000, pg 36-41.
[8] Feng, Weizhong, Technology Innovation of Most Efficient Coal Power Plant and Plan for
Future, presented at EPRIs CoalFleet Technical Meeting, Mobile, AL, December 2012.
[9] Richardson International Construction Factor Manual, Cost Data On Line, Inc., Prescott, AZ,
2011.
[10] Coal Trader International, Platts, Volume 13, Issue 135, July 13, 2013
73
mechanical testing),Steam Turbine (WPs rotor forging, rotor welding and casting) and
Integration (WPs operating conditions and environments, steam cycle modeling integrating
carbon capture and superheater life modeling).
The partners in the project are DNV KEMA, Doosan Babcock, Skoda Power, E.ON, Cranfield
University, Goodwin Steel Castings, Monitor Coatings, Saarschmiede, Aubert & Duval, VTT,
VZ, TU Darmstadt and Special Metals. The project started May 1st, 2010 and has a duration of
48 months. The budget is 10.3 million (6 million EU contribution).
BOILER
Fireside corrosion
Co-firing biomass and higher metal temperatures increase the risk on high-temperature corrosion
and its rate. Co-firing biomass causes a more severe oxidation due to the higher alkali and
chlorine content in biomass. Alkalis can form low-melting eutectics causing Hot Corrosion. The
oxidation rate in chlorinated atmospheres is more severe compared to sulphidation. Generally,
salts containing chlorides have a lower melting point compared to salts including only sulfates.
Advanced materials contain, in general, Ni and Cr. It was generally found that a higher Crcontent and (Ni+Cr)-content will increase the fireside corrosion resistance under coal firing
conditions [3], [4], although test results for Ni-alloys in [5] do not confirm this findings. Ni
alloys in general suffer from fireside corrosion due to Hot Corrosion and internal sulphidation,
depending on the temperature [6].
A test program was set up including lab screening trials and rig trials for investigation of
materials and coatings at A-USC temperatures, allowing systematic research in well-defined
conditions. Plant trials are performed to demonstrate the material behavior in service for a longer
time.
Fireside corrosion screening tests
Cranfield University executes a screening program with base materials T24, T92, A316, Sanicro
25, S304H, TP347HFG, A617, A263 and A740H, coated and uncoated, with and without
deposits and under different gas environments in a temperature range of 600 800C. The tests
were carried out in a furnace (Fig. 1). Different coatings are applied: NiCr, FeCrAl, NiCrAlY,
NiCrWMoCu, NiCrMoWFe, CrNiC, and NiCrMo(Nb+Ta).
Results after 1,000hrs [7] show that Ni-alloys A617, A263 and A740H have a broad front type
corrosion attack at 650C and 700C without internal damage. The corrosion mechanisms in all
three alloys changed at higher temperatures (750C and 800C) and the alloys suffered from
significant internal corrosion. A263, A617 and A740H all suffered from similar metal losses at
the lower temperatures (650 and 700C); however, at the higher temperatures (750C and 800C)
A740H outperformed A263 and A617.
75
Figure 1: Schematic diagram of a controlled atmosphere furnace setup for fireside corrosion in
simulated air-firing combustion gases at Cranfield University
Coatings A625, NiCr, FeCrAl and NiCrAlY were deposited on T91 using HVOF (High Velocity
Oxy Fuel) and plasma spraying. The thermally sprayed coatings suffered significant corrosion
attack. The plasma-sprayed coatings showed less corrosion than the HVOF-sprayed coatings due
to a lower porosity. NiCr showed the lowest thickness reduction of ~87m (HVOF-sprayed) and
~13m (plasma-sprayed). In general, the median degradation for coatings had the following
ranking (in the descending order: most to the least damage): NiCrAlY > A625 > FeCrAl > NiCr
[8]. Based on the screening tests, a selection of the base materials and coatings will be tested in a
100kW burner test rig at Cranfield University.
VTT tested substrates X20, Sanicro25 and A263 with coatings NiCr, A625, Diamalloy 4006 and
Nanosteel SHS9172 (DJ, Diamond Jet Spray by Sulzer Metco and CJS, Carbide Jet Spray by
Thermico) [9]. The materials were covered with 6.5wt%NaCl-59wt%Na2SO4-34.5wt%KCl salt
and exposed to a air-0.1%HCl-1%SO2-10%H2O atmosphere for 168hrs at 575C and 625C.
The Diamalloy 3006 DJ and SHS9172 CJS coatings had the best corrosion resistance against
molten salt attack. SHS9172 DJ showed good corrosion behavior, but vertical cracking should be
prevented with sufficient coating optimization. NiCr DJ, A625 CJS and A625 DJ formed
protective but thick corrosion layers especially at 575C. High melting state coatings NiCr, A625
and Diam4006 showed sufficient corrosion protection.
Fireside corrosion plant demonstrations
VTT performed corrosion tests [10] at the 550MWth CFB Alholmens Kraft power plant (Finland)
firing 30% peat, 10% coal, 50% biomass (mainly wood) and 10% SRF (Solid Recovered Fuel).
During the measurements (~1,300 hrs) an air/water-cooled superheater probe contained two sets
of specimen rings, one controlled at 550C, and one at 750C. T92 was used as substrate for the
550C set and exposed both uncoated and with five different coatings: NiCr, A625, Diam4006,
NiCrTi and SHS9172. An identical test was carried with A263 substrate at 750C. As a result the
coated T92 showed a decreased corrosion compared to the uncoated martensitic steel. For A263
the uncoated material as well as A263 coated with NiCr and NiCrTi showed the lowest
degradation while A625 showed severe corrosion. DIAM4006 was nearly completely oxidized.
Two additional measurement campaigns will be carried out.
76
To investigate membrane wall corrosion, DNV KEMA installed KEMCOPs i.e. M8 probes
protruding the strip of the membrane. The materials 15Mo3 (450 500C), 10Cr9-10 (450
550C), T24 (500 600C), T92 (450 500C), A617 (550 750C) and A263 (500 750C),
are exposed for 5,000 15,000 hours. The probes are installed at three Dutch coal/biomass fired
power plants of GDF Suez, RWE/Essent and E.ON. The length reduction rate was determined
after 5,000 hours for materials T24, A617 and A263. Figure 2 compares the results from RWE
(C) and E.ON (B) plants with results from an earlier corrosion test (coal plant (A)). Both Nialloys showed similar length reduction which was lower compared to T24. Superheater probe
tests are currently running for 15Mo3, A263 and Alloy 740H at 540 750C at the above
mentioned plants including electrochemical noise measurements.
120
100
T24 Coal boiler A
80
60
40
20
0
400
500
600
700
800
temperature (C)
77
Cranfield University conducts lab-scale exposure tests with small ring sections of test materials,
either coated or uncoated, in a flowing steam atmosphere at 600 800C. The steam is supplied
in a closed system, with de-ionized water supplied to the tube furnace where is it converted into
steam directed over the samples. The materials include T24, T92, A316, Sanicro 25, S304H,
TP347HFG, A617, A263 and A740H. Two aluminum coatings are tested, a slurry coating and an
ionic liquid application coating.
The results show that mostly thin oxides are formed on the highly alloyed materials - as expected
for samples with ground surface finishes. Nodular growths increased with time and temperature.
Sanicro 25 outperformed other stainless steels (304H, 316, 347 HFG) at 700- 800 C and all
stainless steels, except for Sanicro 25, suffered from scale spallation at 800 C. Ni-based alloys
showed small mass gain at 700C and 750C (~0.2 and ~0.4 mg/cm2 respectively). At 800 C,
A617 and A740H outperformed A263. After the screening tests, exposure tests are performed in a
pressurized rig at Cranfield University (up to ~40bar, 800C) and at VTT (~40bar, 700C).
Relaxation Cracking
Relaxation cracking occurs in zones with residual stresses that are relieved by time dependent
inelastic deformation during PWHT or service. Materials with low (creep) ductility cannot
withstand the inelastic strains due to relaxation, and exhibit cracking within 3 years of operation.
Precipitations of second phases in the material matrix hinder relaxation of the residual stresses in
the matrix. As a result, the stresses preferentially relax in a small precipitate-free zone along the
grain boundaries. This may result into inter-crystalline cracking and brittle rupture.
A hot tensile test serves as a screening test to observe if A263 can accommodate plastic
deformation in the temperature range of 700 750C, where the lower the ductility, the higher
the susceptibility to relaxation cracking. The test is performed by VZ and is strain controlled.
Material before and after PWHT is tested, base metal and cross weld specimens are compared. A
notched stress relaxation tests is performed to show the effect of heat treatment at 980C for
180min on stress relaxation (according to standard EN 10319-1:2003).
TU Darmstadt performs a cyclic notch stress relaxation test which is considered to be similar to
service conditions. A263 samples specimens are tested in the as welded condition, after PWHT
and after service simulation (i.e. strain aged at temperature to 1% creep strain, over 3,000hrs).
The load controlled tests are performed at 700 750C, with dwell times (1h and 10h) to allow
for relaxation, and without dwell time for comparison. Strain is locally measured with an
extensometer, in and outside the notch. Stress in the notch is calculated with Neuber parabola and
the re-distribution of stress in the notch is studied.
Gas Phase Embrittlement
Ni-based alloys contain the hardening precipitates NbC. Oxidation of NbC can form CO2 gas
bubbles, forming intergranular cavities. Cracking follows on grain boundaries leading to brittle
failure. NbC can also oxidize to Nb2O5 but it is still investigated whether Nb is a crucial factor in
the cracking system. Gas phase embrittlement is identified with a Slow Strain Rate Test (SSRT).
Tensile and strain are controlled while a strain rate of 0.006%/min is applied. Specimens include
parent material and cross welds, and in all cases pre- and post-service material is tested.
Microscopic investigations of the base material (both pre and post-service simulation) show
disaggregation indicating gas phase embrittlement, see Fig. 3.
78
Figure 3: Base material (left), base material after SSRT at 750C (middle) and base material
with service simulation after SSRT at 750C (right)
Creep-Fatigue Interaction
Creep, fatigue and its interaction of A263 is investigated in the region 700 750C. Doosan
Babcock performs creep rupture tests (load controlled) on parent material and longitudinal welds,
both at virgin material and pre-strained (service simulation) material. LCF tests (R=0) are
performed on parent material and longitudinal welds, only at virgin material. Dwell times of 168h
and 1,000h are applied. VTT and TU Darmstadt perform LCF tests with R = -1 that are strain
controlled. Tests without dwell time and with dwell times of 3min, 20min, 1h and 10h are
performed. More precisely, virgin parent material and with longitudinal weld (dwell times of 0, 3,
20min. and 10h) and post-service parent material and with longitudinal weld (dwell times 0 and
10hrs).
Negative Creep
Negative creep describes the time dependent contraction of a material due to microstructural
changes as opposed to the elongation seen for a material experiencing normal creep behavior.
Negative creep is an ordering effect explained by existence of two phases occurring in a Ni-base
super alloy: a disordered matrix (r) and small ordered precipitates (r'). Al and Cr atoms diffuse
through r-r' interface and part of the Ni3Al transforms into Ni3Cr resulting in lattice contractions
[13]. The effect is researched by VZ for A263 where a conventional creep specimen is loaded in
a gleeble at 700 750C with a stress close to 0MPa and strain is monitored using laser
dilatometry to measure any contraction as a function of time (max. 20,000hrs) and temperature.
STEAM TURBINE
Rotor forging and welding alloy selection
Creep strength and the ability to fabricate full-scale forgings (e.g. segregation sensitivity,
forgeability, large-scale ingot manufacture) and weldability are the main parameters for alloy
79
selection. A230, A263, A282, A625, A706, A718, A901, A740, A740H, Waspaloy and A105
have highest creep strength at 750C. While A105 was discarded due to its low toughness and
expected difficulties in the forging process, the pre-selected alloys based on creep strength were
A263, A282, A740, A740H and Waspalloy. Weldability of A740 and Waspalloy was considered
problematic and were discarded. A263 was selected as the best option due to its commercial
availability, low sensitivity for segregation, experience of the partners with the material, and
ability to weld the material to 10Cr-steels.
Rotor Forging Alloy Optimization
After long time ageing eta () phase precipitates arise in A263 [14] where is an intermetallic
phase: Ni3Ti. As the phase is formed at the expense of the hardening gamma prime phase and the
precipitates are large platelets extending across grains, the phase generally has an effect on
long-term creep behavior in superalloys. However, no effect on creep behavior for A263 was
observed by [15] while [14] state that further research on creep behavior would be needed.
Aubert & Duval optimized the composition of A263 in order to remove phase. Five trial melts /
forgings (80mm) have been produced, one reference alloy 263 and four with optimized
composition. The standard heat treatment for A263 (1150C/2hours/water quench and
800C/8hours/air cooled) was applied. After ageing (870C/100hours) the reference alloy 263
showed phase whereas the optimized 263 alloys with identical heat treatment and ageing did
not show phase. Tensile tests, creep tests (Fig.6 (left)) and toughness tests were performed,
showing that for the short term, the optimized alloy had better creep properties. Based on the
results, one modified alloy 263 composition was selected and a new trial melt / forging was made
(160mm). Longer ageing was performed (750C/3,000hours) and the optimized alloy showed
improved creep properties and toughness compared to the reference alloy 263. The mechanical
test program is not yet completed and final conclusions can be drawn on basis of long-term test
results. Meanwhile, two large-scale rotors are produced (300 and 500mm) which are
subjected to a mechanical test-program and welding trials. The rotors were free of cracks and the
rotor produced from the optimized alloy showed good workability.
Figure 4: Creep properties of reference A263 and optimized compositions of alloy 263; trial
forgings produced by Aubert & Duval (left). Creep properties of C263; 300mm trial forging
produced by Saarschmiede (right). Measurements performed by TU Darmstadt.
80
For the dissimilar joint of A263 and COST F, the PWHT temperature is very important with
respect to the tempering temperature of COST F. PWHT #2 was chosen as the best option (good
combination of strength and toughness). The hot tensile test results (see figure 10) show that the
tensile strength is in the range of 650 750 MPa for temperatures of 700 - 750C. All samples
were broken in the weld metal.
Based on the experience of welding A263 to A263, a dissimilar weld of A263 to COST F was
made. These were made on 300mmx160mm discs produced by Saarschmiede. Two approaches
were taken: with and without buttering on the COST F side. A nickel based alloy was used both
for filler and buttering material. The COST F material was preheated during buttering. Both
welds were mechanically tested. Tensile tests at room temperature showed that the Rm of cap,
filler and root lies around 800MPa where the value for buttered material is slightly lower than for
material without buttering. The Rp0.2 values lie around 600MPa. Both the Rm and Rp0.2 are
reasonable values for future rotor applications. Charpy impact tests show that the most critical
point is the HAZ between A263 filler metal at the root and cap (impact energies 31 - 72J while
20J is considered a minimum allowable value based on experience). The macrostructure was
investigated at three different locations for both welds and showed no cracks. Also the
microstructure was investigated and both welds meet the requirement of grade B according to EN
ISO 5817. Welding of the 500mm and 1000mm discs is performed at the time of writing of
this paper.
Casting
Materials with sufficient creep strength for cast heavy section components at 750C are A105,
A282, A740, A740H, and A263. A105 has low ductility at room temperature which is a concern
for casting applications and the Al+Ti content raises concerns for their affinity to oxygen causing
oxygen defects with casting in air. A105 was therefore discarded as well as A740 that has more
susceptibility for formation of and G phase than its technically updated variant 740H. A740H,
A263 and A282 were considered materials with at least sufficient strength at 750C, sufficient
room temperature ductility (although values reported in [18] for 740H raise some concerns), good
oxidation performance, reasonable Al + Ti content, and a good perceived weldability (repair and
fabrication) and castability.
The chemistry of the three materials was optimized for casting in conjunction with Special
Metals, Haynes and Loughborough University. Casting was simulated using the finite element
software MagmasoftTM which is a computer program calculating flow, heat exchange, etc., for a
meshed 3D model, on basis of the casting parameters and the material properties. Solidification
simulations carried out to calculate the feed demand of the step blocks (see further) so that the
correct size feeder can be used for the production of each block. The feeder pipe in Ni alloys is
much longer than in conventional materials and it is important that allowance is made for this
phenomenon. Results from simulation and practice are shown in Fig. 6.
Step blocks were cast from the selected alloys (A263, A740H and A282). The mold is produced
with an induction furnace. The aluminum and titanium are added as late additions. As Al and Ti
can form oxides that can get trapped especially in thinner sections causing weak points, the whole
mold and pouring are protected by an inert atmosphere. However, all step blocks castings
produced, to varying degrees, suffered from microstructural cracking during the heat treatment
process, which resulted in volumetric cracks that were detected upon radiographic examination.
The volumetric cracking, although different in each alloy, was always associated with cracked
carbides dispersed along the grain boundaries and often worse in the heaviest sections of the
material. Therefore, the material chemistry and heat treatment of the three alloys was optimized
82
and in cooperation with the FP7 project MACPLUS, new step blocks are cast. Full scale castings
will be made in collaboration with MACPLUS after mechanical testing of the material obtained
from the step blocks.
Figure 6: X-ray of feeders (carbon steel and A625) compared with feeder pipe prediction using
MagmasoftTM for solidification simulation. Courtesy of Goodwin Steel Casting Ltd.
INTEGRATION
Cycle Calculations
An optimal boiler/steam system configuration has to be defined that has a CO2 emission
comparable to a coal fired power plant with 90% CO2 capture and 45% net efficiency requiring
an optimal steam turbine and boiler design. To achieve the required efficiency, the system is
equipped with a double reheat and 750C steam temperatures for all pressure levels. Integration
with the CCS unit is optimized. Design a high efficient power plant and integrate a CCS unit later
on is not optimal and not realistic because optimal integration of a CCS unit will result in a
different boiler and steam turbine design. An integrated approach has therefore been taken. All
other approaches will result in a lower efficiency of the system. Three different candidate steam
turbine designs were studied each with their own advantage. Firstly, the normal cycle (close to
existing cycles) is studied. For optimization of investments, the low pressure (LP) turbine is
reduced in size because the necessary steam for regenerating the solvent is taken just before the
LP-turbine. Disadvantage is that operation without CCS is not possible. Secondly, the master
cycle is taken into consideration. Steam for regenerating the solvent is supplied via the T-turbine,
so that the T-turbine will be larger compared to a design without CCS. With this system, the
steam turbine efficiency increases but it turned out that this system is not able to operate without
CCS and start-up of this system could be difficult. Thirdly, a combination of a normal cycle and a
master cycle is calculated where the necessary steam for the CCS unit is extracted from the cold
reheat and expanded through a separate turbine. This system is able to operate with and without
CCS and the resulting efficiency is in between the normal and master cycle. This cycle is selected
to be applied for the boiler design. As CO2 capture processes the Econamine FG Plus is selected
as state-of-the-art (and only commercial available) technology and is compared with the Cansolv
process which is the most promising technology with respect to low energy consumption in the
future.
The steam turbine and boiler are designed based on the capture techniques. As the steam demand
for the capture processes differs, so does the reheating steam flow and therewith the sizing of heat
83
exchanger surface in the boiler. All calculated metal temperatures (SH 777C, RH 752C,
membrane wall 578C) are within the operating range of the materials with a margin of 20 - 30K
that allows for actual higher metal temperatures in practice. Only 1% biomass (based on thermal
heat input) has to be co-fired to achieve the outlined prerequisites.
Superheater Life Modeling
The objective of the superheat lifetime modeling is to explore the optimization of component
lives while balancing steam conditions and any limits on percentage of co-firing/oxy-firing (and
while maintaining CO2 emissions in the target range (equivalent to >90% reduction for a coalonly plant)). The effects of steam-side degradation and any enhancement due to oxy-combustion
will also be included. The life model includes corrosion models that are derived from extensive
laboratory testing and are a function of gas composition, deposition composition and flux, metal
temperature, time and alloy composition. The model has been validated against plant data,
recognizing the differences between laboratory and plant, e.g. isothermal conditions in the lab vs.
a temperature difference between gas and surface and that deposition in plants is governed by
fuels, design and operating conditions rather than simulated deposits.
CONCLUSIONS
Fireside corrosion testing includes lab screening, lab rig tests and plant trials which are ongoing.
740H outperforms A263 and A617, the latter two perform equally. NiCr coatings performance is
amongst the best. Steamside oxidation screening tests show equal performance of A617, A263
and A740H 750C while A617 and A740H outperform A263 at 800C. LCF-testing of A263 is
ongoing, as well as investigation of relaxation cracking, gas phase embrittlement (indication of it
is found) and negative creep. Full scale rotors have been forged successfully of A263 in reference
and optimized composition. Cast step blocks showed volumetric cracking but new blocks with
optimized composition dont show cracks in the as cast condition. Casting of a full-scale
component is foreseen. An optimal 750C steam cycle with integrated capture has been designed
showing that for a 45% (LHV) efficiency only little biomass has to be co-fired to meet the
required CO2-emission levels. Superheater life modeling for 750C steam and co-firing is
planned work.
ACKNOWLEDGMENTS
The European Union is acknowledged for their financial contribution. Alhomens Kraft, RWE,
and GDF Suez are acknowledged for making their boilers available for corrosion testing.
REFERENCES
[1] Blum, R., Burgge, J., Kjaer, S. USC 700C Power Technology A European Success
Story, VGB Power Tech, Vol. 4 (2009), pp. 26 32.
[2] Viswanathan, R., Henry, J.F., Tanzosh, J., Stanko, G., Shingledecker, J., Vitalis, B., Purgert,
R., U.S. program on materials technology for ultra-supercritical coal power plants,
JMEPEG, Vol. 14 (2005), pp. 281 292.
[3] McDonald, D.K., Coal ash corrosion resistant materials testing program evaluation of the
first section removed in November 2001, Proc 28th Clean Coal Conference on Coal
Utilization and Fuel Systems, Clearwater, FL, USA. 2003.
84
[4] Stein-Brzozowska, G., Flrez, D.M., Maier, J., Scheffknecht, G., Fireside corrosion of
dedicated austenitic steels in ultra-supercritical coal-fired power plants, Proc 37th
International Technical Conference on Clean Coal and Fuels Systems, Clearwater, FL, USA.
2012.
[5] Stein-Brzozowska, G., Flrez, D.M.; Maier, J., Scheffknecht, G., Nickel-base superalloys in
ultra-supercritical coal-fired power plants: fireside corrosion. Laboratory studies and power
plant exposures, Fuel, Vol. 108, No. 62 (2012), pp. 521 - 533.
[6] Spiegel,
M.,
Krein,
R.
Werkstoffentwicklung
fr
Kohlekraftwerke
85
ABSTRACT
Increasing the efficiency of the Rankine regenerative-reheat steam cycle to improve the
economics of electric power generation and to achieve lower cost of electricity has been a long
sought after goal. Advanced ultra-supercritical (A-USC) development for materials to reach 760C
(1400F) is a goal of the U.S. Program on Materials Technology for Ultrasupercritical Coal-Fired
Boilers sponsored by the United States (U.S.) Department of Energy and the Ohio Coal
Development Office (OCDO). As part of the development of advanced ultra-supercritical power
plants in this program and internally funded programs, a succession of design studies have been
undertaken to determine the scope and quantity of materials required to meet 700 to 760C (1292
to 1400F) performance levels. At the beginning of the program in 2002, the current design
convention was to use a two pass steam generator with a pendant and horizontal tube bank
arrangement as the starting point for the economic analysis of the technology. The efficiency
improvement achieved with 700C (1292F) plus operation over a 600C (1112F) power plant
results in about a 12% reduction in fuel consumption and carbon dioxide emissions. The reduced
flue gas weight per MW generated reduces clean up costs for the lower sulfur dioxide, nitrogen
oxides and particulate emissions.
The operation and start up of the 700C (1292F) plant will be similar in control methods and
techniques to a 600C (1112F) plant. Due to arrangement features, the steam temperature control
range and the once through minimum circulation flow will be slightly different. The expense of
nickel alloy components will be a strong economic incentive for changes in how the steam
generator is configured and arranged in the plant relative to the steam turbine. To offer a view
into the new plant concepts this paper will discuss what would stay the same and what needs to
change when moving up from a 600C (1112F) current state-of-the-art design to a plant design
with a 700C (1292F) steam generator and turbine layout.
INTRODUCTION
Much of the previous work published on the development of A-USC steam generators has
covered the materials developments needed to make operation possible at greater than 700C
(1292F) [1, 2]. The development effort has also included a task for conceptual design of the
steam generator in order to provide information on material temperature conditions and an
estimate of size and quantity of the components [3]. The arrangement configurations started with
current two-pass designs used for 600C (1112F) ultra-supercritical (USC), as this meets current
acceptance and expectations of the industry. The two pass style has pendant surface over the
furnace and arch and horizontal heating surface in a down pass that is divided for gas biasing to
86
control reheat steam temperature. With A-USC there will be about 150C (300F) increase in the
outlet mainsteam temperature and the furnace wall enclosure will deliver about 66C (150F)
higher fluid outlet temperature over the present supercritical design, which has been in U.S.
utility service for more than 55 years. Selection of higher alloy materials for the lower and upper
furnace enclosure and the convection pass enclosure and tube banks is a primary activity of the
sponsored A-USC boiler materials development program and Babcock & Wilcox Power
Generation Group, Inc. (B&W PGG) research and development activities [1-5]. The program
includes participation of the U.S. boiler suppliers on the basis of being limited to pre-competitive
information needed for ASME data and the understanding of material/mechanical properties
needed industry wide. The power industry needs solutions which demonstrate that operation at
greater than 700C (1292F) will be economic, sustainable and will deliver the higher efficiency
expected.
Due to the high cost of nickel steam piping, new concepts have been proposed for the
arrangement of the steam generator and the turbine in the plant. Siemens AG has proposed a
horizontal boiler. China has some interest in the two-turbine concept with the HP and IP sections
at high elevation by the steam outlet headers and the LP section and condenser on the ground
level. Horizontal tube banks could provide a means to better handle the exfoliation of steam side
oxidation where distribution and removal can be improved. The higher feedwater temperature
from A-USC turbine cycles makes it difficult to achieve low boiler outlet gas temperature
entering the air heater. The soot blowing steam requirements could be met by a lower pressure
steam generator, similar in function like a two pressure heat recovery steam generator (HRSG).
Soot blowing with compressed air would save high pressure water. Flue gas cooling using
condensate may be needed. Some new revisited designs will be presented later.
The expectation that some steam generator design changes will occur is valid. These must be
understood and gain acceptance through proof of performance. The U.S power generation
industry is particularly conservative and functions in a risk-averse commodity market with
constraining forces that seek to achieve lower electricity prices. Still the industry needs to remain
economically vital by advancing technical development. This paper provides a discussion of what
will certainly change, what will probably change and what should remain unchanged in the plant
and steam generator design.
A-USC DESIGN TECHNOLOGY DEVELOPMENT
Supercritical Furnace Enclosure Design for 540C (1005F)
B&W supercritical 540C (1005F) once-through steam generators use SA213 T-2 for the entire
vertical tube furnace enclosure. The enclosure is called UP-UP, having a first and second pass of
alternating tubes from the lower inlet headers so the fluid moves up twice through the same
elevation, then a third pass continues up to the roof [6]. Exit fluid temperature reaches about
385C (725F). Enclosure circulation requires increasing pressure to 24.1 MPa (3500 psi)
supercritical operation (called constant pressure) after the convection pass outlet reaches about
232C (450F) at 6.9 MPa (1000 psi). This prevents two-phase flow overheating due to boiling
crisis (dryout). On start up, a division valve separates the enclosure from the superheater until the
fluid conditions are high enough to produce steam by throttling the fluid into the start up flash
tank and the superheater. When the superheater is pressurized to match the upstream furnace
enclosure, the division valve is full open and the flash tank system is taken out of service.
87
88
Figure 2 T-92 Wall Panel for Welding Fabrication, Installation and Repair Testing
89
Operating Concept for Variable Pressure (A-USC) Steam Generator +700C (1292F)
New steam generator designs are expected to be capable of variable pressure operation. The
purpose of variable pressure, also known as sliding pressure, is to not change the temperature of
the steam turbine high pressure components with load cycling. Figure 3 shows the enthalpypressure operating domain results for an A-USC steam generator with suitable partial load
characteristics. A constant pressure steam generator can maintain the turbine inlet temperature.
However, the turbine control valve will throttle the steam at partial loads and thereby lower the
metal temperature during load cycling. Variable pressure operation means the turbine inlet valves
operate nearly wide open and do not throttle the steam resulting in maintaining high full load
steam temperature and metal temperatures of the turbine and superheater outlet headers and
piping at partial loads. Lower temperature intermediate components of the steam generator will
cross some isotherms during load cycling while the higher temperature outlet components do not
cross very many isotherms until shut down.
Figure 3 B&W A-USC 700C (1292F) Steam Generator Operating Domain h-P
90
Variable pressure is an important operating mode capability due to the increase to higher steam
temperature with A-USC and the situation with electric grids needing units to load cycle. The
load change rate of response will be slower than a constant pressure with some throttle pressure
reserve. Variable pressure needs to use additional methods to improve load change response. A
technique called frequency control or condensate throttling is used to quickly start the load
change without serious over-firing from the delayed control action. Condensate throttling works
by using fast valves on the turbine steam extraction lines to the LP feedwater heaters so the
turbine quickly retains more steam to produce the power increase. The slow coal pulverizers can
then meet the firing demand for the load change without the catch up delay creating severe
temperature overshoot and damage. Firing rate control should not be too fast. Condensate
throttling control is fast. Water storage design of the hotwell and deareator are increased to
handle the condensate flow transient.
First B&W Conceptual A-USC Design Air Fired with Gas Biasing
The first B&W conceptual design was developed to provide the materials quantity and service
temperature requirements for early cost analysis in the materials development program [3]. The
steam conditions produced 750 MW net at 34.5 MPa (5003 psi) 735C/760C (1355/1400F). The
design fuel was an Ohio, U.S. bituminous coal. This once through steam generator arrangement is
the most typical in U.S. utility service and is called a two pass or B&W Carolina type, Figure 4.
The top supported pendant heating surface may be set on any spacing intervals and is not
governed by stringer supports. The down pass is baffled to provide for gas biasing to control
reheat steam temperature through a wider load range.
The gas side operation is set by the fuel design limitations. For the design fuel, the gas velocity
limits are high so the convection heat transfer is more effective. The lower differential
temperature between the gas and steam increases the heating surface requirements. The steam
outlet terminals are at the very top of the structure.
Figure 4 B&W A-USC Conceptual Study-Two Pass Air Fired Steam Generator
91
Figure 5 B&W A-USC Conceptual Study-Two Pass Oxy Fired Steam Generator
B&W A-USC Conceptual design- 898 MW Modified Tower
Figure 6 is a modified tower design that was developed for a Toshiba steam turbine 30 MPa
(4351 psi), 700C/730C (1292F/1346F). The design fuel is an Indian coal [5]. Featured is the use
of stringer supports for horizontal surface. All bank heating surface in the gas upflow pass must
be on a multiple of the interval spacing of the stringers. The material of the stringers is T-92
92
supporting nickel superheater and reheater tubing. The down pass is also stringer supported and is
typical of current practice. A series down pass may be used when the reheat temperature control
range can be limited. A parallel down pass is used when a wider temperature control range is
required. The high ash coal requires much lower gas velocity limits so the convective heat
transfer degrades quickly with reduced load. Gas recirculation and gas biasing may be employed
to meet performance requirements. A low pressure steam generator is placed after the economizer
to reduce exit gas temperature and provide auxiliary steam instead of extracting very high
pressure and high temperature steam.
This modified tower arrangement puts the outlet headers closer to the steam turbine although, due
to the high ash fuel the height, of the furnace is much higher. By locating the base of the steam
generator below grade the nickel steam leads are shorter and offer significant savings. The
feedwater heaters and deareator building bay may also be moved from between the steam turbine
and steam generator to along one side of the steam generator.
Steam generator configurations will most likely evolve because of the high nickel steam lead
cost. The first Babcock & Wilcox once through steam generator was a low profile, nearly
horizontal configuration, Figure 7 (UP-1 for American Electric Powers 125 MW Philo 6, 31.4
MPa /621C/565C/538C (4550 psi /1150F/1050F/1000F) [6]. Some of these new forms have
already started appearing for A-USC alternatives to the Figure 1 convention. The horizontal
93
boiler was proposed by Siemens for the planned Thermie 700C European demonstration plant. A
conventional tower arrangement was also proposed. A plant arrangement might change with the
entire steam turbine partially elevated relative to the boiler. Another solution has been suggested
to divide the steam turbine where the HP and IP sections are placed at high elevation closer to the
superheater and reheat outlet headers, and the second part, the LP sections and condenser remain
on the ground. For A-USC to become economical, the steam generator and steam turbine
configuration and relative placement is most likely going to change.
Figure 7 Babcock & Wilcox UP-1 AEP Philo 6 125 MW 31.4 MPa /621C/565C/538C
Comparison of Supercritical, Ultra Supercritical, Advanced Ultra Supercritical
Table 1 shows a comparison of the key features of supercritical, USC and A-USC. Most A-USC
features are the same as for USC. Particular exceptions are:
1. Final superheater and reheater tube banks will use materials like 740H and 230 nickel.
2. The furnace enclosure material in the upper enclosure is creep strength enhanced ferritic
steel requiring field PWHT of the tube to tube joints and possibly the membrane panel
seams.
3. Minimum circulation flow load is more likely 5% to 10% higher than USC which limits
temperature control load range.
4. Steam piping is 740H nickel or better.
5. The arrangement will continue to evolve.
94
Feature
Supercritical
Ultra Supercritical
~25.5MPa (3700psi)
600C to 650C(1112F to 1200F)
Variable Pressure
~30MPa (4350psi)
700C to 760C (1292F to 1400F)
Variable Pressure
Load Control
Arrangement
Configuration
Piping Material
Two Pass
P22
P92
Furnace Enclosure
Material
Steam Temperature
Control
Feedwater Control
Water Treatment
Chemistry
Turbine Bypass
Start Up System
Start Up Operation
Superheater Material
95
CONCLUSIONS
An important next step in A-USC development is to build at significant scale and demonstrate the
features that extend beyond present USC experience. The first demonstration will test the
capability of suppliers to support the new materials required. Confidence in meeting the quantity
and schedule commitments for plant projects is needed by power plant suppliers. Material
suppliers will need to make investments based on increased certainty of the timing when the AUSC market demand will form. The first lead plants will establish procurement standards and
quality specifications for A-USC components. It is also important to place the technology into the
hands of utility operations and maintenance personnel to gain industry acceptance. The most
important step is to provide a plant design that is high performing and cost acceptable.
ACKNOWLEDGMENTS
The U.S. Department of Energy and the Ohio Coal Development Office support for the A-USC
Materials Development project is greatly appreciated. The efforts of industry-wide organizations
have fostered an environment of cooperation in working toward the common pre-competitive
needs for ASME Code materials development for A-USC. The goal of these efforts is to advance
the state-of-the-art for higher efficiency power generation using abundant low cost coal while
reducing carbon emissions of a major energy source of electric power.
REFERENCES
[1] Viswanathan, R., et.al., U.S. Program on Materials Technology for Ultrasupercritical CoalFired Boilers, in Proceedings of the 5th International Conference on Advances in Materials
Technology for Fossil Power Plants, ASM International, (2008).
[2] Rao, K.R., (ed.), Energy and Power Generation Handbook, ASME, (New York, 2011),
Chapter 17.
[3] Bennett, A.J., Weitzel P.S., Boiler Materials for Ultrasupercritical Coal Power Plants Task 1B,
Conceptual Design, Babcock & Wilcox Approach, USC T-3, Topical Report, DOE DE-FG2601NT41175 & OCDO D-0020, (February 2003).
[4] Weitzel, P.S., Steam Generator for Advanced Ultra-Supercritical Power Plants 700 to
760C, ASME Power 2011, Denver, CO, 2011.
[5] Weitzel, P.S., et al., Advanced Ultra-Supercritical Power Plant (700 to 760C) Design for
Indian Coal, Power Gen Asia, Bangkok, Thailand, October 2011.
[6] Kitto, J.B, Stultz, S.C., Steam/its generation and use, Edition 41, The Babcock & Wilcox
Company, (Barberton, OH, 2005).
Benson is a registered trademark of Siemens AG
B&W and Babcock & Wilcox are registered trademarks of Babcock & Wilcox Power Generation
Group, Inc.
Copyright 2013 Babcock & Wilcox Power Generation Group, Inc. All rights reserved.
96
DISCLAIMER
Although the information presented in this work is believed to be reliable, this work is published
with the understanding that the Babcock & Wilcox Power Generation Group, Inc. (B&W PGG)
and the authors are supplying general information and are not attempting to render or provide
engineering or professional services. Neither B&W PGG nor any of its employees make any
warranty, guarantee, or representation, whether expressed or implied, with respect to the
accuracy, completeness or usefulness of any information, product, process, method, or
apparatus discussed in this work, including warranties of merchantability and fitness for a
particular or intended purpose. Neither B&W PGG nor any of its officers, directors, or
employees shall be liable for any losses or damages with respect to or resulting from the use
of, or the inability to use, any information, product, process, method, or apparatus
discussed in this work.
97
The highest temperature components of 600-700 A-USC steam turbines are different stage
blades. These blade materials can be Nimonic80A and Waspaloy.
The long time structure stability of these advanced austenitic steels TP347H, Super304H, HR3C
in the temperature range of 650-700 and Ni-base superalloy Inconel740/740H, Nimonic80A
and Waspaloy in the temperature range of 600-800 till 10,000h have been detailed studied in
this paper.
MATERIALS AND EXPERIMENTS
Materials
The nominal chemical compositions of 7 investigated advanced heat-resistant steels and
superalloys are listed in Table1. They are namely in two groups of austenitic steels TP347H,
Super304H, HR3C and Ni-base superalloys Nimonic80A, Waspaloy and Inconel740/740H.
Table 1: Nominal chemical compositions of 7 investigated austenitic heat-resistant steels and Nibase superalloys(in Mass%)
Alloy
C
Cr
Ni
Co
Fe
Mo
Nb
Ti
Al
Cu
N
TP347H
0.08 18
10
Bal. 0.8
Super304H
0.08 18.5 9.5
Bal. 0.5
3
0.1
HR3C
0.06 25
20
Bal. 0.5
0.2
Nimonic80A 0.06 20
Bal. 2.4
1.7
Waspaloy
0.04 20
Bal. 14
4.5
3
1.5
Inconel740
0.03 25
Bal. 20
0.5
2
1.8
0.9
Inconel740H 0.03 25
Bal. 20
0.5
1.5
1.35 1.35 Heat treatments of investigated materials are as follows:
o
1. TP347H: 1150 C 30/WC
o
2. Super304H: 1150 C /30/WC
o
3. HR3C: 1150 C /30/WC
o
o
o
4. Nimonic80A: 1080 C /8h/AC+845 C /24h/AC+700 C /16h/AC
o
o
o
5. Waspaloy: 1080 C /4h/AC+845 C /24h/AC+760 C /16h/AC
o
o
6. Inconel740: 1150 C /30/WC+800 C /16h/AC
o
o
7. Inconel740H: 1150 C /30/WC+800 C /16h/AC
Experiments
All advanced austenitic steels TP347H, Super304H and HR3C tubes were received from steel
plants after mill annealing and followed by long time thermal aging at 650 C till 8,000-10,000hrs
for TP347H and Super304H and aging at 700 C till 5,000hrs for HR3C.
Ni-base superalloy Nimonic80A for 600C USC steam turbine blade application was conducted
long time aging at 550C to 750C for 10,000hrs.
Ni-base superalloy Waspaloy is selected for 700C A-USC steam turbine blade application was
conducted long time aging at 550C to 800C for 10,000hrs.
Ni-base superalloy Inconel740/740H for 700C A-USC boiler superheater/reheater application
was conducted long time aging at 700,750 and 800C for 10,000hrs.
Structure characterization of long time aging samples of investigated materials were analyzed by
SEM, TEM, HRTEM, XRD and EDAX. For quantitative determination of precipitates in several
investigated materials by electrolytic isolation of precipitates and followed by micro-chemistry
99
Figure 1: Precipitation hardening curves of TP347H and Super304H at 650C long time aging
till 8,000-10,000h
Figure 2: Precipitation hardening curves of HR3C at 700C long time aging till 5,000h
100
HR3C
98.1
84.0
Typical microstructure of these 3 austenitic steels are nano-size strengthening phases precipitated
in austenitic matrix and M23C6 carbide distributed at grain boundaries. The main precipitation
strengthening phase for TP347H in austenitic matrix is NbC phase as shown in Fig.3 by high
resolution transmission electron microscope(HRTEM). The precipitation strengthening phases in
Super304H are Cu-rich phase, Nb(CN) type MX phase in austenitic matrix and M23C6 carbide
mainly at grain boundaries and occasionally in grains as shown in Fig.4. It can be seen that Curich phase particles with the finest sizes homogeneously distribute in austenitic matrix, and Curich phase occupies the largest amount of the total precipitates. The high resolution TEM image
of Cu-rich phase can be seen in Fig.5. Except MX the main precipitation strengthening phase in matrix phase of HR3C is nano-size NbCrN. The HRTEM image of NbCrN is clearly shown in
Fig.6.
500nm
Cu-rich phase: 3%
MX: 0.38%
M23C6: 0.99%
Figure 4: The main precipitates M23C6, Cu-rich phase and MX in Super304H
101
102
Figure 7: Typical precipitation hardening curve of Super304H at 650 aging till 1,000h
The precipitation procedure of very fine Cu-rich phase can be described by 3DAP technology[3].
o
The Cu atoms have quickly segregated to form Cu-rich clusters just after 1h aging at 650 C as
o
shown in Fig.8. Fig.9 shows the growth of a Cu-rich particle after 100h aging at 650 C. The Cu
atoms continuously concentrate to Cu-atom segregated regions(Cu-rich clusters). As Fig.9 and
o
Fig.10 show that the Cu-content(at%) has almost reached 90at% in a Cu-rich phase at 650 C
aging for 500h. The Cu-rich phase formation from Cu atom segregated regions(Cu-rich clusters)
characterizes with an evolution process, because there is Cu atom concentration process only but
no crystallographic structure change. Cu-rich phase and Fe-Cr-Ni -matrix both characterize with
FCC structure and they are only in a small difference of crystallographic parameters(small misfit
between Cu-rich phase and -matrix) and keep in coherent relationship between Cu-rich phase
o
and -matrix. The growth rate of Cu-rich phase at 650 C aging is quite slow as shown in Fig.11.
o
The Cu-rich phase can still keep nano-size(34nm) even at 650 C aging for 10,000h. It is an
important reason for excellent strengthening effect of Cu-rich phase precipitation in Super304H
heat-resistant steel[2,4].
Solution treatment
650C /1h
Figure 8: The concentration of Cu atoms to form Cu-rich clusters in Super304H just after 1h
o
aging at 650 C (size of selected box is10nm10nm70nm)
103
Figure 9: The Cu atom concentration procedure during 650 aging from 5h to 500h: (a)5h,
(b)100h and (c)500h
(a)
(b)
(c)
Figure 10: The precipitation procedure and formation of Cu-rich phase in Super304H: (a) after
solid solution treatment (10nm10nm1nm ), (b)aged at 650 for 1h(2nm2nm1nm ) and
(c) aged at 650 for 100h(12nm12nm1nm )
Figure 11: The growth rate of Cu-rich phase at 650 long time aging till 10,000h in Super304H
Experimental results show that MX type NbC or Nb(C,N) nano-size can be precipitated in
TP347H, Super304H and HR3C steel because of Nb addition in these 3 steels. Except MX phase
the Cu-rich phase and NbCrN nano-size precipitates can be formed in Super304H and HR3C
respectively. Among these 3 steels Super304H characterizes with the highest stress rupture
strength because of the Cu-rich phase precipitation strengthening effect. In fact of these
experimental results a new idea is developed to design an advanced Ni-Cr austenitic heat-resistant
104
(a)
(c)
Figure 12: Typical microstructure of Nimonic80A alloy at standard heat treatment condition (a)
Grain structure; (b) Carbides at grain boundaries; (c) precipitates in grains
105
Table 3: Factions of different precipitates in Nimonic 80A at standard heat treatment condition
Phase
matrix
phase
M7C3+M23C6
MC
Fraction (wt. %)
81.615
17.713
0.636
0.036
precipitation
The effect of long-time aging on phase is illustrated in Fig.13. It can be seen that
morphology has no apparent change below 700C, almost the same as that at standard heat
treatment condition. However, phase becomes unstable and its morphology changes after
750C long time aging (see Fig.13h and 13i). Fig.13 clearly shows the coarsening process
at high temperature long time aging. The radius of phase increases with aging
temperatures and times, especially more rapidly after 750C, 1,000h aging. Through these
observations, it can be concluded that aging temperature more intensively contributes to
coarsening than ageing time. Quantitative phase analyses (see Table. 4) show that the
fraction of phase for 10,000h at 700C (18.038%) is lower than those at 600 (19.382%)
and 650C (19.468%).
Figure 13: Effect of aging on behavior in Nimonic80A alloy (a) 550 C, 500h; (b) 550 C,
o
o
o
o
o
5000h; (c) 600 C, 1000h; (d) 600 C, 10,000h; (e) 650 C 1000h; (f) 650 C, 10,000h; (g) 700 C,
o
o
10,000h; (h) 750 C, 2000h; (i) 750 C, 5000h
o
Table 4: Factions of different precipitates in Nimonic80A aged for 10,000h at 600, 650 and
700C
10,000h aging
600C
650C
700C
phase (wt. %)
19.382
19.468
18.038
M7C3+M23C6 (wt. %)
0.641
0.676
0.755
106
growth
Fig.14 represents the growth of with aging times at 550~750C. It is clearly seen that
radius almost has no change at 550C long-time aging till 5,000h. And phase grows more
slowly at 600~650C than at 700C with aging times. These average radiuses at 600, 650
and 700C long-time ageing till 10,000h by quantitative phase analyses are 38.7, 37.2 and
42.1nm, respectively. From Fig.14(a), it can be seen that growth at 750C is the most rapid
among 550~750C and its average radius has reached about 87.5nm with aging times up to
5,000h, which would be harmful to the mechanical properties of the alloy for hightemperature long-term service.
3
The correlation of effective radius r of precipitates with aging times is plotted in Fig.14(b). It
can be seen that the results show linear relationships at 550~750C (Fig.14(b)). It is suggested
3
Figure 14: The relationships between size and aging time for Nimonic80A at different
temperatures (a) r -t; (b)
r -t
107
Figure 15: Effect of aging on grain boundary carbides behavior in Nimonic 80A alloy (a) 550C,
500h; (b) 550C, 5000h; (c) 600C, 1000h; (d) 600C, 10,000h; (e) 650C, 1000h; (f) 650C,
10,000h; (g) 700C, 10,000h; (h) 750C, 2000h; (i) 750C, 5000h
Stress-rupture strength after long time aging.
Fig. 16 shows a very positive result that the stress-rupture test (750C, 310MPa) lives of Nimonic
80A alloy specimens after 10,000h long time aging at 600, 650 and 700C can still meet the
specification requirement ( 100h).
Figure 16: Stress rupture tests (750C, 310MPa) of Nimonic80A samples after 10,000h long time
aging at 600, 650 and 700C
108
Above mentioned results show that Nimonic 80A characterizes with good structure stability at
high temperatures[7]. This alloy can be not only used for 600C USC turbine blades, also can be
possibly used for 700C A-USC steam turbine blades.
Waspaloy
WASPALOY is a Ni-Cr-Co-Mo base superalloy with Ti and Al to form -Ni3(Al,Ti)
precipitation strengthening for creep strength at high temperatures. WASPALOY has been wildly
used as blades, disks, fasteners and other forgings for aero-engine application in the temperature
o
range 700-750 C even above. WASPALOY has been also adopted for gas expander blades and
o
disks application in petro-chemical industry for long time service at temperature 650-700 C ever
higher. Now WASPALOY is considered to be used as blade material for 700 A-USC steam
turbine application.
Typical microstructure and fraction of precipitated phases after standard heat treatment is shown
in Fig.16. It can be clearly seen that about 22% wt homogeneously distributed in Ni-Cr-Co-Mo
-matrix and about 0.2% M23C6 carbide discontinuously precipitated at grain boundaries. A small
amount (0.1%) of MC carbide formed during solidification and randomly distributes in the alloy.
Precipitate
MC
M23C6
Composition
(Ni0.883Fe0.03Cr0.048Co0.039)3.28(Al0.38Ti0.62Mo)
Ti(CN), (TiN)
(Cr0.746Mo0.094Ni0.084Co0.041Fe 0.023Ti0.012)23C6
Wt%
~22
Small amount
~0.5
Figure 17: Typical microstructure and phase fraction of WASPALOY at standard heat treatment
condition (1080/4hrs/AC+ 845/24hrs/AC+760/16hrs/AC.)
The microstructure of WASPALOY looks very similar to Nimonic80A (see Fig.17 and Fig.12).
However, WASPALOY contains more solid solution strengthening elements such as Co and Mo
and higher fraction (~22%) of than that of Nimonic80A (~17%). In results of that WASPALOY
characterizes with higher creep strength and to be used at higher temperature than Nimonic 80A.
The main strengthening effect of WASPALOY is contributed by precipitation in Ni-Cr-Co-Mo
-matrix. So the stability of phase is the key issue for guarantee high creep strength at high
temperatures. The structure stability study of WASPALOY has been conducted by long time
thermal aging in the temperature range from 550-850[8]. Fig.18 shows the morphology after
long time aging at 700,5000h and 750,4500h respectively. The long time aging at 700-750
is still continuing until 10,000h. The growth rate of in WASPALOY is shown in Fig.19. It can
be seen that strengthening phase is quite stable in the temperature range of 550-750 .
109
However its growth rates in the temperature range of 800-850 are quite high. It can be
concluded that from view-point of structure stability WASPALOY is suitable to be used as 700
blade application for A-USC steam turbine.
Figure 18: precipitation behavior in WASPALOY after long-time aging at 700 for 5000h(a)
and 750 for 4500h(b)
110
Figure 20: The calculated stress rupture curves for WASPALOY in the temperature range of 600850
Inconel740
Inconel740, a new Ni-Cr-Co-Mo-Nb-Ti-Al superalloy, is recently developed by Special Metal
Corp.(SMC, Huntington) USA for European THERMIE AD700 A-USC project with steam
parameters of 700 , 35MPa. At this condition the superheater and reheater fire-side metal
temperature can be 750-760 even higher. The superheater and reheater require stress rupture
strength(100MPa, 105h) at temperatures 750-760 , together with the high corrosion
resistance(2mm cross-section loss in 2105h). Inconel740 characterizes with the highest stress
rupture strength and corrosion/oxidation resistance among todays available candidate
materials(such as Haynes230, HR6W, Inconel617B and Nimonic263) and can meet above
mentioned strict requirements.
Typical microstructure and phase fraction of Inconel740 at standard heat treatment are shown in
Fig.21. The main strengthening phase (12.98%) homogeneously distributes in Ni-Cr-Co matrix, M23C6 carbide(0.115%) and a very small amount(0.054%) of high Si-containing G-phase
mainly precipitate at grain boundaries and MC-(Nb.Ti)C(0.183%) carbide formed at solidification
process randomly distributes in the alloy.
phase
MC
M23C6
G
Wt%
12.980
0.183
0.115
0.054
Figure 21: Typical microstructure and phase fractions of Inconel740 after standard heat
treatment
111
The microstructure of Inconel740 is quite stable at 700 long time aging as shown in Fig.22.
However, it is quite different at 760 long time aging. There are a lot of plate-like -phase
nearby grain boundaries and rapidly grow to the grains. Moreover the large globular high Sicontaining G phase distributed at grain boundaries as determined by EDAX(see Fig.23).
(b)
(a)
Figure 22: Stable micro-structure of Inconel740 at 704 long time aging: (a) 704 /1000h and
(b) 704 /2000h
Si (at%):
19.25%
A6B16Si7:
24.13%
Figure 23: The large amount of -phase and G-phase in Inconel740 after 760 long time aging
Detail quantitative determination of brittle high Si-containing G-phase after 704-760 long time
aging is shown in Fig.24. It is very harmful for Inconel740 that the amount of G phase(0.471%)
after 2000h aging at 760 is almost 10 times than the amount of G-phase(0.054%) as at standard
heat treatment condition. Moreover the unstability of strengthening phase and the formation of
-phase have been also detaily studied as shown in Fig.25.
112
G phase percent/%
0.5
0.4
0.3
0.2
0.1
0.0
500
1000
1500
2000
Aging time/h
Figure 24: High Si-containing G-phase formation and plate-like -phase precipitation in
Inconel740 at 760 long time aging
(a)
(b)
Inconel740H
Inconel740H is a modification of Inconel740 for improvement of structure stability by the
adjustment of Nb, Ti, Al and Si[11]. Chemical composition and phase fraction comparison between
Inconel740H and Inconel740 is shown in Table.5 and 6 respectively. Fig.26 shows the
comparison of calculated phase diagrams of Inconel740 and Inconel740H. It can be seen from
these results that the strengthening phase is more stable in Inconel740H than Inconel740. The
-phase is eliminated in Inconel740H and there is not existence of brittle high Si-containing G
phase in Inconel740H.
Table 5: Chemical composition (in wt%) comparison between Inconel740H and Inconel740
Alloy C
Cr
Ni
Co
Mo
Nb
Ti
Al
Mn
Fe
Si
740
0.03
25
bal
20
0.5
2
1.8
0.9
0.3
0.7
0.5
740H 0.03
25
bal
20
0.5
1.5
1.35
1.35
0.3
0.7
0.15
Table 6: Phase fraction(wt%) comparison between Inconel740H and 740
Alloy
MC
M23C6
740
12.980
0.183
0.115
740H
14.623
0.220
0.202
(a)
(b)
500nm
Figure 27: Typical microstructure of Inconel740H after standard heat treatment
114
G
0.054
0
Typical microstructure of Inconel740H after standard heat treatment as shown in Fig.27 is very
similar to the structure of Inconel740 in comparison with Fig.21. The main strengthening phase
(14.623%) homogeneously distributes in Ni-Cr-Co -matrix, M23C6 carbide(0.202%) and also
MC-(Nb,Ti)C carbide(0.220%) formed at solidification process randomly distributes in this alloy.
However, the comparison of structure stability of Inconel740H and Inconel740 at 750 and
800 long time aging is quite different(see Fig.28 and Fig.29)[12]. Inconel740H keeps stable
strengthening in Ni-Cr-Co -matrix and M23C6 carbide at grain boundaries. However, plate-like phase formation and high Si-containing G-phase precipitation obviously happen in Inconel740.
Moreover the growth rate comparison between Inconel740H and Inconel740(see Fig.30) clearly
shows that Inconel740H characterizes very good structure stability at 750 long time aging.
Figure 28: Long time structure stability comparison between Inconel740H and 740 at 750
aging
115
Figure 29: Long time structure stabiltiy comparison between Inconel740H and 740 at 800
aging
(b)
(a)
Figure 30: growth rate comparison between Inconel740H(a) and 740(b) at high temperatures
The structure stability study has been also conducted after high temperature stress rupture tests.[12]
The structure of Inconel740 sample tested at 775, 170MPa, after 2779hrs shows a large
amount of -phase near grain boundaries and G phase formation at grain boundaries(see Fig.31a).
However, the structure of Inconel740H sample tested at 750, 280MPa, after 1087hrs still keeps
stable precipitation in -matrix and M23C6 carbide distributed at grain boundaries and there are
no existence of plate-like -phase and brittle G-phase at grain boundaries(see Fig.31b).
116
(b)
(a)
1m
Figure 31: Microstructure comparision of Inconel740(a) and Inconel740H(b) stress rupture
tested samples
The impact toughness of Inconel740H after high temperature long time aging is much higher than
Inconel740 as shown in Table.6.
Table 6: Impact toughness comparison of Inconel740H and Inconel740 after high temperature
long time aging
CVN J/cm2
Alloy
Exposure
740
740H
0h
45
750-2000h
13.6
0h
90.6
700-1050h
29.5
750-1000h
35.7
800-1000h
50.5
700-3042h
23.3
750-3000h
29.8
800-3000h
46.2
700-5000h
34.7
750-5000h
23.8
800-5000h
45.3
93.7
51.2
44.4
45.2
117
CONCLUSIONS
1. Almost 80% of total electricity is generated by coal-fired power plants in China. It will be
still kept around 70% of total electricity till the year of 2020.
2. China started her 1st 600 1000MW USC power unit in November 2006. To the end of
2012 China already put more than hundred 600 USC units in service. These are about 80%
of 600 USC power units in the world.
3. The structure stability of advanced austenitic steels(TP347H, Super304H and HR3C) for
600 USC power units have been studied in detail and all these heat-resisting steels can be
made in China.
4. China has started 700 A-USC Project for coal-fired power plants in June, 2011. A series of
Ni-base superalloys (such as Nimonic80A, Waspaloy and Inconel740/740H) have been
studied for Chinese 700 A-USC Project.
5. Nimonic80A shows good structure stability at 600 and up to 700. This alloy has been
used as blade material for 600 USC steam turbines in routine production. From the
viewpoint of structure stability Nimonic80A is possible to be used as blade material for USC
steam turbines under 700 .
6. From creep rupture strength and structure stability view point Waspaloy should be a good
candidate blade material for 700 A-USC steam turbine application.
7. Inconel740H developed from Incoenl740 shows good structure stability especially no phase
nor G phase formation. Impact toughness of Inconel740H is obviously improved after longterm high temperature aging in comparison with Inconel740.
8. Inconel740H can meet the requirements of 105h creep strength 100MPa and
oxidation/corrosion resistance 2 105h 2mm for 700 A-USC technology. So,
Inconel740H is one of the excellent candidate materials of tube and pipe application for
700 A-USC power plant technology.
9. For world-wide promotion of 700 A-USC power plant project China is seeking the
international cooperation in this field.
ACKNOWLEDGMENTS
University authors appreciate China Natural Science Foundation(NO. 50931003), Central Iron &
Steel Research Institute, China. Special Metals Corporation(Huntington) WV, USA and CBMM
Brazil for partial funding on heat resisting steels and superalloys joint projects and appreciation
also to Shanghai Power Equipment Research Institute for providing long time aged heat resistant
steel samples.
REFERENCES
[1] Fusheng Lin, Shichang Cheng and Xishan Xie., Ultrasupercritical power plant development
and high temperature materials applications in China, Energy Materials, Vol. 3(2008), pp.
201-207.
[2] Hongyao Yu, Jianxin Dong and Xishan Xie., 650 Long-Term Structure Stability Study on
18Cr-9Ni-3CuNbN Heat-Resistant Steel, Materials Science Forum, Vol. 654-656(2010),
pp. 118-121.
118
[3] Chengyu Chi, Jianxin Dong, Wenqing Liu, et al., An Investigation on Precipitation Behavior
of Cu-Rich Phase in Super304H Heat-Resistant Steel by Three Dimensional Atom Probe,
Material Science Forum, Vol. 654-656(2010), pp. 110-113.
[4] Chengyu Chi, Hongyao Yu, Jianxin Dong, et al., The precipitation strengthening behavior of
Cu-rich phase in Nb contained advanced Fe-Cr-Ni type austenitic heat resistant steel for USC
power plant application, Progress in Natural Science: Materials International, Vol. 22, No.
3 (2012), pp: 175-185.
[5] Hongyao Yu., Ph. D Dissertation, University of Science & Technology Beijing, (2013).
[6] Hongwei Shen, Lihong Zhang, Xishan Xie, et al., The Application of Ni-Base Alloy
Nimonic80A for Buckets of USC Steam Turbine in China, Proc of Advances in Materials
Technology for Fossil Power Plants, ASM, 2008, pp. 402-411.
[7] Qiuying Yu, Zhi Shen, Maichang Zhang, et al., Long time Thermal Structure Stability
Study on NiCr20TiAl Alloy, Advanced Materials Research, Vol. 399-401(2012), pp: 71-75.
[8] Zhihao Yao, Jianxin Dong, Xu Chen, et al., Gamma Prime Phase Evolution during Long
Time Exposure for GH738 Superalloy, Transactions of Materials and Heat Treatment, Vol.
34(2013), pp: 3084-3098.
[9] Zhihao Yao, Maichang Zhang, Jianxin Dong, Stress Rupture Fraction Model and
Microstructure Evolution for WASPALOY, Metall. Trans. A, Vol. 44(2013), pp: 30843098.
[10] Xishan Xie, Shuangqun Zhao, Jianxin Dong, et al., An Investigation of Structure Stability
and Its Improvement on New Developed Ni-Cr-Co-Mo-Nb-Ti-Al Superalloy, Materials
Science Forum, Vol. 475(2004), pp: 613-516.
[11] Xishan Xie, Shuangqun Zhao, Jianxin Dong, et al., A New Improvement of Inconel
Alloy740 for USC Power Plants, Proc of Advances in Materials Technology for Fossil
Power Plants, ASM, 2008, pp. 220-224.
[12] Chengyu Chi, Shuangqun Zhao, Fusheng Lin and Xishan Xie., High Temperature Longterm Structure Stability Study on Inconel740/740H Ni-Base Superalloy, Keynote Lecture at
Proc of The 5th Symposium on Heat Resistant Steels and Alloys for High Efficiency USC/AUSC Power Plants 2013, May 26-29, Seoul, Korea,2013.
119
ABSTRACT (#106)
In an earlier paper, preliminary data for HAYNES 282 alloy was presented for potential advanced
steam power plant applications [1]. Since then, 282 alloy has continued to be evaluated for a
variety of A-USC applications: superheater boiler tubing, large header piping, rotors, casings, etc.
Per current practice the alloy achieves its strengthening by a two-step age hardening heat
treatment. Given the difficulty of such a procedure, particularly for larger components in the
power plant, interest has focused on the development of a single step age hardening treatment.
While considerable work on 282 alloy is still going on by a number of investigators, during the
preceding years a large amount of data was generated in characterizing the alloy at Haynes
International. This paper will briefly review the behavior of 282 alloy in air and water vapor
oxidation (10% H2O) at 760C (1400F), low cycle fatigue properties at 649C to 871C (1200F
to 1600F) and long-term thermal stability at 649C to 871C (1200F to 1600F). Special focus
of the paper will be mechanical behavior: tensile and creep; microstructural analysis, and
weldability of 282 alloy as a result of single step age hardening heat treatment: 800C
(1475F)/8hr/AC.
HAYNES, 230, and 282 are registered trademarks of Haynes International, Inc.
INTRODUCTION
It is recognized that for long-term service at high-temperature high-pressure conditions operative
in A-USC power plants, nickel based alloys would be required. In contrast to solid solution
strengthened alloys, -strengthened alloys offer considerable strength advantages to many
components at 760C (1400F) at 24 MPa (3.5 ksi). HAYNES 282 alloy is a -strengthened
nickel-based alloy combining superior creep strength, stability, and fabricability vis--vis other
age-hardened alloys.
Since being introduced in the market place in 2005 [2], the alloy has been a commercial success
and has been produced and sold in a variety of forms such as sheet, plate, bar, and forgings of
various configurations. The alloy has been specified for a number of applications for flying as
well as land-based gas turbines. A preliminary account of the alloy was presented during 5th Intl.
Conference on Advances in Materials Technology for Fossil Power Plants [1]. Since then, the
alloy has continued to be evaluated for a variety of A-USC applications: superheater boiler
tubing, large header piping, rotors, casings, etc. This paper will briefly update on environmental
characteristics, low cycle fatigue properties at 649C to 870C (1200F to 1600F), and long-term
thermal stability at 649C to 871C (1200 to 1600F). In subsequent sections, the paper will
120
focus on mechanical behavior and weldability of 282 alloy as a result of the one step age
hardening heat treatment (1475F/8hr/AC).
Physical Metallurgy
The nominal composition of 282 alloy along with alloys mentioned in this study are given In
Table 1.
Table 1: Nominal compositions of the alloys in this study (wt.%)
Alloy
Ni
Cr
Co
Mo
Ti
Al
Fe
Mn
282
57a
20
10
8.5
--
2.1
1.5
1.5*
0.3*
R-41
52
19
11
10
--
3.1
1.5
5*
0.1*
0.5*
0.09
0.006
--
Waspaloy
58a
19
13.5
4.3
--
1.5
2*
0.1*
0.15*
0.08
0.006
Zr-0.05
263
52a
20
20
--
2.4*
0.6*
0.7*
0.4
0.2
0.06
0.005
Al+Ti-2.6
22
5*
14
--
0.3
3*
0.5
0.4
0.10
0.015*
0.2La
230
a
57
As Balance
Si
0.15*
Other
0.06
0.005
--
*Maximum
The development of 282 alloy was described in Ref [3]. The main goal in its development was to
achieve exceptional creep strength concomitant with superior fabricability. These were achieved by
optimizing the composition of the alloy to form significantly less amount of than R-41 and
Waspaloy yet achieving comparable creep strength. The alloy achieves its strengthening by a twostep age hardening heat treatment to form phase, Ni3 (Al,Ti) with L12 structure. The phase in
282 alloy forms, presumably due to a lower - mismatch, in a spherical morphology as would be
seen later in the paper. The phase fraction of in 282 alloy is estimated to be 19% versus 27% in
R-41 alloy. A much lower phase fraction of along with the sluggish kinetics of its formation, is
the key to its superior fabricability especially for thicker parts.
Environmental Properties
Cyclic oxidation studies were carried out in flowing air [4] and in air + 10% H2O at 760C
(1400F) [5], cycled weekly for 1008 hours. The results are tabulated below.
Table 2: Oxidation Testing at 1400F, in both air [4] and water vapor [5] environments
Environment
Alloy
Metal Loss, m
(mils)
Air
282
2.5 (0.1)
10.2 (0.4)
263
2.5 (0.1)
12.7 (0.5)
Waspaloy
2.5 (0.1)
15.2 (0.6)
R-41
2.5 (0.1)
10.2 (0.4)
Air + 10% H2O
282
2 (0.08)
13 (0.5)
263
2 (0.08)
10 (0.4)
R-41
2 (0.08)
15 (0.6)
230
1 (0.04)
5 (0.2)
Avg. (Max) Metal Affected = Metal Loss + Avg. (Max) Internal Attack; 1 mil = 0.001 inch = 25.4 m
12.7 (0.5)
15.2 (0.6)
17.8 (0.7)
12.7 (0.5)
18 (0.7)
13 (0.5)
18 (0.7)
8 (0.3)
Details of the experimental procedures can be found in Ref [5]. Many combustion environments
are likely to contain significant amounts of water vapor. It would suffice to state that at 760C
(1400F) 282 alloy suffered little to no corrosion attack in air + 10% water vapor. Comparative
121
static oxidation data for 282 alloy at 871C, 927C, and 982C (1600F, 1700, and 1800F), as
also the dynamic oxidation data at 871C (1600F) were reported in Ref [6]. In static oxidation
test at 871C (1600F), 282 alloy suffered 41 m (1.6 mils) of corrosion attack similar to the
other alloys in the test. Dynamic oxidation testing is much more aggressive wherein samples
are subjected to severe thermal cycling every half hour. At 871C (1600F), 282 alloy suffered
corrosion attack of 117 m (4.6 mils) which was similar to other alloys but more than the solid
solution strengthened 230 alloy which suffered 63 m (2.5 mils) of corrosion attack.
Low Cycle Fatigue
Low cycle fatigue behavior of 282 alloy was reported by Pike [7]. Fully reversed (R = -1.0) axial
low cycle fatigue testing was carried out at 649, 760, 816, and 871C (1200, 1400, 1500, and
1600F) on 282 alloy, and at 1500F (816C) for the Waspaloy, R-41, and 263 alloys. The LCF
resistance was found to gradually decrease with temperature up to 816C (1500F). Above this
temperature, the LCF resistance decreased more rapidly. It was found that 263 alloy had the
lowest LCF resistance at all strain ranges of the four alloys in the study. The 282 alloy, Waspaloy
alloy, and R-41 alloy were found to have very similar LCF resistance for higher total strain range
conditions. The stress amplitude was virtually constant in the elastic regime, while cyclic
softening was observed in tests at a higher total strain range. The paper did not include
examination of hold-time effects where the interaction of creep and fatigue can be determined.
Also, most of tests lasted less than 100 hours as such negative effects of environmental exposure,
as is likely in service, were not a factor.
Thermal Stability
Thermal stability of 282 alloy has been studied in exposures at 649C, 760C, and 871C (1200,
1400 and 1600F) up to 16000 hours [8]. Thermal stability is a key feature of alloys intended for
long-term service at elevated temperatures. For gamma-prime strengthened alloys in particular,
there are two main issues which can arise due to microstructural instability: loss of ductility and
loss of strength. Formation of deleterious phases such as the TCP-type sigma, Laves, or mu
phases can lead to a loss of ductility and embrittlement. The embrittlement is more often seen at
room temperature (RT) than at elevated temperatures (ET). Loss of strength can arise in these
types of alloys due to a number of reasons, including gamma-prime coarsening and/or dissolution
as well as formation of TCP-type phases which can deprive the matrix of critical elements such as
Mo. The 282 alloy did not suffer embrittlement and it did not form deleterious phases within the
1,000 hour exposures at any temperature. Optical micrographs of 282 alloy exposed at various
temperatures for 1,000 hours are shown in Fig 1. The phases present comprise primary TiN and
MC, and secondary M23C6 and M6C in addition to the matrix , being non-observable. The
alloy was found to increase in strength after the 1,000 hour exposure at 760C (1400F). Based on
RT and ET tensile tests of materials exposed for up to 16,000 hours at temperatures between 649
and 871C (1200 and 1600F), the results were very favorable for use in that temperature range in
terms of both elongation and yield strength.
122
a)
b)
c)
d)
123
1010C (1850F)/2h/AC
+788C (1450F)/8h/AC
800C (1475F)/8h/AC
Temp
C (F)
0.2% YS
MPa (ksi)
UTS
MPa (ksi)
Elong.
%
RT
676.6 (98.1)
1115.2 (161.7)
27.3
649 (1200)
608.3 (88.2)
1006.9 (146.0)
31.9
760 (1400)
597.9 (86.7)
838.6 (121.6)
20.4
871 (1600)
496.6 (72.0)
554.0 (80.4)
24.2
RT
705.5 (102.3)
1150.3 (166.8)
30.8
649 (1200)
608.3 (88.2)
1005.5 (145.8)
26.9
760 (1400)
604.8 (87.7)
832.4 (120.7)
12.9
871 (1600)
500.0 (72.5)
559.3 (81.1)
20.0
Temp
C (F)
0.2% YS
MPa (ksi)
UTS
MPa (ksi)
Elong
%
R.A.
%
None
RT
394 (57.1)
831 (120.5)
57
N/A
1010C (1850F)/2h/AC
+788C (1450F)/8h/AC
RT
706 (102.3)
1152 (167.1)
29.9
33.1
760 (1400)
632 (91.7)
866 (125.6)
21.1
22.6
RT
741 (107.4)
1183 (171.5)
31.3
35.4
760 (1400)
658 (95.4)
857 (124.2)
18.3
18.3
800C (1475F)/8h/AC
The strength properties as a result of the both aging heat treatments were similar. The most
significant difference was a discernible drop in ductility at 760C (1400F), more so in the sheet
product than in the plate. These observations can be interpreted with the help of microstructural
observations as shown in Figures 2 and 3.
The images on the left correspond to the two step heat treatment: 1010C (1850F)/2hr/AC +
788C (1450F)/8hr/AC; on the right correspond to the single step heat treatment: 800C
(1475F)/8hr/AC. The two step heat treatment leads to a discontinuous blocky morphology of the
carbides precipitating (presumably M23C6 type) in the grain boundaries. At the higher
magnification, the carbide particles show a stone wall construction. In contrast, the carbides
forming at 800C (1475F) during the one step aging heat treatment show a nearly continuous
network and ledges protruding into the matrix. The apparent difference in the width of grain
boundaries for the two conditions is attributed to the predominance of the growth morphology at
1010C/2hr/AC.
124
Figure 2. SEM micrographs of 282 alloy grain boundaries; Left Two step heat treatment; Right
One step heat treatment. Bottom images are at higher magnification.
The strength properties are interpreted with the help of SEM images shown in Fig. 3. In the case
of the two step age hardening heat treatments, particle size was estimated to be in the range of
21-33 nm; for the single step in the range of 38-71 nm. Though in both instances, the spherical
shape of particle indicative of a low mismatch strain is observed.
The equilibrium mole fractions after either heat treatment would not be expected to be
significantly different. However, the difference in the particle sizes as a result of the two heat
treatments does not lead to a substantive difference in strength properties.
125
Figure 3. Gamma prime particle distribution in 282 alloy; Top two step heat treatment;
Bottom single step heat treatment.
Creep Strength
Effect of age-hardening treatments on creep-rupture properties for sheet is shown in Table 4.
Table 4: Effect of Different Age-Hardening Treatments: Creep-Rupture at 927C (1700F)/
48.3MPa (7 ksi); Sheet, 0.062
1% Creep,
Rupture Life,
Age-Hardening Treatment
hours
hours
1850F/2h/AC +1450F/8h/AC
318.5
773.0
1475F/8h/AC
237.5
465.2
126
Clearly there is some degradation in 1% creep and rupture lives as a result of the single step heat
treatment. Comparative creep rupture strength data derived over the range of 649C (1200F) to
816 (1500F) from a 0.500 plate showing the effect of different age-hardening treatments is
plotted in Fig 4. The figure clearly shows that the one-step heat treatment resulted in a consistent,
but a very small decrease in creep-rupture strength relative to the two-step treatment. The loss is
attributed to a slight coarsening of the .
100
20
26
90
600
80
500
70
60
400
50
Stress (ksi)
30
200
Stress (MPa)
300
40
20
282 alloy - 1850F(1010C)/2h/AC + 1450F(788C)/8h/AC
282 alloy - 1475F(800C)/8h/AC
263 alloy - 1475F(800C)/8h/AC
100
90
80
10
36
44
42
38
40
Larson-Miller Parameter (R x 10-3, C = 20)
70
46
In addition to the creep-rupture strength data for 282 alloy, data for 263 alloy is also plotted in the
figure. Both aging heat treatments resulted in considerably better creep-rupture strength than 263
alloy. Note that 263 alloy also is strengthened by a single step aging heat treatment at 800C
(1475F)/8h/AC.
FABRICATION
As stated in the Introduction, in addition to its creep strength, the defining characteristic of 282
alloy is its fabricability, which is derived not only from an optimum volume fraction of the
phase, but also equally from the sluggish kinetics of its formation. In R-41 alloy, the formation of
cannot be suppressed by rapid cooling from the mill annealing temperature. In contrast, 282
alloy requires almost two hours of isothermal exposure at ~ 788C (1450F) which is at the nose
of TT Hardening plot. This feature has important implications in processing and fabrication, as it
mitigates the strain-age cracking phenomenon frequently associated with strengthened alloys.
The hardening kinetics of the 282 alloy are similar to those of the 263 alloy. The latter is known
127
for its superior weldability and formability which accounts for its widespread popularity and
applications in the aerospace industry.
During controlled heating rate tensile (CHRT) testing, anomalously large elongations were
exhibited by 282 alloy compared to R-41 and Waspaloy alloys, which indicates better strain-age
cracking resistance than those alloys [9]. This finding is attributed to its relatively sluggish precipitation kinetics. Based on Varestraint test results, 282 alloy also exhibits excellent weld
solidification cracking resistance, with crack lengths comparable to 263 alloy [10]. All
experimental testing and fabrication experience gathered to date indicate that 282 alloy has
excellent overall weldability when welded in the mill-annealed condition. Enough is not yet
known to determine the overall weldability of 282 alloy in the single-step aged condition.
Effect of Heat Treatment on Welds
In order to further investigate the weldability of 282 alloy, we have studied the effect of different
aging heat treatments on all-weld-metal (AWM) samples. The following three tables show tensile
properties of AWM plate samples subjected to various postweld heat treatments. Comparing the
results of the single-step (Table 5) to the two-step age-hardened (Table 6) AWM samples, it can
be seen that the single-step condition provided higher strength and generally lower ductility at
elevated temperatures up to 760C (1400F). The strength of the single-step condition fell below
that of the two-step condition at 871C (1600F) while its ductility continued to decrease and
remained lower. When compared to samples given a solution anneal treatment prior to the 788C
(1450F) aging (Table 7), the same trends in strength and ductility were observed. Samples given
a solution anneal treatment exhibited higher and more consistent ductility compared to samples
directly aged at 788C (1450F). Compared to the tensile properties of similarly aged base metal,
AWM samples exhibited higher YS, lower UTS, and lower ductility at RT and 760C (1400F).
While the precise microstructural reasons for these differences are not yet known, it is common
for weld metal to exhibit lower ductility than carefully controlled base metal microstructures.
The as-solidified weld microstructure of 282 alloy consists of discrete (Ti,Mo)C MC-type carbide
eutectic formed along the interdendritic boundaries. In addition, Cr-rich M23C6-type carbides
have also been identified in the as-welded condition. The formation of / eutectic in the
interdendritic regions, which is associated with solidification cracking in -strengthened Ni-base
alloys, has not been observed in 282 weld metal. Previous experiments have shown that 282 weld
metal achieves only partial recrystallization during the 1135C (2075F)/30min/AC solution
anneal as some initial solidification grain boundaries are left intact. The higher ductility of
solution annealed samples could be attributed to grain refinement via recrystallization and
dissolution of secondary phases in the weld microstructure. According to thermodynamic
calculations, MC carbides are not stable at 788C (1450F) and there is likely a propensity for
them to transform to M23C6 and upon aging. At 1010C (1850F), both MC and M23C6 are
stable whereas the dissolution temperature is exceeded. While microstructural analyses of
these particular samples have not been conducted, characterization of similar samples revealed
that Cr-rich M23C6 carbides are present along the initial weld solidification grain boundaries upon
postweld aging at 1850F. However, there appeared to be significantly more precipitation of
blocky M23C6 along the recrystallized grain boundaries. Continuous carbide precipitation as
a result of aging at 788C (1450F), similar to that observed in the base metal, may account for
the decreased ductility of single-step aged samples. Microstructural analyses are being conducted
to investigate this possibility. Through both qualitative SEM observations and semi-quantitative
XRD measurements, comparatively fewer carbides were observed in samples aged at 788C
(1450F) only.
128
0.2% YS
MPa (ksi)
857 (124.2)
739 (107.2)
730 (105.9)
714 (103.5)
449 (65.1)
UTS
MPa (ksi)
1109 (160.9)
917 (133.0)
905 (131.3)
847 (122.9)
543 (78.8)
Elong.
%
21.0
20.5
18.5
9.0
5.5
R.A.
%
21.0
24.2
27.6
12.0
7.4
Table 6: Tensile Properties AWM 0.375 Plate: GMAW + 1010C (1850F)/2h/AC + 788C
(1450F)/8h/AC
Test Temp.
C (F)
RT
538 (1000)
649 (1200)
760 (1400)
871 (1600)
0.2% YS
MPa (ksi)
759 (110.1)
646 (93.6)
632 (91.6)
640 (92.8)
488 (70.7)
UTS
MPa (ksi)
1077 (156.1)
887 (128.6)
897 (130.0)
841 (122.0)
563 (81.6)
Elong.
%
19.6
22.5
20.8
12.8
14.8
R.A.
%
17.8
25.8
23.2
19.0
25.7
0.2% YS
MPa (ksi)
730 (105.9)
603 (87.5)
616 (89.3)
621 (90.1)
512 (74.2)
UTS
MPa (ksi)
1079 (156.4)
832 (120.6)
866 (125.6)
836 (121.2)
575 (83.4)
Elong.
%
26.4
25.7
23.7
24.5
25.8
R.A.
%
23.5
30.6
27.3
21.8
29.2
Additionally, previous transverse weld tensile tests indicate that the inclusion of the 1010C
(1850F) aging step does indeed provide for enhanced elevated temperature ductility, which may
be the result of carbide precipitation in the preferred morphology [10].
SUMMARY
1. Since the introduction of 282 alloy a large amount of data has been generated to characterize
the alloy, which includes physical metallurgy, environmental resistance, thermal stability,
weldability, etc.
2. As a result of the single step hardening heat treatment, the material showed similar strength
properties and some loss of ductility at 760C (1400F), especially in sheet product. The one-step
heat treatment resulted in a consistent, but a very small decrease in creep-rupture strength relative
to the two-step treatment. The loss is attributed, at least in part, to a slight coarsening of the .
3. Microstructural analysis showed that the single step treatment led to a continuous network of
carbide morphology as opposed to a discontinuous blocky morphology, the former resulting in
lower ductility at elevated temperatures.
4. While enough is not yet known to determine the overall weldability of 282 alloy in the singlestep aged condition, all experimental testing and fabrication experience gathered to date indicate
129
that 282 alloy has excellent overall weldability. The inclusion of either a post-weld solution
anneal at 2075F or aging step at 1850F provided for enhanced elevated temperature ductility of
AWM samples compared to those in the 1450F single-step aged condition.
5. While it may be necessary to generate even more data for specific applications, it is evident that
the available data reinforces the potential of 282 alloy for A-USC applications.
ACKNOWLEDGMENTS
Authors would like to thank John Cotner, Mark Richeson and John Ryan for help with
metallography, the Weld lab for all-weld-metal samples, and the Test lab for tensile and creep
testing.
REFERENCES
[1] D.L. Klarstrom and L.M. Pike, Materials Solutions for Advanced Steam Power Plants,
Advances in Materials Technology for Fossil Power Plants, Proc. Fifth Int. Conf., Oct. 2007, pp.
107-118, EPRI 2008.
[2] L.M. Pike, U.S. Patent 8,066,938.
[3] L.M. Pike, Development of a Fabricable Gamma-Prime (') Strengthened Superalloy, (Paper
presented at Superalloys 2008, Champion, PA, September 14-18, 2008) 191-200.
[4] V.P. Deodeshmukh, Unpublished Research, Haynes International, Inc., 2013.
[5] V.P. Deodeshmukh and N.S. Meck, Paper No. 11195, NACE Int., Corrosion 2011.
[6] L.M. Pike and S.K. Srivastava, Materials Science Forum, Vol. 595-598 (2008) pp. 661-671.
[7] L.M. Pike, Paper No. GT 2007-28267, ASME Turbo Expo 2007: Power for Land, Sea and
Air, May 14-17, 2007, Montreal, Canada.
[8] L.M. Pike, Long-Term Thermal Exposure of HAYNES 282 Alloy, (Paper presented at
Superalloy 718 and Derivatives, Pittsburgh, PA, October 10-13, 2010) 644-660.
[9] Metzler, D.A., Welding Journal, vol. 91, no. 6, June 2012, pp. 163-s-168-s.
[10] Caron, J.L., unpublished research, Haynes International, Inc. 2013.
130
ABSTRACT (107)
To achieve the necessary creep-rupture lifetimes at the temperatures and pressures associated with
advanced ultrasupercritical (A-USC) steam conditions (100,000 h at 100 MPa and 760C),
precipitation-strengthened nickel-based alloys are required for the superheater and reheater tubing
in A-USC boilers. Two alloys were considered to have potential for this application:
Inconel 740 and Haynes 282 alloy. In support of this application, creep-rupture testing of
several heats of Inconel 740 was conducted over a range of temperatures and stresses to develop
confidence in qualitatively predicting creep lifetimes under conditions relevant to A-USC steam
conditions, with the longest rupture times exceeding 30,000 h. For comparison, the creep-rupture
behavior of Haynes 282 alloy was mapped as a function of temperature and stress, but with a
significantly smaller dataset. Only a small difference in creep-rupture results between Inconel
740 and Inconel 740H was found although the latter alloy showed significantly greater resistance
to phase formation during testing. Little effect of prior aging treatments (for setting the
precipitate structure) on creep-rupture behavior was observed. Results from a modified power law
analysis showed that, while both Inconel 740 and Haynes 282 are projected to meet the A-USC
lifetime requirements, the latter offered the potential for better long-term creep resistance.
INTRODUCTION
There are ongoing efforts worldwide to develop higher-efficiency coal- and nuclear-based
electrical power generation systems utilizing advanced (ultrasupercritical) steam.[1-5] For coalfired plants, the increased energy conversion efficiency from the use of ultrasupercritical (USC)
steam (gains of up to 35%) also, of course, translates to a reduction in CO 2 emissions for a given
plant power output. To achieve such efficiency gains using advanced USC steam, boiler metal
temperatures in excess of 700C and pressures greater than ~30 MPa will be necessary for the
superheater/reheater components. To withstand these steam conditions, non-traditional boiler
alloys will be required in the hottest parts of the boiler in order to achieve adequate strength and
corrosion resistance at these temperatures and stress levels.[6] These higher strength alloys must
also be formable and weldable during fabrication as well as for repair. Any alloy for this
application will have to meet the requirements of the ASME Boiler and Pressure Vessel Code for
creep strength and show acceptable fireside corrosion and steamside oxidation resistance.
131
Table 1. Nominal compositions for several Ni-based alloys under consideration for use in
parts of USC coal-fired boilers (wt%, balance Ni)
Designation
Cr
Co
Mo
Al
Ti
Fe
Mn
Si
Other
Alloy 617
Haynes 282
Inconel 740
Nimonic 105
* maximum
22
20
25
15
12
10
20
20
9
8
0.5
5
1.2
1.5
0.9
4.7
0.3
2.1
1.8
1.2
3.0*
1.5*
0.7
1.0*
1.0*
0.3*
0.3
1.0*
1.0*
0.15*
0.5
1.0*
0.1
0.06
0.03
0.17*
0.006 B*
0.005 B
2.0 Nb
0.007 B
Table 2. Compositions of the various heats of Inconel 740 and Haynes 282 used in this study
(wt%, balance Ni)
Alloy*
Cr
Co
740 (t)
24.4 19.9
740 (p)
24.4 20.0
740 (b)
24.4 19.9
740 (b)
24.9 19.9
740H (p)
24.2 20.3
282 (p)
19.7 10.1
282 (p)
19.6 10.6
* b: bar; p: plate; t: tube
nr: not reported
Mo
0.54
0.50
0.50
0.53
0.49
8.36
8.60
Al
0.94
0.98
0.98
1.20
1.20
1.46
1.48
Ti
1.80
1.78
1.78
1.41
1.51
2.08
2.21
Nb
1.98
1.98
2.00
2.05
1.58
nr
<0.1
Mn
0.28
0.26
0.26
0.30
0.27
0.04
0.03
Fe
0.42
0.46
0.46
0.69
1.09
0.20
0.15
Si
0.54
0.55
0.51
0.48
0.25
<0.05
<0.05
C
0.03
0.03
0.03
0.06
0.03
0.06
0.06
B
0.002
0.004
0.004
0.001
<0.001
0.003
0.005
transmission electron microscopy (STEM) was used to examine thinned sections of specimens
prepared by electropolishing.
The creep-rupture specimens were fabricated from plates or bars of either Inconel alloy 740
(produced by Special Metals Corporation) or Haynes 282 alloy (from Haynes International,
Inc.). Several different heats of each alloy were used (Table 2). With the exception of the H
refinement of the Inconel 740 compositional specification, the results reported in this paper are
not analyzed in terms of the concentration variations amongst the heats of the same alloy. With
respect to the Inconel 740 alloy type, 740H represents a compositional modification to improve
fabricability as described by Baker et al.[11] This was accomplished by refinement of the Ti, Al,
Nb, and Si concentrations. (Table 2).
RESULTS
Creep
Creep-rupture results for the heats of Inconel 740 (Table 2) are summarized in Fig. 1, which
includes, as open symbols, data from specimens that have not yet ruptured at the time of
reporting. The data in Fig. 1 are from specimens that were thermally aged (8 or 16 h at 800C) to
form the precipitate structure (see below) prior to creep testing. The curves for each
temperature are approximate fits to the data, yet it is apparent from simple extrapolation that
lifetimes of the order of 105 h at 100 MPa are achievable for temperatures of 750C and below.
This, of course, assumes no change in failure mechanisms at times beyond the range of those
reached in the current experimental program (~45,000 h at 750C).
In addition to the Inconel 740 data shown in Fig. 1, creep-rupture data for one heat of Inconel
740H were also generated. The data for aged (8h, 800C) Inconel 740H specimens (half-filled
circles) are compared to those for Inconel 740 (filled circles) in Fig. 2, which presents the creeprupture results as applied stress versus a Larsen-Miller parameter (LMP), T{log(t)+C} where T is
the test temperature in K, t is the time at load, and C=19.392.[9] The solid curve represents the
fitted stress vs. LMP curve for Inconel 740. It is clear from Fig. 2 that there is no significant
difference in creep-rupture lives between Inconel 740 and its H refinement at the highest test
stresses. While the H rupture times at intermediate stresses may be lower than the corresponding
Inconel 740, the situation at the lowest stresses may be the reverse in view of the results from the
ongoing Inconel 740H tests (open circles).
133
Figure 1. Applied stress versus rupture time for aged Inconel 740 specimens. Much of
data was used in ASME code case 2702[9]. Open symbols and arrows indicate ongoing
tests.
Some specimens of the Inconel
740H heat were tested in the
solution
annealed
(SA)
condition. The creep-rupture
data for these are shown in Fig. 3
as the square symbols. (For ease
of comparison, the individual
data points for Inconel 740
shown in Fig. 2 have been
removed, but the master curve
remains.) Except for the tests at
the highest stress levels, there
appeared to be little difference in
creep-rupture lives between the
SA specimens and those that
were SA then aged. The shorter
rupture lives of the SA material
at high stresses could reflect the
Figure. 2. Applied stress versus Larson-Miller parameter
fact that the yield stress was
(LMP) for Inconel 740 and 740H specimens (including,
exceeded during the creep
but not limited to, data used in code case 2702). Open
loading; the high-temperature
symbols represent ongoing creep tests
yield strength of Inconel 740H in
this condition was about 60% of
what it was in the aged condition.[12]
A smaller number of creep-rupture tests of Haynes 282 have been completed to date. These
results are shown in Fig. 4, where the solid circles represent data from specimens aged before the
start of the creep exposures. A two-step aging treatment of 1010C for 2 h followed by 8 h at
134
Figure. 4. Applied stress versus LMP for aged and solution annealed (SA) Inconel 740H
specimens. Arrows indicate specimens with a single step aging treatment.
self aging to precipitate might be occurring.
135
Microstructure
Initial microstructural analysis focused on a subset of Inconel 740 and 740H specimens exposed
at 750C at the same three stress levels. Both OM and SEM were used to generally assess
microstructural evolution as a function of time and stress. Thermal aging processes were
distinguished from stress-induced effects by comparing the grip and gage sections from the same
rupture specimen.
Figure 5 shows SEM
micrographs of the grip and
gage sections of crept
Inconel 740 specimens that
were held at 750C at 220,
265, and 370 MPa, with
rupture times as shown. At
this magnification, the most
dramatic
change
in
microstructure as a function
of time at temperature was
the increase in the amount
of eta () phase (Nb 3 Ti)
compare Fig. 5a, c, and e.
The phase is often
recognized by its acicular
shape at certain grain
boundaries.[4,15]
This
morphology can be clearly
seen in Fig. 6, which is a
higher magnification view
of one such grain boundary.
Fig. 5. Secondary electron images of Inconel 740 after
Figure 5 also shows that the
exposures at 750C for indicated times and applied stress
presence of stress promotes
levels.
development. The images
on the right hand side of the figure represent the gage (stressed) section of the same specimen and
there was always a greater amount of phase observed at this location than in the grip, where the
applied stress was essentially nil. Grain boundary carbides are also present but are distinctly
different morphologically (cf. Fig. 6) and were not observed to undergo much change in their
characteristics with time or stress. Figure 7 shows examples of the microstructures of Inconel
740H after testing at 750C. It reveals that, in contrast to Inconel 740, much less phase formed
during thermal aging at the same stresses and temperature (compare Fig. 7a, c, e). Indeed, it was
difficult to observe in these specimens; even at the longest exposure time shown (4864 h,
Fig. 7e), a higher magnification was needed to clearly identify the morphological evidence of this
phase. As with the Inconel 740, development was greater in the presence of stress, with this
being most clearly observed for Inconel 740H at 370 MPa (compare Fig. 7a to b).
The creep resistance of these alloys relates directly to the periodic distribution and shape of the
precipitates (see Fig. 6). The TEM micrographs in Fig. 8 are used to compare the size and shape
of the after short and extended times at 750C in the absence of stress (that is, these images
were taken from grip sections). This comparison shows that there was a 2-3X increase in size
136
over several thousand hours for both Inconel 740 and 740H.
However, there was no change in the cuboidal shape of the . Furthermore, while preliminary,
there was no evidence of depletion near the grain boundaries for either Inconel 740 (2185 h,
265 MPa, 750C, Fig. 6) or Inconel 740H (4864 h, 220 MPa, 750C, Fig. 9)
DISCUSSION
As with any alloy being used for long-term service at elevated temperatures, microstructural
stability over a defined period of operation is key to attaining desired properties and lifetimes.
With precipitation-strengthened alloys such as Inconel 740 and Haynes 282, particular concerns
are with (i) the coarsening of and concomitant disruption of the periodic structure needed for
effective obstruction of dislocation movement and/or (ii) the complete dissolution of near grain
boundaries.[4,10] For Nb- and Ti-containing alloys, there is a further issue of phase formation
and its direct and indirect effect on creep.[4,10] The microstructural data presented in this paper
clearly shows the development of in Inconel 740 at the temperatures of interest for A-USC
conditions (750C) and that stress exacerbates its formation. This influence of stress has been
reported previously (see, for example, refs. 4 and 10), may involve a reduction in the kinetic
barrier to precipitation,[10] and is considered to be relatively minor compared to the thermal
driving forces for formation and growth.[10] Qualitatively, the present observations also
indicated that phase development was certainly more strongly dependent on time at temperature
than on applied stress.
In contrast to Inconel 740, less formed during creep exposures of Inconel 740H, presumably
due to its lower concentration of Ti.[7,12] Despite the differences in susceptibility to phase
development between Inconel 740 and 740H, the creep-rupture lives of these two compositional
variants were similar at low-to-moderate stresses (Fig. 3). This is consistent with the conclusion of
Shingledecker and Pharr regarding a minimal effect of on creep resistance of Inconel 740
despite their observation of a few volume percent of this phase in crept specimens.[10]
In principle, coarsening of the phase during the long-term exposures should decrease creep
lifetimes.[16] However, as moderate coarsening of was observed for both Inconel 740 and
740H, no conclusion about the effect can be made because, taken as a whole, the test results from
the present study indicate comparable creep resistance of the two alloys. Xie et al. reported little
long-term coarsening for Inconel 740.[4] The depletion of near grain boundaries is also a
potential detriment to creep resistance, but no definitive effect can be deduced from the creep data
and the limited amount of microscopy performed to date. As shown above, depletion has not been
observed in the present study for the Inconel 740 and 740H specimens, but it has been reported
for one of these heats of Inconel 740 creep tested under the same conditions.[10] Interestingly,
while depletion was detected in Haynes 282 (Fig. 10), greater creep lifetimes are projected for
138
this latter alloy than that for aged Inconel 740 based on the analysis of the current data (see
below).
As shown in Fig. 3, Inconel 740H specimens that were only solution annealed before creep testing
had comparable rupture lives to those which were aged (4 or 8 h at 800C), except at the highest
applied stresses (> 300 MPa). Additionally, initial creep-rupture data for Haynes 282 (Fig. 4)
showed no difference in lifetimes between solution annealed and aged specimens across the entire
ranges of test stresses (120 to 420 MPa). Any conclusions about the implications of this set of
observations await detailed microstructural analysis and further creep-rupture data. Nevertheless,
these results would seem to indicate that creep testing at or close to the typical aging temperature
provides the necessary heat treatment to precipitate the phase responsible for long-term
strengthening. This self-aging phenomenon, of course, is only possible for alloys, such as those
studied here, that have sufficient intrinsic strength at these temperatures to avoid substantial
deformation damage during the time at which the precipitate structure is being developed. Indeed,
as mentioned above, this may explain why, at the highest stress levels (only), ruptures times for
Inconel 740H in the solution annealed condition were significantly shorter than those were aged
prior to testing.
The ability to predict longer-term rupture lives of a particular alloy based on relatively short-term
creep tests has been a longstanding problem in materials science and engineering that is made
more challenging for power-plant boiler applications where extremely long lifetimes (100,000s
of hours) are required.[3,17] This is even more problematical for boilers operating under A-USC
steam conditions, which require operation at higher temperatures and stresses that can more
readily promote processes that destabilize the creep-resistant microstructures. Indeed, in his recent
review, Evans[17] noted that while progress has been made in creep lifetime prediction for
traditional power plant materials (for example, 9-12Cr steels and austenitic stainless steel), there
is a need to extend such models to nickel-based alloys such as (specifically) Inconel 740 and
Haynes 282 and examine their effectiveness. While such a task is well beyond the scope of this
work, an attempt has been made to apply one of the current models to the present data to gain a
rough approximation of the time to rupture for Inconel 740 and Haynes 282 for A-USC steam
service.
Referring to Fig. 1, a simple extrapolation of the power law curve fit to the data shows that the
A-USC Steam Program goal of a 100,000 h lifetime at 100 MPa and 750C would be met by aged
Inconel 740. Furthermore, an analysis based on the best-fit curve to the stress versus LMP data for
aged Inconel 740 (Fig. 2) predicts, for 750C, a 100,000-h rupture life at 127 MPa. However, as a
first attempt to more rigorously predict long-term rupture time (t f ) based on short-time data, an
analytical treatment proposed by Wilshire et al.[17,18] was used. This approach goes beyond a
simple power law description by relating the applied stress, , to the rupture time, t f , through
where TS is the tensile strength, Q c is an activation energy, T the absolute temperature, R the gas
constant, and k 1 and u best-fit parameters. This analysis constructs, obviously, the right boundary
conditions at t f = 0 and = and has the form of a probability distribution function. It should be
noted that there are certainly other approaches to predicting long-term lifetimes that may be more
sophisticated in terms of physically based mechanics and microstructural models or accuracy.
Indeed, the present findings that, under many conditions, SA Inconel 740 and Haynes 282 show
similar creep-rupture lifetimes to those of their respective aged versions (cf. Figs. 3 and 4)
indicate that the Wilshire relationship between initial tensile strength and rupture time does not
139
(a)
(b)
Based on the Wilshire approach, both Inconel 740 and Haynes 282 are found to meet the A-USC
Steam Program goal of 100,000 h at 750C at an applied stress of 100 MPa. A similar analysis of
the aged Inconel 740H data yielded values of Q c and * (750C) that were physically unrealistic
given the data shown in Figs. 2 and 3. This was thought to be due to the lack of an adequate
number of data points, particularly at low stress values (longer t f s). Completion of the tests
indicated as still running in Fig. 2 should help in this regard. The 740H data shown in Figs. 2 and
3 suggest a similar * as Inconel 740.
SUMMARY
Creep-rupture testing of several heats of Inconel 740 was conducted over a range of
temperatures and stresses to develop confidence in qualitatively predicting creep lifetimes over a
140
range of conditions relevant to advanced ultrasupercritical steam conditions, with the longest
rupture times exceeding 30,000 h. For comparison, the creep-rupture behavior of Haynes 282
alloy was mapped as a function of temperature and stress, albeit not as extensively. Little
difference in creep-rupture results between Inconel 740 and Inconel 740H was found although the
latter alloy showed significantly greater resistance to phase formation during testing. For both
Inconel 740H and Haynes 282, little effect of prior aging treatments (for setting the precipitate
structure) on creep-rupture behavior was found; solution annealed specimens produced results
comparable to aged ones except for high stress tests with Inconel 740H. Results from a modified
power law analysis proposed by Wilshire et al. showed that, while both Inconel 740 and Haynes
282 are projected to meet the A-USC lifetime requirements, the latter offered better long-term
creep resistance.
ACKNOWLEDGMENTS
This research was sponsored by the U.S. Department of Energy (DOE), Office of Fossil Energy,
Advanced Research Materials Program. The authors thank the members of the DOE/Ohio
Economic Development Corporation A-USC consortium for comments on this work and
S.N. Dryepondt (Oak Ridge National Laboratory) and I.G. Wright (retired, Oak Ridge National
Laboratory) for review of the manuscript.
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Purgert, R., U.S. Program on Materials Technology for Ultra-Supercritical Coal Power
Plants, J. Mater. Eng. Perf., 14 (2005), pp. 281-292.
[2] Blum, R. and Bugge, J., The European Perspective and Advancements for Advanced USC
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International, Materials Park, Ohio (2011), pp. 1-10.
[3] Masuyama, F., R&D Program for A-USC Material Development with Creep
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[5] Duffey, R. B., Pioro, I. L., and Kuran, S., Advanced Concepts for Pressure-Channel
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141
[7] Patel, S. J., deBarbadillo, J. J., Baker, B. A., and Gollihue, R. D., Nickel Base Superalloys
for Next Generation Coal Fired AUSC Power Plants, Procedia Eng. 55 (2013), pp. 246252.
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Advanced Ultrasupercritical Coal-Fired Plants, Power 154 (2010), pp. 41-45.
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New York, 2012.
[10] Shingledecker, J. P. and Pharr, J. M., The Role of Eta Phase Formation on the Creep
Strength and Ductility of INCONEL Alloy 740 at 1023 K (750C) Mater. Metall. Trans. A
43A (2012), pp. 1902-1910.
[11] Baker, B. A. and Gollihue, R. D. Optimization of INCONEL Alloy 740 for Advanced Ultra
Supercritical Boilers, in Proc. Sixth Intl. Conf. on Advances in Materials Technology for
Fossil Power Plants, Gandy, D., Shingledecker, J. and Viswanathan, R. (eds.), ASM
International, Materials Park, Ohio (2011), pp. 96-109.
[12] Santella, M. L. and Stevens, C. O., Oak Ridge National Laboratory, unpublished results
(2011).
[13] Haynes International, Inc., Haynes 282 Alloy, technical bulletin H-3173 (2008).
[14] Unocic, K. A. and Tortorelli, P. F., Oak Ridge National Laboratory, unpublished results
(2013).
[15] Evans, N. D., Maziasz, P. J., Swindeman, R. W., and Smith, G. D., Microstructure and
Phase Stability in INCONEL Alloy 740 During Creep, Scripta Mater. 51 (2004), pp. 503507.
[16] Tien, J. K. and Copley, S. M. The Effect of Orientation and Sense of Applied Uniaxial
Stress on the Morphology of Coherent Gamma Prime Precipitates in Stress Annealed
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142
Goodwin Steel Castings Limited, Ivy House Foundry, Ivy House Road, Hanley, Stoke-on-Trent,
Staffordshire, ST1 3NR, UK
ABSTRACT
There is a worldwide drive to increase the efficiency of power plants in order to reduce the
amount of fossil fuel consumed and associated CO2 emissions. Raising the operating temperature
and pressure can improve the thermal efficiency, however, this necessitate the use of materials
which have high temperature performance. Steels are currently used at temperature up to 600C
with the efficiency of 38-40 %. Advanced Ultra Supercritical (A-USC) design plans power plants
to operate at steam temperatures of 700C and pressure up to 35 MPa with a lifetime of at least
100 000 hours. Ni-base superalloys are leading materials due to their significant strength and
creep resistance.
Haynes 282 is one possible candidate to meet the A-USC conditions for turbine engines. This
alloy is a precipitation strengthened material and exhibits very good creep properties and
thermal stability. The alloy examined in this research was produced by sand casting, and
therefore the aim of this research is to investigate the microstructural evolution in large scale cast
components.
The alloy has been examined in both the as-cast condition and as a function of a range of
different pre-service heat treatments. The microstructural changes during different heat treatments
have been fully identified and quantified. The results have also been compared with predictions
from thermodynamic equilibrium calculations using a Ni alloy database. It has been found that
variations in the heat treatment conditions can have a significant effect on microstructural
development and hence, potentially, the mechanical properties of Haynes 282 alloy.
1 INTRODUCTION
Haynes 282 was first introduced in 2005 as an advanced wrought gamma prime strengthened
superalloy for high temperature applications such as aircraft and land based gas turbines [1]. It is
notable for its exceptional high temperature creep strength, good weldability and fabricability and
its resistance to strain-age cracking [1].
After fabrication, wrought Haynes 282 materials often undergo a standard heat treatment: a
solution annealing treatment followed by quenching and then a two-stage precipitation treatment
with air cooling to achieve optimum mechanical properties [1, 2]. The solution annealing
temperature is designed to be above the solvus of M23C6 to make the material soft and ductile [2].
The first precipitation treatment temperature is above the solvus of gamma-prime and it is
designed to precipitate out M23C6 both intergranularly and intragranularly to give optimum creep
strength and high temperature ductility [2]. The second precipitation treatment is designed to
form to strengthen the material [2].
143
It is well known that there are many phases present in Ni-based superalloys, including different
carbides and TCP phases [3] and that these phases can have different effects on mechanical
properties. It has been reported that the microstructure of the heat treated Haynes 282 contains
MC carbide, Cr rich M23C6 both intergranularly and intragranularly, and also a uniform
distribution of spherical particles with a typical size of 20 nm [2].
There are a number of studies in the literature concerned with the microstructure of Haynes 282,
particularly focused on welds [4-8]. One study of the fusion zone in a laser weld of Haynes 282
observed that Co, Cr and Al were homogeneously distributed between the dendrite core and
interdendritic regions, whereas the Ti and Mo were rejected to the interdendritic region and
formed Ti-Mo rich, MC type carbides [6]. Three types of particles have also been identified along
the grain boundaries in Haynes 282 weld metal which were Cr-rich, Mo-rich and Ti-rich [8]. It
was also observed that there was B peak in the Mo-rich particle, and it was suggested that the
Mo-rich phases are M5B3 with lattice parameter of a=0.56 nm and c=1.01 nm [8]. There are
reports of other borides present in the alloy [5], including Nirich, Cr-rich and Mo-rich borides of
the form M3B2. Additionally, it has been reported the grain boundaries were covered by both
M23C6 and M5B3 [4, 7]. However, other authors [9] have also found a Mo rich phase before
precipitation treatment which was also associated with C and Si peaks, and they postulated that
the Mo rich phase was M6C. Therefore, it is still necessary to undertake a detailed microstructural
study of Haynes 282, and in particular most of the literature is focussed on the wrought alloy.
This research therefore is concerned with a full microstructural investigation of cast Haynes 282
in various heat treated conditions with possible application for heavy sections in the power sector.
2 MATERIALS AND EXPERIMENTAL PROCEDURES
The material studied in this research was produced by Goodwin Steel Castings Limited using
sand casting. The material examined was cut from the feeder part of a large cast section. The
nominal composition of Haynes 282 is given in Table 1. The initial solution heat treatment was
slightly modified to allow for the fact that this was a large casting rather than a wrought alloy,
with a two-stage solution treatment being applied comprising of 1100C for 6 hrs and then a ramp
up to 1150C for 15 hrs followed by water quenching. After the solution treatment, a two-stage
ageing treatment was applied which was the same as the standard Haynes precipitation treatment
but with a longer holding time at 1010C for 5 hrs followed by quenching, and then a second
ageing treatment at 788C for 15 hrs followed by air cooling.
Eight samples cut from the cast 282 material were examined in this paper and their condition and
code names are provided in Table 2. The material was examined in the as cast condition (AC) for
comparison purposes, then after solution treatment (ST), after the first stage aged condition (STFA), and after solution treatment and both aged conditions for different ageing times of the
second ageing treatment: 15 hrs, 100 hrs, 1000 hrs, 2000 hrs and 3000 hrs (ST-FA-SA** where
** indicates the length of the heat treatment). Samples were cut to a suitable size and then
mounted in conducting Bakelite. Mounted samples were ground on SiC papers from 220 to 1200
grit, and then polished with 9, 3, 1 m diamond solution and finally polished with colloidal silica
(0.5 m) for 30 min. To quantify gamma prime, the etchant Kallings no.2 (CuCl2-2g, HCL-40 ml
and ethanol-40-80 ml) was used for 10 s to highlight the . The Vickers hardness of all samples
were measured by a Mitutoyo HM-124 machine using a 10 kg load and a 15 s dwell time. For
each sample, ten measurements were performed and the average value was taken.
Table 1: The nominal composition in wt. % of Haynes 282
C
0.06
Cr
20
Mo
8.5
Si
0.15
Ti
2.1
144
Co
10
B
0.005
Al
1.5
Ni
Bal.
Table 2: Conditions and code names of all the samples in this paper. The solution treatment was
carried out at 1100oC for 6 hrs, followed by a ramp to 1150oC for 15 hrs and water quenched.
First ageing was carried out at 1010oC for 5 hrs followed by water quenching, and the second
ageing was at 788oC for various times followed by air cooling.
Sample name
AC
ST
ST-FA
ST-FA-SA15
ST-FA-SA100
ST-FA-SA1000
ST-FA-SA2000
ST-FA-SA3000
As Cast
Second Aged
15 hrs
100 hrs
1000 hrs
2000 hrs
3000 hrs
Thermodynamic calculations were performed using the MTDATA [10] software developed by
the National Physical Laboratory with an appropriate Ni-database [11]. The alloy composition
was used to predict the equilibrium phases between 300-1600C and the chemical composition of
each phase as a function of temperature. Solidification and chemical segregation profiles were
also predicted using the Scheil methodology (Tscheil).
Different microstructural features were assessed using a Carl Zeiss (Leo) 1530 VP field emission
fun scanning electron microscope (FEG-SEM). The backscatter mode was used to show different
phases due to its atomic number contrast. Energy dispersive X-ray (EDS) analysis was also used
for chemical analysis, with an operating voltage of 20 kV. Transmission electron microscopy
(TEM) was used to study small precipitates. A JEOL 2000FX TEM was used to obtain the
diffraction patterns of different precipitates and an fei F20 Tecnai FEG-TEM was used to obtain
EDS maps and spectra of different small precipitates. The site specific TEM samples were
prepared using an fei Nova Nanolab 600 dual beam which consists of a field emission electron
column and a gallium source ion column.
3 RESULTS AND DISCUSSION
3.1 Thermodynamic calculations
The calculated equilibrium phase diagram is illustrated in Figure 1. The phases considered in the
calculation were liquid, gamma, gamma prime, MX, M23C6, M6C, M3B2 and Mu. From Figure 1
(a), it can be seen that the predicted melting range is from 1300C to 1380C. Gamma prime
forms below 1000C and nearly 20 wt. % is precipitated at 788C, which is the standard second
ageing treatment temperature. The magnified phase diagram of the precipitates present in smaller
quantities, including MX, M6C, M23C6 and M3B2, is illustrated in Figure 1 (b). It can be seen that
MX is present until melting, and M3B2 and M23C6 precipitate out below 1250C and 800C
respectively. It should be noticed that M6C is present between 780C to 1080C. This is because
below 780C, the M23C6 is more stable [3].
The equilibrium composition of the different precipitates including gamma prime, MX, M6C,
M23C6, M3B2, and Mu were also predicted as illustrated in Figure 2. It can be seen that MX is a Ti
rich carbon nitride and M23C6 is Cr rich. It should be noted that the M6C, M3B2 and Mu phases
are all Mo rich, however, M6C is Mo and Ni rich, M3B2 is Mo and Cr rich and the Mu phase is
Mo and Co rich.
145
b
Mass percentage of different phases
a
Liquid
100
80
LIQUID
GAMMA_PRIME
Gamma
MX
M23C6
M6C
M3B2_TETR
MU_PHASE
Gamma
60
40
Gamma_prime
20
Mu
0
400
600
800
1000
1200
1400
1600
1.2
1.0
M6C
LIQUID
GAMMA_PRIME
Gamma
MX
M23C6
M6C
M3B2_TETR
MU_PHASE
0.8
0.6
M23C6
0.4
0.2
MX
M3B2
0.0
400
600
800
Temperature (C)
1000
1200
1400
1600
Temperature (C)
Figure 1: Plots of the equilibrium phase diagram of the Haynes 282 (a) and at a magnified scale
for the minor precipitate phases M6C, M23C6, M3B2 and MX (b).
a
b
MX
Gamma prime
0.85
Ni
0.80
0.75
0.9
0.8
0.60
0.15
Ti
0.10
0.05
0.00
400
Co
Al
Cr
500
600
700
800
900
Mo
0.6
0.4
0.2
0.0
400
1000
600
800
Temperature (C)
0.1
1200
1400
0.0
400
1600
Co
840
880
550
920
960
Temperature (C)
1000
1040
1080
0.3
Cr
0.2
400
700
750
800
800
850
0.35
0.4
0.0
650
Mo
0.40
0.5
0.1
600
Mu phase
0.45
Mass fraction
Mass fraction
Mass fraction
Ni
Cr
800
500
0.50
Mo
0.7
0.4
0.1
450
Co
0.6
0.2
Ni
C
Temperature (C)
M3B2 phase
0.8
Mo
0.3
Mo
0.2
M6C
0.5
1000
0.6
Temperature (C)
d
0.6
Cr
0.7
Mass fraction
Mass fraction
0.65
0.0
M23C6
1.0
Ti
0.8
0.70
Mass fraction
0.30
Co
0.25
0.20
Cr
0.15
0.10
Ni
0.05
600
800
1000
Temperature (C)
1200
0.00
400
450
500
550
600
650
700
750
Temperature (C)
Figure 2: Plots of the calculated equilibrium composition of different phases: (a) gamma prime;
(b) MX; (c) M23C6; (d) M6C; (e) M3B2; and (f) Mu
Since segregation is a normal phenomenon during casting, Scheil calculations have also been
carried out and the results are illustrated in Figure 3. From the phase diagram in Figure 3 it can be
seen that the solidification sequence in the Haynes 282 is gamma, MX, M6C, M3B2, Mu and
gamma prime. M6C is present from 1250C to 1175C, then M3B2 forms and followed by Mu
phase. From Figure 3 (b), it can be seen that there is a relatively high amount of MX which forms
together with gamma at the start of solidification, and Figure 3 (c) shows that the initial MX is
rich in nitrogen, a Ti rich carbonitride whereas later it becomes a Ti, Nb rich carbide. This is very
similar to the equilibrium prediction but with much more Nb and Mo due to segregation. Figure 4
146
illustrates the segregation ratio of elements in the liquid during solidification and it is obvious
that Nb and B are most heavily segregated, together with Ti and Mo.
b
Liquid
Gamma_prime
Gamma
MX
Liquid
M6C
M3B2
Mu-phase
80
60
40
20
Gamma
0
1100
1150
1200
1250
1300
1350
1400
0.06
0.05
c
Liquid
Gamma_prime
Gamma
MX
M6C
M3B2
Mu-phase
Gamma
Gamma_prime
0.04
0.03
0.02
M3B2
0.00
1100
1150
0.80
M6C
Mu
0.01
0.85
Mass fraction
100
Mass percentage of different phases
MX
1200
1250
1300
0.70
1350
0.10
Cr
Nb
Mo
0.00
1100
1400
0.15
0.05
Temperature (C)
Temperature (C)
Ti
0.75
1150
1200
1250
1300
1350
C
Ni
Cr
Mo
Nb
N
Ti
Co
B
Al
1400
Temperature (C)
Figure 3: Predictions from Tscheil calculations: (a) phase diagram; (b) enlarged phase diagram
for MX, M6C, M3B2, Mu and gamma prime; (c) predicted composition of MX formed during
solidification
b
70
C
Ni
Cr
Mo
Nb
N
Ti
Co
B
Al
60
50
40
30
Nb
20
10
0
1100
1150
1200
1250
1300
1350
1400
Temperature (C)
C
Ni
Cr
Mo
Nb
N
Ti
Co
B
Al
5.0
4.5
4.0
3.5
Ti
3.0
2.5
Mo
2.0
Co
1.5
Cr
1.0
0.5
0.0
1100
Ni
Al
1150
1200
1250
1300
1350
1400
Temperature (C)
Figure 4: Tscheil calculation predicted plots of segregation ratio of elements in liquid during
solidification (a) and the enlarged plot for C, Ti, Mo, Ni, Co, Cr and Al (b)
3.2 Hardness
The results from hardness testing of all samples are shown in Figure 5. It can be seen that the AC
sample has a higher hardness than the ST sample, which in turn has the lowest overall hardness as
a result of the dissolution of all of the strengthening precipitates. The AC sample was observed to
contain some gamma prime, as indicated in Figure 3 (b). After first and second ageing, the
hardness increased by up to ~160 HV compared to the solution treated sample. However, it was
noted that the ST-FA sample was ~40 HV higher than the ST sample in hardness, implying that
this increase in hardness is a result of precipitation during the first ageing. Therefore, in
comparing the hardness of the FA and SA samples, it can be inferred that gamma prime results in
~120 HV strengthening. Comparing the second ageing samples, it can be seen that the ST-FASA1000 sample and the ST-FA-SA2000 sample approach the highest hardness with very similar
values. The absolute values of hardness are a function of both the amount and size distribution of
147
gamma prime. It was, however, observed that the hardness of the ST-FA-SA3000 sample was
lower than the other aged samples, which could be caused by the coarsening of the gamma prime
distribution, as discussed further in section 3.5.
400
315
350
Hardness (HV10kg)
300
250
243
250
281
314
264
189
200
151
150
100
50
0
AC 282
ST 282 ST-FA
282
Figure 5: A plot showing the hardness of all of the samples examined in this research.
3.3 MX precipitates
Two types of MX precipitates were found in the AC condition: one was a Ti rich nitride with a
cubic morphology as shown in Figure 6 (a) and the other was a Ti, Mo rich carbide with a blocky
morphology along grain boundaries (Figure 6b). These results are in agreement with the predicted
composition of MX in the segregated state, as presented in Figure 3 (c). The diffraction pattern of
the cubic TiN illustrated in Figure 6 (a) is consistent with an FCC structure with a lattice
parameter of 0.425 nm, and the diffraction pattern of the blocky boundary (Ti,Mo)C illustrated in
Figure 6 (b) indicates that the (Ti,Mo)C phase also has an FCC structure with a lattice parameter
of 0.432 nm. Compared to TiN, the increase in lattice parameter of the (Ti,Mo)C is caused by the
larger substitutional atom, Mo, substituting for Ti.
After the solution treatment, the blocky (Ti,Mo)C particles disappeared and instead complex MX
particles formed comprising TiN surrounded by (Ti,Mo)C, as illustrated in Figure 7, which shows
the morphology of the complex MX in different aged conditions. It can be seen that the complex
MX were stable during subsequent ageing treatments. However, it should be noticed that after the
first ageing treatment, white precipitates were observed around the complex MX. From the
equilibrium phase diagram, the white precipitates could be M6C or M3B2. However, the solvus of
M3B2 is above the solution treatment temperature and it was not observed in the ST sample.
Therefore the white precipitates are more likely to be M6C, as discussed in section 3.4, and were
observed to coarsen slightly during the second ageing treatment with increasing ageing time.
148
Figure 6: Micrographs of the microstructure of the AC sample: (a) cubic TiN surrounded by
(Ti,Mo)C on a grain boundary and the diffraction pattern of the TiN, zone axis [-2-11]; (b)
blocky (Ti,Mo)C along a grain boundary and its diffraction pattern, zone axis [0-1-3]; (c) a EDS
spectrum of the TiN; and (d) a EDS spectrum of the (Ti,Mo)C
a
TiN
(Ti,Mo)C
Figure 7: Micrographs of the heat treated samples: (a) the ST sample; (b) the ST-FA sample; (c)
the ST-FA-SA15 sample (d) the ST-FA-SA100 sample; (d) the ST-FA-SA1000 sample and (f) the
ST-FA-SA2000 sample.
149
b
1
1
c
2
Figure 8: A micrograph of the grain boundary in the AC sample (a); (b) a spectrum from the
white precipitate; (c) a spectrum from the dark precipitate; (d and e) the diffraction patterns of
the white precipitate with zone axis [-112] and [-111] respectively and (f and g) the diffraction
patterns of the dark precipitate with zone axis [1-1-2] and [-123] respectively
After the solution treatment both boundary precipitates were dissolved, as illustrated in Figure 9
(a). It can be seen that there are only complex MX particles in the grain boundaries in the ST
sample. This is because the solution treatment temperatures are above the solvus of both M6C and
M23C6. The disappearance of the M6C after the solution treatment also provides further evidence
that the white precipitates are not M3B2 since the solvus of the M3B2 is above the solution
treatment temperature. During the first ageing treatment, M6C re-precipitated and covered the
grain boundaries again as seen in Figure 9 (b). From the equilibrium phase diagram in Figure 2
(b), it can be seen that at 1010C, the microstructure is predicted to comprise gamma, MX and
M6C, which is consistent with those observed in the microstructure of the ST-FA sample. After
the second ageing treatment, M23C6 re-precipitated and covered the grain boundaries, together
with M6C, as shown in Figure 9 (c). A specific lift out sample of the grain boundary in the ST150
FA-SA15 was made and EDS maps from the FEG-TEM also proved the grain boundaries were
covered by alternating Mo and Cr rich carbides. Figure 10 shows micrographs of the ST-FA-SA
samples after different ageing times. It can be seen that with the increasing ageing time at 788C,
both M6C and M23C6 coarsened.
a
Figure 9: Micrographs of the grain boundary structure of different samples: (a) the ST sample;
(b) the ST-FA sample; (c) the ST-FA-SA15 sample; (d) A TEM micrograph of a grain boundary
in the ST-FA-SA15 sample and the corresponding EDS maps of Mo, Cr and C.
a
Figure 10: Micrographs of the grain boundary structure of different aged samples: (a) the STFA-SA100 sample; (b) the ST-FA-SA1000 sample and (c) the ST-FA-SA2000 sample
151
Figure 11: Micrographs of the gamma prime in different samples: (a) the AC sample; (b) the STFA-SA100 sample; (c) the ST-FA-SA1000 sample; (d) the ST-FA-SA2000 sample and (e) the STFA-SA3000 sample.
152
b
250
ST-FA-SA100 282
Average size (nm)
Thousands
ST-FA-SA1000 282
Count
ST-FA-SA2000 282
ST-FA-SA3000 282
200
150
100
50
0
0
0
500
Feret diameter (nm)
1000
5
10
15
Ageing time t1/3 (h)
20
Figure 12: Plots showing the distribution of the gamma prime in the different aged samples (a)
and the coarsening of the gamma prime (b).
4 CONCLUSIONS
Microstructural evolution of cast Haynes 282 has been fully studied using a number of analytical
techniques, focusing on the different precipitates present. The observed phases present within the
microstructures agreed well with the thermodynamic equilibrium and Scheil predictions.
In the AC condition, two types of MX were found, which were TiN and (Ti,Mo)C. M23C6, which
is Cr rich and M6C, which is Mo rich, were found to cover the grain boundaries. Gamma prime
particles present in star morphology were also found in the AC sample, which had a relatively
high hardness value of 243 HV.
After the solution treatment, the (Ti,Mo)C particles dissolved and formed a complex MX
comprising TiN surrounded by (Ti,Mo)C. The other precipitates were all dissolved and thus the
material was measure to have a significantly lower hardness value (151 HV).
M6C was precipitated out during the first ageing treatment and covered the grain boundaries. This
precipitation provided the material a hardness increase of 40 HV. During the second ageing
treatment, M23C6 was precipitated and covered the grain boundaries, alternating with M6C. With
increasing ageing time, both M23C6 and M6C coarsened. Spherical gamma prime particles were
found during the second ageing treatment, and gave the material a maximum hardness increase of
120 HV. The coarsening of the gamma prime particles was observed to be proportional to time to
the power one third. It should be noted that spherical gamma prime particles were found up to
3000 hrs, which could contribute to the alloys relatively good creep properties.
5 ACKNOWLEDGEMENTS
The authors would like to acknowledge the support of Goodwin Steel Castings and
Loughborough University for this study.
6 REFERENCES
[1] Haynes 282 alloy Brochure, Online Literature, Haynes International, Inc. [Online] Access at:
www.haynesintl.com/literature.htm
[2] Pike, L.M., Development of Fabricable Gamma-prime (c9) Strengthened Superalloy, Proc.
11th Int. Symp. Superalloy 2008, Champion, PA, USA, September 2008, TMS, pp.191200.
[3] Sims, C.T., Stoloff, N.S. and Hagel, W.C., Superalloy II, John Wiley & Sons (New York,
1987), pp. 101.
153
[4] Buckson, R.A. and Ojo, O.A., Cyclic Deformation Characteristics and Fatigue Crack Growth
Behaviour of a Newly Developed Aerospace Superalloy Haynes 282, Materials Science and
Engineering A, Vol. 555, (2012), pp. 63-70.
[5] Ghoneim, A and Ojo, O.A., Microstructure and Mechanical Response of Transient Liquid
Phase Joint in Haynes 282 Superalloy, Materials Characterization, Vol. 62, (2012), pp.1-7.
[6] Osoba, L.O., Ding, R.G. and Ojo, O.A., Microstructural Analysis of Laser Weld Fusion
Zone in Haynes 282 Superalloy, Materials Characterization, Vol. 65, (2012), pp. 93-99.
[7] Osoba, L.O. and Ojo, O.A., Influence of Laser Welding Heat Input on HAZ Cracking in
Newly Developed Haynes 282, Materials Science and Technology, Vol. 28, No. 4, (2012), pp.
431-436.
[8] Osoba, L.O. and Ojo, O.A., Improved Resistance to Laser Weld Heat-Affected Zone
Microfissuring in a Newly Developed Superalloy Haynes 282, Metallurgical and Materials
Transactions A, Vol. 43A, (2012), pp. 4281-4295.
[9] Boehlert, C.J. and Longanbach, S.C., A Comparison of the Microstructure and Creep
Behaviour of Cold Rolled Haynes 230 Alloy and Haynes 282 Alloy, Materials Science and
Engineering A, Vol. 528, (2011), pp. 48888-4898.
[10] Davies, R.H., Dinsdale, A.T., Gisby, J.A., Robinson, J.A.J. and Martin, S.M., MTDATAThermodynamics and Phase Equilibrium Software from the National Physical Laboratory, (2002),
pp. 229-271.
[11] Saunders, N., Proc. 8th Int. Symp. On Superalloys (Superalloys 1996), (ed R.D. Kissinger
et. al), 101-110; 1996, Warrendale, P.A., The Minerals, Metals & Materials Society, Seven
Springs.
[12] Zhang, H.R., Ghoneim, A. and Ojo, O.A., TEM Analysis of Diffusion Brazement
Microstructure in a Ni3Al-based Intermetallic Alloy, Materials Science, Vol. 46, (2011), pp.
429-437.
[13] Darolia, R., Labrman, D.F. and Field, R.D., Formation of Topologically Closed Packed
Phases in Nickel Base Single Crystal Superalloys, Superalloys 1988, (ed. S. Reichman, D.N.
Duhl, G. Maurer, S. Anolovich and C. Lund), pp. 255-264, 1988, The metallurgical Society.
[14] Durand-Charre, M., The Microstructure of Superalloys, Gordon and Breach Science
Publishers (1997), pp.71-72.
[15] Zhao, S., Xie, X., Smith, G.D. and Patel, S.J., Research and Improvement on Structure
Stability and Corrosion Resistance of Nickel-Base Superalloy Inconel Alloy 740, Vol. 27,
(2006), pp.1120-1127.
154
ABSTRACT
In several material qualification programs tubes and thickwalled components mainly from Alloy
617 and Alloy 263 were investigated. Results as low cycle fatigue and long term creep behavior
of base materials and welds are presented. Numerical models to describe the material behavior
have been developed and verified by multiaxial tests. In order to ensure the feasibility of A-USC
plants two test loops have been installed in GKM Mannheim one for tube materials and a new
one for thick-walled piping and components. The latter consists of a part with static loading and a
part subjected to thermal cycles and is in operation since November 2012. First results of
measurements and numerical calculations for a pipe bend (static loading) as well as pipes and a
header (thermal cycles) are presented.
INTRODUCTION
At the beginning of this millennium the discussions on CO 2-reduction lead to strong efforts to
develop materials and components for high efficiency fossil fired steam power plants. In this
context world-wide research initiatives were established, Figure 1. Nowadays several new
challenges for power generation arise from the changes in political restrictions and demands.
There are still strong demands on reduction of CO2-emissions and subsequently raising efficiency
of fossil fired plants. All conventional plants are facing the demand of more flexible operation
due to the growing production using renewable energy sources, which are not constantly
available. This means that Nickel based alloys are required to ensure sufficient high-temperature
creep resistance [1],[2]. Research work on qualification and lifetime assessments for all materials
used in a A-USC plant, i.e. new nickel based materials, martensitic steels as VM12 and P92 and
ferritic steels, e.g. 7CrMoVTiB10-10 (T24) and their welds have been performed [3] and the
investigations on cyclic behavior of these materials have been enhanced recently.
For tubes, piping and headers in the boiler of A-USC-plants the Nickel alloys 617, 263 and 740
are under investigation. For these materials which are partly known from other application (e.g.
for gas turbines) first problems of manufacturing of tubes and mainly heavy-section components
had to be solved. Since the material properties which are needed for design and life assessment
are dependent on the manufacturing and heat treatment processes applied, basic material
qualification of material taken from components and weldments were necessary. Therefore the
first sections will focus on properties of Alloy 617, Alloy 263 and their welds.
For the application in a real plant tests under conditions as close to the service as possible are
necessary. This was the reason for installing test rigs in plants as shown in Figure 2. Two test rigs
in the GKM-plant in Mannheim are currently in operation.
155
Figure 2: Test loops to complement material and component qualification by basic research
Up to now, components are being designed with the help of codes and standards or by empirical
knowledge. In order to reduce the costs related to the new nickel based alloys and an economic
and efficient use of other materials, a Taylor-made design of components is required. Extended
steam conditions would also yield high wall thickness in components and piping if they are
designed according to currently existing codes and standards. However, in some cases these
requirements are contrary to the possibilities of manufacturing. Furthermore high thermal stresses
during start-up and shut-down must be taken into account in such components due to high wall
thickness. Actual codes and standards do not take into account the inelastic material response (for
example the relaxation of secondary stresses). One way to improve the design of new high
temperature components is to use modern constitutive equations for design calculations. The
European Pressure Equipment Directive (PED) allows for example the use of Design By Analysis
(DBA). Consequently, Finite Element Method (FEM) can be used to predict the creep and
relaxation behavior of boiler components for 700C fossil power plants. Since these models are
mostly phenomenological, a detailed experimental database is necessary to fit simulation
parameters. Therefore the development of such design and life assessment tools and their
application to components are of growing importance in the recent research projects [4].
156
Status
Finished
Finished
725HWT (1)
Phase 2
Investigation of the long term service behavior of tubes for the future highefficiency power plant
Finished
Ongoing
HWT 2
Investigation of the long term service behavior pipes, bends and headers under
static and cyclic loading
Ongoing
Finished
Ongoing
Finished
06/2013
Turbine application
DT-3
Qualification of dissimilar welds between 10%Cr-steels and Ni-based alloys
Finished
DT-4
Finished
WK2
Ongoing
Workpackage 1:
Sampling and Analysis of
existing data
Workpackage 4 : Creep
and Fatigue Strength and
Ductility of base materials
Workpackage 5:
Microstructural
characterisation
Workpackage 6:
Creep and Fatigue
Strength and Ductility of
Welded Joints
Workpackage 2:
Manufacturing and
Processing
Strength and
Ductility of Alloy 263
Piping and Forgings
and Alloy 617
Forgings in the
longterm range for
use in High
Efficiency Power
Plants
Workpackage 3:
Welding Processes,
Optimisation of
welding consumables,
Welding
Finished
Workpackage 7:
Evaluation of material and
component behaviour
Workpackage 8:
Fracture Mechanics
Characterisation and
Prevention from Brittle
Fracture
Workpackage 9: High
Temperature
Oxydation and
Corrosion
Workpackage 10:
Quality assurance
creep deformation and rupture behavior of tubes, oxidation behavior of coated turbine materials,
functionality of high temperature control and shut down valves. In the first phase almost 9000 h
of operation under more than 700 C have been accomplished with the operation of HWT 1.
Currently a second phase is in progress, tests on some samples are continued and new samples
have been included into the test rig. The test rig and results so far are described in more detail in
[7] and [8].
Test rig two (HWT 2) is aimed towards material behavior of thick walled pipes under static and
cyclic load conditions with additional superimposed secondary stresses [9],[10]. By injection of
cooling steam and water more than six thermal load cycles per day have been achieved. Duration
of one cycle is approximately 105 minutes, approximately 2000 cycles have been accumulated up
to now. The main focus of this test rig lays in the component behavior under primary and
additional secondary stresses, thermal fatigue behavior with temperature cycles between 400 C
and 700 C, stress-strain situation in pipes, bends, headers and T-pieces for lifetime analyses,
operation of high temperature control and shut off valves.
feedwater
feedwater
feedwater
B 3 steam
da = 219,1 x 50 mm
Pipe + weld
Prim. Stress from inner pressure
Therm. gradient from simul. start-up and shut-down
(injection T 300 C steam)
Static load
725C
Bypass
hangers, insulation
PRDS
HT-conditioning valves
Design, reliable
longtime operation
Mass flow control
Set to 725 C/162 bar
KZ steam
< 400 C
2,5 kg/s
from B 4
Figure 4: HWT 2 test loop with thickwalled pipes and bends, T-piece and header made from
Alloy 617 and Alloy 263.
Manufacturing and Qualification
Within the MARCKO 700 and DE4 projects manufacturing processes for tubes, pipes, T-pieces
and headers have been established. In DE 4 the products and weldments shown in Table 2 have
been manufactured and tested. In HWT 2 project numerous welds for the test rig and for
accompanying tests including dissimilar welds (A617/A263) have been produced.
Beside basic pedigree tests, Charpy-V tests in virgin and aged (up to 30,000 h) state have been
performed, Fig. 4. In the virgin state of the pipe specimen taken from the weldmetal show the
lowest values, for all specimens an increase with temperature can be shown, ageing results in a
reduction of impact energy, however this is not significant for higher temperatures. For the tubes
impact energy is highest in hardened state, further reduction after 30,000 h ageing is observed.
Additional results from qualification tests, e.g. tensile tests for A617 and A263 are given in [11]
and [12].
158
100
State: @800C/4h
State: @800C/4h+700C/3000h
State: @800C/4h+725C/3000h
State: LW@800C/4h+725C/30000h
90
80
140
70
60
50
40
30
20
10
0
200
300
400
Alloy263,
263.Rohr
Pipe380x60mm,
TIG weld
Alloy
380x60mm,autom.
Rundnaht,
vWIG-Orbital
80
60
40
20 Grundwerkstoff,
100
500
HWT 2
100
Project
DE 4
120
Kerbschlagarbeit / J
Material
Product
Welds
Weld material
Alloy 617
Forging
TIG (SA)
Similar A617
Alloy 263
Forging
TIG (A) and SMAW (A)
Similar A263
Alloy 263
Seamless Pipe
TIG (SA, A), SMAW (SA, A)
Similar A263
Alloy 263
Tubes
TIG (SA and A)
Similar A263
Alloy 263
Centrifugal Cast
TIG (SA)
Similar A263
Alloy 263
Induction Bend
Alloy 263
Cold Bend (Tube)
Alloy 263
Forging
TIG, SMAW
A617
Alloy 617
Forging
TIG, SMAW
A617
A617/A263
Forging
Dissimilar Welds, TIG
A617
A617/A263
Induction Bends
A617/A263
Header
Tubes: A617, A263, A740
A617
Welded in state: SA.solution annealed, A solution annealed and aged (800 C)
600
700
800
AZ;
700C/3kh;
Schweiverbindung, Kerbe WEZ,
AZ,
Schweiverbindung, Kerbe SG,
AZ,
50
100
150
725C/3kh;
700C/10kh;
700C/10kh;
600
700
700C/10kh;
800
Temperatur / C
Temperature / C
a)
b)
Figure 5: Results from Charpy V tests for tubes (a), with miniaturized specimens) and pipes (b) in
the virgin state and after 3000 and 30,000 h ageing.
Creep Behavior of Base Materials and Welds
One aim of the investigations in DE4 is to provide design data. For Alloy 617 within the project a
reevaluation of existing and new data has been made [13]. The results are shown in Table 3. The
values are in agreement with findings from previous projects and are much higher than the valued
given in the recent standard (DIN-EN-10302). So far this evaluation could be confirmed with all
tests. Assessment of weld strength of similar welds (Alloy 617) result in an overall weld strength
factor of 0.85. These results are confirmed by tests carried out within the recent projects. In Fig. 5
results of creep rupture test for different Alloy 617 melts and various weldments are shown. Most
base material results are in the upper part of the scatterband of the new evaluation.
So far the test results and running tests of TIG-welds with 980C postweld heat treatment are also
in the upper scatterband of the base material evaluation.
Figure 6 shows a summary of results at 700C for Alloy 263. Results are well above the Alloy
617 mean line and higher than the meanlines given by manufacturers. The scatterband of the
standard DIN-EN-10302 which is based on data for thin products is reached by the base metal
results. Only small reduction is visible for the investigated weldments.
159
Table 3:New evaluation of creep rupture properties for Alloy 617 [13]
500
450 Alloy 617 mod.; T=700C
400
350
300
1
250
200
150
100
Location of
fracture:
1 = BM
3 = WM
4 = HAZ
33
33
3
3
3 2x3
1
Weld metal and welds:
3
pure WM, SMAW
pure WM, TIG
3 3
pure WM, TIG, running Forged Material Test (Pipe):
weld, TIG orbital (+980C/3h)
Header Material Test (Pipe):
weld, TIG orbital (+980C/3h), running
weld, SMAW
Base Material Test (Forged) (IfWD):
weld, SMAW, running
BM (Pipe 360 x 80)
weld, TIG orbital
BM (Pipe 360 x 80), running
Tube Material Test:
weld TIG, Tube
Forged Material Test (Pipe):
weld TIG, Tube, running
weld, TIG orbital (+980C/3h)
Base Material Test (SZMF):
weld, TIG orbital (+980C/3h), running
BM (Tube)
Base Material Test (Forged) (IfWD):
BM (Pipe 460 x 80)
BM (Pipe 360 x 80)
BM (Pipe 460 x 80), running
BM (Pipe 360 x 80), running
10
10
Scatterband (A130) :
Average
+-20 %
New scatterband
COORETEC DE4:
Average
+-20 %
10
10
10
Rupture time / h
Figure 6: Creep rupture strength of Alloy617(mod) and its weldments.
600
500
400
300
Location of
fracture:
1 = BM
3 = WM
4 = HAZ
1
1
1
1
1
200
Base material (IfWD) 800C/4h:
BM (forged, Pipe 360 x 60)
BM (forged, Pipe 360 x 60), running
BM (Tube 38x6,3)
BM (Tube 38x6,3), running
100
10
10
10
10
10
Rupture time / h
Creep curves are obtained for the materials in order to describe numerical models as shown in
Fig. 7 for the seamless pipe made of Alloy 263. Using such data it was possible to approximate
parameters for creep models, e.g. the incremental Graham Walles creep law and a Chaboche type
model (CNOW) [14]. In order to qualify the pipe weldments introduced into the test rigs, same
additional welds (TIG and SMAW) were manufactured. From these welds large scale specimens
were taken (cross section appr. 40x40 mm2). Creep strain measured by high temperature strain
gauges over the complete weld zone are shown in Fig. 8. All welds were manufactured using
Alloy 617 weld material. It is visible that similar Alloy 263 welds and dissimilar welds show
smaller creep strains than Alloy 617 welds.
SA: welded in solution annealed state, afterwards hardened (800C/4h)
Strain p / %
10
10
-1
10
-2
10
-3
10
10
100
1000
10000
100000
Time / h
Creep strain / %
Figure 8: Creep curve tests on welded samples of a seamless pipe compared to Alloy 263 base
material
Dissimilar weld
time / h
Figure 9: Measured Creep creep strain of large scale specimens with a cross section of
40x40mm2 taken from pipe welds used in HWT2 project
161
J-integral (N/mm)
900
800
700
600
500
400
300
200
100
0
0,00
0,50
1,00
1,50
2,00
2,50
3,00
Figure 11: J-R curves for Alloy 263 at different temperatures and after ageing
162
Cyclic crack growth behavior is shown in Fig. 11. The comparison of both Nickel alloys gives
somewhat higher crack growth rate for Alloy 617. Creep fatigue crack growth data and creep
crack growth data are discussed and compared in more detail in [12].
1,E-01
da/dN / mm/LW
1,E-02
1,E-03
R=0,1
1,E-04
1,E-05
1,E-06
1,E-07
10
DKI / MPam
100
Figure 12: Cyclic crack growth for Alloy 617 and Alloy 263 at RT and 700C.
COMPONENT TESTING IN TEST LOOPS INSTALLED IN A POWER PLANT
Tube Test Loop (725 HWT 1)
In the tube test loops superheater tubes of various materials (Austenite and Nickel based alloys
where tested. Oxidation and corrosion behavior in the boiler are compared to findings in the
project Cooretec DE1 where tube samples and oxidation plates are investigated as well. Such
plates are also used in the turbine material section of the loop. In the outside loop ferritic and
austenitic materials are subjected to a temperature of about 630C and high Chrome austentitics
and Nickel based alloys are subjected to 725C. The test samples of the materials have a reduced
cross section in order to provoke damage within shorter durations. The investigations on the
oxidation behavior are now ongoing after finishing the first phase of the project. Some new
materials and some of the previously tested samples are now included in the test loops which is
under further operation now.
Test Loop for thick-walled components (HWT 2)
In HWT II a thick walled test rig with components made from the nickel based alloys A617 and
A263 is operated at a maximum temperature of 725C in Mannheim power plant GKM. The test
rig consists of a stationary and a transient part. With the exception of the operational startups and
shutdowns the stationary part is operated with steam at a temperature of 725C and an inner
pressure of 170 bar to investigate the creep behavior. In the transient part of the test rig the steam
at 725C is cooled down to 520C with cooler steam and after this to 400C with water. After
cooling the temperature increases from 400C to 725C, where a short hold time of almost 75
minutes takes place before the cooling starts again. One cycle has a duration of almost 105
minutes. Operation reached approximately 2000 cycles up to now which is close to the aim
formulated in the project. The intention of this operation mode is to simulate the fast and many
startups and shutdowns in future power plants and to investigate the thermal fatigue of the used
nickel base alloys. In the stationary part the main focus lies on a pipe bend made from Alloy 617
that is loaded with internal pressure and loads resulting from the weight and the hanger
construction of the pipework. Furthermore the bend is pre-tensioned with a bar to produce
stresses.
163
Figure 13: Different models to simulate the pipe bend behavior under static creep load
Figure 14: Mises stress and equivalent strain prediction obtained by an incremental creep law
From the section of the test loop which is subjected to thermocycles an analyses for the header is
shown in the following. The header and its model with different bore hole radii is shown in Fig.
14. The plots in Fig. 15 show the transient of steam temperature and mass flow dependent heat
transfer coefficient. The inner pressure is steady during one cycle and amounts to 170 bar.
Three simulations with an elastic-plastic material model, an incremental creep model (GrahamWalles type) and a complex Chaboche model were performed. In the elastic-plastic simulation
the cyclic flow curves from low-cycle fatigue (LCF) tests were used. With this material model it
is only possible to describe the isotropic hardening of the material. For the second simulation
164
using an incremental creep model the Graham-Walles creep law was used. This model is fitted
with uniaxial creep tests and it does not consider deformation due to cyclic plasticity. The
Chaboche Nouailhas Ohno Wang (CNOW) model was used for the third calculation. This model
is able to describe the isotropic and kinematic hardening of the material. The model contains two
different flow rules. The first one is used to describe the flow at high stresses and second one at
low stresses. The results are shown in Fig. 15.
2 capacitive strain
gauges
Figure 15 Header included in the part of the test loop which is subjected to thermocyclic loading
and geometrical model representing different radii for the boreholes of the header
Figure 16: Mises stress, first principal stress and principal strain obtained by a simulation of
the thermal cycle using the Chaboche type CNOW material model
From this simulation a strain range can be derived. Using a Manson-Coffin approximation of the
S-N-curve of the materials as a result for different radii and different material models the number
of cycles to crack initiation can be estimated, Table 4.
Table 4: Estimation of the number of cycles to crack initiation in the header for different radii
and applying different material models
Manson-Coffin
a
N
%
-
elastic-plastic
R3
R10
0,33
5435
0,26
14731
165
GWD
R3
R10
0,33
5435
0,28
10443
CNOW
R3
R10
0,38
3243
0,31
6995
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
166
ABSTRACT #
19
SMST is producing Ni alloy Boiler tubes since more than 10 years with application in
several test loops and R&D programs. This paper will give an overview about the
experience with the common grades A617 as well as C263 plus some additional
information on the new developed austenitic material Power Austenite MoW.
INTRODUCTION
As fuel resources are shrinking and CO 2 emissions are getting more and more
important, global energy policy is adapting to these new challenges. The trade with CO 2
certificates is one of the driving forces to investigate new technologies in PC power plant
technology.
In 2008, European utilities decided to perform a study on a 500 MW coal fired power
plant with net efficiencies of > 50%. The design studies for this project showed that live
steam temperatures of 1290 F are necessary to reach this high efficiency. Latest
austenitic stainless steels have proven to be capable up to 1150F steam temperature
but for the highest temperature range, Nickel Base alloys are necessary to withstand the
tough thermal and mechanical conditions.
EXPERIENCE
During the last 10 years Salzgitter Mannesmann Stainless Tubes has been fully
committed to this technology development and has gained comprehensive experience in
alloys which include DMV617 mod. & DMV263. The most promising candidate is alloy
DMV617mod.
167
Modification and qualification of alloy 617 for the application as boiler tube
Results of several test loops running at 1200 1337 F (650 -725C)
Significant improvement of creep rupture strength of A 617
Prove of creep rupture strength with test durations of up to 200.000h (25
years)
DMV 263
-
Long term creep rupture testing of C 263 in aged and solution annealed
condition
Experience in C-263 boiler tubes fabrication
C
Si
Cr
Ni
Mo
Nb
B
0,020,1-2,0
25-33
22-38
1-6
0,4-1,5
10-100
0,15
ppm
Table 1: Chemical composition of POWER AUSTENITE MoW [weight %]
168
N
0,01-0,2
M23C6
Nb(C,N)
phase
grain boundary
Figure 1: Structure of POWER AUSTENITE MoW
22Cr25Ni alloy
Figure 2: Microstructure of samples after 3,000h flue gas corrosion test under salt
In parallel to the scientific development, Salzgitter Mannesmann Stainless Tubes works
in partnership with the European utilities as well as boiler works to prove our capability of
producing more than 1000t of Ni base boiler tubes in accordance with a rigid project
schedule.
169
CONCLUSIONS
Salzgitter Mannesmann Stainless Tubes is able today to supply the requested stainless
steel and Nickel alloy boiler tubes for a 1300F PC power boiler in accordance with the
latest and greatest industry standards.
A new tube material with good fire side corrosion resistance and excellent creep
properties was developed and will be further qualified.
170
depending the availability and maturity of heat resistant steels and alloys. To fulfill such a goal, a
national consortium has been directly organized by the National Energy Administration (NEA) of
China, including seventeen research facilities, manufacturers and power plant operators, which all
are the leading player in their own sectors. Well known, the critical challenge of 700C A-USC
technology lies in the R&D of high-temperature materials, not only for boiler system but also for
turbine system. Due to the space limitation, the current paper will mainly address on the recent
boiler materials advancement in china, which may be hopefully used for Chinese 700C A-USC
demo plant.
BOILER MATERIALS SPECTRA FOR 700 A-USC PP
Basically, those mature materials successfully used in 600C USC power plant will still be
applied in 700C A-USC power plant, in where the working temperature is below 600C. When
the steam temperature increases from 600C to 700C, different novel materials are necessarily
required for various temperature scopes. According to published literature and our knowledge,
the materials R&D sub-committee of Chinese consortium for 700C A-USC power plant has
discussed, evaluated and summarized the candidate materials spectra used for 700C boiler of AUSC power plant in China, as schematically shown in Figure 2.
Figure 2 Candidate materials spectra used for 700C boiler of A-USC PP in china
For water cooling wall tubing, T23 and T91 are considered to be base-steel, on which some
modification for the improvement of on-site welding performance during plant manufacturing
and following maintain has to be carried out. G102 may be the alternative choice for the
replacement of T23 and T91, upon certain modification and improvement which are under
investigation at CISRI and BaoSteel. Most recently, T92 and G115 were selected as one of
candidate materials by Chinese boiler designers to make tube at superior temperature scope of the
water cooling wall tubing system, due to its outstanding creep strength, which make it possible
that all tubes from lower temperature to higher temperature of the system are of similar outside
diameter and wall thickness. Alloy 617 is not necessary to be a candidate material for the water
cooling wall system, unless the hidden weakness of T92 and G115 for such an application occurs
during manufacturing and in service in the future. Welding is a key concern for the making of
water cooling wall tubing.
For the tube-making of super-heat (SH) and reheat (RH), the candidate materials spectra are
T91, T92, NF709R, Sanicro25 (GH2984G), and Inconel740H equivalent (or an Inconel740HM
alloy), with the increase of steam temperature from 580C to 700C. GH2984 was developed by
Institute for Metals Research of Chinese Academy of Sciences some years ago, and 2984G will
be an upgraded iron-nickel based super-alloy on the basis of GH2984, which is supposed to be
172
used to make tube or pipe up to 680-700C. Thus, GH2984G and Sanicro25 are competitive
materials.
For the pipe/header-making, the candidate materials spectra are P91, P92, G115/G112,
(GH2984G), and CCA617 equivalent alloy, with the increase of steam temperature from 580C
to 700C. G115 was originally developed and patented by the Central Iron and Steel Research
Institute (CISRI) of China in the past years, which is proposed to be used to make pipe or header
up to 650C,although it was selected to be a candidate for water cooling wall tube.
Table 1 The time-table of R&D of materials used for 700 A-USC PP in china
The milestone and time-table of research and development of candidate materials used for
700C A-USC power plant in china were included in Table 2. Hopefully, the final products of
aforementioned candidate materials will be commercially available within five more years from
now on, subject to the determination and certainty of designing requirements. The typical
chemistry of candidate materials used for 700C A-USC power plant was listed in Table 2 and
the typical mechanical property of candidate materials used for 700C A-USC power plant was
listed in Table 3. The desirable creep rupture strength of candidate materials is around 100MPa
under its service temperature for 100,000 hours.
Table 2 Typical chemistry of candidate materials used for 700 A-USC PP
Alloy
Cr
Mo
G102
G115
NF709R
Sanicro25
GH2984
CCA617
In740H
0.12
0.08
0.08
0.08
0.06
0.06
0.03
2
9
21
22.5
19
22
25
0.6
0.4
3.0
Co
3.0
3.6
1.5
1.5
2.0
9.0
0.5
12
20
Nb
0.05
0.25
0.50
1.00
Al
0.35
0.20
Ti
Cu
0.13
0.005
0.015
1.0
3.0
0.4
1.0
1.35
1.50
1.0
0.4
1.35
0.003
Ni
Others
25
25
43
55
48
Fe
Others
Others
Others
33Fe
Others
Others
Table 3 Typical mechanical property of candidate materials used for 700 A-USC PP
Alloy
G102
G115
NF709R
Sanicro25
GH2984*
CCA617
In740H
Room temperature
Rp0.2 Rm
A
Z
345
623
330
366
686
330
705
630
763
700
760
1107
750
1110
>18
23
44.5
48
26.6
66
36
>40
72
74.5
68
46.6
70
42
Rp0.2
325
171
209
539
188
630
Elevated temperature
Rm
A
Z
T,
375
454
513
745
555
850
30
40
44
34.4
80
23
83
65
57
52.3
56
28
650
700
700
700
700
750
174
Figure 5 Evolution of M23C6 and Laves phases of G115 steel during aging
aging are much lower than that of 700 aging. The size of M23C6 is less than 170 nm and Laves
phase is about 200 nm under 650 aging up to 8000 hours. Correspondingly, the yield strength
and tensile strength of G115 at 650 and 700 after 650 aging were drawn in Figure 6. The
mechanical properties of G115 under 650 aging are very stable.
operational temperature window is very narrow and the flow stress is higher during pipe-making.
Further, relatively lower creep strength is another weakness of alloy 617. Modified 617 (or socalled 617B) alloy has been developed at ThyssenKrupp VDM, mainly by the boron addition of
10-50ppm, through which the creep strength is evidently increased. Big 617B alloy pipes were
successfully made and had been qualified in various European test loops. Cracks in the base
metal of an injection cooler, made of 617B alloy, in Scholven power plant were found and the
cracks was analyzed to be stress relaxation cracks. Proposed solution to eliminate the cracks is to
apply stress-relief annealing at 980for 3 hours.[2] In spite of aforementioned problem, alloy
617B is still one of most possible candidate materials for the pipe and header making of 700 AUSC power plant, because of its accumulated creep data and rich engineering experiences. Alloy
263 and 740H are of higher creep strength, but both alloys are in the early stage in the course of
feasibility verification used to make pipes and headers of 700 A-USC power plant.
177
Inconel740H. After the modification, it was reported that there is no acicular eta phase in the
microstructure of Inconel740H after 700-750 aging.
With the light of the modification of USTB and SMC, CISRI melted some heats of
Inconel740H in Laboratory for verification. Among them, one heat of Inconel740H contained
1.98%Nb, 1.08%Al, 1.64%Ti and 0.050%Si. As seen in Figure 10, acicular eta phase clearly
exists along the grain boundaries of the specimens after 5000-8000 hours under both 750 and
800, which implies that the microstructure of Inconel740H should be further modified and
improved.[3]
178
CONCLUSIONS
(1) Candidate materials spectra used for 700 boiler of A-USC demo Power Plant in china was
carefully discussed and summarized. The research and development in laboratory and
industrial trials of all tubes and/or pipes associated with the selected materials spectra are
under their way now.
(2) G115 has been successfully developed at CISRI and BaoSteel and it is an imposing material
for the making of boiler pipes at the temperature scope from 620 to 650 and the water
wall tubing of 700 A-USC power plants, due to its excellent creep rupture strength and
reasonable oxide resistance as well as its economic competitiveness.
(3) Although Inconel740H has been recognized as an excellent candidate alloy for 700 boiler,
the further optimization of chemistry and processing techniques is still necessary and
possible, based on existed and characterized weakness of the imposing alloy.
ACKNOWLEDGMENTS
The authors are very grateful for the continuously financial support from the Ministry of
Sciences and Technology of China under the grant of 2010CB630804 and 2012AA03A501. The
thankfulness of the authors also goes to all collaborative professionals and graduate students
participated in the project.
REFERENCES
[1] Z.D.Liu, P.Yan,H.S.Bao, S.Q.Xu, Q.J.Wang, Development of advanced ferritic heat resistant
steel G115 for A-USC power plants, The 5th Symposium on heat resistant steels and alloys
for high efficiency USC power plants, May,23-26, 2013, Seoul, Korea
[2] J.Klower, Development of nickel alloys for USC boilers, CISRI Heat Resistant Steels and
Alloys Lecture, Oct.,31,2012, Beijing, China
[3] Z.D.Liu, The research and development of heat resistant steels and alloys for 700 A-USCPP in china, IEA-Vienna Workshop-2012, Vienna, Austria, Sept., 19-20, 2012
179
ABSTRACT
To improve efficiency and flexibility and reduce CO2 emissions, advanced ultra super critical (AUSC) power plants are under development, worldwide. Material development and its selection are
critical to the success of these efforts. In several research and development programs / projects the
selection of materials is based on stress rupture, oxidation and corrosion tests. Without doubt,
these criteria are important. To improve the operational flexibility of modern power plants the
fatigue properties are of increased importance. Furthermore, for a safe operation and integrity
issues the knowledge about the crack behavior is essential. Crack initiation and crack growth may
be caused by natural flaws or cracks induced by component operation.
In order to develop new materials, properties like tensile strength and creep strength are an
important part of qualification and subsequent approval by notified bodies. Consequently short
term properties as well as time-temperature dependent properties are generated and taken into
considerations. In the case of high strength '-strengthening nickel-base alloys investigating the
creep crack behavior is also strongly recommended.
This article shows results of currently investigated nickel-based alloys for newly developed
headers, pipes and other high temperature boiler applications and their critical creep crack
propagation behavior.
INTRODUCTION
The nickel-based super alloys Alloy 617 and Alloy 263 are candidate materials for A-USC power
plants. Both alloys are known as materials with good mechanical properties and creep values at
elevated temperatures [1, 2]. Due to the precipitation hardening mechanisms Alloy 263 shows a
higher strength in comparison to Alloy 617.
Future requirements for power plants, e. g. improved efficiency and flexibility, raise the demand
regarding the mechanical properties of the deployed materials in order to avoid dimensional
changes of power plant components, e. g. wall thickness of pipes, which would cause increased
demands on processing and manufacturing of these parts.
Important properties of Alloy 617 and Alloy 263 were investigated and compared in a project
DE-4 [3] founded by the German government. Material was provided by the industry. The main
focus of the investigations has been the determination of creep properties and fatigue behavior.
Especially, the creep crack growth behavior of both candidate materials is of great interest.
Additionally, notch impact energy and fatigue crack growth data were determined. In the
following the results of tensile, creep, fatigue and creep crack growth tests are summarized.
180
MATERIALS
In this study a single melt of Alloy 617 and a single melt of Alloy 263 were investigated and high
temperature mechanical properties were compared. The product forms of the materials are thick
walled pipes with a wall thickness of 80 mm for Alloy 617 and 60 mm for Alloy 263 and an
outside diameter of 360 mm each. The heat treatment, chemical composition and microstructure
are conforming to current specifications [1, 2]. Alloy 617 was investigated in solution treated
state. Alloy 263 was age hardened at 4 h / 800 C / AC (AC - air cooling).
RESULTS AND DISCUSSION
In the following the results of the investigations of mechanical properties on Alloy 617 and
Alloy 263 are presented.
Tensile properties
For determination of the tensile properties at 700 C smooth cylindrical specimens with 8.4 mm
diameter were used. The tensile tests were performed in accordance to DIN EN ISO 6892-2 [4].
Their respective stress-strain-curves are shown in Figure 1.
As expected, Alloy 263 shows higher yield and tensile strength values compared to Alloy 617.
The rupture elongation A for Alloy 263 is much lower than for Alloy 617, but in an expected
range. The values of the reduction of area Z were determined to be 23 % for Alloy 263 and 47 %
for Alloy 617, respectively. In general, both materials show typical tensile properties at 700 C.
*800 C / 4 h / AC
T = 700 C
(MPa)
Alloy 263* / dET
500
50
(%)
181
*800 C / 4 h / AC
T = 700 C
Ru/t/T
(MPa)
1)
100
1)
2)
time (h)
Figure 2: Creep rupture strength Ru/t/T and creep rupture elongation Au of Alloy 617 and
Alloy 263 at 700 C
Low cycle fatigue behavior
The low cycle fatigue tests were performed using smooth cylinder specimens with a diameter of
7.9 mm. The tests were conducted under strain controlled loading conditions at 700 C according
to ISO 12106 [7].
Figure 3 shows the relationship between total strain range and fatigue life. The fatigue life is
determined as the number of cycles corresponding to a 5 % load drop. The fatigue life of Alloy
617 is found to be slightly lower compared to the fatigue life of Alloy 263.
Tests with hold times of 10 min in tension and pressure (Figure 4), respectively, show shorter
fatigue lives compared to tests conducted without hold times (Figure 3). The reduction of fatigue
lives is caused by the interaction of fatigue and creep [8]. Here, too, the fatigue life of Alloy 263
is slightly higher than the fatigue life of Alloy 617.
182
(%)
T = 700 C
R = -1
d/dt = 6 %/min
* 800 C / 4 h / AC
1000
10000
Ni 5 (cycle)
Figure 3: Fatigue life as a function of total strain range of Alloy 617 and Alloy 263 at 700 C,
tests without hold time
(%)
T = 700 C
R = -1
d/dt = 6 %/min
tht = thp = 10 min
*800 C / 4 h / AC
1000
10000
Ni 5 (cycle)
Figure 4: Fatigue life as a function of total strain range of Alloy 617 and Alloy 263 at 700 C,
tests with hold time in tension and pressure tht = thp = 10 min
183
(1)
f(a/W) = [0.886+4.64(a/W)-13.32(a/W)2+14.72(a/W)3-5.6(a/W)4]/(1-a/W)3/2 ,
(2)
with the crack length a, the applied load F, the specimen width W, the specimen thickness B and
the specimen thickness between side grooves Bn.
The parameter C* can be determined by [9]:
C* = (dvLLD/dt)cF/[Bn(W-a)]n/(n+1)
(3)
with = 2.2 for compact-tension specimens, the creep portion of measured load-line displacement
rate (dvLLD/dt)c and the Norton-exponent n.
For the creep crack growth tests on Alloy 263 and Alloy 617 the corresponding results are shown
in Figure 7 and Figure 8. In Figure 7, the creep crack growth rate da/dt is plotted versus the stress
intensity factor KI and in Figure 8 versus the parameter C*.
184
0.71W
1.2W 0.01W
Utilizing the stress intensity factor KI (Figure 7), the difference between the measured creep crack
growth rates in Alloy 263 and Alloy 617 is obvious. At the same loading parameter (e. g.
KI = 50 MPa m1/2) the creep crack growth rate in Alloy 263 is more than two decades higher than
in Alloy 617.
In the C*-diagram (Figure 8), the difference appears to be smaller. However, it needs to be
considered how similar the C*-values for Alloy 263 and Alloy 617 are attained. The high load
line displacements rates in Alloy 263 compensate for the reduced loads.
Metallographic sections were prepared for the Alloys 263 and 617 (Figure 9). Even though the
two materials showed vastly different creep crack growth behavior, no differences can be seen in
the intergranular crack propagation. The fracture surfaces (Figure 10) show no substantial
differences, as well.
The creep crack behavior of Alloy 617 correlates with published results [13, 14]. In contrast to
the results of tensile, creep and fatigue tests on smooth specimens, the creep crack growth
behavior of Alloy 263 was unexpected. Published results of creep crack growth behavior of Alloy
263 do not exist.
It is assumed that the reason for the differences in creep crack growth behavior is the deformation
and damage behavior ahead of the crack tip (Figure 11). In the higher strength Alloy 263,
extremely high strains concentrate on a relatively small volume ahead of the crack tip. Further
investigations to reveal this phenomenon are ongoing.
Bn
W 0.005W
1.25W 0.01W
185
0.47
0.850
U0.46
(V)
0.45
U0.825
(V)
0.800
* 800 C / 4 h / AC
0.44
0.775
0.43
0.750
0.42
0.725
0.41
0.700
vLLD
-250
(m)
vLLD
-250
(m)
-500
-500
-750
-750
-1000
-1000
-1250
-1250
specimen: dEO7c32
-1500
500
1000
1500
2000
2500(h)
time
specimen: dET7c22
3000
-1500
10
15
20
25(h)
time
30
Figure 6: Measured potential drop signal U and load line displacement vLLD at 700 C on creep
loaded Cs25-specimens, Fmax = 18.5 kN, left: Alloy 617/dEO, right: Alloy 263/dET
0.480
0.61
U0.60
(V)
0.59
U0.475
(V)
0.470
0.58
0.465
0.57
0.460
0.56
0.455
0.55
0.450
-1100
-800
vLLD
-1200
(m)
vLLD
-900
(m)
-1300
-1000
-1400
-1100
-1500
-1200
-1600
* 800 C / 4 h / AC
-1300
specimen: dET7c21
specimen: dEO7c33
-1700
2000
4000
6000
8000
10000
time
(h)
12000
-1400
20
40
60
80
100(h)
time
120
Figure 7: Measured potential drop signal U and load line displacement vLLD at 700 C on creep
loaded Cs25-specimens, Fmax = 13.5 kN, left: Alloy 617/dEO, right: Alloy 263/dET
186
da/dt
(mm/h)
T = 700 C
e
atur
liter
C
700
and
er b 617 @
t
t
a
sc Alloy
data
100
KI (MPa m1/2)
Figure 8: Creep crack growth rate da/dt vs. stress intensity factor KI of Alloy 617 and Alloy 263,
T = 700 C
da/dt
(mm/h)
T = 700 C
* 800C / 4h / AC
1000
C* (N/mmh)
Figure 9: Creep crack growth rate da/dt vs. parameter C* of Alloy 617 and Alloy 263,
T = 700 C
187
Figure 10: Details of creep crack growth, T = 700 C, Fmax = 18.5 kN, left: Alloy 617/dEO
(tmax = 2 600 h), right: Alloy 263/dET (tmax = 14 h), creep crack growth direction from left to
right
Figure 11: Details of creep crack growth surfaces, T = 700 C, Fmax = 18.5 kN, left:
Alloy 617/dEO (tmax = 2 600 h), right: Alloy 263/dET (tmax = 14 h), creep crack growth direction
from below to top
Rp0.2*
Rp0.2**
crack tip
rpl*
rpl**
Figure 12: Crack tip stress field (* Alloy 263, ** Alloy 617), schematically
188
CONCLUSIONS
Based on the presented results on two candidate materials (Alloy 617 and Alloy 263) for thick
walled pipes in A-USC power plants, it is strongly recommended to consider short term as well as
time-temperature dependent properties. These properties should be determined in standard tensile,
creep and fatigue tests on smooth specimens. A lack of information on creep crack growth
behavior can lead to an overestimation of the material's properties. Especially Alloy 263 shows a
significant lower resistance against creep crack growth in comparison to Alloy 617. These
findings are unexpected, as the tensile and creep strength values as well as fatigue life times of
Alloy 263 are higher compared to Alloy 617.
Consequently critical crack lengths are to be determined and non-destructive testing methods to
detect cracks in components are necessary in terms of integrity issues.
ACKNOWLEDGMENTS
The investigations were conducted as part of the joint research program COORETEC-DE4. The
work was supported by the Bundesministerium fr Wirtschaft und Technologie (BMWi) as per
resolution of the German Federal Parliament under grant number PTJ 0327705Y. The authors
gratefully acknowledge FDBR-Forschungsstiftung and the members of the project group for their
support. The responsibility for the content lies solely with its authors.
REFERENCES
[1] Alloy 617, "Material Data Sheet No. 4119", ThyssenKrupp VDM, (2005); "SMC-029",
Special Metals Corporation, (2005).
[2] Alloy 263, "Material Data Sheet No. 4020", ThyssenKrupp VDM, (1993); "SMC-054",
Special Metals Corporation, (2004).
[3] COORETEC-DE4: "Untersuchung zum langzeitigen Festigkeits- und Verformungsverhalten
von Rohren und Schmiedeteilen aus Nickel-Basislegierungen", PTJ 0327705Y, (2007-2013).
[4] DIN EN ISO 6892-2, Metallic materials Tensile testing Part 2: Method of test at elevated
temperature (2011).
[5] DIN EN ISO 204, Metallic materials Uniaxial creep testing in tension Method of test
(2009).
[6] DIN EN 10302, Creep resisting steels, nickel and cobalt alloys (2008).
[7] ISO 12106, Metallic materials - Fatigue testing - Axial-strain-controlled method (2003).
[8] Kobayashi, K. et al., "Creep-fatigue interaction properties of nickel-based superalloy 617",
Acta Metall. Sin., Vol. 24, No. 2 (2011), pp. 125-131.
[9] ASTM 1457, "Standard Test Method for Measurement of Creep Crack Growth Times in
Metals" (2007).
[10] Abe, F. et al., Creep-resistant steels, Woodhead Publishing Limited (Cambridge, 2008), pp.
446-471.
[11] Berger, C. et al., "Perspectives on improved life assessment methods for new plants", Proc.
4th Intern. Conf. on Advanced in Materials Technology for Fossil Power Plants, South
Carolina, 2004, pp. 653-671.
[12] Klenk, A. et al., "Developments in the use of creep crack initiation for design and
performance assessment", ECCC Information Day, 2003, pp. 45-57.
[13] Ren, W. et al., "A Review on Current Status of Alloys 617 and 230 for Gen IV Nuclear
Reactor Internals and Heat Exchangers", Journal of Pressure Vessel Technology, Vol. 131
(2009).
[14] Roesler, J. et al., "Wrougth Ni-Base Superalloys for Steam Turbine Applications beyond
700 C", Advanced Engineering Materials, 5, No. 7 (2003), pp. 469-483
189
ABSTRACT
In order to reduce CO2 emissions and improve power generation efficiency, a development
project involving an advanced USC (A-USC) plant has been carried out in Japan since 2008. Nibased alloys are candidate materials for boiler components with high temperature steam
conditions, which are much stronger than conventional heat resistant steel. However, Ni-based
alloys have never been applied with respect to the high pressure parts and thick walled
components of USC coal-fired power plants. In this study, therefore, fabrication and characteristic
properties, such as weldability, the weld joint and bent part properties, and weld cracking
susceptibilities of Ni-based alloys such as HR6W, HR35 and two types of Alloy617 (High B and
Low B) pipes were evaluated. Additionally, two types of HR6W header mock-ups and a HR6W
tube element mock-up were fabricated. With the exception of Alloy617 (High B), the fabrication
trials of Ni-based alloy pipes were conducted successfully, and the long-term creep strength of
weldments and bends of Ni-based alloy pipes were found to be nearly equivalent to those of base
metal. In the case of Alloy617 (High B), hot cracking was observed.
INTRODUCTION
From the standpoint of environmental protection, reduction of CO2 emissions is urgently required.
In the case of power plants, improvement of power generation efficiency with higher steam
temperature and pressure conditions is the most effective set of countermeasures. Research and
development work on A-USC power plants with steam conditions of 700C and higher has been
initiated in Europe, the USA and Japan[1-4]. In Europe, field testing has also begun[2,3]. An AUSC power plant development project has been carried out in Japan since 2008[4]. From 2008 to
2012, boiler, turbine and valve materials were developed and verified. From 2013 to 2016, boiler
components and small turbine tests will be undertaken to verify component level reliability.
To achieve steam conditions of 700C and higher, the application of Ni-based alloy materials
becomes necessary for high temperature components. To date, however, there has been no actual
experience in the application of Ni-based alloy for thick walled components in boilers. Therefore,
the establishment of optimized and practical fabrication procedures such as welding and bending
technology is needed. Furthermore, long-term reliability is also highly important. In this study, in
190
order to establish welding and bending technology for large diameter and thick walled pipes of
Ni-based alloys, weldability, welded joint properties, induction bending properties, as well as
long-term creep rupture properties were evaluated in comparison with those of the base metal. In
addition, mock-up tests were conducted for the purpose of applying the developed technologies to
components.
TEST MATERIALS AND EXPERIMENTAL METHOD
HR6W, HR35, Alloy617, Alloy263, Alloy740 and Alloy141 were candidate materials for A-USC
boiler components in the Japanese project. To evaluate the manufacturability of large diameter
and thick walled pipe, HR6W, HR35 and two types of Alloy617 (High B and Low B) pipes were
tested. The large diameter and thick walled pipes of these alloys were 350mm in outside diameter
and 50mm in wall thickness, and their chemical compositions are shown in Table 1. In the case of
Alloy617, two types of materials differing in the amount of B content were tested. The
appearances of the test materials are shown in Fig.1. Six types of candidate plate materials with
thickness of 25mm were also tested to evaluate weld cracking susceptibilities. In mock-up testing,
large diameter and thick walled HR6W pipes with sizes of 558mm OD x 138mm WT and 635mm
OD x 72mm WT were used, together with small diameter tubes having sizes of 45mm OD x
12mm WT and 63.5mm OD x 12mm WT.
The welding conditions and groove configurations for the Ni-based alloy pipes are shown in
Table 2. Welded joints were made by auto gas tungsten arc welding (Auto-GTAW) with
narrow groove using two types of matching wires, and additional HR6W weldments were made
Table 1 Chemical compositions of tested Ni-based alloy
C
Si
Mn
Ni
Cr
Mo
Co
Al
Ti
(mass%)
Nb
Fe
HR6W
7.54
HR35
4.44
0.73
Alloy617
0.061 0.07 0.04 0.002 <0.001 Bal. 22.22 9.12
(High B)
Alloy617
0.062 0.15 0.04 <0.01 <0.001 Bal. 21.83 9.22
(Low B)
191
Bal. 0.0033
-
0.0041
0.32 0.0023
by shielded metal arc welding (SMAW) using matching filler metals. The inter-pass temperature
was controlled to reduce hot cracking susceptibilities. Post weld heat treatment was not
performed. After welding, side bend testing, metallography examination, tensile testing, hardness
measurement, Charpy impact testing, and creep rupture testing were conducted.
Ni-based alloy materials are characterized by high hot cracking susceptibilities in comparison
with conventional heat resistant steel[5]. In addition, the re-heat cracking susceptibilities of Nibased alloy are higher than that of the conventional heat resistant steel due to strengthening of
phase precipitates in the grain[6]. Therefore, in the case of large diameter and thick walled pipe,
there is concern that re-heat cracking may occur in the grain boundary during relaxation of stress
in high temperature operations. Re-heat cracking was indeed reported in Alloy617 pipe
weldments in European A-USC field testing[6,7]. Given this background, hot cracking
susceptibilities and re-heat cracking susceptibilities were evaluated by trans-varestrain testing[5]
and slow strain rate tensile testing, respectively[8,9]. The trans-varestrain test was conducted with
3% loading strain. Hot cracking susceptibilities were evaluated by comparing maximum crack
length and total crack length. Slow strain rate tensile testing was conducted at 700C, 750C and
800C using weld thermal simulated HAZ specimens. The specimens were heated to 1300C in
about 70 seconds by means of high frequency induction heating, held for 5 seconds, and then
cooled down to 300C in about 80 seconds. The crosshead speed was 0.5mm/min (gauge length:
25mm). The re-heat cracking susceptibilities were evaluated by observing the reduction of area of
the specimens.
The induction bending properties of HR6W pipe were evaluated. Before induction bending,
support piping of carbon steel was welded with the HR6W pipe. Circumferential zone heating was
undertaken using a high frequency induction heater, after which the heated zone was bent. The
heating temperature was controlled such that the temperature of the outer surface could be
maintained between 1050C and 1150C, while the pipe feeding speed was approximately
0.1mm/sec. The pipe was bent at an angle of 50 and the bending radius was 1400mm (4 x OD).
The bent pipe was re-solution heat treated after bending under the condition of 1220C X 1hWQ,
which was the same condition of the heat treatment for base metal. After bending, metallography
examination, tensile testing, hardness measurement, Charpy impact testing, and creep rupture
testing were conducted.
Table 2 Welding conditions for large diameter Ni-based alloy pipes
192
For the purpose of component testing, applying the developed technologies, HR6W superheater
and reheater header mock-ups, as well as a HR6W tube element mock-up, were made to confirm
the manufacturability in the context of actual application for A-USC boiler compornents.
RESULTS AND DISCUSSION
Weldability and Weldment Properties
Figure 2 shows the appearance of GTAW and SMAW applied for HR6W pipes. The results of
side bend testing are shown in Fig.3, with all results being acceptable except for Alloy617 (High
B) were found. In the case of Alloy617 (High B) weldment cracking was observed after side bend
testing. Figure 4 shows the macrostructure and microstructure with respect to the longitudinal
sections of weldment. No defects were found except for Alloy617 (High B). There, hot cracking
in the heat affected zone (HAZ) near the fusion line could be observed. It was considered that the
damage seen in the Alloy617 (High B) weldment after side bend testing was due to hot cracking
in the HAZ. On the other hand, no such cracking in the HAZ of Alloy617 (Low B) could be
observed, suggesting that reduction of the amount of B content may be effective in lowering hot
cracking susceptibilities. However, the grain size of Alloy617 (Low B) was finer than that of
Alloy617 (High B), and thus grain size may also be effective in this regard.
Figure 5 shows the results of the elevated temperature tensile strengths of Ni-based alloy
weldments when compared with base metal properties. Although the tensile strength portions of
HR6W (SMAW) and Alloy617 (High B) weldments were lower than those of base metal due to
weld metal fracturing, other all tensile strengths were higher than for base metal.
Figure 6 shows the hardness distributions in the weldments. Hardness was measured at the inner
and outer sides of the pipes, as well as at midwall. In all Ni-based alloys, a hardening region was
seen in the HAZ. The hardening at the inside of the pipe was the greatest. The higher hardness in
the HAZ was thought to result from work hardening induced by tensile stress during shrinkage
due to solidification, and precipitation induced by the heat input of the welding thermal cycle.
Figure 7 shows the 0C Charpy impact test results of the weldments. The notch positions were
located at the center of the weld metal, the fusion line, the HAZ and the base metal. Although the
portion of absorbed energy at the fusion line and the HAZ of Alloy617 (High B) weldments
(a) GTAW
(a) HR6W
(b) SMAW
193
(b) HR35
were lower than for other specimens due to slight hot cracking, other all specimens showed good
toughness of 100J and over.
194
HR6W
Weld metal
Weld metal
HR35
Alloy 617
Weld metal
250
200
B
A
A
A
1
150
100
Open : GTAW
Solid : SMAW
40
A
B
300
Open : High B
Solid : Low B
Distance
Distance
Distance
(a) HR6W
(b) HR35
(c) Alloy617
1mm
Figures 8, 9 and 10 show the creep rupture properties of HR6W, HR35 and Alloy617 weldments,
respectively, compared with base metal properties. The creep rupture tests exceeding 20,000h
under low stress conditions are still ongoing. The creep rupture strengths of HR6W weldments
made by both of GTAW and SMAW were higher than those of base metal, and no difference of
strength relating to welding method could be observed. The creep rupture strengths of the HR35
weldments were also higher than those of base metal, although the long creep rupture strengths
exhibit a slightly declining trend. It is necessary to verify the long-term properties, i.e., 30,000h
and more. In the Alloy617 weldments, while the creep rupture strength of the weldment at 700C
was slightly lower than that of base metal (caused by weld metal fracturing), the test results at
750C and 800C were nearly equivalent to base metal. The higher creep rupture strength of the
weldments was assumed to result from increased weldment hardness.
195
196
12
10
8
6
4
2
0
Alloy 141
Alloy 740
Alloy 263
Alloy 617
(High B)
HR35
HR6W
Figure 12 shows the results of slow strain rate tensile testing of simulated HAZ specimens. The
re-heat cracking susceptibilities of Alloy617 (High B), Alloy263, Alloy740 and Alloy141 were
somewhat higher than those of HR6W and HR35. In the case of Alloy617, recovery of reduction
of area at 800C due to solid solution of the phase was observed[10]. It was considered that
HR6W and HR35 have good creep ductility due to the absence of phase precipitates in HR6W
and the presence of -Cr precipitates instead of phase in HR35. Accordingly, it is better to
perform post weld heat treatment such as re-solution heat treatment or stress relief heat treatment
so as to prevent re-heat cracking in thick walled components of Ni-based alloy, especially
Alloy617, Alloy263, Alloy740 and Alloy141.
Alloy617
(High B)
70
HR35
HR6W
60
50
40
30
Alloy263
20
Alloy740
Alloy141
10
Crosshead speed:0.5mm/min
0
650
700
750
800
Test temperature ()
850
Figure 12 Slow strain rate tensile test results of Ni-based alloy plates
197
Figure 13 Induction bending process of HR6W pipe and appearance of bent pipe
45
40
Start of bending
Center of bending
End of bending
Straight part
35
Reduction ratio of
wall thickness (%)
-15
-10
-5
a Extrados
b
h
g
c
f
d
e Intrados
0
5
10
15
a
c
d
e
f
g
Location in circumference
198
Figure 15 shows the creep rupture test results of bent pipe, as compared with base metal
properties. Test specimens were taken from the extrados portion, neutral portion and intrados
portion of the bent pipe. The creep rupture strengths were nearly equivalent to those of the
respective base metals, and it was thus recognized that there had been no strength reduction due to
bending. Also, no differences in strength related to sampling location could be seen.
Header and Tube Element Mock-up Testing
Figure 16 shows the appearance of the superheater and reheater header mock-ups, and the tube
element mock-up. These mock-ups test program included butt welding, stub tube welding, stub
welding, tube bending and spacer welding; no particular problems were experienced with these
manufacturabilities. According to the mock-ups test results, it was confirmed that fabrication of
HR6W pipe can be practically applied for A-USC boiler components.
500
Stress (MPa)
300
200
700
750
100
800
70
50
30 1
10
Base metal
Tension side
Neutral
Compression side
102
103
Time to rupture (h)
104
105
Figure 15 Creep rupture properties of HR6W bent pipe after solution heat-treatment
at 1220 for 1h
CONCLUSIONS
1. In order to evaluate manufacturability with respect to welding and bending technology of Nibased alloys for thick walled components in A-USC boilers, fabrication trials of HR6W, HR35
and two types of Alloy617 (High B and Low B) pipes were conducted. The long-term creep
rupture strength of weldments and bent pipes made of these alloy were also discussed.
2. The welding trials of Ni-based alloy pipe materials were conducted successfully, with the
exception of Alloy617 (High B). Although the hot cracking was observed in HAZ near the
fusion line of Alloy617 (High B) weldments, no hot cracking was observed in Alloy617 (Low
B). Also, the mechanical properties and creep rupture properties of Ni-based weldments were
found to be nearly equivalent to those of base metal.
3. In order to prevent of hot cracking, control should be exerted to reduce the heat input and the
inter-pass temperature during welding process, and to optimize the amount of B content and the
grain size in the base metal. Moreover, it is better to perform post weld heat treatment such as
re-solution heat treatment or stress relief heat treatment so as to prevent re-heat cracking in
thick walled components of Ni-based alloy, especially Alloy617, Alloy263, Alloy740 and
Alloy141.
4. The bending trial of HR6W pipe was conducted successfully. The metallic structure,
mechanical properties and creep rupture properties of HR6W bent pipe were nearly the same as
those of base metal.
5. Two types of HR6W header mock-ups and a HR6W tube element mock-up were manufactured
without any particular problems. According to these test results, it was confirmed that
fabrication of HR6W pipe can be practically applied for A-USC boiler components.
REFERENCES
[1] R. Viswanathan et al., U.S. Program on Materials Technology for Ultra Supercreitical CoalFired Steam Power plants, Paper No.Creep2007-26826, Proceeding of 8th International
Conference on Creep and Fatigue at Elevated Temperatures, San Antonio, Texas, July.
2008.
[2] R. Blum, The European Perspective and Advancements for Advanced USC Steam Power
Plants, Proceedings of Sixth International Conference on Advances in Materials
Technology for Fossil Power Plants, Santa Fe, New Mexico, August. 2010, pp. 1-10.
[3] K. Metzger et al., GKM Test Rig: Investigation of the Long Term Operation Behavior of
Tubes and Forgings Made of Alloys for Future High Efficient Power Plants, ibid, pp. 86-95.
[4] M. Fukuda, Advanced USC technology Development in Japan, ibid, pp. 325-341.
[5] M. Suzuki et al., Research for the Quantitative Evaluation of Solidification Cracking
Susceptibilities in Ni-base Alloy Weld Metals, KOBE STEEL ENGINEERING REPORTS,
Vol. 54, No. 2 (2004), pp. 43-46.
[6] G. Schmidt et al., Component Test Facility for a 700C Power Plant, COMTES700,
(2012).
200
[7] H. Schaffon, 700C Power Plant Technology Status and Challenges, Proceedings of 9th
Liege Conference: Materials for Advanced Power Engineering 2010, September. 2010, pp.
20-28.
[8] A. Dhoog, Survey on reheat cracking in austenitic stainless steels and Ni base alloys,
Welding in the World, Vol. 41, No. 3 (1998), pp. 30-43.
[9] K. Okada et al., Sensitivity of Reheat Cracking on Austenitic Stainless Steel Containing
Nb, CAMP-ISIJ, Vol. 17, (2004), pp. 928.
[10] H. Semba et al., Creep properties and strengthening mechanisms in 23Cr-45Ni-7W(HR6W)
alloy and Ni-base superalloys for 700C A-USC boiler, Proceedings of fifth international
conference on advances in materials technology for fossil power plants, Florida, USA,
March. 2008, pp. 168-184.
[11] N. Saito et al., Creep Rupture Properties of HR6W for Advanced-USC Boilers,
Proceedings of Sixth International Conference on Advances in Materials Technology for
Fossil Power Plants, Santa Fe, New Mexico, August. 2010, pp. 962-971.
201
DEVELOPMENT AND TRIAL MANUFACTURING OF NIBASE ALLOYS FOR COAL FIRED POWER PLANT WITH
TEMPERATURE CAPABILITY 800C
Shinya Imano, Naoya Sato, Hironori Kamoshida
Hitachi Research Laboratory, Hitachi, Ltd.
7-1-1 Omika-cho, Hitachi 319-1292, Japan
Abstract
Large scale components of the conventional 600C class steam turbine were
made of the ferritic steel, but the steam turbine plants with main steam
temperatures of 700C or above (A-USC) using the Ni-base superalloys are now
being developed in order to further improve the thermal efficiency. The weight of
the turbine rotor for the A-USC exceeds 10ton. A lot of high strength superalloys
for aircraft engines or industrial gas turbines have been developed up to now. But
it is difficult to manufacture the large-scale parts for the steam turbine plants
using these conventional high strength superalloys because of their poor
manufacturability. To improve high temperature strength without losing
manufacturability of the large scale components for the A-USC steam turbine
plants, we developed Ni-base superalloy USC800(Ni-23Co-18Cr-8W-4Al-0.1C
[mass %]) which has temperature capability of 800C with high
manufacturability achieved by controlling microstructure stability and
segregation property. The 700C class A-USC materials are the mainstream of
current development, and trial production of 10 ton-class forged parts has been
reported. However, there have been no reports on the development and trial
manufacturing of the A-USC materials with temperature capability of 800C. In
this report, results of trial manufacturing and its microstructure of the developed
superalloy which has both temperature capability 800C and good
manufacturability are presented. The trial manufacturing of the large forging,
boiler tubes and turbine blades using developed material were successfully
achieved. According to short term creep tests of the large forging and the tube
approximate 100,000h creep strength of developed material was estimated to be
270MPa at 700 C and 100MPa at 800C.
202
1. Introduction
To reduce CO2 emissions, further improvements of the coal-fired power
generation plants are required. Research and development on the Advanced Ultra
Super Critical (A-USC) power generation is underway in Europe and Japan. The
double-reheat system for steam temperatures of 700C/720C/720C with an
electric power transmission efficiency of 46% is expected to improve by 10%
compared to the conventional USC power plants (electric power transmission
efficiency of 42%). For further improvement of the efficiency, increasing the
main steam temperature to 750C or higher is being discussed (U.S.
ULTRAGEN III). Among the candidate materials for 700C class A-USC plants,
IN617, DT706, Waspaloy, DT750, etc., are being studied in Europe1). In Japan,
the development of the Ni-base alloys such as FENIX-7002), LTES-7003), and
USC1414) have been reported. At 750C, Waspaloy1) exhibits a creep rupture
strength of approximately 100 MPa, which is the highest among the candidate
materials, but manufacturability of the ingot and hot workability are not sufficient
for the large scale components such as steam turbine rotors. With regard to the
USC141 alloy, the manufacturability of large forgings superior to that of the
Waspaloy, whereas the temperature at which the 100,000h creep rupture strength
is 100 MPa (the temperature that is satisfied with the strength for turbine rotors,
hereinafter, creep resistant temperature) is below 750C. The creep resistant
temperature of the other candidate materials is 720C or below. Because the
boiler tube is exposed to a temperature of 750C or higher even when the main
steam temperature is 720C, it is necessary to develop new materials to raise the
main steam temperature and reheat steam temperature to more than 720C and
750C, respectively. The large forgings such as steam turbine rotors and boiler
pipes are formed by hot forging at approximately 1000C. However, it is
generally difficult to satisfy both hot workability at 1000C and high temperature
strength in the range of 750 - 800C, so it is a major obstacle to enhancing the AUSC efficiency. The purpose of this research is to develop the Ni-base alloys
which can be used at 750C or higher, and that have superior large ingot
manufacturability and forgiability. In this study, using a thermodynamic
calculation5), a promising composition of the Ni-base alloys (USC800) was
determined and fundamental high temperature properties are investigated6) using
specimens from 20 kg ingots. Fig. 1 shows the feature of the USC800.
In this report, results of trial manufacturing of the large forging and the tubes for
boiler using the USC800 according to evaluation of the large ingot
manufacturability were reported. And results of short time creep tests using
specimens from large forging and 10,000h class creep tests using specimens from
20kg ingot were also reported.
203
50
40
Service
temperature
30
Forging
temperature
USC800
USC141
20
IN740
10 Nimonic263
IN617
0
600
700
800
900
Temperature (C)
1000
1100
2. Experimental Procedure
2.1 Evaluation of large ingot manufacturability
Fig. 2 shows the dimension of the specimen for the horizontal directionally
solidification furnace shown in Fig. 3. The chemical composition of the specimen
is shown in Table 1. The horizontal directionally solidification furnace enables
the changing of the cooling rate () and solidification rate (R) by controlling the
heater and the water cooled chill. The cooling rate () and solidification rate (R)
were evaluated by the temperature datas from thermo couples. The horizontal
directionally solidification furnace was placed in the chamber filled with high
purity argon. Segregation index (R1.1) 6) was controlled between 7 and 2([K/min]
[mm/min] 1.1). Macro segregation was examined by using the horizontal slice of
the ingot.
For the forging tests, the ingot was sliced into 4 parts which has different and
R respectively and 4 round bars with 15mm were made by high temperature
forging followed by swaging. Temperatures during these processes were kept in
the range from 1000C to 1150C. Each round bar was heat treated at 1160C/4h,
204
50
120
70
50
25
50
200
50
50
25
25
25
50
205
Bal
4.05
23.20
17.00
5.95
<0.01
2.03
0.0027
0.012
0.041
Thermo Couples
Chill
Diffusion Pump
Rotary Pump
Carbon Heater
Ingot
Fig.3 Appearance of Furnace Chamber and schematic of the furnace
optical micrographs of the round bars after hot forging and heat treatment.
Microstructure of the bar from the part D is coarser than that of the bar from the
part A. There are precipitation rich areas (dark contrast) in all the specimens. Fig.
7 shows the SEM micrographs of the bar from the part C. There were lots of
carbides in the precipitation rich areas. Most of the precipitates on grain
boundaries were Cr rich carbides. The precipitates in the grain were Cr rich
carbides and Mo rich carbides. No other phases were found in the precipitation
rich areas of the all bars.
Fig. 8 through 11 show the tensile properties at both room temperature and
800C as a function of the segregation index. These results indicated that the
effect of solidification condition on tensile properties was negligible. And the
ductility is favorable level at both room temperature and 800C. It is concluded
that mass effect due to the difference of solidification condition is negligible.
1.1
SI
(/min)(mm/min)1.1
SI(K/min)(mm/min)
7.0
6.0
5.0
4.0
3.0
Segregation index
SI=R1.1
:Cooling Rate
R:Solidification Rate
2.0
1.0
0.0
0
50
100
150
(mm)
Fig.4 Variation of segregation index in the ingot
207
200
Chill Side
Cr
Mo
Cr
209
1400
1200
Stress(MPa)
1000
800
600
0.2% Yield Stress
0.2%
400
Tensile Strength)
(
200
Room Temperature
0
0
4
6
8
SI (K/min)(mm/min)1.1
Fig.8 Effect of Solidification Condition on Tensile Properties(1)
45.0
40.0
Ductility (%)
35.0
30.0
25.0
20.0
15.0
Elongation
10.0
Reduction of area
5.0
Room Temperature
0.0
0
4
6
8
SI (K/min)(mm/min)1.1
Fig.9 Effect of Solidification Condition on Tensile Properties(2)
210
800
700
500
400
300
200
(800
Tensile Strength )
100
800
0
0
4
6
8
1.1
SI (K/min)(mm/min)
Fig.10 Effect of Solidification Condition on Tensile Properties(3)
60.0
50.0
Ductility (%)
Stress(MPa)
600
40.0
30.0
20.0
800
Elongation
800
Reduction of area
10.0
800
0.0
0
4
6
8
SI (K/min)(mm/min)1.1
Fig.11 Effect of Solidification Condition on Tensile Properties(4)
211
Forging
forging
t = 8mm(38mm)
450mm
Machining
Welding
Fig.12 Appearance of VAR ingot, 3 ton forging and welding test specimen
212
4. Summary
1. Segregation property of USC800 is as good as or much better than that of
Alloy706.
2. It is possible to manufacture 800mm-dia VAR ingot without segregation
defects by using USC800.
3. It is possible to manufacture 3ton forging from 6ton ingot of USC800 by
4,000 ton class open die forging press.
4. Creep rupture strength of the specimens from 3ton forging and tubes is as
high as that of the specimens from 20kg ingot.
Acknowledgments
A part of this work was supported by the New Energy and Industrial
Technology Development Organization (NEDO) under the Ministry of Economy
Trade and Industry of Japan. The authors are grateful to Dr. Katsunari Oikawa
from Tohoku University for the designing the directionally solidification furnace
in this report.
References
1. F. Schubert, H. J. Penkalla, and J. Rosler: Wrought Ni-Base Alloys For Rotor
Shafts in Advanced USC Power Plants. Proceedings from the Fourth
International Conference Advances in Materials Technology for Fossil
Power Plants, (2004), 587.
2. S. Imano, H. Doi, T. Takahashi, and K. Kajikawa, Proc. Conf. Superalloys
213
3.
4.
5.
6.
7.
214
combustion, could extend into the 700C-750C range, with similarly high operating pressures
(25-35 MPa), necessitating the utilization of nickel-base alloys to sustain such operating
conditions. Such systems could be utilized for thermal transfer in generation IV nuclear systems
as well.7
Currently, the most efficient commercial ultra supercritical designs operate only up to 605C with
steam pressures in the 25-30 MPa range, not requiring the utilization of nickel-base alloys.
However, the creep strength enhanced ferritic grades (Gr. 91/92) in use are satisfactory only up to
about 620C. Advanced austenitic stainless steel grades can be used up to about 680C.
However, their high coefficient of thermal expansion, low thermal conductivity and strength
capability limit impose limitations upon their utility. To cope with the conditions described for
A-USC plants, nickel-base alloys must be considered.
Alloy 740H has been developed to meet the myriad demands of high temperature/high pressure
service with imposed corrosion requirements, in the required section thicknesses and forms.
Figure 1. Effect of efficiency upon CO2 emission for steam-generating pulverized coal.5
Figure 2 illustrates the rupture strength capability of the various classes of materials that are being
considered for A-USC conditions.1 Alloys 740H and 617 are primary candidates in most current
A-USC designs.
Figure 2. Stress to produce 100,000 hour rupture life for 9-12 Cr ferritic steels, austentic steels,
and selected nickel-base alloy1.
216
Work by the U.S. A-USC consortium has culminated in issuance of code case 2702 for UNS
N07740 in September of 2011. This action represents significant progress in the A-USC
community as this is a first instance of use of an age-hardenable nickel-base alloy being
approved by a very conservative code body. The code case provides rules for the utilization of
wrought sheet, plate, rod, seamless pipe and tube, fittings and forgings under the auspices of
section I of the ASME code. The code case stipulates allowed ranges for annealing and aging of
supplied material. In addition, welding qualification guidelines, and post-weld heat treatment
requirements are provided. Allowable stresses are specified; see Figure 3 for a comparison with
allowable stresses for alloy 617. Alloy 740/740H possesses an 80% advantage over 617 at
1300F (704C), 74% advantage at 1350F (732C) and 62% advantage at 1400F (760C).
PRODUCTION OF COMMERCIAL-SCALE INCONEL ALLOY 740H PRODUCTS
Steam Header Piping Fabrication, Properties and Weldability
Three full-scale commercial heats of the INCONEL alloy 740H composition have been produced
by PCC Energy. Given that at least one ingot from each of these melting campaigns has been at
30 inches (760mm) in diameter or greater, the melting sequence of following vacuum induction
melting (VIM) with vacuum arc re-melting (VAR) was implemented, in the interest of ensuring
optimal ingot macro/microstructure. Table 1 shows individual electrode and ingot sizes and
weights for the three melts of INCONEL alloy 740H completed to date. Ingot enumeration will
consist of 1-A, 1-B, etc.
Figure 3. ASME maximum allowable stress comparison between alloy 617 (UNS N06617) and
alloy 740/740H (UNS N07740). The advantage of alloy 740/740H is 80% at 1300F (704C),
74% at 1350F (732C), and 62% at 1400F (760C).
217
Table 1. Electrode and Ingot Sizes and Weights for Three Melts of INCONEL alloy 740H
Melt
1
1
2
2
3
3
Ingot
A
B
A
B
A
B
VIM Electrode Diameter, In. (mm) VAR Ingot Diameter, In. (mm) Ingot Weight, lb (kg)
27 (690)
30 (760)
21000 (9520)
18 (460)
20 (508)
10000 (4540)
30 (760)
33 (840)
27000 (12240)
18 (460)
20 (508)
10000 (4540)
27 (690)
30 (760)
19500 (8840)
27 (690)
30 (760)
19500 (8840)
Figure 4 shows a photograph of ingot 1-A after VAR. Table 2 shows the chemical analyses
obtained for the ingots. Values shown are the average of head and toe analyses obtained from
drillings at head and toe of the VAR re-melted ingot.
Figure 5 shows chemical analysis results for a top, or head, end ingot slice acquired after
homogenization and controlled cooling, as a function of location for ingot 1-A. Consistency of
composition across the diameter was excellent. No evidence of intermittent solidification or
macro-segregation was detected. The ingot microstructure was also evaluated, after
homogenization and controlled cooling, with results displayed in Figure 6. A coarse, equiaxed
grain structure was observed. Carbides were observed on the grain boundaries, and a dispersion
of coarse gamma prime was observed.
Figure 7 shows chemical analysis results for a head end ingot slice acquired after homogenization
for ingot 2-A. As with slices evaluated for other ingots, no evidence of intermittent solidification
or macro-segregation was detected.
The homogenized. cropped and conditioned ingot 1-A was transferred to Wyman Gordons
Houston facility for extrusion. The 16660 pound (7570 kg) ingot was pierced and blocked using
a 14 kT press, followed by light machining of OD and ID. Final pipe extrusion was performed at
2175F (1190C) using Wyman Gordon Houstons 35 kT vertical press. The as-extruded pipe
size was 14.9 inches (378mm) x 3.47 inches (88mm) x 34.5 feet (10.5m). Figure 8 shows a
photograph of the as-extruded pipe. The pipe was solution annealed at 2050F (1120C) and
water quenched, and then aged at 1472F (800C) for 5 hours and air cooled. Table 3 shows
room-temperature tensile data for solution annealed and aged pipe. Elevated-temperature tensile
data from the front end at mid-wall are shown in Table 4.
Samples from the solution annealed and aged pipe were subjected to long-term exposures at 700,
750 and 800C. Results are shown in Figure 9. Figure 10 shows SEM photomicrographs of
samples exposed for 10000 hours at each temperature, revealing intra-granular gamma prime
phase and globular grain boundary carbides.
218
Figure 4. INCONEL alloy 740H ingot 1-A, having diameter of 30 inches (760mm) and weighing
21000 pounds (9500 kg), and melted via VIM+VAR.
Table 2: Chemical Analysis Results for INCONEL alloy 740H Ingots
Ingot
1-A
1-B
2-A
2-B
3-A
3-B
C
0.045
0.046
0.024
0.023
0.043
0.043
Cr
24.6
24.7
24.6
24.6
24.6
24.6
Mo
0.01
0.01
0.35
0.32
0.35
0.35
Co
20.2
20.2
20.1
20.1
20.1
20.1
Al
1.34
1.33
1.34
1.34
1.33
1.34
Ti
1.36
1.37
1.35
1.34
1.32
1.33
Nb
1.51
1.52
1.47
1.50
1.46
1.46
Figure 5. chemical analysis results for a top end (head end) 30 inch (760mm) diameter ingot
slice from ingot 1-A acquired after homogenization, as a function of location.
219
Figure 7. Chemical analysis results for a top end 33 inch (840mm) diameter ingot slice from
ingot 2-A acquired after homogenization, as a function of location.
Table 3: Room-Temperature Tensile Data for 14.9 Inch (378mm) OD x 3.47 Inch (88mm) Wall
Pipe Extruded at 2175F (1190C), Solution Annealed at 2050F (1120C) and Aged at 1472F
(800C) for 5 Hours.
Location
in Pipe
Front, Mid-Wall
Front, Mid-Wall
Back, Mid-Wall
Back, Mid-Wall
ksi
105.2
102.3
106.9
108.3
0.2% YS
MPa
725.0
705.0
737.0
747.0
220
ksi
157.3
155.9
160.9
160.6
UTS
MPa
1080
1075
1109
1107
Elong., % R of A, %
31.9
33.4
31.4
29.9
31.5
31.9
32.4
34.3
Table 4: Elevated Temperature Tensile Data for 14.9 Inch (378mm) OD x 3.47 Inch (88mm) Wall
Pipe Extruded at 2175F (1190C), Solution Annealed at 2050F (1120C) and Aged at 1472F
(800C) for 5 Hours.
Test Temperature
F
1112
1202
1292
1382
1472
C
600
650
700
750
800
0.2% YS
ksi
81.3
87.0
83.0
83.1
74.0
UTS
MPa
560
600
572
573
510
ksi
128.3
133.5
129.1
115.9
97.1
MPa
885
920
890
799
670
Elong., % R of A, %
36.1
46.3
29.8
36.0
25.9
21.8
22.5
25.3
22.2
20.4
Figure 8. As-extruded 740H steam header pipe measuring 14.9 inches (378mm) x 3.47 inches
(88mm) x 34.5 feet (10.5m).
Figure 9. Charpy impact results (10mm x 10mm samples) for solution annealed and aged pipe
produced from ingot 1-A, after exposure at the indicated temperatures and times.
221
Figure 10. SEM photomicrographs showing microstructure of pipe samples exposed for 10000
hours (see Figure 9).
Table 5: Chemical Composition of INCONEL alloy 740H Filler Metal
Material
Ni
Cr
Mo
Co
Al
Ti
Nb
Mn
Fe
Si
FM1
0.031
50.81
24.13
0.580
19.76
1.26
1.31
0.93
0.37
0.55
0.19
0.001
Two 24 (610mm) long sections of the steam header pipe produced from ingot 1-A, with final
dimensions consisting of 8.071 (205mm) ID with wall nominally at 3 (76.2mm), were prepared
for a full section welded joint. A full-section girth weld was completed using hot-wire GTAW
using matching filler metal heat FM1 (composition shown in Table 5). The sample was postweld heat treated using ceramic pads with ramping and cooling rates intended to simulate field
heat treatment. A previous publication describes the welding process and heat treatment in
greater detail.8
The macro-etched full cross section can be viewed in Figure 11 as well as the etched
microstructure of a mounted and polished cross section. No micro-fissuring was observed in the
heat-affected-zone (HAZ) or in the weld metal. Side bend testing (4T, Figure 12) and transverse
tensile testing (Table 6) were successfully performed as per ASME section IX.
222
Figure 11. Photograph Showing Hot Wire GTAW Bead Sequence in the 3 (76.2mm) Thick
Steam Header Pipe (left) and microstructure at the fusion line (right).
Samples from the discussed pipe weld have been stress rupture tested, in the post-weld heat
treated condition. Results are shown in Figure 13. So far, to rupture times approaching 10000
hours, a weld strength reduction factor (WSF) of 0.78 has been maintained. ASME code case
2702 calls for a WSF of 0.70 for longitudinal seam welds.
Figure 12. Photograph Illustrating Acceptable Full Section Direct Aged 4T Side bends Sectioned
from the HWGTAW Steam Header Pipe Weldment and a Fractured (outside the weld) Room
Temperature Tensile Specimen
223
Table 6. Room Temperature Tensile Properties for ASME Section IX Qualifications from the Full
Section HWGTAW Steam Header Pipe Weldment
0.2% YS
UTS
Sample
Location
ksi
OD
118.2
815
164.6
1134.9
21.3
22.8
Weld
OD
116.4
802.6
162.8
1122.5
21.2
24.9
Weld
Mid-Wall
110.6
762.6
159.3
1098.4
24.6
22.3
Base
Mid-Wall
109.9
757.8
158
1089.4
20.6
21
Base
ID
108.8
750.2
156.8
1081.1
21.4
22.9
Base
ID
109.7
756.4
157.7
1087.3
24.4
24.5
Base
MPa
ksi
MPa
Elong. %
R of A %
Failure
Location
Samples from the fabricated pipe weld were also exposed at 700, 750 and 800C for up to
10000 samples followed by impact testing and evaluation of microstructure. Impact test results
are shown in Figure 14 and are observed to exceed the values displayed by the base material.
Figure 15 shows weld microstructures after aging for 10000 hours.
Figure 13. Stress rupture data for transverse INCONEL alloy 740H pipe weld samples
compared with data for transverse INCONEL alloy 740 tube weld samples. All samples were
tested after post-weld aging.
Figure 14. Results from impact testing transverse impacts at weld center from alloy 740H header
pipe joined using hot-wire GTAW.
224
Superheater Tubing
Superheater tubing production began with casting a VIM electrode, weighing 10,900 lb (4955 kg)
and measuring 18 inches (457mm) in diameter. This electrode was re-melted via VAR to a
diameter of 20 inches (508mm) ingot 1-B. The resulting ingot was homogenized and open-die
forged at 2175F (1190C) to an 11.375 inch diameter bar. After peeling, billets were cut and
prepared for extrusion by center boring and applying a radius to the front end. Billets were
extruded at 2175F (1190C) to tube shells. Figure 8 shows a shell after extrusion. de-glass,
pickled and solution annealed with water quenching, followed by cold-pilgering. The cycle of
annealing, pickling and pickling was then repeated until the final size of 2 inch (50.8mm) OD x
0.315 inch (8mm) wall. The final annealing temperature was 2125F with water quenching.
Table 7 shows room-temperature tensile properties for three lots of superheater tubing, before and
after aging at 1472F (800C)/4h/air cool; elevated-temperature tensile data for lot 1 is shown in
Table 8.
Samples from lot number 2 (see table 4) were exposed for up to 10000 hours at 700, 750C and
800C and impact tested (samples were exposed in the solution annealed and aged condition).
Figure 16 shows the resulting impact test results (5mm x 10mm sample section). Sample
microstructures are shown in Figure 17.
Figure 15. Alloy 740H header pipe weld microstructure after exposure for 10000 hours at the
indicated temperature.
225
Table 7: Room-Temperature Tensile Data for 2 Inch (50.8mm) Diameter x 0.315 Inch (8mm)
Wall Cold-Pilgered Tubing Solution Annealed at 2125F (1163C) and Aged at 1472F (800C)
for 4 Hours.
Lot #
1
1
2
2
3
3
1
1
2
2
3
3
Condition
SA
SA
SA
SA
SA
SA
SA + Age
SA + Age
SA + Age
SA + Age
SA + Age
SA + Age
0.2% YS
ksi MPa
52 358.5
51.2 353.0
51.2 353.0
51.6 355.8
76.8 529.5
69.9 482.0
105.6 728.1
105.6 728.1
103.9 716.4
106.7 735.7
121.3 836.4
124.0 855.0
UTS
ksi
MPa Elong., % R of A, %
114.3 788.1
57.5
68.0
113.9 785.3
58.5
71.5
113.9 785.3
59.5
66.0
113.9 785.3
54.0
67.0
136.0 937.7
56.0
61.0
125.2 863.3
51.7
65.4
168.7 1163.2
36.0
41.0
168.2 1159.7
36.5
37.5
166.1 1145.3
35.0
31.5
166.3 1146.6
37.0
38.0
175.0 1206.6
34.1
41.1
177.3 1222.5
36.5
40.5
Table 8: Elevated Temperature Tensile Data for 2 Inch (50.8mm) Diameter x 0.315 Inch (8mm)
Wall Cold-Pilgered Tubing Solution Annealed at 2125F (1163C) and Aged at 1472F (800C)
for 4 Hours (Lot 1).
Test Temperature
F
C
1202
650
1202
650
1292
700
1292
700
1382
750
1382
750
1472
800
1472
800
0.2% YS
ksi
MPa
87.6
604.0
89.2
615.0
94
648.1
90.8
626.1
88.5
610.2
88.5
610.2
78.2
539.2
78.2
539.2
UTS
ksi
MPa Elong., % R of A, %
139.8 963.9
28.5
34.5
135.7 935.7
25.5
29.0
131.7 908.1
15.5
19.0
130.9 902.6
17.0
20.5
116.3 801.9
13.0
25.0
113.9 785.3
12.0
19.0
97.2
670.2
10.5
14.5
99.2
684.0
10.5
16.5
Figure 16. Impact strength of solution annealed and aged 2 (50.8mm) OD x 0.315 (8mm) wall
superheater tubing samples (produced from ingot 1-B) exposed for 10000 hours at the indicated
temperature.
226
Ash components were pulverized thoroughly with a mortar and pestle and applied to sample
surfaces as a slurry with acetone. Average mass gain via application of the slurry was 73
mg/cm2. Sample dimesions were approximately 0.75 (19mm) x 0.5 (12.7mm) x 0.25 (6.4mm)
A simulated flue gas comprised of N 15% CO 3.5% O 5% H O 0.1% SO
2
was flowed over the samples at 500 sccm (with platinum catalyst preceding the samples.
Samples of both base metal and weld metal were tested (from GTAW welds made in matching
base plates; alloy 740H samples were fabricated using welding wire made from ingot 1-A).
Cross sections of tested samples were made and evaluated, yielding corrosion depth results
shown in Figure 18 for alloys 740H, 263 and 617. For alloys 740H and 263, both base metal and
weld samples were tested after post-weld aging at 800C (1472F); the alloy 617 samples were
tested in the solution annealed condition (2150F/1177C). Samples were exposed for 1000
hours, with the ash coating re-applied at weekly intervals. Figure 19 shows light
photomicrographs for base metal and weld samples, and SEM photomicrographs for the base
metal samples. Corrosion depths and corrosion product morphologies were similar between base
metal and weld metal samples. External oxide scales were chromium-rich with low levels of
titanium present in all cases. The external oxide scale was thicker in the case of alloys 263 and
617; the alloy 740H samples possessed a thinner, more compact chromia scale. All alloys
developed internal oxides along grain boundaries rich in Al/Ti. Chromium sulfides (verified with
SEM-EDS and backscatter visualization), evident in the micrographs as medium-gray globular
internal precipitates tending to reside on grain boundaries, were much more pronounced in the
227
alloy 617 and 263 samples than in the alloy 740H samples. While the alloy 617 sample exhibited
very significant pitting, the alloy 263 samples exhibited incipient shallow pit development.
Figure 18. Depth of corrosion attack after exposure under simulated coal ash corrosion
conditions at 750C for 1000 hours.
Figure 19. Photomicrographs acquired after exposure under simulated coal ash corrosion
conditions at 750C for 1000 hours; light micrographs of base metal samples are at the top, light
photomicrographs of weld metal samples are at the center, and SEM photomicrographs of base
metal samples are shown at the bottom.
228
CONTINUING CHALLENGES
Significant challenges remain for the commercialization of age-hardenable nickel-base alloys for
applications such as A-USC. Feasibility of fabrication of numerous components must be
demonstrated; wyes, flanges and fittings, and pipe bends, for example. The need for larger forged
components will continue to push the capabilities of nickel-base manufacturers.
The question of relaxation cracking remains a ponderous and pertinent issue, although activity is
beginning to explore this phenomenon for materials of interest. Devising a testing protocol
which is relevant to actual service is still a significant obstacle.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge Ian Dempster and Tom Armstrong of Wyman Gordon who
have contributed greatly to the success of the alloy 740H pipe extrusion. Also, the authors would
like to thank Jim Tanzosh, Joe Dierkscheide and Doug Ziegler of Babcock and Wilcox for their
significant contribution in the completion of circumferential pipe welds and tube-to-pipe welds.
REFERENCES
1. R. Viswanathan, J. P. Shingledecker, J. Hawk and M. Santella, Proceedings of the 34th
International Technical Conference on Clean Coal and Fuel Systems, Coal Technology
Association, Clearwater, FL, May 31 to June 4 (2009).
2. R. Blum and R. W. Vanstone, Materials Development for Boilers and Steam Turbines
Operating at 700C, Proceedings of the Sixth International Charles Parson
Turbine Conference, Institute of Materials, Minerals and Mining, London, pp 489-510
(2003).
3. M. Fukuda, et al., Advanced USC Technology Development in Japan, Proceedings of the
Sixth International Conference in Advances in Materials Technology for Fossil Power
Plants, Santa Fe, NM, USA, August 31-September 3, 2010, EPRI Report Number 1022300
(2010).
4. R. Blum, S. Kjaer, and J. Bugge.Development of a PF Fired High Efficiency Power Plant
(AD700). Proceedings of the Riso International Energy Conference Energy Solutions for
Sustainable Develoment, Denmark, 2007 Riso-R-1608, EN (2007).
5. R. Viswanathan, A. F. Armor, and G. Booras, Power, April 2004, pp 42-49.
6. Concentrating Solar Power Program Review 2013, National Renewable Energy
Laboratory, Phoenix, Arizona, April 23-25, 2013.
7. V. Dostall, M. J. Driscoll, and P. Hejzlar, A Supercritical Carbon Dioxide Cycle for Next
Generation Nuclear Reactors, Report # MIT-ANP-MR-100, Thesis for Doctor of Science in
Nuclear Engineering at MIT, March 10, 2004.
8. Baker, B. A., Gollihue, R. D., deBarbadillo, J. J., Welding and Repair Technology for Power
Plants, Tenth International EPRI Conference, EPRI, Marco Island, FL, June 26-29 (2012).
229
ABSTRACT
Inconel alloy 740/740H (ASME Code Case 2702) is an age-hardenable nickel-based alloy
designed for advanced ultrasupercritical (A-USC) steam boiler components (superheaters,
reheaters, piping, etc.). In this work, creep testing, beyond 40,000 hours was conducted a series
of alloy 740 heats of varying product form, chemistry, and grain size. Long-term creep-rupture
strength was found to be weakly dependent on grain size. Analysis of the time-to-rupture data
was conducted to ensure long-term strength projections and development of ASME stressallowables. Testing was also conducted on welded joints in alloy 740 with different filler metal
and heat-treatment combinations. This analysis shows the current weld strength reduction factor
of 30% (Weld Strength Factor of 0.70) mandated by ASME Code Case 2702 is appropriate for
740 filler metal but other options exist to improve strength. Based on these results, it was found
that alloy 740 has the highest strength and temperature capability of all the potential A-USC
alloys available today.
INTRODUCTION & BACKGROUND
INCONEL alloy 740/740H (ASME Boiler & Pressure Vessel Code Section I Code Case 2702
[1]), hereafter referred to as alloy 740, is an age-hardenable nickel-based superalloy which is
purposely designed for advanced ultrasupercritical (A-USC) steam boiler applications at highstress and temperatures where creep will be the dominate deformation mode [2]. Figure 1 shows
that alloy 740 has the highest allowable stress (highest strength) of any section I alloy at 700 to
800C. Code Case 2702 limits alloy 740 to a maximum use temperature of 800C, but additional
testing is underway to extend this limit to 850C.
A-USC steam boilers with operating temperatures up to 760C will help to increase efficiency and
decrease emissions of all effluents, including CO2, in coal-fired power plants by up to 25% in
comparison to current technology [3,4]. The typical microstructure of alloy 740 is a gamma
matrix containing gamma prime precipitates and very little precipitation at the grain boundaries.
After high-temperature aging, the gamma prime coarsens, and grain boundary M23C6 carbides, Gphase (a complex silicide), and the plate-like eta phase forms [5,6]. Studies on alloy 740 have
shown that this microstructure, and in particular the formation of eta phase, is sensitive to alloy
chemistry [7].
Early research on alloy 740 showed that the formation of a small amount of eta phase, which
grows by consuming gamma prime precipitates, is not detrimental to the creep strength or
ductility at 750C [8].Later work suggested the alloys creep strength and ductility over a larger
range of temperatures was relatively insensitive to chemical compositional differences, but grain
size did have some notable effect on creep-rupture strength [9]. Successful welding of the alloy in
thin and thick sections has been accomplished [10, 11], but the current code case applies a weld
230
strength reduction factor (WSRF) or weld strength factor (WSF) of 0.70 [1] for seam-welded
components. A reduction in creep strength of nickel-based alloys has been observed for other AUSC nickel-based alloys including Haynes 230 [12] and alloy 617 [13], but a thorough analysis of
the available cross-weld creep-rupture data on alloy 740 is required. This paper provides an upto-date analysis of some of the research first reported in [9] with additional analysis of cross-weld
creep-rupture data for multiple filler metals and welding processes.
Figure 1. ASME Section I Allowable Stress Values for Code Case 2702 (Inconel 740/740H)
Compared to Other Nickel-based Alloys (617 and 230), 347H stainless steel, and grade 91
EXPERIMENTAL PROCEDURE
Various heats of alloy 740 were evaluated representing a range of chemistries and product forms
as shown in Table 1. In some cases, the solution annealing (SA) heat-treatment temperature was
varied to modify the grain size of the alloy. All base materials were given the standard aging
heat-treatment of 760 to 800C for 4 to 16 hours per code case 2702. Welds were made and
supplied by Babcock & Wilcox, Barberton, OH USA, using gas tungsten arc welding (GTAW),
gas metal arc welding (GMAW), and hot-wire narrow groove GTAW (hot-wire TIG). Table 2
provides the relevant welding details and post-weld heat-treatments given to the weldments.
Smooth bar creep rupture specimens with a 6.35mm diameter and a 31.75mm gauge length were
utilized for the non-welded base material tests, and specimens with a 6.35mm diameter and a
57.15mm gauge length with the weld centered in the specimen gauge length were utilized for
cross-weld creep rupture testing. Testing was performed at temperatures from 600 to 875C in
accordance with ASTM E139 in lever-arm type creep machines with most test run until failure.
At the time of writing this paper, the longest failure durations exceeded 20,000 hours for base
metal and 15,000 hours for cross-weldments with base metal specimens still running beyond
45,000 hours.
Microstructural analysis was conducted using light optical microscopy (OM) on etched samples
using a solution of 40 ml H20, 40 ml HN03, and 20 ml HF. Grain size was determined by the
manual mean lineal intercept method in ASTM E112. Failure location was evaluated by
specimen observation and in some cases through OM of polished metallurgical mounts of
specimens after testing.
231
82.4
A (1190)
Fe
Si
Cr
Al
Ti
Co
Mo
Nb
0.03 0.28 0.42 0.0010 0.54 24.43 0.94 1.81 20.00 0.55 1.98 0.005 0.0030
165
B (1120)
0.03 0.26 0.46 0.0010 0.53 24.38 0.98 1.77 19.90 0.50 1.97 0.005 0.0043
188
C (1120)
0.03 0.26 0.46 0.0010 0.54 24.34 0.97 1.78 19.80 0.50 1.99 0.005 0.0037
127
D (1200)
0.03 0.27 1.02 0.0002 0.45 24.31 0.75 1.58 19.63 0.52 1.83 0.003 0.0006
169
E* (1190)
E (1120)
Mn
(m)
89.6
0.06 0.30 0.69 0.0060 0.48 24.86 1.20 1.41 19.90 0.53 2.05 0.004 0.0010
**113
F (1121)
0.04 0.31 1.05 0.0100 0.30 24.28 1.30 1.50 19.88 0.53 1.57 0.002 0.0007
-
0.30 1.07
ID
740GMAW
Base
Metal
B
263GMAW
740GTAW
740GTAWSA
282GTAW
A
(1120)
G
232
RESULTS
Base metal rupture data and analysis
To evaluate the large range of times and temperatures, and to provide an estimate of long-term
rupture life, the base metal creep-rupture data were analyzed using the Larson Miller Parameter
(LMP). To find a best fit to the data, a regression to minimize the error in time to rupture (tr) was
performed using the following:
equation 1
Stress (MPa)
where C is the LMP constant, Ax are the regression coefficients, is stress (MPa), and T is
temperature in K. Figure 1 is a Larson-Miller (LMP) plot for all the base metal creep-rupture data
including ongoing tests (open symbols) using the best fit LMP constant of 19.392. Table 3
provides the regression coefficients. Inspection of the figure shows the data are tightly grouped
and fall within a +/- 20% scatterband on stress. The only exceptions are two data points which
are short-term tests at 875C. To analyze the goodness of the fit and its ability to accurately
predict long-term behavior, the rupture data are plotted as actual versus predicted life (equation 1)
in Figure 2. The figure shows excellent agreement and all the data fall within a factor of +/-2 on
life. Inspection of the ongoing test data (open symbols) show the prediction of long-term
performance is very good with all tests exceeding 30,000 hours meeting or exceeding predicted
life. A fit to the rupture data gives a slope of 0.93 which is close to unity (perfect fit) but is
slightly conservative for long-term strength predictions. Based on these results, the equation was
found to be accurate in the assessment of long-term material performance. Earlier research [8,9]
found that alloy 740 was insensitive to microstructural variation due to chemistry, but some effect
of grain size was noted. Figure 3 segments the heats of tested material by grain size. The figure
clearly confirms the trend that the lower scatterband of creep strength is occupied by heats with
finer grain size while slightly coarser grain sizes results in average or above average life with
long-term tests exceeding the average prediction.
A (1120)
A (1190)
B (1120)
C (1120)
D (1200)
E (HR1190)
E (1120)
F (1121)
Average
- 20%
100
LMP C=19.392
1000000
A (1120)
A (1190)
B (1120)
C (1120)
D (1200)
E (HR1190)
E (1120)
F (1121)
100000
10000
1000
Slope = 0.93
100
+/- factor of 2
10
10
100
1000
10000
100000
1000000
Figure 3. Predicted (equation 1) versus actual rupture life for alloy 740. Note, the predicted life
is based off an earlier assessment of the data. All non-ruptured specimens (open symbols) are
within a +/-2 scatterband on expected life with most ongoing tests (including those over 30,000
hours) exceeding predicted life.
1000000
100000
10000
1000
Slope = 0.93
100
+/- factor of 2
10
10
100
1000
10000
100000
1000000
234
Stress (MPa)
All the cross-weld time to rupture results for the welds in Table 2 are plotted against the average
alloy 740 base metal (BM) behavior in Figure 4. All but one data point (black square at LMP =
~23,500) for a variety of weld filler metals and heat-treatment conditions fall between the average
expected behavior and -30% on stress. A 30% reduction in stress is equivalent to a WSF of 0.70.
740GMAW
263GMAW
740GTAW
740GTAW-SA
282GTAW
740BM Ave.
-30%
100
LMP C=19.392
1.0
740GMAW
263GMAW
740GTAW
740GTAW-SA
282GTAW
0.9
0.8
0.7
0.6
0.5
10
100
1000
10000
100000
Figure 6. Inconel 740 measured cross-weld Weld Strength Factors (WSF) as a function of test
time using average Inconel 740 base metal
235
To examine the behavior of the 740 filler metal welds in more detail, the data are plotted in Figure
6 along with information on the failure location. The weld given the solution annealing heattreatment failed in the base metal outside the weld. Because these solution-anneal weldments
were made in heat A with the finer grain size, a WSF of ~0.90 is equivalent to base material heats
in the lower scatterband of the data. In contrast, the GMAW and GTAW welds all failed in the
weld metal with the exception of one test which had a reported heat affected zone (HAZ) failure.
This location was reported based on visual observation and detailed OM was not complete at the
time of writing this paper. Based on these findings, the 740GMAW and GTAW data (note these
data were aged following welding) were combined and analyzed in same manner as the base metal
to determine optimized LMP fits. Table 3 provides the results of this analysis for all the data and
with the HAZ data removed because a different failure mechanism or failure due to a welding
defect may be influencing results. Tables 5 and 6 compare the predicted stress to produce a
rupture in the base metal and a 740 weld metal for various times up to 100,000 hours based on the
LMP constants in Table 3. The optimized fits of the data show, in some cases, a slightly more
pessimistic value for the WSFs compared to the average data in Table 4 since the LMP constants
and equations vary between the base metal and the weldments data. However, the values do not
show any consistent trend with temperature or test time. The values of the WSF calculated from
optimized fits and reported in Table 6 are 0.70+/-0.3 which suggests the value of 0.70 is
appropriate.
Table 4. Average of measured WSFs (Figure 5) for Inconel 740/740H
ID
WSF
740GMAW
0.71
263GMAW
0.82
740GTAW
0.74
740GTAW0.88
SA
282GTAW
0.85
740GMAW
Stress (MPa)
740GTAW
740GTAW-SA
740BM Ave.
-30%
100
HAZ Reported
Failure
Solid symbol = weld metal failure
Open symbol = base metal failure
LMP C=19.392
Figure 7. Inconel 740 Cross-Weld Rupture Results for 740 Filler Metals and Failure Locations
236
Table 5. Comparisons between average Inconel 740 data and an optimized fit to a combined
dataset of cross-weld data on 740GMAW and 740GTAW (aged condition, all failure modes)
Time to
Rupture
Temp.
(C)
700
750
800
Weldment
211.6
132.1
82.3
30,000hours (MPa)
WSF
0.69
0.67
0.72
BM
260.5
160.3
84.8
Weldment
171.8
105
66.3
BM
214.1
123.7
84.8
Weldment
134.4
82.4
-
WSF
0.63
0.67
-
Table 6. Comparisons between average Inconel 740 data and an optimized fit to a combined
dataset on 740GMAW and 740GTAW weldments (aged condition, only weld metal failures)
Time to
Rupture
Temp.
(C)
700
750
800
Weldment
215.5
136.1
83.2
30,000hours (MPa)
WSF
0.70
0.69
0.73
BM
260.5
160.3
84.8
Weldment
177.1
108.5
65.5
BM
214.1
123.7
84.8
Weldment
141.1
84.3
WSF
0.66
0.68
b.
c.
Figure 8. OM of failure (a, b) and fusion line (c) in 740GTAW after1668.9hours at 750C
237
To examine failure modes in more detail, OM was conducted on cross-sections of failed samples.
Figure 7 provides an overview of the typical failure mode observed in the 740 weld metal tests
where creep failure occurred in the weld metal (a) with no evidence of distress in the HAZ (c).
Higher magnification images suggest the interdendritic regions (final region to solidify) had a
large population of creep cavities and microcracks (b). This is consistent with more detailed
ongoing research which shows cavitation initiates in the interdendritic regions having large areas
denuded in gamma prime [14] which is similar to reported initiation sites in base metal [9].
Solution annealing after welding restored base metal strength and moved the failure location from
the weld metal to the base metal. Figure 8 shows the change in microstructure in the GTAW
weldments after creep testing. In this case, it appears the large dendritic weld microstructure was
completely recrystallized resulting in a wrought weld structure after solution annealing. This
suggests very high residual stresses in this tube to tube butt weld. Creep damage was not
observed in the recrystallized weld metal which exhibited a coarser grain size than the base metal.
This is again consistent with the base metal analysis which showed larger grains are beneficial for
creep strength. This data also suggests that the welding processes utilized did not have significant
defects and that they were controlled to minimize loss of specific strengthening elements. If weld
quality were poor, strength restoration via solution annealing would not be possible.
238
Figure 10. Cross-sectional micrographs for failure in 740 welded with 263 after 250.2hrs at
750C. Cavitation is observed in a refined region of the weld metal near the fusion zone.
DISCUSSION
Analysis of the current base metal testing shows an optimized Larson Miller Parameter analysis
can be used to accurately represent the data and to make extrapolations for longer life. Long-term
ongoing tests, beyond 40,000 hours, suggest the equation provided in this paper will be slightly
conservative for such purposes. At 750C, the analysis shows the 100,000 hour rupture life on
alloy 740 is greater than 120MPa which is in excess of the generally accepted criteria of 100MPa100,000 hour rupture life needed for power steam boiler components [2]. At 700C, the value is
greater than 210MPa which confirms the stress allowable values (Figure 1). In the interest of AUSC powerplant construction, alloy 740 has the highest strength of any ASME-approved alloy for
this application.
Cross-weld creep-rupture testing shows that 740 weldments generally have inferior creep strength
to the base metal. For 740 matching filler metals given a standard aging heat-treatment after
welding, a WSF of 0.7 was found, through multiple analysis methods, to be an accurate measure
of long-term creep performance. No clear trend with test time or temperature was observed
suggesting a single factor can be applied in the creep regime. Microscopy shows the interdendritic
regions are prone to creep cavitation and microcracking and at failure no creep damage was
observed in heat affected zone (HAZ) or base metal. More detailed microscopy is required to
understand the failure mechanism in the weld metal and ultimately improve the strength of the 740
weld metal. Solution annealing offers one path for improved weld metal strength. This research
shows that base metal strength can be achieved through application of a standard solution
annealing heat-treatment which results in a stronger weld metal and moves the failure location to
the base metal. A second option to improve the cross-weld strength of alloy 740 weldments is to
use an alternative filler metal. In this work, both alloy 263 and Haynes 282 filler metals improved
the strength of the welded joint to within an acceptable -20% scatterband of the base material.
However, neither alloy 263 nor Haynes 282 restored cross-weld strength in alloy 740 to that of
the base metal. Examination of the 263 joints revealed that creep cavitation was observed in fine
grained regions (associated with weld metal refinement) in the weld metal suggesting process
improvements may be warranted for this combination.
Currently, ASME only applies WSRF (WSF) to longitudinally seam welded components which
are not envisaged for A-USC designs. A WSF less than 1.0 is standard for many power plant
materials including extensively used ferritic steels such as grade 91 which has a WSF between 0.5
and 0.9 (due to the Type IV failure mechanism). Other studies of nickel-based alloys such as
239
Haynes 230 [12] and alloy 617 [13] show WSF around 0.8. Therefore, from a practical
standpoint, a WSF of 0.7 can be successfully utilized in design by avoiding seam welded
components. If seam welds are required, the data clearly indicate alternative filler metals or
solution heat-treatment are viable options for improving weldments strength.
CONCLUSIONS
Analysis of a large set of creep-rupture data on Inconel alloy 740/740H of varying compositions
showed the alloy has sufficient strength to achieve desired lifetimes for A-USC boiler
components. Optimized time-temperature parameter analysis was shown to give accurate results
for the base metal dataset and ongoing tests are meeting predictions. Extensive cross-weld
rupture tests confirm the use of a 0.70 WSRF in the current ASME code case for matching filler
metal made with various processes. Although not needed in most designs, if higher weldments
strength is required, the data show alternate filler metals and solution heat-treatment are both
options available to the end user and manufacturer. Microstructural analysis of failed cross-weld
specimens showed different behavior for different filler metals and heat-treatments which
illuminate the needs for further study. Future work should include microstructural analysis of
weldments samples to understand the failure mechanisms, continued long-term base metal testing,
and interrupted tests to improve understanding of damage development.
ACKNOWLEDGMENTS
The author wishes to acknowledge the significant contributions of Oak Ridge National Laboratory
(ORNL) in performing the long-term creep testing in this work including the leadership of R.
Swindeman (who taught me all I know about creep testing), P. Torterelli and M. Santella and the
experimental work of B. Sparks, J. Moser, F. Adames, and T. Geer. The guidance and support of
the U.S. DOE/OCDO A-USC Steam Boiler consortium R. Purgert (EIO), P. Rawls (NELT), B.
Romanosky (NETL), and R. Conrad (DOE) is appreciated. Special thanks goes to J. Sanders, J.
Siefert, and J. Tanzosh (B&W) who provided the welds. Finally, thank you to J. Siefert for
helpful discussions on the preparation of this manuscript.
REFERENCES.
[1] Case 2702 Seamless Ni-25Cr-20Co Material Section I. Cases of the ASME Boiler and
Pressure Vessel Code. BPV-Supp.7. 2011 American Society of Mechanical Engineers
[2] J.P. Shingledecker, I.G. Wright: Proceedings to the 8th Liege Conference on Materials for
Advanced Power Engineering 2006, Forschungszentrum Jlich GmbH, 2006.107-120.
[3] R. Viswanathan, R. Purgert, U. Rao: Materials for Advanced Power Engineering 2002,
Proceedings Part II, Forschungszentrum Julich GmbH, 2002. 1109-1129
[4] R. Viswananthan, J.F. Henry, J. Tanzosh, G. Stanko, J. Shingledecker, B. Vitalis, R. Purgert:
J. .Mater. Eng. Perform., 2005, 3., Vol. 14. 281-292
[5] N.D. Evans, P.J. Maziasz, R.W. Swindeman, G.D. Smith: Scr. Mater., 2004, Vol. 51. 503507.
[6] S. Zhao, X. Xie, G.D. Smith, S.J. Patel: Mater. Sci. and Eng., 2003, Vol. A355, 96-105.
[7] X. Xie, S. Zhao, J. Dong, G.D. Smith, B.A. Baker, S.J. Patel: Mater. Sci. Forum, 2007, Vols.
561-565. 471-476.
240
[8] J.P. Shingledecker, G.M. Pharr. Met. Mat. Trans. A, Vol. 43 (6) 2012. 1902-1910.
10.1007/s11661-011-1013-4
[9] J.P. Shingledecker, N.D. Evans, G.M. Pharr. Influences of Composition and Grain Size on
Creep-Rupture Behavior of Inconel Alloy 740. Materials Science and Engineering A. 578
(2013) 277-286. 10.1016/j.msea.2013.04.087
[10] J.A. Siefert, J.M. Tanzosh, J.E. Ramirez. Proceedings to the 6th International Conference on
Advances in Materials Technology for Fossil Power Plants, Santa Fe, New Mexico, August
30-September 4, 2010. EPRI, March 2011: 1022300. Distributed by ASM International.
1045-1066.
[11] B.A. Baker, R.D. Gollihue. Proceedings to the 6th International Conference on Advances in
Materials Technology for Fossil Power Plants, Santa Fe, New Mexico, August 30-September
4, 2010. EPRI, March 2011: 1022300. Distributed by ASM International. 96-109.
[12] R. Viswanathan, J. Shingledecker, J. Hawk, and S. Goodstine, Proceedings Creep & Fracture
in High Temperature Components, 2nd ECCC Creep Conference, April 21-23, 2009 ( Zurich,
Switzerland), DEStech Publications, Inc., 2009. 31-43
[13] A. Klenk, M. Speicher, K. Maile. Weld Behavior of Martensitic and Ni-based Alloys for
High Temperature Components. Procedia Engineering 5 (2013) 414-420.
[14] D. Bechetti, J. Dupont, Lehigh University, unpublished research, June 2013.
LEGAL NOTICE/DISCLAIMER
This report was prepared by J. Shingledecker (EPRI) pursuant to a Grant partially funded by the
U.S. Department of Energy (DOE) under Instrument Number DE-FG26-0 1 NT 41175 and the
Ohio Coal Development Office/Ohio Department of Development (OCDO) under Grant
Agreement Number CDO/D-OO-20 (now D-05-02A). NO WARRANTY OR
REPRESENTATION, EXPRESS OR IMPLIED, IS MADE WITH RESPECT TO THE
ACCURACY, COMPLETENESS, AND/OR USEFULNESS OF INFORMATION
CONTAINED IN THIS REPORT. FURTHER, NO WARRANTY OR REPRESENTATION,
EXPRESS OR IMPLIED, IS MADE THAT THE USE OF ANY INFORMATION,
APPARATUS, METHOD, OR PROCESS DISCLOSED IN THIS REPORT WILL NOT
INFRINGE UPON PRIVATELY OWNED RIGHTS. FINALLY, NO LIABILITY IS
ASSUMED WITH RESPECT TO THE USE OF, OR FOR DAMAGES RESULTING FROM
THE USE OF, ANY INFORMATION, APPARATUS, METHOD OR PROCESS DISCLOSED
IN THIS REPORT
241
ABSTRACT
High temperature strength of a nickel-based superalloy, Alloy 740H, was investigated to evaluate
its applicability to advanced ultrasupercritical (A-USC) power plants. A series of tensile, creep
and fatigue tests were performed at 700C, and the high temperature mechanical properties of
Alloy 740H was compared with those of other candidate materials such as Alloy 617 and Alloy
263. Although the effect of the strain rate on the 0.2% proof stress was negligible, the ultimate
tensile strength and the rupture elongation significantly decreased with decreasing strain rate, and
the transgranular fracture at higher strain rate changed to intergranular fracture at lower strain
rate. The time to creep rupture of Alloy 740H was longer than those of Alloy 617 and Alloy 263.
The fatigue limit of Alloy 740H was about half of the ultimate tensile strength. Further, Alloy
740H showed greater fatigue strength than Alloy 617 and Alloy 263, especially at low strain
range.
INTRODUCTION
For enhancement of the thermal efficiency and reduction of CO 2 emission in coal-fired power
plants, an advanced ultra-supercritical (A-USC) power plant in which steam condition is raised
from 600C in the conventional USC power plant to 700C or higher, is under development as a
worldwide activity [1-3]. Conventional ferritic and austenitic steels cannot fulfill the requirement
of creep strength at these temperatures and Ni-based alloys with higher creep strength and greater
corrosion resistance are needed to attain the above target.
Alloy 740 is a relatively new Ni-based superalloy developed on the basis of Alloy 263 at Special
Metals Corporation as a candidate material for boiler tubing and piping in A-USC power plants
[4]. Compared with Alloy 263, the alloy increases the fraction of Cr and decreases the fraction of
Mo for improving corrosion resistance, and adds the strengthening element Nb for high
temperature strength. This alloy exhibits the stress rupture strength over 100MPa at 750C and a
good oxidation and hot corrosion resistance at elevated temperatures [4]. However,
microstructure of the alloy changes during prolonged aging or creep loading, such as gamma
prime () coarsening, to eta () phase transformation and formation of G-phase [5, 6]. The
structure stability of this alloy can be improved by the adjustment of Al, Ti and Si level reported
by Zhao et al. [7], and a new modified alloy was developed as Alloy 740H. Overview of available
literature indicates that the microstructure characteristic of Alloy 740 has been investigated in
detail. However, limited efforts have been made on the topic of high temperature strength for
Alloy 740 or Alloy 740H.
242
The objective of this paper is to study the high temperature strength of Alloy 740H, for evaluating
its applicability to A-USC power plants. Tensile and creep tests were performed at 700C and
effect of strain rate on the tensile properties and creep fracture behaviors was discussed, followed
by the fracture surface observation. Both strain- and load-controlled fatigue tests were also carried
out at 700C and the fatigue strength was discussed in relation to the tensile properties. In
addition, the high temperature strength of Alloy 740H was compared with the data of other
candidate materials such as Alloy 617 and Alloy 263.
EXPERIMENTAL PROCEDURE
The material tested was Alloy 740H piping (205mmID72.5mmt150mmL) of which the
chemical composition and heat treatment are listed in Table 1. The material was received in
solution annealed and aged condition, following the ASME Code Case 2702. Microstructure of
the material is shown in Fig. 1. Almost equiaxed grain structures were observed in both axial and
circumferential sections, indicating that there is no effect of rolling process on the microstructure.
The average grain size was found to be about 150m by a cutting method according to the
JIS0551 [8].
Figures 2(a) and 2(b) show the geometry and dimensions of tensile, creep and fatigue specimens.
Solid bar specimens with a gage diameter of 6mm and 30mm gage length shown in Fig. 2(a) were
used in the tensile and creep tests. The fatigue specimen was a round bar whose diameter and
length at the test section were 8mm and 16mm as shown in Fig. 2(b). All the specimens were
machined in a way that the loading direction is parallel to axial direction of the material.
Table 1: Chemical composition of Alloy 740H (wt%).
C
Cu
0.045
0.031
Ti
Nb
1.36
1.52
Solution annealed and aged
Cr
24.7
Mn
0.246
Mo
0.006
Fe
0.238
Co
20.2
Si
0.137
243
Al
1.33
Ni
Bal.
22 (Tensile)
15 (Creep)
30
10
10
22 (Tensile)
15 (Creep)
21.5
O8
O 14
O 6.3
O6
M10 (Tensile)
M12 (Creep)
16
M18P2.5
103
10 %/s
-2
-3
10 %/s
10 %/s
10 %/s
-1
10 %/s
-4
T=700C
(a) up to failure
(b) up to 1% strain
Fig. 3(b). Comparing Figs. 3(a) and 3(b), the strain rate mainly affected the strain range from
yielding to necking (strain hardening range) in stress-strain curve. That is, the strain hardening
range decreased significantly with decreasing the strain rate.
Figure 4 presents variation of Youngs modulus (E), 0.2% proof stress ( 0.2 ) and ultimate tensile
strength ( B ) with strain rate at 700C. There was a little difference in 0.2% proof stress at the
five strain rates but Youngs modulus slightly decreased with decreasing the strain rate. Ultimate
tensile strength, on the other hand, decreased monotonically as the strain rate decreased. These
results indicate that ultimate tensile strength was more sensitive to the strain rate than Youngs
modulus and 0.2% proof stress, due to a large stress dependency of recovery rate.
In order to discuss the effects of strain rate on the ductility of Alloy 740H, rupture elongation ()
and reduction of area () are plotted against the strain rate in Fig. 5. Elongation as well as
reduction of area decreased as the strain rate decreased. Generally, increasing the strain rate
increases the strength, but decreases the ductility at elevated temperatures in most of carbon steels
and low-alloy steels [9]. However, Alloy 740H showed the positive strain rate dependency of both
ultimate tensile strength and elongation, which may have resulted from the change in fracture
mode due to the strain rate.
B
0.2
E
T=700C
245
Figure 6 shows fracture surfaces observed at three strain rates (100%/s, 10-2%/s and 10-4%/s) at
700C. At strain rate of 100%/s, transgranular fracture with many dimples was dominant and
intergranular fracture was partly found as seen in Fig. 6(a). When the strain rate decreased to 102
%/s as shown in Fig. 6(b), both transgranular and intergranular fracture surfaces were observed
with the ratio of intergranular fracture being larger than that at the strain rate of 100%/s. In
contrast, almost the whole fracture surface was found to be intergranular at the strain rate of 104
%/s. These results mean that the fracture mode was changed from transgranular to intergranular
with decreasing the strain rate, which caused the decrease in ductility with decreasing the strain
rate shown in Fig. 5.
500m
100m
(a) 100%/s
(b) 10-2%/s
(c) 10-4%/s
246
= 855.3t r 0.11
T=700C
T=700C
T=700C
520MPa
430MPa
430MPa
520MPa
395MPa
Primary
Steady
Tertiary
395MPa
247
500m
100m
(a) 520MPa
(b) 430MPa
(c) 395MPa
T+I
I
T: Transgranular fracture
I: Intergranular fracture
T=700C
Figure 10: Relationship between true fracture strain and time to rupture.
Fatigue Life
Figure 11(a) illustrates the variation of maximum and minimum stresses with number of cycles in
strain-controlled fatigue tests at 1.2% and 1.0% strain ranges. Slight cyclic hardening was
observed in the early cycles but the material exhibited a tendency to cyclically soften beyond
about 10% of the life. Similarly, slight cyclic hardening and softening behavior was observed in
the load-controlled tests at stress amplitudes of 500MPa and 450MPa as shown in Fig. 11(b). In
the test at stress amplitude of 400MPa without plastic strain, however, strain range was almost
constant until the end of life, indicating that there is no effect of the cyclic deformation on the
stress-strain relationship in the predominantly elastic region, which is easily understood from the
fact that cyclic hardening or softening is mainly caused by the change of dislocation structure.
248
Figure 12 correlates the fatigue lives in both the strain- and load-controlled tests with stress
amplitude, where the stress amplitudes in the strain-controlled tests are obtained from hysteresis
loops at half life. The solid line is drawn based on all the data at 700C. Fatigue lives in the strain
controlled tests were comparable to those in the load controlled tests, which means that the
control mode and loading frequency have a little effect on fatigue life. Furthermore, it can be seen
that the fatigue limit was about 400MPa. Since ultimate tensile strength at the same strain rate
(0.1%/s) was 870MPa as shown in Fig. 4, the fatigue limit was approximately a half of ultimate
tensile strength.
T=700C
Figure 11: Cyclic deformation behaviors in strain and load controlled fatigue tests.
1/2B
T=700C
249
Figure 13 correlates the fatigue lives in all the tests with elastic ( e ), plastic ( p ) and total strain
range ( t ), where these strain ranges are obtained from the hysteresis loops at half life. In all the
tests, the elastic strain range was larger than the plastic strain range. The fatigue lives were
linearly correlated with the elastic strain and plastic strain range and can be expressed by the
following equations, so the Manson-Coffin relationship [10] holds for this alloy at 700C.
(1)
(2)
Figure 14 shows the photograph of fracture surface after fatigue test at strain range of 0.7% as a
representative case. Crack initiated at surface and propagated macroscopically in the normal
direction to the specimen axis. Transgranular fracture with clear striations morphology was
observed.
T=700C
e = 1.25N f 0.08
p = 7.65N f 0.44
200m
2mm
200m
Figure 14: Fracture surfaces observed after fatigue test at strain range of 0.7%.
250
T=700C
Alloy 740H
Alloy 617
[11]
Alloy 263
700C, 10 h
[12]
Figure 17 compares fatigue life of Alloy 740H to those of Alloy 617 [13] and Alloy 263 [11] at
700C. The largest fatigue life was found in Alloy 740H and fatigue lives of Alloy 617 were
almost same as those of Alloy 263.
The above discussion has revealed that Alloy 740H exhibits better tensile, creep and fatigue
strength than Alloy 617 and Alloy 263 and is a leading material for constructing A-USC power
plants from a viewpoint of the high temperature strength. Ductility of Alloy 740H tends to be
smaller than those of other two alloys, but the thermal stress/strain can be reduced by decreasing
the thickness of components due to its enhanced strength and the possibility of creep-fatigue
failure is not necessarily larger.
T=700C
Figure 17: Comparison of fatigue life of three kinds of Ni-based alloys at 700C.
CONCLUSIONS
There was a little effect of strain rate on the 0.2% proof stress but the Youngs modulus slightly
decreased with decreasing strain rate in the tensile tests. The ultimate tensile strength and the
elongation significantly decreased with decreasing strain rate with a transition from the
transgranular fracture at higher strain rate to intergranular fracture at lower strain rate.
The time to creep rupture of Alloy 740H was similar to that of Alloy 740. Almost the whole
intergranular fracture was found in all the tests, indicating that intergranular fracture is dominant
at 700C even though the creep loading time is short. Creep rupture ductility of the alloy was
similar to that in the tensile test at slow strain rate.
Alloy 740H exhibited a slight cyclic hardening initially and softening behavior subsequently in
the fatigue tests and the control mode had a little effect on fatigue life. Fatigue limit of this alloy
was approximately a half of the ultimate tensile strength.
Ultimate tensile strength of Alloy 740H as well as creep strength was larger than those of Alloy
617 and Alloy 263 but elongation was the smallest among three alloys. In addition, Alloy 740H
showed greater fatigue strength compared with Alloy 617 and Alloy 263 especially at low strain
range.
252
ACKNOWLEDGMENTS
The authors gratefully acknowledge Daido Steel Co., Ltd. for providing the testing material and
Mr. Katsuaki Hosino for the supports in conducting the tensile and fatigue tests.
REFERENCES
[1] Fukuda, M., Advanced USC Power Generation Technology, Journal of the Japan Society
of Mechanical Engineers, Vol. 114, No. 1109 (2011), pp. 22-25.
[2] Kjaer, S., Klauke, F., Vanstone, R., Zeijseink, A., Weissinger, G., Kristensen, P., Meier, J.,
Blum, R and Wieghardt, K., The advanced Supercritical 700 Pulverised Coal-Fired
Power Plant, VGB Power Technology, Vol. 82, No. 7 (2002), pp. 46-49.
[3] Palkes, M., Boiler Materials for Ultra Supercritical Coal Power Plants Conceptual Design
ALSTOM Approach, NETL-DOE, USC T-1 (2003).
[4] Patel, S.J., Introduction to Inconel Alloy 740: an Alloy Designed for Superheater Tubing in
Coal-Fired Ultra Supercritical Boilers, Acta Metallurgica Sinica (English Letters), Vol. 18,
No. 4 (2005), pp. 479-488.
[5] Zhao, S., Xie, X., Smith, G.D and Patel, S.J., Microstructural Stability and Mechanical
Properties of a New Nickel-Based Superalloy, Materials Science and Engineering A, Vol.
355 (2003), pp.96-243.
[6] Evans, N.D., Maziasz, P.J., Swindeman, R.W and Smith, G.D., Microstructure and Phase
Stability in INCONEL Alloy 740 during Creep, Scripta Materialia, Vol. 51 (2004), pp. 503507.
[7] Zhao, S., Xie, X., Smith, G.D and Patel, S.J., Research and Improvement on Structure
Stability and Corrosion Resistance of Nickel-Base Superalloy INCONEL Alloy 740,
Materials and Desigh, Vol.27 (2006), pp.1120-1127.
[8] Japanese Industrial Standards Committee ed., JIS G 0551: Steel-Micrographic Determination
of the Apparent Grain Size, Japanese Standards Association (2005), p. 12.
[9] JSMS Committee on High Temperature Strength of Materials ed., High Temperature
Strength of Materials, Japan Society of Materials Science (2008), p. 38.
[10] Manson, S.S., Fatigue: a Complex Subject: Some Simple Approximations, Experimental
Mechanics, Vol. 5 (1965), pp. 193-226.
[11] Yamamoto, M., Shingledecker, J., Ogata, T and Santella, M., High Temperature Strength
Evaluation of an Advanced USC Candidate Material Alloy 263, CRIEPI report, Q08003
(2009).
[12] http://www.specialmetals.com/products/inconelalloy617.php
[13] Noguchi, Y., Miyahara, M., Okada, H., Igarashi, M and Ogawa, K.,Creep-Fatigue
Properties of Fe-Ni Base Alloy HR6W for Piping in 700 USC Power Plants, Journal of
the Japan Society of Materials Science, Japan, Vol. 57, No. 6 (2008), pp. 569-575.
253
ABSTRACT
Significant development is being carried out worldwide for establishing advanced ultra
supercritical power plant technology which aims enhancement of plant efficiency and reduction of
emissions, through increased inlet steam temperature of 750C and pressure of 350 bar. Nickel
base superalloy, 50Ni-24Cr-20Co-0.6Mo-1Al-1.6Ti-2Nb alloy, is being considered as a
promising material for superheater tubes and turbine rotors operating at ultra supercritical steam
conditions. Thermal fluctuations impose low cycle fatigue loading in creep regime of this material
and there is limited published fatigue and creep-fatigue characteristics data available. Scope of
present study includes behavior of the alloy under cyclic loading at operating temperature. Strain
controlled low cycle fatigue tests, carried out within the strain range of 0.2%-1%, indicate
substantial hardening at all temperatures. It becomes more evident with increasing strain
amplitude which is attributed to the cumulative effects of increased dislocation density and
immobilization of dislocation by ' precipitates. Deformation mechanism which influences fatigue
life at 750C as a function of strain rate is identified. Hold times upto 500 seconds are introduced
at 750C to evaluate the effect of creep fatigue interaction on fatigue crack growth, considered as
one of the primary damage mode. The macroscopic performance is correlated with microscopic
deformation characteristics.
Keywords: Ultra supercritical, Low cycle fatigue, Alloy 740
INTRODUCTION
Establishment of state of the art advanced ultra supercritical (AUSC) power plant is being pursued
worldwide to meet ever increasing demand of electricity due to increased population and global
warming due to CO2, SOX and NOX emissions. A key aspect of this strategy of development of
AUSC technology is to have an operating inlet steam temperature of 750C and pressure of
350bar which will in turn increase the efficiency of Rankine cycle. Henceforth performance of
superheater tubing, headers and HP rotors becomes crucial in terms of creep strength, low cycle
fatigue strength. Because of the structural stability of newly developed nickel base superalloy
(50Ni-24Cr-20Co-0.6Mo-1Al-1.6Ti-2Nb (alloy 740) primarily strengthened by gamma prime
and additionally solid solution strengthened by Co, Cr at 750C, it is considered as the potential
candidate material for A-USC power plant [1]. Low cycle fatigue damage caused by cyclic
thermal stress and strain generated during daily operation, start-up and shut-down of a thermal
power plant is a critical issue to be addressed. As limited published data is available about fatigue
and creep fatigue properties of alloy 740 and thus deformation behavior under cyclic loading and
in creep fatigue interaction condition need to be investigated.
254
The scope of present study includes preliminary tensile and creep property characterization,
assessment of low cycle fatigue life at room temperature and operating temperature range of an
industrial scale heat of alloy 740. The effect of reducing strain rate and introduction of hold time
during cyclic loading at 750C is also investigated. In order to generate complete understanding
of mechanisms of failure, macroscopic fracture mode is correlated with microscopic damage
mechanisms.
EXPERIMENTAL
Material
50Ni-24Cr-20Co-0.6Mo-1Al-1.6Ti-2Nb alloy was manufactured at industrial scale through
vacuum induction melting followed by consumable electrode vacuum arc remelting. Composition
of product sample is given in Table 1.
Table 1. Chemical composition of alloy
Element
C
S
P
Si
Mn
Cr
Co
Mo
<0.002 <0.004 0.02
0.03
24.7
20.8
0.56
Weight% 0.02
Element
Ti
Al
Nb
Fe
B
N2
O2
Ni
1.70
1.98
0.26 50ppm 30ppm 10ppm Balance
Weight% 1.16
This ingot was subjected to long term homogenization cycle followed by various
thermomechanical processing steps to obtain 100mm forged bar and was subsequently hot
rolled to 28mm . Heat treatment at 28mm involved solution annealing at 1150C for 30
minutes minimum, quenching in water and aging at 800C for 16hrs followed by air cooling.
Microstructural observation (Fig. 1) revealed that the material is having austenitic grains with
annealing twins of average grain size of 100 microns, a small quantity of un-dissolved primary
MC carbides and fine discontinuous M23C6 along the grain and twin boundaries. On aging fine
particles precipitate in the matrix.
100X
Fig. 1 Microstructure of solution treated alloy
Tensile properties obtained at room temperature and application temperature range in the alloy
under study in comparison with international standard [2] are given in Table 2.
Table 2. Tensile properties of alloy
Tensile properties
0.2% YS (MPa) UTS (MPa)
620
1035
Specified at RT (Code case 2702)
890
1250
Obtained values at RT
621
1023
Typical values at 650C
716
985
Obtained values at 650C
608
766
Typical values at 750C
650
907
Obtained values at 750C
255
%El
20
30
38
36
32
40
As application of this high temperature material demands primarily creep strength, creep rupture
tests were carried out to qualify the creep characteristics of the material before evaluating the
creep fatigue interaction behavior at application temperature. Creep rupture strength of 280MPa
for 1000 hours was obtained at 750C.
Methods
The specimens used in low cycle fatigue test were 4.5mm and 14mm in gauge length. A
digitally controlled servo hydraulic fatigue testing machine equipped with an electrical resistance
furnace was used for the test. Fully reversed (R= -1) strain controlled isothermal low cycle fatigue
tests were conducted by using an extensometer with a gauge length of 12 mm. A symmetrical
triangular waveform with 3X10-3 s-1 strain rate was applied for tests with axial strain range of
0.2% to1% at room temperature and 750C. The test temperature of 750C was chosen to
reproduce the condition of AUSC. Also fatigue tests with lower strain rate i.e. 3X10-5 s-1 were
carried out at 750C. Tensile hold time upto 500 seconds were introduced at 750C by applying
trapezoidal waveform. Fracture surfaces were examined by optical and scanning electron
microscope to determine the fatigue crack initiation and propagation modes. Studies were also
conducted on longitudinal section of the specimen to characterize the microstructural changes that
occur during fatigue and creep-fatigue damage.
RESULTS
The relationship of total strain range with fatigue life at room temperature and operating
temperature i.e 750C was shown in Fig. 2. Although relatively low strain range ( = +1%) led
to endurances of around 500 cycles, the gradients of endurance curves were shallow and yielded
endurance of 5000 cycles at = +0.3%. Effect of decreasing strain rate to 3X10-5 s-1 on fatigue
life was observed at 750C. There was a trend towards lowering of fatigue life by 1/4th with
decreasing strain rate (Fig. 3).The hysteresis loop of stable cycle at 750C with different strain
rate were shown in Fig. 4, where it was observed that, a significant drop in peak tensile stress
occurred at lower strain rate test. It indicated that there was considerable amount of increase in
inelastic strain per cycle and henceforth identified as the possible reason for lower fatigue life
with reducing strain rate.
Fig. 2 Relationship between total strain range and low cycle fatigue life at RT and 750C
256
Fig. 4 Hysteresis loop of stable cycle at different strain rate at 750C, = +0.4%
Change in peak stress with number of cycles in all strain ranges at 750C is shown in Fig. 5. Alloy
740 does not show typical cyclic hardening or softening behavior instead cyclic softening follows
a rapid hardening similar to precipitation strengthened nickel base superalloys [3]. This general
behaviour of hardening does not change with increase in strain range, but the magnitudes of
hardening have been found to be dependent on strain range. At lower strain range a stable phase is
observed in between cyclic hardening and softening. Also at all temperatures cyclic hardening
behaviour is prominent followed by a stable phase and cyclic softening (Fig. 6).
257
900
800
Peak stress(MPa)
700
600
500
400
300
200
= + 0.8%
= + 0.6%
= + 0.4%
100
0
500
1000
1500
2000
No of cycles
2500
800
700
RT
600
500
400
750 deg_C
300
650 deg_C
200
100
0
2000
4000
6000
8000
10000
No of cycles
Fig. 6 Cyclic hardening behaviour at different temperature, = +0.4%
Figure 7 showed the relationship between the stress ranges obtained at half of fatigue life. The
lives in terms of stress range were shorter in lower strain rate test. Stress range of alloy 740 was
notably higher than those of other alloys [4]. Masing behaviour was observed in alloy 740 at room
temperature upto total strain range under study as indicated in Fig. 8. By bringing the compressive
tips of all stable hysteresis loops belonging to various strain levels to a common origin, it was
observed that all the loading branches overlap and form a common envelope curve. Hold times at
the tensile peak strain led to pronounced reduction in fatigue life. A tensile hold of 100s seconds
resulted in shorter fatigue life by 60%. It was noted that fatigue life reduction increased
258
continuously, but at lower rate with an increase in hold time above 100 seconds (Fig. 9). Load
drop was similar with hold time above 200 seconds as observed in hysteresis loops of stable
cycles (Fig. 10).
2000
At 3X10-3/s
At 3X10-5/s
1000
900
800
700
600
500
10
100
1000
10000
100000
No of cycles to failure,Nf
Fig. 7 Total stress range vs no of cycles to failure in different strain rate at 750C
1000
Stress(MPa)
500
-500
-1000
-0.8
0.8%
0.6%
0.4%
-0.6
-0.4
-0.2
0.0
0.2
Strain(%)
0.4
0.6
0.8
1.0
No of cycles to failure,Nf
10000
1000
100
10
100
200
300
400
500
Hold time(sec)
(a)
(b)
Fig. 11 Fracture surfaces of fatigue tested samples (a) at room temperature, (b) at 650C
260
(a)
(b)
(c)
Fig. 12 Fracture surfaces of fatigue tested samples (a)) at 750C, (b) at 750C with 3X10-5 strain
rate and (c) at 750C with tensile hold of 200seconds.
Deformation behaviour study
Total strain range of around 0.3% for endurance of 5000 cycles as required by the steam turbine
application is achieved by alloy 740 at 750C in air [5]. Masing behavior is observed when a
material has very stable microstructure under cyclic deformation. Specifically matrix containing
finely dispersed non-shearable precipitates and low stacking fault energy [6]. Cyclically deformed
substructure consists of planar arrays of dislocation, instead of dislocation cell, in this case. At
room temperature slip was predominantly planar and concentrated in parallel slip band which
have highest resolved shear stress and there is no change in precipitate morphology even within
the slip band. The tendency of planar slip is attributed to characteristic ordering and coherency of
precipitates, relatively difficult cross-slip of dislocation around the particles due to sufficient
low stacking fault energy of Ni-Cr-Co matrix [7]. This phenomenon is strongly supported by
occurrences of slip band step in SEM microphotograph (Fig. 13) and masing behavior too.
261
Fig. 13 Slip band step observed at broken fatigue sample tested at room temperature
Alloy 740 does not show typical hardening or softening behavior. It hardens till it reaches a
cyclically stable structure then continuous softening follows until failure similar to other
precipitation strengthened superalloy. The extreme hardening and softening behaviour reflects
precipitates are in peak aged condition. The peak aged particles are very strong, but once slip is
initiated on a few relatively weak planes, they soften drastically, concentrating further strain in
these few slip bands. When dislocation structure reaches towards a saturated state with increasing
strain range, resistance to deformation is reduced leading to lower fatigue life due to decreased
precipitation contribution, owing to the reduced precipitation cross section. With increasing strain
range, the dislocation density increases. Severe dislocation interaction leading to dislocation
tangles gives rise to increased peak stress as well as faster rate in cyclic hardening at higher strain
ranges. Cyclic hardening behavior is predominant even at 750C because of more slip system in
operation with increasing temperature, leading to frequent slip band interaction and dislocation
tangle formation.
The drop in number of cycles to failure with the introduction of hold time and decreased strain
rate is associated with higher dwell period at 750C. It induces grain boundary oxidation as
indicated in Fig. 14 by Cr2O3 scale on crack surface which results into accelerated intergranular
crack propagation. Once initiated crack will open exposing new material surface to gas phase,
oxidation of the crack edge would occur eventually with growth of Cr rich oxide. Figure 15 shows
the features of a typical grain boundary failure.
C r 2O 3
[4] Kobayashi, K. et al, Creep Fatigue interaction properties of Nickel-based superalloy 617,
Acta Metallurgica, Vol. 24, No. 2(2011), pp. 125-131.
[5] Blum, R. et al, Materials Development for Boilers and Steam Turbines Operating at 700C,
Proceedings of the Fourth International Conference on Advances in Materials Technology
for Fossil Power Plants 2004 (ASM International), South Carolina, USA,June. 2005, pp.
116-136.
[6] Plumtree, A. et al, Cyclic stress strain response and substructure, International journal of
fatigue, Vol. 23 (2001), pp. 799-805.
[7] Sims, C. T. et. al., Superalloys II, Wiley-Interscience publication, (New York, 1987), pp. 263267.
264
ABSTRACT
Inconel alloy 740H is designated for boiler sueprheater/reheater tubes and main steam/header
pipes application of advanced ultra-supercritical (A-USC) power plant at operating temperatures
above 750. Microstructure evolution and precipitates stability in the samples of alloy 740H
after creep-rupture test at 750, 800 and 850 were characterized in this paper by scanning
electron microscopy, transmission electron microscopy and chemical phase analysis in details.
The phase compositions of alloy 740H were also calculated by thermodynamic calculation. The
research results indicate that the microstructure of this alloy keeps good thermal stability during
creep-rupture test at 750, 800 and 850. The precipitates are MC, M23C6 and during
creep-rupture test. The temperature of creep test has an important effect on the growth rate of
phase. No harmful and brittle phase was found and also no to transformation happened
during creep. Thermodynamic calculations reveal almost all the major phases and their stable
temperatures, fractions and compositions in the alloy. The calculated results of phase
compositions are consistent with the results of chemical phase analysis. In brief, except of
coarsening of , Inconel alloy 740H maintains the very good structure stability at temperatures
between 750 and 850.
INTRODUCTION
The challenge and pressure on environmental protection and energy saving have been more and
more serious since the last decade of the twentieth century in the world wide. In one hand, new
energy, such as solar energy, wind energy, biomass energy, etc, are paying more and more
attentions and their developmental speed and increasing rate are very high in the last ten years, in
other hand, the great efforts to improve the thermal efficiency of the traditional fossil power
plants by increasing the steam temperature and pressure are also carried out in this century. The
600-class ultra-supercritical (USC) coal-fired power technology has been the major choice of
the newly-built power plant. There are more than 110 units (600~660MW & 1000MW) of
600-class USC coal-fired power plant put into operation in China from 2006 to 2012, which
accounts for about more than 80% of USC units in the whole world.
Simultaneously, the 700 advanced ultra-supercritical (A-USC) coal-fired power technology
has moved forward into the researchers insight. Since 1998, European Union initiated the
Thermie AD700 project to develop 700A-USC coal-fired power technology and several
265
successive projects were carried out to develop or demonstrate the new materials and key
components in Europe in the following years [1, 2]. USA, Japan and China also started their
research project to develop the 700A-USC pulverized coal-fired power technology in the last
decade [3, 4].
Inconel alloy 740 is a precipitate-strengthened Ni-Cr-Co superalloy and was invented by Special
Metals Corporation, Huntington from 1998 to meet the requirement (750/105h creep rupture
strength larger than 100MPa and metal loss of flue gas/coal ash corrosion/oxidation less than
2mm in 2105h) as boiler superheater/reheater tubing materials in Europe 700A-USC project
[5,6]. The patent of this Ni-Cr-Co alloy was issued in 2001. However, according to the
experimental research results, the microstructure instability of Inconel alloy 740 in the elevated
temperatures are as follows: (1) high growth rate at temperature >750; (2) large amount of
plate-shape phase formation nearby the grain boundaries and in the grains and (3) big block of
Si-containing G-phase precipitation at grain boundaries [7-10]. Base on the consideration of
improving the microstructure stability and the elimination of liquid cracks in thick-wall welded
joint of Inconel alloy 740, chemical composition modification of Inconel alloy 740 was carried
out through adjustment of the precipitation-strengthened elements of Al, Ti, Nb and Si, B as well
[11-15]. The new alloy, Inconel alloy 740H, was specifically developed in 2009 for
superheater/reheater tubes and main steam/header pipes applications and has been the main
candidate materials in 700 A-USC power plants.
Over the past decade, the corrosion resistance, microstructure evolution and mechanical
properties of the alloy 740 have been extensively investigated in the world. From 2009, the
researchers interests concentrate on the microstructure stability, creep-rupture property,
workability and weldability of Inconel alloy 740H. As one of the most important candidate
materials for Chinese 700 A-USC power plant, Inconel alloy 740H is still being evaluated in
several research institutes, boiler companies and universities in China.
In this paper, several creep-ruptured samples of Inconel alloy 740H were investigated through
SEM and TEM observation, chemical phase analysis and Thermodynamic calculation as well to
detail the microstructure evolution and precipitates stability during creep at different high
temperatures. Creep-rupture tests are still ongoing and creep-rupture property, mechanism and
the influencing factors will be discussed in the future.
EXPERIMENTAL MATERIALS AND METHODS
The chemical compositions of alloy 740H used in the present investigation and the ASME
specification are given in Table 1. The chemical compositions of alloy 740H are in the range of
specification of ASME Code Case 2702. The sample material was solution annealed and aged
according to the specification of ASME Code Case 2702. The actual aging conditions are carried
out at 800 for 5hrs for the sample of alloy 740H. The optical microscopy was performed on
mechanically polished and chemical etched specimen of alloy 740H to get its ASTM grain size
grade. The kinds and weight fractions of the precipitates were ascertained through microchemical phase analyses method. Creep-rupture tests were carried out at 750, 800 and 850
in several stresses. The longest rupture-life samples of alloy 740H were selected for
microstructure characterization, which were electro-polished and electro-etched first and then
were carried out using scanning electron microscopy (SEM). The samples of longest rupture-life
of alloy 740H were mechanically ground to about 80m-thickness and then were double-jet
266
electro-polished or argon-ion milled to produce better thin regions for transmission electron
microscopy (TEM) observation. Then, TEM was employed on these samples to get the
morphology of phases and their characteristic patterns of the selected area diffraction (SAD).
Thermodynamic calculations were performed to predict the precipitate stability of alloy 740H by
using Thermo-calc software and a corresponding Ni-database developed by Thermo-Tech. The
calculation results were also compared with the results of chemical phase analysis of the alloy.
Alloy 740H
ASME CC
2702
(Continued)
Alloy 740H
ASME CC
2702
Nb
1.55
Ti
1.61
Al
1.60
Cu
0.06
3.0
0.5-2.5
0.5-2.5
0.2-2.0
0.5
B
0.002
0.00060.006
Zr
0.03
-
Mo
0.53
2.0
Ni
Bal
Bal
chemical compositions between alloy 740H and alloy 740. The total atomic fractions of
precipitation-strengthening elements Ti, Al and Nb of alloy740H are larger than that of alloy 740
especially for Al fraction.
(b)
[110]
[110]
Figure 3: TEM images and SAD patterns of (a) and (b) M23C6 of alloy 740H
Table 2: Fractions of the precipitates of alloy 740H (wt.%)
Precipitate
MC
M23C6
coarsening, the shape of particle is also changed from global to cubic. The cubic shape
indicates that there is a large mismatch degree of crystal lattice between matrix and phase. It
is worth mentioning that there isnt phase formation nearby the grain boundary and also no free zone nearby the grain boundary. On the contrary, phase was found to accumulate at or
nearby the grain boundary. This is different from the alloy 740, in which phase forms very fast
nearby the grain boundary and then a -depletion zone happens at and above 750 during longterm aging or creep-rupture test.
(b)
M23C6
M23C6
[211]
Figure 5: TEM images of (a) and (b) M23C6 of alloy 740H after creep-rupture test at 750
SEM image in Figure 6 shows microstructure of alloy 740H after creep-rupture test at 800
/160MPa for 2807h. The growth of particles in the grain and carbides at grain boundary is
remarkable and also no other phase can be found in this sample.
The morphologies of particles and grain boundary carbides of the sample after creep-rupture
test at 800 are shown in Figure 7. The phase was also found to form at or nearby the grain
boundary. The average dimension of phase is about 130nm. Same as in Figure 5, the phase,
269
grain boundary carbide also have same orientation relationship with the matrix in [110] and
[211] zone.
(b)
M23C6
M23C6
[110]
[211]
Figure 7: TEM images of (a) and (b) M23C6 of alloy 740H after creep-rupture test at 800
SEM microstructure of the alloy 740H after creep-rupture test at 850/100MPa for 2943h is
shown in Figure 8. There are many big size particles form at and nearby the grain boundary.
This is same as the samples crept at 750 and 800. Figure 9 shows the morphologies of
phase and carbide of the sample after creep-rupture test at 850 and their distributions are same
as in former figures. The average size of phase is about 270nm. The size homogeneity of
particles of the sample creep-rupture test at 850 is worse than the former samples after creeprupture test at 750 and 800.
From the above results of microstructure of samples creep-ruptured at 750, 800 and 850,
except for the phases of , MC and M23C6, no other phase was found in the samples after creeprupture test. The coarsening of particle is the main style of structure evolution. Even the
rupture life is different, the creep test temperature also can be considered as the major influencing
factor on the growth rate of phase. With different from the previous alloy 740, although the
270
creep test temperature is relatively high, the formation of phase nearby the grain boundary and
the transformation of -to- phase t didnt happen in the crept samples of alloy 740H.
(b)
M23C6
Figure 9: TEM images of (a) and (b) M23C6 of alloy 740H after creep-rupture test at 850
On the formation and accumulation of at and nearby grain boundary, the reason can be
explained as follows. The surrounding area of matrix around the carbide particle has a different
composition from the matrix composition. Both chemical phase analyses and Thermo-calc
predictions, shown in the following Figure 11, Table 3 and Table 4, reveal that M23C6 carbide
contains no Nb, Al and Ti and only small amounts of Ni and Co. As a consequence, the matrix
region surrounding the carbide is rich in the rejected -forming elements, and Cr as a M23C6forming element is depleted in this region. Thus phase is easy to nucleate and finally
precipitate at or nearby grain boundary.
Calculation of precipitate stability of alloy 740H
The calculated equilibrium phase diagram of the alloy 740H is shown in Figure 10 by Thermocalc software using exact chemical compositions in Table 1, in which all the predicted
equilibrium phases and their weight fractions are given. Thermodynamic calculation result
271
reveals that the equilibrium phases above 600 include , , , , MC and M23C6. The stable
temperature scopes of precipitate of the alloy, , and , are 766, 920~1100, and
1021, respectively. The predicted solidification temperature range of this alloy is about 65
and the solid phase and liquid phase coexist at temperatures between 1304 and 1369.
Compared with the calculation results of alloy 740 [7, 9, 10], the fraction and dissolution
temperature of phase increase dramatically and the stable temperature scope of phase also
becomes narrow and especially no phase forms in the potential operating temperature scope of
750-800 in A-USC units.
1304
1369
Weight fraction
Liquid
1021
1100
766
920
M23C6
MC
Temperature /
Figure 10: Calculated phase diagram of alloy 740H showing equilibrium phase and their weight
fractions
The compositions of precipitates were also calculated by Thermo-calc and the change tendencies
of major elements are presented in Figure 11. For the composition of phase, with the increase
of equilibrium temperature, the fraction of Ni decreases and the fractions of Co and Cr increase
slightly. However, the fractions of precipitation-strengthening Al, Nb and Ti almost keep same
with the temperature increasing and the fraction of Ti is larger than those of Nb and Al. For the
composition of M23C6 carbide, with the increase of equilibrium temperature, the fractions of Cr,
Co and Ni increase slightly and the fraction of Mo decrease obviously. M23C6 carbide is rich in
Cr and the fraction of Cr accounts for about 75%. For the composition of MC carbide, with the
increase of equilibrium temperature, the fraction of Nb decreases and the fraction of Ti increase.
The fraction of Nb is much more than the fraction of Ti in the composition of MC carbide.
The calculated phase compositions of precipitates at 800 are shown in Table 3 and the
measured phase compositions of precipitates at standard heat-treatment state by chemical phase
analysis are shown in Table 4. Thermodynamic calculation is on the basis of complete balance of
the system. Although there is deviation between the results of calculated and measured, the
calculated results have good agreement with the experimental results and the major composition
and their variation trend of the precipitates are almost same. The big difference is the calculated
composition and measured composition of MC carbide. The results of calculation and
measurement show that M23C6 carbide is very rich in Cr, and it is based on Cr23C6 with some Mo,
272
Co and Ni replacing the Cr, and that it is obvious that is (Ni,Co,Cr)3(Ti,Nb,Al) and MC carbide
is (Nb,Ti)C with small amount of Mo and Cr in it.
0.9
0.8
(a)
(b)
0.7
Ni
Co
Ti
Nb
Al
Cr
0.6
Ni
Co
Ti
Nb
Al
Cr
0.1
0.0
Weight Fraction / %
Weight Fraction / %
0.8
600
700
800
900
Cr
0.7
Cr
Mo
C
Co
Ni
0.6
Mo
0.1
0.0
1000
C
Co
Ni
600
Temperature /
700
800
900
1000
Temperature /
0.9
(c)
Weight Fraction / %
0.8
0.7
Nb
Nb
Ti
C
0.6
0.2
Ti
C
0.1
0.0
600
700
800
900
1000
Temperature /
Figure 11: Calculated phase compositions of alloy 740H ((a) , (b) M23C6 and (c)MC)
Table 3: Calculated compositions of precipitates of alloy 740H by Thermo-calc(wt.%)
M23C6
MC
Cr
Co
Mo
Nb
Ti
Al
Ni
5.390
11.460
1.751
77.747
0.130
9.023
3.620
0.029
10.669
0.069
6.874
78.450
7.272
9.891
5.451
69.601
3.261
M23C6
MC
Cr
Co
Mo
Nb
Ti
Al
Ni
5.582
14.997
6.811
84.266
0.455
4.818
3.688
0.191
1.425
0.408
5.175
52.418
6.591
31.722
5.142
71.272
5.040
From Figure 10, the fractions of precipitates also can be predicted and the precipitates at 800
are 21.7% weight percent and 0.6% weight percent M23C6. These results are higher that the
experimental results shown in Table 2, which is from the samples aged at 800 for 5h and
therefore it is not in a complete equilibrium state theoretically. Generally, thermodynamic
calculations correctly predicted almost all the phases and their compositions in this alloy, except
harmful phase, which was not founded in the sample of creep-rupture test at 750. This is
273
probably due to the relatively poor assessment of the thermo-dynamic parameters for phase.
Either thermodynamic calculations probably overpredicted the stability of phase, or it is
possible that phase precipitation is some very sluggish and the exposure time was not so long
enough to form this phase. In addition, it is noted that the thermodynamic calculation predicts the
formation of phase between 920 and 1100. The results of calculation and measurement
didnt reveal the existence of phase in alloy 740H crept at temperature between 750 and
850, which forms very fast above 750 in original alloy 740. However, the temperature scope
of experiment carried out doesnt cover the range of 920-1100and the existence of phase
cannot be confirmed in the present stage.
CONCLUSIONS
Inconel alloy 740H after creep-rupture test at elevated temperatures was investigated on its
microstructural evolution and precipitate stability by means of SEM, TEM, chemical phase
analysis and Thermodynamic calculation. The precipitates observed in this alloy are , M23C6
and MC. The phases of , M23C6 and MC are mainly composed of Ni3(Ti,Nb,Al), Cr23C6 and
(Nb,Ti)C respectively. After creep-rupture test at 750, 800 and 850, the category of phase
doesnt change and the major difference is the growth of particle. The particle dimension of
phase increases fast with the increasing of creep temperature. No , G and phase were found in
all samples.
Thermodynamic calculation predicts that the structure stability of this alloy including the stable
temperature, fraction and composition of , M23C6 and MC. The calculated phase compositions
of , M23C6 and MC are in good agreement with experimental results of chemical phase analysis.
REFERENCES
[1] R. Blum, Advanced (700oC) PF Power Plant, EC Contact No SF/1001/97/DK(1997).
[2] R. Blum, Vanstone R.W., and Messelier-Gouze C., Materials Development for Boilers and
Steam Turbines Operating at 700, Proceedings from the Fourth International Conference
on Advance in Materials Technology for Fossil Power Plants, Hilton Head Island, South
Carolina, October 25-28, 2004, pp.116-136.
[3] R. Viswanathan, J. F. Henry, J. Tanzosh, G. Stanko, J. Shingledecker, and B. Vitalis, U.S.
Program on Materials Technology for USC Power Plants, Proceedings from the Fourth
International Conference on Advance in Materials Technology for Fossil Power Plants,
Hilton Head Island, South Carolina, October 25-28, 2004, pp.3-19.
[4] M. Fukuda, E. Saito, Y. Tanaka, T. Takahashi, S, Nakamura, J. Iwasaki, S. Takano, S.
Izumi, Advanced USC Technology Development in Japan, Proceedings from the Sixth
International Conference on Advance in Materials Technology for Fossil Power Plants,
Santa Fe, New Mexico, August 31-September 3, 2010, pp. 325-341.
[5] G. D. Smith, S. J. Patel, N. C. Farr, The corrosion resistance of nickel-containing alloys in
coal-fired boiler environments Paper presented at Corrosion 99, San Antonio, Texas,
April, 25-30, 1999, pp.12.
[6] G. D. Smith, H. W. Sizek, Introduction of an advanced superheater alloy for coal-fired
boilers Paper presented at Corrosion 2000, Orlando, Florida, March, 26-31, 2000,
pp.00256.1.
274
275
ABSTRACT
Delivered condition of Inconel740H specified in ASME Code Case 2702 is solution heat treated
and aged condition, fabricating performances are also based on the condition, and a re-annealing
and aging shall be performed if cold forming to strains is over 5%. These almost harsh requirements bring great inconvenience for its engineering practice and utilization. The comparative
bending tests on 740H tubes in solution heat treated + aged condition and solution heat treated
condition were performed, and the rules reasonability of the specification on delivered condition
was discussed and analyzed from point view of deformability and weldability in the paper. The
bending test results showed that tube bent was difficult because of its high strength and limited
deforming capacity in solution heat treated + aged condition. Therefore, the material supplied in
the solution condition may be better from fabricating points. Whether re-solution for the bent
tube is performed after bending depends on its bending radius, followed by welding and post
weld heat treatment of component (this treatment can also be the aging treatment for annealed
sector at the same time), this treating manner can meet regulatory requirements. For solution
tubes, however, there are some inconveniences to its engineering application because fewer researches were carried out on its properties up to now, and no regulations on them were given for
the material in the specification. Suggestions are: 1) deeply investigating the properties of tubes
in solution condition, including mechanical and fabricating performances, 2) adding the mechanical properties, maximum allowable cold forming to stain without performing re-solution and
weld strength reduction factor of solution material to the code case.
1. INTRODUCTION
Inconel740H, a Ni-based super-alloy, is further modified by Special Metals Corporation on the
basis of Inconel740 developed from alloy Nimonic263. The alloy has better oxidation and fireside corrosion resistance because of being of higher Cr and lower Mo content, very good creep
rupture strength because of more dispersed precipitation of and its stability after adding of Al,
Ti and Nb. Now, Inconel740H was approved by ASME code case 2702 in September, 2011, and
is as an important candidate tube for A-USC boiler parts with about a temperature of 750[1-2].
The delivered condition specified in ASME Code Case 2702 is material shall be supplied in the
solution heat treated and aged condition. Following regulations such as allowable stress, fabricating performances and control of cold strains without re-annealing are also specified based on
the aged condition.
Of course, the tube shall be used in solution annealed and aged condition because the tube in this
condition will have better strength and good structural stability. However, aged hardenable alloys
276
are of poor formability, compared with those of annealed condition, especially for parts needing
bending or welding.
The comparative bending tests on 740H tubes in solution heat treated + aged condition and solution heat treated condition were performed and the rules reasonability of the specification on
delivered condition was discussed and analyzed from point view of deformability and weldability
required in boiler manufacturing processes in this paper, it is expected that this may be helpful for
the perfect of the specification and easy to be used in the future.
2. MATERIALS AND EXPERIMENTAL PROCEDURES
2.1. Test Materials
The materials used in this experiment were 740H tubes, with the dimension of 50.88 and
chemical compositions shown in Table 1.
Tubes in solution annealed (referred to as simply SA): Provided by Special Metals Corporation.
Tubes in solution annealed + aged (referred to as simply "SG"): Cut from tubes in SA, and
aged as per ASME Code case 2702, the same as aged by SMC: at 800oC for 4 hours, followed by
air cooling. The mechanical properties at room temperature were shown in Table 2.
Table 1: Chemical compositions
Element
Composition
(wt)
Element
Composition
(wt)
C
0.005
0.08
Ti
0.5
2.5
Mn
Fe
Si
Cu
1.0
3.0
0.03
1.0
0.50
Co
15.0
22.0
Mo
Cb+Ta
0.5
2.5
B
0.0006
0.006
2.0
0.03
Cr
23.5
25.5
Zr
Al
0.2
2.0
0.02
277
As shown in Figure1, solution annealed tube exhibited excellent cold deformation capacity, metal
deformed uniformly, there was no wrinkle, deflated and appearance quality defects on the elbow
in Figure1-a.
Compared to elbow made by solution annealed tube, elbow from aged tube had relatively poor
cold deformation ability, uneven deformation, obvious transition zone, obvious rebound and apparently deflated uniform deformation region on the elbow in Figure1-b.
This phenomenon was closely related to the different strengths in two conditions, because of the
stronger strength, the greater resistance deformation, the harder deformation. Aged tube had
higher strength, hardness and lower ductility than annealed tube, as stated in Table 2. Therefore,
annealed 740H tube had better cold deforming ability than the aged tube.
a) SA
b) SG
a) SA
b) SG
mation resulted in stress concentration during hot extrusion deformation, the plastic flow of partial location was affected and defects prone to be produced in pre-cold elbow. On the other hand,
because of very high heating rate and no keeping time, strengthening phases in the alloy cannot
completely be re-solution annealed into solid solution; these residual phases would block dislocation movement in plastic deformation. Therefore, pre-cold elbow in aged condition appeared
lesser hot ductility and larger deformation resistance than those of annealed, and was worse hot
bend ability.
The results from tests mentioned above showed that annealed tubes has much better formability
than that of aged tubes, whether it is cold forming or hot forming.
On the other hand, alloy microstructures markedly influenced its weldability. Annealed alloy,
phases mainly solved in solution, was in softened condition with lower strength and better ductility; In contrast, aged alloy with precipitated and dispersed phases, and higher strength and lesser ductility, enhanced the restraint degree during welding and increased sensitivity of the welding
crack[3]. At the same time, since there were some low melting of eutectic phases at grain boundaries for the aged alloy, liquation crack was easy to form while welded, so welding for precipitation strengthening alloy is better to be performed in annealed condition as far as possible.
4. DISCUSSION OF CONDITION SPECIFIED IN ASME CODE CASE 2702
Reply (a) in ASME Code Case 2702 specified that Material shall be supplied in the solution heat
treated and aged condition. Solution heat treatment shall be performed at 2010F (1100) minimum for 1 hour per inch (25 mm) of thickness but not less than hr. Aging shall be performed at
1400F to 1500F (760 to 816) for 4 hours minimum up to 2 inches (50 mm) of thickness,
plus an additional hour per additional inch (25 mm) of thickness. Aging shall be followed by
air cooling. This regulation for the alloy means that alloy delivered condition by manufacturer of
tube or pipe is solution annealed and aged. Allowable stress in Reply (b) and fabricating performances such as Reply (c), (d) and (e) are also based on the aged condition.
In Reply (e), the regulation is After cold forming to strains in excess of 5%; after any swages,
upsets, or flares; or after any hot forming of this material, the component shall be heat treated in
accordance with the requirements specified in (a) above. No local solution annealing may be performed. The entire affected component or part that includes the cold strained area and transition
to unstrained material must be included in both heat treatments.
However, deformation strain of all elbows will exceed 5% in the manufacturing process of actual
boiler parts; these almost harsh requirements bring great inconvenience for its engineering practice and utilization. From point view of fabricating, as mentioned above in bending tests results
and discussions, firstly, boiler parts with elbows have difficulty manufacturing by aged alloy
with poor bending performances and weldability; Second, even if they are able to be fabricated
into component, followed complete solution annealing of the parts would have huge work; Third,
because of solution annealing temperature very high, fabricated parts re-annealed would face the
problem of difficulty correcting deformation caused by high annealing temperatures; Finally, if
fabricator is to re-anneal in-work for bending after purchased from manufacturer of aged tube and
then bending, this will cause the waste of resources and increase of costs.
Of course, the tube shall be used in solution annealed and aged condition because tube in this
condition will have better strength and good structural stability. However, material in solution
heat treated will be better from engineering practice as solution tube has good forming performance from the test results mentioned above.
There may be a way out of the dilemma. Actually, whether elbows from solution tubes were resolution annealed or not depends on the bending radius (namely the strains), welding and post
weld heat treatment (PWHT) followed. This PWHT may also be as aging treatment for parent
solution tube, elbow (re-solution or not) and weldments. This can meet the requirements of appli-
279
cation condition specified in the case, and the treating manner may be an access to possible engineering application for the tube, too.
However, all properties are specified in aged condition and there are no regulations on annealed
condition in the specification, it is necessary to deeply study the properties in solution annealed
later, such as mechanical properties, welding, cold and thermal forming performance, so that requirements on solution tube can put forward into the case. For example, 1) mechanical properties
for annealed tube at room temperature may be added in Table 2; 2) are the other welding methods
allowed to be used? Reply (c) may give answer; and, 3) Reply (e) may answer what strain for the
elbow needing re-solution annealing, because annealed tube seems may not be same as strains in
excess of 5% of requirements for aged tube.
5. CONCLUSIONS
From comparative bending tests on 740H tubes in solution heat treated + aged condition and solution heat treated condition and mentioned analysis above, the conclusions and suggestions are
as follows:
(1)Annealed tubes has much better formability than that of aged tubes, whether it is cold forming
or hot forming.
(2)Suggestions: a) deeply investigating the properties of tubes in solution annealing condition,
including mechanical and fabricating performances; b) adding the regulation on the solution annealing tubes, such as mechanical properties, maximum allowable cold forming to stain without
performing re-solution and weld strength reduction factor of solution material to the code case.
ACKNOWLEDGMENTS
The financial support from the National Energy Utilization Technology Research and Engineering Demonstration Program of China under grant No. NY20110103A-1 and materials support
from Special Metals Corporation are greatly acknowledged.
REFERENCES
[1] S.J. PATEL. Introduction to Inconel alloy 740: an alloy designed for superheat tubing coal
fired ultra supercritical boilers, Acta Metallurgica Sinica (English Letters), Vol.18, No.4
(2005) , pp.479-488.
[2] S.Q. Zhao, Y. Jiang and J.X. Dong. Experimental Investigation and Thermodynamic Calculation on Phase Precipitation of Inconel 740, Acta Metallurgica Sinica (English Letters),
Vol.19, No.6 (2006), pp.425-431.
[3] J.T. Guo. Materials science and engineering for super-alloys (Part II). Beijing: Science Press,
(2009), pp.425-427 (in Chinese).
280
ABSTRACT
Sufficient available energy in combination with lowest environmental pollution is a basic
necessity for a high standard of living in every country. In order to guarantee power supply for
future generations it is necessary to use fossil fuels as efficient as possible. This fact calls for the
need of power plants with improved technologies to achieve higher efficiency combined with
reduced environmental impact. In order to realize this goal it is not only a challenge for power
station manufacturers, but also for manufacturers of special steels and forgings, who have to
produce improved components with more advanced materials and more complex manufacturing
processes.
This paper reports about experiences in the fabrication of forged components for gas and steam
turbines followed by achievable mechanical properties and ultrasonic detectability results. The
materials are the creep resistant martensitic Cr steels developed in the frame of the European Cost
research programme.
Whereas Boron containing 10% Cr steels are suitable for steam temperatures of 625C and
slightly higher, Ni-based alloys shall be used for temperatures of 700C and above. One pilot
rotor forging, representing a HP-rotor for welded construction, has been manufactured out of
alloy Inconel 625 within the frame of the European Thermie project AD700.
KEYWORDS
Forgings for power generation, melting processes, Cost programme, 10% Cr steels, Boron
containing 10% Cr, Cost E, F and FB2, properties, AD700 project, Inconel 625
INTRODUCTION
The continuous trend towards more economic electricity production in parallel with reduced
environmental pollution can only be sustained by improving the thermal efficiency of power
generation plants. The efficiency is increased by raising the temperature and also the pressure of
the steam which finally results in the need for improved materials for the boiler and turbine
design.
Since many years Boehler Edelstahl GmbH & Co KG is a premium supplier of forged
components for the power generation industry, e.g. discs, centre shafts, turbine shafts, shaft
components and accessories for gas and steam turbines. Based on a complete range of special
steelmaking equipment, consisting of an electric steel plant (electric arc furnace, AOD converter,
secondary metallurgy equipment), a special melting shop with vacuum and re-melting facilities
281
(VIM-VAR, ESR, PESR), a 52 MN hydraulic forging press and the R&D support of FEM
modelling to achieve a uniform deformation, Boehler is in a good position for the manufacture of
high-quality forgings, which are further processed in downstream facilities for heat treatment,
machining and testing.
Our customers are counted among the most important manufacturers of steam and gas turbines
such as Siemens, Alstom and licensees.
Seen from the material side Boehler manufactures all the typical steels introduced in energy
engines application so far, but more or less focussed on higher alloyed steels (Figure 1).
Materials
Analysis [%]
DIN
Bhler
Si
Mn
Cr
Mo
Ni
V116
0,30
0,06
0,30
1,50
0,40
2,90
0,10
<0,010
0,40
3,70
0,10
<0,010
26NiCrMoV 11 5
26NiCrMoV 14 5mod
(Super Clean)
V128SA
Al
Nb
30CrMoNiV 5 11
D102
0,32
0,10
0,80
1,10
0,65
0,30
<0,010
X20CrMoV 12 1
T550
0,22
0,30
0,50
0,30
<0,015
T505
0,12
0,10
0,75
0,18
T507
0,12
0,10
0,60
0,18
T559
0,13
0,10
0,35
0,15
0,25
X12CrMoWVNbN 10 1
(COST E)
X12CrMoVNbN 10 1
(COST F)
X12CrMoCoVNbB 9 1
(COST FB2)
1,30
Co
9,50
1,50
1,30
0,030
0,010
Figure 1: Most common materials for gas and steam turbine components in Europe
Those higher alloyed steels are specifically the 9-10% Cr class, developed in the frame of the
European Cost research programme, where Boehler Edelstahl participated since 1987 (Cost 501),
manufacturing experimental heats as well as trial rotor shafts. Today Boehler is also active in the
current KMM-VIN action, the continuation of Cost.
During the last years Boehler Edelstahl Open Die Forge has gained a lot of experience in the
manufacturing of forgings in highly alloyed steels. Many rotor forgings, discs and hollow shafts
have been manufactured for high temperature applications primary in the creep resistant
chromium steels COST grade E (10%CrMoWVNbN), grade F (10%CrMoVNbN) and also FB2
(9%CrMoVNbNB). Figure 2 gives the scope of the forgings produced so far, covering all turbine
relevant components.
Quantity
Product
Cost E
Cost F
Cost FB2
GT-Discs
924
---
---
Hollow Shafts
414
---
---
HP-Shafts
101
60
113
195
---
282
Fig. 3: FEM model for optimised forging steps to achieve uniform deformation
and reproducibility
When forged, the preliminary heat treatment is of great importance in order to provide the
necessary preconditions. After pre-machining, the QHT is performed by austenitising at 1050C
followed by double tempering to a yield strength 800 N/mm2, machining for ultrasonic testing
(UT), mechanical testing and final machining. The achieved ultrasonic detectability as well as
FATT test results are shown in Figure 4.
283
284
Fig. 5: Relationship of sound path and final ultrasonic detectability (COST F steel)
Figures 6-7 show some examples of forgings produced for the power generation industry.
Si
Mn
Cr
Mo
Ni
Co
Nb
B2
0,17
0,07
0,06
9,3
1,55
0,12
0,27
0,064
0,015
0,010
0,13
0,05
0,82
9,32
1,47
0,16
0,96
0,20
0,05
0,019 0,0085
0,13
0,09
0,33
9,08
1,43
0,16
1,26
0,22
0,054
0,022 0,0076
285
The first full size FB2 rotor forging with a final weight of 17 to was manufactured by Boehler in
2000-2001 via the Best melting route; then forgings from Societa delle Fucine Terni / Italy
(conventional steel making method) and Saarschmiede (ESR process) followed. Manufacturing
the test melts, trial rotor forgings and test results have already been reported in several papers
[10-13].
The results of creep tests gained so far show that all data lies in one narrow scatter band
confirming the trial melt behaviour of FB2. In Figure 9 [11] the values are all above the rotor B2
line, a Boron containing steel from COST 501 and the basis for the development of FB2.
During creep, under the influence of temperature and stress, usually dislocation densitiy
decreases, sub-grains form und grow, M 23 C 6 particles coarsen, the martensite laths become much
wider and also new phases as the Laves phase, appear. Not so in FB2; the good high temperature
stability is caused by:
- a martensitic structure with narrow martensite laths; which are decorated with and
therefore stabilised by M 23 C 6 carbides, stabilised itself by Boron [15]
- a high dislocation density, which is preserved for longer times
- and Nb, V carbonitrides (up to about 1 m); which avoids grain growth during
austenitisation and are stable during creep.
A representative TEM image of steel FB2 is shown in Figure 10, [14]
Under the influence of temperature, Laves phase also appears in FB2, but very small (0-6-0,8m)
and homogeneously distributed and therefore has no negative effect on creep.
The excellent creep resistance of FB2 and the successful transformation of trial melt behaviour to
large components led to the start of industrial production and to orders for new USC power plant
projects in Germany, USA and Asia, which have been placed within the last years.
2.2.1. Experiences in manufacturing FB2 rotor forgings
Based on the experience with the Cost FB2 trial rotor forging, the manufacturing technology had
to be fitted to the appropriate dimensions and the melting route has been changed from Best to
conventional casted ingots with total weights of 22 to 28 to due to the smaller dimensions of the
286
shafts. Till today seven forgings have been manufactured with delivery weights from 7 to 9,2
metric to.
The basic manufacturing steps for the forgings were set as follows:
Melting the steel in an EAF, than ladle furnace followed by AOD and LF with VD, casting the
ingot by bottom pouring process, homogenising, hot-forming, preliminary heat treatment, premachining, ultrasonic testing, quality heat treatment (QHT), machining and final testing (Figure
11).
Fig. 12: Quality heat-treated and machined FB2 Forging; final weight 9,2 to
287
80
60
40
20
670
680
690
700
710
Fig. 13: Yield strength and Charpy impact properties of FB2 rotors
In addition, short-term creep tests at 600C and 160 MPa load were performed on one shaft part
at t = 1300h in order to compare the creep behaviour with the results achieved on the FB2 trial
melt and the FB2 trial rotor forging from the Cost programme. Four test specimens in total, one
from each test location, were taken in tangential direction, two from the edge and two further
from the near centre position. The achieved results, plotted as a creep strain versus time curve, are
shown in Figure 14.
Up to 1200 hours testing time the creep strain is on an average on the same level as the FB2 trial
rotor.
0,45
0,40
0,35
0,30
0,25
Temp. = 600C
Stress = 160 MPa
0,20
0,15
0,10
0,05
0,00
0
200
400
600
800
1000
1200
1400
1600
Time [hrs]
Fig. 14: Results of short term creep testing in comparison to FB2 trial melt
as well as trial rotor forging
Metallographic examinations showed, that the microstructure in the edge as well as the near
centre position are tempered martensite with a grain size of 0-1 acc. to ASTM E112 in the edge
and about 00 in the near centre area. Furthermore, in all examined sample locations the
microstructure was free of -ferrite, but contained some isolated Boron nitrides.
288
In order to check the homogeneity of the chemical composition and in particular the distribution
of Boron, analysis checks were carried out again at the end positions and the near centre area.
Figure 15 represents 5 investigated forgings so far. It can be seen, that the chemical composition
is very homogenous from top to bottom as well as from edge to centre related to the ingot. The
scatter of max 8 ppm Boron over the length / cross section of the ingot demonstrates an excellent
Boron distribution.
In order to improve the quality of the forgings especially MDDS, development work is carried
out mainly in respect of further improvement the grain size for a better ultrasonic detectability.
290
REFERENCE
(1) Berger C., Mayer K.H., Jaffe R.I.; Superclean 3,5% NiCrMoV Rotor Steel for
advanced Steam and Gas Turbines; 3rd Int. Conference on Improved Coal-Fired
Power Plants EPRI-Meeting, San Francisco, April 1991
(2) W. Meyer, R. Bauer, G. Zeiler: Development of Production Technology and
Manufacturing Experiences with Super Clean 31/ 2 NiCrMoV Steels, Conf. on
Superclean Steel, London, UK, March 6-7, 1995, Proc. p. 89-100
(3) Berger C., Scarlin R.B., Mayer K.H., Thornton D.V., Beech S.M.; Steam turbine
materials: high temperature forgings October 3-6, 1994, Liege, Belgium.
(4) C. Berger, S.M. Beech, K.H. Mayer, R.B. Scarlin, D.V. Thornton; High
Temperature Rotor Forgings of High Strength 10% CrMoV Steel; Chicago, Illinois,
September 11-17, 1994
291
(5) T.U. Kern, K.H. Schoenfeld; Improved 10% CrMoWVNbN Steel for Gas Turbine
(7) Meyer W., Zeiler G., Bauer R.; Recent Developments on 9 to 12% Chromium
Steel Open Die Forgings for Steam and Gas Turbine Applications at Boehler;
14th International Forgemasters Meeting, 03-08. September 2000, Wiesbaden.
(8) T.U. Kern, M. Staubli, K.H. Mayer, K. Escher, G. Zeiler; The European Effort
in Development of new High Temperature Rotor Materials up to 650C COST
522, 7th Liege COST Conference, 29. Sep.-Oct. 2002, Liege, Belgium
(9) K.H. Mayer, T.U. Kern, K.H. Schoenfeld, M. Staubli, E. Tolksdorf; Long-term
Investigations of Specimen of 8 Production Rotors manufactured of the Advanced
Martensitic 10% Cr-Steels X12CrMo(W)VNbN 10 1 1, 14th International
Forgemasters Meeting, 03-08. September 2000, Wiesbaden, Germany.
(10)
(11)
(12)
(13)
(14)
(15)
(16)
292
ABSTRACT
Microstructural change of 10 % Cr steel trial forgings subjected to different heat treatment
conditions which aim to improve the creep rupture strength and microstructural stability during
creep was investigated. Creep rupture strength of the forging subjected to the quality heat
treatment with the austenitizing temperature of 1090 oC is higher than that of the forging solutiontreated at 1050 oC, however, the difference of creep rupture strength is reduced in the long-term
region around 40,000 h. Decrease in creep rupture ductility of the forging until 43,300 h is not
observed. Progress of the martensite lath recovery in the forging solution-treated at 1090 oC is
slower than that in the forging austenitized at 1050 oC. Higher temperature solution treatment
suppresses the recovery of lath structures. Formations of Z-phase are found in the specimens
creep-ruptured at 37,300 h in the forging solution-treated at 1050 oC and at 43,400 h in the
forging austenitized at 1090 oC. Z-phase precipitation behavior in this steel is delayed in
comparison with the boiler materials, regardless of austenitizing temperature.
KEYWORDS: 9-12 % Cr steels; turbine rotors; forgings; heat treatment; microstructure
INTRODUCTION
Higher creep strength is required for turbine components for fossil fuel power generations since
the generating efficiency increases with increase in steam temperature. Alloy design is one of
important factors to improve the creep rupture strength of 9-12%Cr steel turbine rotor forgings as
well as the boiler materials and a lot of research work on alloy design has been done [1-4].
However, the effect of heat treatment conditions, particularly solution temperature in the quality
heat treatments on creep rupture strength and microsturctural stability during creep exposure
remains unclear, whereas they control the microstructures which affect the creep deformations.
For instance, in CrMoV steel turbine rotors, it is well known that the long-term creep strength
with notched specimens is lower than that with smooth specimens in the case of forgings
austenitized at 1010 oC, so that the solution temperature is restricted to 954 oC at the highest [5].
Based on these experiences, the selection of solution temperature is very important in the case of
low alloy steel rotor forgings, but there are not so many reports regarding the effect of
austenitizing temperature on creep strength. Thus, 10 % Cr steel trial forgings have been
subjected to different heat treatment conditions in order to investigate a possibility of
293
improvement in the creep rupture strength and microstructural stability of them by means of
higher temperature solution treatment, and their creep strength and microstructural change during
creep exposure have been investigated [6, 7]. The results of previous work have revealed that the
creep strength of the forging solution-treated at higher temperature was higher than that of the
forging austenitized at lower temperature until 30,000 h testing time [7]. This paper describes the
results on creep rupture tests and investigations of the microstrucural evolution after 43,400 h
creep exposure.
EXPERIMENTAL PROCEDURES
Two trial rotor forgings examined were made from a single ingot with the weight of 69.5 metric
ton. These two forgings were manufactured through same process from the steel and ingot making
to the preliminary heat treatments [6]. In the quality heat treatments, forging-A was solution
treated at 1050 oC, and another forging-B was done at 1090 oC as shown in Figure 1. After that,
each forging was quenched in oil followed by double temperings (T T1 , T T2 ) and additional
tempering (T A ) treatments. Materials for creep tests and microstructural investigations were cut
from center of both forgings. There is no large difference in chemical composition between the
both materials as shown in Table 1. Detail information of the manufacturing sequence of forgings
are described in the previous work [6, 7]. The specimen dimensions for creep tests are 5.5 mm
7.1 mm in diameter and 25 mm in gage length, the testing temperature is 600 oC. Observations of
microstructure were performed by optical microscope, transmission electron microscope (TEM)
and scanning electron microscope (SEM) equipped with electron back scattered diffraction
(EBSD) system. Analyses of precipitates with carbon extracted replicas were examined by
scanning transmission electron microscope (STEM) with energy dispersion X-ray (EDX)
analyzer.
Additional
Tempering
TT1
TT2
TA
Forging-A
1050C
(1922F)
570C
(1058F)
680C
(1256F)
680C
(1256F)
Forging-B
1090C
(1994F)
570C
(1058F)
685C
(1265F)
690C
(1274F)
Oil
Quenching
TT1
TT2
Furnace
Cooling
Furnace
Cooling
TA
Additional
Tempering
Furnace
Cooling
Si
Mn
Ni
Cr
Mo
Nb
Forging-A 0.12 0.06 0.43 0.008 0.001 0.76 10.45 1.04 1.02 0.20 0.047 0.053
Forging-B 0.13 0.07 0.44 0.009 0.001 0.78 10.52 1.07 1.03 0.20 0.052 0.054
RESULTS AND DISCUSSIONS
Creep Rupture Strength of Trial Forgings
Figure 2 shows the creep rupture strength (a) and creep rupture ductility (b) of two trial forgings
as a function of time. Creep tests under 100 MPa continue beyond 60,000 h. Creep rupture
strength of the forging-B solution treated at 1090 oC is higher than that of the forging-A
austenitized at 1050 oC, however, the difference of both curves is reduced in the low stress and
long-term region around 40,000 h as shown in Fig.2 (a). On the other hand, the creep rupture
ductility of specimen ruptured at 43,300 h in the forging-B still keeps higher level, and a decrease
in ductility at long-term exposure is not observed in spite of higher solution temperature. Further
long-term tests are required to evaluate the efficacy of higher temperature solution treatment on
the creep strength.
200
El (%)
Stress (MPa)
300
100
(a)
RA (%)
400
Ongoing
100
90
80
70
60
100
Forging-A (T =1050oC)
Forging-B (T =1090oC)
1000
(b)
Center
80
60
40
Forging-A, T =1050oC
Forging-B, T =1090oC
20
o
10
10
10
10
295
(a)
(b)
200um
(c)
200um
(d)
200um
200um
Figure 3: Optical micrographs after additional tempering heat treatment of forging-A (a),
forging-B (b), after creep rupturing at 37,300 h in forging-A (c) and at 43,400 h in forging-B (d).
TEM images of specimens after the additional tempering heat treatments and creep exposures are
shown in Figure 4. Whereas fine martensitic lath structures containing high-density dislocations
are observed after the additional tempering heat treatments in Figs. 4 (a) and 4 (b), coarsened
laths with low-density dislocations and cell-like sub-grain structures are found after creep rupture
in Figs. 4 (c) and 4 (d). Martensitic lath widths after the additional tempering heat treatment of the
both forgings are estimated to be about 0.5 m, and those width after creep rupturing of the both
forgings are estimated to be around 1 m. Figure 5 shows some preferential recovery of the lath
structure observed in the creep-exposed specimens of the both forgings at a point distant from
Figs. 4 (c) and (d), respectively. Coarsened sub-grains with about 2 m in diameter are observed
in the fine sub-micro size martensitic lath structure as shown with arrows in Figure 5. It is found
that they are long and thin shape inherited from the initial martensitic lath structures in many
cases, but specific laths in the vicinity of prior austenite grain boundary are coarsened in some
cases. The recovery of martensitic lath microstructure accompanying the preferential recovery
during creep exposure is found from the results of TEM observations. However, the influence of
the solution temperature on martensitic lath width after the additional tempering heat treatment
together with long-term creep exposure is not clear by observations on small area of thin foils.
Then, microstructural observation was performed by SEM equipped with EBSD to investigate the
preferential recovery of lath structure in the large areas.
296
(a)
(b)
2um
(c)
2um
(d)
2um
2um
Figure 4: TEM images after additional tempering heat treatment of forging-A (a), forging-B (b),
and creep ruptured specimens after 37,300 h in forging-A (c) and 43,400 h in forging-B (d).
(a)
(b)
2um
2um
Figure 5: Preferential recovery of lath structures observed in forging-A and forging-B creep
ruptured after 37,300 h in forging-A (a) and 43,400 h in forging-B (b).
297
Figure 6 shows the backscattered electron images of creep ruptured specimens on the both
forgings. There are cell-like structures displayed with gray contrast caused by the difference in
crystal orientations between martensitic laths or blocks as well as bright white particles on the
surface of those specimens. Cell-like sub-grain sizes of the creep ruptured specimen after 37,300
h in the forging-A seemed to be larger than those after 43,400 h in the forging-B. Then, crystal
orientation analyses were examined by EBSD to estimate the degree of lath recovery found in
backscattered electron images clearly. The boundary mapping and the crystal orientation image
around prior austenite grain boundaries on creep ruptured specimen of the forging-A at 37,300 h
are shown in Figure 7, together with the back scattered image. The comparison of the boundary
mapping, Fig. 7 (b), with the crystal orientation image, Fig. 7 (c) indicates that there is a close
correspondence between the prior austenite grain boundaries or the martensitic block boundaries
and the high angle boundary shown by yellow lines in Fig. 7 (c). The martensitic lath boundaries
are unclearly detected and represented as the areas where contain densely low angle boundary in
the case of fine lath structure. On the other hand, they are represented as low angle boundaries in
the case of coarsened lath structure. Therefore, the identifications of the recovered areas in the
microstructures are possible by the observations of grain boundary mapping as shown in Fig. 7
(c). Figure 8 shows the grain boundary maps on creep ruptured specimens of the both forgings.
The progression of recovery towards grain interior of the forging-A is faster than that of the
forging-B during creep exposure since sub-grain sizes expressed by black areas in the forging-A
(Fig. 8 (a)) are larger than those in the forging-B, which is consistent with the observation results
of the back scattered images as described above (Fig. 6). On the other hand, there is the
progression of preferential recovery near the prior austenite grain boundaries in the both forgings
because the areas where the densities of lath boundaries or sub-boundaries are low shown by
white lines are found in the vicinity of prior austenite grain boundary of the both specimens. It can
be said from the results of microstructural investigations that higher temperature solution
treatment seems to suppress the progression of the martensitic lath recovery in the prior austenite
grain.
(a)
(b)
10um
10um
Figure 6: SEM back scatter images of creep-ruptured specimens in forging-A at 37,300 h (a) and
forging-B at 43,400 h (b).
298
(a)
(b)
(b)
15um
15um
Figure 7: SEM back scatter image (a), boundary mapping (b) and orientation image micrograph
(c) after creep rupturing at 37,300 h in forging-A.
(b)
(a)
15um
15um
Figure 8: Boundary mapping after creep exposure at 37,300 h in forging-A (a) and at 43,400 h
in forging-B (b).
299
(a)
(b)
1um
1um
(d)
(c)
1um
1um
Figure 9: TEM images with extract replicas after heat treatment in forging-A (a), forging-B (b),
after creep rupturing at 37,300 h in forging-A (c) and at 43,400 h in forging-B (d)
300
(a)
(b)
1um
(c)
1um
(d)
1um
1um
Figure 10: Elementary mapping after additional tempering heat treatment in forging-A (a),
forging-B (b), after creep exposure at 37,300 h in forging-A (c) and at 43,400 h in forging-B (d).
White arrows showing Z-phase particles.
(a)
(c)
1um
(b)
1um
Figure 11: EDX analysis showing Z-phase particle after creep exposure at 37,300 h in forging-A.
301
Table 2 is a summary of the phases found in this research and the previous work [7] during creep
at 600 oC. Several particles of M 23 C 6 , M 2 X, NbX and few VX exist after the additional tempering
heat treatments, Laves phase appears during short-term creep exposure around 1,000 h but Z
phase is not observed after long-term creep exposure, up to approximately 28,000 h at least in this
steel. It is known that formation behavior of Z-phase in the 9-12 % Cr steels boiler materials is
affected by Cr content and Z-phase appears after 10,000 h in Grade T91 and after 2,500 h in
Grade T122 (11%Cr) at 600 oC [10]. Precipitations of Z-phase in the both forgings are delayed in
comparison with those boiler materials whereas the steel investigated contains Cr of 10.5 %.
Sawada et al. have mentioned that tempering at lower temperature (953 K) provides M 2 X instead
of VX, the presence of such M 2 X does not promote Z-phase formation and no Z-phase is
observed after creep even after 20,000 h in the case of 9Cr-1Mo-V-Nb-N steel [11]. According to
the paper, the reason of retard precipitation of Z-phase in the both forgings is assumed to have a
relationship with the tempering at lower temperature. Also, there is a possibility that the reason of
why the creep rupture strength of the forging-B decreases and close to that of forging-A in the
long-term creep region is connected with Z-phase formation. It may means that solution
temperature does not affects nucleation of Z-phase. However, it is still unclear that reason why the
higher temperature solution treatment suppresses the recovery of the martensitic lath structures
from the results of the phase analyses described above. Further creep rupture data and quantitative
evaluations of the particles in detail are required to assess the efficacy of higher temperature
austenitizing on long-term creep strength.
Table 2: Summary of particle observed in previous and this work.
Phase detected
Specimen
M 23 C 6
M2X
VX
NbX
Laves Z-phase
As HT
y
y
y
y
950h
y
y
y
y
y
Forging-A
T=1050C
15,700h
y
y
y
y
y
37,300h
y
y
y
y
y
y
As HT
y
y
y
y
1,850h
y
y
y
y
y
Forging-B
14,800h
y
y
y
y
y
T=1090C
28,500h
y
y
y
y
y
43,300h
y
y
y
y
y
y
CONCLUSIONS
Microstructural change of 10 % Cr steel trial forgings subjected to different solution tempeature
treatments which aim to improve the creep strength and microstructural stability during creep was
investigated. The results obtained were as follows:
Creep rupture strength of the forging subjected to the quality heat treatment with the
austenitizing temperature of 1090 oC is higher than that of the forging solution-treated at
1050 oC, however, the difference of creep rupture strength is reduced in the long-term
302
region around 40,000 h. Decrease in creep rupture ductility of the forging until 43,300 h is
not observed.
Progress of the martensite lath recovery in the forging solution-treated at 1090 oC is slower
than that in the forging austenitized at 1050 oC. Higher temperature solution treatment
suppresses the recovery of lath structures.
Formations of Z-phase are found in the specimens creep-ruptured at 37,300 h in the forging
solution-treated at 1050 oC and at 43,400 h in the forging austenitized at 1090 oC. Z-phase
precipitation behavior in this steel is delayed in comparison with the boiler materials,
regardless of austenitizing temperature.
REFERENCES
[1] Y. Kadoya, T. Kitai, A. Matsuo, I. Tsuji, M. Kishimoto, T. Tsuchiyama and M. Okamura,
Practical Application of an Advanced 12Cr Rotor to 593oC-700MW, Tetsu-to-Hagane,
Vol. 78 (1992), pp. 910-917.
[2] M. Yamada, O. Watanabe, Y. Yoshioka and M. Miyazaki, Development of Advanced
12Cr Steel Rotor Forgings, Tetsu-to-Hagane, Vol. 76 (1990), pp. 1084-1091.
[3] M. Shiga, Y. Fukui, S. Kirihara, R. Kaneko, F. Ito and S. Sugai, Improved 12Cr Rotor
Forging for Ultra-Super-Critical Steam Turbine, Tetsu-to-Hagane, Vol. 76 (1990), pp.
1092-1099.
[4] C. Berger, S. M. Beech, K. H. Mayer, R. B. Scarlin and D. V. Thornton, High Temperature
Rotor Forgings of High Strength 10% CrMoV Steels, 12th International Forgemasters
Meeting, Chicago Illinois (September 1994)
[5] J. D. Conrad and N. L. Mochel, Operating Experience With High-Temperature SteamTurbine Rotors and Design Improvements in Rotor-Blade Fastening, Trans. ASME, Vol. 80
(1958), pp. 1210-1224.
[6] M. Mikami, Y. Wakeshima, T. Miyata and K. Kawano, Manufacturing Experiences and
Investigation of Properties of 12%Cr Steel Forgings for Steam Turbines, Proceedings of 5th
International Conference on Advances in Materials Technology for Fossil Power Plants,
Marco Island Florida USA (2007).
[7] M. Mikami, Y. Wakeshima and T.Miyata, Creep Rupture Strength and Microstructural
Investigation of 12 % Cr Steel Large Forgings for Ultra-Supercritical Steam Turbine Rotors,
Advances in Materials Technology for Fossil Power Plants, Proceedings of 6th International
Conference, Santa Fe, New Mexico, USA (2010), pp. 408-422.
[8] Strang and V. Vodarek, Z Phase Formation in Martensitic 12CrMoVNb Steel, Materials
Science and Technology, 1996, pp. 552-556.
[9] K. Sawada, H. Kushima and K. Kimura, Z-phase Formation during Creep and Ageing in 912% Cr Heat Resistant Steels, ISIJ International, Vol. 46 (2006), pp. 769-775.
[10] K. Sawada, H. Kushima, K. Kimura and M. Tabuchi, TTP Diagrams of Z Phase in 9-12%
Cr Heat-Resistant Steels, ISIJ International, Vol. 47 (2007), pp. 733-739.
[11] K. Sawada, K. Suzuki, H. Kushima, M. Tabuchi and K. Kimura, Effect of tempering
temperature on Z-phase formation and creep strength in 9Cr-1Mo-V-Nb-N steel, Materials
Science and Engineering A 480 (2008), pp. 558-563.
303
304
class of the 9-12% Cr steels offers the highest potential to meet the required creep
resistance level for the critical components in steam power plants.
In Europe the main efforts to improve the 9-12%CrMoV steels were concentrated in the
COST (CO-operation in Science and Technology) Programmes: COST501 (1986-1997),
COST 522 (1997-2003) [1-6]. In these programmes new ferritic steels for forging,
casting and pipework were developed and characterised to increase the operating
steam temperatures:
- from the subcritical plant: with live steam pressure (PLS) of 166bar, live steam
temperature (TLS) of 540C and reheat steam temperature (TRH) of 540C,
- to the supercritical plant: PLS 250bar, TSL 540C, TRH 560C,
- to the first generation of Ultra Super Critical (USC) plants PLS 270bar, TLS 580C,
TRH 600C,
- up to the second generation USC plants: PLS 300bar, TLS 600C, TRH 620C.
The qualifications of these materials are still on-going after the end of COST 536
Programme (2004-2009), in to the KMM-VIN, WG2 EMEP.
2. Materials development for 600C turbine rotor applications
In COST 501 forged and cast 9 to 10%Cr steels were developed with additions of
1.5%Mo (type E) or a combination of 1%Mo and 1%W. They showed much improved
creep strength, resistance to embrittlement in operation and weldability [1]. In addition
samples from production components were subjected to low cycle fatigue and long term
creep testing permitting a statistical evaluation of the results. They are in use at
temperatures up to 600C.
The trend to even higher steam conditions was the subject of the COST 522 programme
which explored the possibilities of stabilising the tempered martensitic microstructure
through addition of small quantities of Boron. These are the steels (forged steel FB2 and
cast steel CB2) now being employed in orders currently being executed in Germany and
the USA.
Within COST 501 a series of advanced steels for forgings, castings and pipe/tube
application as given in Table 1 was qualified and currently the Type E composition is
utilized for rotor manufacture.
After the good results obtained in the COST 501 on composition E, F and B a new
modified steel called FB2 was produced as trial melt. Furthermore the promising
properties of the trial melt, at the beginning of the new COST 522; it was decided to
scale up FB2 steel to industrial heat in order to manufacture a trial forged rotor.
Boehler/Austria has manufactured a full-size rotor forging with a final weight of
17,000kg. The steel making process was Boehler-BEST, consisting in a pouring process
with special measures to improve the homogeneity of the ingot [7].
A second proposal for a FB2 trial rotor manufacturing was brought into COST522 by the
Italian Societ delle Fucine (SdF) in Terni; it produced a 52,000kg ingot by conventional
steel making (Ladle Furnace and Vacuum Degassing) with a final rotor weight of
28,000kg [2].
One more trial rotor has been produced by ESR remelting of 57,000kg ingot in
Saarschmiede [8].
305
Forged
Steels
1CrMoV
Cr
Mo
0.25
1.0
1.0
0.25
12CrMoV
0.23
11.5
1.0
0.25
501
Type F
0.1
10
1.0
501
Type E
0.1
10
501
522
Type B
0.2
Type FB2 0.13
(SdF)
9.0
9.32
COST
Ni
Nb
0.2
0.7
0.05
0.05
1.5
0.2
0.6
0.05
0.05
1.5
1.47
0.2
0.2
0.1
0.16
0.05
0.05
0.02
0.019
0.01
0.085
100MPa Status
100.000h
550C
Long
term
operating
570C
Long
term
operating
597C
Operating
in
plant
597C
Operating
in
plant
620C
Trial
rotor
manufactured
Table 1: Compositions of improved ferritic steels developed in COST 501 and operating
temperature for 100MPa/100.000h. [2]
3. The manufacture of FB2 trial rotor at Societ delle Fucine (SdF)
The aim of the investigations is to qualify the different steelmaking processes for this
class of Boron containing 10CrMoCoVB alloys. One of the main tasks is how to increase
and optimise the composition homogeneity and the properties of the final rotor forging
are. Figure 1 shows the lay-out of the SdF manufacture route: from the melting shop to
the final machining. Due to the characterisation work on experimental rotor the
component machining was stopped at the step of NDT control after quality heat
treatment.
306
FB2
min
max
cast
C
0.12
0.14
0.14
Si
0.006
0.032
Mn
0.3
0.4
0.32
P
0.01
0.007
S
0.005
0.003
Cr
9.0
9.5
9.1
Mo
1.45
1.55
1.5
Ni
0.1
0.2
0.14
Al
0.008
0.001
B
0.006
0.009
0.009
Co
1.2
1.4
1.23
N
0.015
0.030
0.015
Nb
0.04
0.06
0.046
V
0.18
0.22
0.2
Table 2: Required and obtained chemical composition of FB2 trial forged rotor
(residual elements: H2= 1,2ppm; Sb= 0,001%; Sn=0,001%; As=0,006%; Cu=0,035%; W <0.01%)
The final dimensions of the trial component are shown in Figure 2. After forging the trial
rotor has been treated as follows:
- Austenitizing: 1100C/ 17h/oil quenched;
st
Total (L1+L2+L3)
4380
D1
D2 D3
925 1110 790
1.0
1.5
Top
D1
L1
D
E
D2
L2
Bottom
D3
L3
307
1.5
a
b
Figure 2. COST trial rotor forgings (type FB2) dimensions [9]; SdF rotor during US NDT
control.
3.1 Product characterisations
In order to verify the homogeneity of the properties of the trial rotor, the specimens for
chemical analysis and mechanical tests have been obtained from different parts of the
component (A,B,D,E and C) positions from the core (see Figure 2a). The chemical
analysis (Table 4) shows a very good homogeneity in the composition of the main alloy
elements as well as for the Boron and Nitrogen content that could be critical for their
distribution in a large component processed without remelting.
Position/Element
A
B
D
E
FB2 trial melt
C
0,12
0,13
0,13
0,15
0,13
Cr
9,08
9,13
9,11
9,02
9,32
Mo
1,57
1,59
1,59
1,62
1,47
Ni
0,14
0,14
0,14
0,14
0,16
V
0,21
0,21
0,21
0,22
0,20
Nb
0,054
0,054
0,054
0,060
0,05
B
0,0095
0,0096
0,010
0,012
0,0085
N
0,015
0,016
0,015
0,014
0,019
Co
1,28
1,27
1,27
1,29
1.23
Table 4: chemical composition (wt%) of forged trial rotor in different positions compared
with the nominal composition.
The chemical composition of FB2 steel guarantees a fully martensitic structure. Also with
very low cooling rate, corresponding to claim air, no traces of ferritic transformation
appear. In fact the microstructural analysis performed after the final heat treatment
(normalizing + tempering) (Figure 3a) shows a typical tempered martensitic structure
with a 0-2 ASTM grain size. In Figures 3b is showed the FB2 microstructure as obtained
by Transmission Electron Microscopy on thin foils. The prior austenite and the
martensitic lath boundaries are decorated by a typical precipitation of M23C6 carbides.
The microstructure contains a high dislocation density.
Conventional mechanical tests have been performed in different positions and
orientation. The results, just discussed in previous papers [10-11], shown a quite good
homogeneity of the obtained values in term of YS, UTS and ductility: elongation and
reduction of area.
308
400 m
2 m
Figure 3: fully tempered martensitic microstructure of trial rotor after quality heat
treatment: a) by Light Microscopy; b) by Transmission Electron Microscopy on thin foil
3.2 Microstructural characterisations
In the COST 536 Alloy Design Group discussion it is still open on the effect of B addition
not only as M23C6 and grain boundary stabiliser, but also on the correct amounts of B
and N to avoid the formation of BN particles as defined by Abe & Co-workers [12] in
figure 4. The formation of these particles have the double negative effect to reduce the
amount of B available in solution and able to diffuse into the M23C6 and otherwise to form
particles reducing the ductility in creep as demonstrate for the FB2 trial melt.
The FB2 material from SdF it is on the border line of the equilibrium (red point in the
figure 4) and therefore BN formation could be present.
Figure 4: BN equilibrium diagram [12]: circle point is the FB2 from SdF
Then investigations have been made by FEG-SEM +EDS on RT tensile test specimens
fracture surface: no BN pure particles have been identified, but some dimples appears
sometime associated with particles identified as complex inclusions that contain also BN
particles:
- Figure 5a shows a BN particles jointly with a MnO inclusion,
- Figure 5b shows a BN associated with other complex oxide
309
As conclusion of these analyses the following consideration can be made: SdF FB2
seems have a quite good balancing of B and N, because pure particles have not been
discovered and the dimensions of the discovered BN particles are very small. The SdF
FB2, conventionally processed without remelting, shows small sulphide and oxide
inclusion where sometime BN can nucleate.
good both in term of elongation and reduction of area, as shown in figure 8 without
evidence of ductility drop for the longer tests at the different temperatures.
Figure 7: Creep master curve of tests of SdF FB2 trial rotor (open point = specimens
running) compared with B2 and E + F rotors curves [15]
90
30
Elongation (%)
25
20
15
10
5
0
19,5
20
20,5
21
21,5
22
22,5
PLM (C=20)
80
70
60
50
40
30
20
10
0
19,5
20
20,5
21
21,5
22
22,5
PLM (C=20)
Precipitates/
Dimensions
(nm)
MX
FB2
SdF
180
45
M23C6
98
125
Grade 91
1070+780
Frequency
(%)
Cr
(%)
Mo
(%)
V
(%)
Nb
(%)
Fe
(%)
50
35
17
68
130
139
96
56
14
1,5
22
Table 5: mean dimension of precipitates present in N+T forged FB2 compared with the
other and quantitative analysis (% in weight) of FB2 precipitates [13-14]
3.5 Microstructural analysis on aged specimens
Microstructural analysis by SEM+ EDS and STEM+EDS started on crept aged
specimens in order to investigate the evolution of the precipitates: the first 2 specimens
have been selected after 23.576 hours at 625C and after 10.026 hours at 650C (figure
9).
It was possible to observe that in aging condition there are:
- still a relevant amount of small M23C6 particles without appearance of
coarsening process,
- the precipitation of some small MX particles, not present in the as treated
condition,
- the appearance of Laves phase in the specimen aged at 625C,
- the start of transformation of the bigger MX in to Z-phase (only 1 particle
analysed) (Figure 10).
Figure 9: Microstructure after 23576 hours at 625C and after 10026 hours at 650C
312
Figure 10: Precipitation after 23576 hours at 625C; a) general view; b) Z-phase particle
(extraction replica)
The M23C6 dimensions in FB2 aged specimens have been compared with the dimension
of the precipitates in the grade 91: it was observed that the coarsening phenomena are
strongly reduced [14-18]. This effect could be related to the introduction of B in the
chemical composition, that seems have a stabilising effect on the M23C6 and on grain
boundary [19-21], but this item is still under discussion worldwide.
4. Type E Rotor
After this quite good results on this experimental steel in year 2001 Societ delle Fucine
decided to made some other forged rotors in Steel X12CrMoVWNb10-1-1 (COST Type
E), following Technical Specification suggested by COST program. The ingots have
been melted in ThyssenKrupp Acciai Speciali Terni.
An example of the chemical composition (%wt) obtained in one delivered rotor is
reported in Table 6. It is possible to observe that all the elements in the component are
in the range the standard. The other residual elements analyses are: Cu<0.06%; Sn
<0.003%; As <0.004%.
Figure 12: Tempered martensite microstructure in different positions of the rotor (x100;
Vilella etching)
An example of the basic mechanical characteristics of Rotor E components are shown in
table 7. The scattering of strength values are quite low: these results confirm the good
heat treatment practises and the homogeneous mechanical properties. [23].
The FATT value has been evaluated as 38C. Tensile tests have been carried also in
the temperature up to 620C. Figure 13 shows the tensile tests results which are
summarized in in table 8.
The material strength values are in the range of nominal values of the Rotor E [17]. No
recordable indications were found in all the forging components.
314
UTS
YS
El.
RoA
KCV
SdF
nim
824
706
17
54
35
max
880
740
19
63
96
1000
900
900
800
800
700
600
T.Stress [MPa]
T.Stress [MPa]
700
500
400
300
Rotor E R.T.
Rotor E 300C
Rotor E 550C
Rotor E 620C
200
100
0
0.00
0.04
0.08
600
500
400
300
Rotor E R.T.
Rotor E 300C
Rotor E 550C
Rotor E 620C
200
100
0.12
0.16
0.20
T.Strain [mm/mm]
0
0.000
0.004
0.008
0.012
0.016
0.020
T.Strain [mm/mm]
UTS(MPa)
YS (MPa)
Elongation
(%)
882
775
16
760
665
15
745
658
15
513
484
16
409
383
18
378
346
18
Table 8: Rotor E tensile tests report
Red. Of
Area (%)
59
58
60
83
89
89
In order to have a full qualification of the material Rotor E a large and comprehensive
testing program including tests on smooth and notched specimens, cracked and uncracked specimens were planned as follows:
Creep program: 550-600-650C,
high cyclic fatigue tests (HCF),
Low cycle fatigue tests at high temperature (HCF),
Thermo-mechanical fatigue tests (TMF),
Crack growth tests at high temperatures and static loads and under isothermal
conditions (CG),
Fatigue and creep/fatigue crack growth (CCG/FCG) characterisation of crack
propagation on CT specimens under TMF condition.
315
900
620C
Linear Fit
Confidence bands (95%)
400
850
[MPa]
[MPa]
420
RT
Linear Fit
Confidence bands (95%)
800
Equation
Adj. R-Square
380
y = a + b*x
-0.08046
Value
750
Ds
Intercept
Ds
Slope
3.03557
0.1175
-0.01448
0.01828
1000000
Equation
Adj. R-Square
Standard Error
y = a + b*x
0.78187
Value
1E7
Intercept
549.74927
32.34484
Ds
Slope
-23.30839
4.91309
1000000
Cycles to failure
Standard Error
Ds
1E7
1E8
LCF tests were carried out in agreement with ASTM E606. The LCF tests were
performed at three temperature levels: room temperature (RT), 300C and 620C. The
test temperatures were achieved by an induction furnace. The actual temperature test
was measured and monitored by thermocouples welded directly onto the specimen. The
test has been conducted in strain control with imposed strain rate of 0.01 s-1 with the
triangle waveform, and a load ratio R= -1. Figure 15 summarize the LCF results in
comparison with the HCF results.
316
400
350
350
300
300
250
Stress [MPa]
200
200
150
100
100
150
100
Rotor E 600C
Cost E 600C
Cost E 550C
Rotor E 550C
1000
10000
100000
50
50
100
1000
150
Stress [MPa]
Stress [MPa]
250
100
Rotor E 650C
Cost E 650C
50
100
1000
10000
100000
317
10000
100000
Rotor E creep data have been elaborated to evaluate nmin and Amin .The minimum strain
rate,
has been plotted against stress to find nmin, Amin for each temperature. Table
9 shows the nA and AA Rotor E found parameters at the different temperatures.
Rotor E
nmin
Amin
550C
9.82
3.51E-30
600C
6.78
3.39E-21
650C
3.18
2.11E-12
Table 9: Summary of the Rotor E creep parameters
5. Summary and Conclusions
The result obtained up to now on FB2 trial rotor and on Steel X12CrMoVWNb10-1-1
(COST Type E) produced at Societ delle Fucine, without ingot remelting, demonstrate
that it is possible to realise full scale forged components by conventional process route
with very good homogeneity of chemical analysis, mechanical behaviour and creep
properties.
The FB2 from SdF has a quite good balancing of the B and N content, therefore a very
low amount of BN that are present and there are always in connection with MnS or
inclusion oxides particles.
In term of creep behaviour FB2 seems to offer a significant improvement over the
parent E-F-B type steels and it could be suitable for 625C applications. In fact the
experience gained during the last few years seems guarantee that the 9%Cr are more
stable materials from the microstructural evolution point of view, and suggests that the
formation of some Z-phase precipitates may not significantly affect by mean of the long
term creep behaviour of this steel.
Obviously these results have to be confirmed with longer creep tests in order to
generate a more consistent database, assessment and extrapolation. Tests still running
are planned to reach 100.000 hours life.
The TEM investigation on long term aged specimens shown that the microstructural
evolution is significantly different respect to the other 9%Cr steels: the dimension of the
M23C6 seems not slightly affected by time and temperature precipitates and few Z-phase
particles have been found in FB2 after 23576 hours at 625C.
If the slower coarsening of the M23C6 particles will confirmed by the analysis of the more
aged specimens, these will be an experimental confirmation of the positive effect the
Boron on the microstructural stability of this steel and therefore on the creep behaviours.
Also the parent Steel X12CrMoVWNb10-1-1 (COST Type E) has been successfully
produced in Societ delle Fucine and the microstructural analysis, mechanical and creep
tests shown properties in agreement with the literature values.
Currently about 20 rotor components have been produced in Societ delle Fucine
starting from a maximum ingot of 75tons: the dimension of the components have a
maximum delivered weight of 27 tons and a maximum diameter of 1200mm.
Acknowledgement
The authors are grateful to their colleagues and partners in the programme COST522
and 536 for their contributions and many discussions during the course of this
endeavour. Many thanks are also extended to the COST Management Committee for
their guidance. A special thanks to Dr. Silvia Tiberi Vipraio, Dario Venditti, Marcello
nd
Ballone (CSM) for the TEM investigations and Dr. Riccardo Polini (2 University of
Rome, Tor Vergata) for the support in FEG-SEM analysis.
318
REFERENCES
1. T.U. Kern, K. Wieghardt, H. Kirchner: Material and design solutions for advanced
steam power plants, EPRI Fourth International Conference on Advanced in
Materials Technology for Fossil Power Plants; October 25-28, 2004, Hilton Head
Island, South Carolina USA
2. R.W. Vanstone, Alloy design and microstructural control for improved 9-12%Cr
power plant steels, Annex A, COST 522 Steam Power Plant, Final Report, 19982003
3. B. Scarlin, R. Vanstone, R. Gerdes: Materials developments for Ultrasupercritical
Steam Turbines, EPRI Fourth International Conference on Advanced in Materials
Technology for Fossil Power Plants; October 25-28, 2004, Hilton Head Island,
South Carolina USA
4. B. Scarlin, T-U. Kern, M. Staubli: The European efforts in material development for
650C USC power plants cost522, Ibidem
5. Y. Tanaka, T. Azuma, K. Miki: Development of steam turbine rotor forging for high
temperature application high temperature steel forgings for power generation,
Ibidem
6. P. Peel, B. Scarlin, R.Vanstone: From materials development to advanced steam
turbines: PARSONS 2007: 7th International Charles Parsons Turbine Conference,
Power Generation in an Era of Climate Change, 11-13 September 2007, Univ. of
Strathclyde, Glasgow, UK.
7. G. Zeiler, W. Meyer, K. Spiradek, J. Wosik: Experiences in manufacturing and longterm mechanical & microstructural testing on 9-12 % chromium steel forgings for
power generation plants, EPRI Fourth International Conference on Advanced in
Materials Technology for Fossil Power Plants; October 25-28, 2004, Hilton Head
Island, South Carolina USA
8. N. Blaes, B. Donth, K.H. Schnfeld, D. Bokelmann: High temperature steel forgings
for power generation, Ibidem
9. T.U. Kern, M. Stabli, K.H. Mayer, B. Donth, G. Zeiler, A. Di Gianfrancesco: The
European effort in development of new high temperature rotor materials COST
536: Int. Conf. Materials for Advanced Power Engineering, 19-21 September 2006
Liege, Belgium
10. T.-U. Kern, B. Scarlin, B. Donth, G. Zeiler, A. Di Gianfrancesco: The European
COST536 project for the development of new high temperature rotor materials: 18
International Forgemaster Meeting: 3-6 November 2008 Santander, Spain
11. A. Di Gianfrancesco, L. Cipolla, D. Venditti, S.Neri, M. Calderini: High Temperature
Properties and Creep Behaviour of a CrMoCoB (FB2) Steel Trial Rotor, Ibidem
12. F. Abe: Alloy Design of Creep and Oxidation Resistant 9Cr Steels for Thick Section
Boiler Components Operating at 650C: EPRI Fourth International Conference on
Advanced in Materials Technology for Fossil Power Plants; October 25-28, 2004,
Hilton Head Island, South Carolina USA
13. A. Di Gianfrancesco, L. Cipolla, D. Venditti, S.Neri, M. Calderini: Creep Behaviour
and microstructural stability of FB2 (CrMoCoB) Steel Trial Rotor Sixth International
Conference on Advances in Materials Technology for Fossil Power Plants August
31September 3, 2010 Santa Fe, New Mexico, USA
14. Microstructural evolution of ASTM P91 after 100,000 hours exposure at 550C AND
600C: L. Cipolla, S. Caminada, D. Venditti, H. K. Danielsen, A. Di Gianfrancesco:
9th Lige Conference on Materials, for Advanced Power Engineering: September
27th 29th, 2010, Lige Belgium
319
15. The European efforts in development of new high temperature rotor materials
COST536: T.-U. Kern, K.H. Mayer, B. Donth, G. Zeiler, A. Di Gianfrancesco: ibidem
16. Long term creep properties and microstructural evolution of IN718 prototype forged
disk: M. Calderini, S. Neri, A. Di Gianfrancesco, P. Lombardi, L. Foroni, R. Montani:
18th International Forgemasters Meeting: September 12-16, 2011 Pittsburgh, PA,
USA
17. J. Hald, H. Danielsen: Z-phase in 9-12%cr steels: EPRI Fourth International
Conference on Advanced in Materials Technology for Fossil Power Plants; October
25-28, 2004, Hilton Head Island, South Carolina USA
18. S. Caminada, G. Cumino L. Cipolla, A. Di Gianfrancesco: Long term creep
behaviour and microstructural evolution of ASTM grade 91 steel; ibidem
19. Fujio Abe: Effect of boron on creep deformation behaviour of 9cr steel for USC
boilers at 650C: PARSONS 2007: 7th International Charles Parsons Turbine
Conference, Power Generation in an Era of Climate Change, 11-13 September
2007, Univ. of Strathclyde, Glasgow, UK.
20. H.O. Andren, A. Golpayegani: Microstructure of a high boron chromium steel for
steam turbine applications: ibidem
21. H.O. Andren, A. Golpayegani: Creep resistant high boron 9-12% chromium steels
for steam power plants: Int. Conf. New Developments on Metallurgy and
Applications of High Stregth Steels: Buenos Aires, Argentina 26-28 May 2008
22. P. Lombardi, S. Budano, A. Di Gianfrancesco, K. Nikbin, F. Biglari, M. A. Gomes, A.
Sanguineti, E. Poggio, S. Neri: Development of methods for the characterisation,
fracture assessment and life prediction of new high strength steels under variable
temperature operating conditions: DELOC: RFSR CT 2007-00021; 01/01/2007
30/06/2010, Final Report
23. Y. W AKESHIMA, M. MIKAMI, MANUFACTURING OF TRIAL ROTOR FORGINGS OF COST E
STEEL (X12CRMOWVNBN10-1-1), IFM 2006, 16TH INTERNATIONAL FORGEMASTERS
MEETING,15 19 OCTOBER 2006, CUTLERS HALL, SHEFFIELD, UK
320
ABSTRACT
9%Cr steel containing Co and B, X13CrMoCoVNbNB9-2-1, has been manufactured by electro
slag remelting to confirm the qualities and compare creep strength and microstructure of that
forging with those of a forging made from electro slag hottopping ingot. It is confirmed to
manufacture rotor forgings with homogeneous composition and good properties by electro slag
remelting process. Creep strength of the forging made from electro slag remelting ingot is similar
to that of the forging applied electro slag hottopping process from the results of creep rupture tests
up to 5000h. Martensitic lath microstructures with high density dislocations and the precipitations
of M 23 C 6 , VX, NbX and M 2 X are observed after the quality heat treatments at the center portion
of the both forgings. There is no large difference in the martensitic lath widths, distributions and
sizes of those particles between the both trial forgings.
KEYWORDS: FB2 material; rotor forgings; ingot making process; creep strength; microstructure
INTRODUCTION
To increase thermal efficiency and reduce CO2 emissions, advanced 9-12%Cr steels containing
Co and B have been actively developed in Japan and Europe [1-4]. Recently, FB2 material,
X13CrMoCoVNbN9-2-1, which was developed by COST program in Europe has been utilized
for USC plants and its demands have been increased [4]. Quality and reliability of the high Cr
steel rotor forgings are required because those rotor forgings turn at 3000 or 3600 revolutions per
minute. Therefore homogeneous large ingots which are obtained with special process such as
electro slag remelting (ESR) and electro slag hottopping (ESHT) have been needed to
manufacture the high quality turbine rotors [5,6]. Figure 1 shows a schematic illustration of ingot
making process, conventional, ESHT and ESR. In the case of high Cr steel ingot by conventional
ingot making process, macroscopic segregation arises at center and top portion of the ingot [6].
For this reason, it is difficult to manufacture the homogeneous large ingot of high Cr steel. ESHT
process controls the segregation by melting dilution electrode heated with graphite electrode and
slag. On the other hand, ESR process controls the segregation by continuously melting and
solidifying electrodes manufactured with conventional ingot making process in the water cooling
mold. Japan Casting & Forging Corporation has manufactured a lot of 9-12% Cr steel rotor
forgings since 1991, and ESHT trial rotor forging of FB2 material made from 80 metric ton ingot
in 2007 [7,8]. However, the workability and productivity such as yield ratio in ESHT process are
321
not so good for large size ingots. Thus, 145 ton ESR facility has been installed in 2012 to improve
the workability and productivity. This paper describes the results of FB2 trial rotor forging made
from ESR ingot to confirm the qualities and compare the creep rupture strength and the
microstructure of that forging to those of a forging manufactured with ESHT process.
COMPOUND
HOTTOP MOLD
REFRACTORY
Conventional process
UNSOLIDIFIDE ZONE
SOLID
MOLD
CONSUMABLE ELECTRODE
GRAPHITE ELECTRODE
SLAG
HOTTOP MOLD
REFRACTORY
ESHT process
UNSOLIDIFIDE ZONE
SOLID
MOLD
ELECTRODE
SLAG
WATER COOLING MOLD
ESR process
UNSOLIDIFIED ZONE
SOLID
Figure 1: Ingot making process of Conventional, ESHT and ESR process [5, 6].
322
Forging
Preliminary heat treatment
Isothermal transformation
Pre-machining
Ultrasonic test
Quality heat treatment
Machining
Ultrasonic test
Mechanical tests
323
715mm (28.1)
3040mm (119.7)
ESR Trial forging 21ton
Figure 3: forging process of ESR trial rotor forging.
1100C
(2012F)
Oil
Quenching
700C
(1292F)
570C
(1058F)
Figure 4: Schematic the heating cycle for quality heat treatment of ESR trial rotor forging.
Mechanical Tests and Microstructural Investigations
Materials for metallurgical investigations and mechanical tests were cut from each location of the
trial forging after ultrasonic inspection. Chemical analyses, tensile, Charpy impact, creep and
creep rupture tests were carried out. microstructural observations were performed by optical
microscope (OM) and transmission electron microscope (TEM). Observations and Analyses of
precipitations were examined by scanning transmission electron microscope (STEM) and energy
dispersion X-ray (EDX) analyzer with carbon extracted replicas. Comparison of creep strength
and microstructure between the trial forging manufactured with ESR process and the forging
made from ESHT ingot was done [5,6].
324
709mm
(27.9)
1309mm
(51.5)
1109mm
(43.7)
S2
S1
C1
Locations
809mm
(31.9)
C2
Si
Mn
Ni
Cr
Mo
Nb
Co
Electrode
0.13
0.09
0.34
0.005
0.001
0.12
9.13
1.52
0.20
0.050
1.28
0.0099
0.020
S1
0.13
0.09
0.34
0.005
0.001
0.12
9.14
1.52
0.20
0.050
1.28
0.0100
0.020
S2
0.13
0.08
0.34
0.005
0.001
0.12
9.16
1.53
0.20
0.050
1.29
0.0097
0.020
C1
0.14
0.09
0.34
0.005
0.001
0.12
9.20
1.53
0.20
0.051
1.28
0.0090
0.019
C2
0.13
0.09
0.34
0.006
0.001
0.12
9.15
1.55
0.20
0.052
1.30
0.0101
0.020
Table 2: Results of tensile and Charpy impact tests on ESR trial rotor forging.
0.02%Y.S.
[MPa]
(ksi)
0.2%Y.S.
[MPa]
(ksi)
T.S.
[MPa]
(ksi)
El.
[%]
R.A.
[%]
S1
574
(83)
677
(98)
811
(118)
19
S2
571
(83)
668
(97)
800
(116)
C2
596
(86)
695
(101)
832
(121)
Locations
325
Impact Energy
[J]
(ft-lb)
FATT
[C]
(F)
at 20C
(68F)
at 40C
(104F)
63
20
(15)
35
(26)
67
(153)
19
63
20
(15)
37
(27)
74
(165)
17
60
14
(10)
31
(23)
68
(154)
Comparison of Creep Strength between Forgings Made from ESR and ESHT Ingot
Figure 5 shows creep rupture strength at the center portions of the forgings made from ESR and
ESHT ingot. Creep testing time of the ESR forging is around 5000h and that of ESHT beyond
27000h, and these tests still continue. There is no large difference in creep rupture strength
between the both forgings since creep rupture curve of the ESR forging is in good agreement with
that of the ESHT. Figure 6 displays change in creep rate at the center portions of the both
forgings. Minimum creep rate of the forging manufactured with ESR process under the testing
condition of 650 degrees C and 150MPa is 8.0x10-6/h and that of the forging manufactured with
ESHT process 7.0x10-6/h, furthermore both curve are similar. It can be said from the results of
creep tests up to 5000h that there is no large difference in the creep strength between both
forgings. However, long-term creep strength is important for high temperature materials, thus
long-term creep test has to be continued.
400
Center Portion
40
30
200
20
100 Ongoing:
90
ESR Trial Forging in 2012
80
ESHT Trial Forging in 2007
70
60
22
23
24
25
L.M.P.=T(25+log(t))
Stress (ksi)
Stress (MPa)
300
50
10
26
27
Figure 5: Creep rupture strength of trial rotor forgings made from ESR and ESHT ingot.
326
-1
10
-2
10
Center Portion
650C (1202F)
150MPa (22ksi)
-3
10
-4
10
-5
10
-6
10
10
100
Time (h)
1000
10
Figure 6: Change in creep rate of trial forgings manufactured with ESR and ESHT process.
Comparison of microstructure between Forgings Made from ESR and ESHT Ingot
It was found from the results described above that the difference in creep strength between the
forgings made from ESR ingot and ESHT is not so large, which suggested that the both forgings
assume to be similar in microstructure since the creep strength is strongly affected by the
microstructure. Then, the microstructures of both forgings were investigated. Figure 7 shows the
optical micrographs at the center portion of trial forgings manufactured with ESR ingot (a) and
ESHT ingot (b). Tempered martensitic structures are observed and no delta ferrite is found at the
both forgings, but the difference in structures between them is not found by optical microscope.
TEM images of the both forgings with thin foils are shown in Figure 8. Martensitic lath structures
with high dislocation density are observed on the both forgings. The martensitic lath widths of the
both forgings are around 0.6m. A lot of ellipsoidal particles with the average diameter of about
120nm are found on the lath boundaries and about 30nm fine particles are observed in and on the
lath boundaries. Analyses with the carbon extracted replicas were carried out by STEM and EDX.
Figure 9 shows the STEM image (a) and phase mapping (b) of the replica at the center portion of
the forging made from ESR ingot. Figure 10 shows the STEM image (a) and phase mapping (b)
of the forging made from ESHT ingot. Each particle was identified by the chemical analysis
results of individual phases from the papers [9,10]. In Figures 9 (b) and 10 (b), M 23 C 6 is labeled
by red, MX including a lot of V (VX) blue, MX including a lot of Nb (NbX) green and M 2 X
cyan. Mainly M 23 C 6 and coarsened NbX with the average diameter of about 80nm are observed.
However, precipitation densities of VX, NbX and M 2 X in the both forgings are extremely low in
comparison with 9Cr-1Mo-V-Nb-N steel [10]. Figure 11 shows the result of extracted residue. Fe
and Cr are thought to be mainly included in M 23 C 6 . Amounts of V and Nb in the both forgings are
327
around 0.04% and 0.03% respectively. These amounts are in good agreement with the distribution
density of fine M 2 X, VX and NbX found in Figure 9 (b) and Figure 10 (b). However, the amount
of extracted residue of the both forgings is not so large difference. It can be said from the results
of these microstructural investigation that there is no large difference in martensitic lath widths,
phase distribution and sizes of the particles observed between the both forgings.
(b)
(a)
100m
100m
Figure 7: Optical micrographs at center portion of the forging manufactured from ESR ingot (a)
and ESHT ingot (b).
(a)
(b)
Figure 8: TEM images at center portion of the forging manufactured from ESR ingot (a) and
ESHT ingot (b)
328
(a)
0.5m
(b)
M23C6
Red
VX
Blue
NbX
Green
M2X
Cyan
Figure 9: STEM image (a) and phase mapping (b) with carbon extracted replica at center
portion of forging made from ESR ingot.
329
(a)
0.5m
(b)
M23C6
Red
VX
Blue
NbX
Green
M2X
Cyan
Figure 10: STEM image (a) and phase mapping (b) with carbon extracted replica at center
portion of forging made from ESHT ingot.
330
Fe
Cr
Mo
Co
V
Nb
Residue(%)
ESR
1
ESHT
2.
Creep rupture strength of the forging made from electro slag remelting ingot is almost similar
to that of the forging applied electro slag hottopping process from the results of creep rupture
tests up to 5000h.
3.
Martensitic lath microstructures with high density dislocations and the precipitations of
M 23 C 6 , VX, NbX and M 2 X are observed after the quality heat treatments at the center
portion of the both forgings. There is no large difference in the martensitic lath widths,
distributions and sizes of those particles between the both trial forgings.
Further long-term investigations on the creep strength and microstructural evolution in the both
forgings will be performed.
331
REFERENCES
[1] Y. Kagawa, F. Tamura, O. Ishiyama, O. Matsumoto, T. Honjo, T. Tsuchiyama, Y. Manabe
and H. Kawai, Development and Manufacturing of The Next Generation of Advanced 12%Cr
Steel Rotor for 630C Steam Temperature, 14th International Forgemasters Meeting, (2000), pp.
301-308.
[2] M. Arai, H. Doi, T. Azuma and T. Fujita, Development of High WCoB-Containing 12Cr
Rotor Steels for Use at 650C in USC Power Plants, 15th International Forgemasters Meeting,
(2003), pp. 261-268.
[3] Y. Tsuda, M. Yamada, R. Ishii, Y. Tanaka, T. Azuma and Y. Ikeda, Development of High
Strength 12%Cr Ferritic Steel for Turbine Rotor Operation above 600C, 13th International
Forgemasters Meeting, (1997).
[4] T. -U. Kern, H. Cerjak, K.H. Mayer, M. Staubli, R. Vanstone, G. Zeiler and K. -H.
Schoenfeld, Development and Qualification of Rotor Steels for 600 to 650C Application in
COST501/COST522, 14th International Forgemasters Meeting, (2000), pp. 270-276.
[5] K. Morinaka, Y. Futamura, I. Kitagawa and S. Watanabe, The Manufacture of the Large
ESHT-J Ingot, I&SM (1989), pp. 9-15.
[6] D. L. Newhouse, C. J. Boyle and R. M. Curran, A Modified 12-Percent Chromium Steel for
Large High Temperature Steam Turbine Rotors, Preprint of the ASTM Annual Meeting, (1965).
[7] M. Mikami, K. Morinaka, Y. Okamura, S. Tanimoto, Y. Wakeshima, R. Magoshi, Y. Kadoya
and A. Matsuo, Manufacturing of 12%Cr Rotor Forgings for High Temperature Steam Turbines
from Electro Slag Hot Topped Ingot, 14th International Forgemasters Meeting Proceedings,
(2000), pp. 295-300.
[8] K. Kawano, Y. Wakeshima, T. Miyata, Y. Okamura, F. Gatazka and S. L. Breitenbach,
Manufacturing of COST-FB2 Trial Rotor Forgings, 17th International Forgemasters Meeting,
(2008), pp. 303-308.
[9] M. Mikami, Y. Wakeshima and T. Miyata, Creep Rupture Strength and Microstructural
Investigation of 12 % Cr Steel Large Forgings for Ultra-Supercritical Steam Turbine Rotors,
Advances in Materials Technology for Fossil Power Plants, Proceedings of 6th International
Conference, Santa Fe, New Mexico, USA (2010), pp 408-422.
[10] K. Sawada, K. Suzuki, H. Kushima, M. Tabuchi and K. Kimura, Effect of Tempering
Temperature on Z-phase Formation and Creep Strength in 9Cr-1Mo-V-Nb-N Steel, Materials
Science and Engineering A 480 (2008), pp. 558-563.
332
DEVELOPMENT AND PRODUCTION OF MONOBLOCK LOWPRESSURE TURBINE ROTOR SHAFT MADE FROM 670 TON INGOT
ABSTRACT
Monoblock low-pressure (LP) turbine rotor shaft forgings for nuclear power plants have been
produced from up to 600 ton ingots. However, ingots greater than 600 tons are necessary to
increase the generator capacity. Segregation, non-metallic inclusions, and micro porosities
inevitably increase with the increase in ingot size. Manufacturing such massive ingots with high
soundness is a quite difficult. Thus, the development of 650 ton ingot production was carried out
in 2010. The 650 ton ingot was dissected and investigated to verify its internal quality. The
internal quality of the 650 ton ingot was found to be equal to that of 600 ton ingots. Subsequently,
in 2011, we produced a 670 ton ingot, the worlds largest, to produce a trial LP rotor shaft
forging with a diameter of 3,200 mm. Results show that the internal quality, mechanical
properties, and heat stability are the same as LP rotor shaft forgings made from 600 ton ingots.
INTRODUCTION
To increase the unit capacity of power plants, the power generation efficiency is being improved
with the maximum unit capacity reaching 1,700 MW. Rotor shafts for power generation, nuclear
reactor components, and petroleum refining reactors used at an advanced power plants have
become larger and heavier. Since 1985, The Japan Steel Works, Ltd. has been manufacturing
monoblock low-pressure turbine rotor shafts forgings using 600 ton ingots[1]. To date, more than
280 turbine rotor shaft forgings have been produced using 600 ton ingots. However, with the
increasing unit capacity of power plants, the next-generation designs of nuclear turbine rotor
shafts calls for ingots larger than 600 tons. Segregation, non-metallic inclusions, and
microporosities inevitably increase with the increase in ingot size. Manufacturing such massive
ingots with high soundness is quite difficult. Thus, we developed 650 ton ingot production in
2010. The 650 ton ingot was dissected and investigated to verify its internal quality. Factors
related to internal quality, such as segregation, non-metallic inclusions, and microporosities of
the 650 ton ingot were found to be equal to those of 600 ton ingots[2][3]. We subsequently
333
produced a 670 ton ingot, the worlds largest, to produce a trial LP rotor shaft (hereinafter
referred to as trial LP rotor), which has a body diameter of 3,200 mm. Such a large LP rotor shaft
has never been produced as a mono-block forging. Enlarging the drum diameter will decrease the
toughness and ultrasonic permeability at the center of the rotor. Therefore, it is an enormous
challenge to obtain good mechanical properties and ultrasonic permeability in such a massive
forging. In this study, we investigated the internal quality, mechanical properties, and heat
stability of the trial LP rotor.
PRODUCTION OF TRIAL LP ROTOR
Production plan of trial LP rotor
A body diameter of 3,200 mm for the trial LP rotor was chosen based on design information
from heavy electric machinery companies to evaluate the ultrasonic permeability and mechanical
properties at the center of the body section. A target tensile strength of 870 MPa was chosen as
the highest strength demanded. Furthermore, we planned to adjust the tensile strength of the trial
LP rotor from 870 MPa to 780 MPa by second tempering to evaluate the mechanical properties
at low-level strength.
Figure 1 shows the manufacturing process and quality control of the trial LP rotor. Ultrasonic
and mechanical tests were conducted to investigate internal quality and mechanical properties.
Furthermore, a heat stability test was conducted after gashing to evaluate the deflection-related
base metal.
Press
V.C.D.
Ladle Refining
Periphery ultrasonic Test
Dimensional Test
Visual Test
Vac.
Vac.
Horizontal Furnace
Ar
Forging
Cleaning
Rough Machining
Inspection
A.C.
W.Q.
Tempering
Tensile Test
Impact Test
Product Analysis etc.
Tensile Test
Impact Test
Product Analysis
etc.
F.C.
Rough Machining
Inspection
Center Core
Trepanning
10
11
12
Tempering &
Mechanical Test
13
Axial Bore
Finishing
No7
Inspection
14
15
Gashing
16
No1 3
Macrostructure
observation
Mechanical Test
No3
17
Dissection &
Investigation
Figure 1. Manufacturing process and quality control plan of the trial LP rotor
334
12
The trial LP rotor was forged using a 14,000 ton hydraulic press.
Heat treatment
Heat treatment comprises two processes. One is preliminary heat treatment for normalizing and
tempering to attain inspectability. Obtaining a fine grain structure from repeat austenitization is
important so that there is good penetration of ultrasonic waves. The other is quality heat
treatment, consisting of quenching and tempering, to obtain the optimum mechanical properties.
For the trial LP rotor, preliminary heat treatment was carried out in a horizontal furnace. Similar
to the LP rotors made from 600 ton ingots, normalization was implemented three times for the
trial LP rotor. After finishing the preliminary heat treatment, the trial LP rotor was machined to a
diameter of 3,200 mm and an ultrasonic test was performed to confirm the internal quality. The
quality heat treatment was then conducted. In the quality heat treatment process, heating was
carried out in the vertical furnace and spray quenching was performed in the vertical position to
obtain a homogeneous microstructure. However, for the trial LP rotor, which has a body
diameter of 3,200 mm, the cooling rate decreases, which in turn decreases the toughness at the
center of the rotor. Consequently, a fourth normalization stage was added in the quality heat
treatment process.
RESULTS
Ultrasonic testing
After the quality heat treatment, oxide scale was removed from the trial LP rotor by machining,
and the internal quality was inspected via an ultrasonic test in accordance with ASTM A418.
Figure 4 shows the minimum detectable flaw size (MDFS) measured at a frequency of 2.25 MHz.
The MDFS at the center of the body section was 1.0 - 1.2 mm, which is equal to or greater than
that of the LP rotors made from the 600 ton ingots.
4941
3260
Bottom of ingot
894
3182
895
1528
1176
3234
Surface MDFS(,mm)
0.3
0.2
0.4
0.4
0.4
0.2
0.3
Center MDFS(,mm)
1.0
0.7
1.0
1.0
1.2
0.7
1.0
MDFSMinimum detectable flaw size
Sensitivity multiplication factor such that a 10% indication at the forging center will be
equivalent to 1.6mm diameter flat bottom hole.
336
This MDFS value is a good value for the ultra-large forging with a diameter of 3,200 mm.
Furthermore, no indication exceeding MDFS, such as non-metallic inclusions, was detected in
the trial LP rotor.
Mechanical properties
A tensile test and Charpy impact test were performed in accordance with JIS Z 2241 and 2242.
Figure 5 shows the distribution of tensile properties and impact properties of the trial LP rotor at
a tensile strength of 870 MPa class. It was confirmed that a aim of properties, i.e., the tensile
strength, yield strength, and elongation and reduction in area at the surface and center, could be
fully achieved and that these are equal to the date for an LP rotors made from 600 ton ingots.
Regarding the Charpy impact test, the absorbed energy is rather low and the fracture appearance
transition temperature (FATT) is rather high at the center of the body section compared with the
date for the LP rotors made from 600 ton ingots. One of the reasons for the deteriorating
toughness is the change in cooling rate during quenching with the increase in the body diameter.
Furthermore, in the body center portion, the absorbed energy and the FATT gradually
deteriorated toward the top of the ingot. The main reason is that the element increased toward the
top of the ingot as a segregation. Figure 6 shows the distribution of the FATT from the body
surface to the center of the trial LP rotor. The FATT increased toward the center of the rotor,
with a maximum value of 22 , because the cooling rate decreased during quenching. This
result is similar to the data for the LP rotors made from 600 ton ingots at a tensile strength of 870
MPa class.
Trial LP rotor
3200mm
Body surfaceradial
Body centeraxial
3200
Body centerradial
Bottom of ingot
0.2%YS , TS Carbon content
2
at center(wt,%)
(N/mm )
B ottom of i ng ot
Top of i ng ot
0.25
0.20
950
900
850
TS
40
0.2%YS
20
800
750
Body diameter
2650mm
2720mm
3200mm
0.30
Top of ingot
Remarks
- LP rotor made from
600
ton
ingot
Trial LP rotor
700
740
700
FATT ()
Absorbed energy
(J)
EL.,RA. (%)
660
100
80
60
40
20
0
RA.
FATT ()
0.02%YS
2
(N/mm )
780
EL.
-20
-40
-60
After quality heat treatment
TS870MPa class
300
-80
200
100
-100
0
40
-120
0
-40
-80
-120
200
400
600
800 1000 1200 1400
Depth of test specimen from body surface (mm)
1600
To evaluate the mechanical properties at a tensile strength of 780 MPa class, the trial LP rotor
underwent tempering and mechanical testing. In addition, test specimens were taken from bottom
of a gash to the center. This area has never been investigated because it is equivalent to the
delivery contour. The distribution of the FATT is shown in Figure 7. The FATT was -20
which is equal to that at the center of the body section of an LP rotors made from a 600 ton ingot.
Bottom of ingot
Top of ingot
Body diameter
2850mm
3200mm
Remarks
LP rotor made from
40
After re-tempering
(TS870MPa780MPa
20
FATT ()
0
-20
-40
-60
-80
-100
-120
0
200
400
600
800 1000 1200 1400
Depth of test specimen from body surface (mm)
1600
IC
JIC
JC
IC
JIC
JC
338
that these test results fall on and in the scatter band of a conventional LP rotors made from 600
ton ingots
10-6
Trial LP rotor
Middle of body
Top of body
Bottom of body
Trial LP rotor
Middle of body
Top of body
Bottom of body
10-7
da /dN (m/cycle)
10
10-8
10-9
103
104
105
10-10
10
100
K MPam1/2
135mm
The macrostructure observation was performed for a cross section based on the JIS G0553
method using the core bar taken from the center of the trial LP rotor. The macrostructure of the
cross section of the center core bar is shown in Figure 11. Compared with the body section, the
shaft section had a dense dendritic structure. The main reason is that the forging ratio is defferent
between the body and shafts. However, it was confirmed that a sound microstructure was
obtained at all positions.
G1
Bottom of ingot
G2
G1G3Sampling position(135mm10mm)
G3
Top of ingot
339
Chemical analysis was performed using the center core bar. To compare the trial LP rotor and
650 ton ingot dissected in 2010, the positions of the test pieces sampled from trial LP rotor was
restored to their original ingot state. Figure 12 shows the distribution of the carbon content at the
center of the ingot as an example of the chemical analysis. Carbon has a relatively severe
segregation profile in the ingot. The carbon content gradually increased toward the top of the
ingot. This behavior is inevitable in the progress of the solidification process for the ingot.
Although the ingot is large, the chemical profile in the trial LP rotor was almost the same as the
650 ton ingot and LP rotors made from the 600 ton ingots.
0.50
650 ton ingot
Trial LP rotor
LP rotor made from 600 ton ingot
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0
1000
2000
3000
4000
5000
6000
Furthermore, the area fraction of non-metallic inclusion in the trial LP rotor made from the 670
ton ingot ranged from 0.0024 % to 0.0064 %, and the inclusions consist of oxides and sulfides.
This result is almost the same as the that of 650 ton ingot, which ranged from 0.0002 % to
0.0082 %.
Heat stability test
After the mechanical test, the trial LP rotor was gashed to investigate the heat stability. The
contour of the trial LP rotor was decided based on design information acquired from heavy
electric machinery companies. The heat stability test was performed in accordance with ASTM
A472 as the international standard, and the test temperature was 400 , the highest demanded.
Moreover, a new heat furnace was produced because the trial LP rotor has a large body with a
diameter of 3,200 mm. Figure 13 shows the results of the heat stability test. The deflection was
evaluated as the deference of the movement of center between in 400 and room temperature
were within the 2.5 / 100 mm limit stipulated by ASTM A472. The deflection of the trial LP
rotor was equal to the LP rotors made from the 600 ton ingots.
340
Measurement points
Top of ingot
Bottom of ingot
Measurement points
Movement of shaft center
(1/100mm)
Specified range
ASTM A472 (1/100mm)
0.35
0.80
0.50
2.5
40
Trial LP rotor
LP rotor made from 600 ton ingot
Test temparature 400
Number of rotor 22
35
Number of data
30
25
20
15
ASTM A472
Specified range2.5 / 100mm
10
5
4.54.9
4.04.4
3.53.9
3.03.4
2.52.9
2.02.4
1.51.9
1.01.4
0.50.9
00.4
Macrostructure observation
The macrostructure observation was performed for the entire longitudinal section of the trial LP
rotor based on the JIS G0553 method using flat polished specimens for macrostructure
observation. The macrostructure is shown in Figure 14. Inverse V segregation (A segregation)
streaks are observed at the top side of the ingot in the journal near the body. Observed V
segregation streaks in the top side of the ingot in the journal are shown in Figure 15. Although
inverse V segregation has a tendency to become severe with increasing ingot size, not much
inverse V segregation was found in the trial LP rotor. And the inverse V segregation was slightly.
500mm
341
Observed position
Surface side
Center side
Bottom side of ingot
We have established the technology for manufacturing rotor shafts made from a 670 ton ingot.
Consequently, we can contribute to increase the unit capacity at the power plants.
342
REFERENCES
[1]
[2]
[3]
343
The current work is dealing with presentation of the experimental approach for blade material
testing taking into account multiaxial loading conditions and development of testing equipment
for high cycle fatigue tests at temperatures up to 700C under superheated steam condition.
EXPERIMENTAL APPROACH
In order to assess appropriately fatigue life of the components considered, analyze of the in
service loading conditions was performed. A turbine blade is loaded by a complex loading
consisting of mechanical, thermal and corrosive components as main loading factors. All of these
factors are considered in the current investigations.
345
Figure 3: FEM ananlyze results with the blade critical spot detection.
FEM simulation of the blade loading condition was performed and the critical location was
detected on the blade, Fig. 3. For this critical spot sensitivity analyzes using Fatigue Index (FI)
was performed on the basis of fatigue criterions according to Dang Van (DV) and MansonMcKnight (MMK). The simulation was performed for tilt angle of the blade 45 and appropriate
axial load and torque. The analyze shown, that round sample with a notch radius 1,5mm should
provide similar fatigue behavior. There was performed verification of the notched sample
comparability of the fatigue behavior with the blade. There were applied three loading cyclic
forces for the FEM simulation within the expected range of service loads: 1, 2 and 3 kN. Results
of this analyze are shown in Fig. 4 together with results obtained for the blade loaded by the same
forces. There can be clearly seen very good agreement between the results for the blade and
proposed notched sample for all considered load levels and both applied approaches. Based on
these results notch with radius 1,5mm was further used for the uniaxially loaded round samples
that can be tested under high temperature and superheated steam.
346
The mechanical loading unit should provide cyclic loading to the testing sample at desired load
level. In the current case, magnetoresonant testing system with the load capacity +/- 150kN
allowing testing frequencies up to 250Hz was employed.
The heating unit goal in the testing system is to provide a stable testing temperature of the testing
chamber with sample. A three zone split furnace was utilized here. The operation range of the
used furnace was up to 800C. Internal space of the furnace had to be sufficient for the steam
chamber accommodation
The last and the most difficult part was the system for superheated steam production. There was
not found any commercially available system applicable for considered case. Therefore, it was to
be developed so, that it fulfills all demands on a steam parameters and it fits with the other system
parts and provides desired functionality
347
348
349
Figure 7: Example of the high cycle fatigue results obtained for smooth and notched samples at
room temperature as well as at 560C.
CONCLUSIONS
The presented work summarizes results of fatigue tests of steam turbine blades material under
superheated steam environment at high temperatures. There were explained blade service
mechanical loading conditions together with developed experimental set up enabling laboratory
simulation of these conditions on the blade model at first. The proposed experimental fixture for
multiaxial loading did not allow tests at high temperatures. Secondly, a simplification of high
temperature tests had to be done. On the basis of the FEM simulation of the blade critical point
and the fatigue index analyze was executed for this point and notched round fatigue samples with
similar fatigue conditions were proposed. Finally, fatigue testing set up for high temperature
testing under superheated steam environment up to 700C was developed and successfully applied
to tests of the smooth and notched samples. Results obtained at high temperatures were compared
with results obtained at room temperature for samples of the same geometries.
The work presented here is initial part of the project dealing with development and modernization
of turbine blades and there are expected further activities leading to procedure proposal for
fatigue life optimization from fatigue point of view for steam turbine blades.
ACKNOWLEDGMENTS
The paper was realized due to the support of project TA01020985 - Development and
modernization of turbine blades from the perspective of the reliability and service life increase
sponsored by Technology Agency of the Czech Republic.
REFERENCES
[1] Jan Dzugan et al., 2012, Advanced Materials Research, 538-541, 1630
350
ABSTRACT
This paper presents the creep and creep-fatigue crack growth behaviors of 30Cr1Mo1V turbine
rotor steel which had been in service for 16 years. Two typical sections of the rotor, i.e. high and
low temperature sections, are examined at 538, with crack initiation and propagation monitored
by D.C. potential drop method in a compact tension (CT) specimen. The material of the high
temperature section has the lower resistance to creep and creep-fatigue crack growths than the low
temperature section. The creep crack initiation (CCI) time decreases with the increase of initial
stress intensity factor. The creep-fatigue crack growth (CFCG) is dominated by the cycledependent fatigue process when the hold time at the maximum load is shorter, but it becomes
dominated by the time-dependent creep process when the hold time becomes longer. The high
temperature section shows a larger influence of time-dependent creep behavior on CFCG than the
low temperature section.
1. INTRODUCTION
The turbine rotors in power plants are often subjected to variable loading conditions during
service such as creep, fatigue and creep-fatigue, which leads to the initiation of cracks from the
pre-existing defects in manufacturing or the damages in deformation. The creep arises from the
high pressure on the rotor at high temperature, and the fatigue is due to the alternating thermal
stresses developed during turbine start and stop. Such multiple loading conditions can induce the
appearance of a macro-crack evolved from some inherent micro-defects or deformation damages
such as inclusions and voids. The crack initiation, from the viewpoint of fracture mechanics, does
not mean the failure of component since the unstable crack propagation happens only when the
initiated crack grows to a certain size. There is generally a long period of time for the crack to
initiate and grow to the critical size under creep-fatigue loading condition. To ensure the safety
and reliability of operation, it is necessary to study the creep-fatigue lifetime of turbine rotor in
service conditions.
Cr-Mo-V steel is the typical material for turbine rotors in supercritical power plants. Many
experimental and theoretical studies have been made to predict the service lifetime, focusing on
the effects of stress level, hold time and temperature on the creep-fatigue crack initiation and
growth [1-2]. However, most of them are based on the as-received material, and fewer are
reported for the performance of Cr-Mo-V steel which has been in service for a long time.
Studying the changes of the creep-fatigue crack growth behaviors of rotor steel after long-term
service is helpful to not only the better understanding of the effect of service conditions on the
351
material property, but also the reliable analysis of material degradation and life expenditure that
serve basis for the management and assessment of rotor lifetime.
In this paper, an experimental investigation on the crack growth behavior of 30Cr1Mo1V (1Cr1Mo-0.25V) rotor steel that has been operated for 16 years is carried out in both creep and creepfatigue conditions. Tests are performed in the compact tension (CT) specimens at 538 for two
typical sections of the rotor, i.e. high and low temperature sections. The effects of initial stress
level and hold time on the crack initiation and propagation are studied via D.C. potential drop
method.
2. EXPERIMENTAL PROCEDURES
2.1 Materials and specimens
The material used is 30Cr1Mo1V turbine HP-IP rotor steel, which had been in service for 16
years in subcritical plant. The chemical composition of the steel is shown in Tab.1. Two typical
sections of the rotor, i.e. high and low temperature sections, are investigated as shown in Fig.1.
The mechanical properties of materials at these two sections are shown in Tab.2. The property of
high temperature section has degraded after long-term service, but the low temperature section
still satisfies the performance requirement of ASTM A470-03[3]. The service temperature and
stress calculated by finite element analysis according to the rotors service condition are shown in
Tab.3. The high temperature section worked at a temperature more than 500 and the other at
the room temperature, but the stresses in both of the sections are very small.
The specimen used is a standardized CT specimen for creep crack growth tests based on ASTM
E1457-00[4]. The height, width and thickness are 24, 25, and 10mm, respectively. All specimens
were notched by Electrical Discharge Machining (EDM).
Tab.1 Chemical composition of 30Cr1Mo1V steel (wt.%)
Si
Mn
Ni
Cr
Cu
Mo
Al
0.29
0.22
0.75
0.007
0.002
0.43
1.12
0.06
1.20
0.27
0.005
RP0.2/MPa
Rm/MPa
A/%
Z/%
608
761
19.0
60.3
640
810
19.1
54.2
Original material
630
790
22.4
65.2
ASTM A470-03
620
725-860
17
43
352
Temperature()
25
525
67.4
22.6
353
Fig.3 Creep crack growth length versus time for different initial stress intensity factor KI of (a)
the high temperature section and (b) the low temperature section.
354
Fig.4 Creep crack initiation time t0 versus initial stress intensity factor KI
Fig.5 Creep crack growth rate da/dt versus stress intensity factor K
3.2Creep-fatigue crack growth behavior
Different from the CCG curves, the creep-fatigue crack growth (CFCG) curves have marginal
incubation stages, especially when the hold time becomes short, as shown in Fig.6. The
introduction of fatigue condition effectively reduces the creep-fatigue crack initiation (CFCI)
time, which is found to decrease with the reduction of hold time at the maximum load. When the
hold time is reduced to 1 min, no visible incubation period can be observed from the CFCG
355
curves for both high and low temperature sections. Similar to the situation in pure creep
condition, the high temperature section has the lower resistance to CFCG than the low
temperature section.
The CFCG rate can be defined as crack growth length per time (da/dt) or crack growth length per
cycle (da/dN). They are often used together to differentiate the effects of creep and fatigue on the
crack growth, as to be discussed below. The relations of da/dt and da/dN with the stress intensity
factor range K are shown respectively in Figs.7a-b for the high temperature section, and
respectively in Figs. 8a-b for the low temperature section. The CFCG rate da/dt is generally larger
than the CCG rate, but the difference in between decrease with the increase of hold time (Fig. 7a
and 8a). . As for the rate da/dN, it shows weak dependence on the hold time when the hold time
itself is shorter (e.g. 1-10 min in Figs. 7b and 8b). Only when the hold time becomes longer
(e.g. >30 min) da/dN increases with the increase of hold time..
To examine the influences of creep and fatigue on the crack growth behavior, a relationship
between the CFCG rate at a given stress intensity factor of K=36MPam1/2 and the frequency is
constructed, as shown in Fig.9. The frequencies are transferred from the hold times. The CFCG
rate da/dt depends greatly on the frequency when the frequency itself is higher, so the crack
growth behavior in this case is dominated by the cycle-dependent fatigue process. With the
decrease of frequency, i.e. the increase of hold time, the dependence becomes weaker due to the
contribution of the time-dependent creep process. Similar effects were reported by O Yokota et al.
[7] for the creep-fatigue crack growth of 12Cr steel.
The influence of time-dependent creep behavior on CFCG at the high temperature section is
larger than that at the low temperature section. This is supported by the facts that the slope of
da/dt-f curve of the high temperature section is smaller than the low temperature section (Fig. 9a),
and the scope of hold time in which the CFCG rate da/dN changes little is narrower in the former
than in the latter (Fig.9b). The reason could be that the creep property of the high temperature
section has degraded after long term service compared to the low temperature section.
Fig.6 Creep-fatigue crack growth rates of (a) da/dt and (b) da/dN versus stress intensity factor
range K of the high temperature section.
356
Fig.7 Creep-fatigue crack growth rates of (a) da/dt and (b) da/dN versus stress intensity factor
range K of the high temperature section.
Fig.8 Creep-fatigue crack growth rates of (a) da/dt and (b) da/dN versus stress intensity factor
range K of the low temperature section
357
Fig.9 Creep-fatigue crack growth rate of (a) da/dt and (b) da/dN with range of stress intensity
factor K
4. CONCLUSIONS
An investigation has been carried out on the creep and creep-fatigue crack growth behaviors of
30Cr1Mo1V steel which had been operated for 16 years. The following conclusions can be
drawn from the current investigation:
(1)The material resistance to creep and creep-fatigue crack growth of the high temperature section
has decreased, comparing to the low temperature section.
(2) Introduction of fatigue condition promotes the crack initiation and growth. The creep-fatigue
crack growth behavior is dominated by the cycle-dependent fatigue process when the hold time is
shorter, but it turns to be dominated by the time-dependent creep process when the hold time is
longer.
(3) The time-dependent creep behavior affects the CFCG at the high temperature section more
greatly than at the low temperature section.
REFERENCES
[1] Henrik Andersson, Rolf Sandstrom. Creep Crack growth in service-exposed weld metal of
2.25Cr1Mo [J].International Journal of Pressure Vessels and Piping, 2001, 78: 749-755.
[2] Takeo Yokobori, Toshimitsu Yokobori. High Temperature Creep, Fatigue and Creep-fatigue
Interaction in Engineering Materials [J].International Journal of Pressure Vessels and Piping,
2001, 78: 903-908.
[3] ASTM A 470-03, American Society for Testing and Materials, Standard Specification for
Vacuum-Treated Carbon and Alloy Steel Forgings for Turbine Rotors and Shafts [S]New
York: ASTM International, 2003.
358
[4] ASTM E 1457-00, American Society for Testing and Materials, Standard Test Method for
Measurement of Creep Crack Rates in Metals [S]New York: ASTM International, 2000
[5] Ellisonet E.G. International Conference on Creep Fatigue in Elevated Temperature
Application [C], Philadelphia 1973 and Sheffield UK 1974: Paper 173/73
[6] Duo Wang. Fracture Mechanics [M]. NanningGuangxi People Press, 1982
[7] Yokota O, Sugiura R, Yoda M ,et al. Crack Growth Characteristics and Damage in 12Cr Steel
Under High Temperature Creep and Creep-fatigue Conditions [J]. Strength Fracture and
Complexity, 2006, 4: 41-46.
359
ABSTRACT
While the water vapor content of the combustion gas in natural gas-fired land based turbines is
~10%, it can be 20-85% with coal-derived (syngas or H2) fuels or innovative turbine concepts for
more efficient carbon capture. Additional concepts envisage working fluids with high CO2
contents to facilitate carbon capture and sequestration. To investigate the effects of changes in the
gas composition on thermal barrier coating (TBC) lifetime, furnace cycling tests (1h cycles) were
performed in air with 10, 50 and 90 vol.% water vapor and in CO2-10%H2O and compared to prior
results in dry air or O2. Two types of TBCs were investigated: (1) diffusion bond coatings (Pt
diffusion or simple or Pt-modified aluminide) with commercially vapor-deposited yttria-stabilized
zirconia (YSZ) top coatings on second-generation superalloy N5 and N515 substrates and (2) high
velocity oxygen fuel (HVOF) sprayed MCrAlYHfSi bond coatings with air-plasma sprayed YSZ
top coatings on superalloy X4 or 1483 substrates. In both cases, a 20-50% decrease in coating
lifetime was observed with the addition of water vapor for all but the Pt diffusion coatings which
were unaffected by the environment. However, the higher water vapor contents in air did not
further decrease the coating lifetime. Initial results for similar diffusion bond coatings in CO210%H2O do not show a significant decrease in lifetime due to the addition of CO2.
Characterization of the failed coating microstructures showed only minor effects of water vapor
and CO2 additions that do not appear to account for the observed changes in lifetime. The current
50-100C de-rating of syngas-fired turbines is unlikely to be related to the presence of higher
water vapor in the exhaust.
INTRODUCTION
While the exhaust in natural gas-fired land based turbines contains ~10 vol.% water vapor, the
exhaust gas with coal-derived fuels or innovative turbine concepts for more efficient carbon
capture may contain 20-85% H2O [1,2]. Turbines designed for coal-derived synthesis gas (i.e.
syngas) or hydrogen fuels are expected to have higher water vapor contents than natural gas or jet
fuel due to the combustion reaction or the use of steam diluents to assist with combustion [3,4].
Syngas-fired turbines, such as those being installed in two gasification plants in the US (one began
operation in June 2013, the other is under construction), are de-rated (i.e. fired at a lower maximum
temperature). This is a significant concern as the de-rating will reduce the turbine efficiency
resulting in lower plant electricity output for the same amount of fuel. Improved
materials/coatings may enable a reduction in the de-rating; however, it is critical to understand the
syngas/H2 turbine environment. Sulfur or ash contamination from imperfect syngas cleanup (or
Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract
360No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States
Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up,
irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.
upset conditions) could certainly degrade materials performance as could the higher water vapor
content [3]. While sulfur or ash contamination could be mitigated, especially by carbon capture
processes applied to the syngas prior to combustion, the higher water vapor content is determined
by the fuel and combustion conditions. The effects of water vapor on high temperature oxidation
have been widely studied in the past 15 years [5-17], including alumina-forming alloys and
thermal barrier coating (TBC) bond coatings. There is a general need to understand the role of
water vapor and, in this case, to understand the effect of higher water vapor levels on coating
performance.
The first phase of this work studied Pt-containing bond coatings, including single phase and two
phase (+) Pt diffusion coatings [9,15,18-22] in furnace cyclic testing at 1150C because of the
extensive prior experience and in-depth characterization database available for these coatings. The
second phase examined the 1100C performance of MCrAlY bond coatings , which are typically
used in land-based gas turbines [23,24]. Included in this study is the current change in superalloy
compositions in land-based gas turbines to lower cost, low Re 2nd generation compositions [25]
or returning to 1st generation superalloys without Re, such as alloy 1483 [26].
EXPERIMENTAL PROCEDURE
For fabricating the Pt-containing coatings, superalloy Ren N5 or N515 (Table 1) coupons 1.5mm
thick, ~16mm diameter with chamfered edges were first grit blasted with alumina and then
electroplated with 71m of Pt in a laboratory scale bath at Tennessee Technological University.
For the Pt diffusion coatings, the plated coupons were then annealed in a vacuum of 10-4 Pa
(10-6 Torr) for 2h at 1175C resulting in a ~25m thick coating [19]. For Pt-modified aluminide
coatings, the plated specimens were aluminized for 6h at 1100C to form a ~40m thick layer in
a laboratory-scale chemical vapor deposition (CVD) reactor, described elsewhere [27]. A ~125m
thick ceramic YSZ top coating was deposited on one side of the coupons by electron-beam
physical vapor deposition (EB-PVD) using a standard commercial process that included a light grit
blasting prior to YSZ deposition. For the thermally sprayed coatings, 2mm thick CMSX-4 and
1483 coupons, ~16mm diameter were high velocity oxygen fuel (HVOF) coated using a
commercial-type process and commercial NiCoCrAlYHfSi [28,29] (Table 1) powders at
Stonybrook Univ. The HVOF-coated specimens were annealed in a vacuum of 10-4 Pa (10-6 Torr)
for 4h at 1080C and had a bond coating thickness of ~100m. Coupons were then returned to
Stonybrook University for air-plasma spraying (APS) a ~200m-thick YSZ layer on one side using
standard conditions.
For both types of coatings, four specimens were evaluated at each condition: three were coated
with YSZ and the fourth was tested without YSZ (and without grit blasting for both diffusion
coatings) to study the surface morphology evolution. The specimens were hung by a Pt-Rh wire
in an automated cyclic rig and were exposed for 1h at 1100C (MCrAlY) or 1150C (PtTable 1. Chemical compositions (atomic% or ppma) determined by inductively coupled plasma
analysis and combustion analysis.
Material
Ni
Cr
Al
Re Co
N5
N515
X4
1483
MCrAlYHf
64.7
66.5
62.8
60.8
41.2
8.0
6.6
7.5
13.6
16.2
Ta
Mo Ti
Other (ppma)
1.6
2.0
2.1
1.3
0.01
2.2
2.1
2.2
1.7
<
0.9
1.2
0.4
1.2
<
0.29
0.02
0.36
0.05
26C,132Zr,70Y,540Hf,17S
66Zr,104Y,1993Hf,13Ce,<1S
<3Y,270Hf,17S
<3Y,7Hf,80Si,<1S
3860Y,710Hf,6500Si,3S
361
0.01
<
1.2
4.9
<
containing) in (1) dry air or O2, (2) air with 101%, 502% or 902% vol.%H2O or (3) buffered
90%(CO2-0.15%O2)+10%H2O and cooled in laboratory air for 10min for each cycle. Oxidation
in wet air was conducted by flowing air at 850 ml/min with distilled water atomized into the gas
stream above its condensation temperature. The injected water was measured to calibrate its
concentration. Mass change was measured using a Mettler-Toledo model XP205 balance. Every
200 cycles, the specimens without YSZ were characterized by scanning electron microscopy
(SEM) equipped with an energy dispersive x-ray spectrometer (EDS) to examine the surface scale
adhesion and roughness [15-17]. After completing testing, the specimens were metallographically
sectioned and examined by light microscopy and electron probe microanalysis (EPMA) using a
JEOL model 8200.
RESULTS & DISCUSSION
Pt diffusion bond coatings
Figure 1 shows the average lifetime data for the Pt diffusion bond coatings in various environments
[15,16,22,30,31]. Massive YSZ spallation defined the coating lifetime and the average and a
standard deviation of the three specimens is shown. The lifetimes in dry O2 are higher than other
studies [32,33] but numerous experimental differences make comparisons difficult. For the Ptdiffusion bond coatings, the addition of water vapor appeared to have little effect on YSZ lifetime.
With 10%H2O, a similar lifetime was noted for the N5 and N515 substrates and the average
lifetime was highest in CO2-10%H2O. In contrast, water vapor had a significant effect on the
lifetime of Pt-modified CVD aluminide bond coatings on N5. The reduction in average lifetime
was inversely proportional to the water content, 53% with 10%H2O, 37% with 50%H2O and 16%
with 90%H2O (the 90%H2O life is within the standard deviation of the dry O2 lifetime). A similar
drop in lifetime was observed for coatings on X4 substrates [34]. For the same bond coating
on the N515 substrate in 10%H2O, the lifetime was more than double that observed on N5 and
slightly higher than for N5 in dry O2, Figure 1. No comparable dry O2 data has been generated
Figure 1. Average lifetimes (number of 1 h cycles to failure) for EB-PVD YSZ-coated superalloy
specimens with two different Pt-containing diffusion bond coatings exposed at 1150C in several
environments. The bars note one standard deviation for 3 specimens of each type. [15,16]
362
for coated N515. Replacing air with buffered CO2 in the experiment further increased the lifetime.
For the environments containing H2O, the coating lifetime appeared to increase with decreasing
pO2. However, the oxidation of alumina-forming alloys is thought to be independent of pO2 [35]
even in steam [36] and changes in environment had only minor effects on the thermally grown
alumina scale thickness [16]. Previously, the coating results were explained by an observed
effect of water vapor on the rumpling of the bond coating [15,30], however, more recent
experiments could not confirm that hypothesis [34]. For the N515 substrates, the increased
coating lifetime is attributed to the higher Hf content in this alloy (Table 1) and the well-known
benefit of Hf on improving the oxidation resistance of NiAl and aluminide coatings on Hf-doped
substrates [37-39], including improving the creep strength of the alumina scale [40]. The Pt
diffusion coating lifetime did not increase with the N515 substrate because of the difference in
coating phases. For -, the higher Hf content increased the amount of internal oxidation, which
has been shown previously in model alloys and coated superalloys [41,42]. The difference in
reaction products between the two types of Pt diffusion coatings on N515 is shown in Figure 2.
EPMA x-ray maps from a similar - coated specimen show that the internal oxidation contains
numerous bright particles (Z-contrast in the backscattered image) that are rich in Hf, Figure 3.
Both coatings appear relatively flat with failure at the alumina-coated metal substrate interface.
Limited rumpling of the coating, which is widely observed on similar coatings without a ceramic
top coating [43,44], was likely suppressed by the adjacent ceramic top coating [30,45]. There was
no evidence of carbide formation in the CO2-rich environment.
NiCoCrAlYHfSi bond coatings
While diffusion coatings are widely used in aero-engines, these turbines are not likely to operate
with coal-derived fuels. Larger land-based power generation turbines typically use sprayed
MCrAlY-type bond coatings and sprayed YSZ top coatings. Figure 4 shows current results for
HVOF (widely used in land-based turbines [23]) NiCoCrAlYHfSi-coated X4 and 1483 substrates
but with a rougher bond coating (Ra~8) than prior X4 results with a lower (Ra~5) roughness
[17,30]. In this case, the exposure temperature was reduced to 1100C because the higher
coefficient of thermal expansion (CTE) of these coatings [46] induces more rapid spallation of the
low CTE alumina scale [45]. As for the bond coatings in Figure 1, the addition of 10% water
vapor decreased the lifetime for coatings on both X4 and 1483 substrates. Comparing the results
for these two substrates, in both dry and wet environments, the lifetimes were reduced for the 1483
substrates compared to X4. This reduction is attributed to the lower Al content in the 1483
substrates, Table 1. Exposure at 1100C greatly accelerates the Al loss from the coating (as will
be discussed later), likely leading to early failures. The roughness was increased in the 2nd set of
YSZ
YSZ
alumina scale
epoxy
epoxy
N515
50 m
internal oxidation
- coating
N515
Figure 2. Light microscopy of polished cross-sections of failed N515 substrates with EB-PVD
YSZ top coated specimens at 1150C in buffered CO2-0.15%O2+10%H2O (a) -NiPtAl bond
coating after 1320 1-h cycles and (b) - bond coating after 2680 cycles.
363
10 m
Al
Hf
Figure 3. (a) Backscattered electron image of a polished cross-section of - bond coated N515
after 2080 1-h cycles at 1150C in buffered CO2-0.15%O2+10%H2O with corresponding x-ray
maps (b) O, (c) Al and (d) Hf.
specimens to be more similar to commercial HVOF coatings. With the same X4 substrate, the
higher roughness did not increase coating lifetime as expected. With the observed scatter in the
data, the average lifetimes were very similar. However, the bond coating was thinner in the second
batch, ~100m, compared to 125m in the first batch which may have affected the results. Finally,
one set of coated 1483 specimens were exposed in air with 50%H2O. The lifetime was slightly
lower than for 10%H2O and all three specimens failed after 240 cycles.
Figure 5 shows the affect of coating roughness on the failure. Rougher interfaces lead to mixed
failure near the YSZ-bond coating interface compared to the smoother diffusion bond coatings,
Figure 2. When the top coat spalls (usually in one piece), interfacial cracks proceed through the
Figure 4. Average coating lifetimes (number of 1 h cycles to failure) for APS YSZ coated X4 and
1483 16mm diameter superalloy coupons with HVOF NiCoCrAlYHfSi type bond coatings with
two different average roughness (Ra) values exposed at 1100C in dry and wet environments.
Bars note one standard deviation for three specimens of each type. [17,46]
364
epoxy
epoxy
YSZ
Al-rich denuded zone
YSZ
alumina scale
20 m
alumina scale
alumina scale and the YSZ, leaving some metal exposed but also some YSZ on the substrate
surface. Thus, higher roughness is thought to inhibit this failure. However, the large asperities in
the higher roughness bond coating appeared to be undercut by oxidation, arrow in Figure 5b. In
some cases, the asperities sheared off leaving small pieces of metal in the spalled YSZ coating.
This behavior may be due to the high temperature and short 1h cycles used to induce rapid failures
in laboratory testing. (Previous work with 100-h cycles at 1100C resulted in an average YSZ
lifetime of 3733h.) Figure 5a shows the region of the coating near the surface was depleted in the
Al-rich phase in the coating. The phase depletion occurs both due to formation of the alumina
scale (and reformation when spallation occurs) on the gas side and interdiffusion with the substrate
on the substrate side. An example line profile from a coated 1483 specimen exposed at 1100C in
air with 50%H2O is shown in Figure 6. After only 240 1-h cycles, the Al content had dropped to
~6%, about 50% of the starting powder composition, and there is no evidence of Al-rich phase
remaining in the ~100m thick coating after this exposure. In addition, the Ti content in the
Figure 6. Electron microprobe line profiles across failed a 1483 HVOF (Ra=8)/APS-coated
specimen at 1100C after 240 1-h cycles in air with 50% H2O. The gas interface is on the left
and the substrate is on the right in both cases.
365
YSZ
YSZ
epoxy
epoxy
YSZ
alumina scale
50m
1483
X4
b
alumina
Figure 7. Light microscopy of polished cross-sections of failed HVOF (Ra=8)/APS-coated
specimens exposed in 10% water vapor at 1100C (a) X4 substrate after 340 1-h cycles
(b) 1483 substrate after 280 cycles.
coating is 1.4% throughout the coating and both Mo and Ta have diffused from the substrate to
similar levels in the coating. At this level, Ti is thought to be detrimental to alumina scale adhesion
[22] but this has not been conclusively established. However, Ti has been minimized or excluded
from most 2nd generation superalloys like N5 and N515, Table 1.
Figure 7 compares the failed coatings on X4 and 1483 substrates after cycling in air with 10%H2O.
Both failures appear similar. Chemical analysis has not been completed on these specimens but
the coating on 1483 appears to be fully depleted in the Al-rich phase after 280 cycles, consistent
with the profile in Figure 6, and some phase is apparent in the coating on X4 after 340 cycles.
Slower interdiffusion on X4, due to its higher Al content, likely accounts for this difference. Also,
the higher Ti content in 1483 may cause an additional effect on interdiffusion, explaining the
decreased coating lifetimes at 1100C for 1483. In Figure 7a, the larger dark particles at the
coating substrate interface are alumina, presumably embedded grit used to clean the surface prior
to coating. The particles appear slightly larger for the less oxidation-resistant 1483 substrates,
Figure 7b. This difference needs to be further investigated. Comparing Figure 7 to Figure 2b,
there is an obvious difference in internal oxidation. The lower Hf content in the NiCoCrAlYHfSi
coating reduced the amount of internal oxidation expected. In addition, some or all of the Hf (and
Y) may be oxidized during deposition. In both Figures 5 and 7, the small dark precipitates in the
coating are oxides present after deposition. When tied up as oxides, the Hf is less mobile and
unlikely to form large internal oxides as shown in Figure 3. Furthermore, recent results on model
NiCrAlY, YHf and YHfTi alloys suggested that co-doping (i.e. adding both Y and Hf to the
coating) reduces the depth of internal oxidation [47].
While water vapor is well-known to have a detrimental effect on oxidation behavior, including
TBC life, these results suggest that higher levels of water vapor do not appear to further affect
lifetime under these conditions. For alumina-forming alloys and coatings, water vapor has been
shown to increase internal oxidation and the amount of scale spallation observed [7]. While some
studies on FeCrAl alloys suggest that water vapor could affect the growth rate of the scale, the
observations are that it reduces the growth rate [48,49]. However, measurements of the scale
beneath YSZ have seen little effect or a slight increase in the scale thickness [16,17]. Evidence of
366
evaporation of Al(OH)3 at 1100C also has been observed [9] but this should not be a factor
beneath a YSZ top coating. Scale adhesion appears to be the most likely mechanism for a water
vapor effect, perhaps accelerating cracking at the metal-oxide interface [10]. While ideal model
alloys, such as Hf-doped NiAl or NiCrAlYHf, do not spall more with the addition of water vapor,
these coatings include a variety of substrate and coating impurities and may be more susceptible.
A few recent studies have considered the effect of CO2 on the oxidation behavior of aluminaforming alloys [50,51]. As with the current results, these studies suggest that the effect of CO2 is
minimal. Additional experiments are being conducted with HVOF bond coatings, but using 100h
cycles to better simulate a base load turbine duty cycle [17].
Actual metal temperatures in turbines are not likely to exceed 900C in order to achieve 25kh
coating lifetimes. Water vapor effects may need to be examined over a broader range of
temperatures. For syngas fired turbines, the higher water vapor contents are not likely to affect
coating performance. Thus, other environmental factors such as S and ash should be evaluated in
order to better understand coating performance in these systems.
CONCLUSIONS
Laboratory furnace cycling at 1100 and 1150C was used to compare the YSZ coating lifetime in
two different types of TBC systems with and without the presence of H2O and CO2. At 1100C,
NiCoCrAlYHfSi bond coatings with APS YSZ top coatings on X4 and 1483 substrates showed a
~15-30% reduction in average TBC lifetime in air with 10%H2O compared to dry O2 or air. When
the H2O content was increased to 50%, only a slight further decrease in lifetime was observed.
Compared to 2nd generation superalloy X4, the average coating lifetimes on 1483 were lower and
this was attributed to the lower Al and higher Ti in this alloy and the accelerated interdiffusion
occurring at 1100C, compared to the application temperature of 900C. At 1150C, the average
EB-PVD YSZ lifetime with Pt diffusion bond coatings on N5 substrates were relatively unaffected
by 10%-90% H2O additions and increased in buffered CO2-10%H2O with a N515 substrate. In
contrast, Pt-modified aluminide coatings on N5 showed a 50% lifetime reduction with the addition
of 10% H2O. Higher water vapor contents of 50 and 90% reduced the lifetime only 37 and 16%,
respectively. Longer YSZ coating lifetimes were observed for phase coatings on the higher Hf,
low Re N515 substrates in air with 10%H2O and buffered CO2-10%H2O. This was attributed to
the beneficial role of Hf on alumina scale growth and adhesion. Higher water vapor contents do
not appear detrimental to YSZ coating lifetime and other factors unique to coal derived H2 and
syngas-fired turbines should be investigated.
ACKNOWLEDGMENTS
The authors would like to thank G. W. Garner, T. M. Lowe, K. M. Cooley, H. Longmire, T. Jordan
and D. Leonard for assistance with the experimental work. Plating of Pt was conducted at
Tennessee Tech. University by Prof. Y. Zhang. B. Hazel and B. Nagaraj at General Electric
Aircraft Engines provided the N5 and N515 substrate materials and coated the specimens with EBPVD YSZ and Stonybrook Univ. applied the HVOF and APS coatings. The X4 substrates were
provided by K. Murphy at Alcoa Howmet and the 1483 substrates by A. Kulkarni at Siemens. P.
F. Tortorelli provided helpful comments on the manuscript. This research was sponsored by the
U.S. Department of Energy, Office of Coal and Power R&D, Office of Fossil Energy, (R. Dennis
program manager).
367
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ABSTRACT
Coatings are an essential part of the materials system to protect the turbine blades from oxidation
and corrosive attack during service. Inter-diffusion of alloying elements between a turbine blade
substrate and their coatings is a potential concern for coated turbine blades at ever increasing
operating temperatures because this can cause the formation of undesirable Secondary Reaction
Zones (SRZs), which may degrade the mechanical properties of coated Ni-based superalloys.
Understanding the effects of each element on the SRZ formation is essential in order to
understand both the mechanism and inter-diffusion behaviour between coatings and substrates. In
this research, a number of simpler aluminized ternary Ni-Al-X (where X is Co, Cr, Re, Ru or Ta)
alloys were investigated in order to elucidate the separate effects of each element on the
microstructural evolution, especially at the coating/substrate interface. The aluminized ternary
alloys developed distinctive diffusion zones, depending on the third alloy element, X.
Specifically, it has been found that both Ni-Al-Re and Ni-Al-Ta alloys developed a continuous
SRZ-like diffusion layer. This diffusion zone persisted in the Ni-Al-Re alloys after high
temperature exposure, indicating that Re has a stronger effect on SRZ formation than Ta.
INTRODUCTION
Higher operating temperatures of power plant improve thermodynamic efficiency, which in turn
leads to a reduction in CO2 emissions and lower fuel consumption. Ni-based superalloys, used as
substrate materials for turbine blades in gas turbines, have excellent high temperature capability.
Coatings also have an important role to play: these are frequently applied to the surfaces of the
turbine blades to provide additional protection against oxidative and corrosive environments
during service.
As the operating temperature increases and the environment becomes more aggressive, the
oxidation and corrosion resistance of turbine blade materials becomes more crucial than before.
Furthermore, inter-diffusion of alloy elements between a coating and a substrate becomes more
important, as this will be very significant at higher temperature, and will accommodate
microstructure changes during service, such as the formation of Secondary Reaction Zones
(SRZs) [1-6] and Topologically Close-packed (TCP) phases [7]. The term SRZ was suggested
by Walston [1], and they were first observed in coated third generation Ni-based superalloys. The
SRZ [1] which can form between a coating and a Ni-based superalloy substrate is generally
considered to be a detrimental layer for coated turbine blades because it can degrade the
mechanical properties of the blades. Sato et al. compared the mechanical properties of various
aluminized Ni-based superalloys and uncoated Ni-based superalloys [8], and concluded that the
SRZ formation in aluminized Ni-based superalloys potentially degrades creep properties. These
SRZs typically have been observed in the case of aluminized or Pt-aluminized coated turbine
blades, however, SRZs can also appear in other coating systems. In general, SRZs consist of , '
371
and TCP phases growing into substrate by the migration of high-angle grain boundaries. The
propensity to form such a layer is a sensitive function of composition and surface finish prior to
coating. Coatings are an essential part of the materials system to protect the turbine blades from
oxidation and corrosion attack during service, and thus it is essential to fully understand the
microstructural evolution of SRZs.
Previous studies have shown both positive and negative effects of different alloying elements in
the case of Pt-aluminized fourth generation Ni-based superalloys, e.g. Ru encourages SRZ
nucleation [5], and Mo is an effective element in impeding SRZ formation [4]. However, these
effects have been observed from various multicomponent Ni-based superalloys, with complex
alloy compositions, and are not always consistent across alloy systems. Some alloying elements,
such as Co shows clear effects in controlling SRZ formation in Pt-aluminized third-generation Nibased superlaloys, whereas this is not the case for Pt-aluminized fourth-generation Ni-based
superalloys [6]. This suggests that the effect of some alloy elements on SRZ formation can be
overwhelmed by the other elements within Ni-based superalloys.
For turbine blade applications, both the alloy and coating compositions can vary significantly, and
therefore how each element affects the formation of SRZs in coated turbine blades is key to
understanding their nucleation mechanism and predicting their growth behavior. In this research,
Ni-Al-X (where X is Co, Cr, Re, Ru or Ta) ternary alloys have been used as substrates in order to
simplify the effect of alloying elements on SRZ formation. This paper presents a possible
mechanism of diffusion zone formation in aluminized ternary alloys, especially in terms of their
microstructural changes during coating preparation and high temperature exposure. It is
anticipated that a greater understanding of the formation of SRZs will facilitate the development
of materials systems with superior mechanical properties and greater microstructural stability. The
results of this study will also act as an indicator of possible problems in terms of microstructural
stability when the alloy compositions are varied for future generations of Ni-based superalloys.
EXPERIMENTAL
The ternary alloy compositions used in this study are presented in Table 1. The Ni-Al-Co, Ni-AlCr, Ni-Al-Re and Ni-Al-Ru alloys were designed to contain both the ' and phases at 1100 C
from ternary diagrams [9-15], and the Ni-Al-Ta alloy was designed to have ' phase at elevated
temperature using the thermodynamic equilibrium software package, MTDATA [16]. The alloys
were prepared via arc melting under an argon atmosphere, followed by an appropriate
homogenization heat treatment. Ternary alloys were cut into coupons with a 3 mm thickness. The
alloys were grit-blasted and then an aluminizing coating process was applied by a Low
Temperature High Activity (LTHA) process, followed by post-production heat treatment (PPHT)
at 1100C for 1 hour under flowing Ar. CMSX-4 was also used as a reference material, and its
composition is also listed in Table 1. Isothermal oxidation tests were subsequently conducted at
880C for up to 500 hours, followed by cooling in air. The resulting microstructures were
analysed using scanning electron microscopy (SEM) with a back-scattered detector (BSE), and
scanning transmission electron microscopy (STEM) and Transmission Electron Microscopy
(TEM) with energy-dispersive X-ray analysis (EDX). Cross-sectional TEM samples were
prepared using a dual-beam focused ion beam scanning electron microscope (FIBSEM).
372
Alloy
Ni-Al-Co
Ni-Al-Cr
Ni-Al-Re
Ni-Al-Ta
Ni-Al-Ru
CMSX-4
Ni
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
Al
20.3
20.0
18.0
20.7
20.0
12.6
W
-----2.0
Ti
-----1.3
Hf
-----0.03
Ru
----2.1
--
RESULTS
As Aluminized Microstructures
Figure 1 shows cross-sectional microstructures of all of the aluminized ternary alloys. All alloys
formed a coating layer within a thickness range of 35 to 70 m, and consisted of a -NiAl phase.
The Ni-Al-Cr system consisted of two distinctive coating layers, which are indicated as layers 1
and 2 in Fig. 1. Both layers consisted of the phase, however, layer 1 was found to contain less
than 1.5 at.% of Cr, whereas layer 2 contained approximately 6 at.% of Cr. However, the coating
layer in the Ni-Al-Re specimens did not contain Re, suggesting that Re is not incorporated into NiAl. The coating layer in Ni-Al-Ta developed a number of discrete particles. EDX analyses also
indicated that there was a small amount of Ta content in the coating layer, and therefore it is likely
that the discrete particles observed are Ta-rich precipitates. CMSX-4 exhibited typical crosssectional microstructures of as aluminized Ni-based superalloys [17]. The thicknesses of the
coating layer in the specimens were in the order: Cr>Co, Ru> Ta>Re>CMSX-4.
Ni-Al-Co and Ni-Al-Ru alloy did not form any clear diffusion zones after aluminizing at the
interface between coating and substrate, however, the other ternary alloys developed continuous
diffusion layers with distinct morphologies which depended on the third alloy element, X. The
diffusion layer in Ni-Al-Cr in Fig. 1 was approximately 20 m thick. In the diffusion zone in NiAl-Cr, dark phases were observed which were composed of 30.8Al-10.6Cr-58.7Ni (at.%),
whereas bright phases contained 14.9Al-23.1Cr-62.1Ni (at.%). These phase compositions are
comparable with the phase composition of the and phases reported in Ni-Al-Cr ternary
diagram by Dupin [12], and this means that the diffusion zone in Ni-Al-Cr consists of the phase
surrounded by a matrix phase, which was probably formed due to the outward diffusion of Ni
during post-production heat treatment. CMSX-4 formed a typical inter-diffusion zone (IDZ)
microstructure, consisting of -NiAl with topologically close-packed (TCP) phases. Except for
the TCP phase precipitation in the IDZ, the interfacial morphology between -NiAl and substrate
('/ phases) formed in CMSX-4 was similar to that in Ni-Al-Cr, and therefore was classified as an
inter-diffusion zone.
However, both the Ni-Al-Ta and Ni-Al-Re alloys formed a diffusion zone, which was more
similar to a SRZ, as in Fig. 1. Ni-Al-Ta formed the narrowest diffusion zone of all the specimens,
which was approximately 6 m in extent, and consisted of a number of grains with a phase
matrix and Ta-rich precipitates, which grew perpendicular to the substrate with a rod shape and
bright contrast in Fig. 1. Earlier work [18] has shown using EDX mapping that the particles
precipitated in the diffusion zone of Ni-Al-Ta were rich in Ta, but with an absence of Al.
373
Whole microstructure
Diffusion zone
Whole microstructure
Diffusion zone
Figure 2: Bright field images with the selected area diffraction patterns (SADPs) of Ta-rich
precipitates in the diffusion zone of as aluminized Ni-Al-Ta: (a) Ni2AlTa and (b) Ni2Ta.
Table 2: TEM-EDX analysis results of the
precipitates formed within the diffusion
zone of aluminized Ni-Al-Ta. (Numbers
corresponds to Fig. 2.)
However, the diffusion zones started to show some microstructural changes after 20 hours, as
shown in Fig. 4. The phase in the diffusion zone in Ni-Al-Cr showed decreases in both the
number and the size of particles. With respect to Ni-Al-Ta, very fine precipitates, having a needle
morphology, appeared above the diffusion zone, whereas the size of the Ni2Ta and Ni2AlTa
precipitated in the diffusion zone decreased. Ni-Al-Ru started to form a layer consisting of very
fine precipitates, with a brighter contrast and located just above the substrate. In terms of Ni-AlCo, Ni-Al-Re and CMSX-4, the microstructural changes in their diffusion zone after 20 hours
exposure were less significant than the other alloys.
Diffusion zone
Whole microstructure
Diffusion zone
500 hours. Most of the other alloys retained the phase as matrix phase, however, some
transformation from to ' phase was observed in Ni-Al-Ru.
Figure 5: STEM-EDX mapping of the diffusion zone in Ni-Al-Ru at 880oC after 500 hours.
(Numbers correspond to Table 3.)
Table 3: STEM-EDX point analysis of diffusion
zones of aluminized Ni-Al-Ru at 880oC after
500 hours (at.%).
Al
Ni
Ru
(1)
27.3
72.7
0.0
(2)
42.4
41.5
16.1
(3)
45.9
35.1
19.0
Ni-Al-Re retained the SRZ-like diffusion zone, and some matrix transformation from to ' was
observed, as shown in Fig. 4. However, the thickness of the diffusion zone in Ni-Al-Re did not
change significantly. The very fine needle-like precipitates formed in the diffusion zone of Ni-AlTa coarsened, and started to form discrete precipitates along the grain boundaries. Also, under the
diffusion zone, some needle-shaped small precipitates, appeared after 500 hours. CMSX-4
demonstrated some TCP phase precipitation underneath the IDZ, which are frequently observed
after thermal exposure [17].
In the case of Ni-Al-Ru, the diffusion zones increased in extent. The brightly imaging precipitates
shown in Fig.4 became more noticeable, and increased in number with exposure time. The
precipitates formed in the diffusion zone of Ni-Al-Ru after thermal exposure were investigated
further with STEM. Fig. 5 shows the STEM-EDX mapping results for diffusion zones in Ni-AlRu at 880C for 500 hours, and Table 3 shows the EDX point analysis results. Needle-like
precipitates were distributed within the matrix phase ('- Ni3Al). The width of the precipitates was
less than 500 nm, but their length varied. The EDX data presented in Fig. 5 demonstrated that the
precipitates contained higher concentration of Al and Ru, compared to the matrix phase. Point
analysis in Table 3 revealed that the precipitates consist of approximately 35~41 at.% Ni, 43~46
at.% Al, and 16~19 at.% Ru; these compositions are comparable to the NiAl based 1 phase,
which was reported by Chakravory [13,19].
DISCUSSION
In this study, aluminized Ni-Al-X ternary alloys showed a distinctive morphology within the
diffusion zone before and after thermal exposure, depending on the third element present. In the
LTHA process, Al is the predominant diffusing species, and Al diffuses inwardly to form a
coating layer. The coating layer after the aluminizing process typically consists of -Ni2Al3, and
the -Ni2Al3 in the coating layer transforms to -NiAl during the post-production heat treatment at
376
1100C for 1h. During this process, a diffusion zone is also formed at the interface between the
coating layer and the Ni-based superalloy substrate [20, 21]. During the LTHA process, Al
diffuses into /' phases to form -Ni2Al3 [22], and Ni moves towards the surface to form -NiAl
during the post-production heat treatment. In Ni-Al-X ternary systems, the formation of diffusion
zones after aluminizing depends on the solubility of X elements in the -Ni2Al3, -NiAl and '
Ni3Al phases. For example, Co and Cr have a large solubility in the -NiAl phase [9,11,12]. Co
can form a complete solid solution in Ni-Al and Ni, and this resulted in no diffusion zone
formation after the aluminizing process, as shown in Fig. 2. In terms of Cr, the binary -Ni2Al3
phase also has approximately 12 at.% of Cr solubility [23]. However, the relatively small
solubility of Cr in -NiAl is responsible for the formation of phase diffusion zones.
The solubility of both Re and Ta into -Ni2Al3 and -NiAl phase is much smaller than that of Cr
[10, 24-28]. Specifically, the Re solubility in the -NiAl phase is 0.53 at.% in the as cast
condition [24], and 0.5 at.% in -Ni2Al3 [28]. Therefore, Re rejected from the -NiAl and Ni2Al3 phases and forms Re-rich phase precipitates, as observed in Fig. 2. Nrita et al. [29]
reported that Re has limited diffusion in Ni aluminides. This also suggests that Re in the substrate
was rejected from the -NiAl phase, with segregation occurring at the interface between the
coating and substrate.
With respect to Ta, the low solubility in the phase, which is less than 1 at.% [28], contributed to
the formation of discrete particles in the coating layer and diffusion zone. In particular, a variety
of precipitates and intermetallic compounds have been reported in the Ni-Al-Ta system [25,30]. It
can be considered that the small solubility and variety of possible precipitates in the Ni-Al-Ta
system contributed to the formation of an SRZ-like diffusion zone. Ni-Al-Ta contained a number
of discrete particles within the coating layer in both as coated and as received conditions.
Therefore, it is expected that the lower solubility of a particular X element in -NiAl and Ni2Al3 is strongly associated with diffusion zone formation, as observed in the aluminized
condition in this study.
The morphology of the diffusion zones observed in these systems were particularly distinctive
(see Fig. 2). Although the matrix phase of the diffusion zone in both Ni-Al-Re and Ni-Al-Ta is NiAl, the morphology and the interface between the diffusion zone and substrate is almost
identical to the typical SRZ formed in coated Ni-based superalloys [1,2]. Many of the X-rich (X:
Re or Ta) precipitates within the diffusion zone also grow perpendicular to the substrate in Fig. 2,
and this is a consistent propensity of TCPs growing in SRZ formed in coated Ni-based superalloys
[1-4]. However, the interfacial morphology between -NiAl and the substrate (/' phases) formed
in Ni-Al-Cr was very similar to that in CMSX-4, and therefore was classified as an inter-diffusion
zone. It has been noted that the interface morphology between the diffusion zones and the
substrates was very different, and therefore the diffusion zone in Ni-Al-Cr is defined as an interdiffusion zone, whereas the one in Ni-Al-Re and Ni-Al-Ta has been defined to be an SRZ.
The X-rich precipitates (X: Re or Ta) in the diffusion zones were observed to preferentially
segregate at grain boundaries [2]. X-rich precipitates may cause the formation of many grains in
the diffusion zone during the aluminizing process or post-production heat treatment. A SRZ is
generally formed via a phase transformation from -NiAl to '-Ni3Al in the IDZ during the postproduction heat treatment, however, the results from the aluminized ternary alloys have indicated
that the SRZ can nucleate before the phase transformation occurs. It is believed that the formation
of X-rich precipitates can also act as a nucleation site of a SRZ, and may accelerate the formation
of SRZ nuclei during the post-production heat treatment.
377
The ternary Ni-Al-X alloys demonstrated microstructural changes in both the coating layers and
diffusion zones during the exposure at 880C, however the changes were slower than at 1100C
as expected [18]. In Ni-Al-Co, the coating layer changed to and ' phase, suggesting that all the
-NiAl phase was consumed. This might be due to the inferior oxidation resistance of Co at
elevated temperatures [31]. All of the other alloys still contained the phase after 500 hours
exposure, however, Ni-Al-Ru exhibited some transformation from -NiAl to '-Ni3Al phase near
the specimen surface. The effect of Ru on the oxidation resistance of coatings and Ni-based
superalloys is the subject of debate [32-35], however, it is clear that Ni-Al-Ru showed slightly
faster coating layer degradation than the other samples, except for the Ni-Al-Co.
With respect to the diffusion zones, it must be noted that Ni-Al-Ru exhibited slightly different
diffusion zone formation from the other ternary alloy systems. All alloys except for Ni-Al-Ru
formed the diffusion zones before exposure, however Ni-Al-Ru developed the diffusion zones
consisting of very fine Ru-rich precipitates during exposure. This is likely to be associated with
the solubility of X elements into the various Ni-Al phases. In the case of Ru, there is complete
solid solubility between the NiAl and RuAl phases at 800oC and a high amount of Ru solubility in
NiAl at 1000oC [9]. However the solubility reduced as Al receded. This suggests that Ru
remained within the NiAl phase during the aluminizing process, and it was gradually rejected and
appeared as precipitates during the exposure, due to the Al loss during exposure. The matrix
phase around the Ru-rich precipitates was the Ni3Al phase, with a very limited solubility for Re,
which explains the formation of Ru-rich precipitates during the exposure. Although the formation
of the diffusion zones was observed in Ni-Al-Ru during the exposure, all of the other ternary
alloys exhibited microstructural degradation of diffusion zones in respect of di diffusion zone
thickness and precipitate morphology.
The matrix phase of the diffusion zones transformed into the '-Ni3Al phase, in particular in NiAl-Re and Ni-Al-Ta, and the some precipitates were reduced their numbers, and integrated into
other precipitates in both Ni-Al-Re alloys and Ni-Al-Ta, with the progress of interdiffusion of
alloying elements. Also, Ni-Al-Ta exhibited a greater reduction in precipitates than those in NiAl-Re. At 900C, the diffusion coefficient of Ta in Ni is approximately 8x10-17-2x10-16 m2/s and
that of Re is 4-5x10-17 m2/s respectively [36], with Ta clearly having a faster diffusion rate than
Re. It is expected that part of the Ni2Ta/Ni2Al2Ta phase was consumed into the '-Ni3Al phase
during the phase transformation of matrix phase in the diffusion zone, resulting in a reduced
density of the precipitates in Ni-Al-Ta after the exposure.
In this study, both as aluminized Ni-Al-Ta and Ni-Al-Re alloys formed distinctive diffusion zones
which were defined to be SRZs, indicating that both Ta and Re are prone to SRZ formation at an
early stage. Comparing the microstructural degradation of the diffusion zone between Ni-Al-Re
and Ni-Al-Ta, Re maintained a clear layer and the effect of Re for SRZ formation is persistent
after the exposure. It should therefore be concluded that both Re and Ta promote SRZ formation,
and the effect of Re is stronger than that of Ta. Ni-Al-Ru did not show any diffusion zone
formation after aluminizing, however 1 precipitates appeared after the exposure. Due to the
formation of precipitates, it is rationalized that Ru might have similar effect on diffusion zone
formation to Re and Ta. On the other hand, it can be concluded that Ni-Al-Co and Ni-Al-Cr have
no clear negative effect on the diffusion zone formation. Ni-Al-Cr formed a precipitate-free
diffusion zone, and Ni-Al-Co did not show any diffusion zones. The solubility of X elements
into - Ni2Al3, -NiAl, '-Ni3Al and phases, and the diffusion coefficients of X element in Ni
are contributing factors to the change in diffusion zone thickness and their morphology.
378
CONCLUSIONS
Ni-Al-X ternary alloys designed to contain and ' phase were aluminized, and their
microstructural evolution, especially in terms of diffusion zones, was investigated. The following
conclusions can be drawn from this research:
Aluminized ternary alloys developed distinctive diffusion layers depending on the third
elements: Ni-Al-Cr alloys formed a layer consisting of both and phases, which is more
similar to a traditional inter-diffusion zone in coated Ni-based superalloys, whereas Ni-AlRe and Ni-Al-Ta formed a continuous layer consisting of phase and Re-rich/Ni2Ta or
Ni2AlTa precipitates with high-angle grain boundaries present.
Ni-Al-Ru did not form a diffusion zone after aluminizing, however, the microstructure
developed to contain '-Ni3Al phase and NiAl based 1 precipitates.
The matrix phase of the diffusion layer formed in Ni-Al-Re and Ni-Al-Ta alloys comprised
the phase, however, this layer can be defined to be a secondary reaction zone, because the
layer also consisted of many grains and Re or Ni2Ta/Ni2AlTa precipitates with high-angle
grain boundaries between the layer and substrate.
After exposure at 880C for 500 hours, the diffusion layer disappeared in the Ni-Al-Cr
system, and the diffusion layer in Ni-Al-Re and Ni-Al-Ta demonstrated a loss of Rerich/Ni2Ta and Ni2AlTa precipitates and phase transformations in the matrix phase.
Both Re and Ta can promote the formation of SRZs. The effect of Re is persistent after
thermal exposure, and it is concluded that Re has the stronger effect than Ta.
ACKNOWLEDGEMENTS
This research was supported by the Japan Society for the Promotion of Science (JSPS)
Postdoctoral Fellowship for Research Abroad scheme and the Department of Materials,
Loughborough University. The authors would like to acknowledge Mr K. Roberts (University of
Cambridge), Mr S. Pickering and Dr Z. Zhou (Loughborough University) and Dr R. Jones (RollsRoyce plc) for their technical assistance.
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381
V.P. "Swami" Swaminathan, TurboMet International, 8026 Winter Park, San Antonio,
TX 78250
Jeffery S. Smith, Material Processing Technology, LLC, 1965 Forest Park Road,
Norton Shores,
MI 49441
David W. Gandy, Electric Power Research Institute
P.O. Box 217097, Charlotte, NC 28221
Abstract
Solid Particle Erosion (SPE) of hardware remains an ongoing concern with the operation of Steam
Turbine power plants as well as Land Based Gas Turbines. SPE of steam piping, rotating and
stationary components in turbines leads to loss of efficiency, higher cost of operation and
maintenance downtime and cost. Ultra Supercritical (USC) and advanced USC programs
underway in North America, Europe and Asia have created renewed interest in the understanding
of the effects of SPE on the advanced alloys at high temperature. The Gas Turbine industry has
also been conducting studies for improving the elevated temperature erosion resistance of
compressor and hot section components and coatings. ASTMs G76 Standard Test Method for
Conducting Erosion Tests by Solid Particle Impingement Using Gas Jets defines a standard test
method for conducting room temperature SPE erosion testing but has many limitations that
restrict its usefulness to evaluate alloys and coatings used in turbines.
The objective of the current Electric Power Research Institute (EPRI) sponsored program is to
develop an elevated temperature SPE standard that will provide more appropriate reference
parameters for SPE conditions encountered in current and next generation steam turbines, gas
turbines as well as in the selection and qualification of alloys used in other steam path
components. Currently such test standard is not available from any of the standards organizations.
Various laboratories around the world have developed their own equipment and procedures to
conduct their elevated temperature (ET) SPE tests. This makes it difficult to compare these interlaboratory test results for the purpose of screening and selecting alloys and coatings for erosion
mitigation. Organizations from the United States, United Kingdom, China, Germany, Italy and
India have been participating in the EPRI inter-laboratory Round Robin test program to develop
a new ASTM ET erosion test standard. Standard test coupons from Type 410 stainless steel have
been tested using a standard alumina erodent powder at specified test conditions at room
temperature and 600C. Impingement angles of 30 and 90 degree were used. An international
conference on solid particle and liquid droplet erosion was organized in 2012 to gather the world
experts in erosion testing, modeling and application [1]. Valuable information was obtained at
this conference which helped in the preparation of the first draft standard which has been
382
submitted to ASTM for balloting by the committee membership. This presentation will describe
the program structure, test conditions used, test results and the development of the draft ASTM
ET SPE test standard.
Key Words: Solid particle erosion; high-temperature; round-robin testing; ASTM Standard;
steam turbines; gas turbines; particle velocity measurement
INTRODUCTION
Solid particle erosion has been a pervasive generic problem in fossil power generation equipment.
Exfoliation of oxide particles from the steam side surfaces of high-temperature steam path
components in boilers and stem pipes lead to erosion of turbine blades, nozzles and control
valves. Electric Power Research Institute (EPRI) conducted studies on the extent of this problem
and costs associated with this on utility steam turbines [2,3,4]. While thermal spray coatings
have been effective at increasing the SPE resistance of the uncoated component, component
erosion damage is still observed in service.[5] Some examples of the effects of SPE on hightemperature steam turbine parts are shown in Figure 1.
Figure 1. SPE Damage on High Pressure Steam Turbine Blades (courtesy of Encotech)
This SPE problem is expected to be more pronounced in USC turbines which operate at much
higher temperatures and pressures. Several high-temperature steels and exotic alloys in
combination with protective coatings are being developed and evaluated for the USC application.
Several papers on this subject were presented at the EPRI conference in 2010[6].
However, their erosion properties and resistance to SPE of these alloys under plant operating
conditions have not been reported.
It is important to understand the SPE behavior of the alloys used in high-temperature application
under various conditions in order to develop effective erosion mitigation options which may
include coatings and other surface modification techniques. The variables which control the SPE
behavior are the temperature, particle size, velocity impact angle, hardness of the particles as well
as the substrates, morphology of the particles (sharp, blunt, angular etc). The particle size
distribution found in a typical boiler scale of a fossil power plant is shown in Figure 2 [7] The
composition of the scale is mainly magnetite (Fe3O4). The particle size distribution varies from
about 5 microns to 100 microns. Depending on the volume fraction, velocity, angle of the
particles, the erosion characteristics will vary.
383
Figure 2. Particle size Distribution of Boiler Scale Recovered from Boiler Water and Superheater Steam Drains[7]
SPE in aero engines is also a problem for engines operating in dusty environment. Damage to
the compressor blades as well as the hot section components reduce the efficiency and life of the
engines resulting in costly change outs and repairs. The effect of SPE on an aero engine
compressor blade is shown in Figure 3. Increasing the SPE resistance of aero engine compressor
components with protective coating continues to be an active area of development.[8,9]
Figure 3 Comparison of compressor blade damaged by SPE (left) with a virgin blade (right) [10]
A brief overview of the SPE behavior of some of the materials under different conditions is
presented below.
Solid Particle Erosion Characteristics
The topic of solid particle erosion has been studied by numerous researchers over the years.
Several good reviews of the particle erosion literature can be found in articles by Wright [11],
Finnie [12], and Mathews.[13] One of the key concepts that has been identified is the difference
in the erosion behavior of ductile materials such as metals and that of brittle materials such as
most ceramics. With ductile materials the erosion response as a function of particle impact angle
384
has been show to approach zero at very low angles of attack, increases to a maximum as the angle
of incidence is between 15-20 degrees and then drops to 1/2 to 1/3 of the maximum erosion rate
as the particles impacting the surface approach 90 degrees. The erosion rate of brittle materials is
at a maximum at 90 degrees with the rate decreasing continually to a negligible mass loss at very
low angles of impact. This response reflects fracture induced mass loss where the extent of the
erosion is dependent on the vertical component of the particle impact energy. This difference in
ductile and brittle material behavior is plotted in Figure 4.
~ 1.7 mg/g
~ 10 mg/g
Figure 4. Erosion Behavior of Ductile (Al) and Brittle (Al2O3) Materials [12]
In ductile erosion, the metal is indented by the particles impacting the surface and material is
extruded around the indentation. At high angles the energy of the particle is dissipated through
ductile deformation and is more resistant to erosive wear than at low angles were the metal
indentation proceeds by a plowing or micromachining action. At high angles the material removal
mechanism is thought to proceed by work hardening of the extruded material by repeated impacts,
leading to local fatigue or fracture based loss of material. With brittle materials the particle
impact generates brittle fracture within the near surface zone of the material, with cracks radiating
outward and downward from the point of impact. These mechanisms are illustrated in Figure 5.
Figure 5. Particle Erosion Mechanisms. A) Plowing and Extrusion Mechanism for Ductile
Materials B) Brittle material Erosion Proceeds through Lateral and Radial Cracking around the
Crush Zone. (From DAlessio 1994) [14]
385
Conduct a literature search and survey of high-temperature erosion test facilities and
capabilities around the world
2.
Define the various testing parameters and develop a test matrix for elevated temperature
erosion testing
3.
Conduct round robin tests and perform statistical analysis of the results
4.
5.
Develop a high-temperature solid particle erosion test standard which could be used by
the international community to conduct SPE testing and compare the results on a
common basis
The standard testing method or guideline developed under this EPRI project is used to develop an
ASTM standard for high-temperature SPE testing. The SPE test methods used for the evaluation
and characterization of various alloys and coatings vary greatly among the various laboratories.
Several test equipments, techniques and procedures were used by the participating laboratories
and provided results to develop this test standard.
Elevated Temperature Erosion Testing
Under this EPRI program, a detailed survey of the high-temperature erosion testing capabilities
around the world was conducted. All of the steam and gas turbine manufacturers, independent
testing laboratories, universities, coating manufacturers and turbine repair companies were
surveyed to gather information. The data collected include temperature limits, velocity, methods
used to obtain high-velocities (compressed air jets vs. combustion tunnels), methods used in
velocity measurements, types of erodent and sizes used. Details of the test equipment and
methods used by the laboratories were presented in Reference [15].
In general this test method utilizes a repeated impact erosion approach involving a small nozzle
delivering a stream of gas containing abrasive particles which impacts the surface of a test
specimen. A standard set of test conditions for the elevated temperature testing were provided to
the test labs. However, deviations from some of the standard conditions are permitted if described
thoroughly. This allows for laboratory scale erosion measurements under a range of conditions.
Test methods are described for preparing the specimens, conducting the erosion exposure, and
reporting the results. Among the key variables are the type of erodent (i.e. Alumina, Silica,
Arizona Road Dust, Iron Chromite, Magnetite, etc.), particle size range (10 micron 200 micron
or larger), particle velocity (30 m/s to 215 m/s or higher) and angle of impingement (15 to 90
degrees). In reporting erosion test results it is important for these parameters to be specified. The
ASTM G76 test method for conducting solid particle erosion via gas jets is often referenced for
erosion test studies conducted at room temperature. It was developed for erosion characterization
of structural materials and is not completely suited for conducting studies of turbine components
or coatings. This has resulted in a number of different approaches being taken for testing these
386
materials. Initial room temperature screening is generally carried out with some form of a
modified G76 test since it is the simplest test to set up [16].
A schematic diagram of the elevated temperatures testing system used by the participating
laboratories around the world is shown in Figure 6.
Insulated Mixing Chamber
and Supply Tube
Figure 6. Schematic drawing of test system used for elevated temperature SPE testing and
erosion scar geometry achieved for two angles of impingement (30 and 90 degrees) on Type 410
stainless steel test coupons
Typically researchers will modify the test conditions to be more representative of field conditions
and to be better at monitoring erosion of coatings especially those that are in the 10 -20 micron
thickness range for compressor airfoil applications [9]. Typical modifications are use of silica,
instead of alumina, to use higher particle velocities to better simulate turbine conditions, a larger
diameter nozzle to increase the area tested and evaluating weight loss instead of volume loss.
Erosion results are influenced by the hardness, friability and angularity of the particles. Silica
provides results that are closer to conditions in the field than alumina does for aero engine
applications [6]. Several particle size ranges may be used depending on the SPE test objective.
The larger test area helps to screen for coating defects that might be present and to improve the
resolution of the test. Erosion rates are usually defined as the number of grams of material or
coating eroded per gram of erodent impacting the sample (mg/g) rather than as a volume loss
(mm3/g) as specified in G76. For coatings it is difficult to establish a reliable density to calculate
volume loss from the weight loss.
387
A critical feature in all erosion testing is the use of a witness coupon for comparison of erosion
results taken at different times. Often it will be the substrate material being coated (e.g., Ti-6Al4V, IN-718, 17-4 PH etc.) rather than 1020 steel called out in G76. This also provides some
measure of erosion performance compared of the substrate to guide the development of any
surface modifications needed. It is difficult to make comparisons erosion data generated in
different labs since there are often differences in the actual practice of the test that lead to
different erosion rates. Two keys areas of variation are the actual particle velocity and geometry
factors with the amount of erodent hitting the coupon. In the case of particle velocity it is
difficult to measure accurately without specialized equipment (e.g., laser doppler velocimeter
(LDV) or particle image velocimeter (PIV) etc). Some of the laboratories use double rotating disc
(DRD) method to determine the particle velocity [17]. Another factor is the amount of erodent
actually hitting the sample. At low angles this can be especially significant since the erosion
footprint may be larger than the coupon being tested.
The following organizations have high-temperature erosion test facilities and provided details of
their testing capabilities and participated in the EPRI sponsored round-robin test program to
develop the ASTM test standard..
Air Force Materials Lab (AFML) / University of Dayton Research Institute (UDRI),
Dayton, USA (room temp testing only and baseline data); LDV used for real-time
velocity measurements
General Electric Company, Schenectady, USA (test facility at GE Global Research Ctr,
Bangalore, India) - room temperature and 600C tests; DRD for velocity measurements
Cranfield University, Cranfield, UK Room temperature and 600C tests; no direct
velocity measurements but fluid dynamics principles used to compute particle stream
velocity
ERSE SpA, Milan, Italy Room and 600C tests; DRD used to measure the velocity
Institute of Turbomachinery, Xian Jiaotong University, Xian, P.R. China Room and
600C tests; PIV used in real time for velocity measurements
DUCOM, Bangalore, India Room temp and 600C tests; DRD used for velocity
measurements
Configurations and photos of the test systems, their maximum velocity (at RT) and temperature
capabilities from these test facilities are shown below in Figures 7 through 12.
388
sample
holder
screw feeder
heating system
acceleration tube
compressor
exhaust
pressure vessel
Figure 8. Test system schematic (left) and photo at Cranfield University, UK, (200 m/sec; 850C
max. )
Figure 9. Schematics of the test system at the Turbomachinery Labs, Xian University, China
(450 m/s; 650C)
Figure 10. High-temperature erosion test rig at GE Global Research, Bangalore, India (305 m/s;
982C)
389
As can be seen in these figures the architecture of the test systems and their capabilities are
diverse. The nozzle, specimen design, mounting methods, stand off distances, erodent feeding,
mixing, temperature control, etc., vary among these test facilities. Two of the test rigs employ
combustion gases and the others use compressed air with external heat. Velocity measurements
methods are also unique to each of these systems.
Round Robin Test Matrix
The material selection was based on the alloys used in high-temperature steam turbine application.
Type 410 stainless steel or similar steels are used in the steam inlet regions of most of the
turbines. The erosion test coupons size is fixed at 75 mm x 25 mm x 4.5 mm which is suitable for
all of the laboratories. Some of the labs need to make minor modification of their specimen
fixture arrangements to accommodate this sample size. The test matrix is shown in Table 1.
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Table 1. EPRI Round Robin Test Matrix for room temp. and 600C in comparison to
ASTM G76 specification
EPRI ROUND ROBIN TESTS
(Room Temp. & 600C)
200 m/s particle velocity
Adjust nozzle to test coupon standoff
distance to create 14 mm diameter erosion
scar
1.5 - 9 mm (0.060 0.360) Nozzle Diameter
(dependent on lab)
50 Alumina erodent (from a single batch)
410 Stainless Steel Substrates
2 grams/minute powder feed
5 - 10 minute min. test intervals per sample
RT & 600C Test Temperatures
30 & 90 degree impingement angles
mg/gram of erodent to be reported
The chemistry and mechanical properties of the Type 410 stainless steel coupons used in this
program are given below.
Table 2. Chemistry of Type 410 Stainless Steel Test Coupons
Grade 410 SS
Fe
Cr
Ni
Mn
Si
min.
bal
11.5
Coupon Lot
bal
12.1
max.
bal
13.5
0.75
Ti
The erodent selected was 50 alumina for this round robin test program. This powder lot was
evaluated for particle size distribution and particle characteristics. It is highly desirable to keep
the size distribution tightly around 50 . A single master lot of white alumina powder was
procured from Japan and distributed to the test labs. (JIS 6001-320: D10 = 33.8; D50 = 50.3;
D90 = 74.6). Additional details on the particle size distribution are covered in Reference [18].
391
Figure 13. Tight clustering of baseline erosion test data on Type 410 Stainless Steel at Room
Temperature (24 C), 200 m/s at 90 degrees with 50 micron alumina at 2 g/min feed rate
Table 3 summarizes the results of room temperature tests conducted by the various labs. Five
readings were taken on each coupon at 20 g intervals. Thus a total dose of 100 g erodent was
applied for each coupon. Five coupons were used for repeat tests and the average of the five
reading from each coupon was reported along with the individual readings. Thus a total of 25
readings were obtained for each angle of incidence at a given temperature. The baseline data by
Lab 9 with known measured velocity (by LDV) of 200 m/s was used to compare the results from
the other labs. As mentioned previously, each of the labs used different methods to measure or to
estimate the particle velocities. The reported velocities are 200m/s +/- 10m/s. However, it can be
seen from this table that the results reported by Lab 3 are much lower than that of the other labs.
This raised the question about the particle velocity measurement accuracy at these various labs.
Additional tests by selected few laboratories were conducted at different velocities to understand
the effect of velocity on the erosion rates and arrive at a common basis for cross comparison of
the results among these labs.
392
Table 3.
Results of the solid particle erosion tests conducted at room temperature by the
laboratories at 90 and 30 degree impingement angles at 200m/s (Note: the lab ID
numbers were assigned at random)
Since the Type 410 stainless steel is a ductile material, the erosion rates follow the trend similar to
that shown in Fig.4 for ductile materials. The erosion rates at 30 degree impingement are higher
by approximately a factor of 2x compared to the 90 degree data in Table 3.
Test Data at 600C
Out of the seven labs that conducted room temperature testing only five of the labs were able to
conduct high-temperature tests at 600C at 200 m/s particle velocity due to equipment limitations.
Labs 1 employed direct in-situ velocity measurements by PIV whereas three labs used DRD and
the one of the labs estimated the velocity using fluid dynamics principles and prior calibration
data. When DRD is used, the particle velocity is measured prior to the erosion tests on the
coupons. Then the DRD is removed from the test chamber and the test coupon is positioned for
the erosion tests. These velocity measurements are done at room temperature since DRD cannot
be used in high temperature environments. The hopper which supplies the erodent powder is kept
at room temperature. The particle stream is exposed to high temperature as it enters the career hot
gas stream or the heated test chamber depending on the test system.
The results from the 600C tests from five labs are summarized in Table 4. For comparison, data
from room temp from Lab 9 is also included in this table.
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Table 4. Summary of results of erosion tests at 600C by five laboratories at 200 m/s along with
the baseline room temperature data from Lab 9.
The rests fall with an acceptable scatter band. The data at 90 impingement angle at both
temperatures (RT and 600C) show very small difference. This infers that the erosion mechanism
is similar at both temperatures. The 30 degree data at 600C show higher erosion rates with more
scatter than the room temperature data. It should be noted that there was no noticeable oxidation
on the Type 410 stainless steel test coupons at 600C. This is expected since the cumulative
exposure time to high temperature is less than an hour for any given sample during these tests.
The interlaboratory study (ILS) group at ASTM International conducted a precision and bias
study on all of the test data. Both the repeatability and reproducibility were determined for the
data sets and they ascertained that all of the data are within acceptable limits. A detailed treatment
and discussions will be presented in a research report prepared by ASTM in support of the
proposed test standard.
Erosion Tests at Additional Velocities
Additional tests were conducted by two of the laboratories at velocities ranging from 60 m/s to
232 m/s at room temperature and 90 degree impact angle. The velocities were measured by
different techniques at each of these labs using PIV, LDV or a DRD system. One of the labs
conducted a series of tests at predetermined velocities. The test data summary and a plot are
presented in Fig. 14.
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Figure 14. Summary of average erosion rate data and power-law plot at additional velocities at
room temperature and 90 degree impact angle
The relationship of erosion rate (E) and impact velocity () is shown below in Equation 1.
E=kvm
(Equation 1)
Figure 15. Power Law data fit for the erosion rate as a function of particle velocity at 600 C and
90 degree impingement angle
395
A summary plot of erosion test data obtained at 600C/30 deg. angle is shown in Fig. 16. Again,
the velocity exponent is close to 2 which indicate the parabolic nature of the erosion phenomenon
with velocity and the erosion mechanism seems to be independent of temperature under the
testing conditions used in this program. Of course, the elative positions of the curves, i.e., the
actual erosion rates, are determined by the pre-exponential constants.
Figure 16. Power-law erosion rate plot at additional velocities at 600C and 30 degree
impingement angle
Erosion Scar Analysis
Erosion scars formed on some of the randomly selected test coupons were analyzed using optical
microscope and contact profilometry techniques. The diameter of the circular scar formed at 90
degree impingement angle, major and minor axes of the elliptical scar formed at 30 degrees and
the maximum depth of the scar are important parameters. Scar analysis is more important when
the erosion tests are conducted on coated samples. Volume and the depth of the coating removed
are critical since the weight may vary depending on the composition of the coating. Also,
breaching of the coating is undesirable to have valid data on the coatings. Typical surface
profilometry of a scar for 90 degree impingement is shown in Fig. 17 and that for 30 deg. is
shown in Fig. 18.
Figure 17. Contact profilometry data of RT test scar at 90 deg. impingement; 5mm nozzle dia,;
14 mm stand-off distance; 25 g dose; Scar diameter = 10mm; maximum depth =
0.42mm
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Figure 19 shows the results obtained using an optical profilometry system on a scar of a specimen
tested at room temperature at 30 degree impingement. The difference in the measured parameters
between Fig. 18 and 19 are due to the differences in the nozzle diameter, SOD and the total dose
applied. These results illustrate methods of scar analysis and the variability in the scar geometry
due to test system set-up parameters and test conditions. Such scar analysis will help refine the
test coupon set-up and standoff distance to obtain desirable scar sizes.
Summary
Currently high-temperature solid particle erosion testing is conducted by many organizations
around the world using their own equipment and procedures developed in-house. This EPRI
sponsored round-robin testing and ASTM test standard development program was directed at
developing a high-temperature solid particle erosion test standard which will help the industry to
perform such tests and compare the results on a common basis. Such common test method and
data analysis procedure is essential to screen materials and coatings which may be selected for use
in USC and other high-temperature steam power plants as well as gas turbine applications. This
program was very successful in organizing an international conference on this critical subject to
assemble many well known experts in the field of solid particle and liquid droplet erosion to share
the current technology, ideas and information developed over many years. There was a consensus
in this forum for the development of a common test standard which could be used by any
organization to conduct these erosion tests. Many laboratories around the world voluntarily
participated in a round robin test program to perform tests on standard coupons provided by
EPRI. Type 410 stainless steel coupons from a single heat and 50 micron alumina powder from a
single batch was distributed to these laboratories.
Tests were conducted at room temperature and at 600C at impingement angels of 90 and 30
degrees. The test results
reported by these labs show good general agreement at these different test conditions. The erosion
rates show a linear relationship with the applied erodent dose at all test conditions. However,
noticeable difference was found in the initial reported erosion rate results from some of the labs
for the same reported velocity. Additional tests were conducted at different known particle
velocities by selected few labs. A power law with an exponent of 2 applies to the erosion rate as a
function of particle velocity. Due to this power law nature of the erosion rate, it is highly critical
397
to accurately measure the particle velocities. A master calibration curve relating the erosion rate
and velocity is proposed. Rigorous statistical analysis of all the data conducted by the ASTM
interlaboratory study group show good repeatability and reproducibility of the results. Limited
erosion scar analysis was also conducted to provide some guidance on the use of two different
methods. A draft test standard has been developed and submitted to the ASTM subcommittee
G02-10 for balloting. At the time of this writing, first ballot has been completed. With further
revisions and next balloting by the main committee, it is anticipated that the final test standard
will be issued in early 2014.
Acknowledgements
The authors thank EPRI for funding this program under the guidance of Program Manager, David
Gandy. The authors also gratefully acknowledge the participation and help of all of the staff from
the participating laboratories in this EPRI round-robin test program. Their expertise, cooperation
and advice as well as the internal financial support from their respective organizations to conduct
these tests are highly appreciated. We also thank the experts who participated in the International
Conference on Solid Particle and Liquid Droplet Erosion in June 2012 to share their experiences
and provided us valuable feedback on the proposed ASTM test standard.
References
1
Proc. of the International Conference on Solid Particle and Liquid Droplet Erosion: Testing,
Modeling and Applications, Milan, June 18-19, 2012, by Electric Power Research
Institute, USA and RSE, SpA, Italy
Thomas H. McCloskey, Minimizing the Effect of Solid Particle Erosion in Utility Steam
Turbines, Proc. EPRI/ASME Conference on Solid Particle Erosion of Steam Turbines,
March 1989, New Orleans, LA, EPRI Report No. GS-6535
T. H. McCloskey, Proc. EPRI Workshop on Solid Particle Erosion of Steam Turbines, 1985,
New Orleans, LA, EPRI Report No. CS-4683; 1986
Wlodek,ST,"Development and Testing Plasma Sprayed Coatings for Solid Particle Erosion
Resistance", in J.F. Ouilliam, ed ., Solid-Particle Erosion of Utility Steam Turbines: 1985
Workshop, held November 13-15,1985 in Chattanooga, TN, Proceedings CS-4683, EPRI,
Palo Alto, CA, August, 1986, pp. 4-43 through 4-60
Proc. of the Sixth International Conference on Advances in Materials Technology for Fossil
Power Plants, Santa Fe, NM, August 2010, Electric Power Research Institute
398
A. Feuerstein, A. Kleyman; TiN multilayer systems for compressor airfoil sand erosion
protection; Surface & Coatings Technology 204 (2009) 10921096
10
Thomas Brendel; Dr. Falko Heutling; Wolfgang Eichmann; Markus cker; Dr. Thomas
Uihlein "MTU solutions against erosive attack and loss of EGT margin in turbo engines ERCoatnt" MTU Technical Publication 2008
11.
12. Finnie, I., Some Reflections on the Past and Future of Erosion. Wear, 1995. 186-187: p. 110
13. Erosion-Corrosion of Cr3C2-NiCr High Velocity Thermal Spray Coatings; Steven James
Matthews PhD thesis, The University of Auckland, 2004.
14. G. DAlessio & D. Nagy; Performance of Erosion Resistant Coatings for Compressor
Airfoils Journal of the Canadian Ceramic Society, Vol 63 No1 February 1994 p59-63
15
16
Standard Test Method for Conducting Erosion Tests by Solid Particle Impingement
Using Gas Jets G76-07, Published by ASTM International. West Conshohocken, PA, USA
17
A. Ruff and L Ives; Measurement of solid particle velocity in erosive wear; J. of Wear (35
(1975) 195-199
18
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INTRODUCTION
In the last decade there has been increasing legislation requiring industry to cut and control
carbon emissions that are believed to be linked to climate change. EC directives designed to limit
CO2 emissions and international treatise such as the Kyoto Protocol led the EU to commit to an
8% reduction in CO2 emissions by 2008 2012 [2]. Whilst there are efforts to control and limit
CO2 emissions there is an increasing world energy demand [3]. As a consequence the power
industry is actively seeking methods to capture and control the emissions. In fact the UK
Electricity Market Reform (EMR) White Paper 2011 states that there should be an Emissions
Performance Standard (EPS) set at 450 g CO2/kWh to reinforce the requirement that no new coalfired power stations are built without CCS, which not only enforces the need for Carbon Capture
and Storage (CCS) in new build but also imposes stricter limits on CO2 emission than current EC
directives. Whilst CCS is one method being developed, other alternatives are being pursued
which include the retrofitting of existing plant and the conversion of coal fired plant to biomass
combustion, either 100% or co-fired with coal. Whilst this will use a more carbon neutral fuel it
does not eliminate the problem of erosion, and in the case of some biomass fuel will exacerbate
the problem on the fireside components in boilers.
Erosion and wear can dramatically reduce the efficiency and life of high value components across
a range of industrial sectors. In the European power industry this form of degradation alone costs
an estimated 200M a year in lost efficiency, forced outages and repair costs [1]. In conjunction
to a financial impact there is also a clear environmental impact from high temperature erosion, for
example it has been estimated that reducing the erosion of the leading edge of turbine blades
could result in improved efficiency, in the order of 7%, and thus avoid, in the case of a large
power plant (~800 MW), the emission of an extra 250,000 tonnes of CO2 over the lifetime of the
plant. Solid particle erosion at elevated temperatures is not only an issue for aerospace and power
generation, but can also impact on heavy industry such as steel processing plants which can have
issues from erosion in materials handling plant that causes major losses.
It is well documented that capture methods impact the efficiency of high temperature plant so
using this method alone is not desirable; rather increasing the efficiency of plant through higher
temperatures and pressures, improved materials and process control coupled with capture
technologies is the route being pursued. Whilst increasing operating temperatures does increase
the efficiency of the plant, current materials are at the limits of their performance. Higher
temperatures are likely to lead to increased oxidation rates and exfoliation, thereby exacerbating
the occurrences of high temperature solid particle erosion of components. Major improvements in
the efficiency of power generating plant (7% to10%) and aero-engines will be made possible by
the development of new materials that have improved resistance to high temperature particulate
erosion. A recent EPRI (Electric Power Research Institute) survey [4] of High Temperature Solid
Particle Erosion (HTSPE) testing exposed a serious deficiency within the EU to perform HTSPE
tests.
For many years HTSPE testing has been limited to purely being able to rank materials
comparatively under conditions which were believed to nominally replicate service conditions.
Assessment of the erosion resistance of candidate materials and surface engineering solutions has
been hampered by a lack of metrology and standardisation for issues such as the measurement of
damage, the temperature of the erosive particles and the supporting gas stream, the gas stream
flow rates, erosive particle size and shape. The lack of control of these parameters has been
identified as the cause of a lack of reproducibility in measurements, up to 100%, by an EPRI
workshop. There is a requirement to understand the variability in erosion measurements between
different laboratories. Once this is clearly defined there will be sufficient understanding to
401
develop a standard test procedure for HTSPE testing, which is currently not available, and enable
advanced modelling for improved design routes and more accurate predictions of performance.
The implementation of improved in-situ measurement and rigorous characterisation of the
erodent and the erosion scar will provide greater phenomenological understanding of the erosion
processes at high temperature and the use of a more controlled test will enable better repeatability
and reproducibility of testing. Without this necessary metrological framework, the development
of new materials will still be based on a largely empirical approach that will significantly delay
the improvements that are needed to meet the challenges of reducing environmental impact, and
meeting the EU targets for CO2 emissions.
Funding for this programme of work METROSION has been obtained through the European
Metrology Research Programme (EMRP). This is a metrology-focused European programme of
coordinated R&D that facilitates closer integration of national research programmes. The EMRP
is jointly supported by the European Commission and the participating countries within the
European Association of National Metrology Institutes (EURAMET e.V.), with the main aim to
ensure collaboration between National Measurement Institutes (NMIs) thereby reducing
duplication and increasing impact. Through this programme a consortium of National
Measurement Institutes form the UK, Germany, Denmark and the Czech Republic has been
formed to address the metrological challenges in developing a framework for HTSPE testing.
Two leading research organisation from the UK and Italy have also been included in the
consortium through Researcher Excellence Grants (REGs) to form the final METROSION
consortium.
MEASUREMENT OF HIGH TEMPERATURE SOLID PARTICLE EROSION
A recent EPRI survey [4] of High Temperature Solid Particle Erosion (HTSPE) testing exposed a
serious deficiency within Europe to perform HTSPE tests, with few facilities available worldwide
for the measurement of high temperature particulate erosion. Within Europe facilities which met
the EPRI requirement were principally located at Cranfield University (UK) and Ricerca Sul
Sistema Energetico Spa, (IT), but even these test systems were limited in terms of the particle
velocity and operational temperature required by the EPRI specification.
Outside of the EPRI programme and intercomparison described by Swaminathan et al [4], within
the testing community it has been realized that there are also major limitations in terms of the
understanding and control of uncertainties associated with the measurements undertaken during
the test, and their applicability to real industrial applications. Current practices have the potential
to result in large errors in measurement, for instance the normal method for measurement of the
velocity of erodent particles is through a twin disc test system where rotating discs are used to
give a measure of velocity. This method is generally considered to have measurement errors of
the order of 20-30 % as described below.
Erosion is defined as a progressive loss of original material from a solid surface due to
mechanical interaction between that surface and a fluid, a multi-component fluid, or impinging
liquid or solid particles [5]. In determining the erosion rate of a particular system it is normally
found that the rate increases with the exposure time, the most accurate method of determining this
rate has been through the use of mass change, determined through periodic weighing of the
specimens as a function of exposure time, although the erosion rate can also be measured by
volume change. For accurate determination not only does the erosion rate need to be carefully
determined but it is also critical to understand, measure and control the main parameters which
402
influence the rate of erosion. This is strongly dependent on the material properties of the material
being eroded as well as the following test parameters:
Particle Velocity
Perhaps the most important variable is the particle velocity, since under most conditions; it has a
strong influence on the erosion rate. For many materials, once steady-state conditions have been
reached the erosion E (expressed as the mass removed by unit mass of erodent particles) can be
expressed [6] as a simple power function of particle impact velocity v.
=
(1)
where the constant of proportionality k includes the effects of all the other variables. The value of
n is the velocity exponent and is typically found to be between 2 and 3. The velocity exponent
does not vary considerably with the impact angle although it is suggested that higher values of n
can be due to impact angles close to perpendicular to the surface.
Particle velocity is difficult to measure accurately and requires advanced techniques, such as laser
doppler velocimetry (LDV) or particle image velocimetry (PIV). The more traditional and widely
used method of measurement is by using the double disc method popularised by Ruff and Ives
[7]. In this method two disks are rotated on a common shaft, and the stream of erodent particles is
arranged to strike the upper disk which has a thin radial slot cut in it (see Figure 1a). The lower
disk is coated with a thin paint or dye film to show where particles strike it (see Figure 1b and c).
Two erosion scars are formed: one with the disks stationary, with the particles passing through
the slit in the upper disk, and the other with the disks rotating at a known speed. The angular
displacement between the two scars is measured and can be used to calculate the time taken for
the particles to travel the distance L between the disks, and hence their velocity, v. The velocity is
given by
(2)
=
where is the angular velocity of the rotating disks. In practical examples of this device a high
rotational speed is needed to achieve reasonable displacement of the scars and thus accuracy of
measurement of the angle . Values between 3,000 and 10,000 revolutions per minute are
common, with a distance L of about 20 to 40 mm, according to test conditions. The method is
well suited to use in a gas-blast erosion test, since velocity calibration can be carried out under
exactly the same conditions of particle feed rate and air pressure as used in the erosion test.
However, the random error in measuring velocity in this way is 10% and there can also be a
systematic error due to the aerodynamic influence of the rotating disks on the particle stream,
which may be 10% or even greater for very small particles of low density.
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Figure 1 Schematic of the double disk particle velocity measurement showing (a) the side elevation of
the apparatus, (b) the top elevation of the disk and (c) an image of a disk post exposure (Ref [6]).
An example data obtained from this method is shown in Figure 2, this shows how the velocity of
particles varies with gas pressure. The data provides a good fit, but note how the intercept of the
line does not pass through the origin. Whilst this data would appear to be good, and this is an
example of a good set, this method in general has cumulative measurement errors of the order
of 20-30 % leading to much greater uncertainty in the overall measurement. Moreover, the double
disk method can only provide an estimate of the maximum particle speed achieved, but does not
account for the velocity distribution which is dependent on particle size distribution, thus a
significant spread in particle velocity is possible but unaccounted for.
Figure 2 Variation of particle velocity as a function of gas pressure as measured using the double disk
method.
404
Impact Angle
The impact angle in erosion is often defined as the angle between the direction of particle motion
and the plane of the surface, such that a normal angle of incidence corresponds to an impact angle
of 90. Ductile materials eroded by angular particles show maximum erosion at shallow angles of
incidence, with the peak erosion rate typically at an angle of 20 to 30, Figure 3.
Figure 3 Typical dependence of erosion for different particle impact angle on different types of target
material (Ref [6]).
Under these conditions the material is removed by a ductile ploughing and cutting mechanisms.
The erosion of a ductile metal at 90 incidence may be about one half to one third of the peak
value. Conversely materials which are brittle, such as ceramic coatings fail by the formation of
brittle fractures and localized cracking. In these cases the maximum rate of erosion is found to
occur for impact angles of 90. For different erodents with different mechanical properties the
erosion mechanism would not change but the extent of erosion would.
Particle Size and Shape
The particle size and size distribution are important parameters as these define the mass of
erodent particles, and thus, together with the particle velocity, the kinetic energy of impact for
erodent particles. This is further complicated when accounting for the contribution of the powder
feed system, which could alter the size distribution through use. Moreover, depending on the
nozzle geometry, particles can follow different trajectories depending on their size thereby
affecting the erosion rate. For these reasons, it is clear that wherever possible the size range of the
particles used in an erosion test should be known, and be as narrow as possible.
In normal situations the particles are often classified by a simple sieving operation [8].
Specification of the sieve sizes may be sufficient to define the range of particle size used in a test.
In reality the size and distribution of erodent particles can vary as demonstrated by Figure 4.
The shape of the particles is also important in determining the relative erosivity of different
particles [9], and is inherently difficult to separate from other properties, since particle shape is
often determined by the fracture processes by which the particles themselves are formed. As in
the case of particle size, there is an intrinsic effect of shape on the erosion rate, which can lead to
angular particles producing up to ten or more times the erosion caused by spherical particles of
the same material. Measurement of particle shape is not straightforward, since although there are
405
many possible methods of assessing shape, it is unclear which method is most appropriate in the
context of erosive wear testing. Qualitative descriptors such as rounded, sub-angular and
angular etc, are often used and may be adequate in conjunction with a more detailed
specification of the material and source of the erodent particles.
Figure 4 Particle size distribution of boiler scale recovered from boiler water and Superheater steam
drains [4].
It is important that if the purpose of erosion testing is to compare material behaviour or obtain
quantitative measurements of erosion rate in the context of a particular engineering application,
appropriate erodent particles are used in the test. Not only should the particle size and shape be
representative of the application in question but the particle material should also provide a
realistic simulation of the properties of the actual particles. Figure 5 shows how the erosion rate
varies as a function of impact velocity and erodent, for erodent particles of a similar size
specification.
Figure 5 Influence of particle velocity and erodent material on the erosion rate of a sintered glassbonded alumina ceramic, after Ref [9]
406
Selection of materials
Test system construction, test parameter effect and modelling
Measurement of volume, mass and shape
Measurement of temperature, velocity and flow
Selection of materials
Materials are key foundation to the project, it is critical therefore that those used are carefully
selected to ensure that, not only do they meet the requirements of the project but that they are
relevant to the industrial stakeholders. To ensure this is the case a period of consultation is
underway to gather information from the partners and stakeholders to gauge the range of
materials, erodents and conditions of most interest. The final selection will consist of two
substrates, relevant to high temperature applications, and four coatings, two of which will be
chosen from the current leading coatings, with two new coatings developed by the project
partners. This will give a set of 10 different materials combinations (two substrates, uncoated and
four coatings). Also crucial will be the selection of four different erodents. These will include
silica sand (Figure 6), aluminia (rounded and angular) and other industrially relevant erodents,
such as fly ash. All the materials included in the programme will be thoroughly characterised.
407
408
In addition to monitoring the test specimen techniques are also required to evaluate the size, size
distribution and shape of erodent particles. These key parameters have only been evaluated
poorly in the past, but have a dominant effect on the magnitude of wear that occurs. For this
purpose the use of industrial computed tomography (CT) as an emerging 3D coordinate
measuring technology [10] will be investigated to determine the shape, size and size distribution
of particles.
Having addressed the monitoring of the specimen during and after the test, it is also of crucial
importance to monitor and control the dynamic test parameters such as temperature, velocity and
flow. As a result there will be efforts to develop and apply accurate methods for the measurement
of the velocity and velocity distribution of the erodent particles as they strike the test samples. As
discussed previously techniques are available for velocity measurement which greatly improve on
the double disk method, the accuracy and repeatability of these optical based techniques such as
particle image velocimetry (PIV-S), particle shadowing and laser Doppler anemometry (LDA)
will be assessed and compared with more traditional techniques such as the double disk
technique.
The flow of the gas is inherently linked to the velocity of the erodent particle and will affect the
spatial distribution of the erodent particles. The flow of the gas will additionally impact on the
temperature of the system, therefore it is also necessary to develop and apply accurate methods
for the measurement of the gas flow and temperature of the samples, the erodent particles, and the
gas. Although the measurement of the sample temperature is relatively straightforward, care is
still needed to ensure that appropriate methods are available to monitor the variation of
temperature across samples and understand any heat flux effects through the sample thickness,
this can be important depending on where the reference temperature measurement is being made.
High speed thermal imaging of the sample surface will be considered as an appropriate technique
for the sample. The measurement of the temperature of the high velocity erodent particles is more
challenging. However, it is essential that robust measurement techniques are developed as it is
essential that the temperature of the erodent is the same temperature as the sample to achieve high
quality erosion measurements.
To date little modelling of long term performance of the high temperature erosion process has
taken place [11], so that prediction of material life-time is very uncertain. Currently, empirical
models exist for predicting solid particle erosion but by their very nature, these models are
heavily dependent on experimental data in the form of erosion coefficients. These models are
suitable for predicting erosion rates in well-defined situations where a wealth of experimental
data already exists. They are useful in comparative work e.g. material ranking. If modelling of a
more general erosion process or a more complex geometry is required, the empirical models are
no longer applicable.
The limitation on the applicability and development of predictive models to date has been the
lack of well-defined interactions between the erodent and the surface. The metrological
framework outlined above will facilitate the delivery of these critical input parameters and
physical understanding. This will ultimately be realised in a new high temperature solid particle
test apparatus which will be able to perform and monitor these tests in a much more controlled
and accurate manner than previously possible.
CONCLUSIONS
Current methods of measurement and control of test parameters, such as particle velocity, are
known to have large uncertainties attached to them, leading to variability and imprecise
409
An outline of the approaches to be adopted has been presented for the key parameters,
measurement of these will allow for the evaluation of the uncertainty in HTSPE tests to be made
and through the use of improved techniques and test control the uncertainty will be reduced.
ACKNOWLEDGMENTS
This work is funded through the European Metrology Research Programme (EMRP) Project
IND61 Metrology to Enable High Temperature Erosion Testing (METROSION). The EMRP is
jointly funded by the EMRP participating countries within EURAMET and the European Union.
REFERENCES
[1] K. J. Stein, B. S. Schorr and A. R. Marder, Erosion of thermal spray MCr-Cr-C cermet
coatings, Wear, vol. 224, pp. 153-159, 1999.
[2] P. Dechamps, The EU Research Strategy Towards Zero Emission Fossil Power Plants,
Materials for Power Engineering, pp. 25-36, 2006.
[3] IEA World Energy Outlook, 2009.
[4] V. P. Swaminathan, J. S. Smith and D. Gandy, High-temperature erosion testing standard
and round robin testing, in Advances in Materials Technology for Fossil Power Plants,
Proceedings from the Sixth International Conference, Santa Fe, 2010.
[5] M. J. Neale and M. G. Gee, Guide to Wear Problems and Testing for Industry, Professional
Engineering Publishers, 2000.
[6] I. M. Hutchings, Tribology: Friction and Wear of Engineering Materials, Boca Raton, Fl:
CRC Press., 1992.
[7] A. Ruff and L. Ives, Measurement of solid particle velocity in erosive wear, Wear, vol. 35,
no. 1, pp. 195-199, 1975.
[8] ASTM Manual 32. Manual on Testing Sieving Methods., American Society for Testing
and Materials, West Conshohocken, PA., 1998.
410
[9] S. Bahadur and R. Badruddin, Wear of Materials, K. C. Ludema, Ed., New York: ASME,
1989, pp. 143-153.
[10] J. P. Kruth, M. Bartscher, S. Carmignato, R. Schmitt, L. De Chiffre and A. Weckenmann,
Computed tomography for dimensional metrology, C I R P Annals, vol. 60, no. 2, pp. 821842, 2011.
[11] L. E. Crocker, A review of current methods of modelling erosive wear, NPL Report MAT
52, Teddington, 2001.
411
the outcome of any refurbishment heat treatments, and also to make predictions of coating
evolution with time at temperature. The single crystal nickel superalloy PWA1483 has been
selected in this work to undergo mechanical and thermal degradation, followed by a subsequent
rejuvenation process and the effect on the microstructure explored fully using a range of analytical
techniques.
EXPERIMENTAL AND MODELLING METHODS
Experimental
Creep test pieces of diameter 5 mm and gauge length 25 mm were machined from samples of the
as-received homogenised PWA1483 alloy and were subsequently coated with a 100 m thick
oxidation resistant coating (NiCoCrAlYHf) typical of those applied to industrial components. An
ex-service single crystal blade of PWA1483 which had undergone ~27,000 hours of engine
exposure was used as an additional source of test coupons for comparison purposes. Table 1
provides a summary of the nominal chemical compositions of the alloy, the coating used on the
creep samples and the coating present on the ex-service blade (NiCoCrAlYRe). The coated
samples were sprayed using high velocity oxyfuel with a commercially available NiCoCrAlYHf
powder, followed by common post-coating heat treatments involving a high temperature diffusion
treatment and a lower temperature ageing; this condition is subsequently referred to as as coated.
Constant load creep tests were performed at 950C in air with a load calculated to give rupture at
approximately 8000 hours. A selection of creep samples were interrupted after half life, i.e. 4000
hours, and the remainder were stopped after 8000 hours if rupture had not occurred.
Microstructural evaluation was then carried out on as-received material, coated material, materials
from interrupted and ruptured creep tests and the ex-service blade sample, with respect to both the
bulk microstructure and the coating. The initial microstructural evaluation studies were carried out
on prepared microsections, which had been lightly electrolytically etched with a mixture of 1%
citric acid and 1% ammonium sulphate in distilled water to selectively dissolve the phase. These
were subsequently examined in directions parallel to the [001] single crystal growth direction
using scanning electron microscopy (SEM) in conjunction with an energy dispersive spectrometer
(EDS).
Table 1. Nominal chemical composition in weight percent of the nickel based superalloys and
oxidation coatings used.
Element
PWA1483
NiCoCrAlYHf
NiCoCrAlYRe
Al
3.6
12.5
10.7
Ti
4.0
-
Cr
12.1
17
24.4
Co
9.1
22
8.8
Mo
1.9
-
Hf
0.25
-
Ta
5.0
-
W
3.8
-
Re
2.3
Y
0.6
0.5
Zr
-
Ni
Bal
Bal
Bal
A subsequent heat treatment, based on thermodynamic calculations, was carried out on the
PWA1483 crept samples to alter the structure, which were then also examined to quantify the
changes to the . The ex-service blade had the coating removed and received the same heat
treatments as the creep samples. The ex-service blade was recoated with the same NiCoCrAlYHf
powder as the creep samples but with a thickness of ~300m and a thermal barrier coating (TBC)
coating of ~200m. The recoated blades samples were then thermally exposed for ~10,000 hours
using similar thermal conditions and were examined to quantify changes in the NiCoCrAlYHf
coating.
Thermodynamic and Kinetic Modelling
Thermodynamic equilibrium calculations have been performed using JMatPro 4.1 (Java-based
Materials Properties software)[1] to determine a heat treatment window between the solvus and
413
the liquidus, in order to specify a possible rejuvenation heat treatment for . The calculations
used the nominal composition of the alloy, actual measured compositions of the base alloy and
from the interdiffusion zone and slight theoretical changes to the composition as a function of
possible segregation in the alloy to give a range of possible solvus temperatures and liquidus
temperatures.
Coupled thermodynamic and kinetic calculations were undertaken to determine how the chemical
composition varied between the coating and the substrate as a function of time and temperature of
exposure. The initial calculations mimicked the thermal exposure of the creep and blade samples,
with a further round of calculations undertaken incorporating experimentally measured
compositions for additional predictions. The numerical model used for the calculations combined
multicomponent diffusion with equilibrium thermodynamics and surface oxidation[2]. The
diffusion calculation was based on finite-differences which took into account the phase
composition and diffusion within phases by linking with MTDATA[3] and a database of
thermodynamic parameters[4] whereas the surface oxidation of Al was simulated using a published
model[5]. The calculations were performed on a parallel cluster, typically with 72 nodes and 504
grid points. The removal and re-deposition of coating layers were simulated numerically by
interpolating concentration profiles using cubic splines.
RESULTS & DISCUSSION
Evolution
The shape and size of precipitates changes with applied temperature and stress and therefore
when considering refurbishment of such an alloy system, it is important that the size differences
are characterised and quantified to understand the effects of heat treatment.
The effects of heat treatment have been considered using the thermodynamic calculations to
determine the temperature difference between the solvus and the liquidus. This has resulted in
the prediction of a temperature window within which it would be expected that the
precipitates would be fully taken into solution before the onset of melting. This is shown
graphically for PWA1483 in Figure 1, and Table 2 contains a summary of the results.
Temperature
Window
Figure 1. A summary plot of thermodynamic equilibrium calculations for solvus and liquidus
temperatures for PWA1483, each symbol on a line represents a different composition variant.
414
The calculations show that there is a temperature window that can be used to fully solution the
whilst trying to reduce the risk of any incipient melting. An appropriate temperature within the
temperature window was subsequently used to rejuvenate the structure for the alloy.
Table 2 Summary of the highest ' solvus and lowest liquidus temperatures which have been
calculated for PWA1483.
Alloy
' Solvus
/ C
Liquidus
/ C
Difference
/ C
PWA1483
1175
1270
95
The size was characterised using image analysis from SEM images to determine a
thickness/diameter if cubic/spherical and in the case that the had elongated to form rafts, the
raft thickness was determined: all of these dimensions are referred to as a width. The specific
details on the methodology used to characterise these microstructural forms have been detailed
elsewhere[6].
The PWA1483 microstructure evolved during creep testing and Figure 2 shows how the
structure changes during creep testing. There is a clear change from cubic to an elongated, or
rafted, microstructure.
Figure 2. Strain against time plot for the coated creep test conducted at 950C with inlays of '
morphology at different times during the creep test for PWA1483 at 125 MPa, The direction of
the applied stress to the inlays of the ' morphology is top to bottom for all images which are at
the same magnification. Classification of the ' width: Red: 0-0.5 m, Green: 0.5-1.0 m, Blue:
1.0-1.5 m; Yellow: 1.5-2.0 m, Cyan >2.0 m.
The rafted microstructure from the creep samples had a heat treatment which was within the
temperature window expected to rejuvenate the microstructure. Figure 3 i) shows the as coated
microstructure and Figure 3 ii) shows that for an 8000 h creep sample which originally had a
rafted microstructure it is possible to fully re-solution the alloy to form a more cubic
microstructure. Figure 4 shows a histogram distribution for the microstructure width
measurements from the samples which had received different heat treatments and creep testing.
The distribution obtained from the fully re-solutioned sample is observed to be similar to the
distribution of the as-coated sample. The images presented in Figures 3 i) and ii), show that the
415
structure after full re-solution does not quite have the same regular cubic appearance as the ascoated microstructure. The subsequent creep testing for the fully re-solutioned samples should
indicate if there has been a significant change to the creep properties of the alloy.
i)
ii)
Figure 3. Secondary electron SEM images taken from alloy PWA1483 shows the ' appearance in
the dendrite core for i) after coating and aging heat treatments(0 h) ii) ' appearance after high
temperature heat treatment and subsequent cooling for full re-solution of '. The images have
been processed to identify individual particles with the different colours indicating particle width.
Classification of the ' particle width: Red: 0-0.2 m, Green: 0.2-0.4 m, Blue: 0.4-0.5 m;
Yellow: 0.5-1.0 m, Cyan >1.0 m.
Figure 4. Histogram distribution plot for width at different points during the PWA1483 creep
sample life from original homogenised casting, coating, creep exposure and a full solution heat
treatment after creep exposure.
Coating Evolution
Creep Samples
The oxidation coating on the creep samples has been examined using EDS to determine how the
chemical composition and coating phases have changed during creep exposure. These measured
compositions and phases have then been compared to the predictions of the coupled
thermodynamic and kinetic calculations.
416
i)
ii)
iii)
Figure 5. A series of plots for PWA1483 i) as coated, ii) 4000 hours of creep exposure and iii)
8000 hours of creep exposure showing how the elemental concentrations of Al, Co, Cr, Ti, and W
vary as function of position. The points are from measurements taken using EDS in an SEM and
the lines on the plots are the predictions from the combined thermodynamic and kinetic
calculations. The ~100m position represents the original coating/alloy interface. The data are
overlaid on a corresponding SEM backscattered detector image.
417
Figure 5 shows how the composition of the coating and interface changes with thermal/creep
exposure together with the corresponding SEM image. It can be seen that original Al content of
around 12.5 wt.% has decreased significantly to around 5 wt.%; the thermodynamic and kinetic
calculations also identify this change. The thermodynamic and kinetic calculations indicate that
the beta phase in the coating after 4000 hours has been transformed to . Indeed, no significant
levels of beta phase were found by measurement for the 4000 and 8000 hours creep samples,
which was consistent with the coupled thermodynamic and kinetic calculations. SEM examination
of the original coating showed that beta occupied an area of ~45%, as shown in Figure 6, which
can be assumed to correspond to ~45 wt.% beta. The thermodynamic and kinetic calculations
indicate the starting beta proportion would have been ~52 wt%, and given that this figure
excludes the porosity present in the coating, there is a reasonable correlation between the
predicted and observed amounts.
Figure 6. A plot showing how the beta phase varies through the as coated creep sample. The
points are from measurement and the lines are from coupled thermodynamic and kinetic
calculations. The data are overlaid on a corresponding SEM image with red indicating the phase
being analysed.
The measured Cr concentration in the creep sample was observed to be different from the
thermodynamic and kinetic calculations in the interface region. However, the model prediction is
for the mean Cr level, whereas it was observed that the points at which the Cr levels were
measured, when overlaid on the back scattered electron SEM image, aligned with particular
microstructural features and in particular with Cr-rich precipitates.
The coupled thermodynamic and kinetic calculations then used both the predicted and measured
compositions after 4000 hours to simulate what would occur during refurbishment and repeated
thermal/creep exposure. The results in Figures 7 are for the predicted composition after 4000
hours, whereas Figure 8 uses the measured composition after 4000 hours as the starting reference
for the subsequent calculations to determine the likely effect of the refurbishment process. The
results shown in Figures 7 and 8 are for two refurbishment conditions considering scenarios when
both 100 m and 120 m of material has been removed. There are only limited differences
observed between the two data sets after repeated 4000 hours of thermal exposure at 950C. This
may suggest that the amount of material taken from the base metal has little impact on the coating
behaviour in the long term. This was also the case where the 100 m of material removal
418
intersected the Cr depleted region from Figure 5 ii), because after the full re-solution the Cr level
has appeared to have redistributed, as shown in Figure 8 i). This will need to be confirmed with
measurement taken from processed creep samples in the future.
i)
iv)
ii)
v)
iii)
vi)
Figure 7. A series of combined thermodynamic and kinetic calculations plots for the calculated
composition of the PWA1483 4000 hour creep sample i) after 100m material removal and full
solution ii) after coating diffusion and age, iii) after 4000 hours of thermal exposure at 950C, iv)
after 120m material removed and full solution v) after coating diffusion and age and vi) after
4000 hours of thermal exposure at 950C.
419
i)
iv)
ii)
v)
iii)
vi)
Figure 8. A series of combined thermodynamic and kinetic calculations plots for the measured
composition in the PWA1483 4000 hour creep sample i) after 100m material removal and full
solution ii) after coating diffusion and age, iii) after 4000 hours of thermal exposure at 950C, iv)
after 120m material removed and full solution v) after coating diffusion and age and vi) after
4000 hours of thermal exposure at 950C.
Blade Samples
In order to compare the crept samples, with an ex-service blade, the original NiCoCrAlYRe blade
coating which was ~150m thick was removed and the blade samples were then given the same
heat treatment as the creep samples for the base alloy in order to re-solution the . The
NiCoCrAlYHf coating, which was the same as that used for the creep samples, was applied to the
blade samples to a thickness ~300 m; the last ~50m was made more porous and undulating
prior to the addition of a ~200 m thick TBC. The blade samples were then thermally aged for
10,000 hours.
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Coating
i)
TBC
Coating
ii)
TBC
Coating
iii)
Figure 9. A series of plots for the PWA1483 i) ex-service blade, ii) blade refurbished sample and
iii) refurbished sample after 10,000 hours of thermal exposure all showing how the elemental
composition of Al, Co, Cr, Ti, W, O for i) ii) and iii) and N for i) vary as function of position. The
points and white dashed lines are from measurements taken using EDS in an SEM and the
coloured lines on the plots are the predictions from the combined thermodynamic and kinetic
calculations. The data are overlaid on a corresponding SEM backscattered detector image.
421
The coupled thermodynamic and kinetic calculations used the original coating composition but
with a thickness of 300 m and PWA1483 base metal and then a simulated engine age for 27,000
hours. The measured and calculated values are shown in Figure 9 i) and indicate that there is a
discrepancy in the Al levels, although the calculated level correlates well with the measured Al
levels in the creep samples which had undergone more controlled exposure. The higher measured
level in the blade sample may indicate the examined region could be undergoing enhanced
degradation. High levels of N were observed in the coating, Figure 9 i), and an absence of S, not
shown on figure, which may suggest that the coating has been degraded by high temperature
oxidation.
The main measured compositional difference in the coating between the refurbished sample and
aged sample is an elevated Al and O content in the first 50 m of the oxidation coating, as shown
in Figure 9 ii) and iii). The phase analysis also showed a significant depletion of the beta phase in
the first ~50 m of the oxidation coating, as shown in Figure 10, while the coupled
thermodynamic and kinetic calculations show beta levels not changing as significantly in this
region. The calculated Al remains at the as coated level even after simulated thermal exposure for
10,000 hours. This is a similar observation to that made in the simulated refurbishment
calculations. The measured composition in the first 50 m showed relatively higher levels of O
compared to the remaining oxidation coating, Figure 9 iii). The coating prior to thermally ageing
in the first 50 m also had higher levels of O compared to the remaining oxidation coating. The
application of the coating in this region was more porous and formed of thinner layers, this would
increase the surface area and aid diffusion in preference to the remaining oxidation coating. The
coupled thermodynamic and kinetic calculations do not currently take the porosity of the coating
into account, and the coating is assumed to be homogenous. The beta level could be measured on
additional samples which had either been exposed for longer or have seen a high temperature to
evaluate if a porous outer layer significantly affects beta depletion.
i)
ii)
Figure 10. A series of plots for PWA1483 i) initial blade refurbished sample, ii) refurbished
sample after 10,000 hours of thermal exposure showing how the amount of beta phase varies
through the coating. The points are from measurement and the line is from the coupled
thermodynamic and kinetic calculations. The data are overlaid on a corresponding SEM
backscattered detector image with red indicating the phase being analysed.
CONCLUSIONS
The work that has been undertaken has shown that using an combination of phase stability
predictions, combined thermodynamic and kinetic diffusional calculations, experimental
measurements of creep, ex-service blade and heat treated samples using electron imaging, image
analysis and chemical mapping techniques it is possible to determine heat treatment windows to
alter morphology and quantify these changes. The initial development of combined
422
thermodynamic and kinetic calculations to simulate the refurbishment heat treatment and recoating process have shown generally good agreement with experimental observations, and have
been able to highlight where future developments are required.
The main conclusions from this research are:
The rafted morphology in PWA1483 can be altered to a cubic form with a
size distribution similar to the initial coated sample.
Thermodynamic equilibrium calculations can be used to aid in the identification
of suitable heat treatment windows.
Coupled thermodynamic and kinetic calculations can give an understanding of
coating ageing behaviour.
The effects of refurbishment of a coating and the base alloy could be initially
assessed using coupled thermodynamic and kinetic calculations.
Further Work
Evaluate and optimise the coupled thermodynamic and kinetic on refurbished and retested creep
samples when they become available.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the financial support of RWEnpower, Swindon, UK for
this research.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
423
ABSTRACT
The microstructural evolution of the Ni-based superalloy CMSX-4 including the change in
gamma prime size and distribution and the degree of rafting has been examined in detail using
field emission gun scanning electron microscopy (FEGSEM) and transmission electron
microscopy (TEM) after high temperature degradation and rejuvenation heat treatments. The
relationship between the microstructure, mechanical properties and the applied heat treatment
procedures has been investigated. It is shown that there are significant differences in the rafting
behaviour, the size of the channels between the gamma prime particles, the degree of rafting
and the size of the tertiary gamma prime particles in each of the different microstructural
conditions studied. Chemical segregation investigations were carried out to establish the cause of
reduced mechanical properties of the rejuvenated sample after high temperature degradation
compared to an as-received sample after the same degradation procedure. The results indicate that
although the microstructure of as-received and rejuvenated samples were similar, the chemical
segregation was more pronounced in the rejuvenated samples, suggesting that chemical
segregation from partitioning of the elements during rejuvenation was not completely eliminated.
The aim of this research is to provide greater understanding of the suitability of rejuvenation heat
treatments and their role in the extension of component life in power plant applications.
INTRODUCTION
Ni-based superalloys are widely used in power generation as gas turbine components due to their
excellent high temperature performance. These components are subjected to a combination of
elevated temperature, high stress and aggressive environments during service, which inevitably
cause various microstructural changes in the material [1-2]. This microstructural deterioration can
lead to a degradation of mechanical properties such as tensile strength and creep resistance, which
can lead to failure in the components and reduce their service life [3-5]. When a superalloy gas
turbine component reaches the end of its predicted life, the user typically has two options: replace
the component or attempt to extend its life. Replacement not only requires expensive materials
but also adds to the maintenance and operational costs of the turbine, which has made the life
extension of components a financially viable alternative. Rejuvenation is designed and used to
recover some extra life for expensive Ni-based components by restoring the pre-service
microstructure (and, hence mechanical properties) ready for the components extended life. In the
case of the CMSX-4 used for power plant applications, the predicted lifetime is primarily
governed by the degradation of the microstructure through the rafting of particles. Therefore,
understanding the changes in the size, morphology and distribution of particles before and after
high temperature degradation and rejuvenation heat treatments becomes very important. However,
424
at present, limited information is available about the effect that these types of heat treatment have
on the integrity of components. In the absence of mechanical loads, the rafting behaviour of is
associated with the dendritic structure of the alloy, which is governed by the local chemical
inhomogeneity or chemical segregation [5]. Hence, it is also important to understanding the
effects of chemical segregation on the microstructure of the alloy and its mechanical behaviour
[6]. In addition, it is essential to evaluate the refurbishment process though the examination of the
microstructure, chemical homogeneity and mechanical performance after application of
rejuvenation heat treatments and subsequent microstructural degradation.
EXPERIMENTAL PROCEDURE
CMSX-4 single crystal tensile specimens were supplied by E.ON New Build & Technology
Limited which, in order to minimise the effects of misorientation had axes within 7 degrees of
<001>. The crystal orientations were determined by the Laue back reflection technique. The
nominal chemical composition of the CMSX-4 alloy used in the investigation is given in Table 1.
Table 1: The nominal chemical composition for CMSX-4 used in this study / wt%
Al
Co
Cr
Fe
Mo
Nb
Re
Hf
Ta
Ti
Ni
5.70
0.0022
9.60
6.28
0.06
0.60
0.01
2.95
0.09
6.49
1.00
6.43
Balance
A heat treatment programme was carried out to enable systematic analysis of the microstructural
evolution of the CMSX-4 samples, in comparison with the results obtained from mechanical
testing. Details of the precise rejuvenation treatment used is proprietary to E.ON New Build &
Technology Limited, but an overview of the heat treatment conditions used in this study are
shown in Tables 2 and 3.
Table 2: The CMSX-4 samples with their heat treatment conditions
Sample
Heat Treatments
S1
As-Received
S2
Rafted
S3
Rafted + Rejuvenation 1
S4
S5
Rafted + Rejuvenation 2
Tensile testing was performed in accordance with ASTM E8/E8M [7] on a servo-mechanical test
frame at room temperature using a stain rate of 0.7 mm min-1. The specimens used were 62 mm
long and 10 mm in diameter as shown in Fig. 1. Mechanical test results are available from S1 to
S4. Mechanical tests for S5, are ongoing and will be reported later but the microstructural
analysis and homogeneity results for all the samples are presented in this paper.
For SEM imaging, specimens were cut and mounted in electrically conductive Bakelite,
mechanically polished and then electrolytically etched using 10% orthophosphoric acid in water
at a voltage of 10 V. The majority of the microstructural examination was then carried out using a
Carl Zeiss 1530VP FEGSEM, operated at voltages of 10-20 kV and at working distances of 3 and
425
15 mm when using Inlens and Everhart Thornley secondary electron detectors respectively. A
number of magnifications were used to obtain details of the size of the secondary and tertiary
precipitates and the channel widths. For chemical segregation analysis, the chemical
composition difference between dendrite cores and interdendritic regions of all heat treated
samples was obtained using quantitative energy dispersive x-ray spectroscopy (EDS) area
analysis by an Oxford Instruments X-max 80 Silicon Drift Detector attached to the FEGSEM.
The dendrite structures were marked by hardness indents on etched samples. In order to avoid the
influence of etching on the chemical analysis, these etching effects were subsequently removed
by polishing. An area measuring 20x20 m was analysed both within the dendrite cores and
interdendritic regions as shown in Fig. 2. The chemical composition difference between the
dendrite cores and interdendritic regions was used to represent the chemical segregation within
the samples.
Table 3: The details of heat treatments applied to CMSX-4 samples
Rafted
Holding at
1050C
for 1000 h
Rejuvenation 1
Rejuvenation 2
Solution
Solution
Ageing
Two step ageing with different
temperature holds
Ageing
Two step ageing with different
temperature holds
426
Figure 2: A schematic illustration of the location of the EDS area analysis in the dendritic core
(DC) and interdendritic region (IDR) with respect to the dendrite structure.
Figure 3: A schematic illustration of the orientation of the perpendicular and parallel channel
widths for the measurement of the channels for Sample 4.
RESULTS AND DISCUSSION
Tensile Test Data
The tensile curves and results obtained from S1-S4 are shown in Fig. 4 and Table 4. S1 and S3
(as-received and rejuvenation 1) performed similarly in the tensile test but S3 showed a reduced
ductility when compared to S1. S1 demonstrated an UTS of 921 MPa and a yield strength of 874
MPa, whilst encouragingly, the measured values of the UTS and yield strength of the
rejuvenation 1 sample (S3) were slightly higher at 900 and 900 MPa respectively. The samples
after high temperature degradation (S2 and S4) exhibited considerably lower yield strength and
UTS, but demonstrated increased levels of ductility.
427
1000
Stress (MPa)
800
600
S1
S2
S3
S4
400
200
10
15
20
25
30
35
Elongation (%)
Figure 4: Tensile test results of the four different heat treated conditions for the CMSX-4 samples
used in this study.
Table 4: Tensile test results for the four different heat treated samples
Sample No.
Heat Treatments
S1
S2
S3
S4
As-Received
Rafted
Rafted + Rejuvenation 1
Rafted + Rejuvenation 1 + Rafted
Yield
Strength
(MPa)
874
724
900
728
UTS
(MPa)
Elongation
(%)
921
832
900
792
19.6
22.7
13.7
31.9
Microstructural Examination
Figure 5 shows the microstructure of the head sections of the CMSX-4 superalloy samples after
five different heat treatments and therefore the microstructures are representative of isothermal
ageing only, rather than the application of external load. S1, S3 and S5 exhibited a uniform
distribution of the secondary (cuboidal) . S2 and S4 had a rafted microstructure with particles
which have increased in size when compared with the as-received (S1) and rejuvenated samples
(S3 and S5) respectively. Tertiary precipitates in the channels between the large particles
were found in all samples except S1. Both very large (>100 nm) and fine (<20 nm) tertiary
particles were found in S2.
TEM was used to further examine the presence of the tertiary particles and their effects on
dislocations within the alloy. The TEM images of the CMSX-4 samples after the five different
heat treatments were consistent with the FEGSEM investigations. Tertiary particles were found
in samples S2, S3, S4 and S5, which can act as barriers to block the movement of dislocations.
For S2, which has undergone a single rafting process, the tertiary particles are relatively large
at ~100-200 nm, whereas those formed in S4 are considerably smaller (~20 nm) as shown in fig.
6. Dislocations were also observed in S2 and S4, where they were mainly present in the
channels, especially near the edge of the secondary particles. These results are consistent with
earlier research [11-14].
428
Figure 5: SEM images of the head sections of the CMSX-4 samples after five different heat
treatment conditions; a) S1, as-received, b) S2, rafted, c) S3, rafted + rejuvenation 1, and d) S4,
rafted + rejuvenation 1+ rafted, e) S5, rafted + rejuvenation 2.
Figure 6: TEM images of the head sections of a) S2, rafted and b) S4, rafted + rejuvenation 1+
rafted with, inset, a high magnification image of the channels with tertiary .
429
1.0
0.9
Rafted +
Rejuvenation 1
As Received
Rafted +
Rejuvenation 2
Rafted +
Rejuvenation 1
+Rafted
0.8
Rafted
0.7
0.6
0.5
S1
S2
S3
S4
S5
Sample Number
Figure 7: The area fractions of the secondary particles from the five different heat treatment
conditions for the head sections of the tensile test specimens measured using image analysis.
In single crystal Ni-based superalloys, the high level of rupture strength and creep resistance
results from the high volume fraction of contained within the alloy [10]. In this study, the area
fraction of the has been used as an approximation of volume fraction. According to both the
tensile test results and the area fraction measurements, the yield and ultimate tensile strength
increases with the area fraction of secondary particles. Although the rafted sample (S2) has the
lowest area fraction of secondary particles, 0.684, it should be noted that there are a large
number of tertiary precipitates in the channels. Moreover, the size of these precipitates is quite
large (100-200 nm). The presence of these large tertiary precipitates in the channels will affect
the movement of dislocations, which increases the yield and ultimate strength but reduces the
ductility [11-14].
Table 5: The channel widths and rafting parameter for the five different heat treated samples
Sample
No
Heat Treatments
S1
S2
S3
S4
S5
As-received
Rafted
Rafted + Rejuvenation 1
Rafted + Rejuvenation 1 + Rafted
Rafted + Rejuvenation 2
Channel Width / nm
Parallel
Perpendicular
Rafting
Parameter
4313
28053
5819
24281
6012
3911
25042
5417
9931
5913
0.56
1.64
0.55
2.65
0.53
In order to quantify any influence of the channel widths on mechanical properties, these were
measured in both the perpendicular and parallel directions with respect to the <001> orientation
and are given in Table 5 and Fig. 8. The channel widths in the as-received (S1), rejuvenation 1
430
(S3) and rejuvenation 2 (S5) samples are very small, ~60 nm, whilst those in the degraded
structures are much larger, ~300 nm. The small channels of S1 and S3 lead to higher yield and
ultimate strengths in the tensile test. The UTS of these samples may be influenced by the
movement of dislocations which is governed by the spacing of the channels [14]. When the
spacing is small, the dislocation has to move through the precipitates by shearing or cutting. The
dislocation movement is thus impeded, leading to an increase in the applied stress and hence
higher mechanical properties. When the spacing is larger, as in the rafted structure, dislocations
can move by glide or climb through the channels, which is a process which requires lower stress
and thus results in poorer mechanical performance.
400
Parallel
Perpendicular
Channel Width / nm
350
Rafted +
Rejuvenation1
+ Rafted
Rafted
300
250
200
150
100
50
0
S1
Rafted +
Rejuvenation2
Rafted +
Rejuvenation1
As Received
S2
S3
Sample No
S4
S5
Figure 8: channel width measurements between the secondary particles of head sections for
the five different heat treated samples measured in parallel and perpendicular directions.
Although the average parallel channel width of S2 (280 nm) and S4 (242 nm) show no
significant difference, the channel widths in the perpendicular direction are substantially
different. S2 has an average width of 250 nm in the perpendicular direction, whilst S4 was only
99 nm. The difference in channel width indicates that the degrees of rafting are different in these
samples. In order to define the degree of rafting, a rafting parameter R was used. For a cuboidal
particle a rafting parameter of 0.5 would be expected. As shown in Table 5, the rafting parameter
of S1, S3 and S5 is very small, around 0.5, because the L and T values are the same. However,
for rafted samples, rafting results in a very large L but small T value, which leads to a greater R
value. The R value for S4 is much larger than S2, which confirms the observation that S4 has a
more continuous rafted microstructure. With these continuous broader channels, dislocations can
move more easily through the structure, which consequently leads to a reduction in tensile
strength.
The microstructure of the rejuvenation 1 sample (S3) showed the same size, morphology and
distribution as the as-received sample (S1), as well as degree of rafting, which was consistent
with the tensile test results. These microstructures indicate that the rejuvenation procedure for S3
used here restores the microstructure of a previously rafted sample to a microstructure which is
apparently equivalent to that of the as-received structure. However, when the rejuvenation 1 (S3)
sample experienced a subsequent further rafting treatment (S4), the microstructure showed a
greater extent of rafting than the sample which had received only one rafting treatment, sample
S2. It is possible that any chemical segregation present within the alloy has not been removed
during rejuvenation, which was then enhanced by the second rafting treatment with an
accompanying reduction in mechanical properties. This could explain why, on the microstructural
level, the as-received (S1) and rejuvenated (S3) sample are very similar but they showed a very
431
Figure 9: Optical microscopy images showing dendrite structures in; a) S1, as-received, b) S2,
rafted, c) S3, rafted + rejuvenation 1, and d) S4, rafted + rejuvenation 1+ rafted, e) S5, rafted +
rejuvenation 2.
432
In Fig. 9, the dendritic structures of S1-S4 are very clear and the structures increase in size after
the rafting treatment. After rejuvenation 2 (S5), no dendritic structure was observed, which may
indicate that a more homogeneous composition and microstructure were obtained. The chemical
composition difference results are shown in Fig. 10, where this defined as the difference in
chemistry between the IDR and the DC. Most of the elements show clear chemical segregation
differences. Therefore, since the behaviour of Al, Ti, Ta, W and Re were most obvious, the
chemical segregation difference of these elements was used to represent the chemical difference
trend in this study. It has been found that Al, Ti and Ta are rich in the IDR, but consistently
lower in DC, whilst Re and W exhibit contrary trends, which is in good agreement with
Karunaratne et al. [17]. According to the chemical segregation results, the sequence of the
chemical segregation from large to small is S4, S2, S3 and S1. The chemical segregation in the
as-received sample is the smallest. It is clearly shown that chemical segregation has increased
when the sample has undergone a rafting treatment. Although, rejuvenation 1 has recovered
some segregation e.g. Ti and Ta, it has not recovered to the as-received condition, but is closer to
the rafted conditions. This residual segregation is due to the slower diffusing elements such as
Re and W. According to Karunaratne et al. [17], the interdiffusion coefficients of Re and W at
the rejuvenation temperature are the slowest, which means chemical segregations of these
elements are very difficult to eliminate with short term rejuvenation or homogenisation [6,
15-17]. When the rejuvenation 1 sample (S3) experiences a further degradation treatment, the
chemical segregation increases even more. Chemical segregation is the key explanation for the
reduction in the performance after the second rafting heat treatment (S4), as the segregation of
slowly diffusing elements such as Re and W, is not fully removed during the short time
rejuvenation.
0.6
0.4
0.2
0.0
Al
Ti
Ta
Re
-0.2
-0.4
-0.6
S1.As Received
S2.Rafted
S3.Rafted+Rejuvenation1
S4.Rafted+Rejuvenation1+Rafted
Figure 10: Chemical composition difference between dendrite core and interdendritic regions
In order to determine whether the length of rejuvenation could eliminate these detrimental
segregation effects, a more extended rejuvenation procedure, rejuvenation 2, was applied to the
rafted sample. On a microstructural level (Fig. 5), the size and distribution of cuboidal is
equivalent to the size of as-received (S1) and rejuvenation 1 (S3). Very fine tertiary with a size
around 30 nm was also found. This microstructure is same as rejuvenation 1(S3). However, the
rejuvenation 2 sample (S5) shows no a clear dendrite structure, which indicates a more
homogeneous structure may be obtained in this sample. Therefore, in order to make a
comparison of chemical segregation in this sample, 20 EDS area analysis boxes with a size of
20x20 m were randomly carried on as-received, rejuvenation 1 and rejuvenation 2, by using the
difference between the maximum and minimum chemical composition to present the
inhomogeneity of the samples, as shown in Fig. 11. It has been found that the chemical
inhomogeneity is smallest in the as-received sample. For the rejuvenation 1 sample, there exists
433
a large degree of chemical inhomogeneity which is much greater than as-received conditions,
especially for heavy elements, such as W and Re. Encouragingly, rejuvenation 2 (S5) has
reduced the inhomogeneity, to levels very close to the as-received condition. The microstructure
and chemical homogeneity results are very positive for rejuvenation 2, indicating that an
extended heat treatment is required for full rejuvenation.
0.8
0.8
As-Received
Rejuvenation 1
Rejuvenation 2
0.6
0.6
0.4
0.4
0.2
0.2
0.0
Al
Ti
Ta
Re
0.0
435
436
2. EXPERIMENTAL
2.1 DEVELOPMENT OF NEW ROTOR MATERIAL: TOS1X-2
Table 1 shows the chemical compositions of prototype alloys that we examined. The chemical
compositions were determined based on thermodynamic consideration by Thermo-calc. All
alloys were prepared by 50 kg vacuum induction melting, followed by hot working down to bars.
The forging ratio was set as 3. After forging, alloys were subjected to solution heat treatment at
1100 C for 4 h and aging heat treatment at 750 C for 30 h. The mechanical properties of the
alloys were evaluated by tensile tests, Charpy impact tests, and creep rupture tests. Tensile tests
and Charpy impact tests were conducted at room temperature. The creep rupture tests were
conducted at a temperature of 800 C and a stress of 230 MPa. Microstructure observations were
also conducted by field emission-scanning electron microscopy (FE-SEM). The chemical
composition of TOS1X-2 was determined from all test results.
Table 1 Chemical compositions of prototype alloys (mass%).
Ni
Alloy 1
Bal.
0.05
Alloy 2
Bal.
0.05
Alloy 3
Bal.
0.05
Cr
Mo
Co
Al
Ti
Ta
Nb
0.8
1.2
0.1
0.3
<0.001
<0.001
1.1
1.4
0.1
0.3
<0.001
<0.001
1.4
1.6
0.1
0.3
<0.001
<0.001
Alloy 4
Bal.
0.05
2.2
1.8
0.1
0.3
<0.001
<0.001
Alloy 5
Bal.
0.05
2.2
1.2
0.1
0.3
<0.001
<0.001
Alloy 6
Bal.
0.05
0.8
2.0
0.1
0.3
<0.001
<0.001
After the chemical composition was determined, the heat treatment conditions were considered.
A 50 kg lab-scale TOS1X-2 alloy was manufactured by the same procedure as described above.
According to a time-temperature-precipitation (TTP) diagram of TOS1X-2 obtained by an
experiment performed in advance, several candidate aging heat treatment conditions were chosen.
Figure 1 shows the aging heat treatment conditions used in this study. Series-1 samples were
subjected to 750850 C heat treatment for 10 h, 30 h, and 48 h after solution heat treatment at
1100 C for 4 h. Series-2 sample was treated with two-step aging, first at 800 C for 10 h and
then at 750 C for 20h, after the solution heat treatment. Series-3 sample was subjected to the
same aging conditions as the Series-2 sample, but intermediate heat treatment was carried out for
the sake of stabilizing the grain boundary structure before aging heat treatment, as will be
described in detail below. Samples that were subjected to each aging condition were evaluated in
terms of their tensile properties and microstructures, just the same as the procedures described
above.
1100C
(Series-1)
(Series-2)
1100C
800C
2.4C/min
10, 30,
48 h
4h
750C
2.4C/min
F.C.
F.C.
4h
10 h
20 h
(Series-3)
1100C
1025C
800C
2.4C/min
750C
2.4C/min
F.C.
4h
10 h
10 h
20 h
1100
Macrostructure observation
Material tests
Chemical analysis points
700
390
150
1050
1200
phase must coexist with the phase in any composition. On the other hand, it seems to be
possible to avoid the phase with 18 mass% Cr content, even if the Al and Ti content are much
higher than conventional Alloy 617. The phase diagrams show that a reduction of the Cr contents
is necessary in order to improve the Al and Ti contents without causing precipitation of the
phase.
3.0
1.0
Alloy 617
0
0
3.0
+
+
+
0
1.0
2.0
Al / mass%
ma
ss %
Ti
/
++
1.0
2.0
+++
+
+
+
+
+
2.0
Ti
/
ma
ss %
3.0
1.0
2.0
3.0
Al / mass%
(a) 23 mass%Cr
(b) 18 mass%Cr
Al content / mass%
Figure 4 shows the optimal range of Al and Ti content based on further thermodynamic
considerations in the case of a Cr content of 18 mass%. The lines (a), (b), and (c) indicate
boundary lines of precipitation of the phase, large-scale forgeability, and alloy strength,
respectively. In particular, (a) is the amount of phase at 750 C, which is 0 %, (b) is the
solution temperature of the phase, which is 1000 C, and (c) is the amount of the phase at
750 C, which is 10 mass%, each calculated using Thermo-Calc. The area A bounded by the
three lines is the area expected to satisfy all required properties. Forgeability and phase stability
might be insufficient in areas with high Al and Ti contents, whereas the material strength might
be poor in areas with low Al and Ti contents. The plotted points in Figure 4 indicate the Al and
Ti contents of the prototype alloys. Alloys 1 to 4 on line (I) were used for evaluating the effect of
the amount of the phase on the material properties, with an almost constant Al/Ti ratio. Alloys
3, 5, and 6 on line (II) were used for verifying the effect of the Al/Ti ratio, without changing the
amount of the phase.
Figure 5 shows the 0.2% proof stress,
18 %Cr
2.5
impact value, and creep rupture time of the
(a)
(b)
alloys on line (I) in Figure 4 as a function of
5
4
Alloy D
2
the total amount of Al and Ti (Al+Ti). The
creep rupture time of each alloy is normalized
1.5
with respect to the creep rupture time of Alloy
(c)
3
3. As the amount of Al+Ti increased, the
()
2
1
0.2% proof stress and creep rupture time
1
Alloy D
Alloy 617
6
gradually increased, whereas the impact value
()
0.5
rapidly decreased when the amount of Al+Ti
reached approximately 3.0 mass%.
A
Figure 6 shows the 0.2% proof stress,
0
impact value, and creep rupture time of the
0
0.5
1
1.5
2
2.5
alloys on line (II) in Figure 4 as function of
Ti content / mass%
the ratio of Al and Ti contents (Al/Ti). The
Figure 4 Optimal ranges of Al and Ti content
439
correlation between the Al/Ti ratio and the mechanical properties seems to be small; however, the
impact value showed a maximum value around Al/Ti = 1.0.
According to the results, the chemical composition of TOS1X-2 was determined as shown in
Table 2. The amounts of Al and Ti are between those of Alloy 2 and Alloy 3, the amount of
Al+Ti is 2.6 mass%, and the Al/Ti ratio is 0.93. Furthermore, Ta and Nb were added to further
improve the creep strength, based on knowledge from past research [8]. The microstructure of
TOS1X-2 is shown in Figure 7, compared with that of the conventional Alloy 617. It was
confirmed that the amount of the phase was higher than that in Alloy 617, and therefore,
improved mechanical properties are expected.
700
60
600
50
500
40
4
3
30
20
10
1.5
2.5
3.5
4.5
800
70
700
60
600
50
500
40
4
3
30
20
10
0.5
1.0
Al + Ti / mass%
1.5
2.0
Al/Ti
-2
70
80
800
900
80
-2
900
0.2%P.S. /MPa
0.2%proof stress
creep rupture time
Impact value
0.2%P.S. /MPa
0.2%proof stress
creep rupture time
Impact value
Cr
Mo
Co
Al
Ti
0.3
Alloy 617
Bal.
0.1
22
12.5
1.1
TOS1X-2
Bal.
0.05
18
12.5
1.25 1.35
Ta
Nb
0.1
0.3
1m
Temperature / C
: M6CG.B.)
: phase
Alloy 617 is characterized by its low
:
M
C
G.B.)+
phase
23 6
tensile strength. Therefore, one of the main
1100
M6C
purposes for heat treatment of TOS1X-2 is
to improve the tensile strength by
1000
controlling precipitation.
Figure 8
441
T.S.
T.S.
T.S.
0.2%P.S.
0.2%P.S.
0.2%P.S.
El.
El.
El.
R.A.
R.A.
R.A.
800C10h
750 C20h
T.S.
0.2%P.S.
El.
R.A.
100.0
120
90.0
100
80.0
70.0
60.0
20
40
Aging time / h
80
60
40
750C
800C
850C
40.0
20
800C10h
750 C20h
30.0
50.0
-2
1200
1100
1000
900
800
700
600
500
400
300
200
El., R.A. / %
750C
800C
850C
60
20
40
Aging time / h
60
442
T.S.
El.
1200
0.2% P.S
R.A.
1
Virgin
100
80
750C5000h
90
1000
80
-2
50
40
400
30
With
Int.H.T.
Without
Int.H.T.
With
Int.H.T.
Without
Int.H.T.
60
50
40
30
20
20
200
0
600
E l., R .A . / %
T .S., 0 .2 % P.S. / M Pa
60
750C5000h
70
800
Virgin
70
10
10
With
Int.H.T.
Without
Int.H.T.
With
Int.H.T.
Without
Int.H.T.
According to the results of the Series-1 and Series-2 samples, it is considered that an aging
temperature of 850 C is too high, and a temperature range of 750800 C is suitable for the
aging heat treatment. Compared with the tensile properties of the samples aged at 750800 C,
the sample aged at 750 C for 30 h and the two-step aged sample showed excellent tensile
strength and 0.2% proof stress. The tensile properties are sufficient in both cases, but it is
considered that the two-step aging is more suitable because a higher temperature is preferable in
order to inhibit microstructure evolution during operation. Therefore, a two-step aging, first at
800 C for 10 h and then at 750 C for 20 h, was adopted for the aging heat treatment.
As for the intermediate heat treatment, it seems that the intermediate heat treatment had no
detrimental effect on the tensile strength and 0.2% proof stress but a positive effect on the grain
boundary stability during long-term aging. For that reason, intermediate heat treatment of 1025
C for 10 h was adopted. In summary, suitable heat treatment includes intermediate heat
treatment at 1025 C for 10 h and aging heat treatment at 800C for 10 h followed by 750 C for
20 h, in addition to solution heat treatment at 1100 C.
Figure 15 and Figure 16 show the tensile properties and creep properties of TOS1X-2 lab-scale
material subjected to the above heat treatment, together with those of Alloy 617 for comparison.
The tensile properties and creep properties were drastically improved by modification of the
chemical composition and optimization of the heat treatment conditions.
TOS1X-2 T.S.
Alloy 617 T.S.
TOS1X-2 0.2%P.S.
Alloy 617 0.2%P.S.
700C105h 750C105h
800
300
Stress / MPa
1000
600
400
250
200
160
140
100
200
0
200
400
600
TOS1X-2
TOS1X-2
Alloy
617 617
Alloy
22000
800
Tempearture /
23000
24000
25000
26000
L.M.P (C=20)
Top
Middle
Bottom
Al
1.25
Top
0.1
Middle
Bottom
0.05
0.75
1.85
0
12
Ti
1.35
0.85
0.2
6
16
Ta
0.1
12.5
0
0.6
9
20
Nb
0.3
18
16
Mo
Co
Cr
Surface
3/4R
1/2R
1/4R
Core
Surface
3/4R
1/2R
1/4R
Core
Surface
3/4R
1/2R
1/4R
Core
Surface
3/4R
1/2R
1/4R
Core
Surface
3/4R
1/2R
1/4R
Core
Surface
3/4R
1/2R
1/4R
Core
The chemical analysis and macrostructure observation results show that the variation in
chemical composition is negligible and that the macrostructure has no irregularities. Generally,
Ni-based superalloys are more likely to have segregation problems compared with ferritic steels
because they contain a lot of alloy elements. It is considered extremely difficult to make a Nibased superalloy ESR ingot with a diameter over 1000 mm; however, this study demonstrated
that even a 1300 mm diameter ESR ingotcould be manufactured without any defects by an
adequate melting procedure.
1/2R
Surface
500
500m
5m
1m
Figure 21 shows the tensile tests results. The tensile strength and 0.2% proof stress were
slightly higher in the surface parts, but the variation of the tensile properties was negligible. The
0.2% proof stress of the rotor model was almost the same level as that of the lab-scale material.
In practice, the tensile properties are sufficient for an A-USC turbine rotor material.
Figure 22 shows the creep rupture strength of the core part and the T-direction estimated using
the Larson-Miller parameter with lab-scale data. The longest rupture time of the rotor model was
about 5,000 h, and the lab-scale data includes a data point at 24,000 h. The creep rupture strength
of the rotor model was as good as or better than the lab-scale material. The 105 h creep rupture
strengths of rotor model at 700 C and 750 C were estimated to be approximately 200 MPa and
120 MPa, respectively, which are much stronger than that of conventional Alloy 617. The creep
strength of the TOS1X-2 rotor model satisfy the creep strength requirements of not only 700 Cclass but also over 700 C-class A-USC turbine rotors.
700C105h 750C105h
300
800
Stress / MPa
1000
600
400
R
L
T
200
200
160
140
100
Rotor
Lab-scale
22000
Surface
3/4R
1/2R
1/4R
Core
250
23000
24000
25000
26000
L.M.P (C=20)
All metallurgical and mechanical features of the TOS1X-2 rotor model satisfied the
requirements for A-USC turbine rotor material. The long-term creep properties and other material
properties, such as fatigue properties, steam oxidation properties, and so on, are currently being
evaluated.
4. CONCLUSION
We developed a Ni-based superalloy called "TOS1X-2" as a material for A-USC rotors. An
actual-scale model rotor was manufactured, and we evaluated its metallurgical and mechanical
properties. Our conclusions are summarized as follows:
1. We developed a Ni-based superalloy called "TOS1X-2" based on Alloy 617. Its material
strength was greatly improved without loss of long-term phase stability and large scale foreability
by reducing the Cr content, optimizing the Al and Ti contents, and adding Ta and Nb.
2. A two-step aged sample, aged at 800 C for 10 h and then at 750 C for 20 h, showed excellent
tensile strength and 0.2% proof stress. Intermediate heat treatment at 1025 C for 10 h had a
446
detrimental effect on the tensile strength and 0.2% proof stress but a positive effect on the grain
boundary stability during long-term aging. For this reason, suitable heat treatment conditions
were determined to be intermediate heat treatment at 1025 C for 10 h and two-step aging heat
treatment, first at 800 C for 10 h and then at 750 C for 20 h, in addition to solution heat
treatment at 1100 C.
3. A 31-ton ingot and 14-ton model rotor made of TOS1X-2 were manufactured without any
defects. The 105 h creep rupture strengths of the rotor model at 700 C and 750 C were
estimated to be approximately 200 MPa and 120 MPa, respectively. All metallurgical and
mechanical investigations showed that TOS1X-2 has sufficient manufacturability and material
properties for not only 700 C-class but also over 700 C-class A-USC turbine rotors.
ACKNOWLEDGMENTS
This work was conducted as a part of the A-USC national project in Japan funded by the
Ministry of Economy Trade and Industry.
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447
ABSTRACT
The European Cost programmes have led to the development of improved creep
resistant 9%-Cr-steels alloyed with boron, which are designed for turbine shafts
subjected to steam temperatures up to 620C. The production of forgings in steel Cost
FB2 for application in power plants has commenced. Production experience and results
are presented in the paper.
Beyond that, Saarschmiede participates in projects targeting at steam temperatures
above 700C. In the frame of a Japanese development programme the worldwide largest
trial shaft in a modified Alloy 617 Ni-Base material has been manufactured successfully
from a 31 t- ESR ingot. Manufacturing route and results are presented.
Contributing to the European NextGenPower project Saarschmiede has started activities
to produce a large rotor forging in Alloy 263. Simulations of main manufacturing steps
have been performed and a large trial forging has been produced from a triple melt ingot.
First results are presented.
INTRODUCTION
In order to improve the efficiency of fossil-fuel steam power plants, it is necessary to
operate with the highest possible steam temperatures. The European Cost Programmes
have led to the development of the 10% Cr steels known as Cost E and Cost F for
turbine rotors [1,2], which are nowadays used as standard for steam temperatures of up
to 600C. The latest development in the programmes Cost 501 to Cost 536 resulted in
the 9%-Cr steel Cost FB2 (X13CrMoCoVNbNB9-2-1), which has the special
characteristic of containing 100 ppm of boron. Here, the production of turbine shafts has
already started. [3] The aim is to achieve a steam temperature of 620C.
In order to exceed this temperature limit, it is necessary to use Ni base alloys. These
were and still are the subject of intensive research and development projects in Europe
and Japan. The aim is to have steam temperatures exceeding 700C.
The greatest progress in development has been made in this field by a cooperation
between Toshiba Corporation Power Systems Company and Saarschmiede GmbH
Freiformschmiede in the manufacture of trial rotors in production dimensions based on
Alloy 617 [4].
Also, in the European programmes MACPLUS and NextGenPower, Ni base alloys are
considered as candidate materials for turbine rotors. In the frame of the NextGenPower
project, for example, a trial rotor was manufactured from Alloy 263 by Saarschmiede.
448
component
Melt No.
dimensions
for QHT
[mm]
weight for
QHT [kg]
delivery
weight [t]
Year of
delivery
880
930974
1100x2144
15936
9.6
10-2007
589
931084
1068x1910
13795
9.3
04-2008
590
315
931084
931163
1068x1910
1142x1882
13795
14178
9.3
8.6
04-2008
10-2009
316
931163
1142x1882
14178
8.6
10-2009
347
931173
1154x2194
18002
11.9
02-2009
414
931336
1163x2152
17945
11.5
02-2011
683
931510
1082x2087
15051
10.2
03-2013
931508
1082x2087
15051
10.1
05-2013
931524
1086x2056
14936
9.9
04-2013
684
574
The chemical composition developed in the Cost programme was used for the
production parts according to Table 2.
All ingots in this grade are produced at Saarschmiede using the electro slag remelting
(ESR) process. Ingots with weights of up to 56 t and a diameter of 1,300 mm were used
for the parts delivered. Immediately after remelting, forging was carried out and then
followed by martensitic preliminary heat treatment. The parts were machined for
quenching and tempering. Hardening took place from a temperature of 1,100C by
cooling with oil.
Table 2: Standard Composition of Cost FB2 (X13CrMoCoVNbNB9 2 1)
C
0.13
Mn
0.35
Cr
9.25
Ni
0.15
Mo
1.5
V
0.2
N
0.023
Nb
0.05
B
0.01
Co
1.3
Annealing treatment was carried out at 700C. After quenching and tempering, the parts
were subjected to mechanical testing at segments as well as in deep seated rings. A
summary of the results is shown in Fig. 1.
449
Elongation [%]
60
50
40
30
20
10
0
650
660
670
680
690
700
710
720
730
The minimum detectable defect size (MDDS) in the centre core was determined at an
ultrasonic frequency of 2 MHz. The results can be found in Fig. 2.
MDDS [mm]
UT Attenuation [db/m]
4
3
2
1
0
750
850
950
1050
1150
1250
Diameter [mm]
Fig. 2 Minimum Detectable Defects Size (MDDS) and UT-attenuation for FB2 parts
versus testing diameter
MDDS is mainly below 2 mm whereas for the lower diameter range, figures are between
1.5 mm and 2 mm. Attenuation to UT reveals wide scattering of values from between
approximately 2 db/m up to almost 5 db/m.
For verification purposes, on one production, namely part No. 414, two longer creep
rupture tests were carried out at 650C//125 MPa whereby rupture times of over 5600 h
were reached (Fig. 3). The results proved to be better than in previous trial shaft.
450
300
200
150
100
24000
24500
25000
25500
26000
26500
27000
Fig. 3: Creep test on a production part compared to the SSF trial shaft [5,6]
1100 mm
700 mm
1100 mm
One of the most promising candidates for rotor forgings subjected to steam
temperatures of above 700C is Alloy 617, which was investigated for example in the
European Thermie programme and of which some trial parts were manufactured. [7,8]
In cooperation with and by order of Toshiba Power Systems Company, Saarschmiede
manufactured the worlds largest rotor part from Ni-base alloy (Fig. 4).
150 mm
1200 mm
1200 mm
2400 mm
451
Cr
Mo
Co
Ni
Ti
Al
Nb
Ta
0.05
22.0
9.0
12.0
Bal.
0.4
1.0
0.003
Fe
max.
2.0
TOS1X
0.05
18.0
9.0
12.5
Bal.
1.35
0.003
max.
1.5
Fig. 5: Creep properties for different materials in the elevated steam temperature range
[3,9,10,11]
Manufacture was carried out according to the sequence shown in Fig. 6. The ingot for
the rotor was manufactured on the melting route vacuum induction furnace (VIM) ESR
with an ingot diameter of 1,300 mm and a weight of approx. 31 t.
In order to achieve a sufficiently good microstructure, a forging process with triple
upsetting was used. Due to the great size of the ingot and its considerable resistance to
forming, the ingot was forged in the 120 MN press to a forging of 2,400 mm in length with
a diameter of 1,100 mm. Solution annealing was carried out in machined condition and
the workpiece was quenched in water. The final delivery weight of the rotor was 14.1 t.
After heat treatment, slices were removed from each end for examination purposes. It
could be shown that there was good uniformity of the microstructure on the slices from
the top and bottom ends and that there was no segregation.
Tensile tests were carried out in the solution annealed condition at the edge and in the
centre and the results are shown in Table 4.
No indications of defects were found during the ultrasonic inspection.
452
Test
Location
Surface
Center
0.2%
YS
MPa
379
346
UTS
MPa
Elongation
%
RA
%
797
755
59.0
58.8
71.5
61.5
453
Si
Mn
Cr
Mo
Ni
Co
Cu
Ti
Al
Al
+Ti
Fe
melt
analysis
bal.
product
analysis
(core)
0,04
bal.
0,1
0,2
With regards to ingot segregation, which is a well known risk in larger ingots,
Saarschmiede chose the triple melt process for producing the ingot. This comprises
primary melting in the VIM furnace followed by ESR and finally remelting in the vacuum
arc remelting furnace (VAR). One of the advantages of this process is, that in VAR a
swallow melt pool can be realized. An ingot of 20 t in weight and a diameter of 980 mm
was produced (Fig. 7).
uniformity of the microstructure and the grain size were calculated. The aim was to
achieve optimum ultrasonic MDDS. Another aim was to counteract any potential risk of
cracking.
Finally, using a forging process with triple upsetting, a forging of 1,080 mm x 1,850
mm in length with a weight of 16 t was produced from the ingot (Fig.8). The material
proved to have good forgability (Fig. 9).
Fig. 9: Pre-forged billet of the Alloy 263 rotor shaft shows smooth surface
After the forging process, the forging was cooled down to room temperature.
Immediately after forging, a microslice was removed from each end for examination. The
slices proved to be free of segregation. The cross-sections of both slices were used to
455
determine the grain size. Fig. 10 shows the distribution from the centre line to the rim.
While the grain size in the centre is mainly within the range ASTM 0.5 to ASTM 3, the
values at the rim are far better.
9
Maximum Grainsize
Minimum Grain Size
8
7
6
5
4
3
2
1
0
0
100
200
300
400
500
600
Fig. 10: Grain size from centre to rim of the Alloy 263 trial shaft
Before solution annealing, the MDDS of the rotor was tested using manual ultrasonic
inspection in machined condition. Values of between 2.8 mm and 4.9 mm were
determined at 2 MHz. It remains to be seen how the maximum defect size is after
solution annealing and ageing. Defects were not found during the US inspection.
Table 6: Mechanical properties of Alloy 263 trial shaft after solutioning and ageing
Melt No.
Type
988346
2.4650
Alloy 263
Melt
No.
988346
Type
2.4650
Alloy 263
Top
25
0.02%
YS
[MPa]
562
Bottom
25
560
Sample Temp.
Location [C]
0,2%
YS
[MPa]
642
646
UTS Elongation
[MPa]
[%]
993
27,0
24,0
986
29,0
24,7
Sample
Location
Temp.
[C]
Inpact [J]
Cristallinity
[%]
Top-1
25
48
95
Top-2
25
45
95
Top-3
25
43
95
Bottom-1
25
57
95
Bottom-2
25
59
95
Bottom-3
25
60
95
456
RA
[%]
Solution annealing took place at 1,130C and subsequent quenching in water was
carried out. Ageing was carried out at 800C.
After that, testing of the mechanical properties has been performed at bottom and top of
the shaft. Results for tensile and impact test are given in Table 6. It can be seen, that for
this large shaft the figures are well in the usual range of Alloy 263.
SUMMARY
Great efforts are still being made to increase the efficiency of fossil power plants. The
steel Cost FB2 has proven to be suitable for operation with higher steam temperatures at
production scale. However, with regard to toughness, it was necessary to make
significant concessions in comparison with Cost E or Cost F steels.
Ni-base alloys show good potential for achieving steam temperatures exceeding 700C
whereby the Japanese modification of Alloy 617, that is TOS1X, has good properties and
the manufacturability of a rotor at production scale has been successfully demonstrated.
It was the first time that an ingot weighing over 30 t had been produced in such an alloy.
Manufacture of a rotor in a precipitation hardening alloy is still in the first stages of
development. A trial rotor was produced from Alloy 263 at production scale with very
promising initial results. Further results are awaited.
ACKNOWLEDGEMENT
The manufacture of the trial rotor in Alloy 263 is performed in the frame of the Seventh
Framework Programme of the European Commission with funding by the European
Commission.
REFERENCES
[1] Blaes, N., Donth, B., Bokelmann, D., High Chromium steel forgings for
steam turbines at elevated temperatures, Energy Materials, Vol. 2 No. 4
(2007), pp. 207-213
[2] Kern, T.U., Staubli, M., Meyer, K-H., Donth, B., Zeiler, G. and
DiGianfrancesco, A., The European Effort in Development of New High
Temperature Rotor Materials Cost 536, Proc. 8th Liege Conference, Liege,
Belgium, September 2006, pp 843-854
[3] Blaes, N., Donth, B., Diwo, A., Bokelmann, D., Rotor Forgings for
Supercritical and Ultra supercritical Fossil Power Plants, Proc. 18th
International Forgemasters Meeting, Pittsburgh, PA, September 2011,
pp 233-238
457
[4] Diwo, A., Donth, B., Blaes, N., Bokelmann, D., Yoshioka, Y., Miyashita, S.,
Kubo, T. Largest Steam Turbine Rotor Ever Manufactured From A Nickel
Base Alloy, Proc. 18th International Forgemasters Meeting, Pittsburgh, PA,
September 2011, pp 219-223
[5] Kern, T.U., Scarlin, B., Donth, B., Zeiler, G.,DiGianfrancesco, A., The
European Effort Cost536 Project for the Development of New High
Temperature Rotor Materials, 17th Int. Forgemasters Meeting, Santander,
Spain, November 2008, pp 316-320
[6] Kern, T.U., Meyer, K-H., Donth, B., Zeiler, G., DiGianfrancesco, A. The
European Efforts in Development of New High Temperature Rotor
Materials-Cost 536, Proc. 9th Liege Conference, Liege, Belgium, 2010,
pp 29-38
[7] Donth, B., Blaes, N., Diwo, A., Bokelmann, D., Manufacturing of Advanced
Rotor Forgings for Highly Efficient Fossil Power Plants, Proc. ETD Int.
Conference on New High Temp. Materials, Chicago, USA, August 2011
[8] Blaes, N., Donth, B., Diwo, A., Bokelmann, D., Advanced Forgings for
Highly Efficient Fossil Power Plants, Proc. 6th International Conference on
Advances in Materials Technology for Fossil Power Plants, Santa Fe, NY,
USA, August 2010 pp 436-449
[9] Takahashi, T. Development of Advanced-Ultra Super Critical Steam
Turbine System, 8th International NIMS-IFW-Workshop on Advances in
High Temperature Materials for High Efficiency Power Plants, 2010
[10] Miyashita, S., Yamada, M., Suga, T., Imai, K., Nemoto, K., Yoshioka, Y.,
Development of a rotor for advanced ultra super critical turbine power
generation system,
Procedings of the 34. MPA-Seminar, 2008,
pp 15.1-15.18
[11] Mayer, K-H., Werkstoffentwicklungen zur Effizienzsteigerung von fossilen
Kraftwerken. Stahlinstitut VDEh, Dsseldorf, 2006
458
ABSTRACT
Carbon Capture and Storage (CCS) has become promising technology to reduce CO2 emissions.
However, as a consequence of CCS installation, the electrical efficiency of coal fired power plant
will drop down. This phenomenon requires increase in base efficiency of contemporary power
plants. Efficiency of recent generation of power plants is limited mainly by maximum live steam
temperature of 620C. This limitation is driven by maximal allowed working temperatures of
modern 912% Cr martensitic steels. Live steam temperatures of 750C are needed to compensate
the efficiency loss caused by CCS and achieve a net efficiency of 45%. Increase in the steam
temperature up to 750C requires application of new advanced materials. Precipitation hardened
nickel-based superalloys with high creep-rupture strength at elevated temperatures are promising
candidates for new generation of steam turbines operating at temperatures up to 750C. Capability
to manufacture full-scale forged rotors and cast turbine casings from nickel-based alloys with
sufficient creep-rupture strength at 750C/105 hours is investigated. Welding of nickel-based
alloys in homogeneous or heterogeneous combination with 10% Cr martensitic steel applicable
for IP turbine rotors is showed in this paper. Structure and mechanical properties of prepared
homogeneous and heterogeneous weld joints are presented.
INTRODUCTION
Reduction of CO2 emissions is one of the main goals of EU in the next years. Particularly, 20%
reduction will be required by EC in 2020. To reduce CO2 emissions to above mentioned level
implementation of Carbon Capture and Storage (CCS) in coal power plants is needed. However,
application of CCS technology is related with decrease of power plant efficiency. To compensate
this decrease in efficiency, higher temperatures of live steam flowing through turbine are needed.
Of course, higher steam temperature has significant impact on material selection for boiler and
turbine components. Live steam temperatures of 700 750C call for application of nickel-based
superalloys with sufficiently high creep rupture strength at 750C/105h [1, 2].
NEXTGENPOWER is unique international collaborative project demonstrating application of
new alloys and coatings in boiler, turbine and interconnecting pipework and should show new
directions in design of A-USC power plant. In this project, precipitation hardened gamma-prime
nickel-based alloy Nimonic 263 (A263) was selected as a promising material for high pressure
(HP) steam turbine rotor. In the case of intermediate pressure (IP) steam turbine rotors, it is really
demanded to master dissimilar weld joint of nickel-based alloys with advanced 9-12% Cr
martensitic steels in order to manufacture welded IP rotor. Based on the heat balance calculations
of NEXTGENPOWER A-USC power plant, inlet steam temperature of IP turbine is 750C.
However, IP turbine outlet stem temperature is around 350C. Thus, it is not necessary to
manufacture whole IP turbine rotor from A263 as a single piece, but combine this material with
less expensive 9-12% Cr martensitic steels that can be applied in less hot section of IP turbine, see
459
Fig. 2. This will significantly reduce the price of turbine set. Manufacture of welded rotors
combining 12% Cr and low alloy martensitic steels has been developed and demonstrated [3-4].
With respect to A263, similar weld joint has been mastered in past [5]. Recommended approach is
to weld this material in solution treated condition. As a filler metal, Nimonic 263 is typically used.
However, precipitation hardening 800C/8hours should be carried out after welding in order to
achieve sufficiently high strength and creep resistance of both base material and filler metal. This
approach cannot be used for dissimilar weld joint of A263 with 9-12% Cr martensitic steel
because of tempering temperatures of 9-12% Cr steel. Particularly, COST F (X14CrMoVNbN101) martensitic steel with tempering temperatures around 700C was chosen as a rotor material for
less hot section of the IP turbine in this project because of its very good creep properties at
temperatures up to 600C.
Figure 1: Dissimilar weld joint Nimonic 263 + COST F applicable for IP turbine of A-USC
power plant.
With respect to above mentioned aspects, A263 has to be welded in precipitation hardened
condition (800C/8h) in the case of dissimilar weld joint A263 + COST F, because precipitation
hardening cannot be carried out after welding due to tempering temperatures (~700C) of COST
F steel on the other side of the weld joint. Post-weld heat treatment (PWHT) overcoming
tempering temperature of COST F would negatively affect strength and creep properties of this
material. Dissimilar welding process for above mentioned material combination A263 + COST F
is described and studied in this paper. TIG hot wire narrow gap welding was used to demonstrate
manufacture of welded rotors. Optimal PWHT was found with respect to the best combination of
strength and toughness given by rotor design point of view. Mechanical properties of similar
(A263 + A263) and dissimilar (A263 + COST F) are analyzed and discussed in this paper.
EXPERIMENTAL
All discussed similar and dissimilar weld joints were processed by TIG hot wire narrow gap
welding. Unique experimental welding stand allowing welding of rotor parts in vertical position
was used. Welding head was kept in fixed position whereas the welded samples rotated on the
table. Example of the welded samples in vertical configuration on the table of the experimental
welding stand is shown on Fig. 2. Nickel-based welding consumable not requiring post-welding
precipitation hardening was used. Two different welding torches V2 and WP27 were applied for
root and filling passes, respectively. Samples with diameter of 160 mm and welding depth 50 mm
were used for similar combination A263 + A263. In the case of dissimilar weld joint A263 +
COST F, discs with diameter of 300 mm and welding depth 100 mm were used. Table 1 shows
material composition of base materials used. In the case of similar weld joint A263 + A263, no
pre-heating was applied on welded samples. The interpass temperature was kept below 100C in
order to avoid hot cracking. Welding parameters found for similar combination were used as a
background for welding of heterogeneous combination A263 + COST F. In the case of dissimilar
combination, two approaches, with and without cladding of COST F with nickel-based cladding
metal, were applied. Pre-heating of COST F was used during welding process without cladded
460
COST F. In the case of option with cladded COST F, pre-heating of COST F discs was used
during cladding process. However, no pre-heating of cladded COST F was applied during
dissimilar welding A263 + COST F. For both variants with/without cladded COST F, interpass
temperature was kept again below 100C during narrow gap welding of A263 + COST F.
160 mm
A 263
Si
0.051
0.024
Mn
Si
Mn
0.109
0.16
Ni
Cr
Mo
Al
Co
Cu
Ti
52.0
19.59
5.77
0.422
19.89
<0.01
2.21
Ni
Cr
Mo
Al
Co
Cu
Ti
0.001
53.0
19.2
5.7
0.51
19.3
0.008
2.27
0.02 0.00051
300 mm
A 263
0.041
C
Si
Mn
Ni
Cr
Mo
Al
Nb
300 mm
COST F
0.13
0.08
0.54
0.001
0.57
10.42
1.50
0.009
0.17
0.05
0.057
of the weld joint in turbine and typical tempering temperatures of COST F steel used in dissimilar
combination of A263 + COST F. Results on tensile test at 20C are shown in Fig. 3. Cap, filler
and root of the weld joint were analyzed. All the samples were broken in the filler metal. As can
be seen in Fig. 3, longer PWHT leads to increase of tensile strength. This phenomenon is most
likely attributed to carbide formation and precipitation of gamma prime phase in filler metal.
Results on Charpy impact tests are shown in Fig. 4 for various PWHTs. V-notch was placed in
filler metal and heat affected zone (HAZ) for cap and root of the weld joint. As expected,
decrease in impact energy is related with growing tensile strength of weld joint. Longer PWHT
time leads to more strength but less ductile structure of filler metal and HAZ.
Figure 3: Room temperature tensile strength of weld joint A263 + A263 measured for various
PWHTs. Tensile properties were measured in cap, filler and root area of the weld joints.
Figure 4: Charpy impact test performed at 20C of weld joint A263 + A263 treated with various
PWHTs. Impact energy was measured for filler metal and HAZ in root and cap area of the weld
joint.
462
From rotor design perspective, optimal combination of the strength and toughness is required.
Thus, PWHT T(C)/time_2 was chosen as the best option optimizing tensile and fracture
toughness properties of filler metal and HAZ between A263 and filler metal. T(C)/time_2
PWHT was selected as a default heat treatment for dissimilar combination A263 + COST F. For
optimal PWHT T(C)/time_2, hot tensile test at 700 and 750C was carried out and compared to
results measured at room temperature, see Fig. 5. Cap, filler and root of the weld joint were
analyzed. Elevated temperatures of tensile test led to decrease of tensile strength from 1000 MPa
to 700 MPa. All the samples were broken in filler metal.
Figure 5: Tensile strength at elevated temperatures measured for similar weld joint A263 + A263
treated with optimal PWHT T(C)/time_2. Tensile properties were analyzed for cap, filler and
root area of the weld joints.
Dissimilar Weld Joint A263 + COST F
To demonstrate dissimilar welding of A263 + COST F, welding parameters found for similar
combination A263 + A263 were used. As has been indicated, two approaches were applied to
master dissimilar welding of A263 + COST F. In the first case, easier approach was chosen and
COST F steel was welded without nickel-based cladding. Material A263 was used in precipitation
hardened condition. In this case, it was necessary to pre-heat COST F prior and during welding
process. Applied pre-heating caused difficulties in keeping of interpass temperatures below
recommended 100C, which increases risk of hot cracking. In the second case, pre-heated
COST F was cladded with nickel-based cladding metal at first. After cladding process, residual
stress relief heat treatment was carried out. Then, the nickel-based cladding of COST F was
machined down to required shape of the bevel. Welding of A263 and cladded COST F was
performed without preheating of cladded COST F counter piece. This approach enables to keep
interpass temperatures as low as possible. For both variants, with/without cladding of COST F,
optimal PWHT found for similar weld joint A263 + A263 was used to relief the internal stresses.
Results of room temperature tensile test are shown on Fig. 6 for both variants with/without
cladding of COST F. All the samples were broken in COST F base material, which indicates that
tensile strength of filler metal is higher than tensile strength of COST F base material. In previous
paragraph dealing with similar weld joint A263 + A263, all the samples were broken in filler
metal. For PWHT T(C)/time_2, tensile strength Rm and yield strength Rp0.2 of similar weld joint
463
A263 + A263 ranged in 950 1050 MPa, which is significantly higher value than certified tensile
strength Rm = 870 MPa of COST F base material used for dissimilar welding tests. These findings
point out that COST F is the weakest material in dissimilar weld joint from the tensile strength
point of view. As mentioned, certified tensile and yield strength of COST F base material are Rm
= 870 MPa and Rp0.2 = 730 MPa, respectively. However, tensile test of both variants of weld
joints showed that tensile and yield strength of COST F after welding operation and application of
PWHT are lower than those of the same material prior welding, see Rm = 750 800 MPa and
Rp0.2 = 600 650 MPa after welding and PWHT in Fig. 6.
Figure 6: Tensile test results of dissimilar weld joint A263 + COST F carried out at room
temperature for both variants with/without cladding of COST F.
This decrease of tensile and yield strength of COST F after welding is most likely related with
PWHT of weld joint at temperatures very close to tempering temperature of COST F base
material. Moreover, approach with cladding of COST F provides slightly lower tensile and yield
strength then approach without cladding. This can be explained by longer exposition of COST F
base material during PWHT to temperatures close to tempering temperature of COST F for
464
variant with cladding of COST F. Particularly, two PWHTs, one for cladding and one for whole
weld joint, were applied. On the other hand, only one PWHT was used for variant without
cladding of COST F. Elongation A(%) and reduction in area Z(%) have opposite manner than
tensile strength. For variant with cladding of COST F, A(%) and Z(%) are higher than for variant
without cladding. From perspective of tensile properties and complexity of weld joint
manufacture, variant without cladding of COST F is simpler and provides higher tensile strength
at still sufficiently high elongation.
Results on Charpy impact test are shown on Fig. 7. V-notch was placed in various areas of the
weld joints. Particularly, HAZ between COST F and cladding, cladding, HAZ between cladding
and filler metal, filler metal, HAZ between filler metal and A263 were analyzed for cap and root
of the weld joint for option with cladding of COST F. For variant without cladding on COST F,
HAZ between COST F and filler metal, filler metal, HAZ between filler metal and A263 were
analyzed for cap and root of the weld joint.
Figure 7: Charpy impact test of dissimilar weld joint A263 + COST F carried out at room
temperature for both variants with/without cladding of COST.
As can be seen on Fig. 7, most critical area of the weld joint is HAZ between filler metal and
A263 (see the lowest impact energies measured in this location for both variants with/without
cladding of COST F). This phenomenon is most likely related with microstructure changes of
A263 due to welding process. To confirm this theory, further and more detail investigation of
microstructure especially in this transition zone would be needed. However, from the perspective
of rotor design and structural calculations, even the lowest measured impact energies are
sufficiently high and acceptable.
465
Macrostructure of dissimilar weld joint A263 + COST with/without cladding of COST F is shown
on Fig. 8. Cross-sections taken from three different locations were analyzed for both variants. No
defects and cracks were indicated on all analyzed cross-sections. Both weld joints met
requirements of quality degree B (the highest quality) given by EN ISO 5817.
Figure 8: Macrostructure of dissimilar weld joint A263 + COST F taken for both variants
with/without cladding of COST F.
Next step in NEXTGENPOWER project in terms of dissimilar rotor welding is demonstration of
full-scale rotor welding on production welding stand in Doosan Skoda Power. Based on achieved
experiences, dissimilar full-scale weld joint A263 + COST F with diameter of 1000 mm will be
welded and extensively tested.
CONCLUSIONS
It was demonstrated that Nimonic 263 can be successfully welded in precipitation hardened
condition. Optimal PWHT was found for similar weld joint A263 + A263 with respect to optimal
combination of tensile strength and toughness. Dissimilar welding of A263 + COST F was
demonstrated. Two approaches with/without cladding of COST F with nickel-based cladding
metal were investigated. With respect to tensile strength, toughness and severity of welding
process, variant without cladding of COST F seems to be more effective approach for this
material combination. Macrostructure of both dissimilar weld joints A263 + COST F with/without
cladding of COST F met requirements on the highest quality degree given by EN ISO 5817.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the support of NEXTGENPOWER project (Project no:
ENER/FP7EN/249745/NEXTGENPOWER) and to the European Commission for financial
support.
466
REFERENCES
[1] N. Lckemeyer, H. Kirchner, H. Almstedt, Challenges in advanced-USC steam turbine
design for 1300F/700C, Proceedings of ASME Turbo Expo 2012, Copenhagen, Denmark,
June 2012.
[2] M. Fukuda, E. Saito, Y. Tanaka, T. Takahashi, S. Nakamura, J. Iwasaki, S. Takano, S.
Izumi, Advanced USC technology development in Japan, Proceedings of Advances in
Materials Technology for Fossil Power Plants 2010, Santa Fe, New Mexico, USA, August
2010.
[3] T. Shige, S. Itou, R. Magoshi, T. Ichimura, Y. Kondou, Development of Large-Capacity,
Highly Efficient Welded Rotor for Steam Turbines, Mitsubishi Heavy Industry Ltd.
Technical review, Vol. 38, No. 1 (2001).
[4] J. Hutchinson, R. Conroy, R. Stalker, Fabricated Turbine Rotors for Advanced Steam
Turbines, Siemens Power Generation, Public Report, August 2004.
[5] J. Minwoo, L. Jae-Hyun, W. T. Kwan, K. Sangshik, Effect of Welding and Post-weld Heat
Treatment on Tensile Properties of Nimonic 263 at Room and Elevated Temperatures,
Metallurgical and Materials Transactions A,Vol. 42, No. 4 (2011), pp. 974-985.
467
ABSTRACT
Advanced 700C-class steam turbines require using austenitic alloys instead of conventional
ferritic 12Cr steels, which are insufficient in creep strength and oxidation resistance above 650C.
Austenitic alloys, however, possess a rather higher coefficient of thermal expansion (CTE) than
the 12Cr steels. With respect to design aspects for the reliability, operability and performance, the
austenitic alloys for the advanced steam turbine are required to have low CTE properties. In
addition, from the viewpoint of the residual stress on welded components, the CTE between
developed material and conventional 12Cr steels to be welded should be similar to each other. So
far, the authors have examined the effects of alloying elements on CTE, high-temperature
strength, phase stability and manufacturability. Consequently, LTES700R was developed for
steam turbine rotors.
CTE of LTES700R is lower than that of 2.25Cr steel and conventional superalloy, proof
strength at room temperature was close to that of advanced 12Cr steel rotor material, and the
creep rupture strength around 700C was notably higher than that of 12Cr owing to strengthening
by gamma-prime phase precipitates.
For a trial production of the turbine rotor, medium-sized forging was applied in order to evaluate
the manufacturability of LTES700R and properties. In the trial production, VAR process was
applied to reduce risk of segregation and a forging procedure was designed by simulation
technology using the finite element method. Accordingly, the trial production was successfully
manufactured and its quality was verified satisfactorily by a destructive evaluation.
INTRODUCTION
Global warming due to increased CO2 levels in the atmosphere and resource saving have been the
focus of world attention in the past decades. Efforts to improve generating efficiency by
increasing the turbine inlet steam temperature and pressure in large capacity fossil-fuel and
combined-cycle power plants are being made together with efforts to improve the internal
efficiency. Most of modern steam turbines, including the combined cycle plants, have a 600C
class USC inlet steam conditions. 700C class Advanced USC (A-USC) technology is one of the
remarkable technologies being developed to reduce CO2 emissions, and one, which was chosen by
Japans Cool Earth- Innovative Energy Technology Program[1], which was launched in 2008 to
468
469
order to satisfy this design concept, new Ni-based superalloy LTES700R with a low thermal
expansion has been developed [8].
This paper describes a trial manufacturing of LTES700R with a medium size to evaluate its
manufacturability and properties.
ALLOY DESIGN
From equation (1) obtained by regression analysis of conventional Ni-based superalloys database,
Mo and W were expedient elements to reduce CTE[9].
CTE=13.87+7.28x10-2xCr+3.75x10-2x(Ta+1.95Nb)+1.98x10-2Co+7.3x10-5xCoxCo
-1.84x10-2xAl-7.95x10-2xW-8.24x10-2xMo-1.63x10-1xTi
(1)
Large amount of Mo content may precipitate Laves[Ni2(Mo, Cr)] phase. Although the Laves
phase enhanced the strength, it has been ascertained that the Laves phase resolved in the matrix
between 700C and 750C. From view of the future development of A-USC, phase stability over
700C should be considered so that the alloy design was examined without Lave phase. On the
other hand, the excess W content might deteriorate ductility due to the precipitation of alpha-W.
Therefore, within the range of Laves phase and alpha-W free, Mo and W contents were
maximized. In addition, Al and Ti in the proper quantity were added precipitation strengthening
of gamma-prime phase, which contributes high temperature strength even if over 700C.
Concerning Cr content, minimum amount of Cr was added for oxidation resistance though
positive element for CTE. Based on the above consideration, the new superalloy LTES700R was
designed. The nominal is Ni-12Cr-6Mo-7W-1.6Al-0.7Ti in mass%.
Fig.2 (a) and (b) show microstructure of LTES700R after aging heat treatment by optical
microscope and TEM respectively. Blocky precipitates in the optical microstructure are retained
carbide. On the other hand, the TEM photo shows densely precipitated gamma-prime phases that
are spherical in shape. The precipitation of the Laves phase is not observed in LTES700R. The
mean CTEs of LTES700R from RT to 700C are shown in Fig.3 along with the conventional steels
and superalloys[10]. The CTE of LTES700R is higher than LTES700 and the conventional 12Cr
steel but lower than conventional superalloy (ex. A286, Alloy 625 and Alloy 617) and the 2.25Cr
steel. The strength of LTES700R is shown in Fig.4 comparing with the modified 12Cr steel
TMK1 used as rotor material for 600C class steam turbines. Compared with TMK-1, LTES700R
has a similar 0.2% proof strength at room temperature, higher strength at elevated temperature,
especially tensile strength[11].
1400
LTES700R(50kg melt)
12Cr steel (TMK-1)
Stress (MPa)
1200
1000
Tensile Strength
800
0. 2% Pr oof St r engt h
600
400
0
200
400
600
800
Temperature ( C)
TRIAL MANUFACTURERING
Commitment to Larger Production
The final development target of LTES700R was applied to the real large steam turbine rotor of AUSC. In the former report, the result of the small-sized trial production quality whose shape was
disk (910mm x H235mm) was good [12]. As the next step, the medium-sized trial production
simulated the turbine rotor shape was carried out. The trial production size of comparison the
small-sized forging and the medium-sized forging are shown in Fig.5. The diameter of both trial
productions were almost the same, but the height of medium-sized forging was about three times
as high as the small size forging. Both manufacturing processes are shown in Fig.6. ESR process
was applied for the small-sized ingot in remelting process. But it was predicted that the quality of
the medium-sized ingot deteriorated because of slower rate of solidification with large ingot
diameter. So VAR process was applied for the medium-sized ingot. The 35MN hydraulic press
was used in forging process for the small-sized forging. On the other hand, the 70MN hydraulic
press was used for the medium-sized forging because of needs of larger load. Then it was
considered about the optimization of forging process design in order to obtain the good
microstructure. And the shape of column and large size of the superalloy production was the first
trial. It was needed long times for trial and estimation with tried and errors in conventional
development process. So the microstructure prediction system of LTES700R was developed
newly in order to design the correct forging process quickly without try and errors.
In this paper, the development of the microstructure prediction system of LTES700R, the
optimization of forging process using the system and results of various properties of mediumsized trial production compared with that of small-sized were reported.
471
(a)
(b)
850
235
910
845
Figure 5: Comparison small size with medium size about trial production shape.
(a)small size, (b)medium size
Small size
Medium size
Forging
(35MN hydraulic press)
Forging
(70MN hydraulic press)
15D
22.5
Compression
Holding time
WWW
Strain
Strain rate
Water quench
0.1sec
30sec
100sec
1800sec
1050C
500m
Fraction of recrystallization and recrystallization grain size were measured about all conditions of
the Rastegaeph compression test and shown in Fig. 10. Fig. 10 (a) shows the relationship between
fraction of recrystallization and holing time for each temperatures and fitting results using
equation (2) which are indicated by lines. The equation (2) represents constitutive equation about
fraction of recrystallization using Avrami type equation. Fig. 10 (b) shows the relationship
between recrystallization grain size and holding time for each temperatures and fitting results
using constitutive equation (3) which are indicated by lines. Both fitting results were well
corresponded to experimental datum.
Xrex=1-exp{-0.693(t/t0.5)2},
(2)
t0.5=C1C2d0C3exp(-Qs/RT),
where Xrex is recrystallization fraction, t is holding time, t0.5 is the time when Xrex is 0.5, is
strain, d0 is initial recrystallization grain size, Qs is reactivity energy of recrystallization, R is gas
constant, T is temperature, C1, C2 and C3 are constant values.
(3)
drex10=d010+C4tmexp(-Qgrow/RT)
where drex is recrystallization grain size, Qgrow is reactivity energy of grain growth, C4 and m are
constant values.
(a)
(b)
474
(a)
Strain
(b)
Symmetry
5.0
Symmetry
#3.5
4.0
3.0
Production
profile
Production
profile
#3.0
2.0
1.0
#2.5
Figure 11: Result of prediction using forging simulation. (a) strain distribution at final forging ,
(b) ASTM grain size distribution after solution treatment
Trial manufacturing of medium-sized trial production
The medium-sized trial production was manufactured using the forging pass schedule designed by
the microstructure prediction system of LTES700R. The outlook of the trial production after
forging and machining are shown in Fig. 13. It was confirmed that the shape after forging was
almost same with the shape designed by the microstructure prediction system.
100mm
100mm
Figure 12: Photograph of Medium-sized trial production after forging and machining
475
C
Cr
15
Mo
W
Al
Ti
LTES700R
10
Center
D/4
Outer
D/4
Outer
Top
Center
D/4
Middle
Outer
Top
Middle
Bottom
Small size
Bottom
Medium size
Figure 14: Schematic illustration of analysis positions in the trial production (Cross section)
Macrostructure
Fig. 15 shows macrostructures of the medium-sized trial production, which were observed in the
direction of the cross section at top, middle and bottom area. Abnormal structures such as harmful
segregation and coarse grain were not observed.
Top
Middle
Bottom
Microstructure
Fig. 16 shows microstructure observed by optical microscope at three positions that are
corresponding to the same in Fig. 14. Harmful non-metallic inclusions werent observed and the
microstructures were homogenous at various positions.
Size
Center
D/4
Outer
Medium
Small
100m
ASTM grain size of the medium-sized trial forging is shown in Fig. 17 compared with the smallsized trail production. The grain sizes at D/4 and center were higher than that at outer and close to
that of the small-sized trial production.
Medium
Small
4
3
2
1
0
Center
D/4
Outer
Position
477
1000
40
Elongation, Reduction(%)
50
800
strength(MPa)
1200
600
400
Mediu-0.2%PS
Small-0.2%PS
Medium-TS
Small-TS
200
D/4
20
Medium-EL
Small-EL
Medium-RA
Small-RA
10
0
0
Center
30
Outer
Center
Position
D/4
Outer
Position
Figure 18: Tensile properties at room temperature of the trial productions at each position
50
Enlogation, Reduction(%)
1000
800
strength(MPa)
1200
600
400
Medium-0.2%PS
Small-0.2%PS
Medium-TS
Small-TS
200
0
Center
D/4
40
30
20
Medium-EL
Small-EL
Medium-RA
Small-RA
10
0
Outer
Center
Position
D/4
Outer
Position
Figure 19: Tensile properties at 700C of the trial productions at each position
The result of Charpy impact test is shown in Fig. 20. The average impact value near outer position
was high and those of the medium-sized trial production at D/4 and center were a little lower than
that of the small-sized production.
200
Medium
Small
150
100
50
0
Center
D/4
Outer
Position
The stress to the rupture of LTES700R is plotted against Larson-Miller parameters in Fig. 21
compared with the mean data of the advanced 12Cr steel MTR10A[14] used as the rotor material
for 630C class turbines. The creep rupture strength of the medium-sized production was similar to
that of the small-sized production and the creep rupture strength of LTES700R was enhanced
100C and above higher than that of MTR10A, and the 100,000hr creep rupture strength at 700C
was higher than the target for the A-USC turbine rotor.
700oCX100,000hr
1000
Stress (MPa)
500
LTES700R
Labratory sample
Small-sized forging
Medium-sized forging
100
18
19
20
21
22
23
24
25
LMP=(T+273)(20+log tr)/1000
Figure 21: Creep rupture strengths of LTES700R and the advanced 12Cr steel(MTR10A).
Fatigue test results of the small and the medium-sized productions are shown in Fig. 22 and 23
compared with the small-sized trail production. The low cycle and high cycle fatigue strength of
the medium-sized production were homogenous from outer to D/4(center) and same as that of the
small-sized production.
1000
a (MPa)
(%)
700C
Small-sized forging
Medium-sized forging - Outer
Medium-sized forging - D/4
1
0.9
0.8
0.7
0.6
500
0.5
700C
Small-sized forging
Medium-sized forging - Outer
Medium-sized forging - D/4
0.4
0.3
2
10
10
Nf (cycles)
10
100 4
10
10
10
10
10
10
N (cycles)
It was confirmed that these results of the medium-size production were superior qualities and
almost same as the small-sized results due to the design of forging process. To develop the next
trial manufacturing for the larger size production required for the A-USC turbine rotor, a largesized production with an actual rotor dimensions was applied and its evaluation has been
continued.
CONCLUSIONS
The trial manufacturing of the medium-sized production of LTES700R, which was developed for
steam turbine rotor of A-USC with low thermal expansion and high creep performance, was
carried out and evaluated the qualities.
(1) The microstructure prediction system of LTES700R was developed and applied to design of
the trial forging in order to optimize forging process and obtain superior microstructure.
(2) As the result of the evaluation of the medium-sized trial production, chemical composition,
macro and microstructure and mechanical properties were superior qualities and equivalent to
the small-sized production of previous study. The medium-sized trial production of
LTES700R has suitable qualities for the A-USC steam turbine rotor.
REFERENCES
[1] Ministry
of
Economy,
Trade
and
Industry,
2008,
Website,
http://www.meti.go.jp/english/newtopics/data/pdf/CoolEarth_E_revised.pdf, pp. 4.
[2] N. Blaes, B. Donth, A. Diwo and D. Bokelmann, Advanced Forgings for Highly Efficient
Fossil Power Plants, Proceeding from the Sixth International Conference on Advanced in
Materials Technology for Fossil Power Plants, Santa Fe, NM, USA, August 2010, PP. 436449.
[3] Shinya Imano, Jun Sato, Hironori Kamoshida and Eiji Saito, Material design and Trial
Manufacturing of Ni-base Superalloy for A-USC Steam Turbine Large Components, Proc.
10th International Gas Turbine Congress, Osaka, Japan, November, 2011, IGTC2001-0176.
[4] Takeo Takahashi, Yuya Murakami, Shogo Iwai and Shigekazu Miyashita, Turbine Design
and Materials Aspects for A-USC Power Plant, Proc. 10th International Gas Turbine
Congress, Osaka, Japan, Novenber, 2011, IGTC2001-0210.
[5] H. Kamoshida, S. Imano, E. Saito, T. Uehara, T. Toga and T. Nonomura, Low Thermal
Expansion Ni-Base Superalloy for 700C Class Steam Turbine Plant (USC141), Proceeding
from the Sixth International Conference on Advanced in Materials Technology for Fossil
Power Plants, Santa Fe, NM, USA, August 2010, PP. 373-385.
[6] Robin Schwant, Chen Shen and Monica Soare, New Materials Enable Unprecedented
Improvement in Turbine Performance, ADVANCED MATERIALS & PROCESSES, 2013,
PP. 18-22.
[7] Y. Tanaka, R. Magoshi, S. Nishimoto, M. Setoyama R. Yamamoto, Y. Hirakawa and K.
Kawasaki, DEVELOPMENT OF ADVANCED USC TECHNOLOGIES FOR 700C
CLASS HIGH TEMPERATURE STEAM TURBINES, Proceedings of ASME Turbo Expo
2012, Copenhagen, Denmark, June 2012, GT2012-69009
[8] R. Yamamoto, Y. Kadoya, T. Nakano, Y. Tanaka, R. Magoshi, S. Ueta and T. Noda, ,
Development of Ni-based Superalloy for Advanced 700C-class Steam Turbines,
Proceeding from the fifth International Conference on Advanced in Materials Technology
for Fossil Power Plants, Marco Island, FL, USA, October 2007, EPRI report number
1016250.
480
481
Tennessee, Knoxville, TN
ABSTRACT
Hardfacing alloys are commonly used for wear- and galling-resistant surfaces for
mechanical parts under high loads, such as valve seats. Cobalt-based Stellite, as well
as, stainless-steel-based Norem02 and Tristelle 5183 alloys show similar
microstructural features that correlate with good galling resistance. These
microstructures contain hard carbides surrounded by a metastable austenite (fcc)
phase that transform displacively to martensite (hcp or bcc or bct) under deformation.
As a result, the transformed wear surface forms a hard layer that resists transition to a
galling wear mechanism. However, at elevated temperature (350C), the stainless steel
hardfacing alloys do not show acceptable galling behavior, unlike Stellite. This effect is
consistent with the loss of fcc to bcc/bct phase transformation and the increase in
depth of the heavily deformed surface layer. Retention of high hardness and low depth
of plastic strain in the surface tribolayer is critical for retaining galling resistance at high
temperature.
INTRODUCTION
Hardfacing alloys are commonly used to provide wear resistance on surfaces under
high contact stresses similar to that of valves in the power generation and chemical
industries. The mechanisms of wear for these tribological surfaces depend on the
mechanical system (part geometry, surface roughness, and loading conditions) and
material properties (hardness and fracture strength), and therefore can undergo abrupt
transitions for relatively small changes in load or sliding conditions [1]. The transition
between adhesive wear and galling is one of the important considerations in materials
selection for hardfacing, as the resulting high friction and seizure can render the part
inoperable.
In industrial applications, the cobalt-based Stellite alloys are the standard choice for
hardfacing; offering low friction, low wear under a wide range of surface conditions and
environments, and unparalleled galling resistance. In nuclear applications however,
cobalt is highly undesirable, as it activates upon neutron irradiation. Wear particles
from hardfacing on valve seats in the primary cooling system activate in the reactor
482
core and are distributed around the system, and are responsible for 90% of abovebackground worker exposure [2]. Eliminating cobalt from valve hardfacing with an
alternative galling-resistant alloy is thus highly desirable to reduce worker exposure
and total downtime costs.
The mechanical conditions of the wear surface are significantly different from the
apparent macroscopic conditions due to surface contact mechanics. Small asperities
on mating interfaces contact with each other and plastically deform, which has the
combined effects of magnifying the total local strain (exceeding of 25%) and the strain
rate (exceeding 1000 s-1, for typical surface conditions). These high strain rates also
lead to adiabatic heating component to the surface deformation. Typical temperature
increase, in excess of 300C, has been predicted by by Jaegar by assuming steady state
conditions. These predictions had been confirmed by experiment using a variety of
techniques, including embedded thermocouples and thermal spectroscopy [1]. These
extreme conditions require alloy design criteria not associated with the ambient
environment: high work hardening, high hot hardness, and high strain-rate
strengthening, as well as temperature stability of these properties. The ideal
combination of properties, however, depends on the wear mechanism, which can itself
be highly dependent on loading conditions and environment.
Galling is defined as a form of severe adhesive wear characterized by large material
excrescences or prow formation accompanied by high rates of material removal and/or
part seizure [3]. As a result of this broad definition, a number of material appearances
and behavior have fallen under the description of galling in literature; other names for
this behavior include scuffing, scoring, burnishing, seizure or cold welding[2, 4].
Standard test methods for determining galling characteristics of a given material pair
involve sliding torsion of a button on block under load, which is followed by optical
examination under a 10x optical loupe and subsequent categorical ranking. The
subjective nature of the ranking and pass/no-pass system of measurement, as well as
the statistical nature of wear itself, makes quantitative correlation and repeatability of
galling resistance measurement difficult [5]. As a result, quantitative models for galling
are still the subject of ongoing research, and the effect of material properties and
behavior in relation to galling are not yet well understood. Increasing hardness, work
hardening, and microstructural heterogeneity usually correlate to a higher Threshold
Galling Stress (TGS) for self-mated materials, but not in all cases, as for nickel alloys, like
Inconel or Monel [3]. Additional material deformation mechanisms, including strain
localization, fracture mode and toughness, and diffusion processes, may be integral to
the mechanism of galling, but have not been systematically investigated.
483
The standard tribological solution for wear resistance has been coatings technology or
surface treatment. Surface treatments including shot peening, carburizing, nitriding,
laser hardening, diffusion coating, ion implantation, vapor deposition (PVD and CVD),
and thermal spray processes, among many other processes, have been used to modify
and improve the properties of surfaces in contact [6]. Often, these layers are harder
and stiffer than the underlying material, as the wear rate in the steady-state (or
Archard) wear regime is inversely proportional to hardness[7]. Simultaneously, these
hard tribolayers are ideally thick enough to prevent subsurface yielding, but thin
enough to allow the underlying more compliant material to absorb elastic energy,
acting as a shock-absorber to limit the depth of the strain field and prevent brittle
fracture or spalling. As a result, hard coatings or surface layers are typically between 5
and 50 m in thickness [8]. Even with improved wear rates, however, this leads to part
lifetimes of 5 to 10 years under high loading conditions, at which point the coating
must be re-applied or the part replaced. Hardfacing overlays can eliminate this need by
forming the hardened layer on the alloy surface during deformation, continuously reforming as material is removed from the surface, in effect, forming a self-healing
tribolayer. The goal of the current investigation is to validate the above mechanisms of
galling in both Stellite and iron-base hard facing alloys that are produced by powder
metallurgy process.
EXPERIMENTAL
Three hardfacing alloys were chosen for investigation, one cobalt-based Stellite 6, and
two stainless steel alloys, NOREM 02 and Tristelle 5183, with compositions listed in
Table I. Each alloy was fabricated using powder metallurgy, and tested for galling
threshold stress according to the ASTM G98 standard for self-mated surfaces. As per
the standard, cylindrical button samples of each alloy were loaded against a plate of
the same alloy and twisted along the cylinder axis for one full rotation, and repeated
using new samples at progressively higher load until galling is observed on the surface.
Threshold galling stress (TGS) was determined for each alloy at two conditions, at room
temperature (25C), and at 350C in a steam environment to simulate coolant system
conditions. The results of the galling tests are reported in Table II.
484
Cr
Ni
Mn
Mo
Co
Si
Fe
Stellite 6
30
1.5
Bal.
1.5
NOREM 02
24.5
4.1
4.2
1.9
0.06
3.3
1.2
0.17
Bal.
Tristelle 5183
19.5
9.97
0.02
5.1
1.98
0.04
Bal.
Other
6.55
Nb,
0.03
Ti
The resulting galling buttons were then used for X-ray diffraction analysis of the
contacting surfaces, with the diffraction plane oriented parallel to the surface. Cu K
radiation ( = 1.54 ) source radiation in a Bragg-Brentano diffractometer configuration
was used. Powder metallurgy samples in the as-made condition (unloaded) were also
characterized for baseline comparison. Subsequently, the galled samples were
prepared for cross sectioning with proper attention to protect the wear surface. A
layer of copper was electroplated on to surface to protect the wear surface, as well as,
to retain wear particles. Cross-sections of the galled button samples were
characterized using optical and electron microscopy.
RESULTS
Table 2: ASTM G98 Threshold Galling Stress, MPa
Test Temperature
Alloy
25C
350C
Stellite 6
> 240
200
NOREM 02
> 240
70
Tristelle 5183 *
> 240
>240
All hardfacing alloys showed acceptable results at room temperature, with the asterisk
in Table 2 indicating that the surface finish of the Tristelle 5183 sample could not be
ground to the specified roughness of the ASTM G98 test, complicating the TGS ranking
for this alloy. At elevated temperature, all alloys showed worse performance, with
Stellite still having acceptable properties.
485
25
350
FCC
HCP
* M23C6
FCC
BCC
* M23C6
* *
* *
FCC
BCC
* M7C3
NbC
Figure 1: Hardfacing alloy ASTM G98 button surface XRD, at RT and 350C. Bragg-Brentano XRD geometry,
Cu K radiation
XRD spectra of room temperature galling test samples (Fig. 1) showed the stainless
steel hardfacing alloys to consist of a primarily austenite (FCC) structure with secondary
carbide phases. The carbide phase in consists of M23C6 carbides, whereas the Tristelle
alloy has M7C3 and NbC carbide phases. Additionally, as can be seen in the figure, the
matrix austenite in all these alloys transforms under mechanical stress to a BCC/BCT
martensite. Similarly, the cobalt-based Stellite 6 also consists of M23C6 carbides in an
austenitic matrix which transforms to an HCP martensite under strain.
486
Figure 2: NOREM 02 ASTM G98 gall surface cross-sections, a) tested at 25C and b) 350C. Angular features
are chromium carbides in an austenite matrix, with BCC lathes. Note Scale Differences
Figure 3: Stellite 6 ASTM G98 gall surface cross-sections, a) tested at 25C and b) 350C. Dark regions are
chromium carbides in an FCC matrix, with martensite lathes
reduced or eliminated in the stainless steels, respectively (Fig. 1). Stellite appears to
actually have an increased FCC to HCP transformation, presumably due to the larger
depth of plasticity from thermal softening at elevated temperature.
DISCUSSION
The increase in wear layer depth for all alloys at high temperature suggests that
softening takes place which leads to lower TGS as reported by the ASTM G98 tests.
Lack of BCC/BCT diffraction peaks in XRD results suggest that this softening is due to
the lack of deformation-induced martensite strengthening. Due to the ex-situ nature of
the analysis, however, whether this is due to deformation-induced martensite
transformation and subsequent thermal transformation back to austenite, or due to
instability of the deformation-induced transformation at surface temperatures is
currently not known. Additionally, calculated X-ray penetration depths for these
materials are 8-10 microns, which is deeper than the room temperature tribolayer but
are approximately the same size as the tribolayer in stainless steel samples tested at
elevated temperature. The absence of significant fcc to bcc/bct transformation
strengthening in the elevated temperature stainless steel samples leads to galling.
The mechanism by which deformation-induced martensite (DIM) provides galling
resistance is not fully understood, primarily because the galling process is not well
characterized. Most previous investigations have concentrated on the effect of DIM on
plastic deformation mechanics, particularly the strain-hardening rate. Several
mechanisms for this strengthening have been proposed, including dislocation
generation, grain size refinement, and composite strengthening effects, all of which
may be of importance and are not mutually exclusive[9]. Regardless, strain hardening
at the surface effectively forms a hard coating that resists further plastic deformation
and is more brittle, making wear particle formation from fracture energetically
preferential to plastic deformation. In effect, a hard tribolayer is formed on the surface
of the bulk metal, with improved wear behavior similar to the effect of tribological
coating technologies.
The rate of strain hardening is strongly affected by the presence of DIM in metastable
stainless steels. At higher temperatures, where the strain-induced transformation
becomes unstable, work hardening in stainless steels is greatly reduced [9]. Asperity
deformation and adhesive wear will then become more severe and wear layer depth
should thus increase, especially as applied stresses approach a significant fraction of
the bulk yield stress where asperity densification and wear mechanism transitions
occur. This regime of high surface densification however is not completely understood,
488
and remains an active area of research[10], especially as it has direct application for
Friction Stir Welding, Ultrasonic Additive Manufacturing, and other solid state joining
processes .
While hard tribolayer formation will affect the wear properties of metal alloys, other
authors have also outlined other possible contributing factors to wear and galling
resistance. Strain localization may play a large role in the process of galling[11].
Multiple phases in the matrix preferentially partition strain to the softer (parent) phase,
preventing large-scale strain localization [12]. Indeed, deformation induced martensite
reduces strain localization by competing with shear band formation in steels during
high-velocity forming operations. Additionally, the irregular surface relief caused by
the martensitic transformation may also reduce surface conformation, and thus
lowering surface adhesion which allows for load transfer between surfaces that drives
galling. What all these proposed mechanisms share, however, is a dependence on
deformation-induced transformations to affect wear and galling properties.
CONCLUSIONS
The existence of strain-induced martensitic phase transformations is correlated with
galling resistance in high-hardness FCC metals that show deformation-induced
martensitic transformations. Galling properties are degraded for elevated
temperature testing, where the deformation-induced transformation is no longer
observed by X-ray diffraction on the wear surface. Although the mechanism by which
this occurs is not yet certain, the highly worked layer on the surface becomes larger at
high temperatures, indicating that higher deformations are experienced at the surface
that are consistent with higher friction and seizing that accompanies galling. These
results suggest that retention of high hardness and work hardening at high
temperatures are necessary for resistance to galling, and that a deformation-induced
martensitic transformation which is stable at higher temperatures is one possible way
to achieve this.
REFERENCES
1.
2.
3.
Bhushan, B., Introduction to Tribology. 2002, New York: John Wiley & Sons.
732.
Galling Wear of Cobalt-Free Hardfacing Alloys. 1994, Electric Power Research
Institute. p. 124.
Bayer, R.G., Mechanical Wear Prediction and Prevention, ed. L.L. Faulkner.
1994, New York: Marcel Dekker, Inc. 657.
489
4.
5.
6.
7.
8.
9.
10.
11.
12.
Markov, D., and Kelly, D., Mechanisms of adhesion-initiated catastrophic wearpure sliding. Wear, 2000. 239: p. 189-210.
Hummel, S.R. and J. Helm, Galling 50, a Stochastic Measure of Galling
Resistance. Journal of Tribology, 2009. 131(3): p. 034502.
Chattopadhyay, R., Surface wear: analysis, treatment and prevention. 2001,
Materials Park, OH: ASM International, .
Rabinowicz, E., Friction and Wear of Materials. 2nd ed. 1995: John Wiley &
Sons.
Holmberg, K., et al., Friction and wear of coated surfaces scales, modelling
and simulation of tribomechanisms. Surface and Coatings Technology, 2007.
202(4-7): p. 1034-1049.
Spencer, K., et al., The strain induced martensite transformation in austenitic
stainless steels: Part 1 Influence of temperature and strain history. Materials
Science and Technology, 2009. 25(1): p. 7-17.
Persson, B.N.J., Contact mechanics for randomly rough surfaces. Surface
Science Reports, 2006. 61(4): p. 201-227.
Korshunov, L.G., V.A. Shabashov, and N.L. Chernenko, Structural
transformations in wear resistance of iron- and cobalt-based amorphous alloys
during abrasive wear. Russian Metallurgy (Metally), 2010. 2010(4): p. 273-280.
Talonen, J., Effect of strain-induced -martensite transformation on
mechanical properties of metastable austenititc stainless steels, in Department
of Mechanical Engineering 2007, Helsinki University of Technology: Helsinki. p.
127.
490
be more complex, and therefore, require much more stringent process controls,
especially with regards to thermal treatments. The ability of the foundry to accurately
predict liquid shrinkage in nickel alloys is also essential for the production of a high
integrity component. This is an important issue as the solidification characteristics of
nickel alloys are different than for conventional steels, and therefore, the value of
accurate material data sets and calibration of predictive tools cannot be under estimated.
This paper will discuss, in summary, the issues when producing these advanced
materials in heavy sections, outline the state of the art advances made in over coming
these problems, and detail future work required to further advance the casting
technology of these materials.
What is the State of the Art in 2013 for Nickel Alloy A-USC Alloy Castings?
The technology to produce large thick wall nickel alloy castings such as steam valves
and casings has been a 15-year progression. Many technical issues have arisen and
advances made to counteract such problems. In 1998 Goodwin produced for the
European AD700 program first cast candidate materials in the form of test blocks. After a
material selection process, subsequent work packages within the program focussed on
medium size prototype components in Alloy 625 and 617. Now in 2013, large full scale
Alloy 625 components have been produced in both European and Pacific Basin A-USC
programs, with section sizes up to 435mm, which has demonstrated manufacturability.
Alloy 617 has also been successfully produced in cast sections up to 300mm.
Fig 1: A Representation of Casting Material Processing/Manufacturing Complexity
Precipitation
Hardened
**Most Difficult
Solid Solution
Strengthened *Difficult
CB2
(P91, P92, E911)
(Cr-Mo; Cr-Mo-V)
492
Alloy 617 is more difficult to produce than Alloy 625 as an air melted casting. However,
Goodwin have successfully manufactured in heavy sections both alloys, making them a
commercial reality with regards to manufacturability for A-USC applications today.
Table 1: Summary of maximum casting sizes that have been produced in the cast from
for A-USC applications by Goodwin
Alloy Type
Alloy 625
Alloy 617 Mod
Alloy 263
Alloy 282
Alloy 740
Alloy 740H
Largest unit
Weight Single Item Produced
Largest
Section Size
Largest
Fabrication Weld
11,000kg
1800kg
900Kg
900kg
800Kg
900kg
435mm
300mm
300mm
300mm
330mm
300mm
55mm
None
None
45mm
None
493
Fig 5: Nozzle Box Castings: Alloy 617 Mod and Alloy 625
Net Weight: 1,800Kg both castings supplied in the proof machined condition:
Section size up to 300mm prior to machining
The castings detailed in Fig 2 & 5 were successfully produced using Goodwins
Induction Heating Feeder System. This system is used to control solidification of the
cooling casting and to mitigate the risk of solidification stress cracking. The system is
important when producing very large section castings, although can be used to produce
smaller items such as the nozzle box castings.
How do we melt and pour nickel alloys in air on a production scale?
Nickel alloys, by their very nature, often contain substantial quantities of aluminium and
titanium and for small scale components are usually produced by vacuum melting. These
elements are added primarily to promote the formation of gamma prime (') for
strengthening purposes and have a high affinity for oxygen which when cast in air readily
oxidise to produce lower than expected recoveries, and oxide film/ inclusion defects.
Air Melting Routes:
The preferred air melting route for these alloys is either electric arc or induction primary
melted, followed by secondary AOD refinement. Utilising AOD refinement produces
optimised residual element control along with very low gas content. The aluminium and
titanium are added as late additions and are protected by an inert atmosphere.
494
For smaller quantities, induction melting can be used; however, special melting
techniques have to be employed to prevent residual gas content pickup, and to protect
aluminium and titanium during melt out. Additionally, silica reversion from furnace linings
previously exposed to steel melting can cause major problems with silicon pickup in
nickel alloys, and pre conditioning often is essential in maintaining low silicon levels
required in the final material grade.
Filling the moulds and oxidation prevention:
Running and gating design is essential for the prevention of turbulence in the molten
metal stream as the metal discharges from the ladle and enters the mould cavity. The
runner and gating system is the key factor that allows the methods engineer to control
the molten metal flow into the mould cavity. If not controlled correctly, then the metal can
be damaged by oxidation both in the running, gating system and in the mould cavity.
Damaged metal (metal that has been heavily oxidized), and the oxide produced drifts
throughout the mould cavity. Due to the density difference between the nickel alloy and
the oxide, most oxide will float and gather at the top surfaces (called the cope) of the
casting and can be subsequently removed by machining or upgrade repair. However, in
thinner wall components where solidification time is relatively quick, the films can be
trapped within the solidifying casting, and can constitute a weak point that is difficult to
detect by conventional NDE techniques.
Fig 6 & 7: Oxide defects seen in an Alloy 617 casting cast without adequate protection
Fig 6
Oxide Defects
Fig 7
Oxide Defects
The higher the amount of aluminium and titanium in the material being poured, then the
greater tendency for oxide formation. The prevention of these oxide defects is only
remedied by improved pouring technologies, with low turbulence running systems and
utilising sealed pouring systems where the mould and pouring stream are protected with
inert gas. For the ' series of alloys, Goodwin use the their Total Emersion System
(TES), where the whole mould and pouring takes place within an enclosed inert gas
environment.
Why do nickel alloys have a longer shrinkage cavity than conventional alloys?
The shrinkage characteristics of nickel alloys are far different than for conventional
steels. Therefore, the prediction of the solidification characteristics of nickel alloys is
more difficult than in steel castings especially when producing heavy section castings,
495
with wall sections over 150mm. Poor prediction will lead to the casting feeders being in
adequate and the shrinkage cavity extending into the casting.
Fig 8
Fig 8: Shows the X-ray of two feeders, one in Alloy 625 and the other in Carbon Steel.
The length of shrinkage (X) is approximately 25% greater in Alloy 625 than seen
conventional carbon and low alloy steels.
The reason for the additional length of the feeder pipe is associated with a combination
of factors:
a) Thermal conductivity of the material.
b) Freezing range of the last metal to solidify (non-equilibrium composition).
d) Liquid shrinkage characteristics.
Table 2: Theoretical Freezing Range of Typical Cast Alloys:
Alloy
Estimated
Equilibrium
Liquid Shrinkage
Freezing range
Carbon Steel
5.5%
65C
Stainless Steel
5.8%
55C
Alloy 625
7.9%
60-70C
P91 9% Cr Steel
5.2%
85C
Super Heat
above Liquidus
70C
100C
150C
90C
Fig 9: Shows the simulated cooling curves of three alloys taken from a point within a
heavy section casting. The red line is the cooling curve for Alloy 625, and it can be seen
that the thermal arrest time (TA) is 51.5% greater than that of carbon steel. This means
that heavy sections take much longer to solidify than conventional materials and then late
feed demand is required from the feeders, meaning the feeder pipe or cavity extended
far beyond what would be expected with conventional alloys.
496
Fig 9
The ability to accurately predict the liquid shrinkage in nickel alloys is an essential part of
successful manufacture. Predictive tools such as solidification simulation software
packages have to be accurately calibrated for nickel alloys, and out of the box in our
view, may not be as accurate as what would be anticipated when dealing with heavy
section components.
Casting Solidification Stress Cracking:
This phenomenon is far more prevalent in nickel alloy castings than conventional steels
partly due to the poor thermal conductivity of nickel alloys. The cracks are a function of
the solidification stresses built up within the casting and feeder arrangement during
solidification and further cooling in the mould. The cracks can often appear under risers
in heavy section component, and can cause in extreme cases, the castings having to be
scrapped.
Fig: 10 Shows an example of
solidification stress cracks seen in a
modified Alloy 617 casting after
knockout.
Fig 10
38mm
497
Ni Alloy
Casting
Thermocouple
498
499
Alloy
Inconel 740
Inconel 740H
Cast 740 MOD
Haynes 282
Alloy 282 MOD
Alloy 263
Alloy 263 MOD
Si
Mn
0.047
0.046
0.21
0.32
0.24
0.30
0.034
0.36
0.03
0.057
0.34
0.37
Ni
BAL
BAL
Cr
Mo
Nb
Co
Al
Ti
Fe
20.62
19.57
0.94
1.22
2.16
1.36
0.66
0.22
10.0
1.40
2.10
0.21
19.6
0.42
2.05
0.07
Inconel 740
Inconel 740H
Alloy 263
Haynes 282
Cast 740 MOD
Alloy 282 MOD
Alloy 263 MOD
UTS
Elongation
R of A
Impacts @ RT (J)
(%)
(%)
600
575
4
10
36/28/46 Avg 37
560
545
5
11.5
22/43/37 Avg 34
496
444
9
No result samples fractured early no results could be obtained
691
410
30
42
128/136/110 Avg 125
751
588
15
18
52/50/50 Avg 51
718
506
29
28
150/184/205 Avg 180
(N/mm2)
Yield
(N/mm2)
500
Fig 15: Shows an impact specimen from the standard cast chemistry for Alloy 740H.
The specimen has broken outside of the notch and is showing brittle fracture
characteristics. This was caused by cracked carbide precipitates at the grain boundaries.
(Results 10Joules) The tensile specimens showed the same problem with fractures
taking place outside of the gauge length.
NEW MODIFIED MATERIAL: Goodwin Variant Chemistry
Fig 16: Broken Tensile and Impact Specimens: Alloy 740 Modified Composition
UTS: 691N/mm
2
Yield: 410 N/mm
Elongation 30%;
Reduction of Area 42%
Room Temp
Impact Results
128/136/110
Joules
The mechanical property of the new modified cast chemistry variant 740H is a little
weaker at room temperature than the original cast specification. However, the first goal is
to make the material castable, and then further optimisation with chemistry and aging
can be considered if lower strength is considered an issue.
Conclusions:
Over the last 15 years, Goodwin has been involved in the advancement in technology of
cast nickel alloys for advanced ultra super critical applications. (A-USC)
Ni Alloys for 700C Application:
Castings in the materials Alloy 625 and Alloy 617 have now been successfully produced
in very heavy section for A-USC applications. Therefore, full-scale castings are now a
commercial reality with regards to manufacturability.
501
502
References
1.
2.
3.
4.
5.
6.
High-Temperature Mechanical Properties and Microstructure of Cast Nibased Superalloys for Steam Turbine Casing Applications P.J.Maziaz,
N.D.Evans, P.D. Jablonski, 2009 -Paper presented at EPRI conference 2010
(Santa Fe)
7.
Steel Castings Handbook Six Edition Dec 1995; Steel Founders Society of
America and ASM International
8.
503
Boiler
Material development
Verification of
material
manufacturability
Turbine
Material development
2009
2010
2011
2012
2013
2014
2015
2016
In and after
2017
100,000
hours
Trial designing
100,000
hours
Trial production
Equipment Equipment designing
planning
Equipment
manufacturing and
installation
Demonstration
Testing and evaluation equipment
As candidate material of 700C class A-USC turbine, the use of Ni-base alloys are necessary for
high temperature component such as rotor forgings and casing castings, because conventionally
developed 9-12% Cr heat resistant steels were lack of creep rupture strength. With respect to
casting material, the commercial alloy 625 and alloy 617 were chosen, and then trial
manufacturing of large valve body castings has been carried out in the European A-USC
programs. [3]- [6]
In the Japanese A-USC project, there were three candidate alloys for Ni-base casting materials,
namely alloy 625, alloy 617 and alloy 740. Alloy 625 has good castability of large component and
many manufacturing result. Alloy 617 has a slightly large amount of Al, Ti, so tensile strength at
room temperature is high rather than alloy 625. In the case of bolting structure castings, high
tensile strength is required at flange position to secure a clamping stress. Moreover, according to
the data of alloy 617 forging, stability of microstructure and ductility during long-term aging is
superior [7]. Finally, alloy 740 has extremely high strength with high Al, Ti, but castability is very
difficult. Due to the above reason, MHI worked on alloy 617 to confirm thick wall step block
castability and material properties, and then carried out the trial production of Nozzle block in
actual size.
DEVELOPMENT OF ALLOY 617 STEP BLOCK
Trial Production
An alloy 617 Step Block was designed with steps at varying thickness of 100, 200 and 300mm.
The maximum thickness resembles the thickness of the flanges of steam turbine casings. The
production weight was approximately 1.7 ton.
The alloy 617 Step Block was casted in air with argon gas shield to reduce oxide inclusion.
After casting, solution heat treatment (1200C/WQ) and aging heat treatment (800C/AC) were
performed.
Subsequently, non-destructive inspections (Visual check, Radiographic test and Penetrant test)
were performed and it was confirmed that no apparent crack was observed at the outer surface and
the inside especially thick position as shown in Fig. 2.
Step side
600mm
300mm
200mm
Straight side
100mm
505
Microstructures of the step block at eight different positions were shown in Fig. 4. Injurious
non-metallic inclusions werent observed. However, there was much course carbide on the grain
boundary at 300mm thickness position. As a result of EPMA analysis, it was estimated that course
carbide was Si and Mo rich carbide. This course carbide was rarely observed at 100mm and
200mm thickness positions.
The results of tensile test at room temperature were shown in Fig. 5. Specimens were sampled
at longitudinal direction. There was a small difference in the 0.2% yield strength and tensile
strength among the evaluating positions. However elongation and reduction of area at 300mm
thickness position were lower than 100mm and 200mm thickness position.
Creep rupture strength and creep rupture ductility of the step block at four different positions
was shown in Fig. 6. Specimens were sampled in longitudinal direction. There was small
difference of creep rupture strength among the evaluating positions. It was estimated that
100,000hrs creep rupture strength at 700C of the step block was higher than the target value of
80MPa for the A-USC turbine casting. Long-term evaluation tests are being continued.
Creep rupture ductility of the step block was more than 50% even at 300mm thickness position,
and the ductility did not change during long term creep test (more than 10,000h test).
24
22
20
300mm
200mm
100mm
18
16
14
Step side
Straight side
Cr
Co
12
10
8
1.0
t300mm
Mo
Surface Center Surface
(straight side)
(step side)
Al
t200mm
0.8
300mm
200mm
100mm
0.6
0.4
0.2
t100mm
Ti
Surface Center
Center Surface
Surface
(straight
side)
(step
side)
Surface
(Straight side)
(Step side)
506
Tensile Strength
600
Elongation
Room Temperature
Room Temperature
500
400
300
200
100
Reduction of area
30
20
10
300mm,
Center
300mm,
Surface
200mm,
Center
200mm,
Surface
100mm,
Surface
300mm,
Center
300mm,
Surface
200mm,
Center
200mm,
Surface
100mm,
Center
100mm,
Center
0
100mm,
Surface
40
700
Straight side
Center
Step side
t100mm
t200mm
t300mm
1000
100
Alloy 617 step block data
80
Reduction of Area ,
Stress , MPa
100
80MPa
t100mm :
t200mm :
t300mm :
t300mm :
Center
Center
Center
Surface
22
40
t100mm Center
20
t200mm Center
t300mm Center
t300mm Surface
10
21
60
23
24
25
26
21
T+273(log tr 20)/1000
22
23
24
25
T+273(log tr 20)/1000
26
700
Alloy 617 Long term exposure
Special Metals data : forging
Present work : casting
70
700 Aged
700 Aged
700 Aged
750 Aged
750 Aged
750 Aged
705 Aged
760 Aged
60
500
Elongation %
600
400
300
700 Aged
700 Aged
700 Aged
750 Aged
750 Aged
750 Aged
705 Aged
760 Aged
200
100
0
10
100
1000
50
40
30
20
10
10000
Aging time h
10
100
1000
Aging time h
t100mm
t200mm
t300mm
700C5,000h
Aging
750C5,000h
Aging
Fig.8: SEM observation photo of the step block after 700-750C5000h aging.
508
10000
Mn
Ni
Cr
Mo
Co
Al
Ti
0.06
0.27
0.33
Bal.
21.17
8.93
11.98
0.89
0.49
0.02
0.17
0.29
Bal.
21.32
8.90
0.16
0.15
0.22
Others
B
0.004
Nb+Ta
3.30
Properties
Cutting position of the nozzle block casting to evaluate material properties was shown in Fig.
10. Macro structure, tensile and creep test pieces were sampled at inlet position and flange
position.
Macro-structure of the both nozzle blocks was shown in Fig. 10. It was confirmed that no
remarkable defect, shrinkage and crack were observed at the inside of both materials. The
columnar grain was observed near the surface of flange position and other position was the
equiaxial grain.
509
Test piece of
inlet position
Test piece of
flange position
Section A-B
Section A-B
Section B-C
Section B-C
510
600
120
Alloy617_Step Block
Alloy617_Step Block
500
100
400
Elongation %
300
200
100
0
80
60
40
20
100
200
300
400
500
600
700
800
100
200
Test Temperature
300
400
500
600
700
800
Test Temperature
1000
Stress , MPa
100
80MPa
Alloy617 Step block (t100mm, Center)
Alloy617 Step block (t200mm, Center)
Alloy617 Step block (t300mm, Center)
Alloy617 Step block (t300mm, Surface)
10
Alloy625 Nozzle
Alloy625 Nozzle
Alloy617 Nozzle
Alloy617 Nozzle
21
22
23
24
T+273(log tr 20)/1000
25
26
511
REFERENCES
[1] Masafumi Fukuda, Eiji Saito, Yoshinori Tanaka, Takeo Takahashi, Shinji Nakamura, Jun
Iwasaki, Shinichi Takano and Sakae Izumi, Proceeding from the Sixth International Conference
on Advances in Materials Technology for Fossil Power Plants (2010), EPRI Report No 1C-01.
[2] Y.Tanaka, R.Magoshi, S.Nishimoto, M.Setoyama, R.Yamamoto, Y.Hirakawa, K.Kawasaki,
Proceedings of ASME Turbo Expo 2012, GT2012-69009.
[3] M.Staubli, R.Hanus, T.Weber, K-H.Mayer, T-U.Kern, Proceedings from the 8th Liege
Conference : Materials for Advanced Power Engineering 2006, Liege, Belgium.
[4] R.Blum, R.W.Vanstone: Proceedings of the Sixth International Charles Parsons Turbine
Conference 2003 (2003), 489.
[5] R.W.Vanstone: AD700 Advanced 700C PF Power Plant A Clean Coal European
Technology October 27th 2005, Milan.
[6] S.Birks, Proceeding from the Sixth International Conference on Advances in Materials
Technology for Fossil Power Plants (2010), EPRI Report No 2D-04.
[7] Special Metals Corporation, Alloy 617 Technical Bulletin, SMC-029 (2005).
[8] Quanyan Wu, Hyonjin Song, Robert W. Swindeman, John P. Shingledecker, and Vijay K.
Vasudevan, Metallurgical and Materials Transactions A, Vol.39A, November (2008), pp.25692585.
512
ABSTRACT
The use of the bainitic class of creep strength enhanced ferritic steels T/P23 and T24 has
increased over the last decade in a wide range of applications including replacement headers,
superheater and reheater tubing and in waterwall tubing. Many issues have been reported in one
or both of these materials including hydrogen induced cracking, reheat cracking and stress
corrosion cracking. To appropriately address these issues, work has been initiated that includes a
literature review, development of a database of phase transformation temperatures, investigation
of tempering behavior, and an analysis of the effect of phase transformation on residual stresses.
Such information will be provided in the context of understanding why these two materials appear
highly susceptible to these cracking mechanisms.
INTRODUCTION
The progression of alloy development for higher strength materials including a new generation of
high strength bainitic and martensitic materials, termed creep strength enhanced ferritic (CSEF)
steels, has occurred in recent years to improve the efficiency and economy of fossil fuel
generation. Fundamentally, these materials are divided into martensitic grades (such as Grades 91,
92, 911 and VM12-SHC) and bainitic grades (such as Grades 23 and 24). The composition ranges
for the two advanced bainitic materials of interest in this paper, T23, P23, T24 and P24,
(generally referred to collectively here as Grades 23 and 24), are given in Table 1. Although it is
convention to compare Grades 23 and 24 to mainstay CrMo alloys like Grades 11, 12 or 22, it
should be mentioned that these two bainitic CSEF steels share more in common with respect to
chemical composition, weldability and mechanical behavior with CrMoV materials. It appears
this fact was not recognized or at least acknowledged earlier in the development of Grades 23 and
24. Thus, the CrMoV legacy would have enlightened industry on the fact that these materials
share similar issues that are now facing industry in specific applications of Grades 23 and 24.
These new bainitic CSEF steels, possessing relatively large increases in strength, have been
widely utilized in recent years to reduce section thicknesses in boiler and HRSG headers, tubing,
waterwall panels and other components. This increase is shown as a function of allowable stress
for CSEF steels T23, T24 and T91, as compared to T22 in Figure 1. A reduced section thickness
for a given component provides an advantage in thermal fatigue behavior, reduced complexity
during erection and field installation in the form of lower lifting capacities, structural steel
requirements and welding considerations, and decreased inspection time. Unfortunately, this
perceived reduction in complexity has not fully come to fruition in many cases as issues have been
identified and will be detailed in this paper.
513
Table 1: Chemical Composition of Bainitic Materials T/P22, T/P23 and T/P24 [1,2]
Element
T/P22
T/P23
T/P24
Carbon, C
0.15
0.04-0.10
0.05-0.10
Manganese, Mn
0.30-0.60
0.10-0.60
0.30-0.70
Silicon, Si
0.25-1.00
0.50
0.15-0.45
Sulfur, S
0.010
0.010
Phosphorous, P
0.030
0.020
1.9-2.6
2.2-2.6
Chromium, Cr
1.9-2.6
Nickel, Ni
Molybdenum, Mo
0.87-1.13
0.05-0.30
0.90-1.10
Tungsten, W
1.45-1.75
Vanadium, V
0.20-0.30
Niobium, Nb
0.02-0.08
Nitrogen, N
0.015
0.012
Boron, B
0.0010-0.0060
0.0015-0.0070
Aluminum, Al
0.030
0.020
Titanium, Ti
0.005-0.060
0.06-0.10
Ti/N
1
0.40
3.5
0.20-0.30
514
Figure 1: Allowable Stress Values for T23 and T24, as compared to T22 and T91 [1-3]
The increased susceptibility to cracking for the bainitic class of CSEF steels may arise, at least in
part, from the fact that these materials accumulate higher levels of residual stress on-cooling from
welding thermal cycles than their martensitic counterparts. Figure 2 shows a comparison of stress
accumulation for representative bainitic (T22), martensitic (T9) and austenitic (316) materials, as
determined using the Satoh Test [8]. Grades 23 and 24, like 2.25Cr-1Mo, predominately consist
of bainite. The reported transformation temperatures for Grades 23 and 24 are shown in Table 2
[9, 10]. The transformation to martensite or bainite compensates for the thermal contraction
strains that accumulate on-cooling and the observed re-accumulation of stress occurs following
the completion of the transformation [8]. Similar shear components (0.22 for bainite and 0.24 for
martensite) suggest that the magnitude of the transformation plasticity on-cooling should be nearly
identical for both phase transformations. Because of this, the major consideration which affects
the accumulation of residual stress on-cooling is the temperature at which the transformation
occurs. The higher transformation temperatures (start and finish) of bainite results in a higher
accumulation of residual stress from thermal cycles (such as in welding) exceeding the A1
temperature. This phenomenon is complicated by the fact that bainitic materials do not require
PWHT in thin sections (regardless of applied extrinsic restraint) and therefore may enter service
with high residual stress resulting from welding.
The accumulation of residual stresses from welding will have an adverse affect on the
susceptibility of bainitic materials to cracking mechanisms that are highly influenced by the
residual stress state. These cracking mechanisms include hydrogen induced cracking, stress
corrosion cracking and reheat cracking. Both Grades 23 and 24 have demonstrated susceptibility
to these cracking mechanisms in the fabrication and erection of modern power plant components.
As with most cracking mechanisms, there are other complicating factors that affect the global
susceptibility of a given material to these mechanisms. However, it is interesting to note that
515
martensitic CSEF materials are generally not susceptible to the previously mentioned cracking
mechanisms. In the case of HIC, susceptibility to cracking likelihood is substantially reduced
because pre and post weld heat treatments are typically required. This is can be attributed to two
important factors: First, regardless of application or component thickness, preheat and PWHT
have always been required for martensitic CSEF steels. Second, as described above, martensitic
materials accumulate less residual stress during welding.
Figure 2: Interpretation of experimental data (determined using Satoh Test) showing how
residual stresses develop on cooling for an austenitic steel (no transformation), a bainitic low
alloy steel (relatively high temperature of transformation) and a martensitic steel (relatively low
temperature of transformation). Adapted from [8].
Table 2: Transformation Temperatures of Grade 23 and 24 Base Material, as Compared to
Grade 91 Base and Weld Metal [9, 10]
Grade
MS
MF
BS
A1
23 (Base)
999
537
615
324
1148
~620
1490
810
24 (Base)
860
460
500
260
1022
~550
1499
815
91 (Base)
702-740
372-393
318-385
159-196
1450-1495
788-813
91 (Weld)
734-784
390-418
392-459
200-237
1418-1474
770-801
N/A
SERVICE EXPERIENCE
A range of cracking phenomena during fabrication, field erection, commissioning and repair have
been observed in Grades 23 and 24 including stress corrosion cracking (SCC), hydrogen induced
cracking (HIC), reheat cracking (RHC) and crater cracking. In addition to these identified issues,
516
Figure 3: Example of Stress Corrosion Cracking (SCC) in a Grade 23 Tube to Tube Butt Weld
Hydrogen Induced Cracking (HIC)
HIC has been observed in various components including tube to tube butt welds in Grade 23 and
tube to fin waterwall welds in Grades 23 and 24. Initially, both Grades 23 and 24 were reported to
be weldable without an applied and controlled preheat temperature. Despite this early guidance, it
is clear from field and fabrication experience that a controlled preheat temperature is required for
both materials to avoid HIC. In Figure 4, HIC in waterwall panels was identified near tube to tube
butt welds where inserts were welded to seal around the field tube to tube butt welds. These
inserts were fairly small and as such, were susceptible to creating high levels of localized residual
517
stresses. In this instance, cracking was isolated primarily to the CGAHZ, propagated in a
transgranular fashion and exhibited some branching consistent with HIC.
Figure 5 shows an example of a RHC in a high crown seal where the seal weld was made using a
B3 (matching to Grade 22) filler metal around T23 material. The cracking morphology included
classic signs of RHC such as cavitation ahead and isolated from the main crack tip as well as
cracking isolated to the CGHAZ and immediately adjacent to the fusion line. Reported fabrication
experience of thick-section girth welds, the development of Grade 23 consumables and the
welding of stub to header welds suggests that fabrication of thick-section components from Grade
23 must be appropriately considered [23-24]. Lastly, although initial data developed using the
BWI controlled strain rate test suggested Grade 24 was immune from RHC, more recent data
obtained from higher carbon Grade 24 has shown this material to be potentially susceptible to
RHC [25]. Thus, RHC must be considered prior to welding both steels in either thick-sections or
in highly restrained situations.
6 was attributed to a retransformed region in the tube caused by the hot straightening that resulted
in stress corrosion cracking. Uncontrolled hot straightening and/or flame heating will reaustenitize the microstructure. The austenite on-cooling will transform to fresh bainite and/or
martensite. Fresh bainite and martensite will have elevated levels of hardness and cause an
accumulation of localized residual stress. This scenario creates a condition in which a base
material may become susceptible to SCC, RHC or brittle fracture.
520
following section. Weld repair will not only result in the formation of fresh bainite and/or
martensite, but successful implementation of weld repairs remains a challenging prospect.
Figure 8: Example of Stress Corrosion Cracking Initiation at a Weld Repair Performed where
Excessive Grinding had occurred [17]
521
Brittle Fracture
Brittle fracture has been reported in tube bends and swages. Specifically, brittle fracture in swages
was recently reported during the weld repair roof tubing near high crown seals, Figure 9. In this
instance, cracking initiated from these welds and propagated across the roof tubing panels through
T23 swages. Some of the T23 swages exhibited charpy impact toughness values below 10 ft-lbs.
Such low values indicate that the swages were improperly manufactured, inappropriately
renormalized and tempered, or some combination of fabrication and heat treatment resulted in
non-optimum microstructures.
Figure 9: Brittle Fracture through T23 Swages and T23 Welds in the Vicinity of High Crown
Seals
Ferritic Dissimilar Metal Welds (DMWs)
The inability to procure Grade 23 plate material manufactured to SA387 (or similar
specifications) has resulted in Grade 23 headers being manufactured with Grade 91 end-caps. The
use of a matching filler material to either Grade 23 or Grade 91 is insignificant; the difference in
chromium between these two materials will result in carbon migration during welding, post weld
heat treatment and service in either filler metal selection. If a filler metal matching to Grade 23 is
used, this carbon migration will result in a carbon-denuded, creep weak region in the deposited
Grade 23 filler metal and adjacent to the fusion line. If a filler metal matching to Grade 91 is used,
the creep weak region will be located in the Grade 23 base material and adjacent to the fusion
line. When specifying Grade 23 or Grade 24 components, and especially in the instance of
replacement parts, it is critical to ensure that ferritic DMWs are minimized and that the design of
unavoidable ferritic DMWs is given proper engineering consideration with respect to filler
material and post-weld heat treatment.
ON-GOING AND FUTURE WORK
EPRI is working closely with its membership to collaborate with industry and recognized world
experts in Grades 23 and 24 to address the fundamental issues which challenge successful use of
these materials. Regardless of material, there are three key issues that material users must address
when these two materials are utilized in their plant components: procurement of acceptable
material through more tightly controlled specifications, life assessment of components and weld
522
repair of existing components. To address these key, underlining issues, a multitude of studies are
being conducted through EPRI, Lehigh University, Oak Ridge National Laboratories and RIF to
examine fundamental material behavior, susceptibility to stress corrosion cracking in a variety of
environmental conditions, accumulation of residual stresses in weldments, tempering behavior of
weldments and creep crack growth behavior.
CONCLUSIONS
In general, few issues have been reported in Grades 23 and 24 when welded in loose tubing
applications such as in reheaters and/or superheaters. More extensive issues in tubing applications
have been reported where highly restrained welds have been made in waterwall panels, roof
tubing, high crown seals, and erection lugs. Additional problems in welding these materials have
been documented in stub to header welds and girth welds in thick-section components. Challenges
with common fabrication techniques like flame heating, flame straightening, grinding and weld
repair have been detailed. The issues in these two materials demonstrate the need to better
understand these complex steels from a fundamental standpoint to address needs surrounding
material specification, life assessment and weld repair.
REFERENCES
[1] Code Case 2199. ASME Boiler and Pressure Vessel Code. Approved June 28th, 2012.
[2] Code Case 2540. ASME Boiler and Pressure Vessel Code. Approved June 28th, 2012.
[3] ASM E Boiler & Pressure Vessel Code, ASME B&PV II, Part D: Properties (Table 1A),
2010. New York: ASME.
[4] Masuyama, F. and Mitsuura, H. High Strength Heat-Resistant Low Alloy Steels. Patent
5,084,238. January 28, 1992.
[5] Iseda, A., Sawaragi, Y., Masuyama, F., and Yokoyama, T. Low-Alloy Heat-Resistant Steel
Having Improved Creep Strength and Toughness. Patent 5,211,909. May 18, 1993.
[6] Iseda, A., Sawaragi, Y., Masuyama, F., and Yokoyama, T. Low-Chromium Ferritic HeatResistant Steel with Improved Toughness and Creep Strength. Patent 5,407,635. April 18,
1995.
[7] Komai, N., Masuyama, F., Yokoyama, T., Hirata, H., Kawano, K., and Kan, T. High
Strength, Low Alloy, Heat Resistant Steel. Patent 6,379,611. April 30, 2002.
[8] H. K. D. H. Bhadeshia. Effect of Materials and Processing: Material Factors, Handbook of
Residual Stress and Deformation of Steel, 2002. ASM International, Ohio, USA.
[9] Alexandrov, B. A. and Lippold, J. C. Phase Transformation Behavior in CSEF Steel
Welds. Proceedings of the Sixth International Conference on Advances in Materials
Technology, August 31 September 3, 2010, Santa Fe, NM.
[10] Arndt., J., Bendick, W., Deshayes, F., Haarmann, K., Kottmann, G., and Valliant, J. C. The
T23/T24 Book, 1998. Vallourec and Mannesmann Tubes.
[11] Private Correspondence with Eric DuPont, 7/7/2011.
[12] Private Correspondence with Frank Moore, 10/31/2012.
[13] T24 Experience: An Hitachi Power Europe Perspective. Modern Power Systems, October
2012. pp. 38-40.
[14] Nowack, R., Gotte, C. and Heckmann, S. Quality Management at RWE Using T24 Boiler
Material as an Example. VGB PowerTech Publication, November 2011.
[15] Ullrich, C., Heckmann, S., Tillmann, W., Bodmer, T., Neumann, F., Rademacher, H., and
Gierschner, G. T24 Investigation Program and Derived Measures. 38th MPA-Seminar,
October 1-2, 2012, Stuggart, Germany.
[16] Ludenbach, G. Stress Corrosion Cracking of T24. VGB PowerTech e.V., Mannheim, 2012.
523
[17] Fishburn, J. D., Henry, J. F., and Zhou, G. Service Experience with T23 Material.
Proceedings of the 9Cr Materials Fabrication and Joining Technologies, July 10-11, 2001,
Myrtle Beach, SC.
[18] Dhooge, A. and Vekeman, J. New Generation 21/4Cr Steels T/P 23 and T/P 24 Weldability
and High Temperature Properties. Welding in the World (49); 2005, pp. 75-93.
[19] DuPont, J. N., Marder, A. R., Nawrocki, J. G., Puskar, J. D., and Robino, C. V. The
Mechanism of Stress-Relief Cracking in a Ferritic Alloy Steel. Welding Journal 82 (2), pp.
25-s 35-s.
[20] DuPont, J. N., Marder, A. R., Nawrocki, J. G., and Robino, C. V. The Stress Relief
Cracking Susceptibility of a New Ferritic Steel Part 1: Single-Pass Heat Affected Zone
Simulations. Welding Journal 79 (12), pp. 355-s 362-s.
[21] Barbaro, F. J., Gunn, K. W., and Edwards, R. H. Stress Relief Cracking in CrMoV Steels.
Metals Forum 5 (2), 1982, pp. 119-129.
[22] King, B. L. Intergranular Embrittlement in CrMoV Steels: An Assessment of the Effects of
Residual Impurity Elements on High Temperature Ductility and Crack Growth.
Philosophical Transactions of the Royal Society A 295 (1413), 1980, pp. 235-251.
[23] Park, K., Kim, S., Chang J., Lee, C. Post-weld heat Treatment Cracking Susceptibility of
T23 Weld Metals for Fossil Fuel Applications. Materials and Design 34 (2012), pp. 699706.
[24] R. Fuchs, B. Hahn, and H. Heuser, Affect of inexpert working of heat resistant steels to the
serviceability, in Proceedings of the Sixth International Conference on Welding and Repair
Technology for Power Plants, Sandestin, FL, 2004.
[25] Huysmans, S., De Bruycker, E., and Vanderlinden, F. Complementary Research Related to
SCC Sensitivity of T24 Boiler Tubing. Presented at the VGB Materials and Quality
Assurance Workshop, June 19, 2013, Essen, Germany.
[26] J. Adamiec and A. Hernas. Experiences in Welding of Membrane Panels Made of
7CrMoVTiB 10-10 (T24) Steel. Proceedings of the Trends in the Development of
Machinery of Associated Technology, Mediterranean Cruise, 2010. pp. 5760.
[27] L. Mraz, P. Brziak, P. Bernasovsky, P. Zifcak, J. Kotora, D. Krajci, M. Mraz, J. Pecha, J.
Robinson, and D. Tanner, Experience with Utility Properties of T24 Steel. Proceedings of
the 9th International Trends in Welding Conference 2012, June 4-8, 2012, Chicago, IL. pp.
1003-1010.
[28] Heuser, H. Welding of Ferritic Steel T/P24. Presented at V&M Powergen Technical
Seminar, Orlando, FL, December 13, 2012.
524
ABSTRACT
Xcel Energys Comanche Unit 3 experienced widespread cracking of T23
membrane wall tubes within the evaporator section, initially occurring during the
boiler construction phase, primarily at shop and field tube butt welds. The
majority of the tube cracking was attributed to stress-corrosion cracking (SCC),
and a lesser number of fabricational-related hydrogen induced cracking (HIC),
weld solidification cracking, and brittle cracking within tube swage sections were
also experienced. Hundreds of tubes were replaced prior to Unit commissioning,
due to both actual tube leaks and those replaced due to weldment cracking and
other identified weld defects during radiographic testing. Elevated stress levels
and material susceptibility (i.e. hardness in the as-welded condition) were
considered the critical factors in the tube cracking.
1.0 INTRODUCTION
Xcel Energys Comanche Unit 3 is a 750 MW supercritical boiler with design
conditions of: Main Steam- 257 Bar (3732 psig) at 568oC (1055oF) and Hot Reheat50 Bar (728 psig) at 596oC (1105oF). The Unit construction was completed in early
2010 and commercial operation began June, 2010. The Units evaporator is of
straight tube membrane construction, utilizing conventional ASME SA213, Grade
T12, 29 mm (1-1/8 in) OD by 5.6 mm (0.220 in) minimum wall thickness-mwt rifled
and smooth bore tube, and creep strength enhanced ferritic Grade T23, 31.8 mm
(1-1/4 in) OD by 5.6 mm (0.220 in) mwt, smooth bore tube materials; the T12 to T23
transition was made at Elevation 5022 utilizing a 203 mm (8 in) long T23 swage
section, including shop butt welds (Fig. 1). During the boiler construction phase,
cracking issues were experienced within the Grade T23 tubes, primarily at the
T23/T23 tube butt welds.
Failures occurred within both shop welds and field repair welds of the T23
material, originally performed without post weld heat treatment (PWHT). The
original weld procedure for the T23/T23 butt welds utilized 100% gas tungsten arc
welding-GTAW, with matching ER90S-G filler metal (chemistry similar to Grade 23
o
o
base metal), a minimum preheat of 150 C (300 F), with no backing gas; for the
T23/T12 butt welds the filler metal was intermediate ER90S-B2 (Grade 22) material.
As a result of the tube failures, hundreds of tubes were replaced prior to
commissioning due to either actual tube leaks, or replacement of tubes identified
as exhibiting weldment cracking or other rejectable indications after extensive
nondestructive examination (NDE) was performed.
525
Figure 1: Diagram (top) showing the relative location of the T23/T23 shop weld
failures and photomacrograph (bottom) showing the T23/T23 tube butt welds, the
T23 swage, and the T12 to T23 butt welds at Elevation 5022.
Cracking has occurred within the following: 1) original T23/T23 and T23/T12 shop
welds at the T23 swages at Elevation 5022; 2) repair welds at elevation 5022
made as a result of internal weld metal drop-through flow restrictions- identified
during cold circulation tests; 3) boiler penetration welds- at sootblower ports,
erection lugs, and other penetrations/attachments; 4) within tube swage sections
above the actual swages, due to base metal embrittlement; 5) wall tubes adjacent
to the roofline at Elevation 5065; and 6) within tubes that had been inadvertently
overheated, with no weldment present. It is noted that all of the failures to date
have resulted in very small tube leaks, with none resulting in forced Unit outages.
A historical timeline of the commissioning phase, original leaks, and repairs, is
shown in Table 1. During the initial hydrotest (March, 2009), T23 leaks were
identified within three tubes at the membrane (fin), and one field butt weld, at
various elevations; all leaks were repaired by grinding out the cracks and rewelding (no PWHT).
526
Date
March 8-10,
2009
April 3-8, 2009
April 22, 2009
April 25, 2009
May 4-8, 2009
May 9-20, 2009
May 21-June 16,
2009
June 17, 2009
July 2- Aug 17,
2009
Sep 2-3, 2009
Sep 30, 2009
Comments
(4) T23 tube leaks-3
membrane, 1 butt weld.
Widespread RT and MT
inspections performed.
527
ID
Figure 3: Photomicrograph showing a cross section through tube No. 293, with
the main crack surface at left arrow and ID initiated secondary cracking along the
opposite side of the butt weld at right (circled). Magnification: 10X, 2% nital etch.
528
While the main, circumferential crack was attributed to HIC from the membrane
weld, the secondary cracking associated with the butt weld, near the ID surface,
was branched, oxidized, and transgranular, appearing more typical of SCC. At the
tip of the ID initiated cracking, these features were even more evident, as shown
in Fig. 4. Copper was present within some of these cracks, possibly from
auxiliary steam supply from Units 1 or 2, however that was only observed within a
few of the samples examined and not considered a contributing factor in the
failures.
Figure 4: Photomicrograph showing the crack tip within the butt weld metal, from
secondary, ID initiated cracking within tube No. 293, with the oxidized,
transgranular branching typical of SCC. Magnification: 200X, 2% nital etch.
An example of the more classic HIC appearance is shown in Fig. 5, in the form of
underbead cracking beneath the membrane weld (again E9018-B3 filler) fusion
line of another tube, No. N34 (original shop weld). Extending from the underbead
cracking, secondary intergranular cracking was also prevalent. Microhardness
testing (all Vickers Hardness testing performed at 300 gram load) revealed a
membrane weld HAZ hardness ranging from 272 to 325HV (301HV average).
The base material composition of tube No. 293 was verified as meeting Grade T23
requirements, and microstructurally the base metal exhibited a typical tempered
bainite/martensite structure, and that of the weld metal and heat affected zone
(HAZ) was un-tempered bainite/martensite, considered typical for the material in
the as-welded condition. Microhardness testing revealed a maximum butt weld
hardness value of 316HV and maximum HAZ value of 373HV, while the base metal
hardness was on the order of 213HV. Chemical analysis revealed this repair butt
weld had been made with improper Grade 22 (i.e. ER 90S-B3) filler metal.
Another of the initial tubes submitted in October, 2009, tube No. 250, was an
original shop butt weld that developed a pinhole leak, as shown in Fig. 6.
Figure 6: Photomacrograph showing tube No. 250, and evident is the leak at the
original tube shop butt weld.
The ID surface of tube No. 250 is shown in Fig. 7, and axial cracking was identified
within a start/stop region of the weld root (circled, but the tight crack was not
obvious in Fig. 7); start/stop regions can represent high thermal gradients during
welding, can exhibit stress concentrating mechanical notches, and were often the
location of the axial weld cracks observed during the evaluation. There was no
evidence of pitting damage associated with the crack, but a moderate high
temperature oxide was present throughout the weld root pass, attributed to
oxidation during original welding.
530
Figure 7: Photomacrograph showing the ID surface of tube No. 250, and the
location of axial cracking within the butt weld is shown (circled).
The crack was clearly ID initiated, and at the tip, significant crack branching was
identified, as shown in Fig. 8; this oxidized, transgranular cracking was again
considered typical of SCC.
531
Figure 9: Photomacrograph showing a cross section through tube No. 359, where
the transformed region is shown in white (circled); membrane weld is at arrow.
Very minor ID pitting was present, and branched, oxidized, transgranular cracking
again typical of SCC was observed near the ID surface, as shown in Fig. 10.
Along the ID surface, both high temperature oxide and a thin, loose scale were
also evident. Microhardness testing was performed, with resulting values up to
319HV within the hardened base metal, compared with unaffected base metal
values below 200HV.
Energy dispersive x-ray spectroscopy (EDS) of dry polished metallographic
samples was performed, and the presence of chloride and trace levels of sodium
were identified. EDS of other samples revealed only minor sodium levels within
one other tube section, with most showing no trace of contaminants.
that the areas of excessive grain size were very limited, and the actual crack did
not obviously extend through one of these regions. Charpy V-notch impact
toughness of the embrittled section was only 12 Joules (9 ft-lbs) at 10oC (50oF),
compared with 122 Joules (90 ft-lbs) a few inches away and 163 Joules (120 ft-lbs)
for non-swage section base material.
Figure 11: Photomacrograph showing the brittle cracking within tube No. N344,
above the actual swage section; location of crack initiation is identified (arrow).
After the leaks were discovered during construction, extensive NDE was
performed beginning in November, 2009 throughout elevation 5022 to identify
possible additional cracks within the T23 welds. It was initially unknown whether
conventional NDE methods of radiographic testing (RT) and ultrasonic testing
(UT) would be able to accurately identify these weldment cracks. It was agreed,
however that RT would be performed under the direction of Mike Kerr (Xcel
Energy NDE Specialist), to possibly identify defective welds. The field experience
at Comanche Unit 3 showed that RT was sensitive enough to identify weld
cracking; additionally, magnetic particle testing (MT) was also performed after
swage embrittlement issues were identified; both RT and MT were also performed
at the roof Elevation 5065 and other suspect weld locations.
Following the RT and MT inspections and subsequent field repairs, PWHT was
performed at all Grade T23 welds (shop and repair) within the evaporator section,
which resulted in significant distortion at Elevation 5022, in excess of 63.5 mm
(2.5). After PWHT, RT and MT were again performed, resulting in additional tube
replacement. As a result of the NDE of all 1344 T23/T23 butt welds at Elevation
5022, over 250 tubes were removed due to cracking and other quality concerns.
Additionally, more than 65 tubes (of 856 tubes) were removed at the roof Elevation
5065, and nearly 200 tubes were replaced at varied penetration locations (i.e. test
ports, sootblower openings, etc).
3.0 EXAMINATION-IN SERVICE TUBES
After the Unit was in service for approximately 18 months with only minor T23
issues (3 leaks at Elevation 5065 in April, 2010), re-inspection was performed
during the Fall, 2011 overhaul, including RT and MT at the swage Elevation 5022;
inspection resulted in rejection of an additional 77 welds. In addition, 16 tube butt
weld cracks and 12 membrane weld cracks were identified at Elevation 5065.
Examination of multiple tube samples was performed, including one in which an
533
ID surface.
Figure 12: Photomacrograph showing the oxidized crack surface of tube No. 208,
removed after 18 months of Unit operation.
Microstructural examination verified the different levels of crack surface
oxidation, as shown in Fig. 13, with very thin oxide (arrow) and lack of secondary
cracking near the OD surface (left), as compared with the thick oxide and
secondary cracking appearing typical of SCC near the ID surface (right). The
minor secondary crack observed above the arrow, near the OD surface, was
within the region of laboratory-induced fracture, broken open to expose the crack
surface.
534
As a result of the high number of additional cracked tubes identified by RT, the
observation of crack extension beyond the initiation stage within tube No. 208, the
level of distortion after PWHT, and concerns related to the unknown number of
embrittled swage sections remaining in service, replacement of all 1344 swage
sections at Elevation 5022 was performed during the Fall, 2011 overhaul.
Replacement included installing additional T12 panels, which extended the
evaporator T12 tube length by approximately 61cm (2ft), eliminating the swage,
welding and performing PWHT of the T23/T12 upper welds, and then welding the
lower T12/T12 tube joints without PWHT. This panel replacement eliminated the
majority of the previous wall distortion.
4.0 SUMMARY AND CONCLUSIONS
The majority of Grade T23 evaporator tube cracking was attributed to SCC, with a
lesser number due to welding-related HIC and solidification cracking, and few
tube failures from brittle cracking above the swages. SCC can occur either by
anodic form (i.e. active path corrosion due to specific contaminants such as
caustic), or by cathodic form, associated with hydrogen generated during minor
corrosion reactions for instance; both forms of SCC in high strength steels can
occur in even relatively benign water environments. As reported in the literature,
HIC and SCC in theory are very similar, in that Stress-corrosion cracking in
some material/ environment combinations can be a form of hydrogen-induced
subcritical crack growth [1]. Further, Hydrogen-induced crack growth as the
dominant stress-corrosion mechanism has been suggested for ferritic steels,
[2]. Similar cracking of Grade T23 material has, however been reproduced during
laboratory exposure to caustic solutions [3].
While it was considered possible that cracking could have initiated sometime
during the initial boiler hydro or the chemical clean (sodium hydroxide solution
pre-cleaning and ammoniated citric acid cleaning solution), an operating pressure
hydro test was performed after chemical cleaning and no tube leaks were
reported. Subsequently, there was a very high number of steam blows (>500)
performed during commissioning, and while water chemistry data for the Unit 3
commissioning period was limited, an exact concentrating mechanism of
potential contaminants during these steam blows and other commissioning
phases was not entirely clear, and minimal internal tube deposits were observed.
The source of potential contaminants included auxiliary steam from Comanche
Units 1 and 2 during the Unit 3 commissioning, however that makeup accounted
for a very small percentage of the Unit 3 water supply. Additionally, after 18
months of operation, examination verified similar ID initiated SCC within one tube
that had been replaced during the massive repair efforts, and had not been
exposed to chemical cleaning, the steam blows, and only limited hydro tests.
Since the 18 month service inspection and tube replacements performed during
the Fall of 2011, there were two tube leaks at the upper roofline Elevation 5065
that occurred in January, 2012 due to SCC. However, since then there have not
been any reported tube leaks. Examination has also not shown further cracking
within any of these upper level tubes, while examination at the lower weld
elevation has not been performed since the swage replacement was completed
during the 2011 overhaul.
535
Research by VGB, EON, and RWE in Europe [4] has shown the critical effect of
dissolved oxygen in promoting anodic-type SCC in high quality water for similar
Grade T24 material, especially in the temperature range of 200oC (400oF) to 250oC
(480oF). They reported two Units were completed and operating two years without
cracking of their T24 tubes, after precautions were taken to address weld quality,
stress relieving heat treatments were implemented, and dissolved oxygen levels
were closely controlled during commissioning/startup periods. It is noted that
oxygen levels were not controlled during the Comanche Unit 3 commissioning
phase; during the steam blow procedures and other commissioning periods, the
T23 evaporator tubes were exposed to feedwater within the above temperature
range during which the similar T24 material has exhibited susceptibility to SCC.
The primary contributing factor in the failures was considered to be elevated
stress levels associated with the membrane wall tube configuration; for
consideration, testing and service experience have shown no issues with nonPWHTd Unit 3 Grade T23 reheat panel tubes operating at lower pressure and
under lower residual stress compared with the membrane wall evaporator tubes.
The other major factor was considered to be material susceptibility; the T23 tubes
in the as-welded condition commonly exhibited hardness values in excess of
325HV for weldments and HAZ hardness in excess of 350 HV, to a maximum of
392HV. These conditions led to elevated susceptibility to SCC of the T23 tubes in
even benign feedwater environments during the Unit commissioning stages,
when oxygen levels were not controlled. To address these concerns, Xcel Energy
o
o
has incorporated elevated preheat- minimum of 200 C (400 F), mandatory PWHT
o
o
at 700-730 C (1300-1350 F) for a minimum of 30 minutes, and internal gas purging
to minimize root weld pass oxidation during welding. Laboratory testing has
shown that this level of PWHT has reduced weldment and HAZ hardness levels
from 70 to more than 100 points HV, greatly reducing susceptibility to cracking.
Additionally, oxygen levels and general water chemistry parameters during
Comanche Unit 3 operation are controlled per EPRI guidelines.
5.0 ACKNOWLEDGMENTS
Acknowledgment is given to the following Xcel Energy colleagues: Rick Hellner;
Randy Owens for laboratory work; Mike Kerr for his RT evaluations; Andy Howell
for information and discussion related to the Unit chemistry; and Robert Howard
for his outage support and related information.
6.0 REFERENCES
[1] Jones, R. H., Stress-Corrosion Cracking, Corrosion: Fundamentals, Testing,
and Protection, Vol 13A, ASM Handbook, (ASM International, 2003), pp. 346366.
[2] Ibid.
[3] Henry, J. F., Zhou, G., and Fishburn, J. D. Service Experience With T23
Material, EPRI Conference, July 10-11, 2001.
[4] Ullrich, C., Heckmann, S., Neumann, F., Bodmer, T., Gierschner, G., Tillman,
W., and Georg, H., T24 Failure Mechanism, Measures and Investigation
Program, EPRI International Conference on Advances in Condition and
Remaining Life Assessment for Fossil Power Plants- Coal, Gas and HRSG,
October 17-19, 2012.
536
537
parameter
value
2955t/h
27.9MPa
605C
superheated steam
7
8
9
2443t/h
367C
B-MCR
Reheat steam outlet temperature
603C
B-MCR
Economizer inlet temperature
293C
No.
Boiler
number
1-14
15-17
18-20
21-27
hopper
Upper spiral
Lower vertical
tube
tube
15CrMoG
T23
38.17
38.16.78
15CrMoG
T23
12Cr1MoVG
38.16.8
T23
Upper
vertical
tube
T23
44.57.3
T23
44.57.3
38.17
38.17.2
15CrMoG
12Cr1MoVG
12Cr1MoVG
38.17
38.17.2
388
15CrMoG
12Cr1MoVG
12Cr1MoVG
12Cr1MoVG
38.17
38.17.2
388
44.58
538
38.16.8
T23
44.57.3
ASME SA-213-T23
0.04-0.10
0.50
0.10-0.60
0.08
0.26
0.08-0.15
0.12
T23 tube
38.16.8
GB5310-2008
12Cr1MoVG
12Cr1MoVG tube
38.17.2
Si
Mn
Cr
Mo
0.03
0.010
1.90-2.60
0.05-0.30
0.41
0.009
0.003
2.19
0.14
0.17-0.37
0.40-0.70
0.025
0.010
0.90-1.20
0.25-0.35
0.24
0.55
0.009
0.003
1.03
0.29
Chemical elements
Nb
ASME SA-213-T23
0.20-0.30
1.45-1.75
0.02-0.08
0.24
1.58
0.042
0.15-0.30
0.20
T23 tube
38.16.8
GB5310-2008
12Cr1MoVG
12Cr1MoVG tube
38.17.2
0.0005-
Al tol
0.03
0.030
0.0034
0.004
0.011
0.0060
Tensile strength
Yield strength
Elongation
performance
RmMPa
Rp0.2MPa
(%)
ASME SA-213-T23
510
400
20
T23 tube38.16.8
555
460
25.
470-640
255
21
500
360
27
GB5310-2008
12Cr1MoVG
12Cr1MoVG
38.17.2
Microstructure
Tempered
bainite
Pearlite and
ferrite
800
Critical stress
/MPa
/MPa
700
600
500
400
300
200
100
550
600
650
700
750
800
The SR
sensitive
temperature
T/T/
Figure 1: Curve of the critical initial stress and the corresponding eliminate temperature of T23
steel
3.4 The welded joints hardness of T23 tube
540
The welded joints hardness of T23 tube is shown in Fig.2. The result shows that the hardness of
T23 welded joints without PWHT is too high. It can be reduced to HV250 after PWHT.
Figure 3: The impact toughness of T23 tubes butt welds at different post weld heat treatments
(Sample size: 51055mm)
3.6 Aging properties of the welded joints of T23 tube at high temperature
The aging properties of the welded joints of T23 tube at high temperature is shown in Fig.4. The
result shows that after aging at high temperature, the impact toughness of T23 welded joints
541
without PWHT is poor. However the impact toughness is much better if the welded joints are
performed with PWHT.
sample size: 51055mm, PWHT for welded joints in boiler manufacturer is performed, and
PWHT for that at site isnt performed
3.7 Welded joints performance of T23/T23 tube and 12Cr1MoVG/12Cr1MoVG tube
The welded joints performance of T23/T23 tube and 12Cr1MoVG/12Cr1MoVG tube is shown in
table 5.
Table 5: Welded joints performance of T23/T23 tube and 12Cr1MoVG/12Cr1MoVG tube
No.
Welding type
Heat treatment
Tensile strength
Fracture
RmMPa
location
T23-T23
PWHT
610600
Raw material
T23-T23
No PWHT
620630
Raw material
12Cr1MoVG-
540580
Raw material
550550
Raw material
12Cr1MoVG
4
12Cr1MoVG12Cr1MoVG
PWHT
No PWHT
3.8 Rupture strength of T23 and 12Cr1MoVG tubes and their welded joints at elevated
temperature
The rupture strength of T23 and 12Cr1MoVG tubes can meet the standards. The rupture
strength of T23/T23 and 12Cr1MoVG/12Cr1MoVG welded joints can also meet the
standards no matter if the post weld heat treatment is performed or not.
542
4.
THE LEAKS AND SOLUTIONS OF T23 WATER WALL IN 1000MW USC TOWER
BOILER
4.1 Welding residual stress of T23 and 12Cr1MoVG water wall
The welding residual stress test results of T23 tube manufactured in factory are listed in table 6.
The welding residual stress of T23 water wall are tested at site in two power plants, and the test
results are shown in table 7. The result shows that the welding residual stress has reached about
70% of the yield strength of T23 tube, which is higher than the allowable stress of T23 tube at
working temperature. Post weld heat treatment can reduce the residual stress to 20%.
Table 6: Welding residual stress of T23 water wall manufactured in factory
No.
1
2
3
4
Test site
Butt welds of multi-pass
forgings and tubes
Butt welds of multi-pass
forgings and tubes
Fillet welds of multi-pass
forgings and seal plate
Fillet welds of multi-pass
forgings and seal plate
Heat treatment
Residual stress
MPa
No PWHT
300320
PWHT
3060
No PWHT
180260
PWHT
2040
No PWHT
250300
PWHT
3060
543
Table 7: Welding residual stress of T23 water wall installed at power plant
No.
Power plant
Test site
Transverse
Longitudinal
residual stress
residual stress
MPa
MPa
59mfillet weld of
1
84202
298387
2828
118214
109-129
234352
1
49mfillet weld of
2
28395574
3
7487104135
148184-83
-121
4575102102
117131157181
190245207-371
Table 8 shows the welding residual stress of the water wall of 12Cr1MoVG tubes manufactured
in factory. The test result shows that the welding residual stress has reached about 70% of the
yield strength of 12Cr1MoVG tube, higher than the allowable stress of 12Cr1MoVG tube at
working temperature. Post weld heat treatment can reduce the residual stress to 20%.
544
No.
1
2
Test site
Butt welds of multi-pass
forgings and tubes
Butt welds of multi-pass
forgings and tubes
Heat treatment
Transverse
Longitudinal
statement after
residual stress
residual stress
welding
MPa
MPa
No PWHT
242301357304
PWHT
35406043
Fillet welds of
3
No PWHT
seal plate
Fillet welds of
4
285358292245
267362276
293253342
278
40436541
252364263
297398351
289
40684230
36623438
355940
416533
No PWHT
232224
295304
PWHT
3235
4033
PWHT
seal plate
Fillet welds of spiral
5
545
Table 9: Leakage sites, analysis and countermeasures of T23 water wall in 1000MW USC Tower
Boiler
No.
leakage site
at corner position
installed at power plant
welding
countermeasure
Fillet welds of
analysis
Crack
Figure5: Cracks of T23/T23 welded joints installed at site and without PWHT
546
547
6. CONCLUSIONS
(1) T23 steel is sensitive to welding cold cracking, so preheating is necessary.
(2) The welding reheat cracking susceptibility of T23 steel is serious.
(3) PWHT of T23 water wall is necessary due to its high welding residual stress.
(4) The impact toughness of T23 welded joints without PWHT is poor.
(5) The power plant which has been put into operation has to carry out RT inspection on T23
water wall without PWHT. In order to make sure the unit is under safe operation, the welded
joints with cracks should be replaced with 400mm T23 tubes. GTAW should be chosen for
welding and electric heating plate can be used for PWHT.
(6) The weldability of 12Cr1MoVG tube is better than T23 tube. The water wall of 1000MW
USC tower boiler manufactured with 12Cr1MoVG tube is under safe operation without
leakages.
548
ABSTRACT
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550
min.
max.
min.
max.
C
0.05
0.15
0.05
0.10
Mn
0.30
0.60
0.30
0.70
P
0.025
0.020
S
0.025
0.010
Si
0.50
0.15
0.45
Cr
1.90
2.60
2.20
2.60
Mo
0.87
1.13
0.90
1.10
Ti
Al
n.s.
n.s.
n.s.
n.s.
n.s.
0.06
0.10
0.20
0.30
0.0015
0.0070
0.012
0.020
The major difference between the T22 and the new steel grade T24 is the low carbon content
(0.07-0.09%) to keep good workability in terms of the welding behavior, a fixed Cr content in
combination with a fixed min content of Si for the oxidation behavior and a Mo content around
1% for solid solution hardening. Furthermore the addition of V and Ti as precipitation
hardening/strenthening elements in combination with B lead to increased creep properties when
compared to T22.
Additional requirements like no PWH treatment and a good forming behavior, i.e. cold bending,
were clearly a demand from industry and incooperated in the concepts when developing T24 and
fixing the chemical composition.
temperature in C
A special remark shall be here made on the C content. Carbon plays a key role in the alloy
concept as it directly influences the hardenability of the grade during the usual normalizing and
tempering treatment, and therefore is linked to an increase of tensile properties and is, in
combination with the heat treatment conditions, the key for the martensite bainite formation.
seconds
minutes
time
Figure 2: CCT diagram, carbon content of 0.07 wt %
551
hours
temperature in C
seconds
time
minutes
hours
The three CCT-diagrams (figures 2-4) illustrate that there are only minor differences regarding the
cooling behavior for different C-levels.Nevertheless an adequate carbon content for this type of
CrMoV steel grade is essential. From a tube manufacturers point of view a sufficiently high C
content is important in order to secure a certain level of strength, in the same manner as the
limitation to an upper C content to secure sufficient ductility. As a result of the chemical
composition in combination with a proper heat treatment, which is normalizing at around 9801020C plus tempering at about 730-760C, the following mechanical porperties can be obtained:
Table 2: mechanical properties of T24
acc. to.
Rp 0.2
[MPa]
Rm
[MPa]
EN 10216-2
400
565-840
17
415 (min)
585 (min)
20
Code Case
2540
CVN long.
[J]
@ RT
CVN trans.
[J]
@ RT
Hardness
[HV10]
15
40
27
175 260
---
--
--
---
A
[%] min
Long
trans
Tensile tests
Hot tensile tests
Impact tests
Different mechanical tests under aged conditions
long term creep testing
steam side oxidation tests
In order to prove the weldability of this new grade the Bhler Welding Group started the
development of filler metals by the end of the 1990s.
T24 has been introduced to a national German R&D program AVIF A 77 (1994 1999;
Qualification of materials for application in boilers with increased temperatures [1]) in which
the grade has been tested and certified as QUALIFIED for the use in USC power plants. In
2001 the AVIF Report A 129 Verification of long term properties of welds of modern steels for
boilers up to 620C [2] was published in which different similar and dissimilar welding
combinations were qualified using T24 filler metals.
553
Furthermore the T24 base metal has been integrated successfully in the following test loops:
Asnaesvaerket: unit 4, 2x5 tubes with 38.0 x 6.3 mm, within vaporizer (460C, 228 bar)
in June 1995
Weisweiler: unit G, 2x12 tubes with 26.5 x 5.0 mm, within vaporizer (510C, 160 bar) in
May 1996
Thierbach: unit D, 10 tubes with 26.9 x 5.0 mm, within vaporizer (480C, 148 bar) in
1996
Neckar: unit 2, 2x8 tubes with 38.0 x 6.3 mm, within vaporizer (440C, 280 bar) in
September 1997
554
Table 3: Chemical composition all weld metal for matching filler metal to T/P24 (Bhler P24-IG;
Bhler P24-UP / Union I P24; Thermanit P24)
Base metal
T/P24
Filler metal
(GTA, SMA, SA)
min.
max.
C
0.05
0.10
Si
0.15
0.45
Mn
0.30
0.70
Cr
2.20
2.60
Mo
0.90
1.10
Ni
-----
V
0.20
0.30
0.08
0.25
0.50
2.40
1.0
0.1
0.25
Ti
0.05
0.10
Nb
-----
0.04
B
0.0015
0.0070
0.001
In general a post weld heat treatment (PWHT) is not required if the hardness values are below
350 HV10 [3]. According the continuous cooling temperature (CCT)-diagram of the base metal
the hardness level is between 310 and 360 HV10 [4].
The CCT-diagram of the all weld metal shows a hardness level between 340 and 360 HV10 for
cooling rates which reflect normal cooling rates after welding. Figure 5 shows also that the weld
metal has a bainitic/martensitic structure. The martensitic part can be in the range of 15 to 30 % in
the weld metal.
1000 C 10 min.
Ac1, Ac3 nach ASTM
t 8/5 1-30.000 s
555
Table 4: Mechanical properties of all weld metal for matching filler metal to T/P24 (Bhler P24IG; Bhler FOX P24; Union I P24, Thermanit P24)
Weld process
Base metal
requirements
GTAW
2.4 mm
SMAW
4.0 mm
Temp.
C
PWHT
C/h
YS
MPa
TS
MPa
Elongation
%
CVN
J
Hardness
HV10
730 760
>450
585 840
>17
>27
<250
+20
+20
--740/2
664
595
803
699
19.2
20.3
>250
>250
<350
<230
+20
740/2
577
689
18.1
150
<250
In the as welded condition the CVN-values for GTA-weldments are high and will not significant
increase after a PWHT. The reason is that during welding the multiple layer joint of the all weld
metal specimen every layer has an annealing effect. Nearly the same situation is given on welding
tubes of wall thickness higher than 10 mm. Here always high CVN-values can be realised.
However on welding tubes with only 6 mm wall thickness low CVN-values (<15 J) will be
determined if the welder is not trained. Multiple layer technique is also required for welding thin
tubes. The welding parameter has to be optimised that an annealing effect is given to the layer
beneath [5]. Table 5 shows test results of a girth weld. The unannealed weld metal is much
stronger than the base metal; the location of fracture is in the base metal.
Table 5: Mechanical properties of
T24 (Tube dimension: 38 x 6.3 mm)
Weld process
Base metal
GTAW
PWHT
C/h
730 760
---
TS
MPa
585 840
639
girth
welds
Facture
location
--BM
at
T/P24
CVN (ISO-V)
J
>27
60 76
(transverse
specimen)
Hardness
HV10
175 260
<336
Bending
angle
--180 o.k.
The GTA weldments are sensitive for end crater cracking in the root. This can be avoided by
training of the welders and optimising the welding parameter. The down slope amperage after
closing the root should be reduced not more than 50 % in order to avoid too fast cooling in the
critical area of the root.
Purging gas is highly recommended on welding the root and the hot pass (Figure 6).
556
Figure 7: SMA-welding of T24 without PWHT; different C-content of all weld metal
(Bhler Fox P24-WW / Thermanit P24 WW)
557
558
Figure 9: Bending test of SA-welded T24 tube to T24 fins; no PWHT; no cracks;
mandrel-: 50 mm
T24 is a high strength material, in particular the weldments without PWHT. Therefore much more
attention has to be paid to preheating and Interpass-temperature and the welding parameter than
lower alloyed steels.
SUMMARY
The strict observation of stringent welding parameters is essential, especially for welded joints in
T24 tube without PWHT (Figure 10). Preliminary tests under operating conditions are
indispensable here if hardness values <350 HV10 in the weld metal are to be ensured and cracks
in the welded joints avoided.
Figure 10: Quality of weldments depends on optimization of welding parameter in relation to the
complexity of the base metals
559
All the welding fillers presented here have been approved by VdTV and are thus suitable for use
in pressure-bearing components. The developments were conducted in close cooperation with
V & M DEUTSCHLAND GmbH.
The principal influence factors on the above mentioned failure mechanisms are summarized in
Figure 11. Besides the alloy composition and the environment, the mechanical loading conditions,
which can vary from stress to compression, depending on the location within a water wall panel,
proved to influence the SCC susceptibility.
Figure 11: Influence factors on environmental assisted cracking (EAC) and stress corrosion
cracking (SCC)
560
All those factors take effect during the different steps of an erection of a USC boiler. During the
chemical cleaning operation a decomposition of the inhibitor in corrosive acid with H2S creation
occurred. As H2S is a strong hydrogen induced stress corrosion cracking promoter this
phenomenon was identified as cause for the cracking, especially as no cracks were found in the
absence of hydrogen sulfide. The cracking occurred at pH values of lower than 7 at a temperature
below 90C. As a derived measure the parts where T24 material is used were excluded from the
pickling process [8].
The second mechanism was approached with three more or less different tests. First investigations
were performed using three point bending samples in autoclaves containing high temperature
water. A buffer of air or nitrogen was added. The focus here was on the oxygen content of the
medium. Different loading conditions were applied, samples with and without plastic deformation
tested at temperatures between 150 and 250C and oxygen levels up to 1000 ppb. Three tests at
each conditions were performed and evaluated if cracking occurred or not. At oxygen levels
below 150 ppb no cracks were found. Summarized it can be stated that the critical temperature
range was identified to be between 170 and 220 C and oxygen levels >150 ppb resulted in
cracking of more than one sample. Additionally the stress and strain conditions proved to have a
strong influence on the cracking behavior. The presence of both, elastic stress and plastic strain
were necessary to make the specimen fail [8].
A more detailed analysis appeared to be necessary in order to determine the critical values for
stress, strain rates, oxygen levels, materials properties and temperature. As slow strain rate tests
(SSRT) were already applied in the nuclear power plant research to determine the cracking
susceptibility under certain environmental conditions [9] such an equipment was chosen for the
tests. As many variations of parameters in small ranges is desired to determine the limits of
critical conditions, quite long test series were started and many investigations are still ongoing at
different institutions and laboratories. The major features of the used SSRT are:
-
561
Figure 13 shows typical stress vs. time curves as a result of a SSRT. As reference samples were
investigated at room temperature and in air before different media with various parameters - as
mentioned above were used for the tests. It is evident that the media conditions have a strong
influence on the failure of samples.
562
stress
Inert
time
Environment 1
Environment 2
inert 2
Figure 13: Stress vs. Time curves as a result of SSRTs comparison of different medium
conditions
Several investigations have already been performed as there was urgent need to derive measures
for the start up procedure of new-built power plant projects. As many uncertainties are still
existing a whole bunch of actions were applied such as an overall heat treatment of the boiler and
all connected areas, a ramp up procedures where the above mentioned temperature range is
quickly passed, a limitation of oxygen content in the boiler water (measured after injection).
Additionally the construction companies state that a high quality in welding performance and
surveillance is necessary to avoid any difficulties during operation of the power plant [10].
Several others are not explicitly mentioned here.
6. CONCLUSIONS
Taking all aforementioned circumstances into consideration the following conclusions can be
drawn even though a huge number of Tests and projects are still ongoing:
-
The development targets like, long term, short term properties and fabricability have
been achieved
Welding consumables have been developed, qualified and used in a wide range
A serious number of lectures and trainings for the proper use of this grades have been
given both by V&M and Bhler Welding
The grade T24 has been used, tested and qualified in national and International test loops
or R&D projects
As reported before when using this grade welding operations have to performed and
monitored carefully
the boiler water chemistry is of high importance, especially during the start up process
investigations are ongoing in order to clearly identify the root causes of the difficulties
and to avoid it in the future
failures during operation (experience for > 10.000 h) have not been reported
563
7. LITERATURE
[1] Husemann, R. U. (1999): Qualifizierung von Werkstoffen zum Einsatz in
Dampferzeugeranlagen mit erhhten Temperaturen; AVIF A 77.
[2] Theofel, H., Schemmel, J., Klenk, A. (2002): Nachweis der Langzeiteigenschaften von
Schweiverbindungen moderner Sthle fr den Einsatz in Dampferzeugern im Bereich bis
620C; Stuttgart: MPA Stuttgart.
[3] 12952-6, E. (kein Datum): Water-tube boilers abd auxiliary installations - Part 6: Inspection
during constructions; documentation and marking of pressure parts of the boiler.
[4] Vallourec & Mannesmann. (1998): The T23/T24 book. New grades for water walls and super
heaters.
[5] Fuchs, R., Hahn, B., Heuser, H. (2005): Affect of inexpert working of heat resistant steels to
the serviceability; EPRI Conference, Sandestin.
[6] Seydel, R. (2012): Verarbeitung des hochwarmfesten bainitischen Werkstoffes
7CrMoVTiB10-10 (T24); DVS-Berichte Band 283.
[7] Nowack, R., Gtte, C., Heckmann, S. (November 2011): Quality management at RWE. VGB
Powertech.
[8] Husemann, R., Devrient, B., Kilian, R. (2012): Cracking Mechanism in High-Temperature
Water; 38. VDI-Jahrestagung Schadensanalyse, Wrzburg.
[9] Speidel, M. O., Magdowski, R. M. (1988): Stress corrosion cracking of nuclear reactor
pressure vessel and piping steels. International journal of pressure vessels and piping, S. 119142.
[10] Helmrich, A., Maile, K., Kopp, A., Bse, J., Klenk, A., Metzger, K. (2012): Material Science
based investigations on T24 weldments; VDI Wissensforum, Mannheim.
564
ABSTRACT
T24 tube material (7CrMoVTiB10-10), with its combination of high creep strength and
potential to be welded without using preheat, is regarded as a candidate waterwall
material for Ultra Supercritical (USC) boilers. However, its reputed sensitivity to hydrogen
and potential for secondary hardening may have adverse impacts on construction of
waterwall panels. Doosan Babcock Ltd have investigated the response of welds made in
T24 tubing to secondary hardening via changing hardness in a series of ageing heat
treatment trials. Also, the response of the material to hydrogen infusion has been
investigated
INTRODUCTION
T24 tube material (7CrMoVTiB10-10), with its combination of high creep strength and
potential to be welded without using preheat, is regarded as a candidate waterwall
material for Ultra Supercritical (USC) boilers. However, its reputed sensitivity to hydrogen
and potential for secondary hardening may have adverse impacts on construction of
waterwall panels. The Vallourec and Mannesmann (V&M) T24 Handbook [1] published
data on trial T24 panel welds made with T22 strip, which gave a peak HAZ hardness of
~350 HV in the as-welded condition. It is generally accepted that hardness levels above
this threshold would increase the potential for failure mechanisms such as hydrogen
embrittlement and Stress Corrosion Cracking (SCC) to occur. Secondary hardening
could be an additional factor to consider in the potential selection of T24 as a boiler
material, which could further increase hardness. Mohlya and Foldyna [2] presented
hardness results showing that secondary hardening can occur in T24 but the results
appeared to be based on relatively few data points. Thus a need was perceived for a
more substantial hardness testing programme to confirm if secondary hardening does
occur.
Cracking has been observed in T24 components in units in several locations across
Germany. Neumann [3] has investigated the cause of some of these failures and
identified hydrogen induced stress corrosion cracking (H-SCC) as the failure mechanism.
Cracking was noted at inspections during waterwall panel manufacturing and panel
assembly [3]. For successful fabrication of T24 waterwall panels a wide range of
manufacturing controls was suggested, including heat treatment of membrane welds
throughout panel manufacturing, heating the boiler to 450-500C to effect a partial stress
relief and optimisation of water chemistry and boiler operating procedures [3]. The cited
H-SCC failure mechanism suggests that more work is needed to better understand the
potential response of T24 to hydrogen.
565
This paper presents work on several trial welds made by Doosan Babcock Ltd. in T24
tubing and experiments performed on those welds to confirm the potential response of
T24 to hydrogen embrittlement and secondary hardening. For hydrogen embrittlement, a
group of tensile specimens were infused with hydrogen then tested at slow strain rates to
determine the material response. To investigate secondary hardening, sections of welds
were subjected to ageing heat treatments over a range of times and temperatures to
determine the extent (if any) of secondary hardening.
TEST PROGRAMME
Several TIG butt welds were made in T24 tubing with matching filler to examine the
potential of secondary hardening. Macros of the weldments were taken from the butt
welds and subjected to a series of ageing heat treatments at 550C, 575C and 600C
for various times ranging from 1 hr to ~3000 hrs. After each heat treatment, hardness
traverses were performed on the root and cap regions of the weldment, covering weld,
HAZ and parent material, then compared with the initial hardness of the weldments prior
to ageing. The trial panel welds made in T24 were compared with the butt welds through
comparison of hardness measurements. Results from the 575C and 600C data were
converted to equivalent times at 550C using a T(20+log t) type Holloman Jaffe
relationship. An example of the hardness cap and root traverses and a trial panel weld
are shown below in Figure 1.
Figure 1: Image of weld macro specimen hardness indents and trial panel weld.
The response of the T24 welds to hydrogen was investigated by machining parent and
cross weld tensile test specimens then infusing them with hydrogen for up to 3 weeks by
electrolytic means. The specimens were subjected to slow strain rate tensile testing at a
-7 -1
typical strain rate of 3 x 10 s to observe if the hydrogen infusion had any effects. If
delays occurred between infusion and tensile testing then the specimens were stored in
liquid nitrogen to retain any infused hydrogen. A photograph of the hydrogen infusion
apparatus is shown in Figure 2.
566
Figure 3: Cap coarse grained HAZ hardness variations with temperature and time.
The 575 and 600C data, normalized to equivalent times at 550C, were in broad
agreement with the actual 550C data, though the degree of scatter appears to be
greater at long ageing times. Changes in hardness over time were also noted in the root
HAZ and weld metal (Figs. 4 and 5).
567
568
Hydrogen Infusion
The average measured amount of diffusible hydrogen present in the tensile specimens
was 1.5ml/100g, below the maximum permissible limit of 3ml/100g specified for low
hydrogen welding practice e.g. Scale E in EN 1011-2 [4].
Slow Strain Rate Tensile Testing
The difference in test behavior between the hydrogen infused parent and cross weld
tensile specimens became apparent in the failure of the cross weld specimens at
relatively low strains. Figure 8 shows these failures for the hydrogen infused specimens
labeled W2, W3 and W4 (below)
Figure 8: Slow strain rate tensile test results for parent and cross weld specimens.
Failure events for H2 infused specimens W2, W3 and W4.
Post Test Analysis
Examination of the fracture faces of the failed cross weld specimens revealed
intergranular fracture at the failure initiation region (Fig. 9)
Figure 9::Scanning Electron Microscope images of the failure initiation region and
intergranular fracture present.
570
DISCUSSION
The hardness test results confirmed that secondary hardening does occur in T24 welds
in both weld metal and HAZ. The increases in hardness varied between regions of the
weldment but, from an initial peak HAZ hardness of 388 HV, an effect of the hardness
increases was to effectively prolong the length of time that the cap weld metal and HAZ
hardness could be >350 HV and therefore considered susceptible to failure mechanisms
such as hydrogen embrittlement and SCC. The lengths of time that the cap region was
>350 HV suggests that welded T24 components could be considered susceptible to
hydrogen embrittlement / SCC when in service at 550C for up to 2000 hrs before
sufficient softening occurs to reduce the hardness below the 350C threshold. In using
the Holloman-Jaffe parameter to deduce long term hardness from shorter term heat
treatments at higher temperatures, caution should be exercised as there will be a degree
of associated scatter in hardness testing of weldments that could affect interpretation of
any trends present.
The results from the slow strain rate tensile testing confirm that T24 welds are
susceptible to hydrogen embrittlement and at levels within typical limits specified for low
hydrogen welding practice. An additional factor in the susceptibility of T24 welds to
hydrogen embrittlement is the buildup of residual stresses that can occur during panel
manufacture for various reasons e.g. in-plane and out of plane bending.
A consequence of this is that in order to further reduce the risk of hydrogen related
cracking in T24 welds, additional heating during panel manufacture and a partial stress
relief heat treatment of the type suggested by Neumann [3] may be necessary. The need
for pre heating and preheat boost during panel manufacture would also require capital
investment in additional heating equipment, raising manufacturing costs associated with
T24 components. For butt welds, a post weld / partial stress relief heat treatment may
also be necessary to reduce HAZ hardness in particular to 350 HV or lower in order to
reduce the susceptibility of the weld to hydrogen related cracking, again adding to the
associated fabrication costs.
CONCLUSIONS
T24 welds were made and subjected to various forms of testing to confirm the potential
occurrence of secondary hardening and hydrogen embrittlement. The following points
were concluded from the work.
1. Secondary hardening does occur in T24 welds in both weld metal and HAZ.
2. Hardness peaks / increases were noted to various levels generally after 10 hrs
and 100 hrs ageing times.
3. Secondary hardening effectively prolonged the time that the cap region of the
weld was >350 HV (up to 2000 hrs at 550C) and potentially susceptible to SCC
and hydrogen embrittlement.
4. Hydrogen infused T24 welds, with an average hydrogen content of 1.5ml/100g,
were demonstrated to be susceptible to hydrogen embrittlement by slow strain
rate tensile testing.
5. Additional heating during T24 component manufacture may be required to
further reduce the risk of hydrogen related cracking.
571
REFERENCES
[1] Arndt, J. et al, The T23/T24 Book, New Grades for Waterwalls and Superheaters,
Vallourec and Mannesmann Tubes (1998), pp. 37-41.
[2] Mohyla, P. and Foldyna, V., Improvement of reliability and creep resistance in
advanced low alloy steels, J Mat Sci and Eng A, 510-511, (2009), pp. 234-237.
nd
[3] Neumann, F., Status of Alloy 24 Current Problems with this Material, Proc VDI 2
Int. Conf Alloys in Power Plant Technology, Berlin, June 2012.
[4] EN 1011-2 + A1, Recommendations for Welding of Metallic Materials Pt. 2: Arc
Welding of Ferritic Steels, (2001).
572
ABSTRACT
The objective of this study was to determine the typical range of weld metal cooling rates and
phase transformations during multipass gas-tungsten arc (GTA) welding of Grade 23 (SA-213
T23) tubing, and to correlate these to the microstructure and hardness in the weld metal and heat
affected zone (HAZ). The effect of microstructure and hardness on the potential susceptibility to
cracking was evaluated.
Multipass GTA girth welds in Grade 23 tubes with outside diameter of 2 in. and wall thicknesses
of 0.185 in. and 0.331 in. were produced using Grade 23 filler wire and welding heat input
between 18.5 and 38 kJ/in. The weld metal cooling histories were acquired by plunging type C
thermocouples in the weld pool. The weld metal phase transformations were determined with the
technique for single sensor differential thermal analysis (SS DTA). The microstructure in the aswelded and re-heated weld passes was characterized using light optical microscopy and hardness
mapping. Microstructures with hardness between 416 and 350 HV0.1 were found in the thick wall
welds, which indicated potential susceptibility to hydrogen induced cracking (HIC) caused by
hydrogen absorption during welding and to stress corrosion cracking (SSC) during acid cleaning
and service.
INTRODUCTION
Grade T23 steel has been developed as a material for application in ultra-super critical boilers
(USCB) that can be used without preheat and post weld heat treatment (PWHT) in thin wall
structures [1]. Compared to the conventional Grade 22 steel, T23 has reduced carbon content for
improved weldability, and is micro-alloyed with vanadium, niobium, and nitrogen for
precipitation strengthening with fine MX type carbides and carbonitrides. Part of molybdenum is
replaced with tungsten for solid solution strengthening.
Grade T23 steel is delivered in the normalized and tempered condition with a microstructure of
tempered bainite and martensite [2]. Hardness values lower than 350 HV0.1 are required in Europe
for power generation applications on Grade T23 steels welds [3].
Recently, cracking in welds of water wall panels made of Grade T24 steel has been reported in a
number of newly constructed power plants in Europe. Cracking in T23 steel welds with similar
573
application has been experienced in the US. The nature of cracking in these instances has not been
completely clarified yet. It has been suggested that the observed HAZ and weld metal cracking is
a form of SCC [4, 5]. Absorption of hydrogen due to formation of H2S during acid cleaning,
embrittlement caused by high oxygen content in the boiler water, and the Schikorr reaction that
generates hydrogen on the tube ID surface during service are currently investigated as possible
failure mechanisms [4, 5]. These failure mechanisms operate at the presence of susceptible
microstructure (indicated by high hardness), high residual stress, and exposure to an aqueous /
corrosion environment. It has also been shown that both T23 and T24 welds are potentially
susceptible to hydrogen induced cracking when welded without proper preheating [6, 7].
The objective of this study was to determine the typical ranges of weld metal cooling rates and
phase transformations during multipass GTA welding of Grade 23 tubing and to correlate these to
the weld metal and HAZ microstructure and hardness.
MATERIALS AND PROCEDURES
Multipass gird welds in Grade T23 steel tubes with outside diameter of 2 in. and wall thicknesses
of 0.185 in. and 0.331 in. were investigated in this study. The welds were produced in 5G position
using manual GTA welding process with ER90S-G (Grade 23) welding rods and shielding gas
pure Argon (99.998% Ar). The weld root was also protected with argon. No preheat and PWHT
were applied to these welds. The base metal and filler wire chemical compositions are given in
Table 1.
Table 1. Chemical composition of the tested materials, wt%
Material
C
Si Mn P
S
Cr Ni
ER90S-G
0.06 0.38 0.57 0.005 0.001 2.10 0.05
T23 0.185 in. wall 0.051 0.25 0.47 <0.01 <0.001 2.01 0.11
T23 0.331 in. wall 0.06 0.27 0.45 0.016 0.002 2.48 <0.1
Mo Al Nb
V
W Cu
0.02 - 0.215 1.72 0.04
0.17 <0.10 0.024 0.24 1.55 0.17 <0.10 0.035 0.29 1.46 -
The thin and thick wall tubes were welded in two and three passes correspondingly. Welds with
root pass only, with root and second pass, and with root, second and third pass were produced in
the thick wall tubes, so that the as-welded (non-reheated) microstructure of each pass can be
subjected to metallurgical characterization. Similarly, welds with root pass only and with root and
second pass were made in the thin wall tubes. The weld joint geometries are shown in Figure 1
and the welding parameters are listed in Table 2. The ID side in the root area of the thick wall
tubes was counter-bored as shown in Figure 1b.
37.5
37.5
0.185
2nd Pass
Root
3rd Pass
2.00
OD
0.331
2nd
Pass
Root
3/32
3/32
a)
b)
Figure 1. Weld joint geometries for the thin wall (a) and thick wall (b) tubes
574
2.00
OD
The weld thermal histories were recorded using type C (W W/Re) thermocouples and a fast
sampling rate data acquisition system. Thermocouples were manually plunged in the weld pool as
it reached the top of the tube, as shown in Figure 2. Weld cooling histories were recorded for each
pass of the thin and thick wall welds and processed by the technique for Single Sensor Differential
thermal Analysis (SS DTA) to determine the phase transformation temperatures.
Table 2. Welding Parameters
Tube
Travel
Heat Input (kJ/in)
Current (A)
Weld
Voltage
t8/5
Wall
Speed
Pass Min Max Average
(V)
(s)
Thickness
(in/min) Min Average Max
KR1*
4.7
KR2 100 120
110
10 - 11
5.1
KR3
96 104
100
10 - 11
2.42
23.8
26.1
28.4 2.5
0.331 in. KS1 162 162
162
10 - 11
3.43
28.4
29.8
31.2 15.1
KS2 132 145
138.5
10 - 11
2.32
34.1
37.7
41.2 12.3
KT1
12.6
KT2
15.6
NR1
12.0
0.185 in. NR2
75
85
80
10 - 11
2.73
16.5
18.5
20.6 13.2
NS3 133 133
133
10 - 11
2.44
32.7
34.4
36.0 23.9
* R root pass, S second pass, T third pass
variation between 26 and 38 kJ/in. In the thin wall tube welds t8/5 varied between 12 and 23.9 s as the
heat input varied between 18.5 and 34 kJ/in. A direct correlation between the cooling time t8/5 and
the heat input can not be established due to the inconsistent travel speed in manual arc welding.
However, an almost linear dependence of the cooling time t8/5 on the average welding current has
been found as demonstrated in Figure 4 and Table 2. The tube wall thickness had a strong effect on
t8/5. For the same welding current range, the t8/5 in the thick wall welds was 12 to 15 s shorter than
in the thin wall welds (Figure 4).
Data
1200
Temperature (deg.C)
600
400
200
20
40
60
80
120
100
Time(secs)
140
160
180
200
Figure 4. Effect of the welding current and tube wall thickness on the cooling time t8/5
Weld Metal Phase Transformations
Variations in the welding travel speed during manual welding resulted in inconsistent cooling histories
in weld passes KR3, KS1, and KT1, Figure 3. These cooling rate variations did not allow to identify
the thermal effects related to phase transformations using the SS DTA technique. The phase
transformations determined in the rest of weld metal cooling curves are summarized Table 3.
Typical examples of weld metal phase transformations determined with SS DTA are presented in
Figure 5. Two phase transformations occurring in approximately the same temperature ranges were
determined in all cooling curves within the t8/5 range between 4.7 and 15.6 s. The first one occurred
in the typical temperature range of lower bainite (LB) and had a large thermal effect of heat release,
Figure 5a. A second phase transformation with a thermal effect of much lower magnitude was
576
determined in the temperature range of martensite (M), Figure 5b. A phase transformation that started
in the temperature range of upper bainite (UB) was found in the cooling curve with t8/5 of 23.8 s. It
was followed by two subsequent transformations that occurred in the temperature ranges of lower
bainite and martensite, Table 3. Advanced metallurgical characterization of the resulting weld metal
microstructure is required in order to positively identify the microstructural constituents that formed
during these phase transformations.
The temperature ranges of phase transformations in as-solidified weld metal determined in this study
were in very good correlation with the CCT diagram of T23 steel reported in [2]. It should be noted
that the CCT diagram was developed for T23 steel base metal austenitized at 1060 oC for 15 min. In
the range of cooling rates relevant to our study (t8/5 between 3 and 30 s) this CCT diagram did not
differentiate the temperature ranges of bainitic and martensitic transformation.
Table 3. Phase transformation temperatures in Grade T23 weld metal determined using SS DTA
Weld
Layer
Test
t8/5, s
Thick
Wall
Root
Second
Third
KR1
KS-2
KT2
NR1
NR2
NS1
4.7
12.3
15.6
12
13
23.8
Root
Thin
Wall
Second
R1
800
LBS
LBF
MS
MF
623
567
579
572
559
541
565
491
463
494
483
501
514
454
432
457
458
467
459
389
364
354
394
395
383
R1
750
480
460
650
Temperature
Temperature
700
600
550
X: -0.02079
Y: 566.6
440
X: -1.178
Y: 454.1
420
400
X: 1.255
Y: 398.1
380
500
360
450
400
500
X: -1.092
Y: 327.6
340
0
10
a)
15
20
25
T (deg.C)
30
35
40
45
-2
-1
T (deg.C)
consistently exceeded 350 HV0.1, Figure 6. A continuous path with hardness above 375 HV0.1 and
individual spots exceeding 400 HV0.1 was found in the CG-HAZ. Similar hardness distribution
was found in the center of the weld metal.
Root Pass in 0.331 in. Tube Wall Weld
500
416 HV
400 - 410 HV
Distance, m
375 - 400 HV
350-375 HV
-500
325 - 350 HV
300 - 325 HV
275 - 300 HV
-1000
250 - 275 HV
200 - 250 HV
175 - 200 HV
-1500
150 - 175 HV
140 HV
-2000
-2500
-5000
-4000
-3000
-2000
-1000
Distance, m
Figure 6. Hardness map in the root pass of the 0.331 in. (thick) wall weld
399 HV
375 - 399 HV
350 - 374 HV
325 - 349 HV
5000
300 - 324 HV
275 - 299 HV
250 - 274 HV
200 - 249 HV
Distance, m
4000
175 - 199 HV
150 - 174 HV
116 HV
96.5 HV
3000
2000
1000
0
4000
5000
6000
7000
8000
9000
10000
11000
Distance, m
Figure 7. Hardness map in the root and second passes of the 0.331 in. (thick) wall weld.
The higher heat input (average welding current of 138 to 162 A) and t8/5 values (12 to 15 s) of
the second pass slightly softened the weld metal and HAZ of the root pass, Figures 7 and 9.
However, an area with hardness between 375 and 400 HV0.1 was still present in the CG-HAZ.
Due to the higher heat input, the overall weld metal and CG-HAZ hardness of the non-reheated
second pass were lower than in the as deposited root, Figures 6 and 7.
The third pass was also deposited with a higher heat input (t8/5 12 to 15 s) and softened the weld
metal of the previous passes to a predominant range of 325 to 350 H0.1, Figures 8 and 9. The
continuous hard path (375 to 410 HV0.1) that extended throughout the entire CG-HAZ was not
affected by the deposition of the third pass.
578
9000
Root, Second, and Third Passes in 0.331 in. Tube Wall Weld
8000
416 HV
7000
400 - 415 HV
375 - 399 HV
350 - 374 HV
Distance, m
6000
325 - 349 HV
300 - 324 HV
275 - 299 HV
5000
250 - 274 HV
200 - 249 HV
175 - 199 HV
4000
150 - 174 HV
151 HV
3000
2000
1000
0
2500
3500
4500
5500
6500
7500
8500
9500
Distance, m
Figure 8. Hardness map in the root, second and third passes of the 0.331 in. (thick) wall weld.
Figure 9. Hardness ranges in the weld metal and CG-HAZ of thick wall welds.
In summary, the CG-HAZ and weld metal hardness in the thick wall welds varied correspondingly
between 416 and 350 HV0.1 and between 405 and 300 HV0.1. The lower hardness in the weld
metal can be attributed to its lower content of chromium, molybdenum, and vanadium (lower
hardenability) and possible loss of carbon during welding. The variation in t8/5 between 2.5 and
15.6 s (average heat input between 26 and 38 kJ/in) did not significantly affect the hardness and
microstructure in the non-reheated first, second, and third passes. The deposition of the second
and third passes did not appreciably soften the CGHAZ, but reduced the overall hardness of the
weld metal.
The non-reheated root pass had extremely high hardness at the ID surface areas of CG-HAZ and
weld metal, Figures 6 and 10. The deposition of the second and third passes had a slight softening
effect: the minimum hardness in both areas was reduced by 25 HV0.1 to 350 HV0.1 and 325 HV0.1
correspondingly, Figures 6, 7, 8, and 10. However, peak hardness values of up to 375 HV0.1 in the
weld metal and up to 400 HV0.1 in the CG-HAZ were still present at the ID surface of root pass
after deposition of the second and third passes, Figure 10.
579
Figure 10. Hardness ranges at the ID surface of weld metal and CG-HAZ in thick wall welds.
The hardness maps developed in the root pass and root and second passes of the thin wall welds
are shown in Figures 11 and 12. Figure 13 compares the hardness ranges in the weld metal and
CG-HAZ of these welds, and at the ID surface of the weld metal and CG-HAZ.
3500
3000
2500
383 HV
Distance, m
2000
375 - 378 HV
350 - 374 HV
1500
325 - 349 HV
300 - 324 HV
1000
275 - 299 HV
500
250 - 274 HV
175 - 199 HV
200 - 249 HV
144 - 174 HV
-500
144 HV
-1000
-1500
-6000
-5000
-4000
-3000
-2000
-1000
Distance, m
Figure 11. Hardness map in the non-reheated root pass of the 0.185 in. (thin) wall weld.
Although the thin wall welds were produced with lower heat input, the reduced wall thickness
resulted in larger t8/5 values than in the thick wall welds, Figure 4. The hardness of non-reheated
CG-HAZ and weld metal in the root pass was in the ranges of 375 to 200 HV0.1 and of 375 to 275
HV0.1 correspondingly. The deposition of the second pass softened the weld metal in the root pass
with about 25 HV and reduced the overall hardness in CG-HAZ, Figures 11, 12, and 13a. The
hardness in the ID area of the weld metal was reduced by 25 to 50 HV0.1, Figures 11, 12, and 13b.
Compared to the thick wall welds, the lower overall hardness in the thin wall welds can be related
to the slower cooling rate, the lower base metal carbon and chromium content, and the presence of
about 100 m thick decarburized zone at the ID surface. Decarburized layers typically form on
the tube OD and ID surfaces during hot rolling. The latter had a very strong effect on the hardness
in the weld root (ID surface). The ID areas of CG-HAZ and weld metal in thin wall welds were 75
to 150 HV softer than in the thick wall welds, Figures 10 and 13.
The hardness and microstructure in the root pass and at the ID surface are critical factors of
susceptibility to hydrogen induced cracking (HIC) during welding and of stress corrosion
cracking SCC during service of such welds. Hard microstructure in the weld root area in
combination with high residual stresses and diffusible hydrogen that can be dissolved in the weld
metal due to improper shielding of the weld root can lead to HIC in the CG-HAZ or weld metal.
The first two factors in combination with exposure of the ID surface to corrosion environment
580
during acid cleaning and/or during service can result in SCC. The high hardness in the root pass
and at the ID surface (maximum values between 375 and 400 HV0.1 after deposition of the third
pass) shows a potential risk of HIC and SCC of the thick wall welds analyzed in this study. Such
risk can be significantly reduced by not removing the decarburized layer at the ID surface during
weld groove preparation.
5000
4000
Distance, m
3000
374 HV
350 - 369 HV
325 - 349 HV
300 - 324 HV
2000
275 - 299 HV
250 - 274 HV
200 - 249 HV
175 - 199 HV
1000
140 - 174 HV
140 HV
-1000
-7000
-6000
-5000
-4000
-3000
-2000
-1000
Distance, m
Figure 12. Hardness map in the root and second passes of the 0.185 in. (thin) wall weld.
b)
a)
Figure 13. Hardness ranges in the thin wall welds: a) in the weld metal and CG-HAZ; b) at the ID
surface of the weld metal and CG-HAZ.
Weld Microstructure
Examples of the base metal, weld metal, and CGHAZ microstructure in the thick and thin wall
welds are shown in Figures 14 and 15. Due to the extremely fine morphology these
microstructures could not be fully identified using light optical microscopy. Further metallurgical
characterization with scanning and transmission electron microscopy is needed for complete
identification of the weld metal and HAZ microstructural constituents.
The microstructure of the non-reheated CGHAZ in the thick wall welds consisted of fine parallel
laths aligned in packets with different orientation within the prior austenitic grains, Figure 14a.
Based on the extremely high hardness and on the phase transformations determined using SS
DTA (Figure 5), it could be assumed that this microstructure was composed of a mixture of lower
581
bainite and martensite. A coarser, light etching constituent with rectangular shape was found in
the microstructure of CHGAZ and weld metal at faster cooling rates, Figures 14a, 14c, and 15c.
a)
as shown in Figure 14c. Re-heating of the weld metal by subsequent passes resulted in a visible
coarsening of the lath microstructure and in reduction in hardness, Figures 14d and 14e. Further
investigations are needed to identify the effects of partial and full transformation to austenite, and
of tempering at subcritical temperatures on the coarsening of microstructure and on the softening
of reheated weld metal. The microstructure in non-reheated weld metal in thin wall welds has
coarser laths and does not contain the light etching phase in comparison to the non-reheated weld
metal in thick wall welds, Figures 14c and 14f.
583
584
[5] Ullrich C., S. Heckmann, W. Tillmann, T. Bodmer, and G. Gierschner, Stress Corrosion
Cracking of T24 Service Experience and Investigation Program ETD Seminar, Paper 2-4,
London, May 2013.
[6] Mohyla P. and J. Koukal, Contribution to Research of Weldability of Modern Low Alloy
Creep Resistant Steels, Acta Metallurgica Slovaca, Vol. 9, 2003, 3, pp. 210-216.
[7] Mrz L., et al, Application of Creep Resistant Steel T24 for welding membrane walls, IIW.
Doc. IX-C-1029-13, 2013.
585
Cr
Co
Nb
Ta
VL1
0.076
8.96
1.99
2.06
0.005
0.055
0.0029
VL2
0.076
9.00
1.98
2.07
0.010
0.056
0.0029
VL3
0.074
9.00
1.98
2.07
0.020
0.057
0.0028
VH1
0.075
9.21
2.00
2.04
0.1
0.054
0.0028
VH2
0.074
9.42
2.01
2.04
0.2
0.054
0.0029
VH3
0.072
9.27
2.01
2.05
0.3
0.055
0.0029
N1
0.077
8.98
1.98
2.06
0.012
0.055
0.0029
N2
0.077
9.02
1.98
2.07
0.032
0.056
0.0030
N3
0.075
9.01
1.98
2.07
0.062
0.057
0.0030
VNB1
0.075
9.29
2.00
2.06
0.062
0.012
0.055
0.0029
VNB2
0.074
9.30
2.00
2.07
0.110
0.030
0.056
0.0028
VNB3
0.073
9.28
2.00
2.07
0.210
0.060
0.058
0.0028
Fig. 2.Creep strain curve at 923 K and 70 MPa of the steels studied in
(a)VL, (b)N, and (c)VNB
microstructure recovery is significantly advanced at 50% of the total creep life. In the
creep-ruptured specimen, the microstructure, as shown in Fig. 3 (c), indicates high-angle grain
boundary migration with significant recovery. In all steels, VL and VN precipitates were not
detected before the creep test. Concerning the size of precipitates, M 23 C 6 grew with creep
deformation. VN could not be detected in the specimen even after the creep test. Precipitates in
Fig. 3 (b) were qualitatively identified as M 23 C 6 and Cr 2 N, and Laves phase from the EDX
analyses results.
(b), is higher than that of spherical precipitates with same size [5]. Furthermore, fine needle type
VN, as shown in Fig. 6, was also observed in steel VNB3. This steel contains V and Nb higher
than that contained by commercially advanced ferritic steels. Therefore, the driving force of
precipitation from the supersaturated solid solution is increased, and MX can precipitate during
the tempering. These precipitates seem to be coherent with matrix judging from the morphology.
Such precipitates appear during the creep test and contribute to the creep strength generally.
However, the complex MX precipitated from the beginning of the creep test. Therefore, its
coarsening must be analyzed with creep duration as a further research item. If the coarsening
rate is small because of the precipitates coherency, a longer creep life is expected, as shown in
Fig. 2 (c).
591
Misorientation changing
Fig. 7 shows the inverse pole figure (IPF) map before the creep test. Figs. 7 (a) and 7 (b) indicate
the maps of VL1 and VL3, and Figs. 7 (c) and 7 (d) indicate the maps of N1 and N3,
respectively. Fig. 7 (e) is the color key. As already explained, VL1 and VL3 contain only V in
addition to the base compositions, and N1 and N3 contain only Nb. The sizes of the packet and
block shown in Figs. 7 (a) and 7 (b) were similar to each other. On the other hand, size of grains
shown in Fig. 7 (d) was very fine as compared to that of the grains shown in Fig. 7 (c). The grain
size difference seems to be due to the pinning effect caused by incompletely solved NbC by
normalizing.
(e)
Fig. 7. IPF map of the steels before creep test in (a)VL1, (b)VL3, (c)N1, and (d)N3; (e)color key
Fig. 8 shows the grain misorientation frequency distribution diagram before the creep test.
Misorientation refers to the grain orientation difference between the adjacent crystals across the
boundary. Therefore, the distribution diagram indicates the misorientation angle frequency at the
grain boundary.
Peaks at approximately 60o, 53o, and 6.5o misorientation angles can be distinguished in the
diagrams. These angles are those of block boundaries in martensite transformation, following the
592
Fig. 8.Relationship between grain boundary misorientation and frequency of steels in (a)(b)steel
VL (c)(d)steel N
and analyzed misorientation angle of (a)(c) 565o (b)(d)4565o
Fig. 9 shows change in the grain misorientation frequency distribution through creep
deformation. In ruptured specimens, peaks of block boundary are almost difficult to distinguish,
593
except the peak at 60o . This phenomenon indicates significant microstructural recovery due to
creep deformation. The boundary with the peak at 60o is 3 special coincidence grain boundary.
This boundary is well known as the stable boundary because of the low interfacial energy.
Therefore, the peak at 60o remains even after the creep rupture.
In steel VL1, the misorientation frequency distribution diagram of the creep-interrupted
specimen at 50% creep life is almost similar to that of the ruptured specimen, as seen in Fig. 9
(b), the precise analysis of Fig. 9 (a) at the peat range from 45 to 65o. On the other hand,
microstructure recovery is not significant up to 80% of the total creep life, according to the
analysis of creep interrupted specimens. The chemical composition difference in steels VL1 and
VL3 is the amount of V. Therefore, V precipitation possibly affected the difference in the
crystallographic analysis change.
Table 2 shows the number density per unit area of Cr 2 N in VL1 and VL3 of the heat treated
specimen and of the creep ruptured test specimen. The number density of Cr 2 N did not change
in as heat treated steels VL1 and VL3. However, the number density decrease in VL3 was much
more than that in VL1 after the creep test. From these results, VN precipitated, consuming the N
of the Cr 2 N. Therefore, VN precipitation prevented microstructural degradation through
intragranular precipitation strengthening. Cr 2 N supposedly does not affect the creep strength so
much, as compared to the case of VN.
Table 2. Comparison of number density of Cr 2 N per unit area in VL1 and VL3
As heat treatment
After rupture
ND as -ND r
ND as
ND r
VL1
1.28
0.21
1.07
VL3
1.31
0.18
1.13
CONCLUSIONS
1.VN precipitation increased the creep strength for content higher than 0.02%.
2. Simultaneous addition of Nb and V in the specimen resulted in the complex NbC-VN
precipitates, even in the as heat treated specimen. The coherent and fine needle type VN was
also detected in the steel. These precipitates are expected to increase the creep strength
according to the creep strain curves.
3. V variation up to 0.02% did not affect the crystallographic character of the grain boundary in
the as heat treated specimens.
4. Nb variation affected the crystallographic character of the grain boundary significantly
because of the grain refinement effect by NbC.
5. VN precipitation during the creep restricted the crystallographic misorientation angle profile
degradation.
6. Integrating all intragranular precipitates, VN, restricted the crystallographic degradation
significantly.
REFERENCES
[1] M. Mitsuhara, S. Morioka, S. Hata, K. Ikeda, H. Nakashima, Report of the 123rd Committee
on Heat Resisting Materials and Alloys, Japan Society for the Promotion of Science 50, (2009),
37-43
[2]M. Igarashi, S. Muneki, H. Hasegawa, K. Yamada, F. Abe, Creep Deformation and the
Corresponding Microstructural Evolution in High-Cr Ferritic Steels, ISIJ Int., 41, (2001),
Supplement, pp.S101-S105
[3]Y. Hasegawa, T. Nishiura, T. Sato, The New Metallurgical Precipitation Strengthening
Model of W Containg Advanced High Cr Ferritic Creep Resistant Sreels, Proc. of the 7th
International Conference On Advances In Materials Technology For Fossil Power Plants,
Hawaii, USA, October. 2013, in printing
[4]H. K. Danielsen, Z-phase in 9-12%Cr steels, Ph. D thesis, Technical University of Denmark,
(2007), Appendix D, p10
[5]S.Goto, K.Mori, H.Yoshinaga, Effect of Particle Shape on the High Temperature Yoeld
Strength of Dispersion-Hardened Nickel Bace Alloys, J.Japan Inst. Metals 50 (1986)
154-161
[6]G.Kurdjumov, G. Sachs, U ber den Mechanismus der Stahlhartung, Zeit. f. Phys., 64,(1930),
325-343
[7]Z. Nishiyama, X-ray investigation of the mechanism of the trabsformation from
face-centered cubic to body-centered cubic, Sci. Rep. Tohoku University, 23,(1934), 637-664
[8]G. Wassermann, Uder den Mechanismus der - Umwandlung des Eisens, Mitt. K-W-I
Eisenf., 17, (1935), 149-155
[9] B. Sonderegger, S. Mitsche, H. Cerjak, Martensite laths in Creep Resistant Martensitic
912% Cr Steels Calculation and Measurement of Misorientations, Materials
Characterization 58 (2007) 874-882
595
ABSTRACT
In typically processed creep stress enhanced ferritic steels (CSEF) it has been observed that the
long term performance and creep rupture strength is below that predicted from a simple
extrapolation of the short term creep data. One of the primary microstructural degradation
mechanisms responsible for this behaviour is the development of creep voids. Nucleation, growth
and interlinkage of voids will also result in a significant loss of creep ductility.
In this study, the cavities in creep tested P92 steel have been characterised. It has been found that
in the standard P92 samples studied, the cavities are associated with large (typically 1-2 m)
ceramic particles. Three particle compositions were observed and more detailed TEM
investigations showed that these particles were BN, MnS and -Al 2 O 3 . Statistical analysis of the
ceramic particle types showed that in all samples studied a very high proportion of the cavities
was associated with BN particles. The shape of both the cavity and associated particle were
studied in 3D using a Focussed Ion Beam/ Field Emission Gun Scanning Electron Microscope
(FIB-FEGSEM) slice and view technique. This showed that both the cavity and associated
particle had very irregular shapes.
Analysis in the head-gauge transition area of a creep test bar, where the exposure stress is low,
showed small cavities associated with the BN particles. This provides strong evidence that the
cavities were preferentially nucleating on the hard, irregularly shaped BN particles.
INTRODUCTION
Creep strength enhanced ferritic (CSEF) steels are used in steam pipes, headers and tubes because
of their combination of properties which include; high thermal conductivity, low thermal
expansion coefficient, low susceptibility to thermal fatigue, good corrosion and oxidation
resistance, and relatively good creep resistance [1, 2]. These properties derive from the
microstructure, which when properly processed contains a tempered martensitic matrix containing
a substructure with a high dislocation density and a fine dispersion of second phase precipitates.
However, the microstructures of CSEF steels evolve during service where the materials undergo
long term creep. A number of microstructural degradation mechanisms have been identified which
are thought to be responsible for the loss of long term creep strength. These include; the
precipitation of new phases (e.g. Laves and Z phases), the dissolution of fine M 2 X and MX
596
carbonitrides, the recovery of the dislocation sub-structure and the development of creep voids in
the microstructure [3-6].
It has been found that the creep cavities in high Cr steels start to nucleate in the early stages of a
creep test [7]. The mechanism of creep cavity nucleation in these steels is not fully established;
although several possibilities have been suggested by Kassner and Hayes [8]. In P92 steels, coarse
Laves phase particles have been reported to be the preferential site for cavity nucleation [9]. In
this work by Lee et al. it was suggested that the coarsening of Laves phase to a certain size (over
an average diameter of 130 nm) triggers cavity nucleation at grain boundaries resulting in brittle
fracture. Zhao et al. [10] have suggested that inclusions, such as manganese sulphide and alumina,
are the preferential nucleation sites of the creep cavities.
The addition of boron can improve the creep strength of 9% Cr steels at 650oC [11]. The fine
distribution of M 23 C 6 carbides in the vicinity of prior austenite grain boundaries can be stabilised
by boron additions during creep [12]. The benefits of boron addition are however only realised if
the precipitation of BN can be avoided as this consumes soluble boron and nitrogen. The
solubility of B and N is very sensitive to the absolute concentrations in the steel, and also to the
temperatures used in the initial high temperature processing of the steel. It has been reported that
the concentration of boron and nitrogen at which BN forms is governed by the equation
log[%B]=-2.45log[%N]-6.81 [13]. Li et al. have calculated the boron nitride solubility at elevated
temperatures (1175oC to 1200oC) using thermodynamic simulations which are able to take into
account the full chemical composition of the steel, and particularly the W concentration which can
influence the formation of tungsten borides. These calculations have resulted in a modified boron
nitride solubility line [14].
The aim of the present research is to quantitatively characterise the microstructures of creep tested
P92 samples to understand where the creep cavities are nucleating.
EXPERIMENTAL PROCEDURES
Table 1 gives the chemical compositions of the two P92 steels studied. The creep samples with
composition A and B were normalised at 1071oC and 1066oC respectively and followed by a
temper at 777oC. Table 2 shows the creep testing conditions, reduction in area at failure, and
lifetime of each sample. The samples were all observed to fail in the gauge length, which, before
the creep test, had a diameter of 6 mm. These samples were selected for this study as they
possessed different reductions in area in tests with durations around 10,000 hours yet had only
slight variation in chemical composition.
Table 1: Chemical compositions of the P92 steels studied (wt.%), balance Fe.
C
Mn
Si
Cr
Ni
Mo
Al
Nb
0.09
0.47
0.014
0.006
0.35
8.7
0.38
0.39
0.18
0.005
1.84
0.0036
0.057
0.0464
0.11
0.44
0.015
0.002
0.34
8.8
0.13
0.41
0.20
0.006
1.95
0.0036
0.058
0.0403
597
Table 2: Creep testing conditions, creep life and reduction in area at failure of the samples
studied.
Temperature (oC)
Sample
Composition
Stress (MPa)
Lifetime (h)
550-B
600-A
550
202
10,823
69.3
600
132.4
11,057
2.5
650-A
650
62.5
25,187
2.4
The three creep samples were cross-sectioned along the load direction using a Struers Accutom-5
cutting machine. The sectioned samples were mounted in conductive Bakelite and ground using
240 to 1200 grit SiC in resin bonded pads, followed by polishing using standard cloths with
diamond suspensions down to 1 m. An extended final polishing stage using 0.02 m colloidal
silica suspension was undertaken to provide a deformation-free surface polish.
Scanning electron microscopy was carried out in a Zeiss 1530VP field emission gun system
(FEGSEM). SEM images were collected using an Everhart Thornley (ET) secondary electron
(SE) detector and Solid State Backscatter detector using an accelerating voltage of 10 kV, an
aperture of 60 m and a working distance of ~12 mm. In-lens SE imaging was undertaken at short
working distances also at 10 kV. The chemistry of features of interest was studied with Energy
Dispersive Spectroscopy (EDS) using an Oxford Instruments X-max 80 Silicon Drift Detector
(SDD), which was attached to the FEG-SEM.
An FEI Nova 600 Nanolab dual beam consisting of a Field emission Gun Scanning Electron
Microscope and Focused Ion Beam System (FEG-SEM/FIB) was used for serial sectioning and
preparing site specific thin foil TEM samples. For serial sectioning, a 1 m thick layer of Pt was
deposited on the area to be analysed (20 20 m2) and FIB trenches were cut with ion beam in
front and to the side of the Pt layer. Serial sectioning was carried out using a current of 1 nA and
SEM images were collected after each 55 nm slice. The data stack collected was reconstructed
using Avizo v6 software. TEM samples were prepared using the dual beam using a standard insitu lift out procedure.
Transmission electron microscopy (TEM) was carried out using a JEOL 2000FX microscope
operating at 200 kV and equipped with an Oxford Instruments Inca EDS system. An Erlangshen
ES500W digital camera was used to capture images and selected area diffraction (SAD) patterns.
Thermodynamic simulations were performed using the software package ThermoCalc in
conjunction with the thermodynamic database for ferrous materials, TCFE version 6, to give an
indication of the phases likely to be present at the equilibrium in the steels with the given
compositions. The simulations were carried out over the temperature range 300 to 1300oC.
RESULTS AND DISCUSSION
SEM Examination of Creep Cavities
Creep cavities were observed in the gauge section of all samples studied, a typical example of
which is shown in Fig. 1a. A more detailed examination of this cavity using the in-lens detector in
the SEM (Fig. 1b) clearly revealed that a large particle was accomodated within the cavity.
598
Extending this analysis to a large number of cavities revealed that large particles (~1-2 m in
diameter) were often associated with cavities, typical examples of which are shown in Fig. 2.
EDS analysis in the SEM was undertaken to determine the chemical composition of the particles
within the cavities. Three discrete compositions were found which were consistent with BN, MnS
and Al 2 O 3 type particles. These different types of particles can also be distinguished from their
appearance in the in-lens images as shown in Fig. 3.
Figure 1: SEM micrographs of a cavity in sample 550-B gauge section 6 mm away from the
fracture surface collected using the standard Everhart Thornley SE detector (a) and the in-lens
SE detector (b).
Figure 2: In-lens SEM images showing creep cavities associated with particles in the gauge
section of sample 600-A. High magnification images of selected cavities are also shown.
Figure 3: In-lens SEM micrographs showing the different particle types that associate with creep
cavities; boron nitride (a), manganese sulphide (b), and alumina (c).
599
Using a combination of in-lens SEM examination and EDS, the number and type of particles that
are present within the cavities was measured as a function of distance from the fracture surface.
These data are shown in Table 3 and clearly show that BN-types particles are most commonly
accomodated within the cavities at all distances from the fracture section. A number of cavities
were also observed that did not appear to have a large particle associated with them. This is not
surprising because only a 2D section across a random plane in the cavity is being examined and
consquently the part of the cavity where the particle is present may not always be in this plane.
This effect would be expected to become more significant with increasing cavity size and this is
indeed what was observed. For example, the effect is more significant in the low ductility samples
600-A and 650-A, whose cavities are larger in size and more in number than the high ductility
sample 550-B.
Table 3: The number density of cavities and associated particle types as a function of distance
from the fracture surface in the three samples.
Sample
550-B
600-A
650-A
Distance to
fracture
surface
1 mm
3 mm
5 mm
7 mm
9 mm
1 mm
3 mm
5 mm
7 mm
9 mm
1 mm
3 mm
5 mm
7 mm
9 mm
Number of
cavities per
~50000 m2
60
47
51
42
36
159
108
119
79
100
90
76
74
90
83
BN
MnS
Al 2 O 3
Not detected
25
34
41
26
30
43
32
41
35
18
27
30
17
31
35
6
1
1
3
1
10
7
11
6
9
10
8
9
7
9
2
2
1
2
1
3
3
2
1
4
2
4
4
6
2
27
10
8
11
4
103
66
65
37
69
51
34
44
46
37
3D Examination of Cavities
In order to study the association of cavities with particles more completely, 3D analysis was
undertaken using a FIB based serial sectioning technique. This technique involved slicing using
the FIB and imaging using the SEM until a large particle was present in the cavity. The
composition of the particle was then measured using EDS, and then the FIB sectioning and SEM
imaging processes were completed so that a full set of slices of the particle were collected so that
the shape of the cavity and associated particle could be determined. In the example shown in
Fig. 4 for sample 600-A, 6 mm from the fracture face, the particle was identified as BN. Out of
26 particles analysed in this way 18 were BN, 1 was alumina and 3 were MnS. On some
occasions more than one particle type was observed, in which case the cavity was classified as
being associated with the largest particle present. In four cavities no ceramic particles were
detected, although it is possible that they were present because detecting small low atomic weight
elements such as B and N in serial section experiments is not straightforward. It can however be
clearly concluded that the proportion of cavities with BN particles present is much higher than
was observed in the 2D planar surface analysis.
600
From the 3D data collected, the shape of the creep cavities and the associated particles was
reconstructed. An example of such a reconstruction is shown in Fig. 5. In the reconstruction
shown, the cavity has a diameter of around 2 m, whereas that of the BN particle is around
1-1.5 m. Much smaller second phase particles including Laves phase were found to decorate the
inner wall of the cavities.
Figure 5: An example of a single SEM cross-section slice taken in sample 600-A 6 mm away from
fracture surface (a). A reconstruction of the data stack showing the pore (shown in blue, purple
and green) and associated particle (shown in red) in 3D.
601
Figure 6: Bright field TEM images, SAD patterns and EDS spectra of BN (a), MnS (b) and
alumina (c) type particles associated with cavities.
Boron Nitride Particles in Head Sections and Head-Gauge Transition Areas
Fig. 7 shows a low magnification in-lens SEM image taken in the head section of sample 650-A.
No cavities were observed in the head section but BN particles are present and are highlighted by
arrows in Fig. 7. Fig. 8 shows high magnification in-lens images of the BN particles and they can
be seen to possess a characteristic surface texture and irregular shape that distinguishes them from
other particle types.
602
The BN particles in the head-gauge transition area were also examined using in-lens SEM. In this
area, which is expected to be exposed to a reduced creep stress compared with the gauge section,
tiny cavities can be seen to be associated with the BN particles. This provides strong evidence
that these particles provide the nucleation sites for creep cavities.
Fig. 10 shows the predicted weight fraction of phases present in the P92 steel composition A
against temperature. In addition to the ferritic matrix, three secondary phases; Laves phase,
M 23 C 6 and VN-type MX, are predicted to form in the temperature range of the creep tests (550 to
650oC). The lowest temperature boron nitride is predicted to form is 710oC for composition A. No
boron nitride precipitation is predicted within the temperature range of the creep tests (550 to
650oC), which suggests that the boron nitride particles formed at higher temperatures during
thermal processing. The B and N levels present in the steel compositions studied here are at a
level where Sakuraya et al. [13] and Li et al. [14] predict BN could form depending on the
thermal processing schedule used. Boron is added to improve the creep strength of P92 steels by
suppressing the coarsening of M 23 C 6 precipitates [12]. However, these benefits are not likely to
be realised if the B is present primarily as coarse BN particles. Indeed these large hard irregularly
shaped particles are likely to act as stress concentrators where cavities preferentially nucleate, as
has been observed in this study.
Figure 7: An in-lens SEM micrograph taken in the head section of sample 650-A, in which BN
particles are indicated by arrows.
603
Figure 8: In-lens SEM micrographs of BN particles in the head section of sample 650-A.
Figure 9: In-lens SEM micrographs of BN particles in the head-gauge transition area of sample
650-A.
CONCLUSIONS
Analysis of the creep cavities formed in P92 steel after exposure to a range of creep test
conditions revealed that the majority of them were associated with hard ceramic particles.
Chemical analysis of these hard ceramic particles revealed that the vast majority were BN in this
case, although some Al 2 O 3 and MnS particles were also observed. 3D analysis of the cavities and
particles showed that they both had irregular shapes and that the particles often accounted for a
significant fraction of the cavity volume. Additionally, very small cavities were found to be
associated with the BN particles in the head-gauge transition area of the crept samples, indicating
the onset of creep damage.
Analysis of the head sections using a combined in-lens SEM/EDS approach showed that BN
particles were also present in the regions of the sample free from cavities. This provides evidence
that the BN particles were introduced during the initial thermal processing of the steel rather than
during creep exposure. This is supported by thermodynamic calculations which showed that BN is
predicted to form at much higher temperatures than the samples were exposed to during the creep
tests.
604
1
Ferritic matrix
Mass fraction
0.1
Laves phase
M23C6
0.01
Z phase
1E-3
M2B
M3P
1E-4
MnS
BN
1E-5
300
400
500
600
700
800
900
Temperature ( C)
Figure 10: Thermodynamic simulation of composition A showing the mass fraction of the phases
present as a function of temperature.
ACKNOWLEDGEMENTS
The authors would like to thank EPRI for the support of this project.
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606
ABSTRACT
In order to clarify the effect of stress state on microstructural changes during creep, the
microstructure was observed in the central part of the cross section of the fine-grained heataffected zone (FGHAZ) and in the surface region of the FGHAZ in Gr.92 steel welded joint.
Creep tests were performed under constant load in air at 650oC, using cross-weld specimens. The
creep strength of welded joint was lower than that of base metal. Type IV fracture occurred in the
long-term. Creep voids were detected in the FGHAZ after the fracture. Number of creep voids
was higher in the central part of the cross section of the FGHAZ than in the surface region of the
FGHAZ. It was checked the multiaxiality of stress during creep was higher in the central part of
the cross section of the FGHAZ than in the surface region of the FGHAZ. The recovery of
dislocation structure occurred after creep in the base metal and the FGHAZ. Mean subgrain size
increased with increasing time to rupture. However, there was no difference of change of subgrain
size during creep in the central part of the cross section of the FGHAZ and in the surface region
of the FGHAZ. The growth of M 23 C 6 carbide and MX carbonitrides was observed during creep in
the base metal and the FGHAZ. Laves phase precipitation occurred during creep. There was no
difference of the change of mean diameter of MX carbonitrides in the central part of the cross
section of the FGHAZ and in the surface region of the FGHAZ after creep. However, the growth
rate of M 23 C 6 carbide in the FGHAZ was much higher in the central part of the cross section than
in the surface region.
INTRODUCTION
Thermal power plants are supplying about 80% of electricity in Japan because most of nuclear
power plants were not allowed to operate after the nuclear accident in Fukushima [1]. Therefore,
safe operation of thermal power plants is very important issue in terms of stable power supply.
About 20 units of USC power plants are operating in Japan. Creep Strength Enhanced Ferritic
(CSEF) steels are widely used in the USC power plants. However, creep strength degradation and
Type IV cracking occur in the CSEF steels welded joints [2, 3]. In order to control or retard the
Type IV cracking, it is necessary to make clear the mechanism of the Type IV cracking in terms
of stress state and microstructural changes.
Creep voids are formed in fine-grained heat-affected zone (FGHAZ) of the CSEF steel welded
joints, leading to the Type IV cracking [4]. It is reported that multiaxiality of stress is higher in the
central part of the cross section of the FGHAZ than in the surface region of the FGHAZ [5]. In
many cases, creep voids tend to be formed in the central part of the cross section of the FGHAZ
due to the higher multiaxiality of stress [6]. On the other hand, Hasegawa et al. reported that weak
area was formed in the central part of the cross section of the FGHAZ by means of thermal cycle
of multilayer welding [7]. Therefore, the presence of multiaxiality of stress and microstructural
changes should be focused to clarify the mechanism of the Type IV cracking.
607
In this paper, we investigated the effect of mutiaxiality of stress on the microstructural changes
such as dislocation structure and growth of precipitates during creep in the FGHAZ of the Gr.92
steel welded joints.
Experimental procedures
The materials studied were ASME Gr.92 steel plate with thicknesses of 30 mm. The chemical
composition and heat treatment condition is listed in Table 1. Welded joints were fabricated from
the plate by multilayer gas tungsten arc welding (GTAW). The welding consumable used for
GTAW was a matching filler wire developed for welding this class of steel. PWHT was
conducted at 740oC for 280 min. Creep tests were performed at 650oC under a constant load in air
by using specimens with 18 mm 5 mm cross section and 100 mm gauge length for welded
joints. Extracted carbon replicas and thin foils were examined by using a transmission electron
microscope (TEM) equipped for scanning transmission electron microscopyenergy dispersive XRay spectroscopy (STEM-EDX). The replicas and thin foils were prepared from the FGHAZ (one
is from close to the surface region, another one is from the central part of the cross section) and
the base metal of welded joints before and after creep.
Table 1 Chemical composition (mass%) and heat treatment condition of the steel examined.
C
Si
Mn
Ni
Cr
Mo
0.009
0.16
0.47
0.010
0.001
8.72
0.45
1.87
Nb
0.21
0.06
0.0020
0.050
Normalizing
o
Tempering
o
Figure 1 Creep rupture strength of Gr.92 welded joint and base metal [8].
608
The microstructures of coarse-grained heat-affected zone (CGHAZ), the FGHAZ (surface region
and central part of cross section) and the base metal after creep rupture are shown in Fig.2. A
large number of creep voids were observed in the FGHAZ although no damage was observed in
the CGHAZ and the base metal, meaning that Type IV fracture occurred. The number of creep
voids was obviously higher in central part of the cross section than close to surface region of the
FGHAZ, indicating that multiaxiality of stress is higher in the central part of the cross section. For
observations of dislocation structure and precipitates distribution, the samples were prepared from
close to the surface region and in the central part of the cross section of the FGHAZ, considering
the result of Fig.2.
(b) FGHAZ
(a) CGHAZ
25m
Figure 2 Microstructures of (a) CGHAZ, (b) FGHAZ and (c) base metal after creep rupture.
650oC, 60MPa, tr = 10559.2h
FGHAZ upper : surface region, lower : central part of cross section
609
of stress does not affect the change of subgrain size during creep in the FGHAZ. We have already
confirmed it on the Gr.911 welded joint [9].
base metal before creep
1m
Figure 3 Dislocation structures of base metal and FGHAZ before and after creep.
650oC, 60MPa, tr = 10559.2h
It was reported that the increase in subgrain size during creep strongly depends on the increase in
creep strain for the base metal [10]. The following relation was reported between the subgrain size
w and the creep strain for the CSEF steel [10] :
(1)
(w - w 0 ) / (w s - w 0 ) = k
where w 0 and w s are the initial and stationary values of subgrain size, and k is a constant. The
stationary value of subgrain size w s is given by
(2)
w s = 10Gb /
where G is the shear modulus, b is the length of Burgers vector, and is the applied stress. The
value of k in the equation (1) is estimated to be 8.42 from ref. [10]. If the value of w, w 0 and are
610
known, it is possible to estimate the value of creep strain. We applied the equation (1) and (2) to
predict creep strain for the FGHAZ after creep rupture. The creep strain of the FGHAZ was
estimated to be about 0.01 after creep rupture for about 10000h from the result of Fig.4. The
creep strain of the FGHAZ predicted from the change of subgrain size is very small
Figure 5 demonstrates the relation between the dislocation density inside subgrain and the time to
rupture. The dislocation density decreased after creep rupture for the base metal and the FGHAZ.
The dislocation density was higher in the base metal than in the FGHAZ before creep. However,
there was no large difference of the dislocation density between the base metal and the FGHAZ
(surface region and central part of cross section) after creep rupture. There was no effect of
mutiaxiality of stress on the change in dislocation density during creep.
1m
Figure 6 Precipitates distributions of base metal and611
FGHAZ before and after creep. 650oC, 60MPa, tr = 10559.2h
In order to get the distribution of each precipitate, the elemental maps of Cr, V, Nb and Mo were
obtained using STEM-EDX. Figure 7 shows the results of elemental mappings of carbon
extracted replica before and after creep. The particles were colored based on the elemental maps.
M 23 C 6 (red particles) and MX (blue particles) were observed before and after creep. Additionally,
Laves phase (green particles) was confirmed in the base metal and the FGHAZ after creep. The
size of M 23 C 6 was clearly larger after creep comparing with before creep. The increase in the size
of MX was very small after creep rupture.
base metal before creep
1m
Figure 7 Results of elemental mapping for base metal and FGHAZ before and after creep.
650oC, 60MPa, tr = 10559.2h Red : M23C6, Blue : MX, Green : Laves phase
The relationship between the mean size of particle and the time to rupture are demonstrated in
Fig.8. In the base metal, there was no large change in the MX size after creep rupture. On the
other hand, the MX size rapidly increased with time to rupture and saturated at long-term in the
FGHAZ. However, there was no difference in the mean MX size in the surface region and the
central part of the cross section of the FGHAZ. For the base metal and the surface region of the
FGHAZ, the mean M 23 C 6 size rapidly increased after creep rupture for short-term and changed a
little after creep rupture for long-term. The increase in mean M 23 C 6 size in the central part of the
cross section of the FGHAZ was larger than that in the surface region of the FGHAZ after creep
rupture. This indicates that the multiaxiality of stress promotes the growth of M 23 C 6 in the
FGHAZ during creep. We have already reported that the growth of M 23 C 6 was accelerated near
crack tip after creep crack growth comparing with the area remote from the crack tip [11]. The
higher multiaxiality of stress near crack tip [12] can promote the growth of M 23 C 6 during creep
crack growth. It has been reported that there was no large effect of multiaxiality of stress on the
growth of M 23 C 6 in Gr.911 weldment [9]. The testing temperature was 600oC for the Gr.911
weldment while the result of Fig.8 was obtained at 650oC. Therefore, the effect of multiaxiality of
stress on the growth of M 23 C 6 may be visible at higher temperature. It can be expected that the
accelerated growth of M 23 C 6 in the central part of the cross section of the FGHAZ will be clear in
the very long-term even at 600oC.
It was reported that there was less creep damage near the outer surface of an ASME P122 steel
weldment than in the central part of the cross section of the FGHAZ [6]. This is due to the higher
612
multiaxiality of stress and formation of weak area by thermal cycle of multilayer welding in the
central part of the FGHAZ. Additionally, the accelerated growth of M 23 C 6 in the central part of
the FGHAZ can also promote creep voids formation because the creep voids tend to nucleate at
the interface between large precipitate and matrix [13].
Figure 8 Change in mean particle diameter of base metal and FGHAZ during creep.
CONCLUSIONS
The microstructural changes during creep in the surface region and the central part of the cross
section of the FGHAZ were compared in the Gr.92 welded joint. The results can be summarized
as follows.
1. The creep strength of welded joint was lower than that of the base metal. The fracture occurred
in the FGHAZ of welded joint. Creep voids tended to form in the central part of the cross
section of the FGHAZ compared with the surface region of the FGHAZ.
2. The subgrain size increased with increasing time to rupture in the base metal and the FGHAZ.
There was no large difference of change in subgrain size in the surface region and the central
part of the cross section of the FGHAZ.
3. The growth of M 23 C 6 and MX were observed during creep in the base metal and the FGHAZ.
There was no large difference of growth of MX in the surface region and the central part of the
cross section of the FGHAZ. The size of M 23 C 6 was larger in the central part of the cross
section of the FGHAZ than in the surface region of the FGHAZ after creep rupture.
ACKNOWLEDGEMENTS
A part of this study was supported by a Grant-in-Aid for Young Scientists (B) (No. 20760443) of
the Ministry of Education, Culture, Sports, Science and Technology, Japan.
REFERENCES
[1] http://www5.fepc.or.jp/tokei-eng/
[2] M. Tabuchi and Y. Takahashi, Proc. PVP2006/ICPVT-11, 2006 ASME Pressure Vessels and
Piping Divisin Conference, (2006), PVP2006-ICPVT11-93350
613
[3] Y. Takahashi and M. Tabuchi, Proc. PVP2006/ICPVT-11, 2006 ASME Pressure Vessels and
Piping Divisin Conference, (2006), PVP2006-ICPVT11-93488
[4] J. A. Francis, W. Mazur, H. K. D. H. Bhadeshia, Mater. Sci. Technol. 22 (2006) pp.13871395.
[5] M. Bauer, A. Klenk, K. Maile, E. Roos, C. Jochum, Proc. of 8th Liege Conf. on Materials for
Advanced Power Engineering, ed. by J. Lecomte-Beckers et al., Forshungs-zentrum, Jlich
GmbH, Jlich, (2006), III. pp.1341.
[6] N. Komai, F. Masuyama, ISIJ Int. 42 (2002) pp.1364-1370.
[7] Y. Hasegawa, M. Sugiyama, K. Kawakami, Proc. of Creep and Fracture in High Temperature
Components-Design and Life Assessment Issues, ed. by I. A. Shibli et al., Zurich, April 2009,
pp.995-1006.
[8] NIMS CREEP DATA SHEET No.48A, 2012
[9] K. Sawada, M. Bauer, F. Kauffmann, P. Mayr, A. Klenk, Mater. Sci. Eng. A527 (2010)
pp.1417-1426.
[10] K. Sawada, K. Maruyama, Y. Hasegawa, T. Muraki, Key Eng. Mater. 171-174 (2000)
pp.109-114.
[11] K. Sawada, H. Hongo, T. Watanabe, M. Tabuchi, Mater. Characterization 61 (2010)
pp.1097-1102.
[12] R. Sugiura, AT Yokobori Jr, M. Tabuchi, T. Yokobori, Eng Fract Mech 74 (2007) pp.868881.
[13] M. Tabuchi, M. Matsui, T. Watanabe, H. Hongo, K. Kubo, F. Abe, Materials Science
Research International 9 (2003) pp.23-28.
614
615
recrystallised regions between weld beads [4]. The final microstructure of the weld is sensitive to
both the welding and PWHT conditions [5,6].
Premature creep failure is a known problem in Grade 92 steel welds, although the reasons for this
are not well understood. Failure is often found to occur in the heat affected zone (HAZ) [7, 8] in
these materials, which is commonly termed Type IV behaviour. In this study, two identical Grade
92 cross-weld creep samples, which were post weld heat treated at different temperatures, are
compared in terms of creep strain rate, creep damage location and microstructural degradation.
EXPERIMENTAL PROCEDURES
Materials and Creep Test Conditions
Two cross-weld samples including the HAZ and the weld metal were obtained from a weld
manufactured in a thick section pipe made from Grade 92 steel. Table 1 shows the compositions
of the Grade 92 steel pipe and weld filler, which is a typical matching filler for the steel. After
fabrication of a Gas Tungsten Arc root, the fill involved a multi-pass SAW process.
Table 1. Composition of the Grade 92 pipe and weld filler (wt. %), balance Fe.
Pipe
Filler
C
0.10
0.11
Si
0.31
0.40
Mn
0.46
0.45
Cr
8.60
8.80
Mo
0.39
0.45
Ni
0.38
0.65
V
0.18
0.20
W
1.76
1.65
Nb
0.06
Quadrants from the weld were heat treated using conditions which were close to the limits
defined in applicable codes. Thus, the two quadrants were heat treated at either 732oC or 760oC.
Cross-weld samples were then machined from each quadrant. A picture of a typical specimen is
shown in Fig. 1. The gauge portion of the cross-weld specimens is 60 mm in both length and
width and 9 mm in thickness. The two cross-weld samples were identified for the different
PWHT temperatures used as WA at 732C and WB at 760C and were held for identical time
periods. The two samples were subsequently creep tested at 625C for approximately 11,000
hours at 80 MPa before the test was interrupted prior to sample failure.
(a)
(b)
Figure 1. A photograph showing the Grade 92 cross-weld test bars before creep testing (a) and a
schematic diagram showing the test bar with the weld position illustrated (b). The dotted lines in
(b) show the cuts made using EDM.
616
Microstructural characterisation
After the creep test the cross-weld samples were sectioned using Electrical Discharge Machining
(EDM) to cut off the head portions and bisect the gauge portion along the centre of the weld as
illustrated in Fig. 1(b). The samples were further cut into 4 quadrants using a Struers Accutom
saw to make the samples a more suitable size for detailed microstructural analysis.
The samples were prepared for analysis using conventional metallographic preparation
procedures. A final extended chemomechanical polishing step using 0.02 m colloidal silica
suspension was used to eliminate surface deformations, which are introduced by the abrasive
polishing stages. All evaluations were performed on the longitudinal/width plane at the mid
thickness of the cross weld samples.
An inverted Reichert-Jung MeF3 optical microscope was used to perform the initial
microstructural characterisation before the detailed investigations undertaken using electron and
ion microscopies. The samples for optical microscopy were etched using Villelas reagent (1 g
picric acid, 5 ml hydrochloric acid and 100 ml methanol) for 10 s, with bright field optical
micrographs collected using a Fujitsu HC-300Z digital camera.
A Carl Zeiss 1530VP Field Emission Gun Scanning Electron Microscope (FEG-SEM) was used
to assess the Laves phase population characteristics in the samples. Images were collected using
a solid state backscatter detector using an accelerating voltage of 10 kV and an aperture size of
60 m. Forty micrographs covering a total area of 27,000 m2 were collected in random locations
in the head portion of the samples to obtain data with high statistical significance.
An FEI Nova 600 Nanolab dual beam Focused Ion Beam (FIB)/FEG-SEM was used to provide a
detailed microstructural overview, electron backscatter diffraction of the matrix, and ion beam
imaging of M 23 C 6 particles. An overview of the microstructure was obtained by collecting low
magnification images with the solid state backscatter detector at 10 kV with a nominal current of
2.1 nA. The high precision piezo-electric stage on the system allowed sequential rows of images
to be collected in a convenient manner. These micrographs were then manually stitched using
standard image processing software to obtain an overview image of the entire gauge portion of
the samples. Ion beam induced secondary electron (SE) micrographs were collected from head
portions of the samples to characterise the number density and the average size of the M 23 C 6
carbides. The ion beam was operated at an accelerating voltage of 30 kV and a current of 50 pA,
with XeF 2 gas flowing to enhance the contrast differential between the carbides and other
microstructural features such as the matrix and Laves phase. Eight micrographs were collected
from random areas covering a total area of 1130 m2 per sample. The particle sizes of M 23 C 6 and
Laves phase were quantified from the appropriate images using UTHSCSA image tool software.
Electron backscatter diffraction (EBSD) maps were collected at 20 kV and a nominal current of
24 nA using an EDAX Hikari camera. Each EBSD map was collected over an area of 50 50
m2 using a step size of 0.1 m and all patterns were indexed against a bcc iron structure file.
RESULTS AND DISCUSSION
Creep Testing
Fig. 2 shows the creep strain rate curves of the two cross-weld samples. Different creep strain
rates at the accelerated creep stage have been observed between the two cross-weld samples with
different PWHT temperatures. WA, which was post weld heat treated at a lower temperature, was
617
found to have a lower creep strain rate than WB. The total creep strain of WB was also found to
be about 30% higher than that of WA at the interruption of the creep tests after 11,000 hours.
1.4
Creep Strain, %
1.2
1
WB
0.8
WA
0.6
0.4
0.2
0
1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Time, hour
15 mm
Figure 3. Macro photograph of sample WA
618
The effect of the specific thermal cycles on microstructure depends on the metallurgical system
being considered and the detailed condition of the base metal. Because the welds were made
using the same process and base metal the microstructural regions present in the HAZ of each
weld was similar. The general features of the weld metal and HAZ are shown in Fig. 3 with
summary description as follows:
i.
Coarse grain region (CGHAZ): Material near the fusion boundary reaches a
temperature well above Ac 3 during welding. Precipitates which constitute the main
obstacle to growth of the austenite grains are dissolved, so that once austenite is formed
the growth of austenite grains is relatively rapid resulting in a coarse grain structure.
In the 912 Cr steels, the region containing relatively coarse grained austenite
transforms into martensite on cooling under typical conditions, Fig. 4a.
ii.
Fine grain region (FGHAZ): As the distance from the fusion line increases the peak
temperature during welding decreases. In the FGHAZ, the peak temperature is above
Ac 3 , resulting in complete transformation to austenite. However, this temperature is not
sufficient to dissolve all of the precipitates present. Thus, austenite grain growth is
limited by the incomplete dissolution of carbides, nitrides or carbo-nitrides. The fine
grained austenite produced will mostly transform to martensite in the 912 Cr steels
under typical cooling. In locations where the prior austenite grain size is very small, the
ability of these very fine grains to undergo a fully shear type transformation may be
limited. The typical microstructure is shown in Fig. 4b.
iii.
Intercritical region (ICHAZ): In this region the peak temperature exceeds Ac 1 but not
Ac 3 . Thus there will be some new austenite formed during the heating cycle. Some of
the precipitates may dissolve but the combination of time and temperature is
insufficient for complete dissolution of all precipitates. There will thus be only a partial
reversion to austenite on heating. This new austenite will predominantly transform to
martensite on cooling, but it should be emphasized that the description intercritical
can be used to describe a wide range of conditions. There is some variation of specific
microstructural features within an intercritical region.
iv.
Highly tempered region: Adjacent to the parent, the time and temperature
combination will modify the local substructure. In creep strength enhanced ferritic
(CSEF) steels this modification may relate to changes in precipitates and/or the locally
high dislocation density. In either case, these changes are not easily resolved using
optical metallography and can only be discerned using advanced electron optics.
(a)
(b)
350 m
350 m
Figure 4. Micro photographs of the HAZ in sample WA showing the coarse grained structure (a)
and the fine grained structure (b)
619
Low magnification backscatter electron micrographs were collected across the entire prepared
surface of both welds to provide a microstructural overview of the cross-weld samples. These
images were stitched together and are displayed as a montage in Figures 5 and 6. These
microstructural maps enable the different regions of the sample such as parent metal, weld metal
and the root beads to be clearly defined in both WA and WB.
The location of primary creep damage can be seen to occur in different areas of the two weld
samples. In WA, two cracks with lengths of ~20 mm were observed in the HAZ parallel to the
fusion line, approximately 2 mm from the weld/metal interface (Fig. 5a and Fig. 5b). However,
in WB a crack about 25 mm long was observed at the centre of the weld metal (Fig. 6c).
The microstructure in both the HAZ and in the weld metal of both welds was heterogeneous. In
the weld metal, regions with a fine grain structure were found between the regions with a
columnar coarse grain structure: typical examples of these areas are shown in Fig. 7 for WA.
These fine grain regions were found to be aligned along the axis of the weld within the weld
metal and are possibly caused by the re-tempering of weld beads during the multi-pass welding
process. In the regions away from the major cracks, creep cavities were also observed in the HAZ
and in particular the fine grain regions in both WA and WB. Fig. 8 shows typical examples of the
cavities observed in the HAZ and the fine grain regions in WA. Most of the observed cavities are
non-spherical and are typically 2-3 m in diameter.
Parent
metal
Weld metal
6 m
Figure 5. A montage of systematically collected backscatter electron micrographs showing the
entire gauge portion of WA.
620
Parent
metal
Parent
metal
Weld metal
Weld metal
Weld metal
Parent
metal
Weld metal
Parent
metal
6 m
621
(a)
(b)
100
100 m
Figure 7. Backscatter electron micrographs showing the coarse grained (a) and fine grained
regions (b) in the weld metal in WA.
(a)
(b)
20 m
20 m
Figure 8. Backscatter electron micrographs showing the cavities (indicated by arrows) in the
HAZ (a) and the fine grain region in the weld metal (b) in WA.
Comparisons of base metal in specimen head and gauge
The weld samples possessed heterogeneous microstructures, which depend on the local thermal
effects during fabrication. This heterogeneity complicates the direct comparison between the two
samples with different PWHT temperatures. To overcome this problem and assess quantitatively
the effect of the PWHT temperature on microstructure, head portions of the creep samples (i.e.
containing the parent steel) were analysed. Since head portions are not loaded to the same stress
as the gauge length and both samples were tested for a similar duration it is reasonable that any
microstructural differences observed in the samples can be linked to the different PWHT
temperatures applied.
Fig. 9 shows optical micrographs of the parent metal in the head portion of WA. The matrix
microstructure of the parent metal was found to be predominantly composed of martensitic laths
(Fig. 9a). The lath and prior austenite grain boundaries are outlined by secondary precipitates
which appear dark in the optical micrographs (Fig. 9b).
A quantitative comparison between the parent metal from WA and WB was then carried out to
evaluate the influence of PWHT. Fig. 10 shows EBSD maps that were collected from both
samples to compare the matrix microstructure and the grain boundary properties quantitatively. In
622
Table 2 the low (2-10) and high (>10) angle grain boundary lengths per unit area for both
samples are compared.
(a)
(b)
100 m
25 m
Figure 9. Optical micrographs of the parent metal in the head portion of WA.
(a)
(b)
(c)
(d)
Figure 10. EBSD derived inverse pole figure (IPF) ((a), (c)) and grain boundary maps ((b), (d))
obtained from WA ((a) and (b)) and WB ((c) and (d)). In the grain boundary maps low angle
grain boundaries (2-10) are shown in red and high angle grain boundaries (>10) are shown
in blue.
623
Table 2. Total lengths of low (2-10) and high (10-180) angle boundaries in the parent
material of WA and WB collected in a 50 m 50 m area.
Sample
Low angle (2-10)
High angle (>10)
WA
3.46
4.34
WB
1.75
3.94
The total low angle boundary length in WA was found to be significantly higher than that in WB,
whereas the high angle boundary lengths in the two samples are similar. It is significant that the
sample exposed to the higher PWHT temperature, WB, has undergone increased matrix recovery
(reduced low angle boundary length), which would be expected to result in reduced creep
strength.
Fig. 9a and Fig. 9b show ion beam induced SE images of the M 23 C 6 particles collected in the
parent material of WA and WB respectively. The population densities and average size of the
particles were measured from eight separate images and are compared as shown in Fig. 10a and
Fig. 10b. This analysis showed that the size and number of M 23 C 6 particles was similar for both
samples. The insensitivity of the M 23 C 6 carbides to the variation in PWHT temperature may be
attributable to the addition of B in Grade 92 steel [9].
(a)
(b)
4 m
4 m
(c)
(d)
6 m
6 m
Figure 11. Example micrographs showing the presence of (a), (b): the M 23 C 6 carbides (dark)
and (c), (d): Laves (white) in the parent materials of WA ((a) and (c)) and WB ((b) and (d)).
Fig. 9c and Fig. 9d show the back scatter electron images collected in the parent material of WA
and WB. The bright particles in the images are Laves phase particles and again their average size
and number density were quantified and are compared as shown in Fig. 10c and Fig. 10d. This
624
analysis showed that more Laves phase particles, but with a smaller average size are formed in
WA compared with WB. This difference could be significant because an increased size of the
Laves phase particles is expected to be a factor that contributes to the observed increased creep
strain rate in the sample exposed to the PWHT at the higher temperature.
In addition, the effect of the PWHT temperature on the fine intragranular MX/M 2 X carbonitrides
is likely to be important and studies to quantify these differences are currently being undertaken.
In addition the examination of weld samples at a lower fraction of life (which are free from large
scale creep damage) are planned to provide an opportunity for the trends observed here to be
verified.
400
300
200
325
100
(a) 0
500
Particle number per image
0.15
WA
293
0.2
300
420
364
100
(c) 0
WA
0.05
(b) 0
WB
400
200
0.1
500
WA
0.10
WB
0.15
0.1
0.05
(d) 0
WB
0.098
0.14
WA
0.17
WB
Figure 12. Graphs comparing the number of M 23 C 6 particles (in 141 m2 area) (a), the average
size of M 23 C 6 (b), Laves phase number density (in 668 m2 area) (c) and Laves phase average
size (d) in the head portions of WA and WB. For M 23 C 6 particles the average number of particle
per image (141 m2) and average size were determined from 8 images and the error bars display
the standard deviation between the images. For the Laves particles the average number of
particle per image (668 m2) and average size was determined from 40 images and the error
bars display the standard deviation between the images. The actual values of average size and
particle number are also displayed in the columns of the graph.
CONCLUSIONS
Creep tests showed that the weld with the PWHT at 732C had a significantly lower creep strain
rate compared with the weld with the PWHT at 760C. It was also found that the difference in
creep strain rates was accompanied by a change in the location of primary creep damage; in the
625
lower temperature PWHT it was in the HAZ whereas in the higher PWHT it was in the weld
metal. To understand the influence of PWHT temperature on microstructure, the head portions of
the two cross-weld samples were compared quantitatively. This showed increased degradation of
the microstructure in the samples with the higher PWHT temperature.
ACKNOWLEDGEMENTS
The authors would like to thank EPRI for the support of this project.
REFERENCES
[1] Ennis, P. and Czyrska-Filemonowicz, A., Recent Advances in Creep-resistant Steels for
Power Plant Applications, Sdhan, Vol. 28, (2003), pp. 709-730.
[2] Abe, F., Bainitic and Martensitic Creep-resistant Steels, Current Opinion in Solid State and
Materials Science, Vol. 8, (2004), pp. 305-311.
[3] Richardot, D., et al, The T92/P92 Book, Vallourec-Mannesmann tubes (Boulogne, 2000), pp.
44-46.
[4] Messler, R. W., Principle of Welding: Process, Physics, Chemistry and Metallurgy, John
Wiley (New York, Chichester, 1999), pp. 127-130
[5] Albert, S., Matsui, M., Watanabe, T., Hongo, H., Kubo, K., Tabuchi, M., Variation in the
Type IV Cracking Behaviour of a High Cr Steel Weld with Post Weld Heat Treatment,
International Journal of Pressure Vessels and Piping. Vol. 80, (2003), pp. 405-413.
[6] Cai, G., Andrn, H., Svensson, L., Effect of Cooling After Welding on Microstructure and
Mechanical Properties of 12 Pct Cr Steel Weld Metals, Metallurgical and Materials
Transactions: A, Vol. 28, (2007), pp. 1417-1428.
[7] Francis, J., Mazur, W., Bhadeshia, H., Review Type IV Cracking in Ferritic Power Plant
Steels, Materials Science and Technology, Vol. 22, (2006), pp. 1387-1395.
[8] Kondo, M., Tabuchi, M., Tsukamoto, S., Yin, S., Abe, F., Suppressing Type IV Failure via
Modification of Heat Affected Zone Microstructures using High Boron Content in 9Cr Heat
Resistant Steel Welded Joints, Science and Technology of Welding & Joining, Vol. 11,
(2006), pp. 216-223.
[9] Abe, F., Horiuchi, T., Taneike, M., Sawada, K., Stabilization of Martensitic Microstructure
in Advanced 9Cr Steel During Creep at High Temperature, Materials Science and
Engineering: A, Vol. 378, (2004), pp. 299-303.
626
ABSTRACT
The effects of Cr and W on the creep rupture life of 8.5-11.5Cr steels at 650oC were evaluated.
Throughout this paper the specimen composition is expressed in mass percent. The creep rupture
life of 8.5Cr steel is the longest in 8.5-11.5Cr steels at 650oC under the stress of 78MPa. The
creep rupture life of 9Cr steel at 650oC was extended with increasing W content. The creep
strength of the modified steel, 9Cr-4W-3Co-0.2V-NbBN steel, at 650oC did not decrease sharply
up to 32000h. The 105h creep rupture temperature of this steel under the stress of 100MPa was
estimated to be approximately 635oC using Larson-Miller parameter. M23C6 type carbides and
VX type carbonitrides were observed on the lath boundary of the modified steel. The stability of
these precipitates in the modified steel is likely to suppress the degradation of the long term creep
strength at 650oC.
INTRODUCTION
A much higher thermal efficiency of the coal-fired power station is required for reducing the
amount of CO2 emission and saving natural resources. To raise the temperature and pressure of
the steam is effective to improve the thermal efficiency. High Cr ferritic heat-resistant steels have
been developed for the steam turbine rotor shafts of the coal-fired power plants operated under
the elevated temperature, such as the USC conditions above 600oC[1-3]. However, it is known that
the creep rupture life under the low applied stresses at 600-650oC is much shorter than the
predicted one estimated from the short-term creep data under the high applied stresses [4-8].
Therefore, the accurate data of long-term creep rupture life is strongly demanded.
The recovery of microstructure decreases the long-term creep rupture strength. Some ideas
related to the phenomena are suggested such as Laves phase [6], MX, Z phase [9,10], recovery in
localized area around grain boundary [7-10] and depletion of solid solution strengthening elements
[11]
. However, the detailed mechanism of degradation on microstructure remains unknown. So
far, our group revealed that the fine precipitates of plate-like Laves phase in the laths of
martensite structure early coarsen and disappear with increasing Cr content in high Cr heat
627
resistant steels for steam turbine rotor [12,13]. Coarsening and dissolving of the Laves phase may
promote the recovery of microstructure, resulting in the decreasing of long-term creep rupture
strength. The creep rupture test data for approximately 25000h at 650oC showed that optimum Cr
content for the prevention of decreasing of creep rupture strength is 9% in 8.5-11.5Cr steels [1215]
. The purpose of this study is to reveal optimum Cr content for holding the creep strength high
even around 60000h and the effect of W on creep rupture life of 9Cr steel, creep tests and aging
at 650oC were carried out with the 8.5-11.5Cr steels and modified 9Cr-(2-4)W-0.2V steels. This
W addition is aimed at strengthening by fine plate-like (Fe,Cr)2(Mo,W)-laves phase within lath
[16]
.
EXPERIMENTAL PROCEDURE
Table 1 shows the chemical compositions of the tested steels. The Cr content was varied from
8.5% to 11.5%. The W content in the 9Cr steel was varied from 2% to 4%. The 50kg ingots of
8.5-11.5Cr steels and the 25kg ingots of 2-4W steels were prepared using the vacuum induction
melting method. 50 and 25kg ingots were hot-forged into plates of 35 and 30mm in thickness,
respectively.
After preliminary heat treatment, the quality heat treatment was performed at 1070oC for 5h for
austenitizing, and cooled with cooling rate of 100oC/h, which corresponds to the cooling rate at
the center of turbine rotor shaft forging. Then, the tempering was performed in two states; the
first tempering condition was 570oC for 20h and the second one was 680oC for 20h.
Microstructures of these tested steels were homogeneous tempered martensite except for
11.5%Cr steel with approximately 3% -ferrite in areas. After the quality heat treatment, tensile
test and Charpy impact test were performed at room temperature. Aging treatment and creep
rupture tests under the applied stress of 69MPa to 300MPa at 650oC were performed. The
precipitates and microstructure of the ruptured specimens were observed prior to and after aging
treatments using transmission electron microscope (TEM) equipped with energy dispersive X-ray
spectrometer (EDS). Samples for TEM observation were prepared using thin film method and
replica technique.
Table1
270MPa, the time to rupture of 11.5Cr steel was longer than the other steels. However, the times
to rupture of 11.5Cr steel sharply shortened with decreasing applied stress. The time to rupture of
10-10.5Cr steels also rapidly shortened at the lower applied stress conditions below 157MPa. As
a result, lower Cr content steels such as 8.5Cr steel ruptured at longer time in lower stress region.
The longest rupture time in stress of 98 MPa was 25383h in 9Cr steel. At lower applied stress,
the longest rupture time in stress of 78MPa was 54628h in 8.5Cr steel, which is much longer than
37131h of 9Cr steel. The time to rupture of 8.5Cr steel reached more than 60000h at 650oC under
the applied stress of 69MPa, indicating that the optimum Cr content of 8.5-11.5Cr steel is 8.5%.
629
Reportedly, the disappearance of carbonitrides such as NbX and Cr2X in 10.5Cr steel may
decrease the creep strength in high Cr heat-resistant steels [13]. On the other hand, fine
carbonitrides were observed in 9Cr steel after aging at 650oC for 30000h. On the assumption that
the precipitation behavior of carbonitrides in 8.5Ce steel is not so different from that of 9Cr steel,
fine carbonitrides in 8.5%Cr steel are expected to be remained after long-term aging. Fig.3 shows
the contents of Cr, Nb, and V of carbonitrides observed in 8.5Cr steel aged at 650oC. Fine NbX
and Cr2X were observed just after tempering. After aging for 1000h, VX type of carbonitrides
which were not observed before aging were seen. After aging for 26369h, NbX and VX were
observed and neither Cr2X nor Z phase [17] were observed. Figures 4 and 5 show the TEM
micrographs of the precipitates observed in the grip portions of the creep specimens ruptured at
19034h and 26369h. The fine carbonitrides shown in Fig.4 were NbX and VX. Fig.5 shows that
M23C6 and VX exist on the lines which seemed to be martensite lath boundary. After aging for
26369h, undissolved NbX and a lot of fine VX were still remained. It indicates that M23C6 and
fine carbonitrides such as VX can exist stably for long time in 8.5%Cr steel [13,15], and these fine
precipitates may prevent the martensite lath from coarsening. The long term stability of
precipitates in 8.5Cr steel is one of the reasons that the degradation of long-term creep strength
was not observed in 8.5%Cr steel at 650oC beyond 25000h.
(b)
VX
NbX
100nm
Fig.4 Carbonitrides observed in the specimen aged at 650oC for 19034h on 8.5Cr steel.
(a) NbX, (b) VX.
630
VX
VX
VX
VX
VX
VX
VX
23 C
6
23 C
6
M23C6
M23C 6
23 C
6
C6
M 23
100nm
Fig.5
VX
VX
VX
Fig.6 W content dependencr of tensile strength and 0.2% proof stress at room temperature
and FATT of 9Cr-(2-4)W-0.2V steels.
631
FATT were not recognized regardless of Ni and V content. The effect of W on the creep strength
is shown in Fig.7. Creep rupture life monotonically increased with increasing W content in 2-4W
steels. The stress-time to rupture curves of 2-4W steels and 9.0Cr steel are shown in Fig.8. The
slope of the curve on 9.0Cr steel in a low applied stress region is larger than that in a high applied
stress region. In contrast, remarkably degradation of creep strength was not observed in 2-4W
steels until more than 32000h. A large difference in creep rupture strength between the 4W steel
and 9.0Cr steel was seen at approximately 32000h. These results imply that arrangement of V
and Ni content did not affect the quantity and size of the precipitations which contributes to
initial strengthening, but the quantity or stability of the precipitations which appears during
aging.
633
(a)
(b)
(c)
500nm
100nm
500nm
La
v
es
M2 C
3
M 23C 6
M2 C
3 6
Laves
M2 C
3 6
Fig.11 Microstructures observed in 9Cr-4W-0.2V steel before and after aging for 30000h at
650oC.
(a) martensitic lath structure as tempered
(b) plate-like fine Laves phase in a lath
Lav
es
VX
C6
M 23
M2
La
v
C6
v
La
es
C6
M2
es
Fig.12
M2 C
3 6
23 C
6
C6
M 23
Laths and blocks of martensite can be regarded as elongated subgrains. Sub-boundary plays a
very important role to increase the long-term creep strength in a high Cr heat resistant ferritic
steel with tempered martensite structure. The relationship between sub-boundary hardening sg
and subgrain width sg corresponding to the lath width is given by the following equation [19].
sg=10Gb/sg,
634
Where G and b are the shear modulus and the magnitude of Burgers vector, respectively. This
equation indicates that the small lath width yields the large sub-boundary hardening. Because the
precipitates of VX besides M23C6 along lath boundaries avoid the lath from coarsening, it is
thought that the drop of long-term creep strength was not appeared in the modified steel.
SUMMARY
In order to reveal optimum Cr content for holding the creep strength high even around 60000h,
and the effect of W on creep rupture life of 9Cr steel, creep tests and aging at 650oC were carried
out with the 8.5-11.5Cr steels and 9Cr-(2-4)W-0.2V steels. The main findings obtained are
shown below.
(i)
The creep rupture life of 8.5Cr steel is the longest in 8.5-11.5Cr steels under the stress of
69MPa and 78MPa. The creep rupture life of 8.5Cr steel reached more than 60000h under
the stress of 69MPa.
(ii) VX and M23C6 can remain along the lath boundaries even after aging at 650oC for 25000h.
These precipitates prevent lath from coarsening, creep rupture strength of 8.5Cr steel
would not drop for a long time.
(iii) The creep strength of the modified steels did not decrease rapidly until more than 32000h.
The creep rupture life increased with increasing W content in the 9Cr-(2-4)W-0.2V steels.
(iv) The creep rupture strength of 9Cr-4W-0.2V steel was longest in 9Cr-(2-4)W-0.2V steels.
The estimated temperature at which the time to rupture of the 9Cr-4W-0.2V steel would be
105h under the applied stress of 100MPa was approximately 635oC.
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[1] T. Fujita, Development of High Chromium Ferritic Heat Resistant Steels for Power
Plants, Karyoku-Genshiryoku-Hatsuden, 42(1991), p.1485
[2] Y. Tsuda, M. Yamada, R. Ishii, Y. Tanaka, T. Azuma, and Y. Ikeda, Development of High
Strength 12% Cr Ferritic Steel for Turbine Rotor Operating above 600oC, 13th
International Forgemasters Meeting, Pusan, Korea, (1997), P.417
[3] R. Kaneko, S. Nakamura, Y. Watanabe, Y. Tanaka, T. Fujita, Development of Steam
Turbine Materials at Targeted Temperature 650oC, Karyoku-Genshiryoku -Hatsuden,
46(1995), 968
[4] Y. Hasegawa, T. Muraki, M. Ohgami and H. Mimura, Optimum Tungsten Content in High
Strength 9 to 12% Chromium Containing Creep Resistant Steels, Proceedings of 8th
International Conference on Creep and Fracture of Engineering Materials and Structures,
November 1-5 (1999), p.427
[5] J. Hald, Microstructure Stability of Steels P92 and P122, Proceedings of 3rd Conference
on Advances in Material Technology for Fossil Power Plants, April 5-6 (2001), p.115
[6] F. Abe, Contribution of Tungsten to Microstructure Stabilization and Improvement of
Creep resistance in Simple 9Cr-W Steels, Proceedings of 8th International Conference on
Creep and Fracture of Engineering Materials and Structures, Tsukuba, Japan, (1999), p.395
[7] H. Kushima, K. Kimura and F. Abe, Degradation of Mod. 9Cr-1Mo Steel during long-term
Creep Deformation, Tetsu-to-Hagane, 85 (1999), p.841
[8] M. Igarashi, M. Yoshizawa, A. Iseda, H. Matsuo and T. Kan, Long Term Creep Strength
Degradation in T122/P122 Steels for USC Power Plants, Proc. of 8th Liege Conference on
Materials for Advanced Power Engineering 2006, Liege, Belgium, (2006), p.1095
[9] M. Svoboda, J. Bursik, I. Podstranska, A. Kroupa, V. Sklenicka, and K. H. Mayer, High
Temperature Creep Behaviour and Microstructural Changes of TAF 650 steel Proceedings
of 7th Liege Conference Materials for Advanced Power Engineering 2002, Liege, Belgium,
635
(2002), p.1521
[10] K. Kimura, K. Suzuki, Y. Toda, H. Kushima and F. Abe, Precipitation of Z-Phase and
Degradation Behaviour of Mod.9Cr-1Mo steel, 7th Liege Conference Materials for
Advanced Power Engineering 2002, Liege, Belgium, (2002), P.1171
[11] Y. Kadoya, E. Shimizu, Effect of Co on Creep Deformation and Precipitation Behavior of
High-Cr Ferritic Steels, Tetsu-to-Hagane, 88 (2002), p.539
[12] K. Miki, T. Azuma, T. Ishiguro, R. Hashizume, Y. Murata and M. Morinaga, Effect of Cr
Content on the Creep Strength and Microstructural Change in High Cr Heat Resistant
Steel, 7th Liege Conference Materials for Advanced Power Engineering, Liege, Belgium,
(2002) p.1497
[13] K. Miki, T. Azuma, T. Ishiguro, R. Hashizume, Y. Murata and M. Morinaga, Effect of Cr
on Change of Carbonitrides during Aging in High Cr Heat Resistant Steels, 17th
International Forgemasters Meeting, Santander, Spain, (2008) p.325
[14] R. Hashizume, K. Miki, T. Azuma, T. Ishiguro, Y. Murata and M. Morinaga, Optimization
of Cr Content in High Cr Heat Resistant Steels on the Basis of Long Term Creep Strength,
Tetsu-to -Hagane, 88 (2002), p.793
[15] Y. Murata, K. Yamashita, M. Morinaga, T. Hara, K. Miki, T. Azuma, T. Ishiguro and R.
Hashizume, Effect of Cr on Change of Carbonitrides during Aging in High Cr Heat
Resistant Steels, Journal of Solid mechanics and Materials Engineering, 3 (2009) p.457
[16] Y. Murata, M. Morinaga, R. Hashizume, K. Takami, T. Azuma, Y. Tanaka and T. Ishiguro,
Effect of Carbon Content on the Mechanical Properties of 10Cr-5W Ferritic Steels, Mat.
Sci. and Eng., A282 (2000), p.251
[17] A. Strang and V. Vodarek, Z Phase Formation in Martensitic 12CrMoVNb Steel, Mater.
Sci. Technol., 12 (1996), 552.
[18] F. Abe, Coarsening Behavior of Lath and Its Effect on Creep Rates in Tempered
Martensitic 9CrW Steels, Mater. Sci. Eng. A, 387-389 (2004) P.565
[19] K. Maruyama, K. Sawada and J. Koike, Strengthening Mechanisms of Creep Resistant
Tempered Martensitic Steel, ISIJ-Int. 41 (2001) p.641
636
ABSTRACT
Recovery of microstructure and void formation were investigated in creep-ruptured specimens of
ASME Gr. T91 steels to understand the cause of loss of creep rupture ductility in the long-term
creep condition and its heat-to-heat variation. The specimens studied were two heats (MGA,
MGC) of Gr. T91 steels creep-ruptured at 600 C under the stress conditions of 160-80 MPa. The
reduction of area at rupture (RA) was 55% for MGA, but 83% for MGC in the long-term
condition (under the creep stress of 80 MPa), while RA was higher than 80 % for the two heats in
the short-term conditions (under the creep stresses above 100 MPa). In both heats, equiaxed
grains were observed in the vicinity of ruptured surface in the long-term condition, indicating that
recovery and recrystallization occurred extensively in the creep condition, while grains were
elongated in the short-term conditions. In the uniformly deformed regions with a small area
reduction in the long-term crept specimens, recovered and recrystallized grains were observed in
the limited region close to high angle grain boundaries in MGA, while they were extended into
grain interiors in MGC. In the long-term creep conditions two types of voids were observed: fine
ones with a diameter below 1 m and coarse ones with a diameter from 2 m up to 50 m. Fine
creep voids were found to grow with necking in MGA while they neither nucleated nor grew with
necking in MGC. Coarse creep voids increased in size and in number with necking in both heats
and were larger and denser in MGA than in MGC.
INTRODUCTION
It is well known that creep strength enhanced ferritic (CSEF) steels show a breakdown in creep
rupture strength in the long-term creep conditions, and extensive efforts have been made on the
characterization of a change in microstructure with creep deformation and the re-evaluation of
long-term creep strength [1-3]. The drastic loss of creep rupture ductility in the long-term
conditions has also become apparent on CSEF steels and is considered as a serious issue that is
related to the reliability of power plant operation [4, 5].
The loss of creep rupture ductility in the long-term creep conditions has been reported in a variety
of ferritic heat resistant steels such as CrMoV steels, 2.25Cr-1Mo steels, ASME Gr. 91 steels,
ASME Gr. 92 steels and ASME Gr. 122 steels [6-12]. The conditions in which the loss of
ductility takes place and the degree of the ductility loss depend on the temperature of creep tests
and the type of steel grades, and vary from heat to heat even in the same steel grade. The recovery
of the ductility in further long-term conditions was also reported to occur.
637
A number of researches investigated the nucleation/growth of creep voids and creep deformation
mechanism map to rationalize the loss of creep ductility [13-17]. These aspects, however, cannot
explain the origin of different behaviors between steel grades and heats as well as the dependence
of creep rupture ductility on the creep stress/time. On the other hand, some studies investigated
microstructures in creep ruptured samples and indicated that the loss of ductility is caused by
local recovery at prior austenite grain boundaries [8, 9, 11] and by coarsening of precipitates [12].
A recent work by Gupta et al. [18] showed the shape of creep voids in three dimensions using a
non-destructive way and serial sectioning. However, the cause of the loss of creep ductility in the
long-term and its dependence on stress/time and on the chemical compositions are not fully
understood.
Our creep research at National Institute for Materials Science recently found that the ASME
Gr.T91 steels show a heat-to-heat variation in creep rupture ductility in the long-term conditions
[9]. The objective of the present study is to investigate into recovery of microstructure and void
formation in creep-ruptured specimens of the ASME Gr.T91 steels to understand the cause of loss
of creep rupture ductility in the long-term creep condition and its heat-to-heat variation.
EXPERIMENTALS
The specimens studied were two heats (MGA, MGC) of Gr.T91 steels creep-ruptured at 600 C
under the stress conditions of 160, 140, 120, 100 and 80MPa. The chemical compositions of the
specimen and the heat treatment conditions performed to the specimens are listed in Table 1 and
Table 2, respectively. The reduction of area at rupture (RA) was 55% for MGA, but 83% for
MGC in the long-term condition under the initial stress of 80 MPa, while RA was more than 80 %
for the two heats in the short-term conditions under the creep stress conditions of above 100 MPa.
The ruptured samples were cut into halves in a way that the cross section includes the creep stress
axis. The microstructures and the voids were observed in the creep-ruptured specimens at areas
with different levels of area reduction on the cross section. The area reduction at the region
observed, which is designated as AR to distinguish with RA through the present paper, was
calculated by the following equation.
AR = 1/(d/d 0 )2
Where d is the diameter of crept sample at observed areas and d 0 is the initial diameter, 6 mm.
The microstructures and voids were examined by optical microscope (OM) and high resolution
scanning electron microscopy (HRSEM), which is equipped with a backscattered electron (BSE)
detector and an electron backscattered diffraction (EBSD) detector, and transmission electron
microscopy (TEM). The crystallographic orientations of the matrix phases were identified by
EBSD pattern analysis. The hardness was measured with a Vickers Hardness tester.
The cross sections were prepared by grinding, mechanical polishing down to 1 m-sized Al 2 O 3
oxide polishing suspension, chemical polishing with SiO 2 oxide polishing suspension (OPS) and
electro-polishing. The observations with OM and HRSEM were made before and after electropolishing. EBSD patterns were acquired after electro-polishing and analyzed with an Orientation
Imaging Microscopy (OIM) software. Thin foils for TEM observations were prepared by
punching a 3 mm-sized disc from a thin plate cut from the ruptured specimens, mechanical
polishing and electro-polishing. Hardness was measured under the condition of 500 gf at room
temperature.
638
Heat
Si
Mn
Ni
Cr
Mo
Al
Nb
MGA
0.10 0.38 0.40 0.015 0.001 0.12 8.53 0.96 0.21 0.010 0.050 0.076
MGC
0.09 0.29 0.35 0.009 0.002 0.28 8.70 0.90 0.22 0.001 0.044 0.072
Table 2: Heat treatment conditions of the Gr.T91 steels studied and hardness at room
temperature for the as tempered condition of the steels.
Heat
Thermal history
MGA
1045C/10min AC + 780C/60min AC
MGC
1050C/10min AC + 765C/30min AC
Reduction of area, RA / %
90
80
70
60
50
40
30
20
MGA
MGC
10
0
100
1000
10000
100000
Rupture time / h
Figure 1: RA vs. creep rupture time plot for the two heats of Gr. 91 steels The plots of MGA are
for 200 MPa, 160 MPa, 140 MPa, 120 MPa, 100 MPa and 80 MPa from short time to long time,
those of MGC are for 200 MPa, 160 MPa, 140 MPa, 120 MPa, 100 MPa, 80 MPa and 70 MPa
[19] from short time to long time.
639
(a)
(b)
Stress
axis
(c)
Figure 2: Optical micrographs showing ruptured areas of MGA specimens creep-ruptured under
the stress conditions of (a) 160 MPa, (b) 120 MPa and (c) 80 MPa.
(a)
(b)
Stress
axis
(c)
Figure 3: Optical micrographs showing ruptured areas of MGC specimens creep-ruptured under
the stress conditions of (a) 160 MPa, (b) 120 MPa and (c) 80 MPa.
640
3 mm
(b)
Voids
Indent
3 mm
Figure 4: Optical micrographs of cross sections of ruptured specimens creep-ruptured under the
stress condition of 80 MPa: (a) MGA, (b) MGC. Voids and indents are seen on the micrographs.
Recovery of microstructures
Figure 5 shows EBSD boundary maps taken from areas with an AR of 7 % in the specimens
creep-ruptured at a stress of 80 MPa. Significant differences in the boundary structures are not
recognized although the microstructure looks somewhat more equiaxed in MGC. A difference in
the microstructure was, however, clearly recognized in TEM observations. Figure 6 shows TEM
bright field images of the specimens taken from areas with a low AR value of 7 %. It is seen in
MGA that individual dislocations are tangled with fine precipitates in a packet and equiaxed
grains formed due to recovery are limited in the vicinity of high angle boundaries. In MGC, on the
other hand, equiaxed grains are observed in almost overall the areas. These observations indicate
that recovery of microstructure took place more extensively in MGC than in MGA in the areas
with a low AR value.
641
(a)
(b)
Min
10
Max
180
Stress
axis
Figure 5: EBSD boundary maps taken from areas with an AR of 7 % in the specimens creepruptured under a low stress of 80 MPa. (a) MGA, (b) MGC. Solid lines are for high angle
boundaries with misorientation values between 10 and 180.
(a)
2 m
(b)
2 m
Figure 6: TEM bright field images of the specimens creep-ruptured under a low stress of 80
MPa, taken from areas with an AR of 7 %: (a) MGA, (b) MGC.
Figure 7 shows EBSD high angle boundary maps of the two heats of specimens taken from areas
with relatively high AR values. It is seen that the grain structures are more equiaxed than those at
areas with a low AR value (see also figure 5). The difference in the grain structures between the
two heats is not significant at the areas with the high AR values.
Figure 8 shows changes in hardness of the two heats of specimens as a function of AR at observed
areas. The hardness in both specimens decreases with decreasing AR and reaches to a constant
value of about 155 Hv with a minimum in the case of only MGA. No appreciable difference is
recognized between the heats except in the range of AR values of 30-40 %. The detailed analysis
of EBSD results [20] indicates that the decrease in hardness at low AR values is caused by the
reduction of boundary length per unit area. Hirukawa et al. [21] and Sawada et al. [22] reported
that the hardness was reflected most by block and packet boundaries. The minimum of hardness in
MGA is possibly attributed to low boundary density and/or voids, which are seen in fig. 7 as black
areas. The void formation is explained quantitatively in the next section.
642
25%
34%
41%
(a)
(b)
(c)
26%
34%
42%
(d)
(e)
(f)
Min
10
Max
180
Stress
axis
Figure 7: EBSD boundary maps of the specimens creep-ruptured under a low stress of 80 MPa in
MGA (a-c) and MGC (d-f) taken from an AR of (a) 25 %,(b) 34 %, (c) 41 %, (d) 26 %, (e) 34 %,
(f) 42 %. The value in each map indicates AR at each area. Black areas in (a-c) are creep voids.
MGA
MGC
density and the area fraction of coarse voids as a function of AR, measured before and after
electro-polishing of the two heats. The number density of the voids increases with increasing AR
and is higher in MGA than in MGC. The area fraction of coarse voids also increases when the AR
increases and is higher in MGA than in MGC. It is also recognized that the number density and
the area fraction of the coarse voids increase due to electro-polishing. The increase in the number
density and the area fraction is possibly caused by the occurrence of etching at matrix/void
interfaces during electro-polishing. This result suggests that the quantity and area fraction of voids
might be over-estimated by etching. It should be considered that etching influences on the
quantitative evaluation of voids when a replica is taken from power-plant pipes etc. in operation,
which are normally prepared after etching on the surface. A question arises: when were the coarse
voids formed? The question is, however, answered by the report by Gupta et al. [18] in which
similar sized coarse voids were observed using a synchrotron technique, which is non-destructive,
in a high chromium ferritic steel creep ruptured under a low stress. It is thus reasonable to
consider that the coarse voids observed in the present study were formed not during polishing but
in creep tests and the creep rupture ductility of the present specimens is closely related to the
formation of the coarse voids.
(a)
5 m (c)
50 m (b)
5 m
Figure 9: An optical micrograph (a) and backscattered electron images (b, c) of the specimens
creep-ruptured under a stress of 80 MPa taken after electro-polishing: (a, b) MGA, AR: 2%, (c)
MGC, AR: 26%.
18
Area fraction / %
800
(a)
16
MGA
MGC
14
12
10
8
6
4
2
0
20
40
60
80
(b)
700
MGA
MGC
600
500
400
300
200
100
0
100
Area reduction, AR / %
20
40
60
80
100
Area reduction, AR / %
Figure 10: The number density (a) and the area fraction (b) of coarse voids formed in the
specimens creep-ruptured under a stress of 80 MPa as a function of area reduction at the area
observed, AR. Small symbols are for the values before electro-polishing and large symbols are
for after electro-polishing.
644
Fine voids are observed in fig. 9(b) and (c). The size of fine void is similar to that of voids
observed in previous reports [7, 12]. It can be seen that the sizes of fine voids are larger in MGA
than in MGC. Fine voids were observed at high angle boundaries including prior austenite grain
boundaries, block boundaries and packet boundaries in MGA, while they were formed also at
recovered/recrystallized grain boundaries in MGC. The number density and the area fraction of
fine voids are shown in Figure 11. In MGA the area fraction of fine voids increases with
increasing AR while the number density stays almost constant. This quantitative result indicates
that fine voids grew with necking in the creep deformation in MGA. In MGC, on the other hand,
the number density of voids decreases when the AR increases and the area fraction is almost
constant through the AR. This result suggests that fine voids neither nucleated nor grew during
necking in the creep deformation in MGC. The number density and the area fraction of fine voids
were not changed before and after electro-polishing.
Area fraction / %
50000
(a)
0.40
MGA
MGC
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
(b)
45000
0.45
MGA
MGC
40000
35000
30000
25000
20000
15000
10000
5000
20
40
60
80
100
Area reduction, AR / %
20
40
60
80
100
Area reduction, AR / %
Figure 11: The number density (a) and the area fraction (b) of fine voids formed in the specimens
creep-ruptured under a stress of 80 MPa as a function of area reduction at the area observed,
AR. Small symbols are for the values before electro-polishing and large symbols are for after
electro-polishing.
CONCLUSIONS
Recovery of microstructure and void formation were investigated in two heats (MGA, MGC) of
ASME Gr. T91 steels creep-ruptured at 600 C under stress conditions of 160-80 MPa. The
conclusions obtained are below:
(1) The reduction of area at rupture (RA) was 55% for MGA but 83% for MGC in the long-term
creep condition (under the creep stress of 80 MPa), while RA was higher than 80 % for the
two heats in the short-term creep conditions (under the creep stresses above100 MPa).
(2) In both heats equiaxed grains were observed in the vicinity of ruptured surface in the longterm condition, indicating that recovery and recrystallization occurred extensively in the creep
condition, while grains were elongated in the short-term conditions.
(3) In the uniformly deformed regions with a small area reduction in the long-term creep-ruptured
specimens, recovered and recrystallized grains were observed in the limited region close to
high angle grain boundaries in MGA, while they were extended into grain interiors in MGC.
645
(4) In the long-term creep condition two types of creep voids were observed: fine ones with a
diameter below 1 m and coarse ones with a diameter from 2 m up to 50 m. Fine voids
were found to grow with necking in MGA while they neither nucleated nor grew with necking
in MGC. Coarse creep voids increased in size and in number with necking in both heats and
were larger and denser in MGA than in MGC.
REFERENCES
[1] Kimura, K., Kushima, H., Abe F., Degradation and assessment of long-term creep strength
of high Cr ferritic creep resistant steels, Int. Conf. on Advances and Optimization of Fossil
Power Plants, Orland, Florida, March 11-13 (2002).
[2] Kimura, K., Sawada, K., Kubo, K., Kushima, H., Long-term creep prediction of high Cr
ferritic creep resistant steels based on degradation mechanisms, Proc. 6th Int. Charles
Parsons Turbine Conf., IOM, (2003).
[3] Maruyama, K., Yoshimi, K., Methodology of creep data analysis for advanced high Cr
ferritic steel, Proc. CREEP 8, CREEP2007-26150, (2007), 631-636.
[4] Holdsworth, S., Developments in the assessment of creep strain and ductility data,
Materials at high temperatures, 21(1) (2004), 25-32.
[5] Hald, J., Creep strength and ductility of 9 to 12% chromium steels, Materials at high
temperatures, 21(1) (2004), 41-46.
[6] Shinya, N., Kyono, J., Kushima, H., Creep Fracture Mechanism Map and Creep Damage of
Cr-Mo-V Rotor Steel, Tetsu-to-Hagane, 92 (2006), 327-333.
[7] NIMS CREEP DATA SHEET Metallographic Atlas of Long-Term Crept Materials No. M-6
(2007).
[8] Kushima, H., Watanabe, T., Murata, M., Kamihira, K., Tanaka, H., Kimura, K.,
Metallographic atlas for 2.25Cr-1Mo steels and degradation due to long-term service at the
elevated temperatures, Proc. ECCC Creep Conference (2005) 223-234.
[9] Kimura, K., Sawada, K., Kushima, H., Toda, Y., Heat-to-heat variation of creep strength
property of grade 91 steel, Proceedings of the ETD Int. Conference on New High Temp.
Materials, (2011) Edt by A.Shibli, European Technology Development, Leatherhead, UK.
pp.1-12.
[10] Zhu, L., Zhao, Q., Gu, H., Lu, Y., Effects of long-term creep at elevated temperatures on
rupture ductility in 9Cr-1Mo-V-Nb-N Steel, J. Mater. Sci. Technol., 14(1998), 226-230.
[11] Kimura, K., Kushima, H., Abe, F., Heterogeneous changes in Microstructure and
degradation behavior of 9Cr-1Mo-V-Nb steel during long term creep, Key Eng. Mater., 171174(2000), 483-490.
[12] Lee, J.S., Armaki, H.G., Maruyama, K., Muraki, T., Asahi, H., Causes of breakdown of
Creep strength in 9Cr-1.8W-0.5Mo-VNb steel, Mat. Sci. Eng. A428(2006), 270-275.
[13] Jones, M.H., Newman, D.P., Sachs, G., Brown, W.F., Effects of variation in normalizing
and tempering procedure on stress rupture strength, creep embrittlement and notch sensitivity
for a Cr-Mo-V and a 17 Cr-4Ni-Cu steel, Trans. ASM, 47(1955), 926-954.
[14] Werner, F.E., Eichelberger, T.W., Hann, E.K., The effect of austenitizing, Tempering and
microstructure on the properties of a Cr-Mo-V steel, Trans. ASM, 52(1960), 376-403.
[15] Stone, P.G., Murray, J.D., Creep ductility of Cr-Mo-V steels, J. Iron Steel Inst.,
203(1965), 1094-1107.
[16] Tipler, H.R., Hopkins, B.E., The creep cavitation of commercial and high-purity Cr-Mo-V
steels, Metal Sci., 10(1976), 47-56.
646
[17] Tu, L.K., Seth, B.B., Effect of composition, strength, and residual elements on toughness
and creep properties of Cr-Mo-V turbine rotors, Metals Tech., 5(1978), 79-91.
[18] Gupta, C., Toda, H., Schlacher, C., Adachi, Y., et al, Study of cavitation behavior in
tempered martensitic steel using synchrotron micro-tomography and serial sectioning
techniques, Mater. Sci. Eng. A564(2013), 525-538.
[19] Sawada, K., Kushima, H., Tabuchi, M., Kimura, K., Microstructural degradation of Gr.91
steel during creep under low stress, Mat. Sci. Eng. A528(2011), 5511-5518.
[20] Kobayashi, S., Sawada, K., Hara, T., Kushima, H., Kimura, K., Stress Dependence and
Heat-to-Heat Variation in Creep Rupture Ductility of ASME Gr.91 Steels (In Japanese),
Report of JSPS 123rd committee on heat resisting materials and alloys, 2012, vol. 53(3), pp.
217-230.
[21] Hirukawa, H., Matsuoka, S., Miyahara, K., Furuya, Y., Nanoscopic strength analysis of
tempered-martensitic steels using atomic force microscopy and nanoindentation, Materials
Letters 58(2004), 321-325.
[22] Sawada, K., Miyahara, K., Kushima, H., Kimura, K., Matsuoka, S., Contribution of
microstructural factors to hardness change during creep exposure in Mod.9Cr-aMo steel,
ISIJ International 45(2005), 1934-1939.
647
ABSTRACT
Grade P92 is presently used in most of the Ultra Super Critical Power Plants. However, it is also
susceptible to the formation of small amounts of ferrite under certain conditions, especially in
heavy-wall components and it can affect short and long term mechanical properties. Additionally,
a guideline for determining ferritic microconstituent content has been developed and is now
established and published as a VdTV data sheet.
The 12 % Cr boiler steel grade VM12-SHC, developed and patented by Vallourec &
Mannesmann, represents the first attempt to comprise both characteristics within one material,
good creep properties and oxidation resistance. The aim of this paper is to generally introduce this
newly developed grade.
In parallel the development and welding of matching filler metals for the martensitic steels P92
and VM12-SHC are presented.
The paper consists of four main chapters:
Chapter I: Effect of microstructure on long term properties of P92 creep resistant steel
Chapter II: VM12-SHC a new 12 % Cr boiler steel
Chapter III: Matching filler metals for the martensitic steels P92
Chapter IV: Matching filler metals for a new martensitic material with 12 % Chrome
VM12-SHC
648
1. INTRODUCTION
Grade 92 is a well established steel from the 9-12 % Cr ferritic-martensitic steel family for power
plant components, developed in the 1990s. During the last twenty years, large amount of reliable
information and experience concerning the material behavior in all manufacturing processes, as
well as the long-term behavior, have been collected. This enables design and use of the grade in
piping systems and boiler construction. However, there are still some open questions which need
to be addressed and more closely investigated.
Typical microstructure of P92 creep resistant steel in initial state is tempered martensite, formed
during the final normalising and tempering heat treatment. This microstructure consists of ferrite
subgrains with a high dislocations density and evenly distributed more or less fine stable
precipitates, which block the movement of subgrain boundaries (M23C6 carbides) and
dislocations (MX carbonitrides) and provide needed creep strength. Nevertheless, small amounts
of ferritic microconstituent, usually referred as -ferrite, have often been identified in initial, as
tempered state or after various manufacturing processes.
In the last decade Vallourec & Mannesmann has initiated an extensive internal study on the effect
of ferritic microconstituent on properties of P92 steel [1]. The aim was to understand the origin, to
establish the corrective measures, to identify the limits and to understand the effect on material
performance. The latest results of the study will be presented in this paper.
2. MATERIALS AND METHODS
The chemical composition range of P92 steel according to ASTM A335 standard is shown in
Table 1. Heat treatment is optimized to achieve optimal balance between high creep rupture
strength, favorable hardness and good toughness. It consists of normalizing, carried out at
temperatures ranging from 1040 to 1080 C, and tempering from 750 to 780 C, depending on the
product dimensions.
Table 1. Chemical composition (wt. %) of P92 steel according to ASTM A335 standard and
composition of two heats investigated.
ASTM
A335
Heat
ASTM
A335
Heat
min.
max.
P92 (I)
P92 (II)
min.
max.
P92 (I)
P92 (II)
C
0.07
0.13
0.10
0.088
N
0.03
0.07
0.0405
0.045
Mn
0.30
0.60
0.48
0.42
Ni
Si
0.020
0.017
0.012
Al
0.40
0.18
0.24
0.02
0.010
0.004
0.010
0.006
0.001
Nb
0.04
0.09
0.056
0.063
0.50
0.22
0.15
W
1.5
2.0
1.71
1.67
Cr
8.50
9.50
9.11
9.31
B
0.001
0.006
0.0029
0.0032
Mo
0.30
0.60
0.47
0.49
Ti
V
0.15
0.25
0.18
0.20
Zr
0.01
0.01
An extensive microstructural investigation program has been performed on wide range of hot
finished pipes (produced via piercing & drawing (Ehrhardt process) or piercing & pilgering
(Mannesmann process)) with outside diameter (OD) up to 1500 mm and wall thickness up to 150
mm. Light optical microscopy (LOM) and scanning electron microscopy (SEM) have been used
on polished and etched (V2A) samples to examine microstructure.
649
Two P92 heats without (P92 (I), OD 304 mm and WT 62 mm) and with 8 vol. % of ferritic
microconstituent (P92(II), OD 375 mm and WT 42.5 mm), Table 1, have been selected for more
detailed investigation, including creep rupture testing. A series of ISO-stress tests were performed
at 110 MPa and temperatures of 600 680 C according to DIN EN ISO 204. Additional creep
testing was performed at 600 and 625 C at different stresses. Additionally, a change in impact
toughness and in hardness was investigated using aged material at 600 C up to 104 h.
3. RESULTS AND DISCUSSION
Microstructure
To achieve an advantageous fully martensitic microstructure of 9 % Cr ferritic/austenitic steels
after normalizing, a proper balance of austenite and ferrite forming elements and a hightemperature stability region of austenite is needed. The 0.1 % C vertical section of the Fe-Cr-C
ternary phase diagram (equilibrium diagram) is shown in Figure 1.
L
L+ a
a
a+ g
g
a + M23C6
a + g + M23C6
a + M7C3
a + s + M23C6
ferrite. It is irreversible and has a smooth and fine appearance in the etched microstructure, as
shown in Figure 2. The volume fraction of this ferritic microconstituent in pipes does not exceed 5
vol. % and mostly is below 3 vol. %.
Figure 3 shows position of P92 steel as defined in the ASTM A335 standard (blue rectangle) in
the Schaeffler diagram for this family of steels, a simplified, empirical diagram widely used for
prediction of microstructure in as welded or as cast condition. The diagram reflects that for
compositions in which the austenite formers (C, N, Ni etc.) are on the lower level and the ferrite
formers (Cr, W, Mo etc.) on the upper level of the composition range, small amount of ferrite will
be present in the microstructure at room temperature. Thus, optimized chemical composition and
proper balance of ferrite and austenite forming elements is needed to reduce -ferrite formation
susceptibility, bearing in mind the effect on other properties.
20 mm
a)
Figure 2: smooth morphology types of ferritic microconstituent in the microstructure of P92 steel
(LOM, V2A etchant).
35
Nieq = Ni+Co+0.5Mn+30C+0.3Cu+25N
30
25
P92(I)
P92(II)
ASTM A335
Austenite (A)
20
15
M+A
A+F
10
M+A+F
Martensite (M)
5
M+F
Ferrite (F)
0
0
10
15
20
25
30
35
40
Creq = Cr+2Si+1.5Mo+5V+5.5Al+1.75Nb+1.5Ti+0.75W
Figure 3: Position of two investigated P92 pipe heats and Grade 92 according to ASTM A 335 in
Schaeffler diagram
651
Additional phenomena which can affect formation of ferritic microconstituent are micro and
macro segregations. Segregation is caused by the rejection of the solutes from a solidified alloy
into the liquid phase, which is a result of a different solubility of solutes in liquid and solid phases
at the equilibrium temperature. For alloying elements with high melting point and sluggish
diffusivity, such as W, Mo, V, Cr, the effect is more pronounced, causing a change in the
solidification mode. In P92 steel the last portion of liquid is significantly enriched in ferrite
formers (W, Mo, V, Cr), which was confirmed by mapping of alloying elements distribution. This
ferrite formed from the last portion of the liquid is very stable and its amount can only be reduced
with very prolonged annealing at high temperatures.
Grade 92 is an air hardenable steel, which CCT diagram is shown on Figure 4. However, for
heavy wall pipes, which in addition exhibit a significant macro segregation in ingots, during
relatively slow cooling down from the normalizing temperature austenite can partially decompose
into ferrite and carbide (diffusional phase transformation). Carbides formed by diffusional
decomposition of austenite are larger and on a larger interparticle distance than carbides
precipitated during tempering of martensite. Typical microstructure morphology of this form of
ferritic microconstituent (speckled and coarse) is shown on Figure 5. This form can occur up to
high volume fractions, depending on the cooling conditions. It is reversible and can be removed
completely by means of a re-heat treatment.
652
50 mm
b)
Stress, MPa
600C
100
1.000
10.000
Rupture time, h
653
100.000
1000
Stress, MPa
625C
100
1.000
10.000
100.000
Rupture time, h
Figure 6: Effect of ferritic microconstituent on creep performance of P92 steel at a) 600 C and
b) 625 C.
No significant differences between two heats have been observed. Creep rupture data at 600 C
for both heats are on or near the mean line of ECCC assessment. Only for the longest tests of both
heats (up to 70000 h) at the stress level of 110 MPa the test samples ruptured before reaching the
mean ECCC curve, however still well within the scatter band. This is in agreement with creep
behavior of Grade 92 observed in other studies. Similar behavior has been observed at 625 C.
Creep rupture ductility of two heats has also been studied and compared to available data of
Grade 92. Both, creep rupture elongation and reduction of area are within the scatter band for
Grade 92. Higher creep rupture ductility was observed for heat P92 (II) with 8 vol. % of ferritic
microconstituent than that of heat P92 (I).
Guideline for determining content of ferritic microconstituent
V & M Tubes prepared, in cooperation with other companies and German notifying body
association VdTV, within a working group "Materials Technical Issues" a Guideline for
determining content of ferritic microconstituent in seamless pipes, tubes and forgings of creepresistant ferritic/martensitic 912 % Cr steels by comparison method [2]. The guideline is at
present available in German and an English issue is in preparation.
The aim of the a.m. manual is to offer a quicker and sufficiently accurate method, a harmonized
procedure for determining ferritic microconstituent content in creep-resistant ferritic/martensitic
9-12 % Cr steels pipes, tubes and forgings, which is performed manually by using a series of
graded reference micrographs for the comparison method. The manual does not replace the
standard test method for determining the volume fraction of phases (ASTM E 562), which has
supremacy in any case of discrepancy. It is less time consuming and less tedious than the
standardised stereological method, and therefore more convenient for a daily business and less
biased than a subjective estimation of metallographers. The method is applicable independently
from the form of ferritic microconstituent. Two series of the reference micrographs,
654
corresponding to the two morphology types: fine (F) and coarse (C) grained ferritic
microconstituent morphologies, have been prepared. The guideline gives recommendations for
obtaining clearly distinguishable microconstituents and describes the documentation of ferritic
microconstituent content evaluation.
CHAPTER II: VM12-SHC A NEW 12 % CR BOILER STEEL
1. INTRODUCTION
The main driver for the further development of the power plant technology is the increase of the
operating efficiency, which on the one hand leads to limitation of fuel consumption and operating
costs and on the other hand reduces the CO2 emissions. The improvement of the efficiency in
fossil-fired steam power plants can only be achieved by further increase of steam parameters:
pressure and temperature. The realization of elevated steam parameters can happen by
application/development of materials with improved capabilities with regard to creep rupture
strength and oxidation properties.
Further improvement of thermal efficiency is aspired to meet demand for improved cost
effectiveness, but also to respond to the demands coming from the politics to reduce the CO2
emissions. Increasing the temperature application range of ferritic/martensitic grades to 630 or
even 650 C requires improved oxidation properties, which can only be achieved by an increase
of chromium content from 9 to 12 %. First attempts have been made to combine good creep
properties and oxidation resistance by introducing W modified 12 % Cr steel grades HCM12A
and VM12-SHC.
The general purpose of this paper is to introduce the newly developed boiler steel VM12-SHC, to
present its mechanical properties including creep test results, to describe the oxidation behavior in
steam atmospheres and to show its application in fossil-fired power plants.
2. MATERIALS AND TESTING METHODS
The chemical composition range of VM12-SHC is given in Table 2 and compared with steel
grades T/P91, T/P92 and X20CrMoV11-1. V&M aimed to develop a steel grade, which is
characterized by high oxidation resistance (comparable to X20CrMoV11-1), while keeping good
creep properties of conventional 9 % Cr steels. Since the oxidation behavior of 12 % Cr steels is
superior to that of 9 % Cr steels at elevated temperatures (> 600 C), the minimum chromium
content of the newly developed steel had been fixed to at least 11 %. The creep strength was
supposed to be attained by precipitation hardening by MX. Additional strengthening effects were
achieved by optimized additions of W, Co and B.
655
Table2: Chemical composition of VM12-SHC steel in comparison with T/P91, T/P91 and
X20CrMoV11-1
Chemical Composition (%)
Steel grade
Mn
Si
VM12-SHC
0,10
0,14
0,15
0,45
max.
max.
0,02
0,01
0,40
0,60
T/P91*
0,08
0,12
0,3
0,60
max.
max.
0,02
0,01
0,20
0,50
T/P92*
0,07
0,13
0,30
0,60
max.
max.
max.
0,02
0,01
0,50
X20CrMoV11-1*
0,17
0,23
max.
max.
max.
0,15
1,00
0,025
0,02
0,50
Cu
Cr
Mo
Ni
0,20
0,30
0,10
0,40
0,003
0,006
max.
max
8,00
9,50
0,85
1,05
0,18
0,25
8,50
9,50
0,30
0,60
0,15
0,25
max. 10,00
0,30 12,50
0,80
1,20
0,25
0,35
0,30
0,40
max
0,001
0,40
0,006
Co
Al
Nb
0,030 1,40
0,070 1,80
max.
1,30
1,70
0,03
0,08
0,030
0,070
max.
0,030
0,070
max.
1,50
0,04
2,00
0,02
0,06
0,100
0,04
0,30
max.
0,80
0,04
0,040
0,090
*) acc. to EN10216-2
The alloying design was reviewed and verified on the basis of 7 lab heats. Since the qualification
results obtained on the lab heats were satisfying, the industrialization of the new steel under the
name VM12-SHC has been launched [3]. The industrial tubular products have been subjected to
extensive qualification program, which included the determination of the optimum heat-treatment
(tempering curves), the metallographic investigation, the testing of mechanical properties
including creep tests, the performance of welding experiments and the testing of cold bending
properties. The results of the qualification program are presented in the following chapter.
3. RESULTS AND DISCUSSION
The Cr and Ni equivalents of the first 3 industrial heats are represented in Figure 7. All industrial
heats are near the point, where martensite, austenite and ferrite fields meet. Based on the
Schaeffler diagram one might expect some -ferrite and retained austenite in the microstructure.
35
Heat 1
Heat 2
30
Nickel-Equivalent
Heat 3
25
Austenite (A)
20
A+M
15
A+F
10
Martensite
A+M+F
Ferrite (F)
M+F
0
10
15
20
25
30
35
40
Chromium-Equivalent
However, microstructural investigation revealed that after the final heat-treatment low levels of ferrite below 2 % exist and no austenite (Figure 8). This low amount of -ferrite has no adverse
effect on the rolling behavior and mechanical properties of the steel.
Figure 8: Typical microstructure of VM12-SHC tube material after heat treatment (Tube OD 38 x
6.3mm)
VM12-SHC is used in the heat-treated condition. The typical heat-treatment consists of
normalization (1040 1080 C air cooling) and tempering (740 800 C air cooling).
Yield and tensile strength at room and elevated temperatures are located above the minimum
values of T/P92 indicating that the tensile properties of both grades are very similar.
VM12-SHC is characterized by excellent toughness properties, which are reflected in room
temperature Charpy V-notch impact energy in the range of 100 J.
The creep qualification program comprises the testing in the temperature range between 525 C
and 700 C. 155 specimens have been tested. 10 experiments are still running. The longest test
duration is 35238 h at 575 C. Figure 9 represents a comparison of the ASME allowable stress
values for VM12-SHC with that of T92, T91 and T122. The time-dependant allowable stress
values of VM12-SHC are better than that of T91 or T122, but slightly below the values of T92.
657
200
180
160
140
120
100
80
60
VM12-SHC
T122
40
T91
20
0
T92
0
100
200
300
400
500
600
700
Temperature in C
Figure 9: ASME allowable stress values for VM12-SHC steel in comparison with T91, T92 and
T122 (F and ksi converted in C and MPa)
The oxidation experiments were performed at 600 C and 650 C in pure water vapor (tests done
at Ecole des Mines, Douai, France). The test results at 650 C are presented in Figure 10. For
comparison the T91, T92 and TP347FG material was tested as well. The steam oxidation
resistance of VM12-SHC is comparable with that of the austenitic steel TP347FG and
significantly better than that of T91 and T92.
120,00
650C
100,00
T91
80,00
T91
T92
T92
60,00
VM12SHC
VM12SHC
VM12SHC
40,00
VM12SHC Lab
VM12SHC
TP347
20,00
0,00
TP347
1000
2000
3000
4000
5000
6000
7000
8000
9000
Time [h]
Figure 10: Oxidation behavior of VM12-SHC in steam at 650 C in comparison to T/P91, T/P92
and the austenitic grade TP347FG. (adapted from [4])
Welding consumables and welding procedure specifications for VM12-SHC are qualified and
available. Cold bending experiments were performed on tube material. No cracking was observed.
All requirements with respect to microstructure and hardness in as bent condition and after stress
658
relief treatment at 750 C are met. Creep tests on samples from bends showed similar rupture
times to those obtained on mother tube.
V&M is undertaking strong efforts to include this new steel grade into standards. The VdTV
data sheet was issued in 2009 and the ASME code case is expected to be published in summer
2013. Currently the new grade is widely used in reheaters and superheaters of modern boilers in
Europe. In addition, VM12-SHC is applied as replacement for the old 12 % Cr steel
X20CrMoV11-1 during revamping of old power plants. Very recently, the steel was used in heatrecovery steam generator (HRSG) boiler of combined cycle gas turbine (CCGT) plant Irsching
IV.
CHAPTER III: MATCHING FILLER METALS FOR THE MARTENSITIC STEELS P92
Almost parallel to the development of the base material P92 came the development of welding
fillers of the same composition for GTAW, SMAW, SAW and flux cored arc welding (FCW).
The properties of these welding materials have been the subject of numerous publications [5 9].
At this point therefore it may suffice to mention that, besides precisely controlled additions of the
creep-relevant alloying elements C, V, Nb, N, B and W, what requires particularly close attention,
is the heat control during welding.
The martensitic steel P92 is welded in the martensitic temperature range, i. e. at between 250 and
350 C [10]. Because of the martensitic microstructure, temperature control during welding and
during the PWHT must be carried out with the utmost care.
After welding, the weld metal hardness lies at around 400 HV10. This is reduced to about 250
HV10 by the PWHT, recommended at 760 - 770 C. The holding time depends on the wall
thickness and the welding process.
Due to this relatively low hardness level, the risk of cold cracking in the welded condition is
reduced, so components with low residual stresses may be cooled down to room temperature after
welding. However, they must be stored dry and free from external loads also during transport.
Under this condition there is no time limit between welding and PWHT from the metallurgical
point of view.
Power plant operators and supervisory agencies attach great importance to maximum toughness
properties of the welding filler metals. Metallurgically, however, there is not much scope with the
martensitic grades for raising the impact energy of SMA- and SA-weld metals to a level
significantly above 47 J. The toughness of these weld metals can be influenced to a certain extent
via the selection of the welding and heat treatment parameters. Here it is important to cool down
the welded joint below the martensite finish temperature (Mf) before the heat treatment to ensure
complete transformation to martensite. The Mf temperature for the welding fillers of the same
composition as P92 lies at approximately 150 C, so the welded joint must be cooled to at least
100 C [10]. As an additional safeguard against hydrogen-induced cold cracking, the material can
be soaked immediately after welding (250 to 350 C, soaking time 2 3 h) to allow the
hydrogen to diffuse. This is not necessary at thin wall thickness and welding with the GTAW or
GMAW process.
659
Figure 11 is a schematic illustration of heat control during welding and PWHT. Keeping the
welding passes thin will improve the joint toughness; the thinner the individual passes, the greater
the tempering effect. This must be taken into account especially in submerged-arc welding.
Nb
SMAW
4.0 mm
0.11
0.27
0.65
8.95
0.70
0.53
0.19
1.72
0.044
0.04
30
ppm
SAW
Wire 3.2 mm
0.09
0.36
0.60
8.45
0.73
0.41
0.17
1.57
0.04
0.05
32
ppm
Mechanical properties
Pure deposited metal at RT
Welding process
PWHT
C/h
SMAW
760/2
4.0 mm
SAW
760/4
Wire 3.2 mm
YS
MPa
TS
MPa
A5
%
CVN (ISO-V)
J
675
800
17.6
50 / 55 / 58
621
742
20.8
57 / 61 / 41
Figure 12 shows the dependency of the notched bar impact value on the conditions of the PWHT
for the weld metal matching the base material P92.
660
Figure 12: Influence of the PWHT-condition to the toughness of the all weld metal for P92
Figure 13 shows the notch bar impact values of all weld metals aged at 600 C. After 1000 h
holding time at 600 C the CVN-values at RT drops down from >41 J to 25 J. This behaviour is
well known from other CrMo-steels and should take into consideration at the pressure test after
repair welds of used pipes.
Figure 13: Toughness of the all weld metal for P92 after aging. Aging treatment at 600 C;
SMAW-all weld metal for P92
Different pipe joints were welded in the scope of the weld metal development and qualification
measures.
Table 4 summarizes the results of a procedure qualification test [6].
661
CVN (ISO-V)
J
Hardness
HV10
60 / 58 / 62
236 262
84 / 88 / 96
234 249
Si
0.3
0.3
Mn
0.81
0.36
Cr
8.5
8.4
Mo
0.5
0.5
Ni
0.65
0.41
V
0.2
0.2
Nb
0.04
0.04
W
1.6
1.6
N
0.04
0.04
Mn+Ni
1.46
0.77
Ac1
776 C
818 C
Table 6: Mechanical properties for all weld metal (SMAW) matching P92 with different content
of Mn+Ni (PWHT: 760 C/2 h)
Mn+Ni
wt. %
max. 1.5
0.81+0.65=1.46
0.36+0.41=0.77
Test Temp.
C
+20
+20
+20
YS
MPa
min. 440
633
613
TS
MPa
min. 620
761
744
Elongation
%
min. 15
16.5
16.1
CVN
J
min. 41
50
22
Figure 14 shows the influence of the PWHT-temperature to the hardness of the all weld metal
with Mn+Ni = 1.43 %, which means the Ac1-temperature is 776 C. This figure shows that there
is no negative effect on a small overlapping of Ac1 at the PWHT. Above 780 790 C the
hardness increase, which means the PWHT at temperature higher than 10 C above Ac1 create
Austenite which transform to untempered martensite after the PWHT. On-going creep tests shows
that there is no negative effect to the creep strength if there is only a small overlapping of 10 to 15
C above Ac1. There is no need to limit Mn+Ni from max. 1.5 to 1.2 %. But it is very important
that the PWHT-temperature is measured exactly at the pipe and the scatter band of the
temperature range is small. The PWHT-temperature 760 C 10 C can be recommended if
Mn+Ni is max. 1.5 %. For lower Mn+Ni than 1.5 % higher PWHT than 760 C can be used.
In the tests on P92 joints, all the rupture points at 600 C were within the scatter band of the base
material. At higher temperatures, however, some of the rupture points were located outside the
scatter band, and at high stresses and test periods <20,000 h at few isolated ruptures were found in
the weld metal. Specimens subjected to extended testing >20,000 h suffered creep ruptures in the
heat-affected zone. At 650 C, all the ruptures were located in the heat-affected zone [6, 9].
663
Si
Mn
Cr
Mo
Ni
Nb
Co
Al
min.
0.10
0.40
0.15
11.0
0.20
0.10
1.30
0.20
0.03
0.0030
1.40
0.030
---
max.
0.14
0.50
0.45
12.0
0.40
0.40
1.70
0.30
0.08
0.0060
1.80
0.007
0.020
0.12
0.4
0.5
11
0.3
0.4
1.5
0.2
0.04
0.0010
1.5
0.03
---
Base metal
VM12-SHC
FM
(GTA,
GMA, SMA)
Weld process
Base metal
requirements
GTAW: 2.4 mm
SMAW: 4.0 mm
Test
Temp.
C
+20
+20
+20
PWHT
C/h
760
800
770/2
770/2
YS
MPa
>450
684
689
TS
MPa
620
850
822
832
El
%
CVN
(ISO-V)
J
Hardness
HV10
>17
27 / 40
<260
18.5
17.2
44
44
<297
<281
Compared to P92, this alloy has a higher content of chromium. Since this causes a formation of
ferrite, this must be balanced with an austenite-forming element. For this, the chemical element
cobalt (Co) will be used, since cobalt does not have any influence on the Ac1b point (compared to
nickel).
664
VM12-SHC was VdTV-qualified [11] for wall sizes up to 10 mm and is welded using the GTAand SMA-welding processes. Table 8 includes the results from qualification welding procedures.
The time for the PWHT in the GTA-welding procedure was only 30 minutes which can be
regarded as the lowest limit. The PWHT for welding procedures with SMAW and GMAW should
be specified with a holding time of at least 2 hours.
Table 8: Girth welding of VM12-SHC; Mechanical properties on transverse specimen
Weld
process
Base metal
GTAW
SMAW
Test Temp.
C
+20
+20
+20
PWHT
C/h
740 780
770/0.5
770/2
TS
MPa
620 850
745
728
LoF
--BM
BM
CVN (ISO-V)
J
27 / 40
37 73
31 51
Hardness
HV10
--<351
<322
Creep rupture tests are being conducted at present on the welded joints. Test results at present
after 20,000 hours doesnt show cracks in the weld.
VM12-SHC has been used in Europe in nearly all new coal and gas fired power plants.
CONCLUSION:
Microstructural study of P92 creep resistant steel has shown that two types of ferritic
microconstituent, with different origin, can be observed. A Guideline for determining content
of ferritic microconstituent in seamless pipes, tubes and forgings is prepared and published
(available in German).
It has been shown that up to 8 vol. % of ferritic microconstituent in the microstructure of P92
steel does not significantly deteriorate short term mechanical properties (yield strength,
ultimate tensile strength, toughness). Additionally, no significant changes in the long term
properties have been observed, during both: isothermal ageing up to 10000h as well as creep
testing up to 70000h at 600 and 625C.
A new steel composition aiming at improved oxidation resistance in steam atmospheres and
simultaneously keeping good creep properties was developed. Compared to 9 % Cr steels like
T/P91, E911 and T/P92 it was achieved to significantly improve the oxidation resistance. The
mechanical properties of the new steel lie at the level of T/P92, the creep rupture strength is
at the level of T/P91 up to 620 C, which is the maximum operation temperature. The
processability (welding, cold bending) is comparable to that of conventional 9 % Cr boiler
steels T/P91 and T/P92
This article presents matching filler metals for martensitic and bainitic materials which will
allow steam temperatures of up to 625 C in fossil-fired power plants.
In Europe VM12-SHC is widely used in reheaters and superheaters of modern boilers, but
also as replacement for X20CrMoV12-1 during revamping of old power plants. Very
recently, this new steel was applied in the HRSG boiler of combined cycle gas turbine
(CCGT) plant Irsching IV.
The introduction of the new grade into standards has been launched. The VdTV material
data sheet is available since 2009. The ASME code case will be published presumably in
summer of 2013.
665
Matching filler metals for P92 and VM12-SHC materials which will allow steam
temperatures of up to 625 C in fossil-fired power plants have been developed by Bhler
Welding GmbH
The development of the described welding filler metals must progress almost simultaneously
with the development of the respective base materials. Design engineers need the strength
values of the welded joint determined in creep tests for the reliable design of the components
which are subject to high pressure and temperature loads. Developing filler metals for hightemperature steels which fully meet the strength and corrosion requirements of the base
materials while at the same time ensuring good weldability and sufficient toughness is and
will remain a real challenge.
The strict observation of stringent welding parameters is essential. All the welding fillers
presented here have been approved by VdTV and are thus suitable for use in pressurebearing components. The developments were conducted in close cooperation with V & M
DEUTSCHLAND GmbH
REFERENCES
[1] S. H. Ryu, B. Vandenberghe et al., Proc. 3rd Int. Conf. on Advanced Structura Steels,
Gyeongju, Korea, 2006, p1331.
[2] VdTV-Mb-1272.
[3] W. Bendick, J. Gabrel, J.-C. Vaillant, B. Vandenberghe, Materials for Advanced Power
Engineering 2002: Proceedings of the 7th Liege Conference, Part III, (2002), p.1361-1371
[4] J. Gabrel, W. Bendick, B. Vandenberghe, B. Lefebvre, Energy Materials, Vol.6, No.4,
(2006), p.218-222
[5] Heuser, H.; Jochum, C.; Hahn, B.: Properties of Matching Filler Metals for E911 and P92;
28. MPA-Seminar Stuttgart, 10./11.10.2002, Procedures Vol. 2
[6] Heuser, H.; Bendick, W.; Melzer, B.; Zschau, M.; Cerjak, H.; Letofsky, E.: Ermittlungen der
Langzeiteigenschaften artgleicher Schweigter neuer warmfester Sthle. Forschungsbericht
P297; Studiengesellschaft Stahlanwendung e. V.; Dsseldorf, December 2000
[7] Adam, W.; Heuser, H.; Jochum, C.: Neuartige Schweizustze fr bainitische und
martensitische Sthle; DVS-Bericht Vol. 237, pp. 133-142
[8] Bendick, W.; Hahn, B.; Heuser, H.: Neubewertung der Zeitstandfestigkeit der Sthle E911
und T/P92 Grundwerkstoffe und Schweiverbindung; 28. Vortragsveranstaltung der
Arbeitsgemeinschaft fr warmfeste Sthle (FVW) und fr Hochtemperaturwerkstoffe
(FVHT); 25. November 2005, Dsseldorf, Stahlinstitut VDEh
[9] Fuchs, R.; Heuser, H.; Hahn, B.: Experience with Welding of P92 and VM12-SHC, EPRI
Conference, Fort Myers/Florida; June 22nd to 24th, 2009
[10] The T92/P92 Book; 2011; Vallourec & Mannesmann Tubes
[11] VdTV-Werkstoffblatt 560/2; 09.2011; Warmfester Stahl X12CrCoWMoVNb12-2-2;
Werkstoff-Nr. 1.4915 (VM12-SHC)
666
667
Some studies have already been performed to evaluate creep-fatigue behavior of this steel [4-5].
However, the tests in many of these studies have been conducted at relatively high strain ranges
and short hold times. Thus the results obtained only cover conditions where fatigue damage
dominates. The behavior under conditions of creep damage dominance, obtained at lower strain
ranges and longer hold times, is generally more relevant to plant evaluation. Therefore
accumulating test data and studying the predictability of failure lives under such conditions are of
critical importance to forming a sound technical basis to prevent failures due to creep-fatigue
interaction. The importance is even higher in the case of welded joints (e.g., [5, 6]). Welded
joints in piping systems are subjected to system loads and the failure lives can be significantly
lower than the base metal under long-term service.
EPRI and CRIEPI have been performing a joint study aiming at the development of an extensive
database on the creep-fatigue behavior of Grade 92 steel, including welded joints. This work
included data acquisition and analysis to establish an appropriate life estimation procedure [6-7].
This paper presents a summary of the total results by updating the previous report made in the
middle of the project [8].
PROCEDURES FOR CREEP-FATIGUE LIFE PREDICTION
In order to establish creep-fatigue life prediction methods suitable to apply to Grade 92 steel,
several methods were chosen and the predictions made were compared with the experimental
results. Evaluations of fatigue damage and creep damage constitute equally important portions in
these methods but we placed a larger emphasis on the evaluation of creep damage than that of
fatigue damage, as the evaluation of latter is less problematic and also less influential.
Specifically, classical time fraction and ductility exhaustion approaches were chosen for the initial
analysis as they are equally simple and both have been widely employed in design codes and/or
assessment guidelines [9-10]. In addition, a modified ductility exhaustion method recently
proposed by one of the authors [11], as well as the newest approach focusing on strain energy
density [12] was also applied. Outlines of these procedures will be described in the following.
Time Fraction Approach
In the time fraction approach, creep damage is calculated by the following equation using the
variation of stress during the hold time, or the period for which creep damage needs to be
evaluated in general:
dc =
tH
dt
t R (Tabs , )
(1)
where t H is the hold time in each cycle and t R is creep rupture time at the absolute temperature,
Tabs and the stress, .
Classical Ductility Exhaustion Approach
In the classical or conventional ductility exhaustion approach, creep damage per cycle is
calculated from the inelastic strain rate, in , by
tH
in
(2)
dc =
dt
0 f (Tabs , in )
668
where f is the limit of the strain endured by the material usually called ductility. Various
properties such as rupture elongation, reduction of area, and true rupture strain obtained in
constant load creep tests have been used as its value, depending on researchers and/or materials.
In this study, values of rupture elongation obtained in the creep tests were approximated by a
function of average creep strain rate calculated by f / t R to use as the ductility.
Modified Ductility Exhaustion Approach
In an attempt to improve the life predictability by the conventional ductility exhaustion approach,
the following formula has been derived by redefining creep damage as an amount of ductility loss
with respect to the ductility shown in the absence of creep damage, f 0 [11]:
=
dc
1
1
c dt
0 f (Tabs , in ) f 0
tH
(3)
The modified approach clearly distinguishes the creep damage leading to reduction of ductility
from simple creep deformation. The modified method always gives smaller creep damage than the
classical ductility exhaustion approach. .
Energy-based Approach (type I)
It has been found from a systematic study on various materials [12] that rupture strain sometimes
showed peculiar behavior when plotted against the average inelastic strain rate; taking a maximum
at an intermediate strain rate, rather than monotonically decreasing with the decrease in strain
rate. Average inelastic strain energy per unit volume supplied until rupture does not show such a
behavior and might be a better parameter for characterizing the deformation capability of the
material and its change due to creep damage. Similar processes as used in the modified ductility
exhaustion approach above lead to the equation:
=
dc
1
1
Win dt
0 W f (Tabs , Win ) W f 0
tH
(4)
where Win is the work rate per unit volume calculated by Win = in whereas W f is the total
energy density consumed up to rupture ( W f = f in the case of creep tests), with its saturated
value, W f 0 , at a sufficiently fast loading. This method uses inelastic strain energy density
instead of inelastic strain as a measure of ductility as well as a driving force of creep damage but
it is similar to the above modified ductility exhaustion approach in that the amount of ductility
reduction is regarded as creep damage.
Energy-based Approach (type II)
An alternative approach might be taken by combining the modified ductility exhaustion and the
energy-based approaches described above. In both of those approaches, the parameters employed
as driving force and the index of creep damage are the same, i.e. inelastic strain or inelastic strain
energy density, respectively. However, they do not have to be necessarily the same from the
theoretical point of view. It is considered that the strain energy density may be a better parameter
to describe the creep damage but its reduction can be regarded as controlled by inelastic strain,
rather than by inelastic strain energy density. This assumption leads to the following expression
for creep damage:
669
dc =
tH
W f 0 W f (Tabs , in )
Wf 0
in
dt
f (Tabs , in )
(5)
where W f is the strain energy density at rupture as in the former approach but now it is treated as
a function of the inelastic strain rate, rather than energy density rate.
Evaluation of Fatigue Damage and Failure Life
Fatigue damage per cycle, d f , was simply calculated as a reciprocal of the failure life, N f 0 , at
the pure fatigue condition with the same strain range and temperature as in the creep-fatigue test
to be evaluated. Total strain range or inelastic strain range can be used as a parameter and its
selection may give a significant effect on the failure life when the stress relaxation is relatively
large.
Finally, the following equation based on the assumption of linear damage summation was
commonly applied to predict the failure lives.
Nf =
(6)
d f + dc
However, it has been found that failure often occurs earlier than estimated by eq. (6) especially
when the creep damage is evaluated by the time fraction approach. An interaction diagram which
provides the combination of fatigue damage and creep damage bringing about failure was used in
ASME Boiler and Pressure Vessel Code for design of high temperature nuclear power
components [9] to address such a behavior. The current code has several choices to apply for
different materials but all of them are represented by two linear segments with different
intersection points. When the values of fatigue damage and creep damage at the intersection point
are represented by D f and Dc , the number of cycles to failure can be calculated by
Nf
Dc
Dc d f + (1 D f )d c
Df
D f d c + (1 Dc )d f
when
when
df
dc
df
dc
<
Df
Dc
Df
(7)
Dc
In addition to the simplest equation based on the assumption that damage can be linearly summed,
i.e. eq. (6), eq. (7) with D f =0.1 and Dc =0.01, which is recommended for Grade 91 in the current
ASME code [9] was also applied only in the case of the time fraction approach, whereas only the
linear interaction rule expressed by eq. (6) was applied in other approaches.
TESTED MATERIALS
Three kinds of base metal complying with the Grade 92 specification provided in ASTM/ASME
codes were tested in this study and are called BM A, BM B and BM C . BM A was taken from a
fabricated pipe which had a diameter of 610 mm and a thickness of 102mm. BM B was also
produced as a pipe with a diameter of 298 mm and thickness of 30 mm. BM C was made as
plates with a thickness of 50 mm. Additionally, two kinds of welded joints made from the pipe of
BM A were.
One of them was produced using Submerged Arc Welding (SAW) after
manufacture of a root-pass with Gas Tungsten Arc Welding. The other joint was made using
Shield Metal Arc Welding (SMAW). .
670
Chemical compositions of these base metals and weld metal in the welded joints are summarized
in Table 1, together with the ASTM/ASME SA-335 specification for this steel grade. Nickel
contents in these base metals differ considerably and that in BM A is near the upper limit given in
the specification of 0.40%. There is not manifest difference on other elements. Nickel contents
in the both weld metals are also higher than the maximum limit given in the base metal
specification.
CREEP RUPTURE BEHAVIOR AND MODELING
Constant-load creep tests were performed on cross-weld specimens as well as the base metal
specimens. Tests were performed at three temperatures, i.e. 600C, 625C and 650C for BM A
and the two welded joints but only at 600C and 650C for BM B and BM C. Rupture times of
the base metals are plotted in Fig. 1 as a function of applied stress. Although there is some
scatter, it can be clearly seen that BM A showed the weakest trend among the three base metals
whereas BM C the strongest and the base metal B in between. When comparing these data with
the curves calculated by the equation recently derived by Kimura and Takahashi [2] for
expressing mean property of Grade 92 steel, data of BM C were in good agreement with those.
The results from base metals A and B were consistently weaker than the mean. Rupture time
equations in short and long-term regions were separately derived for each material using the
Larson-Miller parameter. The curves generated by these equations follow the data trends quite
well, as can be seen in Fig. 1.
Furthermore rupture times of the cross-weld specimens made from the two joints are compared
with each other as well as with those of the original pipe, i.e. BM A, as shown in Fig. 2. It can be
seen that the two types of welded joints did not show a systematic difference between each other,
both being weaker compared to the base metal especially at high temperatures and lower stresses,
where Type-IV failure occurred in the heat-affected zone softened by the thermal history
experienced during the welding.
Variations in reduction of area with rupture time are displayed in Fig. 3. Reduction of area in the
base metal samples exceeded 70 per cent up to about 1,000 hours but it started to decrease, down
to about 15 per cent with a further increase in rupture time. This behavior is similar to what was
observed on Grade 122 [13], in contrast to the behavior of Grade 91 which does not show
apparent change even in long-term region [13]. The three base metals of Grade 92 steel show
similar trends, although the number of long-term data is not sufficient especially regarding BM C.
On the other hand, the cross-weld specimens showed earlier and larger reduction of ductility than
the base metal specimens. This trend was associated by a transition of the rupture location from
base metal to HAZ, which also caused a departure of the rupture strength shown in Fig. 1(b).
Table 1: Chamical Compositions of Tested Materials (wt %)
.
Element
BM (A)
BM (B)
BM (C)
WM (SAW)
WM (SMAW)
ASME Min.
ASME Max.
C
0.10
0.13
0.09
0.068
0.100
0.07
0.13
Si
Mn
0.23
0.22
0.23
0.48
0.19
0.50
0.48
0.56
0.40
0.46
0.70
0.30
0.60
0.013
0.013
0.01
0.017
0.012
0.020
0.008
0.002
0
0.007
0.011
0.010
Cr
Ni
Mo
8.88
8.74
9.07
8.49
8.83
8.50
9.50
0.40
0.28
0.20
0.52
0.57
0.40
0.42
0.38
0.43
0.40
0.44
0.30
0.60
1.78
1.61
1.87
1.71
1.54
1.50
2.00
0.19
0.19
0.19
0.17
0.23
0.15
0.25
671
Nb
0.060
0.060
0.06
0.025
0.060
0.04
0.09
Al
0.0029 0.001
0.0023 0.015
0.0035 0.002
0.0004 <0.001
0.0018 <0.001
0.001
0.006 0.020
Ti
Co
0.003
0.002
0.007
0.005
0.010
0.010
0.054
<0.01
-
Cu
0.18 0.0405
0.048
0.051
0.04 0.0500
0.06 0.0454
0.030
0.070
BM A
BM B
BM (A)
BM C
600C
625C
650C
SMAW
BM (model)
WJ (model)
300
300
200
Stress (MPa)
200
Stress (MPa)
SAW
600C
625C
650C
100
90
80
100
90
80
70
70
60
60
50
40
50
1
10
100
1000
104
105
10
100
1000
10000
100000 1000000
100
10
BM A
BM B
BM C
SAW
SMAW
10
100
1000
10000
100000
in
=
ln(in ) + 200, 000 / 8.31/ Tabs
(8)
was used to express the temperature- and rate-dependency of rupture ductility in a unified way.
Here 200,000 is the thermal activation energy in J/mol for self-diffusion of iron atoms in BCC
steels and 8.31 is the value of the gas constant in J/mol/K. The applicability of this parameter to
smoothed and notched bar specimens of Grade 91 and Grade 122 has already been demonstrated
elsewhere [14]. As shown in Fig. 3(a), creep test data taken in the range of temperature from
600C to 650C can be uniquely approximated by the relations given by
672
f f0
=
when ( f 0 a0 ) / a1
= a0 + a1 when U < L
= fL
(9)
when < ( fL a0 ) / a1
with the upper and lower bounds, f 0 and fL as well as constants, a0 and a1 for describing
transient behavior between those limits. As the differences between the ductility of the three base
metals as well as those between the two welded joints appear to be relatively small it was decided
to use a set of common values for all the base metals and another for the both welded joints,. The
upper bound value, f 0 was determined as an average of rupture elongation in the tensile tests
performed at a high strain rate. On the other hand, the smallest value was simply regarded as the
lower bound, fL . In between, all the creep test data were used to represent the transition
behavior given by the second equation in eq. (7).
A similar procedure was applied to formulate the relationship between the inelastic strain energy
rate and the rupture energy density as in the form of
=
Wf Wf 0
when (W f 0 b0 ) / b1
< L
< (W fL b0 ) / b1
= b0 + b1 when U
= W fL
when
(10)
=
ln(Win ) + 200,000 / 8.31/ Tabs
(11)
Again, W f 0 and W fL are upper and lower bounds of the rupture energy density, whereas b0
and b1 describes the transient behavior between them. As can be seen in Fig. 3(b), temperaturedependency could be modeled properly by using the same thermal activation energy as in the
strain-based approach.
In the case of energy-based approach type II, the relationship between the inelastic strain rate and
the rupture energy density was expressed in the form of
=
Wf Wf 0
when (W f 0 c0 ) / c1
= c0 + c1 when U < L
= W fL
(12)
when < (W fL c0 ) / c1
using the parameter defined by eq. (8) along with the constants c0 and c1 in addition to W f 0
and W fL already used in eq. (10). Again, temperature-dependency was modeled properly by
using the parameter given by eq. (8). All the constants included in the above equations as well as
the creep rupture equations used in creep-fatigue life estimation are given in a previous report [7].
Smoothed stress relaxation curves are required to calculate inelastic strain rate as well as inelastic
energy rate for calculating creep damage by each approach. In this study, test records in the midlife cycle in each creep-fatigue test were fitted by the equation:
(13)
= p + q log(t )
as a function of time after the start of hold, t , with two fitting parameters, p and q , in order to
estimate inelastic strain rate by
in = / E
(14)
using Youngs modulus, E . Due to the divergence of logarithmic function at 0, test records were
directly used to estimate the inelastic strain and energy rate in an incremental way for a few
seconds after the start of strain holding and then switched to eq. (13).
673
Temp.
BM A
BM B
BM C
SAW
SMAW
40
30
100
50
20
10
Welded joint modeling
0
Temp.
BM A
BM B
BM C
SAW
SMAW
80
60
Base metal modeling
40
20
Welded joint modeling
0
10
15
20
25
15
30
20
ln(in)+200000/8.31Tabs
25
30
35
ln(Win)+200000/8.31Tabs
10
Temp.
BM A
BM B
BM C
SAW
SMAW
BM C (600C)
0.1
BM A, B, & C (650C)
SMAW
SAW
0.01
100
1000
10000
100000
1000000
1.0%
0.5%
0.35%
600C
625C
650C
Number of cycl es t o f ai l ur e
BM A
BM B
BM C
Grade 91 (BM)
Grade 122 (BM)
100000
Number of cycl es t o f ai l ur e
Strain range
100000
10000
1000
600C
Strain range : 0.5%
10000
1000
100
100
0
0. 01
0. 1
10
Hol d t i me ( h)
0. 01
0. 1
Hol d t i me ( h)
10
10000
92 ( BM A)
91 ( BM)
122 ( BM)
92 ( SAW)
92 ( SMAW)
91 ( GTAW)
122 ( GTAW)
Number of cycl es t o f ai l ur e
Number of cycl es t o f ai l ur e
Gr ade
Gr ade
Gr ade
Gr ade
Gr ade
Gr ade
Gr ade
1000
Gr ade
Gr ade
Gr ade
Gr ade
Gr ade
Gr ade
Gr ade
10000
92 ( BM A)
91 ( BM)
122 ( BM)
92 ( SAW)
92 ( SMAW)
91 ( WJ)
122 ( WJ)
1000
100
100
0
0. 01
0. 1
10
0. 01
0. 1
10
Hol d t i me ( h)
Hol d t i me ( h)
100000
100000
10000
factor of 2
1000
Base metal A
Base metal B
Base metal C
SAW joint
SMAW joint
100
100
1000
10000
10000
Base metal A
Base metal B
Base metal C
SAW joint
SMAW joint
100
10
100000
factor of 2
1000
10
100
1000
10000
100000
100000
Base metal A
Base metal B
Base metal C
SAW joint
SMAW joint
10000
factor of 2
1000
100
100
1000
10000
10000
factor of 2
1000
Base metal A
Base metal B
Base metal C
SAW joint
SMAW joint
100
100
100000
1000
10000
100000
100000
10000
factor of 2
1000
Base metal A
Base metal B
Base metal C
SAW joint
SMAW joint
100
100
1000
10000
100000
10000
factor of 2
1000
Base metal A
Base metal B
Base metal C
SAW joint
SMAW joint
100
100
1000
10000
100000
CONCLUSIONS
Three kinds of Grade 92 base materials as well as two kinds of welded joints have been tested to
see how the materials behave under creep, fatigue and creep-fatigue conditions. It has been
shown based on the analysis of these experimental data, that the modified ductility exhaustion
approach based on inelastic strain as well as its extension employing the inelastic strain energy
density succeeded to make relatively stable and reasonably accurate predictions of failure lives
under a wide range of test conditions and materials.
REFERENCES
[1] Kimura, K., Creep strength assessment and review of allowable tensile stress of creep
strength enhanced ferritic steels in Japan, PVP2006-ICPVT11-93294, Proceedings of 2006
ASME Pressure Vessels and Piping Division Conference, 2006.
[2] Kimura, K. and Takahashi, Y., Evaluation of Long-Term Creep Strength of ASME Grades
91, 92 and 122 Type Steels, Proceedings of the ASME 2012 Pressure Vessels & Piping
Conference, PVP2012-78323, 2012.
[3] Yaguchi, M., Matsumura, T. and Hoshino, K., Evaluation of long-term creep strength of
welded joints of ASME Grades 91, 82 and 122 type steels, Proceedings of the ASME 2012
Pressure Vessels & Piping Conference, PVP2012-78393, 2012.
[4] Sato, M., Kimura, H., Abe, M., Yamauchi, M., Masuyama, F. and Fujita, M., Creep-fatigue
characteristics of advanced high strength Cr-W steels for power boiler applications,
presented at Conference on advanced heat resistant steels for power generation, 1998.
[5] Yamauchi, M., Study on creep-fatigue evaluation methods for high-temperature
component, Kumamoto University Dr. Thesis (2001, in Japanese).
[6] Electric Power Research Institute, Program on Technology Innovation: Evaluation of the
Creep-Fatigue Behavior of Grade 92 Steel and Its Predictability, October 2011.
[7] Electric Power Research Institute, Program on Technology Innovation: Evaluation of CreepFatigue Behavior of Grade 92 Steel, Feb. 2013.
[8] Takahashi, Y. and Gandy, D, Creep-Fatigue Behavior of Grade 92 Steel and Its
Predictability, Proceedings of ASME 2011 Pressure Vessels & Piping Division Conference,
PVP2011-57976, 2011.
[9] American Society of Mechanical Engineers, Boiler and Pressure Vessel Code, Section III,
subsection-NH, 2005.
[10] British Energy, Assessment procedure for the high temperature response of structures R5
Issue 3; 2003.
[11] Takahashi, Y. Study on creep-fatigue evaluation procedures for high-chromium steelsPart
I: Test results and life prediction based on measured stress relaxation, International Journal
of Pressure Vessels and Piping 85 (2008) 406422.
[12] Takahashi, Y., Dogan, B and Gandy, B., Systematic evaluation of creep-fatigue life
prediction methods for various alloys, Proceedings of the ASME 2009 Pressure Vessels &
Piping Conference, PVP2009-77990, 2009.
[13] Takahashi, Y. and Tabuchi, M., Failure behavior of high chromium steel welded joints
under creep and creep-fatigue conditions, presented at Fifth International Conference on
Advances in Materials Technology for Fossil Power Plants, 2007.
[14] Takahashi, Y., Comparison of notched bar creep behavior of various alloys, Proceedings of
the ASME 2010 Pressure Vessels & Piping Division / K-PVP Conference, PVP2010-26096,
2010.
678
ABSTRACT
The creep-fatigue properties of modified 9Cr-1Mo (grade 91) steel have been investigated for the
purpose of design in cyclic service. In this paper test results from creep-fatigue (CF) and low
cycle fatigue (LCF) on grade 91 steel are reported. The tests performed on the high precision
pneumatic loading system (HIPS) are in the temperature range of 550-600C, total strain range of
0.7-0.9% and with hold periods in both tension and compression. Curves of cyclic softening and
stress relaxation are presented. The CF test results and results obtained from literature are also
analysed using methods described in the assessment and design codes of RCC-MRx, R5 and
ASME NH as well as by the recently developed -model. It is shown that the number of cycles
to failure for CF data can be accurately predicted by the simple -model. The practicality in
using the life fraction rule for presenting the combined damage is discussed and
recommendations for alternative approaches are made.
KEYWORDS
Grade 91 steel, creep-fatigue, life fraction rule, modelling.
INTRODUCTION
The modified 9Cr1Mo steel (grade 91) is widely used as structural material at elevated
temperatures in applications of energy industry, such as fossil fired power plants. The grade 91
steel has a good combination of mechanical properties, high thermal conductivity, low thermal
expansion coefficient and good resistance to stress corrosion cracking in watersteam systems
compared to austenitic stainless steels. The 9-12% Cr steels, such as grade 91, are also considered
to be creep resistant and they have found increasing application in thick-section components like
piping, large forgings and castings of steam power plants.
However, the power plant components are often subjected to cyclic thermal and mechanical
stresses as a result of temperature gradients and changes in pressures that occur during start-ups
and shut-downs. During the steady state operation of a power plant creep deformation may occur
under high temperature and pressure. Failure mechanisms under such loading conditions are
complex interactions of creep and fatigue damages. Thus, the evaluation and assessment of the
creep-fatigue interaction is an important issue for the design, maintenance and life assessment
purposes for power plant components.
679
Although the creep, fatigue and creep-fatigue properties of grade 91 steel has been widely
studied, the published data seldom includes all the important details, such as complete relaxation
data, needed for the extensive creep-fatigue assessment. One main objective of the experimental
part of this study was to provide such information for the assessment and modelling.
EXPERIMENTAL DETAILS
Tested material
The test specimens were manufactured from a plate of grade 91 steel with a thickness of 30 mm.
The chemical composition of the material employed in this study is presented in Table 1. The
material was austenized at 1050C for 30 minutes followed by a quenching and tempering
treatment at 780C for 1 hour.
Table 1. The chemical composition of grade 91 steel employed in the study.
Element
C
Mn
P
S
Si
Cu
Ni
Cr
mass % 0.086 0.363 0.017 0.001 0.324 0.068 0.149 8.910
Mo
0.917
Al
0.018
Testing equipment
The creep-fatigue testing was conducted using high precision pneumatic loading system (HIPS).
Although the tests were conducted at air atmosphere, the pneumatic servo-controlled loading
system is capable of operating in a range of extreme conditions such as at high temperature,
pressurized water or steam, supercritical water (SCW) and irradiation environments. The main
benefit of the pneumatic loading system is that there is no moving parts (loading lead-throughs)
required for loading a specimen inside a pressure vessel or otherwise demanding containment
(water, gas, radioactive), only pressure lines and electrical feedback connections together with the
pneumatic loading unit, bellows, are required. [1, 2] More detailed description of high precision
pneumatic loading system and its capabilities is given in reference 1 and 2. A schematic
illustration of HIPS creep-fatigue testing equipment is presented in Fig. 1.
680
Figure 1. a) The main components of the HIPS system, b) the main parts of the displacement
measurement system, c) the loading frame, d) the specimen fixing parts and e) the LVDT fixing
flanges.
681
Test parameters
Creep-fatigue tests with fully-reversed (R=-1) total axial strain control with and without hold
periods were conducted in air atmosphere. The temperature range for testing was between 550
and 600C. The strain rate was 0.1% / sec and the total strain range was 0.7% of the gauge length.
The length of hold periods was 10 minutes. The strain waveform for creep-fatigue testing without
hold periods and with hold periods are shown in Fig. 2.
Figure 2. a) The strain waveforms for creep-fatigue testing without hold periods, b) with hold
periods in tension and compression, c) with hold period in tension and d) with hold period in
compression.
RESULTS
Creep-fatigue test results
In this study the number of cycles to failure used in the assessment is defined as the number of
cycles to 10% load drop. Peak stresses as a function of cycles for specimens tested at 550-600C
are shown in Fig. 3. As expected, the peak stresses and number of cycles to failure increased
when the temperature was decreased from 600C to 550C. All specimens exhibited continuous
cyclic softening both at 550C and at 600C during the creep-fatigue testing. The cyclic softening
was larger for the specimens tested at 600C and a major part of the cyclic softening occurred
during the first 200 cycles for all tested specimens. Introducing a hold period of 10 minutes in
tension or in compression or both slightly increased the cyclic softening. Furthermore, the hold
period in compression was found to be more detrimental than hold period in tension which is in
accordance with the results found in literature [3]. Thus, the number of cycles to failure was
larger for the specimens tested with hold period in tension than for the specimens tested with hold
period in compression.
682
Figure 3. Peak stresses as a function of cycles for tested grade 91 steel specimens.
Life fraction rule assessment
The linear damage rule or life fraction rule has been used extensively in the evaluation of creepfatigue interaction. It is based on the simple assumption that fatigue damage can be expressed as
summed cycle fractions and that creep damage can be expressed as summed time fractions. It is
also assumed that these quantities can be added linearly to represent damage accumulation.
Failure should occur when this summation reaches a certain value, so that:
( ) + ( )
(1)
Where n is the number of cycles of exposure at a given strain range, N f is the cycles to failure at
the same strain range, t is the time of exposure at the same stress-temperature combination and t r
is the time to rupture at the same stress-temperature combination. In some cases, D is assumed to
be unity, because cycle ratio summation should be unity when no creep damage is present. [4] In
nuclear codes such as RCC-MRx, the interaction envelope whose intersection point is (0.3, 0.3) is
used for grade 91 steel for design purposes. This means that from design point of view the
combined fatigue and creep damage that a component experiences should not at any
circumstances exceed the (0.3, 0.3) line, otherwise a failure may occur. Furthermore, in nuclear
codes the fatigue and creep damage are calculated with safety margins for design purposes. [5]
The creep-fatigue test results with hold periods were evaluated with the life fraction rule method
as shown in Fig. 4. The creep component (dc) for one cycle was obtained by using the creep
strain rate rules and minimum creep rupture stresses without safety margins given in the RCCMRx code. The total creep damage (Dc) was obtained by multiplying the dc obtained from the
N f /2 cycle with the total number of cycles to failure. This approach (calculating the total creep
damage from N f /2 cycle) is similar to the method described in the RCC-MRx. In ASME NH, the
creep component for one cycle is calculated from the 1st cycle of the test. The fatigue component
was obtained by comparing the total number of cycles to failure of specimens tested to the fatigue
limits given in RCC-MRx code. No creep damage is assumed to be present in tests performed
683
without hold periods. Thus, the tests without hold periods were not assessed with life fraction rule
method.
684
Figure 5. The measured and predicted relaxation curves using the Feltham equations and RCCMRx procedure of the half life cycle of the test with 0.7% strain and 10 minutes hold period in
tension at 600C
The -model assessment
The creep-fatigue test results and results obtained from literature were assessed with recently
developed -model. The model predicts the expected life under tensile-compressive loading
cycles with or without hold periods. The effective creep-fatigue lifetime (t CF ) and corresponding
number of cycles to failure (N CF ) are predicted utilizing the creep rupture properties and the
ultimate tensile strength of the material [7]. When using a creep model for assessing creep-fatigue
data, the selected model should have good predictive capability both in short and long term range,
which is not usually the case for models optimized for best performance for long term predicted
life. If the creep rupture model of choice is that of Wilshire, then the measured value of the
normalized reference stress m for each CF data point can be calculated from:
= exp {[ exp ( )] }
(2)
Where k and u are material constants from Wilshire model, Q is the apparent activation energy, T
is temperature and R is the gas constant and t CF is the sum of hold times, i.e. t h N f [8]. Now it is
possible to describe the normalized reference stress as a function of strain range, hold time and
temperature by multi-linear regression to the equation:
= 1 +
+ 3 log( ) + 4
(3)
= (
) ()
(4)
(5)
A comparison of the predicted versus measured creep-fatigue life of the test specimens and public
domain data up to 200 000 cycles in terms of total number of cycles to end criterion in
logarithmic scale is shown in Fig. 6. For the data assessed the -model was able to predict the
creep-fatigue life within a scatter factor of 2.88 with 99% confidence.
The scatter factor Z [9] is defined as:
= 10
2.5
(6)
Where N pred is the model prediction, N meas the measured number of cycles and n the number of
test data points.
Figure 6. Predicted versus measured creep-fatigue life in terms of cycles to failure in logarithmic
scale modelled with -model [3, 10, 11, 12, 13].
686
DISCUSSION
The test results demonstrated that decreasing the testing temperature increases the peak stress
levels and the number of cycles to failure. Furthermore, the test results demonstrated that cyclic
softening is accelerated during the first 200 cycles if the testing temperature is increased from
550C to 600C. Introducing a hold period of 10 minutes in tension or in compression or both
slightly increased the cyclic softening. In the near future, tests with 0.9% total strain range in air
atmosphere will be carried out for grade 91 specimens.
Although the life fraction rule is widely used in creep-fatigue damage assessment, there are issues
to be considered concerning the practicality of the method. Safety margins included in the nuclear
codes such as ASME III NH and RCC-MRx may lead to very conservative results where single
test plots are a thousand times above the unity line in the diagram when assessing creep-fatigue
test results. In some cases the evaluation is not even possible, if the determined stress levels
exceed the limits given in the codes. When hold periods are included the determination of the
relaxed stress level, which is not straightforward in some cases, has a strong impact on the creep
component. The ASME procedure, where the creep component for one cycle is calculated from
the 1st cycle of the test, tends to overestimate the stress level used for creep component
calculation. Especially with materials such as P91 which exhibit continuous cyclic softening the
impact to dc can be considerable. When used for design purposes, the conservatism of the ASME
and RCC-MR life fraction procedure may lead to solutions, which are not economically
reasonable.
A significant advantage of the -model to predict creep-fatigue life is that at least for a given
isothermal test type, it is not necessary to consider further details of individual creep-fatigue
cycles, such as features of relaxation, peak stress, softening or hardening behavior. The
extrapolation in hold time may be possible in a similar way as for creep (longest time x 3), but
this has still to be validated with culled data sets or by data with longer hold times. Assuming that
the Wilshire creep rupture model is used, and the temperature dependence of ultimate tensile
strength (UTS) is described by a 3rd degree polynomial, the total number of fitting constants is
four for UTS + three for the Wilshire model + four for -model equaling 11 constants. This is a
very small number considering that the constants for UTS and Wilshire creep model can be
determined separately from relatively simple standard tests. The number of constants may be
further reduced if UTS has been tested for the same material batches and isotherms that have
been used for creep testing.
The -method has been shown in earlier work to predict well the observed creep-fatigue life of
austenitic stainless steel 316FR and nickel alloy A230 subjected to isothermal strain controlled
cycles with tensile hold periods [7, 14]. For grade 91 steel (VTT and public domain data) the
maximum expected error in prediction is within a scatter factor of 2.88 with the 99% confidence
limit. It is a future objective to find adjustment factors for the -model to also predict cross-weld
specimen tests in LCF and CF.
The -method also allows a simple definition of creep-fatigue damage D CF = N/N CF = t h /t CF
where N is the consumed amount of cycles and t h is the corresponding time in hold. For this
damage parameter there is no need to separate creep and fatigue damage or life fractions. The method hence allows for more straightforward damage assessment for both design and later life
assessment than the common methods using summed life (or strain) fractions. It is expected that
the approach is applicable for many creep-fatigue cases in power generation, where strain rates
and cycling frequencies are low and even lower (more creep dominated) than in creep-fatigue
testing in the laboratory.
687
CONCLUSIONS
Creep-fatigue properties of grade 91 steel were investigated and creep-fatigue interaction was
evaluated and compared with the linear life fraction rule and the -model. The following
conclusions were drawn from the test results and evaluation:
(1) The specimens tested at 600C showed larger cyclic softening during the first 200 cycles than
the specimens tested at 550C.
(2) Introducing a hold period of 10 minutes in tension or in compression or both slightly
increased the cyclic softening.
(3) The hold period in compression was found to be more detrimental than hold period in
tension.
(4) All experimental combinations of creep and fatigue damage resided above the interaction
envelope for grade 91 steel provided in RCC-MRx and even above the unity line in life
fraction rule plot due to the large total fatigue component. The total creep component
remained low because the RCC-MRx evaluation method overestimates the relaxation and the
total fatigue component was high because of the strict fatigue limits in the RCC-MRx.
(5) The -model predicted the creep-fatigue life within a scatter factor of 2.88 at 99%
confidence for the grade 91 steel specimens.
ACKNOWLEDGEMENTS
The authors wish to acknowledge the support from the MATTER project (Project no: 269706
FP7-Fission-2010).
REFERENCES
[1] Moilanen, P., Pneumatic servo-controlled material testing device capable of operating at high
temperature water and irradiation conditions, a doctoral dissertation, VTT Publications: 532
(Espoo 2004), pp. 70-130.
[2] Pohja, R. et al, Multifunctional High Precision Pneumatic Loading System (HIPS) for
Creep Fatigue Testing, Procedia Engineering, Vol. 55, No. 1 (2013), pp. 573-577.
[3] B. Fournier. et al, Creep-fatigue-oxidation interactions in a 9Cr1Mo martensitic steel. Part
II: Effect of compressive holding period on fatigue lifetime, International Journal of
Fatigue, Vol. 30, No. 4 (2008), pp. 663676.
[4] Conway, J., ASM Handbook, Vol. 8, Mechanical Testing, ASM International, (USA 1992),
pp. 346-359.
[5] Riou, B., Improvement of ASME NH for grade 91 negligible creep and creep fatigue, ASME
Standards Technology, (New York 2008), pp. 4-98.
[6] Feltham, P., Stress Relaxation in Copper and Alpha-Brasses at Low Temperatures, Journal
of the Japan Institute of Metals, Vol. 89, No. 1 (1961), pp. 210214.
[7] Holmstrm, S. and Auerkari, P. A robust model for creep-fatigue life assessment,
Materials Science & Engineering A, Vol. 559, No. 1, (2013) pp. 333-335.
[8] Wilshire, B. et al, A new approach to creep data assessment, Materials Science and
Engineering A, Vol. 511, No. 1, (2009) pp. 3-6.
[9] Holdsworth, S. et al, ECCC Recommendations, Vol. 5, Creep data validation and assessment
procedures, ECCC publications, (2005), pp. 5-10.
[10] Takahashi, Y., Creep-fatigue behavior of various alloys used in power industry and their
predictability, Transactions of The Indian Institute of Metals, Vol. 63, No. 2, pp. 251-257.
688
[11] Nagesha, A. et al, Influence of temperature on the low cycle fatigue behaviour of a
modified 9Cr1Mo ferritic steel, International Journal of Fatigue, Vol. 24, No. 11 (2002),
pp. 12851293.
[12] Shankar, V. et al, Low cycle fatigue behavior and microstructural evolution of modified
9Cr1Mo ferritic steel, Materials Science and Engineering A, Vol. 437, No. 1 (2006), pp.
413422.
[13] Fournier, B. et al, Comparison of various 912%Cr steels under fatigue and creep-fatigue
loadings at high temperature, Materials Science and Engineering A, Vol. 528, No. 22
(2011), pp. 69346945.
[14] Holmstrm, S. et al, Creep and Creep-fatigue Behaviour of 316 Stainless Steel, Procedia
Engineering, Vol. 55, No. 1 (2013), pp. 160-164.
689
ABSTRACT
Type IV damage was found at several ultra-supercritical (USC) plants that used creep-strengthenhanced ferritic (CSEF) steels in Japan, and the assessment of the remaining life of the CSEF
steels is important for electric power companies. However, there has been little research on the
remaining life of material that has actually served at a plant. In this study, the damage and
remaining life of a Gr.91 welded elbow pipe that served for 54,000 h at a USC plant were
investigated. First, microscopic observation and hardness testing were conducted on specimen cut
from the welded joint; the results indicated that the damage to the elbow was more severe in the
fine-grain heat-affected zone near the inner surface. Furthermore, creep rupture tests were
performed using specimens cut from the welded joint of the elbow, and from these results, the
remaining life was evaluated using the time fraction rule as almost 110,000 h. Finite-element
analysis was also conducted to assess the damage and remaining life, and the results were
compared with the experimental results.
INTRODUCTION
Creep-strength-enhanced ferritic (CSEF) steels have been used for high-temperature steam pipes
at ultra-supercritical (USC) power plants in Japan since 1989. However, it has become clear that
the long-term creep rupture strength of CSEF steels is lower than what was expected when the
plants were designed [1, 2]. Actually, damage in the fine-grain heat-affected zone (FGHAZ),
Type IV damage, was found at several power plants that had operated for less than 105 h. An
accurate assessment of the remaining life of the steels is important for electric power companies.
In this study, a Gr. 91 seam-welded elbow pipe that served at a 600C-class USC power plant was
investigated to evaluate the damage morphology and to assess the remaining life of the material.
WELDED ELBOW AFTER LONG-TERM SERVICE
Material and Service Conditions
The material is a Gr. 91 seam-welded elbow pipe that served for 54,000 h as hot reheating pipe at
600C and 4.0 MPa. This elbow size is nominally 457.2 mm in diameter, 22 mm in thickness, and
685.8 mm in bend radius. This elbow was produced by welding two press-molded KA-SCMV28
steel plates [3] (Gr.91) together at the intrados and extrados. Before this study, the welded joint of
this elbow was examined by performing ultrasonic testing using phased array technologies, and no
indications of creep damage were detected.
690
Figure 1: Cross-sectional view of intrados welded joint and areas of creep void measurements
691
Figure 3: Microstructures of creep voids in (a) left HAZ and (b) right HAZ
Then, the hardness was examined from the weld metal to the base metal in the right HAZ with a
microVickers hardness tester. The examined areas and results are given in Fig. 4. Fig. 5 shows
the distributions of hardness from the weld metal to the base metal along each line in Fig. 4. In
Fig. 5, the value of the horizontal axis is the distance from the bond line normalized to the width
of the HAZ, because the width of the HAZ was different for each line. The hardness value
reached a maximum in the coarse-grain HAZ neighboring the bond line and reached a minimum
in the FGHAZ near the base metal for each line as shown in Fig. 5. The lowest hardness was 166
HV at the FGHAZ on the line 3, where the highest density of creep voids was observed.
Therefore, it is assumed that this material incurred creep damage at FGHAZ during service,
similar to laboratory studies [4, 5]. And the hardness values at FGHAZ were lower near the inner
surface than near the outer. The positions of low hardness matched the positions where creep
voids were observed. From these results, it is suggested that the creep damage to the elbow was
more severe on the inner side of the wall thickness than at the outer side.
692
Figure 5: Distribution of hardness from weld metal to base metal at right HAZ
EXPERIMENTS
Procedures
Two sizes of test specimens were used for the creep rupture tests in this study. Fig. 6 illustrates
the two types of creep test specimens. For one type, the diameter and the length of the test section
are 6 mm and 30 mm, and the specimens are extracted perpendicular to the welding direction at
the mid-thickness position of the welded joint in the intrados and extrados of the elbow. These
specimens included weld metal in the center flanked by the HAZ and the base metal, as shown in
Fig. 6 (a). For the second type of specimen, the diameter and length of test section are 3 mm and
15 mm, and the specimens are extracted perpendicular to the welding direction from the inner
side, the center, and the outer side of the wall thickness of the intrados welded joint of the elbow.
These specimens included the HAZ in the center of test section, as shown in Fig. 6 (b). These
types of specimens will be hereafter called standard specimens and miniature specimens. All
creep rupture tests were conducted at 650C under a constant load in laboratory air, and the
applied tensile stresses were 52 MPa, 60 MPa, and 70 MPa.
Figure 6: (a) Standard specimen and (b) miniature specimen for the creep test
693
Results
In this study, all specimens were fractured through Type IV damage. The creep rupture times
obtained for all specimens are plotted in Fig. 7 as a function of the applied stress. The creep
rupture times of the standard specimens cut from the intrados welded joint were shorter than those
of the specimens cut from the extrados welded joint for all stress conditions. It is conceivable that
the different rupture times are due to differences in the damage occurring during service, because
the intrados joint and the extrados joint were welded with the same groove shape and the same
process. The reduction of area of all specimens are plotted in Fig. 8. The reduction of area of the
standard specimens cut from the intrados welded joint were smaller than those of specimens cut
from the extrados welded joint for all stress conditions. From the result obtained for standard
specimens, it is assumed that the creep damage occurring during service led to exhaustion of the
ductility. The creep rupture time of the miniature specimens cut from the inner side of the intrados
welded joint were longer than those of the miniature specimens cut from the outer side and the
center for all stress conditions, while it is assumed that the creep damage to the intrados welded
joint was more severe at the inner side of the wall thickness based on the microscopic
observations and the results of the hardness test. The reason for this disagreement is supposed to
be the influence of the constraint conditions. The constraint conditions at the HAZ were different
for each miniature specimen, even though the same test conditions were used, because the width
of the HAZ and the angle of the bond line were not consistent in the wall thickness direction, as
shown in Fig. 1. As can be seen from Fig. 8, the reduction of area of the miniature specimens cut
from the outer side were the largest. This suggests that the HAZ was hardly constrained in the
miniature specimens cut from the outer side. The difference in constraint conditions led to
differences in the stress triaxiality, and it is known that stress triaxiality affects the occurrence and
growth of creep voids [4, 5]. Therefore, it is difficult to discuss the differences in the creep
damage occurring during service along the wall thickness through comparison with the results of
the creep testing of the miniature specimens in this study.
694
t
t
+ r =1
t0 tr0
(1)
where t0 and t are the lifetime of virgin material and service time under the operating conditions of
the plant, tr0 and tr are the lifetime of virgin material and creep rupture time under the test
conditions. Here, t0 and tr0 are calculated using the master curve [2], which is the result obtained
by the Assessment Committee on Creep Data of High Chromium Steels, who reviewed all the
latest creep rupture data in Japan, as follows in equation:
log t =
a0 a1
a
a
2
+ log + 2 (log ) + 3 C X
T T
T
T
(2)
where a0, a1, a2, a3, and C are constants for welded joint of Gr.91 [2], t is the lifetime [h], T is the
temperature [K], is the stress [MPa], and X is an optional parameter to estimate the lifetime of
virgin material. In Eq. (1), t0 and tr0 are expressed as functions of X, and t and tr are known.
Therefore, the values of X must be chosen to establish Eq. (1). Here, the operating stress at the
plant was calculated by the mean diameter formula.
695
In this paper, the lifetime of virgin material was estimated from the creep rupture times obtained
for the standard specimens cut from the intrados welded joint using above assumptions. As a
result, the creep damage of the intrados welded joint of the elbow was estimated to be about 33%,
and the remaining life was evaluated as about 110,000 h based on the time fraction rule. In Japan,
the remaining life of CSEF steels are estimated using the master curve [2] and the 99% confidence
lower limit curve is used for maintenance of plant. To confirm the validity of this method, a
comparison between the master curve for welded joint of Gr.91 [2] and the estimated lifetime of
virgin material at 650C is shown in Fig. 9, along with the creep rupture times. The estimated
lifetimes of virgin material were longer than the 99% confidence lower limit for all stress
conditions. Therefore, it is confirmed that evaluations made using this curve are on the safe side.
= A n
(3)
TF =
( 1 + 2 + 3 )
eq
(4)
where 1, 2, and 3 are the principal stresses (1 > 2 > 3) and eq is the equivalent stress. The
equivalent creep strain is concentrated at the cusp areas in each HAZ, where the TF is also high.
Conversely, the equivalent stress is low in each HAZ. The maximum principal stress is higher at
the mid-thickness position than at the nearby surface, but there is no remarkable concentration in
the HAZ. Fig. 11 shows the distribution of the maximum principal stress, equivalent creep strain,
and TF along the wall thickness direction in each HAZ. As indicated in Fig. 11, the equivalent
creep strain is high near the inner surface. Then, the maximum principal stress and TF increase at
the cusp areas because of stress redistribution. Furthermore, the stress-strain conditions were
different in the right HAZ and left HAZ because the forms of the HAZs were different.
Figure 10: Distribution of (a) maximum principal stress, (b) equivalent stress, (c) equivalent
creep strain, and (d) triaxiality factor at the intrados welded joint after 54,000 h
697
Figure 11: Distribution of maximum principal stress, equivalent creep strain, and stress
triaxiality factor in the wall thickness direction in each HAZ
698
(5)
where lim is the limited creep strain, max is the maximum principal stress, and B, p, and q are
material constants, as shown in Table 2 [8]. The distribution of lim in the HAZ can be calculated
using the maximum principal stress and triaxiality factor obtained in the FE analysis. Then, the
creep damage can be defined as equation:
DC =
eq
lim
(6)
where eq is the equivalent creep strain. Fig. 12 shows the distribution of the calculated creep
damage in the each HAZ in the wall thickness direction after 54,000 h. The maximum creep
damage at the intrados welded joint when it was removed from the plant was assessed as about
30%, and the remaining life of the elbow was evaluated as about 126,000 h. The distribution of
the creep damage, which was more severe at inner side of the wall thickness than at the outer side,
roughly corresponded with the above observations, but not exactly. The creep damage in Fig. 12
peaked about 10 mm from inner surface in the left HAZ, but the observations above in Fig. 2
suggested that the creep damage peaked less than 5 mm from the inner surface in the right HAZ.
The equivalent strain is high near the inner surface and is more concentrated in the right HAZ.
This seems consistent with the above observations. From this comparison with the actual
observations of the elbow, it is suggested that the estimated influence of the triaxiality factor and
maximum principal stress is excessive, and the estimated influence of the concentration of strain
is too small in the limited creep strain damage model. In addition, the constants were decided
based on experimental data obtained at 650C, and the effect of the temperature dependency
remains an issue. In addition, it is supposed that the inexact shape of the elbow and the disregard
of the system stress in this analysis influenced the results, contributing to this discrepancy. These
problems must be solved to improve the accuracy of the creep damage assessment methods.
Table 2: Material constants used for analysis
699
Figure 12: Distribution of creep damage in the HAZ along the wall thickness direction
CONCLUSIONS
In this study, SEM observations, hardness tests, creep rupture tests, and FE analysis were
conducted to evaluate the creep damage and the remaining life of a Gr.91 welded elbow that
served at 600C for 54,000 h at a power plant. The results obtained so far can be summarized as
follows:
The creep damage to the elbow was more severe at FGHAZ on the inner side than at the
outer side in the wall thickness direction in the intrados welded joint, and many creep
voids and low hardness were observed near the inner surface.
The creep rupture times obtained for standard-sized specimens cut from the intrados
welded joint were shorter than those obtained for standard specimens cut from the
extrados, and also the reduction of area of the standard-sized specimens cut from the
intrados welded joint were smaller than those obtained for standard specimens cut from
the extrados. It was suggested that the creep damage incurred during service led to
exhaustion of ductility. When small-sized specimens including the HAZ were used in
the creep rupture test, the results were more susceptible to the constraint conditions
than to the creep damage incurred during service.
The remaining life of the elbow based on the time fraction rule was evaluated as almost
110,000 h from the results obtained for standard specimens cut from the intrados
welded joint.
The creep damage to the elbow was estimated to be almost 30% at the intrados joint, and
the remaining life was evaluated as about 126,000 h from the limited creep strain
damage model. The evaluated remaining life corresponded with that estimated from the
creep rupture test results. However the area most damaged by creep was not exactly the
same.
700
ACKNOWLEDGMENTS
The authors would like to acknowledge Mr. Momoi for providing valuable advice on the FE
analysis method.
REFERENCES
[1] K. Kimura, et al., Long-Term Creep Strength of ASME Grades 91, 92 and 122 Type Steels
Proc. ASME2012 PVP Conf., Toronto, Ontario, Canada, July, 2012, PVP2012-78323
[2] M. Yaguchi, et al., Evaluation of Long-Term Creep Strength of Welded Joints of ASME
Grades 91, 92 and 122 Type Steels Proc. ASME2012 PVP Conf., Toronto, Ontario, Canada,
July, 2012, PVP2012-78393
[3] The Interpretation for the Technical Standard for Thermal Power Plant, Nuclear and
Industrial Safety Agency (NISA), The Ministry of Economy, Trade and Industry (METI),
(2007)
[4] T. Watanabe, et al., Relationship between Type IV Fracture and Microstructure on 9Cr1Mo-V-Nb Steel Welded Joint Creep-rupture after Long Term Tetsu-to-Hagane, vol.90,
No.4 (2004), pp.206-212
[5] H. Hongo, et al., Creep Damage Behavior of Mod.9Cr-1Mo Steel Welded Joint Journal of
the Society of Materials Science, Japan, vol.58, No.2 (2009), pp. 101-107
[6] T. Sakai, et al., Clarification of Damage Condition and Development of Damage Evaluation
Method of a Mod.9Cr-1Mo Steel Longitudinal Welded Tube under Internal Pressure Creep
Materials Science Research Laboratory Report, No. Q07002 (2008)
[7] T. Ogata, et al., Uniaxial Creep Rupture Property of Mod.9Cr-1Mo Steel Weld Joint and
Proposal of Creep Damage Evaluation Method Journal of the Society of Materials Science,
Japan, vol.58, No.2 (2009), pp. 94-100
[8] M. Yaguchi, et al., Development of Creep Damage Evaluation Model for High Chromium
Steels Welded Parts Proc. 49th Symposium on Strength of Materials at High Temperatures,
Ishigaki, Japan, Nov. 2011, pp.16-20
701
ABSTRACT
An internal pressure creep test has been carried out on a Gr. 91 steel longitudinal welded pipe at
650oC to examine the type IV failure behavior of actual pipes, using a large-scale experiment
facility "BIPress", which can load internal pressure and bending force on large diameter pipes at
high temperatures. The creep test was also interrupted three times to measure hardness and voids
density in the HAZ region of the outer surface of the test pipe. Results of the measurement of the
hardness and voids density at the interruption did not indicate creep damage accumulation. The
welded pipe suddenly ruptured with large deformation, which caused crushing damage to the
surrounding facility. Type IV cracking occurred in the longitudinal welded portion of the test
pipe, and the length of the crack reached 5000mm. SEM observation was carried out at the cross
section of the welded portion of the test pipe and voids density was measured along the thickness
direction in the HAZ region. To clarify the stress/strain distribution in the welded portion, creep
analysis was conducted on the test pipe, where the materials are assumed to consist of base metal,
weld metal and HAZ. After stress redistribution due to creep deformation, stress and strain
concentrations were observed inside the HAZ region. Then, the authors' creep life prediction
model was applied to the creep test result to examine its validity to actual size pipes. It was
demonstrated that the life prediction model can evaluate damage of the Gr. 91 steel longitudinal
welded pipe with sound accuracy.
INTRODUCTION
It is becoming clear that the strength of welded sections of high-chromium steel (9Cr steel and
12Cr steel) tends to deteriorate in comparison with the base material over long periods of time [15]
. We have systematically performed uniaxial and internal pressure creep tests on welded joints of
high-chromium steel to gain an understanding of the damage mechanism and proposed a creep life
evaluation method for the material [6, 7].
In this study, an internal pressure creep test is conducted on the test specimen of the 9Cr steel pipe
having a large diameter and longitudinal welded sections until a rupture occurs, and damage
mechanism of the welded sections is investigated. Furthermore, we apply the proposed creep life
evaluation method to the test results and assess the validity of the method.
-----------------------------------------------------------------------------------------------------------------Present affiliation
* Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, 275-0016 Japan
702
Longitudinal weld
Hardness [Hv]
400
Base
metal
HAZ
Weld
metal
HAZ
Base
metal
300
200
100
-20
Outer surface
Middle of thickness
-10
10
Position [mm]
20
Test Facility
The test facility used was the verification test facility developed by our institute, the component
facility BIPress: Bending & Internal Pressure on real structural samples[8]. This facility is the
largest in the class of creep testing equipment in the world, which makes it possible to test pipes
of actual equipment with internal pressure and bending load superimposed under high
temperatures. A birds eye view of the principal components of the test facility is shown in Fig. 3.
The electric furnaces consisted of 23 blocks to control temperature distributions of the test sample
with an accuracy of approximately 5C. The facility loaded superheated steam as the pressure
medium for internal pressure.
Load Motor
Load Jack
Test Pipe
Furnace
704
EXPERIMENTAL RESULTS
Rupture Time
The test was completed in 8,624 h because of the rupture of the test specimen. There was only a
slight bulging (amount of displacement) of the pipe due to the internal pressure until immediately
before the end of the test. No signs of rupture were evident with respect to the strains until the end
of the test, as shown in Fig. 4 where strains in the circumferential and axial directions in the HAZ
region was measured by using a high-temperature strain gage.
1
Fracture
Strain [%]
0. 5
Circumferential strain
Axial strain
-0. 5
Interrupt
Interrupt Interrupt
-1
0
2000
4000
6000
8000
10000
705
Inner surface
Outer surface
10mm
706
500
250
0
0
Outer surface
0. 5
1
Inner surface
707
500
400
300
200
100
20
40
60
Damage [%]
80
100
Hardness [Hv]
400
Weld metal
HAZ
Base metal
Damage
Initial
31%
61%
84%
300
200
100
-5
Position [mm]
The procedure used for the life evaluation method is shown in Fig. 10. The definition of
multiaxial stress TF is as follows:
TF =
{(
1 + 2 + 3
2 ) + ( 2 3 )2 + ( 3 1 )2 / 2
2
where 1, 2, and 3 denote the principal stresses. Refer to the reference document [7] for details
on this evaluation. The material constant of the 9Cr steel welded joint at 650C is shown in Table
1.
Start
Creep analysis using 3 materials model
Results
lim
tr
Dc = dt / lim
t r = lim /
End
Figure 10: Flow of creep life evaluation model
Table 1 Material constants
C
9.38E-3
1.62
-5.4
709
StressMPa
55
50
Base
HAZ
metal
Weld metal
HAZ
Base metal
45
40
35
Base HAZ
metal
Weld metal
HAZ
Base metal
710
60
Circumferential
50
Stress [MPa]
40
30
Axial
20
10
0
0.0
-10
0.5
Radial
1.0
Figure 12 Principal stress distributions in thickness direction in HAZ region at steady state
Figure 13 shows the distribution of creep strain in the circumferential direction of the specimen
under the steady state condition. High values of strain were observed in the HAZ region,
particularly in the vicinity of the internal and external surfaces in the HAZ region. The strain at
the center of the wall thickness was approximately constant and minimum, with the strain
increasing progressively towards the internal and external wall surfaces. A comparison of the
external surface and the internal surface indicated that larger values of creep strain in the
circumferential direction were observed on the internal surface than on the external surface.
Creep strain [%]
0.6
0.45
Base HAZ
metal
Weld metal
HAZ
Base metal
0.3
0.25
0.0
Base HAZ
metal
Weld metal
HAZ
Base metal
Damage
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.5
1.0
712
REFERENCES
[1] Brett, S. J., Oates, D. L. and Johnston, C., In-service Type IV Cracking in a Modified 9Cr
Header, Proceedings of ECCC Creep Conference, London, 2005, pp.563-572.
[2] Kimura, K., Review of Allowable Stress and New Guideline of Long-term Creep Strength
Assessment for High Cr Ferritic Creep Resistant Steels, Proceedings of ECCC Creep
Conference, London, 2005, pp.1007-1020.
[3] Takahashi, Y. and Tabuchi, M., Evaluation of Creep Strength Reduction Factors for Welded
Joints of HCM12A (P122), Proceedings of PVP2006-ICPVT-11, Vancouver, 2006,
PVP2006-ICPVT11-93488
[4] Kimura, K., and Takahashi, U., Long-Term Creep Strength of ASME Grades 91, 92 and 122
Type Steels Proc. ASME2012 PVP Conf., Toronto, Ontario, 2012, PVP2012-78323
[5] Yaguchi, M., Matsumura, T. and Hoshino, K., Evaluation of Long-Term Creep Strength of
Welded Joints of ASME Grades 91, 92 and 122 Type Steels Proc. ASME2012 PVP Conf.,
Toronto, Ontario, 2012, PVP2012-78393
[6] Ogata, T., Sakai, T. and Yaguchi, M., Creep Damage Evolution and Life Assessment of P91
Weld Joint, Proceedings of the Third International Conference on Integrity of High
Temperature Welds, London, 2007, pp.285-294.
[7] Yaguchi, M., Ogata, T., and Sakai, T., Creep Strength of High Chromium Steels Welded
Parts under Multiaxial Stress Conditions, Int. J. Pressure Vessels and Piping, 87(2010),
pp.357-364.
[8] Yaguchi, M., Miura, N., Ogata, T. and Sakai, T., Development of Component Test Facility
BIPress: Bending & Internal Pressure on Real Structural Samples, CRIEPI Research
Report Q08001 (2008)
713
714
Detailed research examining the microstructure of 9 to 12% Cr tempered martensite ferritic steels
has provided key information concerning the formation of new phases and the coarsening of
carbides during long term creep. However, the microstructures of CSEF steels evolve during
service at elevated temperatures and pressures, and creep strain can enhance the changes which
take place. Indeed, a number of microstructural degradation mechanisms have been identified
which are thought to be responsible for the loss of long term creep strength. These include; the
precipitation of new phases (e.g. Laves and Z phases), the dissolution of fine M2X and MX
carbonitrides, the recovery of the dislocation sub-structure and the development of creep voids in
the microstructure [3-6].
The complex nature of the long term creep behavior is emphasized by consideration of data
compilations considering creep ductility. Published information showing the variation of the
reduction of area at fracture after creep testing at 600oC is shown in Figure 1 for Grade 91, Grade
E911 and Grade 92 steels. In short term tests the samples fail with high ductility due to local
deformation and necking of the samples. While even in long durations some high ductility type
failures are reported it is apparent that as lives increase there is a tendency for some tests to fail in
brittle manner. This means that for all three steels there is a very large variation in fracture
behaviour in tests at 600oC of greater than 10,000 hours. This is clearly significant since 600oC is
a typical in-service temperature for these steels. Indeed, in the development of steel P92 a target
was set for the minimum reduction of area to be at least 40% at 10,000 hours and 600C. Greater
understanding of the reasons for the wide variation in fracture characteristics of these martensitic
steels is clearly important.
Figure 1. Relationships between reduction in area and creep life for steel grades P91, E911 and
P92 tested at 600oC [5].
The complexities associated with establishing the factors affecting the creep behavior of CSEF
steels mean that it is very challenging to identify and understand the influence of individual
parameters. As emphasized in a recent publication [7], most results published in the literature
suffer from a number of serious drawbacks, for example:
1. Specific elementary processes (for example subgrain coarsening) are studied in isolation
so that the importance of other microstructural events, which are equally important (for
example creep cavitation), are omitted.
2. Microstructural results are often obtained from specimens subjected to accelerated creep
tests. Yet it is well known that the temperature and stress dependence of thermodynamic
driving forces and kinetics affect microstructural development. Indeed, it is unlikely that
the deformation and softening processes which govern short term creep also occur under
long term creep conditions.
715
3.
Specimens are frequently not available from long term creep testing. While efforts have
been made to produce rupture data, much less emphasis has been placed on providing
interrupted material states. Study of controlled samples at different damage levels is
clearly important to assessing trends in behaviour.
4. Even when samples from long term tests are available, post test metallography is rarely
performed,
5. There have been significant recent developments in the hardware and the instruments
which are available for microstructural characterization. Thus, there is a need to use the
advanced techniques and equipment to these steels (many of which were initially studied
in the 1980s and 1990s).
The present paper reviews information on long term creep fracture behaviour in 9 to 12%Cr
martensitic steels and discusses approaches for minimizing the susceptibility for nucleation of
voids so that creep brittle fracture can be avoided.
FACTORS AFFECTING THE FORMATION OF CREEP CAVITIES
There has been some apparently conflicting evidence reported regarding when creep voids form
during creep of martensitic steels. Indeed, several studies have reported that voids can only be
indentified late in creep life [e.g. 8]. In contrast, other work has demonstrated that creep voids
nucleate relatively early in the creep life [9]. These apparently conflicting observations are
considered with respect to the creep behavior of selected CSEF steels where the results of long
term creep testing have been published.
Damage in 12%Cr (X20) steel
The martensitic steel 12% Cr-Mo-V steel has been used in power boiler applications for around
50 years. Interestingly, even in this steel there are conflicting observations regarding the
formation of creep voids. Thus, reviews of performance have been published showing that
remarkable few components have been found with creep voids detectable by optical microscopy
[10]. In contrast, some experience has shown that creep cracking in components has occurred and
replacement of components has been required. While these observations have all been made for
steels operating beyond 100,000 hours, it could be that the variation in observations is linked to
the temperature of operation. It is well known that the accumulation of creep damage is very
dependent on the exposure temperature. However, the information considered here shows that
variable fracture behaviour has been identified even in samples exposed at the same creep
temperature.
The creep behaviour for a number of different X20 steels tested at 550oC is compared in Figure 2
[11]. These results show data up to and even beyond 100,000 hours duration. While there is no
major difference in creep strength for the different casts there are significant differences in the
reduction in area measured after testing. It is apparent that some casts show reduction in ductility
for test lives of around 10, 000 hours.
At the high stress levels, all of the specimens rupture in a ductile manner. These failures are
linked to voids which form and grow plastically at large inclusions. The inclusions are hard
particles within the plastically deforming matrix and at some critical value of strain void
formation occurs. In general, it has been reported that relatively large oxide and sulfide inclusions
are more effective in the initiation of voids which grow by plastic deformation than small
particles. The generally smaller, second phase particles do not appear to play a role in the ductile
high temperature rupture of 12% Cr-Mo-V steel.
716
Figure 3. Creep damage detected at different locations along the gauge length of a sample tested
at 550oC [11]
717
At low stress levels, creep cavitation appears to be the dominant damage mechanism. This change
in the rate controlling mechanism results in much lower strains to rupture, Figure 2. Indeed, as
shown in Figure 3, post test metallographic examination of samples which failed with low
reduction of area (R of A) revealed significant numbers of individual voids. Indeed, not only were
creep voids and micro cracks found at the fracture location but also along the specimen gauge
length even well away from the fracture surface. These observations demonstrate that, under the
testing conditions employed, void nucleation had taken place generally throughout the whole
gauge length. Final link up of damage as expected focused at a specific location but even here the
deformation observed is mostly associated with developing the strain needed to grow cracks
across the section.
Damage development in long term creep tests of tempered martensite ferritic steel (German grade:
X20) at a stress of 120MPa and a temperature of 550oC has been reported [7, 12]. These test
conditions resulted in a creep life of 139,971 hours. Tests were also performed under the same
loading conditions but interruptions after 12,456, 51,072 and 81,984 hours, that is at life fractions
of about 9%, 37% and 59%. It was reported that nucleation of cavities was found in each of the
samples examined. Thus, it appeared that void nucleation occurs continuously during creep.
Detailed study showed that it appeared that the number of creep voids present, i.e. the cavity
density, was proportional to the creep strain. Indeed, this observation has been reported
previously for creep tests on X20 steel samples [13]. Comparison of the results of the test
programmes suggests that, even though the specifics of the steels and the tests performed were
different, a similar relationship reasonably described all the results, Figure 4.
Figure 4. Relationship between the cavity density and creep strain for creep tests performed on
X20 steel samples.
As illustrated in Figure 3, a characteristic feature of creep cavitation in high chromium ferritic
steels, is that cavities are not only found on prior austenite grain boundaries (PAGBs) but also in
the interior of former austenite grains. There are additional internal surfaces such as sub- grain
boundaries and high angle ferrite boundaries, which have formed during tempering, where
segregation can occur preferentially and which will facilitate diffusion. However, a quantitative
metallographic evaluation of the cavity population showed that cavities on PAGBs which were
oriented at 90o to the maximum stress direction play the dominant role in the rupture process.
718
Figure 5. Typical micrograph showing creep voids developed in Grade 91 base metal.
Previous work has shown that there is a relationship between N:Al ratio and creep strength in
tempered martensitic Grade 91 base metal [14]. This trend has been explained on the basis that in
Grade 91 steel the levels of nitrogen are set so that strengthening will involve the formation of
MX type carbides, nitrides and carbonitrides. When excess aluminium is present in the steel, this
combines with nitrogen to form aluminium nitrides [14]. These aluminium nitrides are relatively
large and so do not contribute to creep strength. Thus, since the level of free nitrogen is reduced
by the formation of aluminium nitrides, the volume fraction of MX precipitates is decreased and
the creep strength is decreased. Previous work has shown that there can be a link to the formation
of aluminium nitrides and increased susceptibility for the nucleation of creep voids. This
observation is consistent with the behavior reported for other boiler steels where steels with
higher inclusion levels exhibited lower creep ductilities than clean steels of the same
composition [15].
Examination of Grade 91 steel after creep testing has been performed to measure the number
density of creep voids and to evaluate factors involved in void nucleation. It is apparent that the
creep behaviour of tempered martensitic steels is influenced by nonmetallic inclusions. In cases
where these inclusions exceed a critical size there is established evidence that voids are nucleated
on the hard particles. Photomicrographs in Figure 6 illustrate this behaviour. A back scattered
electron micrograph of the creep voids present is shown in Figure 6a, with Figures 6b and c
showing elemental maps for oxygen and silicon. It is apparent at least some of the creep voids are
associated with particles which have relatively high concentrations of silicon and oxygen.
719
Figure 6. Micrograph showing creep voids developed in Grade 91 steel (a), an elemental map of
the same area showing local concentrations of oxygen (b) and an elemental map of the same area
showing local concentrations of silicon (c).
When considering nucleation of creep cavities the local microstructure and composition are
clearly of particular interest. Elements which have been shown to decrease the resistance to creep
fracture in engineering steels include phosphorus (P), sulfur (S), Copper (Cu), Tin (Sn), Antimony
(Sb), Arsenic (As). A systematic study evaluating the influence of these elements on the strength
and fracture behavior has been published [16, 17]. The reduction in the rupture life resulting from
the higher amount of tramp elements at 650oC does not appear to be caused by the increase in the
creep rate, but rather by the decline in creep ductility. This is consistent with the Sb and Sn-doped
samples exhibiting minimal R of A. Consequently, the rupture life associated with the Sb- and
Sn-doped samples is shorter than that of the P- and S-doped samples, Figure 7. The rupture life
associated with the Cu-doped sample was seen to be independent of the content of Cu. This is
because the Cu doped samples exhibited poor ductility irrespective of Cu content, Figure 7b.
Poor ductility linked to elevated copper levels has also been found in other work (18).
Figure 7. Relationships between Reduction of Area and creep rupture life for Grade 91 steel
samples with different levels of trace elements [16, 17]. Some of the trace elements are not
controlled in applicable component specifications even though elements such as Tin (Sn),
Antimony (Sb) and Copper (Cu) can significantly reduce the creep ductility.
720
The results from Grade 91 provide insight into why the observed distribution of cavities in
tempered martensitic base metal is very variable for different casts. It is apparent that the size and
distribution of non-metallic inclusions and the concentration of trace elements both significantly
influence the nucleation of creep voids. Since these factors will not simply influence the
behaviour at grain boundaries, voids nucleate in different positions. In the steels with lowest creep
ductility, void nucleation starts early in life and continues with increasing strain.
Damage in Grade 92 steel
It is apparent from consideration of Figure 1, that variability has also been noted in the fracture
behaviour of Grade 92 base metal samples. An alternative approach to assessment of creep
fracture behaviour to the typical variation of R of A with rupture life is shown in Figure 8. Here,
the rupture life reported for different test temperatures is shown, with selected ranges in R of A
designated by different symbols. The general key to this Figure is that samples with an R of A
greater than 50% are shown as an open circle, with tests with an R of A below 50% are shown as
a solid square. The difference between open and solid symbols facilitates comparison of the
results.
Figure 8. Variation in Reduction of Area for different test temperatures and creep rupture lives
for Grade 92 steel base metal samples.
Greater definition of the specific ductility ranges are provided through the use of different colors.
The tests included in Figure 8 cover data from many different sources, yet a general trend in the
rupture behaviour is apparent. Thus, for tests at 650oC and durations near to, or above 10,000
hours the ductility is below 50%. In contrast, for tests at 550oC even with durations approaching
100, 000 hours the reported ductilities are above 50%. Interestingly, the results reported for tests
at 600oC, i.e. near to the design temperature for many Grade 92 steel components, tests with
durations above 10,000 hours show a mixed behaviour. Thus, some steel casts show relatively low
ductility at lives around 10,000 hours yet others show R of A above 50% even at creep rupture
lives very close to 100,000 hours. Review of background information provided with the creep test
721
data [19] suggests that different fracture behaviour was related to the level of silicon in the steels.
The reduction in ductility could be linked to the presence of silicates.
Clearly, the fact that very low creep ductilities have been reported in Grade 92 base metal samples
using test conditions near typical operation of advanced boilers requires further study. The fact
that differences in fracture characteristics have been found for tests in different temperature
regimes and for different compositions, suggests that both fabrication and creep testing factors are
important in establishing details of damage. In view of the metallurgical complexities of advanced
tempered martensitic steels, careful planning, selection of samples for examination followed by
the application of advanced microscopy are required to establish trends in behaviour. Details from
these characterization activities have been presented [20]. However, selected information is
provided here to compliment the present review of fracture behaviour in 9 to 12% Cr steels.
A typical micrograph showing the development of cavities after creep testing of Grade 92 base
metal is shown in Figure 9a. Samples were selected for examination after testing at 550oC, 600oC
and 650oC. As indicated in Figure 8, all the tests at 650oC with duration of above about 10,000
hours showed an R of A below 50%. Detailed characterization of samples tested to failure at
9,037, 10,682 and 19,124 hours at 650oC showed that a uniformly high number of creep voids
were present along the gauge length, Figure 9b. This evidence on Grade 92 steel supports the
earlier results showing a high degree of uniformity in void density for long term tests on X20
steel, Figure 3. For the Grade 92 tests, the size of cavities at fracture was generally in the range
from 2.1 to 3 m [20]. However, detailed sizing was difficult because the voids were not
spherical.
Figure 9. Typical micrograph showing creep voids in a Grade 92 steel base metal sample (a) and
the number density of voids present along the gauge length for samples tested to failure at 9,037,
10,682 and 19,124 hours at 650oC (b)[20].
Because of the complex shapes of the creep cavities even careful metallographic preparation and
evaluation has difficulties to unambiguously characterize voids and their relationship to
microstructural details. A sophisticated approach involving serial ion beam sectioning followed
by documentation was therefore applied [21]. This approach allowed both the void shape and the
associated particles to be reconstructed in three dimensions. An example of a reconstruction is
shown in Figure 10. In the reconstruction shown, the cavity has a diameter of around 2 m. This
void was clearly associated with a boron nitride particle of around 1-1.5 m. Much smaller
second phase particles including Laves phase were found to decorate the inside of many of the
cavities. In some cases, fine manganese sulphide (MnS) or alumina (Al2O3 ) particles were found
within the cavities. It is potentially the case that the fine MnS or Al2O3 formed in the steel at very
722
high temperatures act as sites which promote the nucleation of boron nitride during subsequent
cooling.
Details of the characterization process and selected results are presented in another paper at this
conference [20]. Further research examining additional Grade 92 base metal samples is in
progress. It is anticipated that a broader pattern of results for steels with different composition and
after a variation of heat treatments will become available in the future.
Figure 10: An example of a single SEM cross-section slice taken in sample 600-A 6 mm away
from fracture surface (a). A reconstruction of the data showing the pore (shown in blue, purple
and green) and associated particle (shown in red) in 3D (b)[20]
DISCUSSION
For typically processed tempered martensitic steel base metal, it has been observed that the long
term performance and creep rupture strength is below that originally expected from simple
extrapolation of short term creep data. This effect has resulted in reductions in some of the values
quoted as representing long term creep life. The reasons for the loss of long term creep rupture
strength have been investigated extensively [for example 3, 4, 5, 6] for a number of 9 to 12 Cr
steels. The following microstructure degradation effects appear to be primarily responsible for the
loss of creep strength:
The formation of new phases which lead to dissolution of fine M2X and MX carbonitrides,
Recovery of the dislocation substructure (increase in subgrain size) and reduction in the
overall dislocation density. This is believed to initiate as the result of preferential recovery
of microstructure in the vicinity of PAGBs, and
The precipitation of Z phase, M6X carbonitrides and Laves phase during creep can cause a loss of
creep strength at long times. The loss of strength occurs if the formation of these phases is
sufficient to result in a significant reduction in the fine M2X and MX and or M23C6 precipitates.
The size (which determines the climb distance required to overcome the particle and the number
density (which determines the mean particle spacing and thus the particle back stress are critical
to stabilizing the dislocation substructure and hence, play a major role in determination of the
creep strength. It has been the primary focus of the present paper to consider the factors affecting
723
the nucleation and growth of creep voids. This focus was established in part because high
densities of small voids can have a particularly significant influence on approaches to manage the
safe life of boiler components and in part because while the creep dependent microstructural
changes have been widely studied, there is less work reported on creep void development. This is
particularly true for the tempered martensitic microstructures present in base metal.
It is now clearly established that for creep conditions at or close to those of components in power
boilers, creep voids can be nucleated early in life [9]. There have been different opinions
published regarding void nucleation. In particular, several papers have suggested that creep voids
are only formed late in life [e.g. 8]. This diversity of findings is due to a number of factors,
including the following:
Selection of laboratory test conditions which result in damage which is not relevant to
long term behaviour,
Testing steels with a composition and microstructure which are not susceptible to
formation of voids,
Post test examination which is limited to the surface of the samples (when creep damage
in CSEF steels is greatest below the surface), and
Using methods of sample preparation and evaluation which do not properly reveal the
creep voids present
In long term creep tests on CSEF steels, the voids grow throughout the creep life and will be
around 1 to 2m in size at, or very close to, fracture. This size of void is important because it is
only relatively close to fracture that individual voids can be relatively easily identified using
optical microscopy at the magnifications around 400 times magnification. Due to the non
symmetrical shape of the creep voids, sample preparation is critical to identification of voids. It
appears that long term creep exposure of X20 steel can results in the development of higher
densities of voids than in other tempered martensitic steels. In X20 steel it is generally agreed that
the number density of voids increases with creep strain, with the number of voids at or very close
to fracture in the range 2000 to 10,000 mm-2.[11,13].
To provide an evaluation of creep void development in CSEF steels several key publications have
been reviewed [22, 23]. A summary of information reported for the change in void density with
life fraction in the creep strength enhanced martensitic steels is presented in Figure 11. The
development of creep damage is frequently modeled using an equation of the form:
In this equation, t is the exposure time in hours, tr is the time to rupture in hours, is the
instantaneous strain and r is the strain at rupture and is a material parameter r elated to the
creep ductility under the conditions of interest. In most situations encountered in long term creep,
and certainly for in service components, the mechanism of cavity growth is linked to local creep
strain. Thus, the growth or dilation rate is considered to be constrained, thus the volume change
due to void formation and growth must be accommodated by strain.
724
Figure 11. Summary of information regarding the increase in the number density of creep voids
with life fraction for long term creep tests on different creep strength enhanced ferritic steels.
Under these conditions then the strain fraction in the above equation can be replaced by a number
fraction of voids as:
where N is the number of voids per mm2 and Nf is the number of voids per mm2 at fracture.
The values of the parameters in this equation have a significant influence on the form of this
relationship. The way the value of key parameters relates to damage rate is illustrated in Figure
11. Both of the lines drawn in this Figure have been based on the same number of voids at
fracture, namely Nf of 1200 voids mm-2. However, the calculations of the relationship between
number of creep voids and life fraction have been made for different values of . As increases
from 2 to 3, the curve defining the rate of change in void density becomes steeper; this is
particularly true at high life fractions. It is interesting to note in Figure 11 that for a number
fraction of voids of 600 voids mm-2 the calculated life fraction range is 70 to 90%, a range which
approximately bound the experimental data. Clearly having the understanding to define, at least
semi quantitatively, how microstructural factors change Nf and is key to applying observations
of creep voids to component performance. It should be emphasized that details of the most
appropriate value of Nf to use in practice seem to be of lower significance than understanding of
the ductility parameter . The key issue in both cases is how rapidly the creep voids link to form
cracks, i.e. what is the life fraction associated with the transition from a density of say a thousand
voids mm-2 until micro crack formation and crack development occur in a component?
One key microstructural factor related to the number of creep voids nucleated appears to be the
distribution of non-metallic inclusions above a critical size. Inclusions may be directly linked to
void nucleation or the presence of one type of inclusions may promote formation of other, even
larger particles. It appears that this seeding of inclusions can be illustrated with reference to the
formation of BN in P92 and P122 steels. Detailed study indicates that the BN inclusions in P122
are different from those of the P92 steel. In P122 steel it appears that the BN agglomerate in large
colonies, which grow up to about 20m in size [24]. These colonies consist of many individual
725
inclusions of about 2 or 3m in size. In P92 steel [17], coarse size BN type inclusions grown up to
4m are observed. In both of these commercial heat resistant steels, it appears that alumina type
inclusions, which may be sourced to the furnace refractory in melting process, are key to the
formation of large BN type inclusions.
726
Figure 14. Relationship established between total Boron and Boron available for improving
creep performance (as indicated by the amount of soluble Boron) for 9% Cr steels [24].
727
Figure 15. Creep voids observed in an X20 steel main steam bend during an inspection after
around 160,000 hours (a) & after a further approximately 12550 hours (b) [25].
The expected behavior is illustrated by consideration of actual field measurements on a 12CrMoV
steel steam pipe bend which operated at 532C. This bend had been incorrectly heat treated
during fabrication and hence exhibited low creep ductility. After operation for approximately
160,000 hours inspection showed that high numbers of creep voids were present, Figure 15a. The
average void density was estimated as 1025mm-2. Using typical values for the number density of
voids at crack initiation, this void density indicates that cracking was imminent. However, no
replacement component was available. Instrumentation was used to directly monitor the
component and operating conditions were reduced to minimize the rate of creep damage
728
development. A final inspection was performed after an additional operating period of 12,550
hours. Because of the need to monitor the damage in this bend it was possible to track void size
with time. As shown in Figure 16, the percentage of voids greater than 2.5m increased
respectively to 23%, 34% and 43%. Over this same period, the fraction of voids greater than
3.5m increased from 3% to 20%. It is thus clear that significant void growth had taken place.
Figure 16. Change in void diameter for increasing operating time in a 12CrMoV steel piping
bend [25, 26]
CONCLUDING REMARKS
The creep strengthening mechanisms of tempered martensite ferritic steels has been referred to as
carbide stabilized substructure hardening. Thus, the excellent strength of these steels is due to the
fact that high densities of fine carbo-nitrides retain a dislocation substructure during operation at
elevated temperature and stress. Changes in composition and heat treatment clearly have a marked
effect on creep strength. However, it now appears that metallurgical processing factors can also
influence long term ductility through changes in the susceptibility to the nucleation and growth of
creep voids.
Tempered martensitic steels such as X20, Grades 91, 92, E911 and 122 all exhibit a trend to
relatively low ductility as creep rupture times increase. The tendency for brittle behaviour is in all
cases due to the formation of creep voids on prior austenite grain boundaries and at other
microstructural features such as lath boundaries. The detail of the number of voids formed, and
the tendency for reductions in strain to fracture, is different for the different steels. However, it
appears that in all cases, void nucleation is related to the presence of trace elements and hard nonmetallic inclusions. A key factor in determining whether the inclusions nucleate voids is the
particle size. Thus, only inclusions of a sufficient size (the critical inclusion size is directly linked
to the creep stress) will act directly as nucleation sites. However, even fine inclusions formed
during steel making (such as Al2O3) may also play a role in promoting void formation. Analysis of
the creep cavities formed in P92 steel after creep exposure revealed that the majority of them were
associated with hard ceramic particles. Chemical analysis revealed that the vast majority of these
particles were BN which appeared to be associated with MnS or Al2O3 . It appears that the BN
729
inclusions develop on the alumina or magnesia particles which are formed during de-oxidation or
originate from the refractory of the steel making furnace. Once formed, post fabrication heat
treatment above about 1200oC appears to be sufficient to dissolve the BN. Control of composition
in combination with modified heat treatment practices during fabrication offers the potential to
reduce the susceptibility for brittle creep fracture behavior in CSEF steels.
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T. Fujita, Advances in 9-12%Cr Heat Resistant steels for Power Plants, Third Int Conf in
Advances in Material Technology for Fossil Power Plants, (EDS R. Viswanathan, W.T.
Bakker and J.D. Parker) Institute of materials, 2002, pp 33 67
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H.K. Danielsen, and J. Hald, Behaviour of Z phase in 9- 12%Cr steels, Materials Science
& Engineering for Energy Systems, 1 , 2006, pp. 49-57.
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K. Mailer and A. Klenk, Int Conf on Creep and Fracture of Engineering Materials and
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J.D. Parker, Factors affecting Type IV creep damage in Grade 91 steel welds, Materials
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X10CrMoVNb9-1 (P/T91) and X20CrMoV12-1, Third Int Conf on Advances in Material
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Institute of Materials, 2002, pp 33 67
12. G. Eggeler, J. C. Earthman, N. Nilsvang and B. Ilschner, "A Microstructural Study of Creep
Rupture in a 12% Cr Steel," Acta Metallurgica, 37, 49-60, 1989.
13. R. Wu, and R. Sandstrom R., Creep cavity Nucleation and Growth in a 12%CrMoV steel,
Swedish Institute for Metals Research, 1993
730
14. S.J. Brett, J.S. Bates, and R.C. Thomson, Aluminium Nitride Precipitation in Low Strength
Grade 91 Power Plant Steels, Proceedings of the Fourth International Conference on
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Island, South Carolina, EPRI 2005, pp 1183 1197.
15. J.D. Parker and A.W.J.Parsons, "High Temperature Deformation and Fracture Processes in
2CrMo-0.5CrMoV Weldments" International Journal of Pressure Vessels and Piping, 1995,
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16. F. Masuyama and T. Toyoda, Creep Strength and mechanical Properties of air melt modified
9Cr-1Mo cast steel, Int. Symposium on Improved Technology for Fossil Power Plants, New
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Forgings With High Residual Elements, Experience With Creep-Strength Enhanced Ferritic
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21. L. Li, R. MacLachlan, MAE Jepson and R.C. Thomson. Microstructural Evolution of Boron
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Bearing High Cr Ferritic Heat Resistant Steel, Tetsu to Hagane, Vol 90, pp 819-826, 2004
25. F.H.Van Zyl, Condition Monitoring of High Temperature and Pressure Components in South
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Pressure Components in South Africas Power Plant. ECCC Conference: Creep & Fracture
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September 12-14, 2005.
731
ABSTRACT
Conventional time-temperature-parameter (TTP) methods often overestimate long-term creep
rupture life of creep strength enhanced high Cr ferritic steels. The cause of the overestimation is
studied on the basis of creep rupture data analysis on Gr.91, 92 and 122 steels. There are four
regions with different values of stress exponent n for creep rupture life commonly in stressrupture data of the three ferritic steels. Activation energies Q for rupture life in the regions take at
least three different values. The values of n and Q decrease in a longer-term region. The decrease
in Q value is the cause of the overestimation of long-term rupture life predicted by the
conventional TTP methods neglecting the change in Q value. Therefore, before applying a TTP
method creep rupture data should be divided into several data sets so that Q value is unique in
each divided data set. When this multi-region analysis is adopted, all the data points of the steels
can be described accurately, and their long-term creep life can be evaluated correctly. Substantial
heat-to-heat and grade-to-grade variation in their creep strength is suggested under recent service
conditions of USC power boilers.
Keywords: Power boiler steel; Creep life prediction; Time-temperature-parameter method;
Breakdown of creep strength; Multi-region analysis
INTRODUCTION
Allowable strength of structural materials at elevated temperature is usually determined by the
stress that causes creep rupture at 105h. Since creep tests for 105h are not easily carried out, the
creep rupture strength is evaluated from creep data tested at higher stress and temperature for
duration shorter than 105h. When formulating the short-term data, the following equations on
creep rupture life tr are usually employed:
tr = to f() exp(Q / R T)
tr = 10-C exp(g() / R T)
(1)
(2)
where to is a material constant, f() and g() are functions of stress , R is the universal gas
constant, and T is the absolute temperature. The activation energy Q and the Larson-Miller
constant C characterize temperature dependence of creep rupture life. A polynomial of ln is
generally used for f() and g(), for example:
lnf() or g() = a0 + a1 ln + a2 (ln)2 + a3 (ln)3 +a4 (ln)4+a5 (ln)5
732
(3)
where a0 to a5 are constants determined to get the best fit of a regression curve to data points. The
stress function is flexible enough, and no difficulty arises in describing stress dependence of
rupture life. Therefore, the stress function does not cause overestimation of long-term rupture life.
However, Eqs.(1) and (2) are quite rigid in terms of temperature dependence of rupture life. The
values of Q in Eq.(1) and C in Eq.(2) are assumed to be unique in a whole data set to be analyzed.
Figure 1 represents temperature dependence of rupture life at a given stress. The thick solid line is
a band of experimental data, and the thin solid line is a regression line for the data band. If Q is
unique as shown in Fig.1(a), the regression line coincides with the data band. The straight
extrapolation of the regression line (dotted line) can correctly predict long-term rupture life. On
the other hand, let us suppose that there are two regions with different values of activation energy
QH and QL as shown in Fig.1(b), and Q takes a lower value QL in the long-term data. Direct
application of Eq.(1) to such a data set gives the regression line represented by the thin solid line.
The extrapolation of the regression line causes overestimation of long-term rupture life. This is
often the case in austenitic stainless steels [1,2]. The same overestimation should occur in nickel
based superalloys [3] also. In order to avoid the overestimation, a multi-region analysis of creep
rupture data [1] has been proposed. In the analysis, a set of creep rupture data is divided into
several data sub-sets, so that Q in Eq.(1) is unique in each divided data set. Then a conventional
analysis based on Eq.(1) is applied to each divided data set.
Figure 1: Correlation between data band (thick solid line) and its regression line (thin solid line)
determined by Orr-Sherby-Dorn or Larson-Miller analysis of the creep rupture data.
Long-term rupture life of creep strength enhanced high Cr ferritic steels with a tempered
martensite lath microstructure is often shorter than what is predicted from short-term test data by
the conventional time-temperature-parameter methods [4-8]: for example, 11Cr-2.6W-0.1MoCoVNb rotor steel [9], 9Cr-1Mo-VNb (Gr.91) [6,10,11] and 11Cr-2W-0.4Mo-CuVNb (Gr.122)
[12,13] steels. Decrease in Q value in long-term rupture life of the steels has been reported in
literature [4,7,9,12,13]. The multi-region analysis has been successful in correct evaluation of
long-term rupture life of those steels [7,12].
In order to avoid the overestimation of rupture life in creep strength enhanced high Cr ferritic
steels, we should understand general trend on temperature dependence of their rupture life. In the
present paper creep rupture data of Gr.91 [14-16], 92 [17] and 122 [18] steels are examined
thoroughly paying attention to their temperature dependence. Difference and similarity among the
three grades will be studied together with causes of the change in Q value. The examination will
assist correct prediction of long-term rupture life of creep strength enhanced high Cr ferritic
steels.
733
(4)
where n is the stress exponent. There are four regions with different values of n in Fig.2(a). They
are referred to as:
H: high stress, short-term region (n = 19)
M: medium stress, short-term region (n = 8.8)
L1: low stress, short-term region (n = 6.0)
L2: long-term region (n = 2.5)
The solid lines in the figure are regression lines for the data points in each region. The dotted
lines indicate boundaries between neighboring regions. The stress exponent is unique within a
region. Creep rupture lives in each region, at 240MPa in region H, 120MPa in region M, 60MPa
in regions L1 and L2, are plotted against reciprocal temperature in Fig.2(b). The Q values in the
four regions are given in the figure. They decrease gradually with lowering stress from region H
to L1. It is to be noted that the Q value is extremely low in long-term region L2.
6
220
kJ/m
ol
L2, 60
L1, 60
714
10
Gr.91
632
(b)
614
Rupture Life [ h ]
10
10
M, 120
H, 240
10
1.1
1.2
1.3
1000 / T [ K ]
Figure 2: Stress-rupture data of Gr.91 steel together with their regression lines (solid lines)
determined in each region. (a) Stress and (b) temperature dependence.
Gr.122
The stressrupture data of Gr.122 steel [18] with 11%Cr are plotted in Fig.3(a) [19]. It points out
the presence of four regions with different values of n: regions H (n = 16), M (8.1), L1 (4.1) and
L2 (3.5). Temperature dependence of rupture life in each region is shown in Fig.3(b) [19] together
with the value of Q in each region. The Q values are lower in the lower stress regions and in the
longer-term region L2. At 180MPa, the point at 550oC deviates shorter from the regression (solid)
734
10
10
10
(b) Gr.122
34
70
74
7k
J/m
ol
56
Rupture Life [ h ]
line, suggesting decrease in Q in the longer-term. The stress and temperature dependence of
rupture life of Gr.122 steel is quite similar to that of Gr.91 steel.
10
L1, 40
L2, 80
M, 100
H, 180
1.1
1.2
1
1000 / T [ K ]
Figure 3: Stress-rupture data of Gr.122 steel together with their regression lines (solid lines)
determined in each region. (a) Stress and (b) temperature dependence.
ol
65
2k
47
J/m
10
65
6
41
10
69
L2, 40
L1, 80
M, 140
H, 200
854
Rupture Life [ h ]
(b)
10
10
Gr.92
2
10
1.1
1.2
1
1/T [K ]
Figure 4: Stress-rupture data of Gr.92 steel together with their regression lines (solid lines)
determined in each region. (a) Stress and (b) temperature dependence.
Gr.92
Stress-rupture data of Gr.92 steel [17] are plotted against stress in Fig.4(a) [19]. This steel also
has similar four regions with different values of n: regions H (n = 18), M (12), L1 (5.9) and L2
(3.1). Temperature dependence of rupture life in each region is shown in Fig.4(b) [19] along with
the values of Q in each region. The values of Q are lower in the lower stress regions similar to the
735
other two steels. Even within a region the Q values are lower in longer-term, as it is already
suggested in region H of Gr.122 steel.
CAUSES OF CHANGE IN Q
Creep rupture life tr should be described by the following equation, since the steel deforms by a
dislocation creep mechanism:
tr = S (/E)-n exp(Qd /R T)
(5)
(6)
If the strengthening due to microstructure is reduced with increasing temperature, dS /dT < 0. In
addition E decreases with increasing temperature. Therefore, Qa can be greater than Qd as found
in Figs.2-4. The contribution of the change in E (the third term of Eq.(6)) is proportional to n, and
decreases with decreasing n. However, the decreasing contribution of the third term is too small to
explain the decrease in Qa from region H to L1 found in Fig.2(b).
Creep strength enhanced high Cr ferritic steels are strengthened by a fine subgrain microstructure
(tempered lath martensite) [20,21]. Coarsening of subgrains due to strain induced recovery and
thermal recovery is the degradation process in this kind of steel [13]. Strain induced recovery
proceeds during creep under any creep condition, but thermal recovery is controlled by
aggregation of M23C6 and MX particles [20-22]. In short-term regions H and M diffusion distance
during creep exposure is shorter than that during tempering, and the aggregation of precipitates
and thermal recovery of subgrains do not occur. Strain induced recovery of subgrains is the only
degradation process in the short-term regions. The precipitates such as M23C6 and MX particles
should affect the strain induced recovery also. According to phase diagrams of the high Cr ferritic
steels, number density of the precipitates decreases with increasing temperature, and rate of strain
induced recovery should increase more significantly than that expected from the temperature
dependence of diffusion coefficient. In other words, S in Eq.(5) should decrease with increasing
temperature. This change in rate of strain induced recovery can be the major cause of the
substantially large values of Qa typical of the short-term regions.
It has been proposed that the thermal recovery of subgrain microstructure is added to the recovery
process in long-term regions L1 and L2 [13,20,21]. In the long-term regions recovery of subgrain
microstructure finishes in an early stage of creep, and the main part of creep proceeds without
strengthening by fine subgrains. Under such creep conditions, S is insensitive to temperature like
736
Rupture Life [ h ]
solid solution alloys and pure metals. Therefore, dS/dT is negligibly small and the value of Qa
approaches that for diffusion Qd. This should be the value of Qa close to Qd found in region L2.
The value of Qa becomes greater in region L1 due to the decrease in number density of the
precipitate with increasing temperature [20]. The value of Qa defined by Eq.(6) may decrease
continuously with decreasing temperature or stress from a substantially large value to a value
close to Qd, though rupture data can be classified into a few groups and Qa takes a similar value
within each group.
10
10
10
10
10
(b)
40
70
100
200
Gr.91
1.1
1.2
1
1000 / T [ K ]
Figure 5: Stress-rupture data of Gr.91 steel together with their regression lines (solid lines)
determined by the multi-region analysis. (a) Stress and (b) temperature dependence of rupture
life.
Table 1 Stress exponent n and activation energy Q for creep rupture life in each region of Gr.91,
92 and 122 steels
Gr.91
Gr.122
Gr.92
H
n = 20
Q = 720 kJ/mol
n = 16
Q = 714 kJ/mol
n = 19
Q = 659 kJ/mol
MS
835
M
8.9
622
7.9
714
12
ML
659
L1S
656
L1
5.9
618
4.1
563
6.1
L1L
499
L2S
> 540
L2
2.4
213
3.4
338
3.1
L2L
433
(7)
737
The material constant to, the values of n and Q are determined by a least square regression
analysis, so that the three parameters give the best fit of regression lines to data points.
Boundaries between neighboring regions are adjusted to minimize deviation of regression lines
from data points. A result of the analysis on Gr.91 steel is given in Fig.5(a). The data points are
divided into the four regions H, M, L1 and L2. The solid lines are regression lines, and the dotted
lines are boundaries between neighboring regions. The values of n and Q are summarized in Table
1. Rupture lives of Gr. 91 steel at four stress levels are plotted against reciprocal temperature in
Fig.5(b) together with their regression lines. The decrease in Q in the long-term creep is evident in
the figure. Results of the multi-region analyses of the stress-rupture data of Gr.122 and 92 steels
are summarized in Fig.6 and Table 1. The result of Gr.122 steel is essentially same as that of
Gr.91 steel. The result of Gr.92 steel is a little complicated. There are four regions H, M, L1 and
L2 with different stress exponent. Regions M, L1 and L2 are further divided into a short-term
region (S) with greater activation energy and a long-term region (L) with smaller activation
energy. As evident in Figs.5 and 6, the regression lines (solid lines) can very well describe all the
data points. Table 1 points out that the Q values take at least three different values in all the steels.
Figure 6: Stress-rupture data of (a) Gr.122 and (b) Gr.92 steels together with their regression
lines (solid lines) determined by the multi-region analysis.
GROUPING OF RUPTURE DATA POINTS
Half 0.2 Criterion
The multi-region analysis of rupture data requires dividing data points into several groups as
shown in Figs.5 and 6. The n and Q values should be unique within a group. A sufficient number
of data points are needed for correct grouping of data points. However, data points available in
creep life prediction are often limited, and the grouping is not always easy. Kimura et al [11] have
proposed an easier way in which they divided data points into two groups at a half of 0.2% proof
stress 0.2 measured by tensile tests at strain rate of 10-5s-1 at each testing temperature (half 0.2
criterion). They have predicted creep rupture life of a heat of Gr.91 steel [14,15] using the data
points lower than a half of 0.2 only [11]. On the other hand, Maruyama et al [13] have evaluated
long-term creep behavior of the same data following the original procedure of the multi-region
analysis. The two analyses gave different predictions as to its long-term creep rupture life. Let us
738
examine the validity of the half 0.2 criterion. As mentioned in Introduction, decrease in Q value
in long-term creep is the cause of overestimation of rupture life, and the half 0.2 criterion should
foretell the change in Q. As shown in Table 1 there are at least three regions with different values
of Q, contrary to the two regions assumed in the half 0.2 criterion. Therefore, the half 0.2
criterion cannot foretell all the boundaries appearing in Fig.5 and 6. Overestimation of creep life
in region L2 is a concern from practical point of view. The half 0.2 criterion is useful, if it can
foretell the boundary to region L2. The dashed curves in Figs.5(a) and 6 are the boundary
corresponding to a half of 0.2. They do not accord with the boundaries to region L2 in any steel.
Therefore, the half 0.2 criterion is not applicable to the three grades of steels.
HV
240
230
(a)
Gr. 91
220
HV
210
0
10
Stress [ MPa ]
20 (b)
200
(c)
600 C
150
100
Heat 3
Heat 2
Heat 1
80
60
10
10
10
Rupture Life [ h ]
Figure 7: (a) Hardness of heats 2 and 3 and (b) hardness change in heat 1 of Gr.91 steel
measured in a grip portion of specimens after creep rupture at 600 oC, together with (c) stressrupture data of the three heats of steel at 600oC.
Kimura et al [11] have explained that a half of 0.2 corresponds to micro-yield stress. At high
temperature yield stress of steel normalized by Youngs modulus becomes independent of strain
rate and temperature at sufficiently high strain rate, like during loading. The temperature
independent yield stress is called athermal yield stress. Plastic deformation during loading causes
significant changes in dislocation substructure in a specimen crept above athermal micro-yield
stress a, whereas the plastic deformation does not take place below a. Therefore, creep behavior
of steel changes at a [23]. An athermal stress-strain curve of a heat of Gr.91 steel has been
reported in literature [24]. If 0.02% proof stress is taken as the athermal micro yield stress
according to Ref.[23], a = 370 MPa at 450oC in the heat of Gr.91 steel. The athermal microyield
stress is proportional to Youngs modulus, and decreases with increasing temperature: a =
340MPa at 600oC, and 310MPa at 700oC, if significant microstructural degradation does not
occur before loading at the higher temperatures. All the test conditions of Gr.91 steel in Fig.5(a)
are lower than a. Therefore, a half of 0.2 represented by the dashed curve in Fig.5 does not
739
accord with a of the steel. It is to be recalled that all the creep stresses in the figure are above
micro yield stress at the creeping strain rate at each testing temperature. Physical basis of a half
of 0.2 seems not clear.
Onset of Thermal Recovery during Aging
Maruyama et al [13,20,21] have proposed that occurrence of thermal recovery of fine subgrain
microstructure due to aging is the cause of the breakdown of creep strength and the decrease in Q
in regions L1 and L2. The thermal recovery also brings about decrease in hardness measured after
static aging at creep temperature. The hardness drop measured in a grip portion of crept
specimens of the Gr.91 steel analyzed in Fig.5 has been reported in literature [16], and given in
Fig.7(b) (heat 1 in the figure) together with its stress-rupture data tested at the same temperature
(Fig.7(c)). The figure contains results of other heats 2 and 3 of Gr.91 steel reported in Ref. [20];
hardness measured in a grip portion of creep rupture specimens and their stress-rupture data tested
at 600oC. The creep strength of the three heats in the short-term region is similar to each other.
However, the long-term behavior in heat 1 is different from the others. Both hardness drop and
breakdown of creep strength start around 20,000h in heat 1. On the other hand, the breakdown is
absent up to 100,000h in heats 2 and 3, corresponding to the absence of clear drop in their
hardness in Fig.7(a). Similar good accordance between the breakdown of creep strength and the
decrease in hardness after static aging has been reported on several high Cr ferritic steels [13,2022,25,26]. These findings point out that the drop in hardness after static aging can foretell the
boundaries to L1 and L2. It should be noted, however, the hardness drop cannot foretell the
boundaries between regions H and M and between regions L1 and L2.
Figure 8: Long-term stress-rupture curves of Gr.91 (dashed line), 92 (solid line) and 122 (dotted
line) steels predicted by the multi-region analyses, together with experimental data (marks).
LONG-TERM CREEP RUPTURE LIFE
The regression lines obtained in Figs.5 and 6 are extrapolated to longer-term in Fig.8. The vertical
thick solid lines indicate the breakdown of creep strength. At 550oC the lines before the
breakdown belong to region H. Region L2 appears after the breakdown in Gr.91 and 122 steels. In
Gr.92 steel, the change in slope of stress-rupture curve is due to transition to region L1. Nuclear
740
power reactors of the fourth generation are planned to be operated for 500,000h at 550oC. The
service condition is in the region after the breakdown. Variation in creep strength is very small
among the three grades of steel before the breakdown. The variation becomes substantial in
regions L2 and L1 in which thermal recovery of lath martensite microstructure contribute
significantly to damage process in creep.
At 600oC, the regions before the breakdown (shorter than 20,000h) are region M in Gr.91 and 92
steels and region H in Gr.122 steel. Region L2 appears after the breakdown in Gr.91 and 122
steels. On the other hand, region L1 appears after the first breakdown of creep strength in Gr.92
steel and region L2 appears after 600,000h. The service condition of USC power boilers (10 5h at
600oC) is located after the breakdown. The grade-to-grade variation in creep strength is
substantial under the service condition also. The Gr.91 steel in Fig.8 (heat 1 in Fig.7) has quite
low creep strength as compared to the others. It is evident in Fig.7(c) that the heat-to-heat
variation in creep strength is also substantial after the breakdown, and that heat 1 has the
especially low creep strength. It should be mentioned that not all heats of Gr.91 steel have such
low creep strength as heat 1 in Fig.7.
CONCLUSION
1) There are four regions with different values of stress exponent n for creep rupture life
commonly in stress-rupture data of creep strength enhanced high Cr ferritic steels. Activation
energies Q for rupture life in the regions take at least three different values. The values of n and Q
decrease in a longer-term region.
2) The decrease in Q value is the cause of overestimation of long-term rupture life predicted by
conventional time-temperature-parameter (TTP) methods unable to deal with the change in Q.
Before applying a TTP method, creep rupture data should be divided into several data sets so that
the activation energy Q in Eq.(1) or Larson-Miller constant C in Eq.(2) is unique in each divided
data set.
3) When this multi-region analysis is adopted, all the creep data points can be described
accurately by regression curves, and long-term creep life can be evaluated correctly by them.
4) Hardness drop during thermal aging can foretell the boundaries to regions L1 and L2.
5) In long-term regions L1 and L2 in which thermal recovery of lath martensite microstructure
proceeds significantly, predicted creep rupture life exhibits substantial heat-to-heat and grade-tograde variation as compared to short-term regions H and M in which the thermal recovery does
not occur.
ACKNOWLEDGMENTS
A part of the present study was carried out as a research activity supported by ALCA project.
Financial support from Japan Science and Technology Agency is gratefully acknowledged. The
other part of the present study was supported by the Ministry of Education, Science, Sports and
Culture, Japan (Grant No.23360296).
REFERENCES
[1] Maruyama, K., et al, Errors of creep rupture life extrapolated by time-temperature
parameter methods, Tetsu-to-Hagane, Vol. 80, (1994), pp. 336-41.
[2] Maruyama, K., et al, Multiregion analysis of creep rupture data of 316 stainless steel, Int J
Press Vess Pip, Vol. 84, (2007), pp. 171-6.
741
[3] Ashby, M.F., et al, Fracture mechanism maps and their construction for F.C.C metals and
alloys, Acta Metall, Vol. 27, (1979), pp. 699-729.
[4] Maruyama, K., et al, Strengthening mechanism of creep resistant tempered martensitic
steel, ISIJ Int, Vol. 41, (2001), pp. 641-53.
[5] Danielsen, H.K. and Hald, J., Behaviour of Z phase in 9-12%Cr steels, Energy Mater,
Vol. 1, (2006), pp. 49-57.
[6] Masuyama, F., Advanced technology in creep life prediction and damage evaluation for
creep strength enhanced ferritic steels, Proceedings of high-temperature defect assessment5, European Technology Development (Surry, UK, 2010), CD-ROM.
[7] Maruyama, K., Fracture mechanism map and fundamental aspects of creep fracture,
Creep-resistant steels, Woodhead Publishing (Cambridge, 2008), pp. 350-64.
[8] Kimura, K., et al, Evaluation of long-term creep strength of ASME grade 91, 92, and 122
type steels, Proc ASME 2012 Pressure Vessels & Piping Division Conf, Toronto, Canada,
July. 2012, PVP2012-78323, pp. 1-7.
[9] Sawada, K., et al, Dislocation substructure degradation during creep of martensitic heatresisting steels with and without W, Materials for advanced power engineering 1998,
Forshungszentrum Julich GmbH (Julich, 1998), pp. 575-83.
[10] Kushima, H., et al, Degradation of mod.9Cr-1Mo steel during long-term creep
deformation, Tetsu-to-Hagane, Vol. 85, (1999), pp. 841-7.
[11] Kimura, K., et al, Influence of stress on degradation and life prediction on high strength
ferritic steels, ASME PVP, Vol. 476, (2004), pp. 11-8.
[12] Maruyama, K. and Yoshimi, K., Influence of data analysis method and allowable stress
criterion on allowable stress of Gr.122 heat resistant steel, Trans ASME, J Press Vess
Technol, Vol. 129, (2007), pp. 449-53.
[13] Maruyama, K., et al, Cr concentration dependence of overestimation of long term creep life
in strength enhanced high Cr ferritic steels, Int J Press Vess Pip, Vol. 87, (2010) pp. 27681.
[14] National Institute for Materials Science, Data sheets of the elevated-temperature properties
of 9Cr-1Mo-V-Nb steel tubes for boilers and heat exchangers and 9Cr-1Mo-V-Nb steel
plates for boilers and pressure vessels (NIMS Creep Data Sheet No. 43), NIMS (Tsukuba,
1996).
[15] National Institute for Materials Science, Creep deformation properties of 9Cr-1Mo-V-Nb
steel tubes for boilers and heat exchangers and 9Cr-1Mo-V-Nb steel plate for boilers and
pressure vessels (NIMS Creep Data Sheet No.D-1), NIMS (Tsukuba, 2007).
[16] Kimura, K., et al, Long-term creep strength property of advanced ferritic creep resistant
steels, Advances in materials technology for fossil power plants, ASM International
(Materials park, USA, 2011), pp. 732-51.
[17] National Institute for Materials Science, Data sheets of the elevated-temperature properties
of 9Cr-0.5Mo-1.8W-V-Nb steel tubes for power boilers and 9Cr-0.5Mo-1.8W-V-Nb steel
pipe for high temperature service (NIMS Creep Data Sheet No. 48A), NIMS (Tsukuba,
2012).
[18] National Institute for Materials Science, Data sheets of the elevated-temperature properties
of 11Cr-2W-0.4Mo-1Cu-Nb-V stainless steel pipe for high temperature service and 11Cr2W-0.4Mo-1Cu-Nb-V stainless steel plate for power plants and 11Cr-2W-0.4Mo-1Cu-Nb-V
stainless steel tube for power boilers (NIMS Creep Data Sheet No. 51), NIMS (Tsukuba,
2006).
[19] Maruyama, K., to be published
[20] Chen R.P., et al, Premature creep rupture and overestimation of rupture life in modified
9Cr-1Mo steel, Tetsu-to-Hagane, Vol. 96, (2010), pp. 564-71.
742
[21] Ghassemi Armaki, H., et al, Premature creep failure in strength enhanced high Cr ferritic
steels caused by static recovery of tempered martensite lath structures, Mater Sci Eng, Vol.
A527, (2010), pp. 6581-8.
[22] Ghassemi Armaki, H., et al, Creep behavior and degradation of subgrain structures pinned
by nanoscale precipitates in strength-enhanced 5 to 12 pct Cr ferritic steels, Metall Mater
Trans, Vol. 42A, (2011), pp. 3084-94.
[23] Maruyama, K., et al, Examination of deformation mechanism maps in 2.25Cr-1Mo steel by
creep tests at strain rates of 10-11s-1 to 10-6s-1, Mater Sci Eng, Vol. A224, (1997), pp. 16672.
[24] National Institute for Materials Science, Creep deformation properties of 9Cr-1Mo-V-Nb
steel plates for boilers and pressure vessels (NIMS Creep Data Sheet No.D-2), NIMS
(Tsukuba, 2008).
[25] Lee, J.S., et al, Causes of breakdown of creep strength in 9Cr-1.8W-0.5Mo-VNb steel,
Mater Sci Eng, Vol. A428, (2006), pp. 270-5.
[26] Ghassemi Armaki, H., et al, Creep damage evaluation by hardness in advanced high Cr
ferritic steels, Key Eng Mater, Vol. 561-565, (2007), pp. 2217-20.
743
ABSTRACT
The change in hydrogen desorption characteristic due to creep was investigated to examine the
possibility of hydrogen as tracer for detecting and evaluating the creep damage accumulated in
high Cr ferritic boiler steel, Gr.91. Hydrogen charging into the creep specimen was conducted by
means of cathodic electrolysis. Next, the thermal desorption analyses (TDA) were carried out at
temperature range from room temperature to 270C for measuring the hydrogen evolution curve.
The experimental results revealed that the amount of hydrogen desorbed during analysis, CH,
increased with increasing creep life fraction, although the trend of increase in CH was strongly
dependent on the stress level. Moreover, there was an almost linear correlation between the
logarithm of CH measured on the creep ruptured specimen and the Larson-Miller parameter
(LMP), which was approximated by log CH = 0.39 LMP 13.4. This can be a criterion for
creep rupture and means that as far as the CH does not reach the line, the rupture never occurs.
INTRODUCTION
High Cr ferritic boiler steels such as Gr.91, Gr.92 and Gr.122 have excellent high-temperature
strength as well as superior oxidation and corrosion resistances. As schematically illustrated in
Fig. 1, these kinds of steels have a complex lath martensitic structure consisting of several
microstructural units, i.e., in the order of their size, lath, block and/or packet including several
laths, and prior austenite grain [1]. In addition, the precipitation strengthening attributed to Laves
phase, the solid-solution strengthening by molybdenum and/or tungsten, and the dispersion
strengthening by M23C6 and MX contribute to their strength [2-6]. However, their creep damage
and/or materials deterioration mechanisms have not been thoroughly clarified because of the
above-mentioned extremely fine and complicated microstructures. Needless to say, a procedure
for evaluating the damage and/or materials deterioration with high accuracy, which must be based
on those mechanisms, has not as yet been established.
On the other hand, hydrogen is known to be trapped by vacancy, vacancy cluster, dislocation,
grain boundary, precipitate and void in steels and it is easily released from these trap sites by
744
Dislocation
Segregation
0.5 m
Precipitates
(grain boundary) Solid-solution
elements
10 m
Precipitates
(grain interior)
PAG boundary
0.1
As-tempered
600/120MPa
600/100MPa
600/90MPa
650/40MPa
0.08
0.06
0.04
0.02
0
50
100
150
200
250
Temperature,
Figure 2: Effect of applied initial stress on hydrogen evolution curve of Gr.91 [11].
745
Low mag.
As-tempered
10 m
1 m
1 m
High mag.
10 m
170
160
40MPa/700
50MPa/700
90MPa/625
90MPa/650
110MPa/650
115MPa/625
as-tempered
150
140
130
120
33.5 34 34.5 35 35.5 36 36.5 37 37.5 38 38.5 39
Larson-Miller parameter (C=36)
as-tempered
EXPERIMENTAL PROCEDURES
Materials and Creep Tests
The material used in this study was a representative high Cr ferritic steel, Gr.91, which has been
employed for boiler piping and tubing. The creep tests were carried out at a wide variety of
temperature and initial stress using. As shown in Table 1, the tests were stopped at some different
life fractions to prepare the interrupted creep specimens with various degrees of damage in
addition to the creep ruptured specimens.
746
0.12
(a)
100%
66%
44%
22%
as-tempered
0.1
0.08
0.06
0.04
0.02
0
625/90MPa
0
50
100
150
200
250
Temperature,
0.45
(b)
0.4
100%
62%
41%
as-tempered
0.35
0.3
0.25
0.2
0.15
0.1
675/60MPa
0.05
0
50
100
150
200
250
Temperature,
Figure 5: Examples of hydrogen evolution curves measured on creep specimens tested at (a)
625C/90 MPa and (b) 675C/60 MPa.
Hydrogen Thermal Desorption Analysis
The thin plate-type specimen (690.6 mm) parallel to the loading direction was removed from
the gauge portion of the creep specimen. Finally, the thickness of the plate-type specimen was
carefully adjusted to be 0.50.005 mm, because the specimen thickness has a significant influence
on the below-mentioned hydrogen evolution curve. The specimen surface was finished by the
emery paper of #2400.
The hydrogen charging into the specimen was conducted by means of cathodic electrolysis in 0.1
mol/l NaOH aqueous solution containing 0.5 mass% NH4SCN under a current density of 5
mA/cm2. The charging time was 4 h and the solution temperature was kept to be 30C during the
charging.
The thermal desorption analysis (TDA) was carried out at a temperature range from room
temperature to 270C. The heating rate was 100C /h. The desorbed hydrogen carried with high
purity argon gas was quantified by a gas chromatograph at intervals of 5 minutes. The flow rate of
the argon carrier gas was fixed to be 1.210-5 m3/min throughout the analysis. The hydrogen
evolution rate was calculated as the amount of hydrogen desorbed in one minute per one gram of
specimen.
747
2
1.8
40MPa/700
90MPa/625
110MPa/650
as-tempered
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
-0.2
100
10
as-tempered
Time, h
1000
10000
40MPa/700
90MPa/625
110MPa/650
as-tempered
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
-0.2
20
40
60
Creep life fraction t/tr, %
80
100
748
1.6
1.4
1.2
1
0.8
0.6
40MPa/700 rupture
50MPa/700
60MPa/675
75MPa/650
90MPa/625
90MPa/650
110MPa/650
115MPa/625
*
as-tempered
*
0.4
0.2
*
*
-0.2
33.5 34 34.5 35 35.5 36 36.5 37 37.5 38 38.5 39
Larson-Miller parameter (C=36)
as-tempered
749
increase in density of hydrogen trapping site and/or the formation of new trapping site having
higher binding energy.
Changes in Amount of Desorbed Hydrogen
The amount of hydrogen desorbed during analysis was determined by calculating the area below
the hydrogen evolution curve and was denoted by CH. As an example, the logarithm of CH
measured on the creep specimens tested at 650C/110 MPa, 625C/90 MPa and 700C/40 MPa
are plotted as a function of creep time in Fig. 6. The CH increases with increasing time, but the
Criterion for creep rupture
log CH 0.39LMP13.4
log CH
creep rupture
1 > 2
2
1
consuming
creep life
Larson-Miller parameter
(1)
This is a criterion for creep rupture in a sense. As illustrated in Fig. 9, the CH of steel under creep
is increased with accumulating the damage and consuming its life, and the creep rupture
eventually occurs when the CH crosses the line. That is to say, as far as the CH does not get to the
line, the fracture never occurs.
In the previous study [11], it was observed by the authors that the CH showed almost no variation
by the mere thermal aging. Additionally, the hydrogen desorption characteristic of creep ruptured
specimen was almost unaffected by the re-normalizing, which succeeded in recovering the
microstructures. These results suggested that the change in hydrogen desorption characteristic due
750
to creep was predominantly ascribed to the formation of geometric damage such as creep cavities
and microcracks rather than the microstructural changes. At relatively high stresses, that is, in the
long-term creep region, the creep fracture is mainly attended by large deformation and
accompanied with almost no geometric damage such as creep cavities and microcracks, which
generally lead to the reduction of ductility. This transition of damage and/or fracture mechanisms
is likely to be associated with the above-mentioned change in increment of CH with stress level.
Consequently, this technique is expected to exhibit its ability to the full for the steels damaged at
relatively low stresses like the mild conditions of actual components.
SUMMARY
The change in hydrogen desorption characteristic was systematically investigated to examine the
applicability of hydrogen as tracer for detecting the creep damage. The thermal desorption
analysis (TDA) was applied to the interrupted creep specimens of Gr.91with various degrees of
damage. The experimental results revealed that the amount of hydrogen desorbed during analysis,
CH, increased with consuming creep life, although the trend of increase was strongly dependent on
stress level. Moreover, there was an almost linear relation between the log CH measured the
ruptured specimen and the Larson-Miller parameter (LMP), which was approximated by log CH
= 0.39 LMP 13.4. This can be a criterion for creep rupture and means that as far as the CH does
not reach the line, the fracture never occurs. It is expected from the present study that this
technique exhibits its ability to the full for steels damaged at relatively low stresses like the
conditions of actual components.
ACKNOWLEDGMENTS
This study was carried out as a part of the research activities of the Fundamental Studies on
Technologies for Steel Materials with Enhanced Strength and Functions by the Consortium of
JRCM (The Japan Research and Development Center of Metals). Financial support from NEDO
(New Energy and Industrial Technology Development Organization) is gratefully acknowledged.
REFERENCES
[1] Maruyama, K., Sawada, K. and Koike, J., Strengthening Mechanisms of Creep Resistant
Tempered Martensitic Steel, ISIJ International, Vol. 41, No. 6 (2001), pp. 641-653.
[2] Sawada, K., Takeda, M., Maruyama, K., Ishii, R., Yamada, M., Nagae, Y. and Komine, R.,
Effect of W on recovery of lath structure during creep of high chromium martensitic steels,
Materials Science and Engineering A, Vol. 267 (1999), pp. 19-25.
[3] Sawada, K., Kimura, K. and Abe, F., Mechanical response of 9% Cr heat-resistant
martensitic steels to abrupt stress loading at high temperature, Materials Science and
Engineering A, Vol. 358 (2003), pp. 52-58.
[4] Hayakawa, H., Terada, D., Yoshida, F., Nakashima, H. and Gotou, Y., Evaluation of Mobile
Dislocation Density of Modified 9Cr-1Mo Steel by Stress Change Test, Tetsu-to-Hagane,
Vol. 89, No. 10 (2003), pp. 1076-1081.
[5] Abe, F., Taneike, M. and Sawada, K., Alloy design of creep resistant 9Cr steel using a
dispersion of nano-sized carbonitrides, International Journal of Pressure Vessels and
Piping, Vol. 84 (2007), pp. 3-12.
751
[6] Armaki, H. G., Chen, R., Kano, S., Maruyama, K., Hasegawa, Y. and Igarashi, M., Straininduced coarsening of nanoscale precipitates in strength enhanced high Cr ferritic steels,
Materials Science and Engineering A, Vol. 532 (2012), pp. 373-380.
[7] Nagumo, M., State of Hydrogen in Materials II, Zairyo-to-Kankyo, Vol. 54, No.6 (2005),
pp. 251-261.
[8] Hirth, J. P., Effects of hydrogen on the properties of iron and steel, Metallurgical and
Materials Transactions A, Vol. 11 (1980), pp. 861-890.
[9] Valentini, R, Solina, A., Matera, S. and Gregorio, P. D., Influence of titanium and carbon
contents on the hydrogen trapping of microalloyed steels, Metallurgical and Materials
Transactions A, Vol. 27 (1996), pp. 3773-3780.
[10] Tsuchida, T., Hara, T. and Tsuzaki, K., Relationship between Microstructure and Hydrogen
Absorption Behavior in a V-bearing High Strength Steel, Tetsu-to-Hagane, Vol. 88, No. 11
(2002), pp. 771-778.
[11] Komazaki, S., Honda, T., Sakamura, T., Sawada, K., Kimura, K. and Kohno, Y., Changes in
hydrogen desorption characteristics of Mod.9Cr-1Mo steel due to creep, Tetsu-to-Hagane,
Vol. 96, No. 10 (2010), pp. 614-619.
752
Experimental parameters such as water chemistry, the presence of a heat-flux, and excursions in
temperature, pressure, and heat-flux all impart, individually and in combination, on the oxidation
performance. Consequently there is a conflict between performing laboratory exposures in as
inexpensive a manner as possible, and maintaining relevance to the industrial situation.
The influence of pressure on the oxidation of power plant materials has always been considered
to be less significant than the effects of temperature and Cr content, but it still remains a subject
of differing opinions. From a first principles approach, the effect of steam pressure on the rate of
oxidation can be derived by considering the dependence of the diffusion process with respects to
the oxygen partial pressure. Wright and Dooley [1] discuss this derivation which results in a
table showing the expected effect of steam pressure on the parabolic rate constant, k p , and oxide
thickness, as shown in Table I.
Table I Expected effect of increasing steam pressure on oxidation kinetics (after [1]).
P steam , bar
1-17
1-34
34-241
k p factor increase
(magnetite)
1.4-1.5
1.5-1.7
1.2-1.3
In the literature, data presenting the influence of pressure on the steam oxidation behaviour of
structural alloys shows a wide variation in behaviour. Therefore it is difficult to determine any
consistent effect of pressure based on plant data in comparison to atmospheric laboratory data.
Otoguro et al [2] measured the maximum scale thickness on 4 austenitic alloys (SUS347HTB,
17/14CuMo, 20Cr/25Ni and 22Cr/35Ni) after exposure to steam for 500 h at 650 and 700 C and
pressures up to 35 MPa. The results showed that, on increasing the pressure at 650 C, two of the
alloys investigated showed a decrease in scale growth rate of approximately 20%, one of the
alloys showed no influence of pressure on the scale thickness and one alloy showed an increase in
scale thickness by a factor of 4, as shown in Figure 1. The same trend in results was observed at
700 C.
Figure 1 The influence of steam pressure on the maximum scale thickness of 4 austenitic
alloys after exposure to steam at 650 C for 500 h [2].
Montgomery and Karlsson [3] have summarised data on the influence of pressure on scale growth
kinetics during plant exposure of martensitic steels (HCM12 and P92) to steam environments.
The high pressure data for HCM12 implied a decrease in scale growth rate with increasing
pressure whereas the high pressure data for P92 implied either no effect of pressure or a change in
the pressure effect with temperature depending on interpretation. These data from plant exposures
may also have been influenced by deviations in the operating conditions during the day to day
operation. Laboratory measurements under more controlled conditions have shown that the
754
pressure effect maybe dependant on the exposure temperature. Work by Watanabe et al [4]
shows a small increase in the rate of oxidation with increasing pressure (up to 100 bar) for 211wt% Cr steels at 700 C, but a decrease in the apparent oxidation rate for temperatures below
600 C. Work has also been performed by the then British Energy group [5] who conducted a test
programme using a range of autoclave exposures on 9Cr-1Mo steel over a range of pressures (2.7
166 bar) and temperatures (500, 550, 600 and 650 C) for times up to 10,000 hours. They
reported an effect of steam pressure for temperatures of 600 and 650 C but not at the lower,
more realistic, operating temperatures. Metallography of the specimen revealed the development
of porosity (Figure 2) in the scale at the higher temperatures which may explain the increase of
the growth rate. Montgomery and Karlsson [3] also commented on the development of a porous
scale suggesting that the increased porosity decreased the thermal conductivity of the scale
leading to localised temperature increases and hence an increase in the oxidation rate.
Figure 2 Scale morphology of 9Cr-1Mo samples exposed to steam at 166 and 2.7 bar at 650
C [5].
To examine the pressure dependency of the oxidation kinetics further a series of exposures has
been performed using a moderately high pressure flowing steam facility to conduct exposures on
ferritic-martensitic materials and coated materials.
EXPERIMENTAL PROCEDURE
Steam oxidation exposures were conducted under atmospheric pressure and at elevated pressure.
For the atmospheric pressure tests, exposures were performed using horizontal tube furnaces
consisting of three IN625 work tubes, into which alumina boats were placed holding the
specimens. The feed water of the steam furnaces was deionised and deoxygenated by bubbling
N 2(g) through the water reservoir. Dissolved oxygen levels in the range of 5-13 ppb were
recorded. The liquid water was then passed into the furnace at a rate of ~3 ml min-1, the water
was heated and formed into steam which then flowed naturally through the furnace, exiting
through a water trap on the far side of the furnace. The hot zone of the furnace tube was profiled
prior to the start of the test, with the furnace controls adjusted to ensure a uniform hot zone. The
test specimens, compositions shown in Table II, were loaded into the hot furnace tube under the
flowing steam atmosphere. Exposures were conducted at 650 C for 300, 1000 and 3000 hours,
only the 1000 hour data are considered here. At the end of the exposure the specimens were
carefully withdrawn under steam and allowed to cool in laboratory air.
Exposures at elevated pressure were performed using a high pressure recirculating steam loop.
This consisted of a water treatment section which deionises and deoxygenates the feed water
achieving levels of dissolved oxygen and conductivity of 2-5 ppb and ~5 s/cm2 respectively.
The feed water was pumped into an evaporator vessel at a rate of ~10 ml min-1 which heats the
water to produce steam at ~300 C, this then passes through a superheater section which raises
the temperature to ~450 C. The specimens were suspended on a frame in the main pressure
vessel which was heated to attain the desired exposure temperature on the specimens. The
755
specimens were loaded into the pressure vessel which was then sealed. Once installed the rig was
heated with the outlet of the pressure vessel left open. Through this orifice was fed a
thermocouple which was used to set the controls of the heater bands such that the desired test
temperature was achieved. Tests were performed at 650 C at various pressures for 1000 hours. A
thermocouple is embedded in the lid of the pressure vessel to monitor the stability of the
temperature, but this was offset from the actual temperature of the specimen. An optical gate was
installed in the condensed water return leg of the loop to monitor continual flow of water and
steam during the exposure. The loop is capable of operating at temperatures up to 750 C and
pressure up to 100 bar. Figure 3 shows typical performance logs from the rig, in this instance
during a test at 700 C and a pressure of 50 bar. Figure 4 shows the temperature calibration chart
for the steam loop. For this calibration chart the heater used for the vessel cover was set to 50%
power and the heater for the vessel body operated using an automatic set point control. This
figure shows that for a specimen temperature of 700 C, the vessel temperature (as measured in
the thermowell) should be 630 C, which corresponds to the value shown in Figure 3.
600
300
53
49
25
Figure 3 Data log from a high pressure test at 700 C and 50 bar showing the stability of the
rig in terms of temperature, pressure and flow.
700
Temperature, C
600
500
400
300
200
100
Vessel Cover
Vessel Body
0
400
450
500
550
600
650
700
750
Specimen Temperature, C
Figure 4 Steam Loop temperature calibration chart, power to vessel cover set to 50%.
756
After exposure the specimens were weighed for mass change purposes and then plated with
nickel to retain the oxide, sectioned and mechanically polished. Oxide scale thickness
measurements were made along the specimen surface using image analysis software.
In addition to exposures of uncoated materials at elevated pressure, tests have also been
conducted on aluminium slurry coated T91 substrates. The slurry coating comprised of fine
aluminium power dispersed in a binder/carrier, once applied the specimens were heat treated at
350 C for 30 minutes to cure the binder and encourage diffusion into the substrate. The
specimens were then subjected to a further heat treatment of 2 hours at 750 C under argon filled
vacuum to promote densification and formation of an Al-Fe intermetallic phases within the
coating. In all cases it was observed that aluminium oxide formed at the coating/substrate
interface along with intermetallic phases [6]. These were then exposed to 100% flowing steam
environments in a similar manner as previously described at atmospheric and elevated pressure.
Table II Alloy compositions of materials included in the test programme.
Alloy
Fe-10Cr
P92
T91
T92
VM12
C
0.003
0.12
0.12
Si
0.10
0.50
0.40
0.48
Mn
0.061
0.58
0.58
0.37
Cr
10.33
9.37
9.26
9.19
11.61
Mo
0.45
1.08
0.36
0.28
Nb
0.044
N
0.04
0.078
Cu
0.006
B
0.005
Table IV Total mean oxide thickness as a function of pressure for alloys exposed to flowing
steam at 650 C for 1000 hours.
Alloy
Fe-10Cr
P92
T91
T92
VM12
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Figure 5 Specific mass change (a) and average total oxide thickness (b) for alloys exposed to
flowing steam at 650 C for 1000 hours at atmospheric and elevated pressure.
In examining the results, considering the specific mass change at elevated pressure tests it can be
seen that there is a general trend for the alloys to show increasing oxidation rates with increasing
pressure. However, when including the atmospheric pressure data there are clear inconsistencies.
In nearly all cases (apart from T92 which had gross spallation of the outer magnetite layer) the
rate of oxidation at atmospheric pressure is seen to be greater than at the higher pressure.
Examination of the total oxide thickness shows similar trends, with initially thick oxides at
atmospheric pressure, but thinner oxide scales at elevated pressure, which then thicken with
increasing pressure. VM12, containing higher levels of chromium (Table II), presented
decreasing rates of oxidation with increasing pressure. From optical micrographs of the samples,
shown in Figure 6, it is evident that the scale morphology differs considerably when comparing
the atmospheric pressure samples to the elevated pressure samples. In particular the amount of
porosity in the scale generally decreases with increasing pressure, as shown in Figure 7. It should
be noted that the morphologies of the higher pressure scales correspond to those seen in plant
exposed materials [7] much better than those formed at atmospheric pressure.
If the data from the atmospheric pressure exposures is excluded, it is possible to plot the mass
change or oxide thickness as a function of pressure. This has been done in terms of the oxide
thickness for the model Fe-10Cr and P92 alloys (Figure 8a), as these showed no spallation during
the test and have the more complete data set. Using this plot it is possible to extrapolate back to
determine the oxide thickness which would be expected at atmospheric pressure based on a linear
relationship. This would suggest that the oxide thickness should be significantly smaller than that
obtained in the experimental exposures, 64 m and 14 m for Fe-10Cr and P92 respectively.
However, when comparing the percentage increase in oxide thickness as a function of pressure as
detailed in Table I [1] the calculated effect on the increase in oxide thickness does not align with
the theoretical values. Based on a Px relationship, where x is 0.11 to 0.15 for magnetite [1], the
total oxide thickness at atmospheric pressure would be expected to be in the range of 74 to 80 m
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for Fe-10Cr and 69 to 75 m for P92. This would equate to inner oxide thickness values of 37 to
40 m for Fe-10Cr and ~34 to ~37 m for P92.
Porosity, %
14
1
12
25
10
50
60
6
4
2
0
Fe-10Cr
P92
T91
T92
Figure 7 Porosity as a function of pressure for alloys exposed to flowing steam at 650 C for
1000 hours, calculated using image analysis techniques.
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To further investigate the expected oxide thickness at atmospheric pressure a predictive neural
network model has been used. The model has been generated using data from plant measurements
for a range of temperatures, pressures, alloys and times with additional short-term (up to 5,000
hours) laboratory-generated steam oxidation data used to supplement the longer-term plant data
for neural network training purposes. The model uses the metal temperature, pressure, exposure
time and key elemental compositional information of the alloy, from which it provides a
prediction of the inner oxide thickness. The values predicted from this model are observed to
agree well with those from theoretical calculations, whilst still excluding the atmospheric data
points. Figure 8b and 8c show the predicted inner oxide thickness as a function of pressure for
Fe-10Cr and P92 exposed to flowing steam at 650 C for 1000 hours, compared with the actual
experimental values measured. Whilst there is some scatter, the experimental points broadly fall
on the prediction curve. These curves provide predicted values of the inner oxide thickness at
atmospheric pressure of 49 and 44 m for Fe-10Cr and P92 accordingly. These values compare
well with the theoretical values for the inner oxide thickness of 37 to 40 m for Fe-10Cr and 34
to 37 m for P92.
Very little high pressure laboratory exposure data is presented in the literature, while there are
many examples of atmospheric data. Focusing on the commercial P92 alloy, the NPL generated
atmospheric data has been compared to literature data for similar experimental conditions [8] [9]
[10] and is shown to be in agreement with these published data. In his 2009 report, Wright [10]
compared the mass change of T91 and T92 exposed for times up to 4000 hours at 1 and 17 bar
pressure. He reported that after 4000 hours exposure the mass gain was a factor of two higher for
the lower steam pressure, which is consistent with that seen for Fe-10Cr in Table III. The increase
in mass gain was caused by an overall faster rate of oxidation; the parabolic rate constant was
60% higher than those at 17 bar, and a higher mass gain in the initial/transient oxidation period,
approximately 14 times as much as at 17 bar [10].
Figure 8 Average total oxide thickness as a function of pressure (a) for Fe-10Cr and P92
and comparison of neural network prediction with experimental data for inner oxide
thickness for (b) Fe-10Cr and (c) P92.
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In the case of the coated specimens the aluminide coating provided good protection against steam
oxidation for the test durations by growing a protective Al 2 O 3 layer instead of the usual iron
oxides. However, there were notable differences in the diffusion behaviour of the aluminium in
the coating as a function of the exposure pressure, as can be seen on the SEM images of cross
sections through two samples exposed to atmospheric and 60 bar flowing steam in Figure 9. At
atmospheric pressure, the original Al 5 F 2 layer, appearing in dark grey contrast in Figure 9, acts as
the aluminium reservoir for the formation of the protective Al 2 O 3 scale. Aluminium also diffuses
towards the T91 substrate, which progressively transforms the Al 5 Fe 2 layer into an AlFe phase
and creates an Al diffusion zone in the substrate. The reaction between aluminium and nitrogen
present in the T91 substrate produces thin AlN needles in the Al diffusion zone. After 1000 hours
exposure to steam at atmospheric pressure, the thickness of the Al diffusion zone reached ~24
m.
At elevated pressure, 60 bar, similar Al 5 Fe 2 , AlFe and Al diffusion zone layers were observed.
However, their thicknesses are much thinner than at atmospheric pressure, notably the Al
diffusion zone which only reached ~8 m (Figure 9). Whilst the Al 2 O 3 layer is almost twice as
thick at 60 bar than at atmospheric pressure, measuring 0.7 and 0.4 m respectively (Figure 9).
The major difference occurring between the two conditions is the depth of aluminium diffusion
into the substrate material.
7 m
Figure 9 Micrographs of coated T91 exposed at 650 C for 1000 hours to flowing steam at
atmospheric and 60 bar pressure.
Line EDX analysis of the cross sections demonstrates the differences in the aluminium diffusion
as shown in Figure 10. This graph shows the different aluminium concentrations of the layers
constituting the aluminide coating and in the Al diffusion zone on two samples exposed at
atmospheric pressure for 300 and 1000 hours, and one sample exposed at 60 bar for 1000 hours.
From 300 to 1000 hours at atmospheric pressure, in the coating, the size of the phase containing ~
65 at% Al (Al 5 Fe 2 ) diminished to the benefit of the phase containing ~50 at% Al (AlFe). This
reduction in aluminium content is in turn explained by the greater extent of diffusion of
aluminium into the substrate. After 1000 hours under 60 bar however, the Al 5 Fe 2 layer depletes
in Al to the same extent as the Al 5 Fe 2 layer of the sample exposed for 300 hours under
atmospheric pressure and the diffusion of aluminium into the aluminium diffusion zone is less
than both the samples exposed at atmospheric pressure. This clearly shows a reduction of the
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aluminium diffusion under higher pressure, but also a possible change in the aluminium diffusion
behaviour.
Figure 10 EDX line scans showing Al content through the cross-section of the Al slurry
coated T91 samples exposed at 650 C under atmospheric for 300 and 1000 hours and 60
bar flowing steam for 1000 hours.
The precise mechanism responsible for the variation in diffusion of the aluminium as a function
of pressure is not fully understood at this point, but is believed to be linked to Gibbs free energy
which has a pressure dependency as demonstrated by Mehrer [11]. Further work to understand
this effect is ongoing.
CONCLUSIONS
The oxidation rate, in terms of specific mass change and oxide thickness, has been compared for
a selection of ferritic-martensitic alloys exposed to flowing steam at 650 C for 1000 hours at
atmospheric pressure and elevated pressure. Exposures conducted at 25, 50 and 60 bar pressure
show increasing rates of oxidation for both mass change and oxide thickness measurements.
However, greater oxidation was observed for exposures at atmospheric pressure, with an increase
in the oxidation rate at ambient pressure of approximately 60%.
The morphology of the oxide scales formed was also seen to be dependent on the exposure
pressure, with the elevated pressure samples showing a more dense compact oxide with
increasing pressure. Whilst at low and ambient pressure the scale contains a large percentage of
porosity. The presence of the porosity could have two effects on the oxidation rate, one based on
the thermal properties of the scale, the second on the transport processes through the scale. The
presence of the pores could act as an insulative component to the scale and thereby decrease the
thermal diffusivity of the scale, which if a temperature gradient existed across the sample may
lead to an increase in the local temperature in the scale/metal interface and thus promote faster
oxidation kinetics. In this instance the tests were performed under isothermal conditions and so
this would not influence the oxidation process. The pores formed in the scale contribute to rapid
inward diffusion of oxygen via the H 2 /H 2 O- bridges proposed by Rahmel and Tobolski [12]
and discussed by Saunders et al [13]. Under such circumstances if a void contains both hydrogen
and water vapour, oxidation of the surface nearest the metal will occur by reaction with water to
form new oxide and the gaseous reaction product hydrogen, as shown in Figure 11. The increased
porosity in the specimens exposed at atmospheric pressure, illustrated in Figure 7, may account
762
for the increased growth in the oxide via this mechanism compared to more dense oxides formed
at elevated pressure.
Figure 11 Schematic showing oxygen transfer across pores in water vapour containing gas
(after [14])
A neural network model developed using industrial data has been used alongside theoretical
predictions to estimate the expected oxide thickness at atmospheric pressure based on the values
obtained from the elevated pressure exposures. The two approaches agree well, within the limits
of experimental error and statistical variation associated with corrosion measurements, providing
estimates of the oxide thickness for Fe-10Cr of 74-80 m from theory and 98 m from the model,
for P92 69-72 m from theory and 88 m from the model. These values are significantly lower
than the measured values from the actual atmospheric exposure, which were found to be
consistent with literature values. This suggests that material performance and lifing calculations
based on atmospheric laboratory data are overly conservative, and liable to lead to over
predictions of oxide thickness at higher pressures.
It has also been shown that an increase in the exposure pressure used in testing the performance
of aluminium diffusion coatings affects the extent of diffusion into the substrate. The precise
mechanism responsible for this affect is not clear at this point, but is believed to be related to
Gibbs free energy, but further work is required to fully address this effect.
ACKNOWLEDGMENTS
The authors are grateful to David Laing for his assistance with conducting the exposures and Ian
Wright with his assistance in the development of the neural network model. We would also like
to acknowledge the Department of Business Innovation and Science for funding the work
reported in this document.
REFERENCES
[1] I. G. Wright and R. B. Dooley, A review of the oxidation behaviour of structural alloys in
steam, International Materials Review, vol. 55, pp. 129-167, 2010.
[2] Y. Otoguro, M. Sakakibara, T. Saito, H. Ito and Y. Inoue, Trans ISIJ, vol. 28, pp. 761-768,
1998.
[3] M. Montgomery and A. Karlsson, Survey of Oxidation in Steamside Conditions, VGB
Kraftwerkstechnik, vol. 75, pp. 235-240, 1995.
[4] Y. Watanabe, Y. S. Yi, T. Kondo, K. Inui, T. Kishinami, H. Kimura and M. Sato,
763
764
ABSTRACT
As part of the Boiler Materials for Ultrasupercritical Coal Power Plants program, sponsored by
the United States (U.S.) Department of Energy (DOE) and the Ohio Coal Development Office
(OCDO), the steamside oxidation and oxide exfoliation behavior of candidate alloys have been
thoroughly evaluated in steam at temperatures between 620C and 800C (1148F and 1472F)
for times up to 10,000 hours. The results from this test program indicate that the oxidation rates
and oxide morphologies associated with steamside oxidation are a strong function of the
crystallographic lattice structure and the chromium content of the material. Oxide exfoliation
correlates to oxide thickness. The time required to reach the critical oxide thickness for
exfoliation can be estimated based on oxidation kinetic relationships. For austenitic stainless
steels, shot peening is effective in reducing steamside oxidation/exfoliation, but the efficacy of
this technique is limited by the operating temperature. Nickel-based alloys exhibit very low
oxidation/exfoliation rates, but have a propensity to form aluminum/titanium oxides along nearsurface grain boundaries.
INTRODUCTION
The Boiler Materials for Ultrasupercritical Coal Power Plants program is being performed to
determine the most suitable materials of construction for a high-efficiency, low-emissions,
advanced ultra-supercritical (A-USC) fossil boiler. An important consideration in the selection of
materials for any boiler, and particularly for an A-USC boiler that will operate at steam
temperatures up to 760C (1400F), is steamside oxidation. Steamside oxidation has three
primary detrimental aspects, all of which are exacerbated at the higher temperatures planned for
A-USC operation: 1) oxidation leads to wall loss which can eventually compromise structural
integrity, 2) oxidation can act as an insulating barrier to heat transfer and cause local overheating
of tubing, and 3) spalled oxides can plug tube bends and/or erode steam turbines [1]. Because the
control of steamside oxidation is an important factor in the successful operation of an A-USC
boiler, one task of the program is devoted to the study of the steamside oxidation of candidate
alloys.
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Figure 1: Steamside oxidation parabolic rate constants (kp) as a function of alloy chromium
content.
The oxidation behavior of the ferritic and austenitic materials displayed in Fig. 1 is consistent
with steamside oxidation behavior described by other researchers [8]. For iron-based ferritic and
austenitic materials, the steamside oxidation behavior is dominated by the chromium content of
the alloy. Other alloying elements (such as silicon in ferritic alloys) also influence steamside
oxidation behavior, but their impact is minor in comparison to the direct correlation between the
chromium concentration of an alloy and its oxidation behavior. Alloy 214 (a nickel-based alloy
containing only 16.3% chromium) exhibited the lowest oxidation rate in Fig. 1. This alloy
contains 4.4% aluminum (Al) and formed a very protective aluminum oxide instead of a
chromium oxide when tested at 750C (1382F).
766
OXIDE MORPHOLOGY
The oxide morphologies exhibited by the alloys exposed to steam between 620C and 800C
(1148F and 1472F) in the program fall into four main categories: 1) low chromium ferritic
alloys, 2) ferritic alloys containing 9-12% chromium, 3) austenitic stainless steels containing less
than ~20% chromium, and 4) austenitic stainless steels containing greater than ~20% chromium
and chromium-containing nickel-based/nickel-rich alloys. The characteristics of each category
are displayed in Table 1.
Table 1: Morphological characteristics of steam-formed oxides.
Alloy Type
Oxide Morphological Characteristics
Outer Fe oxide containing no Cr
Low Cr Ferritic
Inner Fe oxide containing ~3% Cr
Outer Fe oxide containing no Cr
9-12% Cr Ferritic
Inner Fe oxide containing alternating layers of high Cr
and low Cr
Outer Fe oxide containing essentially no Cr (this layer
<20% Cr Austenitic SS
often exfoliates)
Inner Cr/Fe oxide containing significant Ni
Ni-rich/Ni-based Austenitic
Single layer Cr oxide
The steam-formed oxide morphologies that exist on ferritic materials and austenitic stainless
steels have been described in detail previously [8-10]. Prior to the program, the steamside
oxidation behavior of several nickel-rich/chromium-rich candidate A-USC alloys had not been
well characterized since many of these materials are relatively new and/or have not been used in
high temperature steam environments. Four key alloys that fall into this category are Alloy 740,
Alloy 282, Alloy 230 and Alloy CCA617, the compositions of which are shown in Table 2.
Material
740
0.034
0.450
1.02
24.31
49.45
0.52
1.83
282
0.068
<0.05
0.35
19.63
Bal
8.56
<0.01
230
0.110
0.39
1.25
22.42
Bal
1.31
14.27
0.05
CCA617
0.059
0.17
0.87
21.73
55.0
8.71
0.26
0.03
Other
0.75 Al
19.63 Co
1.58Ti
10.35 Co
2.21 Ti
1.41 Al
0.22 Co
0.33 Al
11.57Co
1.23Al
0.41Ti
Single layer chromium oxides formed on all four of the materials listed in Table 2, and all four
materials exhibited low oxidation rates at all temperatures evaluated. A scanning electron
microscopy/energy dispersive spectroscopy (SEM/EDS) evaluation of Alloy 740 (shown in Fig.
2) reveals additional microstructural features typically associated with these alloys.
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Figure 2: EDS analysis results from a near-surface cross section of Alloy 740 tested for 10,000
hours at 750C showing: 1) Ti oxide / Al oxide grain boundary penetrations immediately beneath
a Cr oxide layer, and 2) Al oxide grain boundary penetrations with no Ti oxide at greater depth.
The thickness of the chromium oxide for these alloys was 1-2 m at 650C (1202F) after a 4,000
hour exposure, increasing only to ~6 m after a 4,000 hour exposure at 800C (1472F) or a
10,000 hour exposure at 750C (1382F). Figure 2 shows that areas of titanium oxide exist
immediately below the chromium oxide layer. Aluminum oxide is found along the near surface
grain boundaries of these alloys, extending from just below the chromium oxide layer to a depth
that is below the titanium oxide layer. At the greatest grain boundary penetration depth (Location
#3 in Fig. 2), the titanium concentration was approximately equal to the base metal titanium
concentration, suggesting that only aluminum oxide existed at this location.
The oxide features in Fig. 2 can be explained thermodynamically through the use of an Ellingham
diagram. At 750C (1382F), the partial pressure of oxygen (pO2) below which chromium will
not oxidize is ~10-31 atmosphere. It can be assumed that this is the pO2 at the bottom of the
chromium oxide layer. The pO2 below which titanium and aluminum will not oxidize at 750C
(1382F) is ~10-36 atmosphere and ~10-40 atmosphere, respectively. These values represent the
pO2 that exists at the bottom of the oxidation zones for these elements shown in Fig. 2.
The maximum depths of aluminum oxide penetration as a function of time and temperature are
displayed in Fig. 3. The penetration depth increases with temperature and increases parabolically
with time, both of which are indicative of a diffusion-controlled process. As described above, the
penetration depth lines presented in Fig. 3 actually represent the depths at which the pO2 is ~10-40
atmosphere. For the program, the pO2 of the steam environment at 750C (1382F) was ~3x10-7
atmosphere. Thus, Fig. 4 presents the pO2 profile across the near-surface cross section of Alloy
740 shown in Fig. 2 (Alloy 740 exposed to steam at 750C for 10,000 hours).
Obviously, the chromium oxide that forms on the surface of these alloys provides an effective
barrier that limits, but does not stop, the ingress of oxygen into these alloys. Mechanistically,
once the chromium oxide layer has formed, aluminum oxide will form along grain boundaries
once the pO2 exceeds ~10-40 atmosphere. As the diffusion of oxygen continues and the oxygen
concentration at a given cross sectional depth exceeds a pO2 of ~10-36, titanium oxide will also
form.
768
Figure 3: Maximum depth of Al oxide grain boundary penetration (depth of pO2 = ~10-40 atm) for
Alloy 740.
Figure 4: Cross sectional view of the oxidation of Alloy 740 in 750C steam after 10,000 hours
showing regions of oxide stability as a function of pO2.
Using the aluminum oxide penetration depths from tests performed at 750C and 800C (1382F
and 1472F), an activation energy of ~117 kJ/mol was derived. A section of Alloy 740 tubing that
was exposed to steam at ~655C for ~10,000 hours in the Niles test loop exhibited aluminum
oxide grain boundary penetrations that were up to ~9 m deep (Fig. 5). This result is consistent
with the projected depth after 10,000 hours at 650C in Fig. 3 (~5 m), and the depth estimated
from an activation energy of 117 kJ/mol after 10,000 hours at 650C (~14 m).
769
After 10,000 hours of exposure in steam at 750C (1382F), Alloy 740 exhibited penetrations up
to 24 m deep, while the other three alloys listed in Table 2 exhibited maximum penetration
depths of 12-14 m. The reason that Alloy 740 has a greater propensity to form grain boundary
aluminum oxide penetrations than the other alloys has not yet been ascertained. It is important to
account for the formation of these penetrations when considering tubing corrosion allowances.
After 100,000 hours at 750C (1382F), the outer chromium oxide on these alloys is expected to
be <20 m thick, but the penetrations are expected to extend to a depth that is ~90 m below the
bottom of the chromium oxide layer. Thus, the structural wall thickness will be reduced by ~100
m (~4 mils) from steamside oxidation after 100,000 hours at 750C.
Figure 5: Aluminum oxide grain boundary penetration observed on Alloy 740 exposed for
~10,000 hours to steam at ~655C in the Niles test loop.
OXIDE EXFOLIATION
Oxide exfoliation is understood to be due to a combination of oxide growth stresses and thermal
stresses resulting from coefficient of thermal expansion (CTE) differences between an oxide and
its base metal, or between two different oxide layers [11], as well as the bond strength between
two oxide layers. Oxide exfoliation occurs during the cool-down from a high temperature
exposure to steam. Over the past few years, steam-formed oxide exfoliation has caused the failure
of austenitic stainless steel boiler tubes due to exfoliated oxide blockage of tight bends. A 2011
Electric Power Research Institute (EPRI) survey of U.S. utilities showed that more than 50% of
respondents experienced exfoliation-related damage in their power plants [12].
In the program, test coupons experienced multiple cool-down cycles from planned and unplanned
furnace shut-downs; thus, the oxides had several opportunities to exfoliate from the coupon
surfaces. Exfoliation rates were calculated for materials tested between 620C and 800C
(1148F and 1472F) by comparing the weight gain and descaled weight loss of identical coupons
removed after times ranging from 1,000 hours to 10,000 hours. Following an exposure, the
removed coupons from a given material were weighed and their weight gain was calculated.
Then, one of the coupons was descaled to remove the oxide and weighed to determine the coupon
weight loss. During the oxidation process, all weight gain is due to the addition of oxygen.
Conversely, all of the weight loss determined following descaling is due to the loss of metal
atoms that had been converted to oxide (metal volatilization is not considered in this
methodology). Using the weight loss value and assuming an oxide composition (as determined
through SEM/EDS analysis), the theoretical weight gain that the coupon would experience due to
the addition of oxygen can be calculated. The difference between the theoretical weight gain and
the weight gain that the coupons actually experienced describes the weight of oxide that has
770
exfoliated from the coupon. The exfoliation rate is calculated by dividing the weight of exfoliated
oxide by the exposure time.
Figs. 6 and 7 display plots of exfoliation rate as a function of measured oxide thickness for
ferritic and austenitic materials, respectively. Since there are several inaccuracies that are inherent
with direct oxide thickness measurements (significant oxide thickness variations over the surface
of a coupon, missing oxide thickness due to oxide exfoliation, etc.), oxide thickness values in
Figs. 6 and 7 were calculated from kp values and an approximated oxide density. The oxide
densities used for the thickness calculations (3.71 g/cm3 for ferritic materials and 2.18 g/cm3 for
austenitic materials) are significantly less than the theoretical densities for these oxides, an
observation that is further explained in Reference 8.
These figures clearly demonstrate that oxide exfoliation correlates with oxide thickness. These
figures also show that the oxide thickness at which exfoliation occurs is significantly greater for
ferritic materials than for austenitic materials, a finding that is in agreement with observations
from operating boilers. EPRI has proposed a critical thickness for oxide exfoliation (tcrit exfol) of
225 m for ferritic material P91, and 46 m for austenitic stainless steel 347H based on a failure
mechanism due to accumulated strain within the oxides [13]. From Figs. 6 and 7, the tcrit exfol in
steam at temperatures between 620C and 800C (1148F and 1472F) is ~80 m for ferritic
materials and ~15 m for austenitic materials.
Figure 6: Oxide exfoliation rate as a function of calculated oxide thickness for ferritic materials
showing a tcrit exfol of ~80 m.
771
Figure 7: Oxide exfoliation rate as a function of calculated oxide thickness for austenitic
materials showing a tcrit exfol of ~15 m.
SHOT PEENING
One method to mitigate steamside oxidation exfoliation that has been successfully implemented
on austenitic stainless steels is shot peening. Shot peening has historically been used to impart
compressive residual stresses on the surface of structural parts, generally to improve fatigue
resistance. However, relative to oxidation, it is the cold work of the material surface that is
responsible for improved oxidation resistance [14]. The resulting cold worked microstructure
permits fast diffusion paths for chromium atoms to the surface of the material, allowing a thin,
protective chromium oxide to form quickly and more extensively than without peening [6].
Steamside oxidation testing of shot peened austenitic stainless steels was initially performed as
part of the program at 750C and 800C (1382F and 1472F). At both of these temperatures,
shot peening imparted no discernible benefit with respect to oxidation rate or oxide exfoliation
rate. Microhardness analyses revealed that the near-surface cold work imparted by the peening
process was rapidly relieved when the material was exposed to steam in excess of 750C
(1382F) [7].
A subsequent steamside oxidation test was performed at 620C (1148F), and coupons from
Types 347H and 304H stainless steels shown in Table 4 were include in this test. These materials
were provided as 50.80 mm outside diameter (OD) x 5.59 mm wall thickness tubing with inside
diameter (ID) surfaces that had been shot peened. To study the oxidation/exfoliation behavior of
peened vs. non-peened tubing, sections of the peened tubes were given a 927C (1701F) heat
treatment for 24 hours in a protective atmosphere. Microstructural analysis indicated that the
grain size at the ID of the peened plus stress-relieved (henceforth refered to as annealed)
material was the same as the grain size at the tubing midwall. Near-surface hardness readings
confirmed that the cold work imparted by the peening process was completely removed by the
heat treatment. Steamside oxidation test coupons were then prepared from the peened and
annealed tube sections.
772
Table 3: Chemical composition, oxidation rate (kp) and exfoliation rate of 347H and 304H
in the peened and annealed conditions exposed to steam at 620C for 10,000 hours.
Chemical Analysis (Wt %)
Exfoliation
kp
Material
Condition
Rate
2
-4
-1
(g cm sec )
Si
Fe
Ni
Cr
Nb
(mgcm-2sec-1)
Shot Peened
6.95E-13
6.06E-07
347H
0.35 Bal 11.08 17.33 0.49
Annealed
2.30E-12
1.16E-06
Shot Peened
1.26E-14
2.01E-08
304H
0.34 Bal
8.1
18.22
--Annealed
4.36E-13
7.97E-07
The oxidation rates (expressed as kp) and exfoliation rates exhibited by the peened and annealed
coupons are displayed in Table 4. These results clearly show the beneficial effect of shot peening
on steamside oxidation and exfoliation at 620C (1148F), even after 10,000 hours of exposure.
As expected, the 304H, which contained nearly 1wt% more chromium than the 347H, exhibited
the lowest oxidation and exfoliation rates for both peened and annealed conditions.
The physical appearance of the ID surface of these coupons, displayed in Fig. 8, indicate that the
peened surfaces are more uniform than the annealed surfaces, and appear to have experienced less
oxide exfoliation. Cross sectional SEM/EDS evaluations of 347H and 304H are displayed in Figs.
9 and 10, respectively.
Figure 8: ID surface of 347H and 304H in the Peened+SR and Peened conditions.
Figure 9: Cross sectional SEM/EDS of 347H in the Annealed and Peened conditions.
773
Figure 10: Cross sectional SEM/EDS of 304H in the Annealed and Peened conditions.
Figs. 9 and 10 indicate that the annealed materials contained only their chromium-rich inner
oxide, the outer iron oxide having already exfoliated. The thickness of the inner oxide suggests
that the exfoliated outer oxide possessed a variable thickness with some locations having an outer
oxide thickness of at least 50 m. Since Fig. 7 predicts that oxide exfoliation occurs on austenitic
stainless steels once the oxide thickness reaches ~15 m and since the outer oxide thickness
typically is approximately equal to the inner oxide thickness, the inner oxide thickness displayed
by the annealed 347H and 304H suggest that multiple exfoliation events have occurred at these
thick inner oxide locations. The peened materials, on the other hand, appear to exhibit a very thin
single layer chromium oxide.
The results from the peened and annealed austenitic stainless steel coupons tested at 620C
(1148F) for 10,000 hours are in agreement with other results on the effect of surface cold work
on steamside oxidation [15], and indicate that shot peening is a viable method to significantly
reduce the steamside oxidation / oxide exfoliation rates of these materials.
CONCLUSIONS
The steamside oxidation and oxide exfoliation behavior of candidate A-USC materials have been
characterized at temperatures between 620C and 800C (1148F and 1472F) and exposure
times up to 10,000 hours. The oxidation rate was found to be a strong function of the chromium
content and crystallographic structure. The oxidation rate was significantly reduced for ferritic
materials containing greater than ~10% chromium and austenitic materials containing greater
than ~19% chromium.
The oxides that formed on the candidate A-USC alloys consisted primarily of iron oxides and
chromium oxides, the exact composition and proportions of which were dependent upon alloy
chemistry. Nickel-rich alloys containing aluminum and titanium formed a single layer thin
chromium oxide and exhibited low oxidation rates; however, they also formed titanium oxides
and grain boundary aluminum oxides below the chromium oxide layer. The sub-surface depth of
the titanium and aluminum oxides increased with temperature and increased parabolically with
time, indicating that this phenomenon was controlled by oxygen diffusion into the alloys.
Results from steamside oxidation tests suggest that a critical oxide thickness exists for oxide
exfoliation. For ferritic materials the critical thickness is ~80 m, and for austenitic materials the
critical thickness is ~15 m. The steamside oxidation and oxide exfoliation behavior of shot
peened austenitic stainless steels displayed dramatic improvement at 620C (1148F), even after
a 10,000 hour exposure.
774
ACKNOWLEDGEMENTS
The authors would like to thank members of the DOE/OCDO consortium for sharing their
invaluable insights during this program. The authors would also like to thank Bill Gwynne, John
Jevec, Barry Conrad, Bob Pelger, and Sandy Ulbricht at Babcock & Wilcox Power Generation
Group, Inc. for their assistance in performing the oxidation testing and SEM/EDS analyses.
REFERENCES
[1] Sarver, J. M. et al, Boiler Materials for Ultrasupercritical Coal Power Plants Task 3,
Steamside Oxidation of Materials, NETL/DOE, 2003. USC T-5.
[2] Sarver, J. M., Tanzosh, J. M. and Mohammed, S., Steam Oxidation Testing of Candidate
Ultrasupercritical Boiler Materials, 28th International Conference on Coal Utilization,
Clearwater, Florida, March 9-13, 2003.
[3] Sarver, J. M. and Tanzosh, J. M., Preliminary Results from Steam Oxidation Tests
Performed on Candidate Materials for Ultrasupercritical Boilers, EPRI International
Conference on Materials and Corrosion Experience for Fossil Power Plants, Isle of Palms,
South Carolina, November 18-21, 2003.
[4] Sarver, J. M. and Tanzosh, J. M., Steamside Oxidation Behavior of Candidate USC
Materials at 650C and 800C, 8th Ultra-Steel Workshop, Tsukuba, Japan, July 21-22, 2004.
[5] Sarver, J. M. and Tanzosh, J. M., An Evaluation of the Steamside Oxidation of Candidate
USC Materials ate 650C and 800C, 4th International Conference on Advances in
Materials Technology for Fossil Power Plants, Hilton Head Island, South Carolina, October
25-28, 2004.
[6] Sarver, J. M. and Tanzosh, J. M., The Steamside Oxidation Behavior of Candidate USC
Materials at Temperatures Between 650C and 800C, 5th International Conference on
Advances in Materials Technology for Fossil Power Plants, Marco Island, Florida, October
3-5, 2007.
[7] Sarver, J. M. and Tanzosh, J. M., Characterization of Steam-formed Oxides on Candidate
Materials for USC Boilers, 6th International Conference on Advances in Materials
Technology for Fossil Power Plants, Santa Fe, New Mexico, August 31 September 3,
2010.
[8] Wright, I. G. and Dooley, R. B., A Review of the Oxidation Behavior of Structural Alloys
in Steam, International Materials Reviews, Vol. 55, No. 3 (2010), pp. 129-167.
[9] Viswanathan, R., Sarver, J. M. and Tanzosh, J. M., Boiler Materials for Ultra-Supercritical
Coal Power Plants Steamside Oxidation, Journal of Materials Engineering and
Performance, Vol. 15, No. 3 (2006), pp. 225-274.
[10] Fry, A., Osgerby, S. and Wright, M., Oxidation of Alloys in Steam Environments, NPL
Report MATC(A)90, September, 2002.
[11] Wright, I. G. et al, Progress in Prediction and Control of Scale Exfoliation on Superheater
and Reheater Alloys, EPRI International Conference on Boiler Tube and HRSG Tube
Failures and Inspections, San Diego, California, November 2-5, 2004.
[12] Shingledecker, A. P. et al, Managing Steam-Side Oxidation and Exfoliation in USC Boiler
Tubes, Advanced Materials & Processes, Vol. 171, No. 3 (2013), pp. 23-25.
[13] Wright, I. G. and Sabau, A., Development of an Integrated Model to Predict and Control
Oxide Scale Exfoliation: Exfoliation Calculations for Ferritic, Austenitic, and Fine-Grained
Austenitic Alloys 2009 Progress, EPRI, Palo Alto, California, December, 2009, 1017625.
775
[14] Sato, T. et al, The Practical Application and Long-Term Experience of New Heat Resistant
Steels to Large Scale USC Boilers, 4th International Conference on Advances in Materials
Technology for Fossil Power Plants, Hilton Head Island, South Carolina, October 25-28,
2004.
[15] Shingledecker, A. P. et al, State of Knowledge for Advanced Austenitics, EPRI, Palo Alto,
California, December, 2009, 1020241.
Copyright 2013 Babcock & Wilcox Power Generation Group, Inc. All rights reserved.
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776
Abstract
CWT (combined water treatment) was introduced in Japan in 1990 and over 50 power generation
boilers are now in operation. However, the effect of oxygenated treatment on the steam oxidation of
the ferritic-martensitic steels and austenitic stainless steels that are used for superheaters and
reheaters is currently far from clear. In this study, laboratory tests were used to examine the effect
of the oxygen level of the feed water on the scale growth and the scale exfoliation propensity of
T91 ferritic-martensitic steel and 300-series austenitic stainless steels, as represented by TP316H
and TP347H (coarse- and fine-grained, respectively). The oxygen level of the feed water had little
effect on the steam oxidation rates of all the steels tested. Hematite (Fe2O3) formed in the outer
layer of the oxide scales on both the ferritic and austenitic steels and is considered to have been
encouraged in the simulated CWT atmosphere. The adhesion strength of the oxide scale formed on
T91 in the simulated CWT atmosphere, that is, scale in which hematite was present, was lower than
that of the oxide scale formed in the simulated AVT (all volatile treatment) atmosphere. The
oxidation rate of fine-grained TP347H was confirmed to be slower than that of coarse-grained
TP316H. Hematite significantly influenced the scale exfoliation of the austenitic steels and the
critical oxide thickness for exfoliation decreased with increasing proportion of hematite in the outer
scale.
Introduction
High-temperature steam oxidation of boiler tube materials has been a long-term issue for
researchers and engineers concerned with power generation boilers [1]. The general problems
resulting from steam oxidation of boiler materials arise from the exfoliation of oxide scales. This
exfoliation of oxide scales occurs with both austenitic and ferritic steels, and it can cause tube bend
blockages in pendant, vertical superheaters or reheaters, leading to short-term tube burst failure, or
erosion damage of the blades and vanes of steam turbines. The Japanese experience of the oxide
exfoliation problem has been mainly with 300-series austenitic stainless steels. As a
countermeasure, steels in which inner surfaces are cold worked by shot peening, or fine-grained
steels have been used [2, 3].
On the other hand, in ferritic steels, although there is almost no serious damage from scale
exfoliation, a recent major problem has been that of lifting of the outer layers in the oxide scales
formed on ferritic-martensitic steels after a relative long operating period, leading to subsequent
short-term overheating failures [4].
In recent years, feed water treatment is being changed from the conventional AVT (all volatile
treatment) to CWT (combined water treatment) in Japanese power generation boilers to minimize
777
the corrosion of and deposition on the water wall tubes. The greatest difference between AVT and
CWT is considered to be the oxygen content of the feed water, that is, the oxygen level of the
former is less than 7 ppb in contrast with that of the latter being approximately 100 ppb. Therefore,
scale morphology might be changed by varying the feed water treatment. In particular, the
formation of hematite (Fe2O3) in steam-grown oxides might be encouraged with an increase in
oxygen level of the feed water. However, the influence of the hematite proportion in oxide scales on
the scale growth characteristics and exfoliation propensity of steels is poorly understood.
In this study, laboratory tests were used to examine the effect of the oxygen level of the feed water
on the scale growth and scale exfoliation propensity of T91 ferritic-martensitic steel and of
TP316H and TP347H (coarse- and fine-grained, respectively) 300-series austenitic stainless steels.
Experimental procedure
T91 ferritic-martensitic steel and two 300-series austenitic stainless steels, coarse-grained TP316H
(ASTM grain size of 6.9) and fine-grained SUS347HTB (ASTM grain size of 8.9), were used. The
chemical composition of these materials is shown in Table 1. Coupon specimens of 1.5 mm x 25
mm x 3 mm were cut from tube walls and were ground on 600 grit emery paper. To remove
processing layers before the tests, the coupon specimens of the austenitic stainless steels were
pickled. Half rings of tube specimens (half tube) were also used. Schematic diagrams of the
specimens used in this study are shown in Figure 1.
Table 1 Chemical compositions of materials used in steam oxidation testing (wt.%)
Steels
Si
Mn
Cr
Ni
T91
0.09
0.42
0.37
8.69
TP316H
0.07
0.57
1.57
16.7
12.7
TP347H
0.08
0.43
1.57
18.8
12.2
(a) rectangular
Mo
Nb
0.93
0.22
0.055
2.7
0.77
Remarks
ASTM
G.S:6.9
ASTM
G.S:8.9
778
779
Figure 4 Schematic diagram and photograph of cyclic steam oxidation test equipment
The test specimens were oxidized in the atmospheric dissolved oxygen controlled steam at 625C
for up to 1000 h. After the steam oxidation tests, cross-sections of the specimens were investigated
by optical microscope and the maximum penetration depth of each specimen was measured. In
addition, the oxide layers of selected specimens were investigated with an electron probe
micro-analyzer (EPMA) and x-ray diffraction (XRD).
Scale adhesion strength measurement
The adhesion strength of the oxide scales formed on the T91 ferritic steel after 1000 h steam
oxidation tests at 625C was measured. A photograph of the test equipment and the sample
attachment setup used for measurement is shown in Figure 3. After the measurements of adhesion
strength, the cross-sections of specimens were investigated by optical microscope to observe places
where detachment had occurred.
Cyclic steam oxidation test
A schematic diagram and photograph of the test equipment are shown in Figure 4. Cyclic steam
oxidation tests were carried out in simulated AVT and CWT environments at 625C for 500 h in a
thermal cycling furnace. Each cycle consisted of 10 h heating at 625C followed by 1 h of cooling
at room temperature under the simulated AVT environment, and that for the simulated CWT
consisted of 23 h of heating at 625C followed by 1 h of cooling at room temperature. During
cooling to room temperature the gas atmosphere was switched from steam to Ar. Changes in the
weight of specimens were measured at the end of each cycle. After the cyclic oxidation tests, the
cross-sections of specimens were investigated by optical microscope, and the surfaces of selected
samples were examined using XRD.
780
Results
T91
Figure 5 shows the metallographic cross-sections of oxide scales formed on the T91 after the steam
oxidation tests for 1000 h at 625C under both the simulated AVT and CWT atmospheres. The
oxide scales formed under the simulated AVT
atmosphere had a two-layered structure consisting of an outer magnetite and an inner,
chromium-containing spinel layer, and through-scale cracks could be observed, along with many
voids. In addition, internal oxidation occurred beneath the inner layer. On the other hand, hematite
could be observed (hematite appears lighter than the magnetite layer) at the outermost layer of
oxides under the simulated CWT atmosphere. The dissolved oxygen levels of the feed water had
relatively little effect on scale thickness.
The change in weight of the T91 specimens during the cyclic oxidation test under the simulated
CWT atmosphere is shown in Figure 6. This figure indicates that weight gain increased following a
parabolic rate law. The metallographic cross-section of the oxide scale formed on T91 after the
cyclic oxidation test is shown in Figure 7, which indicates that a relatively thick layer of hematite
formed on the outermost layer of the oxide.
Figure 5 Cross-sections of scales formed on T91 after 1000h in steam at 625 (a) dissolved
oxygen : <7ppb, (b) dissolved oxygen :100ppb
100
T91
Do:100ppb
80
60
40
20
0
0
100
200
300
400
Hold time at 625 (h)
500
600
781
Table 2 Test results of adhesion strength with the base metal of scales
Specimen
Time
Oxygen content
Adhesion strength
(kgf/cm2)
Adhesion strength
(kgf/cm2) [Mean value]
25
100ppb
T91
13.3
10
5
115
120
135
1000h
<7ppb
123.3
Figure 8 Cross-sections of T91 after measurement of adhesion strength of scales (a) Do:<7ppb, (b)
Do:100ppb
The test results of the adhesion strength of the oxide scales formed on the T91 after 1000 h of steam
oxidation, measured using an Instron, are shown in Table 2. The adhesion strength of the oxides
formed in the simulated AVT atmosphere was approximately 120 kg/cm2, and exfoliation occurred
beneath the inner layers, as shown in Figure 8. On the other hand, the adhesion strength of the oxide
scales formed in the simulated CWT atmosphere was about 15 kg/cm2, and exfoliation occurred at
the interface between the inner and outer layers.
Austenitic stainless steels
Figure 9 shows optical cross-sections of scales formed on the coarse-grained TP316H and
fine-grained TP347H after 1000 h in the simulated AVT atmosphere at 625C. All of the scales had
a two-layered structure consisting of an outer magnetite layer and an inner chromium-containing
spinel layer, but the inner oxides appeared more irregular compared with those of the T91. A small
amount of hematite was detected by XRD analysis in the surface scales formed on the half
tube specimens of the TP347H, while hematite could hardly be detected in the surface scales
formed on the TP316H. The EPMA element maps of the oxide scales formed on the TP316H and
TP347H coupons are shown in Figure 10, respectively. The oxide scales formed on both the
austenitic steels had two-layered scales as mentioned above, and in the fine grained TP347H, a
Cr-enriched protective layer formed at the innermost region of the spinel layer.
The mean thickness of the inner scales of the fine-grained TP347H was less than that of the
coarse-grained TP316H, and for TP347H, the mean thickness of the coupon specimens was greater
782
than that of the half rings of tube. Figure 11 shows optical cross-sections of scales formed on the
coarse-grained TP316H and fine-grained TP347H after 1000 h in the
Figure 9 Cross-sections of TP316H and TP347H after 1000h in steam under AVT condition
(a) TP316H rectangular (b) TP316H half ring (c) TP347H rectangular (d) TP347H half ring
Figure 10 EPMA mapping of scales formed on TP316H half ring specimen of TP316H and
TP347H tubes after 500h in steam under AVT condition at 625
783
Figure 11 Cross-sections of TP316H and TP347H after 1000h in steam under CWT condition (a)
TP316H rectangular (b) TP316H half ring (c) TP347H rectangular (d) TP347H half ring
50
TP316H
TP347H
40
Recutangular
Half ring
30
20
10
0
Ar
100ppb
Ar
100ppb
Figure 12 Effect of dissolved oxygen level on the mean penetration depth of TP316L and TP347H
after 500h in steam at 625
simulated CWT atmosphere. All of the scales essentially consisted of similar oxides to those
formed in the simulated AVT atmosphere, while a small amount of hematite was detected by XRD
in the uppermost layer of the scales formed on the half rings of tubes of both the austenitic steels.
However, the EPMA maps of the scales formed on the coupon specimens of both the austenitic
steels were similar to those in the simulated AVT atmosphere, and the inner scale thickness under
both the atmospheres was in the same range. The thickness of the inner scales formed on both the
austenitic steels after 500 h at 625C in the simulated AVT and CWT atmospheres is shown in
Figure 12, which indicates that the dissolved oxygen levels had relatively little effect on the inner
784
scale thickness in all cases tested. The scale thickness of the fine-grained TP347H was less than
that of the coarse-grained TP316H, and in particular that of the half rings of tube was less than half
of the TP316H. In addition, for the TP347H, the scale thickness of half rings of tube was much less
than that of the coupon specimens.
The changes in weight of the TP316H and TP347H coupon specimens during cyclic steam
oxidation under the simulated AVT and CWT atmospheres are shown in Figure 13 and 14,
respectively. The test results of cyclic steam oxidation in the
1cycle: (ArAr+hydrazine 62510hR.T1h
1cycle:
100ppb)
62523hR.T1h
Ar Bubling
Ar+ Hydrazine
100ppb(1)
TP316H
100ppb(2)
60
1cycle:(Ar,Ar+Hydrazine)
1cycle:
(100pp)
60
40
20
20
-20
-20
-40
100
200
300
400
500
600
Ar Bubling
Ar+ Hydrazine
100ppb(1)
100ppb(2)
TP347H
40
-40
62510hR.T1h
62523hR.T1h
100
200
300
400
500
600
15
TP316H 100ppb
TP347H 100ppb
TP316H <7ppb
TP347H <7ppb
10
0
0
100
200
300
400
500
600
atmosphere with 5% hydrazine added to the water and bubbling Ar in the water tank are given for
comparison. Oxide exfoliation from both the austenitic steels did not occur during the cyclic steam
oxidation (10 h at 625C, 1 h at room temperature, 50 cycles) under an atmosphere that was
generated from water containing 5% hydrazine, while oxide exfoliation occurred after 30 cycles in
the simulated AVT atmosphere. On the other hand, oxide exfoliation from both the austenitic steels
785
occurred after only 2 cycles (23 h at 625C, 1 h at room temperature, 22 cycles) in the simulated
CWT atmosphere. These results confirm that the oxygen content of the steam is an important factor
in determining exfoliation propensity.
The changes in weight of the TP316H and TP347H half rings of tubes during cyclic steam
oxidation under the simulated AVT and CWT atmospheres are shown in Figure 15. The cyclic
oxidation results obtained by using the half rings of tubes differed substantially for TP316H and
TP347H. Oxide exfoliation from the TP316H occurred in both the simulated AVT and CWT
atmospheres, and the number of cycles required to cause scale exfoliation increased in the
simulated AVT
Figure 16 Cross-sections of TP316H rectangular specimens after cyclic steam oxidation tests at
625 (a) Ar + 5%hydrazine (b) Do:<7ppb (c) Do:100ppb and TP347H (d) Ar + 5%hydrazine (e)
Do:<7ppb (f) Do:100ppb rectangular
Figure 17 Cross-sections of half rings of TP316H and TP347H tubes after cyclic steam oxidation
tests at 625 (a) TP316H Do:<7ppb (b)TP316H Do:100ppb (c) TP347H Do:<7ppb (d) TP347H
Do:100ppb
786
atmosphere compared with that in the simulated CWT atmosphere. On the other hand, oxide
exfoliation from the half rings of the TP347 tube did not occur during cyclic steam oxidation in
both the simulated AVT and CWT atmospheres, and the changes in weight increased with time
following a parabolic rate law, as shown in Figure 15.
Optical cross-sections of the oxide scales formed on the austenitic steels after cyclic steam
oxidation are shown in Figure 16 and 17. Detachment of the outer scales occurred at the interface
between the inner and outer layers in all cases, except in the case of the half rings of the TP347 tube.
XRD analyses of the exfoliated scales showed that the scales typically consisted of magnetite with
a large amount of hematite. However, the scales exfoliated in the simulated CWT atmosphere
contained much more hematite compared with those exfoliated in the simulated AVT atmosphere.
Although a large amount of hematite was observed in the outer layer formed on the half rings of the
TP347H tube, scale exfoliation did not occur. However, many voids formed at the magnetite-spinel
interface, and the certain outer layers are on the verge of exfoliation.
Discussion
T91
Distinctive hematite was not observed in the cross-sections of the scales formed on the T91 after
steam oxidation in the simulated AVT atmosphere for 1000 h, while a continuous hematite layer
was observed in the scales formed in the simulated CWT atmosphere. Figure 18 shows the Fe-H-O
phase stability diagram of Fe at 625C and the equilibrium points of the atmospheres used in this
study are presented in the diagram. As shown in this figure, hematite was thermodynamically stable
in the steam tested, except when 5% hydrazine was added. Therefore, it is considered that the
formation of hematite in the outermost scale is possible in this study. As shown in Figure 5, the
outer scales formed in the simulated AVT atmosphere predominantly consisted of magnetite. The
reason for this phenomenon is considered to be due to the fast outward flux of iron ions compared
with the inner flux of oxygen ions in the early stage of steam oxidation [5]. However, as the
787
outward flux of iron ions slows due to the formation of Cr-rich oxides in the inner layer, a gradual
increase in void formation at the interface between the inner and outer layer together with scale
lifting enable oxidation of the magnetite layer to hematite. In this case, the formation of hematite is
encouraged by increasing oxygen potential in the steam, and consequently, the hematite formation
in the outer layer is considered to have been encouraged in the simulated CWT atmosphere.
It is well known that tensile stresses are generated during cooling of ferritic steel tubes in both the
circumferential and axial directions, and the scale exfoliation of ferritic steels caused by the
difference in thermal expansion between the scales and the base metals is not as significant as that
of austenitic steels. According to the results of cyclic steam oxidation of the T91 in the simulated
CWT atmosphere, significant exfoliation did not occur, although a thick hematite layer formed at
the uppermost layer. These facts suggest that the influence of the oxygen content in the steam on
the scale exfoliation of T91 resulting from different thermal coefficients is minimal.
Because the scales formed on ferritic steels are commonly much thicker than those formed on
austenitic steels, the thermal stress generated in the oxide scales upon cooling is tensile, and scale
exfoliation is considered to be affected by radial stress, which is caused by the tangential thermal
strain resulting from different thermal coefficients between the base metal and the oxide scale. That
is, scale exfoliation of ferritic steels is considered to result when the radial stress becomes greater
than the adhesion strength of the oxide scale. Therefore, for ferritic steels, the adhesion strength is
considered to be an important factor in evaluating scale exfoliation [6]. The adhesion strength of
the oxide scales formed on the T91 in the simulated CWT atmosphere, that is, scales in which
hematite is present, is lower than that of the oxide scales formed in the simulated AVT atmosphere,
as shown in Table 2. In addition, the place where exfoliation occurred changed to the interface of
the outer and inner layer. When hematite is present on the scale surface, the compressive stress is
increased, which favors buckling and may lead to cracking of the buckled area [7].
However, scale exfoliation of oxide scales from superheaters and reheaters has not occurred in
many actual boilers operating under CWT control, although a thick hematite layer is present at the
outermost layer of the oxide scale. Therefore, further studies are required in order to clarify the
effect of hematite on the scale exfoliation of ferritic steels.
Austenitic steels
It is apparent that the steam oxidation rates of austenitic steels are not affected by the oxygen
content in the steam as they are for ferritic steels. These facts suggest that the rate determining step
of steam oxidation is the outer diffusion of metal ions through the inner oxide, and the structure of
the inner oxide, especially Cr2O3, is not affected by the oxygen content of the steam. Because Cr
availability at the alloy-steam interface is facilitated by multiple alloy grain boundaries, the steam
oxidation rates of the fine-grained TP347H are slower than those of the coarse-grained TP316L.
For TP347H, the oxidation rates of the half rings of tube were approximately half of those of the
coupon specimens, as shown in Figure 14. The reason for these differences in oxidation rate is
considered to be differences in surface conditions, that is, the surfaces of the half rings of tube were
as received, while the surfaces of the coupon specimens were pickled to remove the processing
layers.
The scales formed in the steam on the austenitic steels had a two-layered structure, as they did for
the T91. The outer layers of the scales formed in the simulated AVT atmosphere mainly consisted
of magnetite, while those formed in the simulated CWT atmosphere consisted of magnetite with
small amounts of hematite. This suggests that the formation of hematite in the outer scale is
facilitated by an increase in the oxygen content in the steam. On the other hand, the amounts of
hematite in the outer layer of the scales formed on the half rings of the TP347H tube are greater
than those of the TP316H, because a protective Cr-rich scale formed at the interface of the base
788
metal and inner scales of the half rings of the TP347H tube.
As shown in Figure 15 and 16, scale exfoliation for both the austenitic steels did not occur after 500
h (50 cycles) of cyclic steam oxidation at 625C in an atmosphere with 5% hydrazine added into the
water and bubbling Ar, in which magnetite is a stable oxide. When the outer scale consists of
magnetite only, the critical scale thickness for scale exfoliation is considered to be more than 25 m,
considering the thickness of the inner scale for TP316H is approximately 25 m after cyclic
oxidation.
Scale exfoliation of both the austenitic steels occurred after 300 h (30 cycles) in the simulated
AVT atmosphere, and small amounts of hematite in the exfoliated scales were detected by XRD.
Scale exfoliation of both the austenitic steels in the simulated CWT atmosphere began after only
46 h (2 cycles) and large amounts of hematite were present in the exfoliated scales, as shown in
Figure 15 and 16. These results suggest that hematite significantly influences the scale exfoliation
of the austenitic steels and the critical oxide thickness for exfoliation decreases with an increase
in the proportion of hematite in the outer scale.
The amount of hematite formed in the outer scales during cyclic steam oxidation is greater than that
in isothermal steam oxidation. It is considered the reason for this phenomenon is repeated rapid
heating and cooling may cause cracks in the interface between the outer and inner scales and
suppress the outward diffusion of iron ions through the scales, resulting in an increase in the rate of
conversion of the magnetite layer to hematite. Scale exfoliation of the half rings of both the
austenitic tubes during cyclic steam oxidation was minor compared with that of the coupon
specimens and, in particular, scale exfoliation of the fine-grained TP347H did not occur, although
an approximately 10 m layer of hematite formed in the oxide scale. Considering the fact that the
scale exfoliation of the coupon specimens occurred after only 2 cycles, the shape of the specimens
seems to have significantly influenced scale exfoliation behavior. It is well known that scale
exfoliation is likely to occur at the corner of coupon specimens. Once scale exfoliation occurs at the
corner of coupon specimens, it is considered to propagate to other locations. Based on the results of
the cyclic steam oxidation tests, which are accelerated conditions, scale exfoliation of fine-grained
TP347H tubes is considered to be minimal if the thickness of the inner layer is less than 15 m.
Conclusion
In this study, laboratory test were used to examine the effect of the oxygen level of the feed water
on the scale growth and the scale exfoliation propensity of T91 ferritic-martensitic steel and
300-series austenitic stainless steels, as represented by TP316H and TP347H (coarse- and
fine-grained, respectively). The following conclusions can be drawn.
1) The oxygen level of the feed water has little effect on the steam oxidation rates of all the steels
tested.
2) Hematite formation in the outer layer of the oxide scales formed on both ferritic and austenitic
steels is considered to be encouraged in a simulated CWT atmosphere.
3) The adhesion strength of oxide scales formed on T91 in a simulated CWT atmosphere (scales
in which hematite is present) is lower than that of oxide scales formed in a simulated AVT
atmosphere.
4) The oxidation rate of fine-grained TP347H was confirmed to be slower than that of
coarse-grained TP316H.
5) Hematite significantly influences the scale exfoliation of austenitic steels, and the critical
oxide thickness for exfoliation decreases with an increase in the proportion of hematite in the
outer scale.
6) It is considered that the shape of specimens significantly influences scale exfoliation behavior.
789
References
[1] Armit, J., Holmes, D.R., Manning, M.I., Meadowcroft, D.B. and Metcalfe, E. The spalling of
steam grown oxide from superheater and reheater tube steels. EPRI Report No.FP686 , 1978
[2] Kinoshita, K. Mimino, T. and Shibata, M. Oxidation of stainless steel tubing in high
temperature steam. Trans. JISI, 15, 1975, p. 334-340
[3] Teranishi, H. Sawaragi, Y. Kubota, M. and Hayase, Y. The Second International Conference on
Improved Coal-Fired Power Plants sponsored by EPRI at Palo Alto, USA in Nov., 1988
[4] Nishimura, N., Komai, N., Hirayama, Y., and Masuyama, F. Japanese experience with steam
oxidation on advanced heat-resistant steel tubes in power boilers. EPRI workshop on scale
growth and exfoliation in steam plant. National Physical Laboratory, UK, September 3-5, 2003
[5] Wright I. G. and Dooley R. B. Morphologies of oxide growth and exfoliation in superheater and
reheater tubing of steam boilers. MATERIAL AT HIGH TEMPERATURE , 28(1) , 2011,
p.40-57
[6] Otuka N. MATERIAL AT HIGH TEMPERATURE, 22(1/2) , 2005 p.131-138
[7] Christl W. , Rahmel A. , and Schutze M. Oxidation of Metals, Vol. 31 No.1/2, 1989
790
ABSTRACT
To improve the efficiency of fossil fuel power plants the operating temperatures and pressures
need to be increased. However, at high temperatures the steam side oxidation resistance becomes
a critical issue for the steels used especially at the final stages of superheaters and reheaters. Apart
from the chemical composition of the material, surface condition is a major factor affecting the
oxidation resistance in steam and supercritical water. In this paper, stainless boiler steels (UNS
S34710, S31035, S31042, and S30942) are investigated for oxidation resistance in flowing
supercritical water. Tests were conducted in an autoclave environment (250 bar, with 125 ppb
dissolved oxygen and a pH of 7) at 625C, 650C and 675C for up to 1000 h. Materials were
tested with as-delivered, shot peened, milled or spark eroded and ground surface finish. The
results show a strong influence of surface finish at the early stages of oxidation. Oxides formed on
cold worked surfaces were more adherent and much thinner than on a spark eroded and ground
surface. This effect was stronger than the influence of temperature or alloy composition within the
tested ranges.
Keywords: steam oxidation, boiler tube material, surface finish
INTRODUCTION
To improve the efficiency of fossil fuel power plants the operating temperatures and pressures
need to be increased. However, at high temperatures the water/steam side oxidation resistance
becomes a critical issue for the steels used especially at the final stages of superheaters and
reheaters. Apart from the chemical composition of the material, surface condition can also affect
the oxidation resistance in steam and supercritical water. High temperature oxidation resistance of
austenitic stainless steels relies on the formation of a protective chromia (Cr2O3) layer. Generally
16-18 wt-% of chromium at least is needed to form the protective oxide, though in practice mixed
oxides are also formed, depending on local conditions. Alloying with additional Cr will improve
the oxidation resistance, and also other alloying elements such as Cu and Mn have an effect on the
formed oxide scale [1,2].
Cold work increases the dislocation density of the material surface, which increases diffusion
rates at the affected zone. The influence of cold work and surface roughness on oxidation and
corrosion has been extensively studied, and the results vary depending on material, environment
and temperature [3,4,5]. In the case of chromium containing steels cold work has a positive effect
in retarding high temperature oxidation and corrosion at temperatures over 600C [6,7,8]. At
791
lower temperatures the effect of additional cold work or a rougher surface has been reported to
have no influence or even to increase oxidation [7,9]. An application where cold work has a
positive influence on steam oxidation resistance at high temperatures is shot peening. Shot
peening the boiler tube interior with chromium has been reported to have a significant influence in
oxidation resistance of low alloyed austenitic boiler steels [10,11]. In this paper, the effect of
surface finish on the steam oxidation of stainless boiler steels (S34710, S31035, S31042 and
S30942) are investigated in a supercritical environment at 625C - 675C. Materials were tested
with different levels of surface finish: as delivered (real boiler tube internal surface), shot peened,
milled, and spark eroded and ground.
MATERIALS AND METHODS
Tube samples were machined to coupon specimens (5 x 15 x 25 mm). To assess the impact of
surface finish on oxidation, the following types of surface finish were tested: milled surface, spark
eroded and ground (to 1200 grit) surface, as-delivered tube surface and shot peened surface.
Oxidation testing was conducted in supercritical water (625C, 650C and 675C, 250 bar)
autoclave environment with 125 ppb dissolved oxygen and a pH of 7. The autoclave system has
been described in detail in [12]. The testing times were up to 1000 h. The test matrix can be seen
in Table 2 and the test materials and their chemical compositions are listed in Table 1.
Table 1: Test matrix (M= milled, S+G= spark eroded and ground, SP= shot peened, AD= as
delivered)
Material
S31042
Surface
M
625C
100h, 1000h
650C
675C
100 h, 300h, 1000h 100h, 300h, 1000h
S31042
S+G
100h, 1000h
S31042
AD
S31035
100h, 1000h
S31035
S+G
100h, 1000h
S31035
AD
S30942
100h, 1000h
S30942
S+G
100h, 1000h
S34710
100h, 1000h
S34710
S+G
100h, 1000h
S34710
SP
1000h
1000h
1000h
1000h
1000h
Surface appearance, oxide thickness and microstructure were characterised by using photography
(before and after testing), 3D profilometry, light optical microscopy (LOM) and scanning electron
microscopy (SEM) after oxidation testing. The surface composition profiles were determined by
glow discharge optical emission spectroscopy (GDOES).
792
Si
Mn
Cr
Co
Nb
Cu
Other
S31042
0.06
0.42
0.42
S31035
0.06
0.18
S30942
0.05
0.4
1.50
S34710
0.09
0.36
22
Ni
15
0.70
0.002B
0.86
a)
b)
c)
Figure 1: S31035 milled surface a) before exposure, b) after 1000 h at 625C and c) after 1000 h
at 675C
Figure 2 shows the corresponding images for the spark eroded and ground surface of S31035.
Here the oxide starts to grow as nodules at grain boundaries or other defect clusters in the
structure. At 625C the nodules are relatively smaller and their appearance frequency is larger
than at 675C, where fewer larger nodules are observed. Figure 3 presents the as delivered
internal tube surface of S31035 after 1000 h at 675C, with fairly uniform oxide that however has
been affected by irregularities on the original surface.
793
Figure 4 shows the 3D profiles S34710 after 1000 h exposure at 675C. The milled surface (Fig.
4a) has uniform oxide growth and the milling grooves are still clearly visible as they were in the
case of S31035. On the spark eroded and ground surface (Fig. 4b) the oxide growth has been
more irregular, with local initiation of nodules (as was the case with S31035), and after 1000 h the
nodules have grown together and formed a web on the surface. The shot peened surface (Fig. 4c)
shows shallow peaks and indentations with a relatively long mean wavelength of about 0.5 mm,
and only few smaller scale peaks in between. This is taken to suggest much reduced oxidation in
comparison to the spark eroded and ground surface.
a)
b)
c)
Figure 2: S31035 spark eroded and ground surface a) before exposure, b) after 1000 h exposure
at 625C, and c) after 1000 h at 675C
a)
b)
c)
Figure 4: S34710 after 1000 h exposure at 675C; a) milled, b) spark eroded and ground and c)
shot peened surface
Figure 5 shows SEM images of the cross-sections of the surfaces of S34710 after 1000 h
exposure. At 625C (Fig. 5a) a thin oxide has formed on the milled surface. On the spark eroded
and ground surfaces of S34710 (Figs. 5b and 5c) at the same temperature, a much thicker layered
oxide has formed, with an outer iron-chromium oxide and an inward grown chromia layer. The
oxides grown on the shot peened surfaces (Figs. 5d and 5e) remained thin and chromia, on which
the temperature increase from 650C to 675C had no apparent effect during the 1000 h of
exposure.
795
a)
b)
c)
d)
e)
Figure 5: Oxides of S34710 after 1000 h exposure: a) milled surface at 625C, b) spark eroded
and ground surface at 625C, c) spark eroded and ground surface at 675C, d) shot peened
surface at 650C and e) shot peened surface at 675C
Figure 6 shows oxide cross-sections of S31042. On the milled surfaces (Fig. 6a) the oxide
remained relatively thin (< 400nm) even at the higher temperatures. On the spark eroded and
ground surface (Fig. 6b) a layered oxide formed, somewhat similarly to the one on S34710. The
796
as-delivered surfaces of S31042 (Figs. 6c and 6d) also showed layered oxide growth, with an
increase in oxide thickness related to the temperature increase from 650C to 675C.
a)
b)
c)
d)
Figure 6: Oxide cross-sections of S31042 after 1000 h exposure: a) milled surface, 625C, b)
spark eroded and ground surface, 625C and c) as- delivered surface, 650C and d) as-delivered
surface, 675C
Similar oxidation behavior as with S31042 was seen in the case of the other high chromium steels
S31035 (Fig. 7) and S30942 (Fig. 8). The oxides grown on the milled surfaces of S31035 (Figs.
7a and 7b) and S30942 (Figs. 8a and 8b) were mainly thin and dense chromia. On the spark
eroded and ground surfaces the oxide growth on S30942 was clearly faster (Figs. 8c and 8d). In
contrast to the as-delivered tube surface of S31042 the as-delivered surface of S31035 (Fig. 7e)
after 1000 h exposure showed only thin oxide similar to those on the milled surfaces.
797
a)
b)
c)
d)
e)
Figure 7: Oxide cross-sections of S31035 after 1000 h exposure: a) milled, 625C, b) milled,
675C, c) spark eroded and ground, 625C, d) spark eroded and ground, 675C and e) asdelivered tube surface, 675C
798
a)
b)
c)
d)
Figure 8: Oxide cross-sections of S30942 after 1000 h exposure: a) milled surfaces, 625C, b)
milled surface, 675C, c) spark eroded and ground, 625C and d) spark eroded and ground,
675C
Figure 9 shows the oxide composition profiles (GDOES) on milled (Fig. 9a) and spark eroded and
ground (Fig. 9b) surfaces of S31042 after 1000 h at 675C. The results show that the thin oxide
formed on the milled surface (Fig. 9a) is chromium-rich, while the oxide formed on the spark
eroded and ground surface is iron-rich up to the top.
Figure 10 shows the GDOES results for S31035 after 1000 h at 625C. The oxide on the milled
surface (Fig. 10a) was again thin and Cr-rich on top, similarly to the one on milled S31042 after
1000 h at 675C (Fig. 9a). The oxide on the spark eroded and ground surface (Fig. 10b) was iron
rich on top but includes a more Cr-rich mixed oxide closer to metal and a Cu-rich layer in
between. Of the tested steels with similar surfaces, S31035 showed generally thinnest oxides (Fig.
11).
799
a)
b)
Figure 9: GDOES analyses of the oxides formed on S31042 after 1000 h exposure at 675C a)
milled surface and b) spark eroded and ground surface
a)
b)
Figure 10: GDOES analyses of the oxides formed on S31035 after 1000 h exposure at 625C a)
milled surface and b) spark eroded and ground surface
Figure 11 shows an average inward grown oxide thickness of the tested materials, or in the cases
of very thin oxides (< 1 m) the whole oxide thickness. From Fig. 11 it can be seen that in all
cases the milled surface retarded oxidation better than the spark eroded and ground surface, and
that the as- delivered tube surfaces showed an intermediate performance. The shot peened
surfaces of S34710 showed thin dense oxide at 650C and 675C. Of the spark eroded and ground
samples, S31035 showed best oxidation resistance. The effect of temperature appears generally
similar consistently for all materials and surface conditions (Fig. 11). The impact of temperature
to the resulting oxide thickness in the range of 625-675C was clearly much less than that from
the applied range of surface finish.
800
Figure 11: Average oxide thickness on the tested alloys (M= milled, S&G= spark eroded and
ground, SP= shot peened) after 1000 h in SC water (250 bar), some data points have been
slightly shifted horizontally for clarity
CONCLUSIONS
In this paper, results are reported of an investigation on the oxidation performance of selected
stainless boiler steels (S34710, S31035, S31042 and S30942) in flowing supercritical water.
Testing was conducted in an autoclave environment (625-675C, 250 bar, with 125 ppb dissolved
oxygen and a pH of 7) for up to 1000 h, with four types of surface finish: as-delivered, shot
peened, milled, or spark eroded and ground.
The results show a clear influence of the surface finish on the early stages of oxidation (up to
1000 h). Oxides formed on strongly cold worked surfaces (milled or shot peened) were
systematically much more adherent and thinner than on a spark eroded and ground surfaces. The
oxide growth particularly on the spark eroded and ground surfaces was increasingly nodular and
extensive with increasing time and temperature. More extensive oxidation was also seen with
decreasing Cr content of the alloy, but this was also largely compensated by the cold work of
milled or shot peened surface of S34710. Of all tested materials, S31035 appeared to exhibit the
best overall oxidation resistance, even though not having the highest chromium content.
801
The results indicate that the material surface condition can have a stronger influence than
temperature or material composition (within the tested range) at the early stages of oxidation of
austenitic boiler steels.
ACKNOWLEDGMENTS
The authors would like to acknowledge the financial support from VTT Technical Research
Centre of Finland and EU-FP7 Energy MacPlus project (contract 249809). The authors would
also like to acknowledge the skilful assistance of A. Toivonen, J. Lukin and A. Kukkonen.
REFERENCES
[1] Young, D., High temperature oxidation and corrosion of metals, Elsevier corrosion series
Vol. 1, UK, 2008, p. 574
[2] Khanna, A.S., High temperature oxidation and corrosion, ASM International, USA, 2002,
p. 324
[3] Nor Asma, R.B.A., Yuli P.A., Mokhtar, C.I., Study on the Effect of Surface Finish on
Corrosion of Carbon Steel in CO2 Environment, Journal of Applied Sciences, 2011, 11, pp.
2053-2057
[4] Uran, S., et.al. Effect of surface roughness on oxidation: changes in scale thickness,
composition and residual stress, Oxidation of metals, 1999, Vol. 54, pp. 74-85
[5] Caplan, D., et.al., Effect of cold work on the oxidation of nickel at high temperature,
Journal of the Electrochemical Society, 1972, Vol. 119, pp. 1205-1214
[6] Caplan, D., Effect of cold work on the oxidation of Fe-Cr alloys in water vapor at 600C,
Corrosion Science, 1966, Vol. 6., pp. 509-512
[7] Khanna, A. S., Effect of cold work on the oxidation resistance of 2 Cr-1Mo steel,
Oxidation of metals, 1985, Vol. 23, pp. 17-33
[8] Penttil, S., Effect of surface modification on the corrosion resistance of austenitic stainless
steel 316l in supercritical water conditions, Journal of Supercritical Fluids, June, 2013, in
Press, Accepted Manuscript
[9] Lozano-Perez, S., The role of cold work and applied stress on surface oxidation of 304
stainless steel, Corrosion Science, 2012, Vol. 56, pp. 78-85
[10] Naraparaju, R., et.al. Dislocation engineering and its effect on the oxidation behavior,
Materials at High Temperatures, 2012, vol. 29, pp. 116-122
[11] Naraparaju, R., et.al. Effect of Shot-peening on the oxidation behavior of boiler steels,
Oxidation of metals, 2011, vol. 76, pp. 233-245
[12] Toivonen, A. Penttil, S. General corrosion and SCC tests on ODS steels in supercritical
water, Baltica IX. International Conference on Life Management and Maintenance for
Power Plants, Espoo, Finland, June. 2013, pp. 174 193
802
ABSTRACT
Because of the problems experienced with steam-side oxide scale exfoliation in commercial power
plants, there has been increased interest in understanding the steam oxidation resistance of 300series stainless steels such as 347H and 304H. Model alloys were used in an attempt to understand
the effect of varying Ni (9-12%) and Cr (16-20%) on steam oxidation resistance at 650C.
However, the model alloys generally showed superior oxidation resistance than commercial alloys
of similar composition. Several surface engineering solutions also were investigated. The
commercially favored solution is shot peening. Laboratory steam testing at 650C found that
annealing temperatures of 850C eliminated the benefit of shot peening and a correlation was
observed with starting hardness in the peened region. This effect of annealing has implications for
the fabrication of shot peened tubing. Another route to improving oxidation resistance is the use
of oxidation resistant diffusion coatings, which can be deposited inexpensively by a vapor slurry
process. Uniform coatings were deposited on short tube sections and annealed at 1065C to retain
good 650C creep properties. The coating was thicker than has been investigated in laboratory
processes resulting in increased brittleness when the coating was assessed using 4-point bending.
INTRODUCTION
The steam-side oxidation behavior of austenitic stainless steel superheater and reheater tubes is a
complicated process. While the reaction product is thinner than that formed on ferritic steels, the
coefficient of thermal expansion (CTE) mismatch between alloy and oxide is higher in austenitic
steels, leading to exfoliation of the outer scale. This phenomenon has led to boiler tube failures
from tube blockage, as well as to increased solid particle erosion damage of steam turbines [1,2].
While efforts to model exfoliation have improved understanding of the underlying issues [3-5],
questions remain as to why exfoliation is more significant in certain boiler designs and why tube
blockage failures have become more of an issue in the past decade. For example, one utility had
stainless steel tubes in trial use for many years with no issue and only experienced blockage
failures when all of the tubes in the boiler were replaced with stainless steel. While complete
understanding of the complex exfoliation mechanism is still in progress, efforts are also being
directed to mitigate exfoliation by preventing the formation of a uniform thick oxide that is prone
to exfoliate. This study reviews three exfoliation mitigation strategies that have been investigated
at Oak Ridge National Laboratory (ORNL): (1) adjusting the Cr and Ni contents within the alloy
specification to improve oxidation resistance, (2) shot peening [6-9], which is widely used
commercially, and (3) aluminizing with a thin Al-rich layer to reduce the corrosion rate [10,11].
Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States
Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up,
803
irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.
EXPERIMENTAL PROCEDURE
These experiments used commercial and model alloys. The model alloys were modifications of
347HFG with the target composition shown in Table 1, which also includes the measured
compositions from relevant commercial alloys. The model alloys were inductively melted and cast
in a chilled copper mold and were then hot rolled at 1050C from 12.7 to 7.6mm to break up the
cast structure. For commercial and model alloys, coupons (1.5 x 10 x 19mm) were typically
machined and polished to a 600grit finish. For the commercially peened 304H tube with a solution
annealed bend, ring and quarter ring specimens (e.g. Figures 1a and 1b) were cut and the cut faces
were cleaned with 600 grit SiC paper to remove any electro-discharge machining residue.
Laboratory heat treatments were performed on specimens cut away from the bend for 30min at
700, 750, 850, 1040 and 1065C in Ar-4%H2. The 1065C anneal followed by air-cooling
(removed from the annealing furnace to cool more quickly) was consistent with industry practice.
Following the lower temperature anneals, specimens were furnace cooled to limit the amount of
oxidation during cooling. After annealing, specimens were mounted and Vickers hardness was
measured with 50 and 500g loads. Coatings were fabricated (1) at ORNL by chemical vapor
deposition (CVD) for 6h at 900C with details reported previously [12], (2) at Tennessee
Technological University (TTU) by pack cementation for 15min at 1050C to produce a ~40m
thick coating [13,14] and (3) with a commercial vapor slurry process. Initially, 347HFG coupons
were coated by two slurry processes and a second batch of coatings also was produced including
coatings on the ID of eight 152mm long 304H tube sections (~63mm OD, ~7.6 mm wall). The
tube ID was polished prior to coating and the tube was slowly rotated while slurry flowed through
the tube. The second batch had much thicker coatings with an annealing time of 4h at 1079C.
Exposures in steam (filtered, deaerated and deionized water with ~0.065S/cm conductivity
atomized into the furnace) were conducted in 500h cycles (1) at 17bar and 650C in a high pressure
test rig at ORNL with an alloy 230 containment tube with the specimens held on a vertical alumina
tube using Pt-10Rh wire as shown in Figure 1a and (2) at 1bar in an alumina tube with specimens
held in an alumina boat with alumina spacers. Similar 1bar exposures in 50%(CO2-0.15%O2)50%H2O also were conducted with the same water atomized into the flowing gas at ~1cm/s
velocity at temperature. After each 500h cycle, mass changes were measured on a Mettler Toledo
model XP205 balance. After exposure, specimens were sectioned and polished to examine the
oxide thickness and morphology. In some cases, the specimens were Cu-plated to protect the
surface oxide. Characterization included light microscopy, a Hitachi model 3400 field emission
gun-scanning electron microscope (SEM), and a JEOL model 8200 electron probe microanalysis
(EPMA) system using wavelength dispersive x-ray analysis for composition profiles and elemental
maps. Creep properties of coated specimens were evaluated using a 25.4mm long dog bone-type
specimen with a 2x2 mm2 gage section [15,16], Figure 1c. Creep testing was conducted at 625C
with a load of 240MPa. Four point bending tests were conducted on coated bars (~6x8x50mm).
Table 1. Chemical compositions (mass%) determined by inductively coupled plasma analysis
and combustion analysis. Nominal composition is shown for the model 347 alloys.
Material
Fe
Cr
Ni
Mo W
Gr.91
304H
Super304H
347HFG
347 Mods
310HCbN
89.7
70.4
67.6
69.0
bal.
51.4
8.3
18.4
18.8
17.3
16-20
25.5
0.1
8.4
8.4
10.1
9-12
20.3
0.9
0.3
0.3
0.5
0.2
0.1
0.01
0.02
0.05
0.02
Mn Si
0.3
1.6
0.8
1.7
1.5
0.01 1.2
0.1
0.02
0.3
0.3
0.4
0.3
804
Cu
Other
0.03
0.4
2.8
0.2
0.2
0.1
0.08
0.06
0.09
0.04
0.09
0.05
0.05
0.07
0.11
0.02
0.06
0.27
0.01Co,0.07Nb,0.3V,10ppm S
0.1Co,0.06V,0.01Nb,29ppm S
0.1Co,0.06V,0.5Nb,2ppm S
0.6Nb,0.1Co,42 ppm S
0.8Nb,0.2Co
0.4Nb,0.3Co,0.08V,<10ppm S
coated
bar
Al2O3
rods
b
furnace
insulation
Figure 1: (a) full ring tube specimen, (b) 1/4 thin wall tube specimen with peened ID preserved
(c) 25mm long creep specimen, 2 x 2 mm gage, (d) specimen arrangement for steam testing on
alumina tube and (e) four point bend bar furnace rig used for testing coatings
The distances between the two inner rollers was 20mm and that between the outer rollers was
40mm. The rig was set up on a thick alumina tube in the center of a resistance furnace to allow
monitoring of surface cracks by a digital camera and tests were conducted from 20-600C, Figure
1e. Tests were interrupted either when cracks were observed or at a given deformation to assess
the coating integrity using light microscopy.
RESULTS AND DISCUSSION
Effect of Cr and Ni on steam oxidation of model 347HFG alloys
The alloy specification of 304 and 347 type stainless steels has a wide range of Cr (17-20%) and
Ni (8-13%) contents along with minor element additions. One hypothesis for the increase in scale
exfoliation issues in the past decade (no exfoliation problems were noted with Eddystone at 650C
steam in 1960 [17]) is that tubing is being purchased from new sources and alloys may be leaner
in Cr and Ni, but still within specification. It is common to rank alloy oxidation resistance based
on the protective oxide-forming element, i.e., Cr [18]. However, prior work on model Fe-Cr-Ni
alloys has shown a synergistic benefit of higher Ni contents on oxidation in simulated exhaust gas
(air + 10%H2O) at 650-800C and in steam at 1200C [19-21]. The present work looked at
modifications of 347HFG with 9-12%Ni and 16-20%Cr including many minor additions, Table 1,
as it has been demonstrated that minor alloy additions, especially Mn and Si, strongly affect
oxidation resistance [20]. Figure 2 shows the specimen mass change after 3,000h exposures at
650C in two environments at 1bar as a function of Cr content: 100%H2O and O2-buffered CO250%H2O, simulating a high CO2 environment used in oxy-firing concepts [22]. As expected,
alloys with higher Cr contents had smaller mass changes, reflecting the formation of a thin,
protective Cr-rich surface oxide. Alloys with lower Cr contents showed large mass losses in both
environments due to the formation of Fe-rich oxide, which spalled during cycling. The model
alloys are grouped by Ni content, clearly showing the benefit of 12%Ni compared to 9%Ni. Figure
805
Figure 2: Specimen mass change after 3,000h exposures at 650C in 1 bar steam and buffered
CO2-50%H2O for model and commercial alloys as a function of alloy Cr content. The model
alloys are grouped by their nominal Ni content (9 and 12%).
3 shows cross-sections of the model alloys exposed for only 1,000h at 650C in 1bar steam.
Rapidly growing Fe-rich oxide nodules can be found on the 16%Cr and 18%Cr alloys. However,
the mass change data in Figure 2 suggest that these nodules are far less prevalent on the 12%Ni
alloys than the 9%Ni alloys. One area of concern about these results was that the performance of
the commercial alloys was not very consistent with the model alloys, Figure 2. The only exception
is 347HFG in steam, which is close to the expected mass loss, although with 10.1%Ni it might be
expected to perform slightly better than the 9%Ni model alloys. Further work is needed to
understand the differences between the model and commercial alloys. Nominally, the average
model alloy grain sizes are 19-43 m (see Figure 3), which is nominally similar to the commercial
alloys (10-30 m for 347HFG). Smaller grain sizes increase the flux of Cr in the alloy to the
reaction front and tend to improve the oxidation resistance [19,23], similar to the peening benefit.
Cu plate
FeOx
(Fe,Cr)Ox
37 m
43 m
16Cr-9Ni
50 m
18Cr-9Ni
16Cr-12Ni
b c 20Cr-9Ni 50m
33 m
33 m
18Cr-12Ni
19 m
27 m
20Cr-12Ni
Figure 3. Light microscopy of polished sections of model 347 alloys after 1000h at 650C in
100% H2O with nominal compositions of (a) 16Cr-9Ni, (b) 18Cr-9Ni, (c) 20Cr-9Ni,
(d) 16Cr-12Ni, (e) 18Cr-12Ni and (f) 20Cr-12Ni. The average alloy grain size is shown.
806
Figure 4. (a) starting 304H tube bend, (b) hardness as a function of distance from the inner
diameter surface of the tube section. Traces are shown for the as-received tube, in the bend and
near the bend as well as after various heat treatments.
807
Figure 5. Peak hardness in the profiles from Figure 4 as a function of (a) annealing temperature
and (b) maximum oxide thickness.
a function of peak hardness. Figures 6a and 6b show the as-received OD and ID of the shot peened
304H tube after 4,000h. The OD shows accelerated oxidation with the formation of a non-uniform
(Fe,Cr)Ox inner oxide. Presumably the outer oxide layer spalled. In contrast, the peened ID
showed a very thin oxide in most locations with occasional inner oxide growth, similar in
appearance to field exposed peened tubes [8]. Figure 7 summarizes some of the oxide thickness
data on 347H tubing from one plant in that study [8,25]. The data are plotted versus the square
root of time assuming parabolic kinetics [26]. At 582C, peening clearly reduced the mean oxide
thickness to ~10m after ~11,900h of service, while much thicker inner oxide thicknesses were
observed on unpeened 347H tubing under nominally the same steam conditions in that boiler.
Figure 6c and 6d show the IDs from full ring specimens that were laboratory annealed at 1065C
and from the commercially annealed tube bend, respectively. In both cases, a thick inner oxide
formed indicating that the benefit of shot peening had been lost. Figures 6e and 6f also show the
tube ID but from quarter ring specimens that were laboratory annealed at 750 and 850C,
respectively. After 750C annealing, a thin oxide was maintained after 4,000h, while nodules of
1065C, ID
750C, ID
Cu plate
50m machined OD
(Fe,Cr)Ox
as fab. OD
b peened ID 50 m bend ID d f
epoxy
850C, ID
h cut face
i peened ID
Cu plate
Figure 6. Light microscopy of polished cross-sections of 304H tubing after 4,000h in 17bar
steam (a) as-fabricated OD, (b) as-received peened ID, (c) 1065C annealed ID, (d) as-received
ID in the annealed bend (3,000h exposure), (e) 750C annealed ID, (f) 850C annealed ID, (g)
machined OD, (h) cut face on quarter ring and (i) as-received peened ID..
808
Figure 7: Box and whisker plots of measured oxide thickness plotted versus the square root of
total exposure time for 347H tubing at 582C (1080F) with and without shot peening. All of the
specimens came from one power plant. The dashed lines are based on the median oxide
thickness measurements. Figure 3a shows an example of the inner oxide and total oxide,
which includes the outer FeOx layer. Adapted from Ref. 8,25.
thicker oxide began to form on the specimen annealed at 850C, Figure 6f. Thus, the summary in
Figure 5b suggests that when the peak hardness remains 350 Hv, the oxide remains thin, while
annealing conditions 850C that reduce the surface hardness below this level compromised the
benefit of shot peening under these steam oxidation conditions.
As noted above, several specimen sizes were evaluated. Figures 6g-6i all come from a quarter ring
specimen exposed for 4,000h with a reduced wall thickness, Figure 1b (whereas Figures 6a and 6b
come from a specimen like that shown in Figure 1a). On the peened ID, a thin oxide formed in
both cases, Figures 6b and 6i. Surprisingly, on the machined OD, a thin oxide also formed,
suggesting that machining produced sufficient cold work to affect steam oxidation, Figure 6g.
However, on the cut faces where the electro-discharge machining residue was removed, thick
oxide nodules formed. Polished coupons of 304H, cut from the same tube, tended to form thin
oxides similar to those on the peened ID, with a few nodules and relatively low mass gains. These
results suggest that a better test protocol for laboratory steam oxidation experiments should include
tube segments with the as-processed ID (and perhaps OD) surfaces rather than parallelepiped
coupons with polished surfaces, as is normally the case (e.g. Figure 2).
Thin Al-rich coatings for improved steam oxidation resistance
Another surface modification strategy is the use of oxidation-resistant diffusion coatings. Various
chromizing and aluminizing strategies have been evaluated for many years for a variety of high
temperature applications [10,12,27-33]. However, steam-side chromizing is not currently popular
because of environmental concerns with the coating process. Recent work at ORNL on thin
(<50m) Al-rich (or aluminide) coatings focused on lifetime predictions [10,34-36] of such
coatings and improving their performance by minimizing (1) the thermal expansion mismatch
between the coating and substrate (especially by eliminating high expansion Fe-Al intermetallic
phases) and (2) the reduction in load -bearing capability relative to the Fe-base steel substrate [10].
Figure 8a shows recent results for CVD aluminized 347HFG, Super304H and Gr.91 at 800C in
17bar steam. Due to rapid Al interdiffusion, the coating on Gr.91 degraded quickly but, since Al
809
Figure 8: Specimen mass gain for coated coupons (a) CVD specimens in 17bar steam at 800C
and (b) commercial vapor slurry 347HFG specimens in 1bar steam at 650C or buffered CO250%H2O at 600C. Dashed lines show uncoated specimens.
interdiffusion was inhibited at the ferrite-austenite phase boundary, the coatings on the austenitic
alloys were protective for significantly longer lifetimes [10]. The main purpose of the most recent
work was to begin exploring commercially-viable coating processes, such as vapor slurry coating
[37], to demonstrate their application to the ID of austenitic tubing and to evaluate the effect of the
coating on the mechanical properties of the substrate [15,33].
Figures 9a and 9b show characterization of the initial commercial slurry coatings deposited on
coupons of 347HFG. High and low Al activity slurry processes were used for the first batch of
coatings. Both coating types were heat treated at 1079C for 2h because heat treating at 900C
was found to reduce the creep strength of 347HFG at 625C, Figure 10a. A heat treatment (HT)
for 6h at 900C was used to mimic the CVD coating cycle used for the specimens shown in Figure
8a. The creep rupture lives of CVD-coated and 900C-annealed 347HFG 25mm dog bone
specimens were significantly shorter than the as-received 347HFG material or specimens vacuum
annealed at 1000 or 1100C. After heat treating at 1079C, both coatings had a typical two layer
outer
~130m
inner
~240m
347HFG
20 m c
50 m
Figure 9: (a) EPMA Al profile of two 347HFG test coupons slurry coated at PST. (b) EPMA
secondary electron image of coating showing outer Al-rich layer and inner layer, (c) light
microscopy of the thicker coating formed in the 2nd batch.
810
CVD coating
b
347HFG
10 m
Figure 10: (a) Deformation as a function of time for 347HFG at 625C and 240MPa: asreceived, with various heat treatments (HT) and coatings. Light microscopy of polished CVDcoated 347HFG creep specimen after rupture at 625C/240MPa (b) in the gage where the outer
layer of the coating fractured and (c) in the specimen shoulder.
structure with an outer Al-rich layer and an inner ferritic layer, with a relatively sharp boundary
between the coating and substrate, Figure 9a. The coating with the high activity process had a
higher Al content in the outer layer, but the composition of the inner layer was very similar to that
for the low activity process. Both coatings had the same thickness of ~130m. The low activity
(vapor slurry [37]) process was selected for the second batch of coatings, as this composition was
similar to the coatings already evaluated, although the thickness was greater [10,12,13].
The second batch of coatings on 347HFG included oxidation coupons, dog bone tensile specimens,
bend bars and 152mm long tube sections. However, instead of a 1h heat treatment at 1079C, a
4h heat treatment was used. Thus, the coatings were thicker and had a higher Al content than
desired, Figures 9a and 9c. Coatings from the second batch were exposed at 600C in CO2-H2O
and 650C in 1bar steam, Figure 8b. Coated 347HFG specimens were exposed for 2000 and 4000h
at 650C and showed low mass gains. In contrast, uncoated 347HFG exhibited a large mass loss
due to the formation of thick Fe-rich oxide under these conditions, similar to those shown in Figure
3a. At 600C, some CVD coatings have performed poorly, presumably because of the low
temperature to form an Al-rich coating [38].
While a higher Al content is expected to be beneficial for oxidation resistance, lower Al contents
were previously found to be beneficial for mechanical properties [10]. In creep testing of the
commercial coating, the load was based on the original ~130m thickness (the coating is known
to be non-load bearing [15]). With the higher coating thickness, the actual load was effectively
390MPa, resulting in a very short lifetime due to the higher stress level, Figure 10a. With a thin
CVD coating, characterization of the coating after creep testing revealed that although the outer
layer cracked in the specimen gage, the cracks did not continue into the substrate, Figure 10b. No
coating cracks were observed in the (non stressed) specimen shoulder, Figure 10c. The results for
the 4-pt bend bar tests are shown in Table 2. While the coating on 347HFG showed some ductility
at 400 and 600C, the room temperature ductility was much lower than in a thin coating made by
811
Table 2. Maximum strain (%) before cracks detected in coated 4pt. bend bars
at three test temperatures.
Temperature
20C
400C
600C
slurry coating
1.05%
2-3; >3 (two bars)
4.3
pack coating
2.3, <3.3% (two bars)
n.t.
n.t.
pack cementation on the same material. (Pack cementation can make a similar coating as the CVD
process [13-15], but on a larger specimen than is possible to coat in a laboratory CVD reactor.)
Finally, Figure 11 shows the coated tube segments and the variation in coating thickness around
the ID of each. Rotating the tube during slurry deposition appeared to result in a fairly uniform
coating, although the 8.5m standard deviation may represent more of a problem if the coating
were the targeted 50m in thickness rather than 200m.
SUMMARY
Three strategies were examined to improve the steam oxidation resistance of austenitic stainless
steels. Higher Cr or Ni contents were found to increase oxidation resistance in laboratory testing
at 650C. Shot peening is a commercially viable strategy for reducing the oxide thickness,
although results from field tubes show that the benefit does not completely prevent oxide nodule
formation. Nevertheless, shot peening (or other cold working processes) does prevent the
formation of a thick continuous FeOx layer that can exfoliate and cause tube blockage. The benefit
of shot peening appears to be lost if the tube is subsequently annealed at 850C. Finally, an initial
commercial trial was successful in showing that a low cost commercial vapor slurry process could
uniformly coat a tube. Subsequent work is needed to demonstrate this process on longer coating
lengths and produce thinner coatings with better mechanical properties.
50 m c
Figure 11: (a) Four coated 304H tubes, (b) example cross-section of coating on tube and (c)
average thickness at four locations on each tube. The dashed line marks the average.
812
ACKNOWLEDGMENTS
The authors would like to thank G. W. Garner, M. Howell, T. M. Lowe, J. Moser, H. Longmire, T.
Jordan and D. Leonard for assistance with the experimental work. I. G. Wright, P. F. Tortorelli and
J. Shingledecker provided helpful comments on the manuscript. This research was sponsored by
the Electric Power Research Institute (peening, coating) and the Office of Fossil Energy, Advanced
Research Materials Program, U. S. Department of Energy (model alloys, CVD coating).
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[37] McConnell, J. J.; Kircher, T. A. and McMordie, B. G. Vapor-phase slurry aluminide coating
for gas turbine components, Proceedings of the ASME Turbo Expo 2005, ASME, Vol. 2
(2005), pp. 835-840.
[38] Pint, B. A. (2012) Effect of oxy-firing on corrosion rates at 600C, NACE Paper C20120001635, Houston, TX, presented at NACE Corrosion 2012, Salt Lake City, UT, March 2012.
814
steel at 1173 K for 864 ks (240 h) before water quench. Fe 2 Nb Laves phase was precipitated in
the pre-aged sample. These steels were cut into 1.5 mm thickness and were ground with abrasive
papers and polished to mirror finish. The electrolytic polishing was carried out prior to oxidation
test. Steam oxidation was conducted at 973 K for up to 4.32 Ms (1200 h). Both the solution
treated and the pre-aged samples were used in this study. The atmosphere of steam oxidation was
Ar-15%H 2 O gas mixture and the oxygen partial pressure was 10-9 Pa, which is in the stable region
of Fe 3 O 4 . After the oxidation, phase identification of the oxide scale was performed by X-ray
diffraction (XRD). Surface morphology and the cross-section of the oxide scale were observed
by a field emission scanning electron microscope (FE-SEM) equipped with an energy dispersive
spectrometer (EDS). Thickness of the oxide scale was measured by using SE images obtained
from FE-SEM.
RESULTS AND DISCUSSION
Morphology of the oxide scale
Figure 1 shows surface morphology of the oxide scale formed on both the solution treated and the
pre-aged samples after steam oxidation for 345.6 ks (96 h). Fe 3 O 4 , -Fe and Ni(-Fe) were
detected on the surface of the both samples by XRD. On the solution treated sample, two types of
scale morphologies are observed, depending on the grain of the steel. Surface is covered with
both thin and thick oxide scales. Figures 2 and 3 show the cross-sectional SE image and
elemental mapping of the oxide scale formed on the solution treated sample. As shown in Fig. 2,
thin part of the oxide scale exhibits duplex scale which consists of outer magnetite and inner Crrich layer. Enrichment of Ni and Nb is observed beneath the Cr-rich layer. Thick part of the
oxide scale is different types of duplex scale, which consists of magnetite as the outer scale and
the mixture of Fe-Cr spinel and metallic Ni as the inner scale. Metallic particles of Ni-Fe alloy
are located at the interface of the duplex scale. There is no Cr-rich layer at the scale/steel
interface. Figure 4 shows the coverage of thick oxide scale on entire surface as a function of
oxidation time. In the initial stage around 86.4 ks (24 h), 23 % of the surface is covered with
thick oxide scale. Thin oxide scale with the Cr-rich layer is formed on the other 77 % of the
entire surface. The coverage of the thick duplex scale increases during the oxidation and reaches
to 86 % at 4.32 Ms (1200 h).
On the other hand, surface morphology of the oxide scale on the pre-aged sample is independent
of grain of the steel. (Figure 1(b)) Figure 5 shows the cross-sectional SE image and elemental
mapping of the oxide scale formed on the pre-aged sample after steam oxidation for 345.6 ks (96
h). The pre-aged sample is covered with thick duplex scale which has the similar morphology as
seen on the solution treated sample and thin Cr-rich layer is observed at the scale/steel interface.
The solution treated sample has a better steam oxidation resistance than the pre-aged sample due
to formation of the thin duplex scale with the Cr-rich layer in the early stage.
816
Figure 1: Surface morphology of the oxide scale formed on the steel after steam oxidation for
345.6 ks (96 h). (a) Solution treated sample and (b) Pre-aged sample.
Figure 2: Cross-sectional SE image and elemental mapping of the thin oxide scale formed on the
solution treated sample after steam oxidation for 345.6 ks (96 h).
817
Figure 3: Cross-sectional SE image and elemental mapping of the thick oxide scale formed on
the solution treated sample after steam oxidation for 345.6 ks (96 h).
Figure 4: Coverage of the thick oxide scale on entire surface as a function of oxidation time.
818
Figure 5: Cross-sectional SE image and elemental mapping of the oxide scale formed on the preaged sample after steam oxidation for 345.6 ks (96 h).
Steam oxidation resistance
Steam oxidation resistance of the Fe-20Cr-30Ni-2Nb (at.%) steels is compared with that of the
commercial austenitic steels based on thickness of the oxide scale. Figure 6 shows the total
thickness of the oxide scale formed on both the solution treated and pre-aged samples after steam
oxidation at 973 K. Thicknesses of both thin and thick duplex scales were measured in the
solution treated sample. Scale growth of the pre-aged sample is the same order of magnitude as
that of type 347 [3]. Steam oxidation resistance of the solution treated sample is determined by
the growth rate of the thick part of the oxide scale. Although thin duplex scale with the Cr-rich
layer forms in the early stage, scale growth of the solution treated sample is almost the same as
that of the pre-aged sample. It is well known that the growth rate of the oxide scale decreases due
to the enhancement of diffusion by cold work and shot peening. Surface defects of the samples
used in this study were removed by electrolytic polishing. It indicates that steam oxidation
resistance of the steel can be improved by surface treatments such as shot peening. Based on the
results, this steel has both enough creep rupture strength and good steam oxidation resistance at
973 K.
819
Figure 6: Thickness of the oxide scale formed on both the solution treated and pre-aged samples
after steam oxidation at 973 K.
CONCLUSIONS
Steam oxidation of the Fe-20Cr-30Ni-2Nb (at.%) steel has been conducted at 973 K to evaluate
steam oxidation resistance based on detail analyses of scale morphology and scale growth.
Although the solution treated sample has a better steam oxidation resistance than the pre-aged
sample due to formation of thin duplex scale with the Cr-rich layer, most of the surface was
covered with thick duplex scale as seen on the pre-aged sample during long-term steam oxidation.
Steam oxidation resistance of the steel is almost the same as that of commercial austenitic steel
and it can be improved by the surface treatment such as shot peening. Based on the results, this
steel has both enough creep rupture strength and good steam oxidation resistance for A-USC
power plants.
REFERENCES
[1] M. Takeyama, Novel concept of austenitic heat resistant steels strengthened by
intermetallics, Materials Science Forum, Vol. 539-543, (2007), pp. 3012-3017.
[2] M. Takeyama, Fundamentals of Physical Metallurgy for High-Temperature Materials Microstructure Control and Design -, NMS-ISIJ, 194195, (2008), pp. 1-23. (in Japanese)
[3] N. Otsuka and H. Fujikawa, Scaling of Austenitic Stainless Steels and Nickel-Base Alloys in
High-Temperature Steam at 973 K, Corrosion, Vol. 47, No. 4 (1991), pp. 240-248.
820
ABSTRACT
A model based on a concept of fraction of exfoliated area as a function of oxide scale strain
energy was developed to predict the extent of exfoliation of steam-side scale from boiler tube
superheater loops. As compared with the Armitt diagram, which can be used to predict when
scale damage and exfoliation would be likely to occur, a fraction of exfoliated area approach
provides an estimation of mass of scale released and the fraction of tube likely to be blocked by
the exfoliation. This paper show results for the extent of blockage expected in a single bend of a
superheater loop was predicted as a function of operating time, bend geometry, and outlet steam
temperature under realistic service conditions that include outages. The deposits of exfoliated
scale were assumed to be distributed horizontally the tubes bends. Three types of bends were
considered: regular bends, short bends, and hairpin bends. The progressive increase in steam and
tube temperatures along a single loop of superheater tubing and the ensuing variation of oxide
scale thickness are considered.
Numerical simulation results for a superheater loop made of TP347H austenitic steel indicated
that tube blockage fractions larger than 50% are likely to occur within the first two years of boiler
operation (with regularly scheduled outages) for outlet tube temperatures of 540-570oC, which is
consistent with practical experience. Higher blockage fractions were predicted for tubes with
hairpin bends than for tubes with regular bends, of length that are larger than five internal tube
diameters. Finally, the blockage model presented can be used with some confidence to devise
operating schedules for managing the consequences of oxide scale exfoliation based on
projections of time to some critical blockage fraction for specific boiler operating conditions.
INTRODUCTION
The driving force for scale exfoliation is assumed to be the accumulation of strains in steam-side
scales that result from the processes involved in their growth under the physical constraints of the
tube configurations employed, and excursions in heat flux, steam temperature, flue gas
temperature, and pressure associated with normal boiler operation [1-4]. Scale failure and
exfoliation is considered to be triggered by temperature variations experienced by the tubes,
particularly during shutdown events. Traditionally, the approach to scale failure and exfoliation
was visualized by superimposing the evolution of strain in the scales on the exfoliation diagrams
developed in the 1970s by Manning et al. of the Central Electricity Research Laboratory (UK)
[1-3, 5]. These diagrams essentially are maps of various scale failure criteria, including cracking
1
Notice: This submission was sponsored by a contractor of the United States Government under
contract DE-AC05-00OR22725 with the United States Department of Energy. The United States
Government retains, and the publisher, by accepting this submission for publication,
acknowledges that the United States Government retains, a nonexclusive, paid-up, irrevocable,
worldwide license to publish or reproduce the published form of this submission, or allow others
to do so, for United States Government purposes.
821
and exfoliation, appropriate for the system considered. These diagrams, commonly referred to as
Armitt diagrams, were used by the present authors in previous studies to identify the propensity
for scale damage and exfoliation [4, 6-8]. While this information can be used to assess the
general effect of operating parameters on the possibility of scale damage and exfoliation, Armitt
diagrams cannot indicate the extent of the exfoliation problem, i.e., the mass of oxide exfoliated.
Thus, only qualitative predictions of exfoliation events are possible using traditional Armitt
diagrams.
Another approach to deal with exfoliation, which received much less attention than the Armitt
diagram, was presented in the same report from 1978 [2], in which a fraction of exfoliated area
concept was introduced. Simply stated, the area fraction of scale exfoliated at each location along
the tube is given as a function of the elastic strain energy accumulated in the scale at that location
(Figure 1). By considering this fraction of exfoliated area concept, an exfoliation model was
developed by the authors by incorporating the effect of oxide regrowth after the exfoliation events
[9]. By calculating the state of strain and stress and ensuing elastic strain energy distribution, the
fraction of exfoliated area and the volume of exfoliated scale can be calculated at each location
along the tube. Then, the total volume of exfoliated scale can be calculated for the entire loop
simply by summing the volumes that were exfoliated at all locations along the tube loop. The
blockage model then was developed in [9] by post processing the total volume of exfoliated scale
to obtain the area fraction that would be blocked by scale deposits in tube bends using
assumptions on the geometry and size of the deposit(s).
Figure 1. Fraction of exfoliated area as a function of the stored elastic energy function [2, 5].
In this study, the exfoliation blockage model that was developed in [9] was applied to prototypical
superheater configurations to evaluate temperature limits that might be used to avoid exfoliation
blockage during typical boiler operation. The geometry of the bend also was considered in the
model considered.
822
Table 1. Assumed operating conditions for TP347H in a supercritical steam boiler cycle.
Load
Cycle duration (hr) Tg (C) Inlet Tst (C) Pg (bar)
Pst
(bar)
Full/Partial
145
950
546
1
243
Shutdown
25
25
25
1
1
tF-P= tP-F=1 h, tF-RT= 100h; tRT-F=6 h
Figure 3 shows the temperature profile along the 347H tube considered, in which:
Tm,max is the maximum metal temperature, which is attained at the outer surface of the tube,
Tm,mean is the mean wall metal temperature; it was included to provide direct comparison with
the values usually reported from thermocouple measurements, and
Tst is the steam temperature
823
Figure 3. Temperature profile along the 347H tube considered for the case when outlet steam
temperature was approximately 570oC.
Bend Geometries
The length of the horizontal bottom loop (or bend length in Figure 4), varies with the tube
placement in the superheater. The length of the horizontal bottom loop was considered to vary,
while the total length of the tube was kept constant in the three different bend geometries
considered. The length of the tube bends for the first two cases considered (regular and short
bends) was taken as 1 m (which is larger than 34 mm, or 5 x ID) and 17 mm (approx. 2.5 ID),
respectively. The bend length for the third case considered was zero, as this is a hairpin bend in
which the two sides of the bend are simply joined together without any horizontal portion.
curvature. The relationship between the deposit volume and blockage fraction for short bends is
shown in Table 2.
(b)
(a)
(1)
where aex is the exfoliated area fraction, Gel, FP is the elastic strain energy, for a flat plate
geometry, in the oxide scale per unit of circumferential area. For tube geometries and inelastic
as the elastic strain energy in the oxide scale per
material behavior, the
unit of circumferential area is used instead of the Gel, FP [Appendix A] and is Poissons ratio. Fex
is a function specific to alloy and was given in Armitt et al. [2] and Manning and Meadowcroft [5]
for the TP316 alloy (Figure 1). In the current work, it is assumed that only the outer oxide layer
(magnetite) exfoliates, as is known to be the case for other 300-series austenitic steels such as
TP304H and TP347H [10].
Without discussing in detail here the interplay between the oxide growth, stress and strain, and
regrowth of the oxide after exfoliation, the exfoliation and blockage model [9] consists of the
steps shown in Table 3. For short bends, the last step in obtaining the blockage area fraction
involves the use of the relationship between the deposit volume and blockage fraction, which is
shown in Table 2.
825
826
(a)
(b)
Figure 6. Predicted (a) thickness of oxide spinel layer along the length of the tube, and (b) fraction
of tube flow section blocked due to magnetite exfoliation from a TP347H superheater outlet loop
as a function of time and outlet steam temperature (To,st) for a deposit density of 25% and a
deposit footprint of 5 for To,st = 540 to 570C.
Effect of Bend Geometry: Tight and Hairpin Bends
For the cases considered in this sub-section, the tubes are considered to have either a tight bend,
with a bend length of 2.5 x ID (however, the Ld was allowed to be larger than 5 ID at high
blockage fractions), or a hairpin bend, practically without a horizontal tube between the two
vertical legs, as shown in Figure 5b. Regardless of the bend geometry, for simplicity the tubes
were considered to have the same total length. For the tight bend, the tube blockage was found to
vary in the same manner as for the regular bend but at slightly different values since although the
bend was tighter the deposits were allowed to be larger than 5 ID (Figures 7a and 6b). For the
hairpin bends, the blockage was more severe. The results show that after the initial operating
period of approximately 1.5 to 2 years (about 15,000 h), the blockage area fraction could be
underestimated by a factor of two for hairpin bends with respect to that for the case of tight bend.
827
In practice, the tubes with hairpin bends usually are shorter and/or are exposed to lower
temperatures than those with regular bends, leading to less exfoliated scale. Thus, the blockage
fraction in Figure 7b may be higher than in those conditions. Nevertheless, the relative
differences between expected blockage fractions of regular, tight, and hairpin bends, provide a
useful starting point for evaluating the blockage behavior of the various loops in a given tube
bank and would be very helpful in quantifying different factors that affect the blockage fractions
in tubes when investigating the main culprit for specific tube blockages.
(a)
(b)
Figure 7. Predicted fraction of tube flow section blocked due to magnetite exfoliation from a
TP347H superheater outlet loop as a function of time and outlet steam temperature (To,st) for a
deposit density of 25% for To,st = 540 to 570C: (a) tight bend with a deposit footprint of 2.5 for
which the deposit length was allowed to be larger than 5 ID at high blockage fractions and (b)
hairpin bend.
spaced at 3 month intervals. As the outage intervals were reduced in the first 5kh of operation,
the maximum blockage fraction was 51% and subsequently was maintained below 50% after the
initial seasoning period that now lasted less than 4kh.
Years
Case
1
2
3
4
5
(a)
(b)
Figure 8. Predicted fraction of blocked tube flow section from a TP347H superheater outlet loop
hairpin bend, a deposit density of 25%, To,st = 570C, as a function of time: (a) all data and (b)
data at times less than 20kh.
It has to be noted that all the results were obtained in this study assuming constant flue gas
temperature over the entire tube length, as the data on the actual distribution was not available.
The actual distribution on flue gas temperature would provide more specific information on the
environment that tube loop is exposed. Depending on the actual distribution of the flue gas
temperature, the amount of heat flux transferred to the tube, and consequently, the steam
temperature and oxide thickness distribution would be more accurate. Thus, the accuracy of the
model predictions would be increased, as more data become available on the flue gas temperature
distribution along both a tube loop and the entire tube assembly.
829
CONCLUSIONS
In this study, a recent the exfoliation blockage model developed by the authors [9] was applied to
prototypical superheater configurations to evaluate the effect of operating temperature on
exfoliation blockage during typical boiler operation. The geometry of the bends in the
superheater loops, which affects how the exfoliated oxide scale would be deposited, also was
considered in the blockage model. Relationships were obtained between the deposit volume and
blockage fraction for hairpin bends and short bends, whose lengths were 2.5 greater than internal
tube diameter. The results for the blockage fraction as a function of volume of oxide deposits
suggested a high dependence on the bend geometry.
Numerical simulation results for a superheater loop made of austenitic steel TP347H indicated
that tube blockages larger than 50% are likely to occur within the first two years of boiler
operation with regularly scheduled outages for outlet tube temperatures of 540-570oC, consistent
with practical experience. Predictions by the model showed that the assumption of a deposit based
on a straight pipe (of 5 x ID-length) could result in underestimating the blockage area fraction for
hairpin bends by approximately 40%. Finally, several outage schedules intended to keep the tube
blockage fraction below 50% for blockages in hairpin-bend tube loops were considered. With the
addition of the tube bend effect, the capabilities of the exfoliation and blockage model become
more comprehensive, include most of the critical factors needed to predict and manage oxide
scale exfoliation.
ACKNOWLEDGMENTS
This work was sponsored by the Electric Power Research Institute (EPRI) under a Work for
Others project (agreement no. EP-P18842/C9306) with the US Department of Energy (DOE), and
was conducted at the Oak Ridge National Laboratory (ORNL) under contract DE-AC0500OR22725 with the DOE.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
E. Metcalfe and M.I. Manning, The Spalling of Steam-Grown Oxide from Austenitic and
Ferritic Steels, CERL Report No. RD/L/R1966 (1977).
J. Armitt, D.R. Holmes, M.I. Manning, D.B. Meadowcroft, E. Metcalfe, The Spalling of
Steam Grown Oxide from Superheater and Reheater Tube Steels, EPRI Report No. FP 686
(1978).
I.G. Wright, P.F. Tortorelli, and M. Schtze, Oxide Growth and Exfoliation on Alloys
Exposed to Steam, EPRI Report No. 1013666 (2007).
A.S. Sabau and I.G. Wright, On the estimation of thermal strains developed during oxide
growth, J. Appl. Phys. Vol. 106, 023503, 2009, DOI:10.1063/1.3157199.
M.I. Manning and D. B. Meadowcroft, Effects of Tube Creep Strains on Laminated Scale
Formation in Ferritic Pressure Tubing, CERL Report No. RD/L/R2102 (1980).
I.G. Wright, A.S. Sabau, and R.B. Dooley, Development of Strain in Oxides Grown in
Steam Tubes, Materials Science Forum, High Temperature Corrosion and Protection of
Materials 7, Vols. 595-598, pp. 387-395, 2008.
A.S. Sabau and I.G. Wright, Development of an Integrated Model to Predict and Control
Oxide Scale Exfoliation: Exfoliation Calculations for Ferritic, Austenitic, and Fine-Grained
Austenitic Alloys 2009 Progress, EPRI Report 1017625, Palo Alto, CA, 2009.
A.S. Sabau and I.G. Wright, Influence of Oxide Growth and Metal Creep on Strain
Development in the Steam-side Oxide in Boiler Tubes, Oxidation of Metals, Vol. 73, pp.
467-492, 2010.
830
[9]
A.S. Sabau, I.G. Wright, and J.P. Shingledecker, Oxide Scale Exfoliation and Re- growth
in TP347H Superheater Tubes, Materials and Corrosion, Vol. 63, pp. 896-908, 2012.
[10] I.G. Wright and R.B. Dooley, Morphologies of oxide growth and exfoliation in superheater
and reheater tubing of steam boilers, Materials at High Temperatures, 28(1), 40-57
(2011).
[11] A.S. Sabau, I.G. Wright, and J.P. Shingledecker, Development of an Integrated Model to
Predict and Control Oxide Scale Exfoliation - 2010 Progress - Industry Experience &
Model Refinement, EPRI Report No. 1019793, Dec 2010.
APPENDIX A. Elastic Strain Energy Formulations
When inelastic effects are considered, the elastic strain energy in the oxide scale can be defined
based on elastic strains, ei,el, with i = r, , or z for the radial, hoop, and axial directions,
respectively. The elastic strains are a function of the total elastic strains, as:
(A1)
where the subscripts th, ox, and cr indicate the thermal strains, oxide growth-induced strains, and
creep strains, respectively, and k indicates the kth oxide layer. The elastic strain energy density for
the kth oxide layer (Wel,k) is given as [A1,A2]:
(A2)
The elastic strain energy per unit of circumferential area,
:
(A3)
The free thermal strain (eth) resulting from a temperature variation (say, T1 to T2) is defined as a
function of the coefficient of thermal expansion (CTE), , as:
(A4)
Most of these strain energy concepts were developed for thin oxides on a flat-plate (FP) geometry,
and inelastic effects were neglected [A3]; nevertheless, these expressions are given here for the
sake of clarity.
For the case considered here, the strains and stresses normal to the plate surface were estimated
using the following simple algebraic equations, respectively:
and
(A5)
where E is the Youngs modulus and is the Poissons ratio. The elastic strain energy density
(WFP,k) and elastic strain energy per unit of circumferential area (GFP,k) become, respectively:
(A7)
and
(A8)
where the last equality is valid when constant thermal expansion coefficients are used.
831
832
INTRODUCTION
Improvements in generation efficiency of coal-fired power plants have been an on-going effort
for the last several years. One of the primary means towards this goal is to improve the efficiency
of the thermodynamic cycle through increased pressure and temperature into the supercritical
(SC) and ultra-supercritical (USC) range. Today, state-of-the-art USC boilers operate with steam
conditions at pressure as high as 250 bar (3600 psi) and temperature within 600-620C (11101150F). Examples of such boilers are RDK8 in Karlsruhe, Germany and Manjung IV in
Malaysia. Achieving higher pressures (350 bar) and temperatures (700-760C) beyond these
current USC conditions require use of high-strength nickel-based alloys. As a founding member
of the USA A-USC materials Consortium [ref.1], Alstom has been working with other
consortium partners - B&W, FW, Riley Power, OCDO, ORNL and EPRI - toward developing
experience and knowhow in advanced materials. One such effort has been in the study of steamside oxidation and fireside corrosion of several different nickel alloys as well as high chromium
alloys in a steam loop in operation at Alabama Powers Plant Barry Unit 4 in Bucks, Alabama for
over a year and a half period since installation. Alstoms experience to-date of the steam loop
operation is described in this paper.
Steam Loop Configuration and Design
As originally proposed by the Department of Energy (DOE) Advanced Ultra-supercritical (AUSC) Consortium, in its Phase I of the program, the performance of advanced alloys was to be
confirmed by long-term exposure of the candidate alloys qualified in the earlier laboratory tasks
to actual boiler environments and operating conditions. The test loop employs a similar design
philosophy to that of the consortiums earlier effort [ref.1].
The test loop was installed
within the boiler behind the
rear waterwall hanger tubes,
as shown in Fig. 1. Stainless
steel tube shields were
placed on the hanger tubes
to reduce the possibility of
steam cutting in the event of
a crack developing in the
steam loop. The steam desuperheater, also shown in
Fig. 1, was installed in this
Figure 1: Steam loop installation on the rear waterwall hanger tubes
area inside the boiler in an
effort to limit personnel exposure to all unconventional boiler materials used in the loop. The
flue gas temperature in this area at full plant load is approximately 927C (1700F).
Design consideration was to ensure personnel safety, unit operation, and unit reliability was not
affected by the steam loop operation. Manual and motorized block valves were installed on all
three pipelines on the test loop: supply steam, tempering steam, and the return steam. In an event
where the material test loop may compromise boiler generation reliability, the operators were
given the ability to remotely isolate the test loop from steam supply preventing steam leaking
from the test loop thereby causing incidental damage to the boiler tubing. The consequence of
this potential action would be that the materials test loop would be lost along with any materialsrelated data accumulated to that point. To assist the operators in this decision, flow meters were
installed on all three steam paths as well. By comparing the inlet and tempering steam flow to the
outlet steam flow, one would be able to determine if the material test loop was leaking. To a
833
lesser extent, trends and patterns might also be used to indicate expected flow at given unit
conditions. Thermodynamic calculations could also be generated if instrumentation on the test
loop failed.
The test loop and its supporting system were designed for full load operating conditions. Supply
steam is extracted from the reheat link piping/header in the penthouse, nominally at 330C
(635F). This flow is controlled such that the steam temperature measures 760C (1400F) at the
outlet of the loop. The outlet steam is then tempered with steam from the radiant reheat wall
header, nominally 310C (590F). This steam is mixed in an Inconel 617 desuperheater chamber
located inside the unit to control the outlet temperature of the desuperheater to 538C (1000F).
This steam is then routed back to the penthouse where it is returned to the hot reheat lead
piping/header. A schematic of the test loop design is shown in Fig. 2. A schematic of the piping
connections outside the boiler is shown in Fig. 3.
The two control valves (supply and tempering) were configured such that minimal operator
intervention would be needed. The valves minimum set-points are configured to prevent zero
flow conditions (never closing). Since there is no drain line in the external piping supporting the
test loop, there was concern with the possibility of a valve closing during operation and collecting
water, and then subsequently being called to open, creating a potential water hammer event,
particularly during start-up and low unit load operation. With the current configuration (of
minimum valve positions being slightly open), a water hammer is unlikely as at least a minimal
amount of steam should always be flowing within the lines. This configuration, however, limits
the outlet temperature of the loop at low unit load operation conditions, as it competes to
maintain return steam temperatures near 538C (1000F). The current limits are 15% open for the
valve controlling supply steam flow, and 4% open for the valve controlling tempering steam
flow.
Steam temperatures for supply, tempering, and return steam flows are measured with standard
thermocouples within thermowells located in the steam piping. The loop outlet steam temperature
is measured with three thermocouples welded to the inlet of the desuperheating chamber inside
the unit. A layer of insulation is wrapped around these thermocouples, while ceramic beads
surround the exposed wiring penetrating the boiler wall and leading to the attachment points
inside the unit. A stainless steel shroud covers this insulation and is secured with stainless steel
sheet metal screws and stainless steel wire.
834
The test steam loop at Barry Unit 4 includes the following features:
Inclusion of alloys qualified by the earlier evaluations in the Consortium program. In addition to the
alloys themselves, additional features were included to permit evaluation of important tubing
fabrication methodologies, i.e. welding and bending, and fireside corrosion-resistant coatings.
Inclusion of test materials to an operating temperature range as needed to produce steam at an outlet
temperature of at least 760C (1400F). Each material would be subjected to a range of exposure
temperature to evaluate trends of performance with increasing temperature.
Exposure of test coupons to a coal-fired environment in a commercial utility boiler firing low-sulfur
coal.
The test loop is supplied with steam; nominally 350C (662F) from the cold reheat line through
isolation valves. The flow of steam in each path is modulated to control the temperature of steam
exiting the test loop, nominally 760C (1400F), and steam exiting the desuperheater, nominally
540C (1000F), for return to the hot reheat line. Instrumentation was provided to permit full
material and energy balances on the loop. The material balance is used to identify steam leakage
and subsequent risk of a forced boiler outage. The energy balance is used as an alternative
method of determining loop outlet steam temperature in the event that triple-redundant
thermocouple measurements fail. Plant operators retained the option to close motor-operated loop
isolation valves if deemed necessary to prevent a forced outage of the unit. The energy balance
data was also desired to confirm the heat transfer rates used in design and thus establish
confidence in calculation of intermediate temperatures of coupons along the length of the loop.
Table 1: A-USC Steam Loop Material Code and Geometry
Material
Super304H
HR3C
HR6W
Haynes 230
CCA 617
Alloy 617B
IN 740
Haynes 282
Haynes 230 with Amstar TS coating
CCA 617 with EN33 Laser clad
CCA 617 with EN622 Laser clad
OD (in)
2
2
2
2
2
2
2
2.125
2
2
2
Thickness (in)
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
Quantity
6
4
8
24
24
4
10
3
3
4
4
Lengths of raw tubing material available. The nickel-based materials, in particular, were custom
ordered by the Consortium at the start of the program and additional material was not available in the
required dimensions.
Distribution of each particular alloy with regard to the overall steam temperature rise along the length
of the test loop and the desired test exposure temperature band.
Minimizing the types of dissimilar metal weld combination since each combination required welding
procedure development.
Host Utility
Alabama Powers Plant Barry is located in Bucks, Alabama, and was first commercially
operational in 1954. Plant Barry has a current nameplate generating capacity of 2.6 GW supplied
by four subcritical coal-fired units, one supercritical unit, and two 2-on-1 combined-cycle units.
The two combined-cycle plants were the sites latest plant generation additions and began
operation circa 2000.
835
Barry Unit 4 began commercial operation on December 31, 1969. The unit consists of a
Combustion Engineering (now Alstom) tangentially-fired boiler coupled with a triple-pressure
General Electric (GE) turbine-generator set. Barry Unit 4 has a nameplate rating of 350 MWe.
Main steam throttle pressure is 165 bars (2400 psig) with full load steam flow nearing
1179 (metric) tonne/hr (2,600,000 lb/hr). Barry Unit 4 final steam temperature is (538C) 1000F
for both superheat and reheat steam. The boiler is equipped with an Alstom low-NOx firing
system (LFNCS II).
In 2010, Plant Barry Unit 4 was selected as the host for the second materials steam loop test as
part of a larger domestic effort to further A-USC coal-fired power plant development. The steamcooled loop was designed for installation on Barry Unit 4 by Alstom Power, and was installed by
site contractors. The loop has been in operation since late 2011.
Plant Operational History
In addition to a consistent fuel source, it is desirable to have a unit with as high a capacity factor
as possible, which in turn provides high temperature and a more constant flue gas exposure to the
steam loop. The installation of the materials loop occurred at a time of unexpected low natural
gas prices, making coal-fired generation capacity more variable under dispatch. While
Barry Unit 4 capacity factor in 2012 was lower than hoped, the total service hours on the unit
were between 4,600 and 5,400 hours in 2012.
The fact that the unit is online a great part of the year
historically, however, does not guarantee that steam
temperatures in the material loop will reach 760C
(1400F). In fact, at low loads estimated loop steam
temperatures are closer to 677C (1250F), as
indicated by surface-mounted thermocouples wrapped
in insulation at the exit of the test sections and prior to
entering the mixing chamber for tempering.
3%
Low S,
Low Cl
Other
97%
Fuel Characteristics
A consistent fuel is beneficial in the analysis of the fireside oxidation performance of the
materials assembled in the steam loop. During test loop operation, Plant Barry Unit 4 has
consistently burned a low-sulfur, low-chlorine bituminous fuel. This has largely remained the
case for the duration of steam loop operation and is graphically demonstrated in Fig. 4.
Coal samples were collected and analysed during months of operation of the test loop. Limited
historical fuel data from other efforts were also collected if applicable. Close agreement of all
fuel data collected indicate fuel consistency since the commissioning of the test. Typical coal
analysis details are given in Table 2.
Table 2: Representative Coal Analysis by % Weight, Dry basis
HHV
(BTU/lb)
12,980
H2O
Ash
75.4
4.8
1.5
11.5
0.6
13.4
6.2
836
Cl
(mg/kg)
22
Na
0.11
The unit did not reach full load post-installation until January 2012, though limited low load
operation allowed the test loop to operate off-design.
Test Loop Operation
On January 30, 2012, the materials test loop became the first steam-cooled material test loop in
the world to reach 760C (1400F) operation. The steam loop continues to operate and is
currently planned to operate until fall 2014 with decommissioning to follow.
The test loop outlet temperature relies heavily on the flue gas temperatures which are
proportional to load. Original installation and operation of the test loop was sans flue gas
temperature measurements in the vicinity of the test loop. Because of the frequency of low load
operation, and after unsuccessful attempts to raise the loop outlet steam temperature by
modulating the two control valves (supply and tempering), temporary thermocouples were
installed near the test loop to record flue gas temperatures during typical operating loads.
837
the boiler wall. These thermocouples were attached to the lugs supporting the test loop by spot
welding metal bands to the lugs to hold the thermocouples in place, while extending the ends of
the thermocouples approximately 3 inches or more into the gas stream downstream of the test
loop. All temperatures were recorded at 10 second intervals.
Flue gas temperatures were recorded for approximately three weeks. Timestamps were adjusted
to coordinate with other process data timestamps from the plant historian. The flue gas
temperatures are plotted against time, as shown in Fig. 6. It is clear from this data that the
material loop outlet steam temperatures cannot reach 760C (1400F) at low load as gas
temperatures are only about 777C (1430F). A distribution of flue gas temperatures also shows
the bimodal distribution with temperatures at approximately 777C (1430F) at low load and
927C (1700F) at full load. These bimodal gas temperatures create a corresponding bimodal
steam temperatures. Relatively low gas temperature at low plant load impedes the ability to reach
760C (1400F) steam temperatures in the test loop. The gas temperature data, however, did
confirm the full load flue gas temperature estimates assumed to be approximately 927C (1700F)
in the area of the test loop. Also, the flue gas temperatures in the material loop area at arbitrary
unit load in this 210 MWe to 350 MWe range can be reasonably estimated from this data, aiding
the calculation of steam temperatures along the loop at different load levels, provided the fuel
characteristics remain consistent.
NDE Results and Inspections
Periodically during 2012, there were opportunities to visually inspect the materials test loop.
There have been no visual indications of problems with the test loop or its installation. On one
occasion, the protective shroud cover for the loop outlet thermocouples was rebuilt as the original
shroud assembly began to deteriorate. The loop outlet thermocouples continue to work properly.
Tube shields and associated bands were also repaired if found damaged.
In the autumn of 2012, a more detailed inspection was conducted. Measurements were taken at
each distinct material segment in the test loop. A visual inspection was conducted without issue.
All welds were tested via dye-penetrant (PT) and no indications were revealed. Outer diameter
(OD) measurements of each section were recorded in both a horizontal and vertical orientation.
Tube temperature is estimated to increase from inlet to outlet (with steam flow direction), i.e.,
from the lowest tube segment number to the highest. The OD measurements indicate that little
wall losses were evident. In fact, the majority of the field calliper measurements were
approximately the same or a few mils lower than the nominal OD and within the tolerance of the
tube OD specifications. There are, however, a couple notable exceptions. Tube segments 55
(CCA 617) with an original specified diameter of 2 inches and the segment 56 (Haynes 282) with
an original specified diameter of 2.125 inches are believed to have been transposed incorrectly
during the NDE field measurements, or during the recording of the as-fabricated data. This will
be investigated at the next opportunity, and both of these tube segments will be closely
monitored.
As further opportunities arise during the performance period of the test loop, additional
inspections will be conducted. Ultrasonic (UT) thickness readings are planned for the latter two
(outlet) segments of the test loop as well as the 304H stainless steel lead tube in the first two legs
of the loop at the earliest opportunity. Visual inspection, weld inspection, and outer diameter
measurements will also be performed.
838
Typical cycles during a month are shown in Fig. 9. This data will be used to further estimate
steam and metal temperatures as described below.
Steam and Tube Wall Metal Temperature Predictions along Steam Loop
The method to determine tube wall temperatures when only steam-side conditions are known is
discussed as follows:
839
The basic thermodynamic heat balance equation for heat transfer of the fluid as a function of
steam-side mass flow (m f ), physical properties of the tube and gas side convection and radiation
can be written as
Eqn.1
=
where is fluid mass flow (lb/hr), is the fluid inlet enthalpy (Btu/lb), and is the fluid
outlet enthalpy (Btu/lb). Assuming one-dimensional heat transfer through a cylinder the heat
balance can also be written and the heat absorbed by the fluid as a function of gas and fluid
temperature can be expressed as
2( )
=
ln( )
1
1
+
+
( + )
where
Temperatures and heat transferred along the length of the test loop are then calculated as follows:
To establish the steam temperature and heat distribution along test loop length the measured fluid
side properties (flow, pressure, and steam temperatures entering and leaving the loop) are utilized
as a calorimeter. The test loop is divided into segments, each representing a test specimen and/or
tube material change. The fluid temperature leaving each section is calculated based on the
enthalpy rise of the fluid in the section
= +
where the heat pick-up for each section is calculated using the above equation for q fs for each
segment. An iterative approach was then employed to adjust the convective and non-luminous
heat transfer rates until the total heat transferred from the gas equals the cumulative measured
heat pick-up on the steam-side.
= =
+
2
where (F):is the tube temperature on the inside surface for each segment, and
=
840
where (F) is the tube temperature on the outside surface of the tube for each segment
Using these equations, steam temperatures as well as the metal temperatures are estimated along
the length of the steam loop for each of the 94 specimens. This steam and metal temperature data
is then used for the steam-side oxidation and fireside corrosion predictions described below.
Interpretation of Fireside Corrosion Data
The prevalence of fireside corrosion of high-temperature boiler tubes has paralleled the
improvements in Rankine cycle efficiency achieved by increased boiler outlet steam temperature
and pressure. An extensive and rich base of literature has been developed covering many aspects
of this topic from theoretical concepts [ref. 6], laboratory testing [ref. 7] and practical methods to
deal with the effects [ref. 8]. The coal-fired, A-USC cycle designs under development reach new
highs in metal operating temperature and pressure, necessitating the use of nickel-based alloys,
with little or no direct experience with their resistance to fireside corrosion. As such, the DOE AUSC Boiler Materials Consortium and Alstom have devoted a significant portion of the research
efforts toward assessing the impact of fireside corrosion on the advanced materials utilized within
the boiler. Work to-date has included extensive laboratory testing and both air-cooled coupon
probes and a steam-cooled test loop installed in commercial utility boilers [ref. 9-11]. A second
steam-cooled test loop, the subject of this paper, is notable for its exposure to the combustion
products of a low-sulfur, low-chloride coal and will thus provide another reference point relative
to the fireside corrosion resistance of the suite of advanced boiler materials.
Corrosion Mechanisms
Fireside corrosion of superheater / reheater materials could potentially be the result of a number
of different corrosion mechanisms. These mechanisms include:
Oxidation - oxide scale formation caused by a generally oxidizing flue gas environment, similar to that
observed on the steam-side of the tube. The oxide layer would generally be protective acting to slow
the rate of corrosion with time.
Sulfidation - metal attack by sulfur species in the flue gas. This is of particular concern with nickelbased alloy since a possible corrosion product, nickel sulfide, has a relatively low melting point,
leading to a liquid phase that is not protective.
Chloridation - metal attack resulting from attack by the chlorine content of the coal. Both iron and
nickel chloride corrosion products exhibit volatility at the temperature range expected in service.
Coal Ash Corrosion this mechanism is the result of the formation of an alkali iron trisulfate phase that
is molten, accelerating the corrosion rate. This mechanism is characterized by a bell-shaped rate curve,
peaking at ~700C (1300F) encompassing the formation of the liquid phase followed by thermal
decomposition as the metal temperature increases.
Carburization corrosion resulting from inclusion of unburned carbon into the fireside ash deposits,
causing a locally reducing microclimate. This microclimate results in the production of metal
carbide formation.
Evaluation Methods
Initial efforts at evaluating fireside corrosion are already in progress. The steam loop is located
with reasonable access to it during unit outages. This accessibility has allowed the loop to be
visually inspected and calliper measurements obtained on all coupons in order to make an
assessment of fireside metal loss. Inspection to-date has not revealed any significant metal loss.
These in-situ evaluations will continue as the loop accumulates exposure time. Early
identification of metal loss is critical and would trigger replacement of coupons with excessive
841
wastage. Development of a single leak could jeopardize the entire loop if commercial needs
would not permit a timely unit outage for repair.
Once the planned exposure period is completed, the loop will be removed and returned to the
Alstom laboratory (Chattanooga, Tennessee) for detailed metallurgical evaluation. Chemical
analysis of external tube deposits will be performed. Dimensional measurements will be used to
quantify metal loss. Metallographic examination will reveal internal attack of the alloy
microstructure. Conclusions will be drawn on the active corrosion mechanism(s) causing metal
loss, the rate of metal loss over the exposure period, and the relative performance of the various
alloys to this fireside environment.
The possibility of multiple fireside corrosion
mechanisms, acting either alone or in concert,
results in a much more complex situation for
quantitative evaluation than present on the steamside of the tube. This is further confounded by the
cyclic temperature variations discussed in the
section on steam oxidation evaluation. A first-level
approach to quantitative analysis of results will
entail characterizing the extent of metal loss of each
alloy versus a characteristic exposure temperature.
Fig. 10 illustrates the spread of exposure
Figure 10: Heat Transfer Calculation
temperatures of several alloys in the steam loop.
Model for the Steam Loop
Inconel 740 (IN740) coupons, for example, have
been spread over the length of the loop with specific coupons having an average full load surface
temperature ranging from ~750C (1380F) to ~820C (1510F). If coal ash corrosion were the
predominant active corrosion mechanism, it would be anticipated that the corrosion loss would
diminish over this temperature range due to thermal decomposition of the corrosive alkali iron
trisulfate phase. On the other hand, Super 304H, with coupons exposed from ~720C (1328F) to
~770C (1,18F) would be expected to exhibit a smaller decline relative to coal ash corrosion,
being above the peak but on a flatter portion of the bell curve than Inconel 740. Oxidation of the
Super 304H coupons would increase over this temperature range. However, a combination of
corrosion mechanisms and the cyclic nature of the temperature exposure may blur the distinctions
discernible by quantitative methods.
Interpretation of Steam Oxidation Data
Oxidation of boiler materials in a steam environment has been studied extensively for years
because of its impact on the life of high-temperature tubing and further impacts on the boilerturbine cycle, e.g. solid particle erosion of the turbine. A number of recent technical articles
provide background on the current understanding of steam oxidation [ref. 2-5] and a distillation
of a large body of information available in literature delving into the subtle and complex details
of the oxidation process. DOE-sponsored programs on both boiler and turbine materials for AUSC boilers/turbines have contributed to this literature via knowledge developed in Task 3
Steam Oxidation of the boiler program and Task 1-Steam Oxidation Testing of the turbine
program.
Quantitative data on oxidation rates has, for the most part, been generated by laboratory testing.
Laboratory test methods include use of a recording microbalance, i.e. thermogravimetric analyzer
(TGA), for short-term exposure of single specimens or an autoclave test rig for longer-term
exposure of multiple specimens. Determination of oxidation kinetics is generally accomplished
842
Eqn.2
where x=weight gain per unit area, t=time, and k p is the oxidation rate constant. Integrating and
solving the integral equation for isothermal oxidation yields the familiar parabolic oxide growth
rate equation:
= 2
Eqn 3
Thus a plot of oxide weight gain/unit area (or thickness) versus the square root of time will be a
straight line with a slope reflecting the value of k p (with appropriate units). The oxidation rate
constant, k p , varies with temperature, T, according to an Arrhenius relationship:
= /
Eqn 4
+1
= 0
Eqn 5
The time, tp n , is defined as a pseudo time representing the time needed to generate an amount of
oxide equal to x n and assuming exposure at an isothermal temperature T n for the time period from
t = 0 to tp n . This pseudo time, tp n , can be calculated using Eqn. 3 and solving for t. Thus:
)2
Eqn 6
+1 = + (+1 )
Eqn 7
= (
843
The amount of oxide growth in the period between t n and t n+1 can now be calculated from Eqn. 5,
evaluated as:
+1 = 2 +1
Eqn 8
Iteration of Eqns. 5-8 over all cyclic isothermal periods in a steam exposure history will generate
an estimate of the accumulated oxide amount at the conclusion of the test period. Parameters A
and Q appearing in the Arrhenius relation (Eqn. 4) can be varied to optimize the model
predictions over all exposure histories for coupons of a particular alloy to best match the oxide
accumulation measured at the endpoint of exposure. The optimized values of A and Q may also
be compared with the laboratory results of isothermal oxidation testing obtained earlier in the
Task 3 portion of the AUSC program and other relevant steam oxidation literature.
Demonstration of Methodology on Laboratory Data
Laboratory TGA testing has been performed with sequential, distinct temperature periods.
Weight-gain data, representing uptake of oxygen during steam oxidation, was recorded as the test
specimen was sequentially exposed at 550C (1022F) for 48 hours, followed 48 hours at 675C
(1247F), followed by 64 hours at 550C (1022F) in atmospheric pressure steam. Fig. 11 details
the oxide morphology generated for this exposure along with isothermal exposure of samples at
the two temperature levels and similar total time interval for comparison. The left and right
samples were exposed at the indicated isothermal temperature for 160 hours. The middle sample
was subject to steam exposure per the schedule described above.
The recorded weight gain vs. time record is shown in Fig. 12. Also shown in the figure is the
result of using the method explained previously to model the Arrhenius parameters, based solely
on matching the endpoint oxide measurement. While the calculated result does show some
variation from the continuously recorded data, the overall results are in reasonably good
agreement. The parabolic oxidation model utilized in the calculation will result in a straight line
when the weight gain data is plotted against the square root of time.
It is apparent that the first and second exposure periods exhibit deviation from a simple parabolic
oxidation model. The deviation in the first exposure period may result from an accelerated
oxidation rate while the specimen forms a complete surface oxide layer that can act as an
effective diffusion barrier. The deviation in the second period is likely the result of changes in
the oxide layer morphology brought on by the higher exposure temperature (note the differences
in appearance shown in Fig. 12 in the scale layers generated at the two temperature levels).
844
These two factors will be of lesser significance in analysis of much longer term exposures with
thicker, well-developed oxide scale layers. This analysis method will be used to generate steam
oxidation kinetic parameters for the alloys exposed in the steam loop for further evaluation of the
long term oxidation characteristics of the nickel alloys used in the steam loop.
845
ACKNOWLEDGEMENTS
The authors acknowledge the support and funding for this research project by the US DOE
NETL, Ohio Coal Development Office (OCDO), Energy Industries of Ohio (EIO), Electric
Power Research Institute (EPRI) and the host site for the steam loop, Alabama Powers Plant
Barry, with supporting efforts from Southern Company Services. Edward Ortman from Alstom
Power led the fabrication and installation of the steam loop. Alstoms Chattanooga, Tennessee
Laboratories designed and fabricated the steam loop. Alstoms field personnel supported the
installation and operation of the steam loop.
REFERENCES
1.
R. Viswanathan, et. al., Boiler Materials for Ultrasupercritical Coal Power Plants, Phase 1
Final Summary Report, February 15, 2007 (US DOE Consortium proprietary report).
2. Wright, I.G. and Dooley, R.B., A Review of the Oxidation Behavior of Structural Alloys in
Steam, International Materials Reviews, Volume 55 Issue 3, May, 2010, pp. 129-167.
3. Wright, I.G., DOE FWP No. FEAA061: Oxidation of Candidate Alloys in Steam at 17
Bar, Oak Ridge National Laboratory, ORNL/TM-2009/232, November, 2009
4. Wright, I.G. and Pint, B.A., An assessment of High-Temperature Oxidation Behavior of FeCr Steels in Water Vapor and Steam, NACE CORROSION/2002, Paper No. 02377, April,
2002.
5. Fry, A., Osgerby, S. and Wright, M., Oxidation of Alloys in Steam Environments A
Review, National Physical Laboratory, NPL Report MATC (A) 90, September, 2002.
6. Rapp, R. A. and Zhang, Y. S., Hot Corrosion of Materials: Fundamental Studies, Journal
of Metals, vol. 48, no. 12, pp. 47-55, Dec 1994.
7. Natesan, K. and Delplane, M. B., Oxidation-Sulfidation Behavior of Materials for Use in
Coal-Conversion Systems, Proceeding of Symposium Corrosion-Erosion Behavior of
Materials, K. Natesan ed., the Metallurgical Society of AIME, pp. 1-29, March 1980.
8. Dooley, R. B. and McNaughton, W. P., Boiler Tube Failures: Theory and Practice Volume
3: Steam-Touched Tubes, Electric Power Research Institute, 1996.
9. Hack, H. and Stanko, G., Experimental Evaluation of Fireside Corrosion Resistance of
Advanced Materials for Ultra-Supercritical Coal-Fired Power Plants, 23rd Annual
International Pittsburgh Coal Conference, Sept 2006.
10. Gagliano, M. S., Hack, H., and Stanco, G., Fireside Corrosion Resistance of Proposed USC
Superheater and Reheater Materials: Laboratory and Field Test Results, 33rd International
Technical Conference on Coal Utilization & Fuel Systems, Clearwater, FL, June 2008.
11. Gagliano, M. S., Hack, H., and Stanco, G., Update on the Fireside Corrosion Resistance of
Proposed Advanced Ultrasupercritical Superheater and Reheater Materials: Laboratory and
Field Test Results, 34th International Technical Conference on Coal Utilization & Fuel
Systems, Clearwater FL, May 2009.
846
ABSTRACT
INCONEL Filler Metal 72, a 43% Cr nickel alloy welding wire, has been used in elevated
temperature service to protect boiler tubing for over 20 years. Along with FM 72 overlays, INCOCLAD 671/800H co-extruded tubing has also been used to great advantage for resisting
sulfidation, oxidation, carburization and wear in boiler environments. INCONEL Filler Metal
72M is an optimized alloy that offers improved weldability and the lowest corrosion rate of any
of the alloys evaluated in our simulated low NOx boiler environment. Testing results are
presented along with illustrations of applications for the above materials. New interest has been
expressed in 72 and 72M for waterwall tubing overlays where the normal failure mode with other
weld overlays has been circumferential cracking and corrosion fatigue. Filler Metal 72 overlays
have shown outstanding resistance to abrasion and wear in soot blower lane tubing and resistance
to corrosion-fatigue-cracking in severe waterwall service. 72M overlays have been chosen to
replace erosion shields in the high wear nose areas of superheater and reheater tubing. 72M
overlays provide protection against corrosive attack even under reducing conditions created by
low NOx firing, and 72M is capable of performing well at the high temperatures experienced in
advanced ultra-super critical (AUSC) boilers. In addition to outstanding corrosion resistance, both
72 and 72M weld deposits increase in hardness and thermal conductivity with exposure time at
service temperatures. As thermal conductivity of weld overlays increase with service time, the
delta T(temperature difference across the tube wall) is reduced and provides substantial
increases in thermal efficiency for the boiler, while providing long life due to excellent corrosion
and erosion resistance and reduced tendency for thermal fatigue (corrosion fatigue). Overall costsavings are derived from lower maintenance costs as well as higher boiler thermal efficiency.
Both waterwall and upper boiler tubing overlays will be addressed with historical commentary
offered on how the optimum alloy choices have been made. Failure mechanisms are discussed
and the attributes of the successful alloy choices are defined.
Keywords: Fossil boiler, water-wall, super-heater, re-heater, alloys 72, 72M 622, 625, and
33
INTRODUCTION:
Investment in fossil-fired boilers in the USA has been stifled in recent years due to stringent
pollution control requirements imposed by the environmental protection agency (EPA) and the
emergence of inexpensive natural gas via fracking. The remaining countries of the world
continue to have strong and growing desires for more electrical energy, and those with access to
fossil fuels pursue conventional and advanced power boilers. It has been reported recently that
some power suppliers in the Middle East have inquired for high efficiency boilers to be fired with
high-impurity residual oil. These boilers would require overlay with alloy 72. In addition, the
power industry in the USA has anticipated sharp increases in the cost of natural gas due to the
coming expected surge in exports of LNG. These factors have prompted a renewed interest in
847
fossil-fired boilers. With this renewed scrutiny comes interest in the improved materials of
construction needed to survive the ever increasing severity of operating conditions brought about
by demands for greater efficiency and smaller carbon footprint.
Nickel-based weld overlays are commonly used in the power industry to extend the life of
equipment subjected to aggressive corrosion environments. Weld overlay via the pulsed gas metal
arc (PGMAW) process is a common form of protection, but more recently, the automatic gas
tungsten arc welding (GTAW) process and the hot-wire laser (HWL) processes have been used.
Good bond integrity, low corrosion rate and high thermal conductivity are desirable
characteristics of such overlays. These characteristics provide optimal life for overlaid
components on water-walls, super-heaters and re-heaters. As boiler conditions have become
more aggressive over the years, nickel based alloy overlays have become more commonly used,
not just for repair and maintenance purposes, but also as a cost effective solution for new boiler
installations. Filler Metal 72, a 43% Cr, balance nickel alloy welding wire has been used for over
20 years in elevated temperature service to protect boiler tubing where resistance to sulfidation,
oxidation, and carburization is required. INCO-CLAD 671/800H clad tubing made using alloy
671 (46 Cr, balance Ni) co-extruded over alloy 800H tubing has been used for over 30 years for
superheater tubing in the AEP system. Filler Metal 72M is an optimized alloy that offers
improved weldability and the lowest corrosion rate of any of the alloys evaluated in our simulated
low NOx boiler environment. Testing results are presented along with illustrations of
applications for the above materials. New interest has been expressed in 72 and 72M for waterwall tubing overlays where the normal failure mode with other weld overlays has been
circumferential cracking or corrosion fatigue.
Filler Metal 72 has shown outstanding resistance to corrosion fatigue in severe service in waterwall tubing and very long service life in upper boiler applications. A large new application for
re-heater service is discussed along with a novel Hot-Wire Laser Beam Welding (HWLBW)
process. This welding method using FM 72M allows a thinner weld deposit to be produced that
increases the thermal conductivity thorough the tube wall. These thinner overlays and the fact that
the thermal conductivities of 72 and 72M weld deposits increase with exposure time provide
multiple advantages. These two accomplishments reduced the delta T (temperature difference)
through the tube wall and allow substantial increases in thermal efficiency for the boiler at lower
overall cost, while providing long life due to excellent corrosion and erosion resistance and
reduced tendency for thermal fatigue.
Power Boilers that make significant contributions to the electrical grid are fired with various
grades of coal (fossil fuels). These boilers suffer from fireside corrosion, but the types and
severity of corrosion encountered vary with the grades of fuel used and operating conditions [1,
2]. Historically alloy 622 (ERNiCrMo-10) overlays have been chosen most often to protect water
wall tubing, and alloy 72 (ERNiCr-4) has been the most popular overlay for super-heater and reheater protection. However, Filler Metal 72 is beginning to show outstanding results in waterwall overlay, Filler Metal 72M is being evaluated for water wall overlay protection, and has just
been chosen for two major re-heater applications, as well as in super-heater tubing in soot blower
lane protection.
The chemical compositions of the alloys discussed in this paper are given in Table 1, along with
their American Welding Society classifications.
848
C
Ni
Cr
0.20 12-15 22-24
0.15
9.0
30.0
0.015
31
33
0.015 60.0 29.0
0.020 58.0 38.0
Fe
Bal.
Bal..
32
9.0
0.2
Mo
1.6
0.02
0.3
Nb
0.01
1
W
0.02
0.01
Al
0.6
1
Ti
0.5
0.6
0.01
0.01
0.01
0.15
0.6
Others
2.0 Mn,1.0 Si
2.0 Mn,1.0 Si
0.6 Cu
AWS Class
ER309
ER312
ER33-31
ERNiCrFe-7
ERNiCr-7
FM72
0.015
56.0
43.0
0.2
625
0.020
60.4
21.6
4.4
9.1
3.60
0.1
0.14
0.24
ERNiCrMo-3
622
0.004
59.3
20.4
2.3
14.1
0.04
3.1
0.25
0.06
ERNiCrMo-10
686CPT
0.01
58.5
20.4
0.4
16.2
3.9
0.32
0.08
Carbon Steel
0.19
Bal.
ERNiCr-4
ERNiCrMo-14
0.3 Cu, 0.5 Mn
---
849
24 Cr, 13 Ni
30 Cr, 9 Ni
33Cr, 31Ni, 32Fe
64 Ni, 21 Cr, 9 Mo, 3.5 Nb
59 Ni, 22.2 Cr, 14 Mo, 3 W
56 Ni, 43 Cr, 0.6 Ti
Temperature Limits
900 deg F- ?
800 deg F-?
885 deg F-?
800 1150 deg F.
800- 1100 deg F.
800- 1300 deg F.
800- 1500 deg F.
800- 1300 deg. F.
800- 1300 deg F.
Exposure Effects
Carbides, sigma phase
Carbides
Carbides, sigma phase, alpha phase
Carbides, double prime, BCT, Orthorhombic
P, Mu phase
Alpha chromium, Ni2 Cr, Ni3 Cr
Alpha chromium, Ni2 Cr, Ni3 Cr
Gamma Prime, carbides
Gamma Prime, carbides
However, when exposed to the acid test of the PP&L system, like 52, another 30%Cr alloy, the
alloy 33 failed. When installed in the Montour station of PP&L, the alloy 33 overlay began to
show cracking after three years and was removed from service after six years when it exhibited
major circumferential cracking. Although the supplier of alloy 33 has not reported on this service
and a sample tube is not available for investigation, we expect that a cross-section of one of those
tubes would appear to be similar to that shown in Figure 1. These failures in alloy 33 and 52 are
not unexpected in view of the previous research done in Niles, Ohio. The failure results (due to
low Ni of 33 and low Cr of both 33 and 52) serve to verify the conclusions of the B&W, OCDO,
DOE, Niles, Ohio study[5] that Nickel + Chromium is the most effective alloy combination to
withstand severe fossil-fired boiler environments as shown in Figure 2.
850
-----100 m
Figure 1. Longitudinal section through FM52 overlay on water-wall tubes exposed to high heat
flux for 5.5 years in base load service in a Northeastern supercritical utility boiler having 1020F
steam and burning coal having 1.5-2.5 pounds of sulfur per MBtu. (This is likely indicative of the
appearance of the sample of alloy 33 removed from the same system after 6 years with major
circumferential cracking).
its lower tendency to segregate during solidification [4]. The watershed 1000 square foot test
panels of 622 versus 625 installed into the defining power plants in the PP&L system (that is
considered to be the acid test for water-wall overlays) over one decade ago established the
preeminence of alloy 622 over 625 for fossil water-wall overlays. Therefore, the remaining best
practice alloy selections for water-wall overlay are 622, 72 and perhaps 72M. While there is a
great deal of experience with 622 overlays, there are sparse data for water-wall weld overlays
with 52 and 72. The recent examination of 5000 square feet of FM52 at AEPs Muskingum River
#5 is the most substantial application to have been evaluated to date, in terms of both square feet
of coverage and time of exposure. The results were no cracking anywhere in the 5000 square feet
after 7.5 years service (these results were reported previously and are available in the long
version of this report). While alloys 52 and 33 have been disqualified at PP&L, a sample of alloy
72 installed in PP&Ls Brunner Island Station has passed its 2.5 year and 6 year inspections with
no cracking. Thus there is hopeful expectation for good performance of alloys 72 and 72M in
severe water-wall service applications. In addition to the sample of 72 overlaid water-wall panel
just described in the PP&L system, there is another water-wall panel overlaid with 28 square feet
of FM72 in the Duke Energy system (Gibson #2) that has 6 years of crack-free service. While
there are test patches of Filler Metal 72 and Filler Metal 72M on water-walls with very good
reports to date, there are no large weld overlay deposits with extended service from which to
draw conclusions regarding performance. A ten tube by 40 foot long test panel made with FM
72M has been installed in Gibson Station Unit Number 1 of the Duke Energy System (650 MW
supercritical plant operating with 3500psi and 1005F steam). Fig. 3 shows the qualification
weld overlaid sample that represents the test panel that has been installed.
Figure 3. Water-wall panel section overlaid using INCONEL Filler Metal 72M via the automatic
GTAW process. The membrane weld was performed using the SAW process.
Fossil-fired Boiler Superheater and Reheater Tubing Applications
In addition to water-wall overlays, a second application that requires protection is the upper boiler
tubing, namely super-heater and re-heater tubing. These tubular structures often suffer from
accelerated erosion-corrosion damage that prompts the use of largely ineffective erosion
shields. These shields often become unattached during service and fall to the bottom of the
boiler. When attached, they offer poor erosion protection, but when they fall off, the offer no
protection and become a major maintenance headache. A new design idea is to replace these
attachments with integral alloy 72M weld overlays that do not fall off, offer much better
protection, and offer greatly improved heat transfer.
In support of upper boiler tube overlays, there is an extensive body of data which reports robust
performance of FM 72 (AWS ERNiCr-4) when used in superheater and reheater overlays. Figure
852
4 shows a section of an overlaid re-heater tube after 6 years of service. The cross section shows
the thickness profile and hardness level of the reheater tube after service in a low- NOx boiler
with an estimated metal temperature of 1200-1250F. . The hardness ranged from Rockwell C 4652. This increased hardness served to enhance erosion resistance. The increase in hardness of 72
and 72M with extended service coupled with the excellent service exhibited in soot blower lane
tubing would indicate these overlays can replace the troublesome thermal shields that are often
used in the upper boiler of many units. There is a wealth of additional data for FM 72 overlaid
INCOLOY 800H that is reported in the Babcock & Wilcox-Ohio Coal Development
Organization-Department of Energy (B&W-OCDO-DOE) study reported by McDonald and
Robitz [5]. These data were generated by exposing the overlays to approximately 1200F for 1, 2,
and 3 years in a boiler environment generated by burning 3.5% S Ohio coal. Overall, the
corrosion rates experienced by super-heater and re-heater overlays of FM72 are about 12mils/year with no cracking of the FM 72 overlays. By comparison, FM 52 overlays exposed to
the same environment perform well, but not well enough to serve for 10 to 20 years as would be
desired for upper boiler tubulars.
Figure 4. Re-heater tube overlaid with filler metal 72, removed from low-NOx boiler service
after 6 years of service. Note overlay integrity and erosion-enhancing hardness levels of 46 to 52
Rc.
The Reliant Energy consortium in southwestern Pennsylvania has several boilers with extensive
FM 72 overlaid upper boiler tubes in their Conemaugh and Keystone facilities. These overlays
have been performing exceptionally well for over 9 years. The Conemaugh super-heater tubes
have their J-legs overlaid while the Keystone facility has FM 72 overlaid re-heaters.
The INCO-CLAD 671/800H previously mentioned was a co-extruded product of INCONEL
alloy 671 powder surrounding an INCOLOY 800H billet. This product produced a nickel-alloy
cladding of about 46% Cr that is characterized in the B&W-OCDO-DOE study.
The final information to report on super-heater tubes is the outstanding performance of FM 72
overlaid super-heater tubes at AEPs supercritical Rockport #1 Station (operating at 1010F
(543C) at 26.5 MPa) that were used as soot blower lane super-heater tubing. Figure 5 shows
overlaid tubes that were in service (at the time of photograph, about 7 years), but now have
853
provided about 14 years of service. Note the strong appearance of ripples still existing after years
of harsh service from soot blowing.
Figure 5. SA213-T2 super-heater tubes overlaid with filler metal 72, after 7 years of service in
AEPs Rockport #1 plant.
Conductivity Hardness and Erosion Considerations
After extended service at typical operating temperatures, changes in the properties of filler metal
72 and 72M overlays have been observed. Fig. 4 has already shown the hardness increase to 4652Rc that can be observed in filler metal 72 deposits after extended exposure. The atomic nickelchromium ratios in filler metal 72 and 72M are nominally 1.14:1 and 1.22:1 respectively. This
would imply that both materials would be subject to long-range ordering. A study by Marucco
showed that long-range ordering in Ni2Cr occurs in 100-1000h below 977F (525C), and at
30,000h in Ni3Cr, accompanied by a significant decrease in electrical resistivity [7]. Filler metals
72 and 72M, at Ni1.14Cr and Ni1.22Cr, respectively, would yield different responses still. Fig 6 and
7 illustrate the measured drop in electrical resistivity (at room temperature) observed in Filler
Metals 72 and 72M, respectively, after exposure under various conditions. Figure 8 illustrates the
correlation between electrical resistivity and thermal conductivity (room temperature data are
shown) for a variety of materials. These dramatic increases in hardness and in overall thermal
conductivity offer huge benefits in overall thermal efficiency and operating efficiency in reduced
maintenance costs. Two super critical boilers are currently being fitted with 304-H reheater
tubing with 72M overlays critically positioned to replace conventional erosion shields that often
fall off and require maintenance for reattachment. Another utility is using 72M overlays over
347H tubing to protect their soot blower lane superheaters against erosion damage without loss of
good thermal conductivity. Thermal fatigue testing was performed to insure the CTE difference
between 72M and 347H would not cause any problems during service. The results of the testing
showed no tendency for cracking in either material even in the presence of intentionally placed
mechanical notches in the test specimens.
854
700
600
500
400
300
200
100
F/
48
,0
00
h
12
00
-1
25
0
90
0
F/
12
00
h
0
As
-P
ro
du
ce
d
800
800
700
600
500
400
300
200
100
14
40
h
14
00
F
/
12
00
F
/
10
00
h
As
-P
ro
du
ce
d
Fig. 6. Electrical resistivity measurements for wrought Filler Metal 72 samples before and after
exposure under the indicated conditions.
Fig. 7. Electrical resistivity measurements for wrought Filler Metal 72M samples before and
after exposure under the indicated conditions.
855
1000
Alloy 201
100
Alloy 625
10
10
100
1000
856
Fig 9. Hot Wire Laser Beam Weld Overlay using INCONEL Filler Metal 72M.
857
Spectrum
Si
Ti
Cr
Mn
Fe
Ni
Line Spectrum(1)
0.99
0.38
35.77
4.9
54.29
Line Spectrum(2)
0.97
0.34
0.69
36.04
4.32
53.61
Line Spectrum(3)
1.06
0.37
0.73
35.54
4.11
52.71
Line Spectrum(4)
1.08
0.4
36.17
5.91
52.68
Line Spectrum(5)
0.93
0.38
35.86
4.82
54.75
Line Spectrum(6)
0.43
20.43
1.08
61.14
13.51
Line Spectrum(7)
0.49
18.81
1.3
66.74
8.1
Line Spectrum(8)
0.54
18.52
1.36
66.68
Line Spectrum(9)
0.47
18.66
1.3
67.34
8.26
Line Spectrum(10)
0.52
18.51
1.38
67.11
8.04
N2
Oxidizing-Sulfidizing
Inlet
Outlet
67
67.2
Oxidizing
Inlet
Outlet
72
72
CO2
16
19.4
17.2
17.2
H2O
CO
H2S
10
5
2
6.8
1.45
1.97
4.9E-10
10.75
10.75
SO2
H2
pS2
pO2
2.07E-08
1.64E-28
858
3.10E-10
Fig. 11 shows the depth of attack values of different alloys after exposure in simulated low-NOx
corrosion test at 1000F (538C) for 4940 hours. Carbon steel, included as a control sample,
exhibits an attack rate which is an order of magnitude greater than that of the nearest nickel-based
sample tested. Alloys 625 and 622 are next in the order of decreasing attack rate. These two
alloys exhibit very similar behavior after 4940 hours, despite the much higher initial attack rate of
alloy 622. Short-term test results for alloy 622 would have greatly underestimated the materials
ultimate performance in this test. The depth-of-attack values provide an accurate assessment of
material performance in this test.
0.1
Carbon Steel
625 Wrought
622 Wrought
FM72 Overlay
0.01
FM72M Overlay
0.001
0.0001
0
1000
2000
3000
4000
5000
6000
Exposure Time, h
Fig. 11. Depth of attack results after exposure in simulated low-NOx corrosion test at 1000F
(538C) for 4940 hours.
Fig. 12 and 13 show the microstructure of cross sections from the alloy 622 and 625 samples,
respectively, after 4940 hours of exposure. The outer corrosion layers were found to be rich in
nickel and sulfur, via SEM-EDS, with chromium increasing moving toward the scale-metal
interface. The sulfide scale on the alloy 625 sample was much more friable in appearance and less
adherent than that of the alloy 622 which seems to be a reasonable explanation for the actual inservice experience where 622 outperforms 625 by a substantial margin.
-----50 m
Fig. 12. Photomicrograph showing alloy 625 wrought sample after exposure for 4940 hours in
simulated low-NOx boiler environment at 1000F (538C).
859
Depth of attack results shown in Figure 11 for the filler metal 72 overlay sample are slightly less
than those for alloy 622. Filler metal 72M, a modification of filler metal 72 with additions of
aluminum and niobium, exhibited superior performance. Fig. 13 and 14 show photomicrographs
of filler metals 72 and 72M after 4940 hours of testing. The sulfide surface scales are less
extensive for the filler metal 72M product than the corrosion product observed on the filler metal
72 overlay sample, and internal oxide layers are also much more compact. Also note the
pronounced flatter slope exhibited by the filler metal 72M maximum attack rate in Fig.15, which
shows the estimated performance of each alloy in one year with a half-cycle extrapolation.
-----50 m
Fig. 13. Photomicrograph showing filler metal 72 sample after exposure for 4940 hours in
simulated low-NOx boiler environment at 1000F (538C).
-----50 m
Fig. 14. Photomicrograph showing filler metal 72M sample after exposure for 4940 hours in
simulated low-NOx boiler environment at 1000F (538C).
860
0.1
Carbon Steel
625 Wrought
622 Wrought
FM72 Overlay
0.01
FM72M Overlay
0.001
0.0001
0
2000
4000
6000
8000
10000
Exposure Time, h
Fig. 15. Depth of attack results after exposure in simulated low-NOx corrosion test at 1000F
(538C) for 4940 hours, showing extrapolation to one year (8760 hours).
Conclusions
Weld overlay technology for protection of boiler tubing and super-heaters and re-heaters in coalfired supercritical plants is a dynamic endeavor. Service exposure of Filler Metal 52 overlays has
resulted in varied results, dependent upon the characteristics of the coal being utilized as well as
heat flux and the cyclic nature of boiler operation. Filler metal 72 has distinguished itself in
super-heater and re-heater service for many years now. The new modification of 72, Filler Metal
72M, shows promise as an improvement over Filler Metal 72. These materials are now being
evaluated as water-wall overlay materials as well. Initial results for Filler Metal 72 after seven
years of service are extremely encouraging, while trials with Filler Metal 72M have a little more
than 2 years exposure to date. Filler Metals 72 and 72M offer intriguing characteristics of
outstanding corrosion resistance coupled with apparent long range ordering effects. The benefits
of these characteristics are clearly demonstrated in remarkably good performances of FM72 and
671/800H in upper boiler tubes. Future benefits expected as a result of long-range ordering by
both are continuing erosion-corrosion resistance and greatly enhanced thermal conductivity
through the tube wall overlay. This increased thermal conductivity provides improved overall
boiler efficiency as well as decreased T through the overlay and tube wall to the steam or water
on the inside. The decreased T results in lower thermally induced strain, particularly in high
heat-flux areas, which offers a reduced tendency for circumferential cracking. Operating
performance data will be accumulated and reported over the next two to five years, as outages
permit. Superior performance is expected due to excellent corrosion resistance and improved
thermal conductivity of overlays.
Acknowledgements
The authors wish to acknowledge Mr. Darrell Wisner of Duke Energy for his assistance with the
application of the Filler Metal 72M test panel installed in Gibson Station Number 1. Also, we
appreciate the assistance of Michael Crichton and Ben Hackett of American Electric Power for
affording the review of Muskingum River Number 5. And we acknowledge the overall technical
861
input from Mr. Ruben D. Choug of Pennsylvania Power and Light. We also acknowledge Mr.
Wayne Penn of Alabama Laser and Mr. Marty Sims and Mr. Tim LeBeau of Southern Company
for their contributions on the laser overlay samples. We are also grateful for overall consultation
provided by Mr. Greg Stanko of Foster Wheeler Corp.
REFERENCES
1.
Wright I.G., Krause H.H., Nagarajan V., Boiler Tube Failures in MSW/RDF
Incineration/Co-firing, EPRI Report TR-103658, Palo Alto, CA. 1994
2. Sorell G., J. Materials at High Temperatures, 13, 137-150, 1997.
3. Thorton C.E. Cooper C., Proc. Stainless Steel World 2004 Conf., Paper No. SSW2005P0468, Houston, TX, USA 2004.
4. Kiser S.D., Cooper C., Proc. Stainless Steel World 199 Conf., Paper No. SSW99-076,
The Hague, Holland, 1999.
5. McDonald D.K., Proceedings of 27th Annual Conference in Fossil Energy Materials,
April, 2003.
6. Luer K., Advanced Materials and Processes, February, 2000, pp 24-25.
7. Marucco A., Atomic Ordering of alpha-Cr Phase Precipitation in Long-Term Aged
Ni3Cr and Ni2Cr Alloys. Journal of Materials Science, 30(1995), pp. 4188-4194.
8. Kiser S.D., T. Orsini and B.A. Baker, Proceedings of Corrosion/2007 Conference,
NACE International, Paper Number 07462, 2007.
9. Takeuchi Y., Kawahara K., Hasodat., Corrosion 2000, Proceedings 55th NACE Annual
Conference, Paper No. 00261, Orlando, FL, USA> March 2000.
10. Baker B.A., Smith G.D., Shoemaker L.E., Proceedings 56th NACE Annual Conference,
Paper No. 01183, Houston, USA. March 2001.
11. Kawahara Y., Haihara Y., Corrosion 2001, Proceedings 56th NACE Annual Conference,
Paper No. 01173, Houston, USA. March 2001.
12. Kawahara Y., Nakamura M., Tsuboi H., Ykawa K., Corrosion 97, Proceedings 52nd
NACE Annual Conference, Paper No. 165, New Orleans, USA. March 1997.
862
INTRODUCTION
The recent development of high-efficiency, low-emission coal-fired utility boilers has led
1
to steam conditions of much higher temperatures and pressures. Examples include the
development of advanced ultra supercritical (A-USC) boiler systems that may push the
o
o
steam temperatures up to 760 C (1400 F) and pressures up to 35 MPa (5000 psi). While
a higher efficiency and lower emissions can be realized from these advanced
combustion systems, the steam conditions inevitably demand the use of increased
creep-resistant alloys for the construction of superheaters and reheaters. Under these
steam conditions, accelerated fireside corrosion is a particular concern for the hightemperature sections of boiler tubes in the upper furnace. The higher steam
temperatures will raise the metal temperatures of superheaters and reheaters
significantly, leading to an increased propensity for coal ash corrosion (also known as
2,3
hot corrosion). The highest coal ash corrosion attack would likely occur in the
superheater and reheater outlet banks, with the tube OD temperatures ranging from 650
o
o
o
o
to 815 C (1200 to 1500 F) and corrosion rates peaking near 1300 F (704 C).
Results of numerous laboratory corrosion studies have been reported in the literature,
mainly comparing the corrosion resistance of alloys and coatings exposed to the fireside
3-5
environments of coal-fired utility boilers. However, the majority of these studies
employed relatively simple test conditions. Since knowledge of the actual combustion
environments existing in coal-fired boilers is generally lacking, especially on the species
most critical to fireside corrosion, most of the laboratory studies have implemented
conditions that were derived from either thermodynamic calculations of the combustion
systems or measurements of product gases from slow pyrolysis of small coal samples in
7-11
Neither approach can fully duplicate the dynamic nature of coal
a batch process.
combustion nor determine the test conditions in commercial coal-fired utility boilers.
In recent years, the implementation of oxy-coal combustion has been considered as a
viable means to capture the majority of the CO2 produced from coal-fired power plants.
Oxy-combustion involves partial recycling of the combustion gas back to the boilers
through the primary and secondary gas streams in a closed boiler system. Besides the
primary purpose of an increased gas velocity, gas recycling can also enrich CO2 to a
concentration level that is economical for downstream capturing, compression, and
purification. As the combustion gas recycles, the concentrations of corrosive species in
the gas phase, such as SO2 and HCl, are also increased if they are not completely
scrubbed prior to the return of the combustion gas. This is especially true for the case of
hot and warm recycling designs in which the concentrations of the corrosive species
can be three to four times of those in the corresponding air-fired boilers burning the
same coal. Such an increase in concentration could pose significant concerns for
fireside corrosion and the performance of oxy-fired boilers.
Various corrosion data from extensive research studies pertaining to oxy-combustion are
available in the literature. However, these data are often inconsistent and at times
controversial. A careful review of these studies revealed that the majority have employed
test conditions that did not properly reflect those anticipated for oxy-combustion in coalfired commercial boilers. In fact, some of the laboratory tests were performed under
environments that deviated so greatly from those anticipated for oxy-coal combustion
that they should not even be considered relevant. Therefore, a comprehensive and
systematic study is needed to quantify the impact of oxy-combustion on the fireside
corrosion of superheaters and reheaters in coal-fired A-USC boilers.
864
Towards this goal, a study consisting of a series of pilot-scale combustion tests and
laboratory corrosion exposures has been performed. During the pilot-scale testing
phase, the concentrations of various gaseous species generated from the air and oxycombustion of each of four U.S. coals were measured in-situ, while deposit samples
were also collected for analyses. For oxy-combustion, part of the flue gas was returned
to the burner via warm recycling. The gas measurements and deposit analyses allowed
the combustion environments near the superheaters and reheaters of coal-fired A-USC
boilers to be realistically characterized under both firing modes. The gas and deposit
compositions were then carefully simulated in a series of 1000-hour laboratory corrosion
tests in which the corrosion resistance of different alloys and weld overlays was
o
o
evaluated at 704 C (1300 F). The corrosion rates of the materials evaluated under both
air and oxy-firing conditions of the four coals are compared here, and the corrosion
mechanisms operating in coal-fired A-USC boilers are proposed.
EXPERIMENTAL PROCEDURES
Four U.S. coals, different greatly in composition and property, were selected for this
corrosion study. The proximate and ultimate analyses, chlorine contents, and heating
12
values of these coals are compared in Table 1. Per ASTM International classifications,
Wyoming (WY) Powder River Basin (PRB) is ranked as sub-bituminous, while the other
three coals are bituminous. The sulfur contents of these coals ranged from high (4.31%)
in OH Gatling to low (0.25%) in WY PRB. The chlorine contents also varied significantly
from nearly 0.4% in IL #6 Galatia to below 10 ppm in WY PRB. The moisture content
was relatively high in the PRB coal compared to those of the bituminous. All of these
coals were processed and pulverized to a particle size of 70% passing 200-mesh, the
same fineness requirements for commercial coal-fired utility boilers.
Combustion tests of the four coals were performed in a pilot-scale testing facility
available at Brigham Young University and rated at nominally 160 kW by thermal input.
The test facility, shown in Fig. 1, was capable of producing a down-fired, swirl-stabilized
coal flame in a cylindrical combustion chamber of 265 cm in height and 75 cm in inner
diameter. The inner surface of the combustion chamber was water-cooled and lined with
a high-temperature refractory. The inset in Fig. 1 depicts the coal burner of the pilotscale testing facility, with streamlines showing the mixture of primary gas and fuel
flowing through the center feed tube and secondary gas swirling around the primary mix.
A swirling secondary gas stream is an important feature of modern burners to achieve
13
superior air/fuel mixing, stabilized flame, and reduced NOx formation. For oxycombustion, a significant modification was made to the test facility by converting the gas
flow from once-through to oxy-firing with warm gas recycling.
For pilot-scale combustion testing, the coal and gas flow rates were adjusted for both air
and oxy-firing conditions of each coal so that (1) approximately 160 kW thermal input
was achieved in the pilot-scale test facility, and (2) 3% excess oxygen in the combustion
gas was maintained at the furnace outlet. An online gas sampling system was used to
measure the concentrations of gaseous species present in the oxidizing zone of the
14
pilot-scale test facility.
Table 2 summarizes the gas compositions determined from the pilot-scale combustion
study of the four U.S. coals under both air and oxy-firing conditions. As mentioned
previously, the flue gas was once-through in the air-firing combustion tests but warmrecycled in oxy-firing. Only the major and selected gases are listed here, as the
presence of other species, including various hydrocarbon and some sulfur and chlorinebearing compounds, were insignificant. Elemental sulfur (S2) and chlorine (Cl2) were not
865
IL #6
Galatia
WY
PRB
Proximate Analysis
5.40
24.59
8.65
5.14
35.68
37.00
50.27
33.27
100.00
100.00
Ultimate Analysis
5.40
24.59
3.74
2.55
70.16
54.75
1.04
0.83
2.69
0.25
8.32
11.89
8.65
5.14
100.00
100.00
0.3693
0.0010
Heating Value
12,575
9,156
Ash Analysis
48.12
36.04
19.65
16.84
17.64
5.86
4.28
21.61
0.95
5.06
1.08
1.69
2.59
0.50
1.05
1.32
0.07
0.02
0.08
1.00
0.03
0.35
0.05
0.62
4.41
9.09
2.79
2.02
0.39
0.64
0.68
0.53
2429
2228
OH
Mahoning
OH
Gatling
2.22
9.92
40.79
47.07
100.00
3.77
11.34
40.73
44.16
100.00
2.22
4.18
74.67
0.93
1.96
6.12
9.92
100.00
0.1946
3.77
4.07
67.11
0.94
4.31
8.46
11.34
100.00
0.0373
13,404
12,191
42.65
29.07
20.45
1.76
0.52
0.34
1.61
1.41
0.00
0.76
0.12
0.07
1.24
1.40
0.34
0.65
2497
40.35
22.56
28.33
2.62
0.69
0.41
1.28
1.04
0.05
0.22
0.09
0.11
2.25
1.25
0.52
0.56
2295
As expected, a major shift in concentration between air and oxy-firing from the
enrichment of nitrogen gas (N2) for the former to CO2 for the latter is revealed in Table 2.
In addition, a significant increase in the moisture content was observed for the oxy-firing
conditions. Important to fireside corrosion, the SO2 and HCl concentrations measured
from oxy-combustion with warm recycle were three to four times of those of
corresponding air-firing cases. In addition, the SO2 and HCl concentrations increased
proportionally with increasing S and Cl contents in the coal, with the highest HCl
concentration observed for the IL #6 Galatia coal and highest SO2 for OH Gatling. Note
that the SO2 concentration for the oxy-combustion of OH Gatling exceeded 1% in the
gas phase. Obviously, such a high concentration of corrosive species is typically
866
avoided in boiler design. However, for the objective of this study, it is important to
quantify the extent of the impact from oxy-combustion of extremely high sulfur (and Cl)
coals on fireside corrosion.
IL #6 Galatia
Air
Oxy
3.00%
2.90%
O2
CO2 16.00% 74.17%
0.0340%
CO
7.00%
17.80%
H2O
SO2 0.2300% 0.6240%
0.0267%
H2S
HCl 0.0200% 0.0640%
73.75%
4.40%
N2
OH Mahoning
7A
OH Gatling
WY Black Thunder
PRB
Air
Oxy
Air
Oxy
Air
Oxy
3.00%
3.00%
3.00%
3.00%
3.00%
3.00%
16.00%
75.61%
15.00%
71.32%
17.00%
67.17%
0.0162%
0.0078%
0.0167%
9.00%
19.16%
7.00%
18.49%
12.00%
26.71%
0.1550%
0.3880%
0.2700%
1.0340%
0.0200%
0.0640%
0.0110%
0.0346%
0.0005%
0.0055%
71.83%
1.79%
74.73%
6.14%
0.0001%
68.00%
3.04%
Table 2 also reveals the presence of some carbon monoxide (CO) at the furnace exit for
the oxy-combustion of all four coals (78-340 ppmv), even though the overall gas
compositions at this location was highly oxidizing. Furthermore, some hydrogen sulfide
867
(H2S) was detected with a FTIR at this oxidizing location during the oxy-combustion of IL
#6 Galatia. The detection of these reducing species clearly indicates that the kinetics of
oxy-coal combustion are more sluggish than those of air combustion, as no measurable
amounts of CO and H2S were observed for all of the air-firing cases. Therefore, even
though the combustion gases were not fully equilibrated in the oxidizing zone of air14
firing, as concluded by Kung, a further deviation from equilibrium was evident for oxycoal combustion. Slower reaction kinetics are expected for oxy-combustion due to a
reduced flame temperature compared to that of corresponding air-firing based on the
same amounts of oxygen and coal burned. A lower flame temperature would inevitably
delay char burnout in the burner zone and result in less completion of the coal
combustion at the furnace exit. The concentrations of CO and H2S were relatively small
so that the combustion gas should not be considered reducing.
Table 3 summarizes the deposit compositions implemented for the laboratory study.
Obviously, the compounds of sulfate, carbonate, and chloride would contribute more
importantly to fireside corrosion than those of oxide, and these compounds were all
readily available commercially for use in the deposit mixtures. Due to the instability of
potassium oxide (K2O) at room temperature, the compound of KOH was used when
needed, which would quickly decompose upon heating to form the desired K2O.
Table 3
Compositions of Deposit Mixtures Used in the Laboratory Test Conditions
Al2O3
SiO2
CaO
Fe2O3
K2TiO3
KOH
TiO2
MgSiO3
Fe2(SO4)3
KAl(SO4)2
CaSO4
K2SO4
MgSO4
Na2SO4
CaCO3
K2CO3
MgCO3
Na2CO3
NaCl
KCl
FeCl3
IL #6 Galatia
Oxy
Air
11.11 11.35
24.42 26.83
2.18
3.17
10.37
7.59
0.68
0.41
0.95
17.31
4.84
10.03
17.71
0.72
0.44
22.70
0.30
0.05
6.68
0.95
8.13
0.80
6.53
3.64
0.01
0.04
0.07
OH Mahoning 7A
Air
Oxy
16.92
16.68
22.62
23.00
0.89
0.71
7.78
8.13
1.02
0.62
0.30
19.84
4.84
10.07
15.11
1.02
0.62
14.59
0.25
OH Gatling
Air
Oxy
13.36 13.78
21.27 21.52
0.97
13.50 14.25
0.90
0.45
3.74
17.77
0.40
0.05
16.77
1.84
4.13
0.60
15.59
9.11
1.90
2.60
0.90
6.31
3.30
18.95
16.55
6.45
4.60
3.45
12.27
5.49
12.70
7.15
3.10
Several high-temperature alloys and two weld overlays were evaluated in the laboratory
study for the potential application of superheaters and reheaters in coal-fired A-USC
boilers, as shown in Table 4. Duplicate samples of each material were prepared and
included in each of the laboratory tests, with one for dimensional measurements and the
other for metallographic examinations. Samples of the weld overlays were EDMremoved from weld-overlaid boiler tubes after the OD surface was machined to eliminate
roughness. Consequently, both curved surfaces of each weld-overlay sample were
smooth for thickness measurements. After sample preparation, the test specimens were
placed in high-purity alumina crucibles and filled with the deposit mixtures shown in
Table 3. These crucibles were then transferred to a horizontal retort inside a high868
temperature furnace with both ends properly sealed. At the end of each 1000-hour test,
corrosion rates of the alloys and weld overlays were calculated based on the measured
weight and thickness losses.
Table 4
Compositions of Alloys and Weld Overlays Evaluated in Laboratory Tests
T23
Ni
Cr
Fe
Mo
Co
C
N
B
Mn
Si
Al
Ti
Nb
Nb+
V
W
Cu
P
S
Oth
2.18
0.21
0.08
0.00
0.00
0.50
0.25
0.02
0.03
0.25
1.46
0.00
<0.0
-
347
H
10.
17.
68.
0.2
<
0.0
1.8
0.4
0.3
0.0
0.0
-
347H
FG
11.98
18.4
Bal
0.09
1.46
0.41
0.9
0.027
0.001
-
S30
4H
8.73
18.6
67.6
0.32
0.14
0.08
0.11
0.8
0.14
0.52
<0.1
2.78
-
304
H
11
18.
Bal
0.0
1.8
0.4
0.0
0.0
-
800
H
32.7
21.0
Bal.
0.08
0.80
0.59
0.45
0.31
0.11
<0.0
-
309
H
12.
23.
Bal
0.0
0.0
1.6
0.3
0.4
0.0
0.0
-
310
H
19.3
25.4
Bal.
0.40
0.04
1.63
0.63
0.17
0.02
0.00
-
310H
CbN
19.97
25.61
Bal
0.05
0.24
1.18
0.36
0.47
0.015
-
230
617
740
120
59.
21.
1.2
1.2
0.1
0.0
0.0
0.5
0.4
0.4
0.0
0.0
14.
-
53.
22.
0.7
9.3
12.
0.0
0.0
0.0
0.1
1.1
0.2
0.0
0.0
-
49.
24.
1.0
0.5
19.
0.0
0.4
0.7
1.5
1.8
-
37.
25.
34.
0.2
0.1
0.0
0.2
0.7
0.4
0.0
0.6
0.1
-
WO
52
56.
29.
12.
0.0
0.0
0.0
0.2
0.2
0.7
0.5
WO
72
47.
>41
10.
0.0
0.0
0.0
0.1
0.1
0.1
0.4
0.0
0.0
ND
0.0
0.0
0.0
0.0
ND
0.0
-
869
Figure 2 - Comparison of Corrosion Rates in mpy for Alloys and Weld Overlays
o
o
Exposed to Laboratory Test Conditions at 704 C (1300 F) for 1000
Hours under Air-Firing and Oxy-Firing.
In general, the materials exposed to the combustion environments of IL #6 Galatia coal
produced the highest corrosion rates among the four coals studied, followed by OH
Gatling and OH Mahoning. There are only a few exceptions to this trend, which would
have been attributed to specific reactions between the combustion environments and
elements in the alloys. The corrosion rates of the higher alloys and weld overlays
measured from the WY PRB tests were quite low compared to those of the other three
coals. Obviously, these low rates reflected the very low sulfur and essentially zero
chlorine contents in this coal. Even when the amounts of SO2 and HCl were increased
three to four times in the gas phase by switching the combustion mode from air-firing to
oxy-firing (with warm recycling) for this coal, the resulting concentrations of these
species were still too low to cause severe fireside corrosion.
One exception to the generally low corrosion rates found in the PRB test conditions is
the T23 ferritic steel. In the absence of air-firing kinetics data for the PRB test, the
corrosion rate of T23 from oxy-combustion exhibited slightly lower but comparable value
to those from the other coals containing much higher sulfur and chlorine contents. In
fact, the corrosion rates of T23 from all of the tests appeared to stay within a narrow
range. Furthermore, the corrosion rates of this low-Cr ferritic steel should have been
noticeably higher than those of the highly corrosion-resistant alloys investigated in the
high sulfur and/or chlorine tests for IL #6 Galatia, OH Gatling, and OH Mahoning. From
this research work, it was uncovered that, due to the lack of sufficient Cr content in the
low-Cr ferritic steel, the alloy did not have the ability to form a more protective oxide
scale on the surface upon exposure to the highly oxidizing/sulfidizing combustion gases
in the upper furnace of advanced coal-fired boilers. As a result, a scale morphology
consisting of both iron oxide and iron sulfide was produced on the metal surface
underneath the porous deposit. With the iron sulfide exposed to the HCl-containing
870
precipitation of these oxides out in the salt phase where their solubilities are lower. The
fluxing and re-precipitation are dictated by a negative solubility gradient for these basic
15
oxides, as proposed by Rapp and Goto. A high local salt basicity in the pit is generated
by local penetration of the protective scale, formation of sulfide, and the release of oxide
ions into the sulfate melt. The Cr oxide solute experienced a positive solubility gradient
in the pit, as there was no evidence for its outward migration in Fig. 3. In fact, the
concentration of Cr exhibits a step change from the pit to the Fe2O3 and NiO reprecipitated zone above, a morphology characteristic of the basic dissolution and fluxing
mechanism.
Figure 4 shows a backscattered SEM micrograph and the associated elemental maps
for the cross-section of 309S after exposure to the oxy-firing OH Gatling laboratory
o
o
condition at 704 C (1300 F) for 1000 hours. The surface morphology of 309S from the
oxy-firing test can be compared directly to those of air-firing in Fig. 3. The magnification
of the images in Fig. 4 is five times of that in Fig. 3. Therefore, the worst localized attack
and penetration found on 309S from the oxy-firing test in Fig. 4 is much shallower than
that of air-firing in Fig. 3. Such a low corrosion attack observed for 309S under the oxyfiring condition is consistent with the significant difference in the measured corrosion
rates shown in Fig. 2, in spite of the SO2 and HCl concentrations present in the oxy-firing
test being three to four times of those in the air-firing case. Reasons for the reduced
corrosion rates in oxy-firing environments will be discussed later.
the initially protective scale was locally penetrated. Chromium remained in the pit, with a
negligible amount found in the re-precipitation zone above the pit. Like the air-firing
case, no evidence of corrosion attack from chlorine was observed on the cross-section
of 309S (or any other samples from this test) under the oxy-firing condition. Therefore,
the corrosion mechanism operating on the superheaters and reheaters of oxy-fired AUSC boilers burning the OH Gatling coal is governed by the hot corrosion mechanism
involving fused sulfate.
Similar SEM/EDS results were observed for all of the austenitic stainless steels, nickelbase alloys, and weld overlays. A generalization for these higher alloys can be made; a
sulfur-rich scale was generally formed beneath the protective scale in contact with the
alloy, and a continuous fused sulfate salt existed throughout the corrosion product.
Chromium was enriched in the salt phase beneath the deposit, although both iron and
nickel were depleted and found deposited in the adjacent deposit layer. Upon scale
penetration, reactions between the fused sulfate and metals led to the formation of metal
sulfide and the release of oxide ions that significantly increased the salt basicity locally
at the metal/scale interface. Consequently, the basic solutes of NiO and Fe3O4, i.e.,
M2NiO2 and MFeO2, respectively, were formed and diffused out in the salt down a
negative solubility gradient. These solutes re-precipitated out as non-protective oxide
particles of Ni and Fe in the salt phase within the deposit. The basic solute for chromium
oxide (probably Na2CrO4), in contrast, did not diffuse out because of a positive solubility
gradient for the chromate ion due to a strong oxygen-pressure dependence for its
15
solubility. No corrosion attack associated with chlorine was observed, including IL #6
Galatia under the oxy-firing condition where a high concentration of HCl was measured
in the pilot-scale combustion facility and subsequently employed in the laboratory test.
An entirely different corrosion morphology was observed for low-Cr ferritic steel. Figure 5
shows an optical micrograph of the corrosion scale and deposit layer exfoliated from a
T23 sample exposed to the air-firing combustion environment of OH Gatling coal with
o
o
high S but negligible Cl at 704 C (1300 F). The heterogeneous multi-layered scale and
deposit shown in Fig. 5 exhibited little variation in layer thicknesses along the height of
the test sample immersed vertically in the crucible filled with the simulated deposit. Thus,
oxidant diffusion through the porous deposit did not contribute significantly to the rate
controlling step or product chemistry, which is consistent with the expectation for hightemperature corrosion involving volatiles in a porous medium.
The scale morphology of T23 exhibited a rather layered and patchy structure. The dense
phase in contact with the alloy substrate (shown separated from the scale) at the lefthand side of the micrograph is about 8-mil thick and is predominantly Fe-Cr oxide
(probably Fe-Cr spinel). This spinel layer was likely the innermost oxide scale formed
initially and was somewhat protective. Farther out into the scale (toward the right), a
similar dense phase consists again of Fe-Cr oxide (still spinel) with a thickness of
approximately 35-40 microns. Patchy porous areas are embedded in this outer spinel
scale, which contain both iron oxide and iron sulfide. The outermost portion of the
compact scale is also mostly Fe-Cr oxide and is probably magnitite. Farther out to the
bright yellow layer as well as the stringers intermixed with the particles of the deposit,
the presence of potassium is evident. Figure 6 shows the backscattered SEM
micrograph and associated elemental maps for the middle section of the scale/deposit
layer in Fig. 5. The elemental maps for Fe and Cr indicate a sharp boundary between
the compact corrosion scale and the deposit layer, which is also consistent with the
maps for the deposit elements of K, silicon (Si) and aluminum (Al) (Si and Al maps are
not shown) that are all confined to the deposit layer but not in the compact scale. These
characteristics do not resemble those consistent with the hot corrosion attack discussed
previously for the austenitic stainless steels and nickel-base alloys.
Generally, farther out in the deposit, above the compact (dark orange) corrosion scale in
Fig. 5, both potassium and magnesium were found associated with sulfur, likely to be
mixed sulfates. Most importantly, in this porous zone of ash deposit, a lacey iron oxide
arising from substrate oxidation was present at a distance several times the thickness of
the compact scale layer. A zone relatively depleted in sulfur is seen between the top of
the compact corrosion scale and sulfate particles farther out in the deposit. The
observation of iron oxide far out into and intermixed with the porous ash deposit can only
be understood in terms of an active volatile-chloride-supported oxidation process of
iron sulfide at the base of the deposit in contact with the gas phase that contained HCl
molecules. Such a corrosion process for low-alloy ferritic steel is denoted here as the
Active Sulfide-to-Oxide Mechanism. The proposed Active Sulfide-to-Oxide Mechanism
16,17
for
differs in detail from the active oxidation mechanism proposed by Grabke, et al.
corrosion of alloys by a much more oxidizing gas in the presence of municipal waste
deposits. In that case, the active oxidation mechanism was proposed to occur by the
formation of volatile FeCl2 (and even condensed FeCl2) from the reaction with iron oxide
at the base of the deposit and the conversion of volatile FeCl2 to iron oxide farther out in
the deposit with the release and recycling of molecular chlorine (Cl2).
In the less oxidizing but more sulfidizing environment of the current study, iron sulfide is
seen to exist to the extremity of the compact scale, and this FeS would have a much
higher thermodynamic activity for iron than the neighboring iron oxide phase. Therefore,
the volatile FeCl2 would form from iron sulfide instead of iron oxide, but would be
deposited as a particulate oxide farther out in the deposit. The Active Sulfide-to-Oxide
Mechanism can be expressed by the following reaction:
FeS + 2 HCl (g) + 2 O2 (g) = FeCl2 (g) + H2O (g) + SO3 (g)
Eq. 1
where the standard Gibbs energy of reaction for Eq. 1 is approximately -112 kcal/mole.
While converting condensed FeS to FeCl2 vapor, Eq. 1 also served as a catalyst to
convert SO2 to SO3. Such a chemical reaction was proven experimentally in this study
by analyzing the SO3 concentrations exiting the testing retort. Results of the in-situ gas
analyses during the corrosion exposures showed that about 25% of the SO2 entering the
retort was converted to SO3. After its formation, the SO3 would either diffuse outward
874
from the base of the porous deposit to the bulk gas or react with oxides of alkalis,
alkaline earth metals, and iron oxide to form more sulfate in the deposit.
Eq. 2
where the standard Gibbs energy of reaction for Eq. 2 is approximately -42 kcal/mole.
The conversion of FeCl2 vapor to condensed Fe2O3, followed by the return of the HCl
product gas to the base of the deposit, could sustain the cycling reactions of Eqs. 1 and
2. Incidentally, the OH Gatling coal was not (at all) one of the high-Cl coals studied.
Therefore, higher corrosion rates would be expected for low-alloy steels exposed to the
combustion environments of coals of higher chlorine contents, as evidenced in Fig. 2.
For comparison, an optical micrograph of the scale/deposit layer exfoliated from the T23
sample exposed to the oxy-firing OH Gatling coal condition is shown in Fig. 7. The
morphology of this scale/deposit combination from the oxy-firing test resembles closely
to that of Fig. 5 from the corresponding air-firing test, except that the thicknesses of the
scale and iron oxide condensed in the porous deposit are less. Such a close
resemblance clearly suggests that the corrosion mechanism operating on T23 was
identical under both air-firing and oxy-firing conditions. However, the corrosion rate from
oxy-firing was lower than that of air-firing, consistent with the corrosion rates shown in
875
Fig. 2. Similar morphologies were also found on T23 for the test conditions of other
coals, except that of air-firing PRB where no chlorine was introduced. These results
indicate that the Active Sulfide-to-Oxide Mechanism would likely operate on low-Cr
ferritic steels even at a very low concentration level of HCl in the gas phase.
higher heat capacity of CO2 than that of N2 (and thus lower combustion temperatures for
oxy-firing). It is also possible that the higher density of oxy-firing combustion gas
discussed above reduced gas phase diffusivity of the combustion gas. Both a reduced
gas temperature and diffusivity would have delayed coal combustion and char burnout in
the burner zone. Under the air-firing conditions, only the OH Gatling coal exhibited some
carbonate in the deposit, although its amount was smaller than that of the corresponding
oxy-firing sample. However, carbonate in the deposit should not be considered as
unburned carbon (UBC).
Thermodynamically, sulfates of alkalis and alkaline earth metals are much more stable
than the carbonates. In fact, the difference in stability is so huge that any carbonate will
be chemically converted to sulfate as long as a very small amount of sulfur exists in the
system. It is unclear, however, how fast the conversion would take place kinetically.
Obviously, the carbonates included in the laboratory deposit would fully convert to
sulfates during the 1000-hour exposure of each test, since no evidence of any carbonate
was found in the deposit from the SEM/EDS examinations. However, the conversion
process would also take some time to complete. Because hot corrosion is fueled by the
amount of sulfate available in the deposit, which has been demonstrated here as the
predominant mechanism attacking the higher alloys and weld overlays under both air
and oxy-firing conditions, the lower availability of sulfate in the oxy-firing cases would
reduce the severity of the corrosion attack, at least initially, compared to the
corresponding air-firing conditions until all carbonate was fully sulfated. Accordingly, the
formation of carbonate from oxy-coal combustion in A-USC boilers could be considered
a beneficial factor.
The third reason leading to the reduced corrosion attack in oxy-firing combustion
environments would be the reduction of salt basicity from a much higher concentration of
CO2, and possibly HCl too, compared to those in the corresponding air-firing conditions.
As mentioned previously, upon penetration of the initially protective scale, fused sulfate
becomes extremely basic (and reducing) due to rapid reactions between the salt and
metal. The higher the salt basicity, the higher the basic solubility is for the solutes of
oxides of the alloying elements. In addition, the higher the salt basicity, the greater the
negative solubility gradient is for the dissolved solutes. A high basic solubility and
solubility gradient would have been responsible for the rapid hot corrosion attack
observed for the austenitic stainless steels and nickel-base alloys exposed to the airfiring conditions. However, when the CO2 and HCl concentrations were increased in the
gas phase from oxy-firing, the acidic nature of these gases would have partially
neutralized the basicity of the fused salt via the following examples.
CO2 (g) + Na2O = Na2CO3
2 HCl (g) + Na2O = 2 NaCl + H2O (g)
Eq. 3
Eq. 4
where the underlined species denote either a basic component of the fused salt or
reaction products that become (dissolved) solutes in the fused salt. Similar reactions can
be written for other basic salt components, such as the solutes of K2O, MgO, and CaO.
When these basic components of fused sulfate were neutralized by the acidic gases of
CO2 and HCl, both the basic solubility of metal oxides and their concentration gradients
were decreased. As a result, the hot corrosion attack of higher alloys and weld overlays
from fused sulfate in the oxy-firing combustion gas was noticeably reduced kinetically
compared to that in air-firing. In comparison, the impact of the neutralization effect on
salt chemistry would be greater for CO2 than that HCl due to their significant difference
in concentration. The formation of a higher concentration of acidic SO3 in the gas phase
877
per Eq. 1 helped neutralize the basicity of the fused salt in hot corrosion. Because the
SO3 concentrations would likely to be even lower than those of HCl, its benefit in the
reduction of hot corrosion attack from oxy-firing was probably small.
The impact from the decreased diffusivity in a higher density gas has impacted more on
the vapor transport of FeCl2 in the corrosion of low-Cr ferritic steel via the newly
proposed Active Sulfide-to-Oxide Mechanism. Therefore, the benefit associated with
reduced gas diffusivity in oxy-firing coal combustion would be relatively small. Such a
smaller improvement is clearly demonstrated in Fig. 2 where a slightly lower corrosion
rate of T23 is observed for oxy-firing than that in the corresponding air-firing. For the
attack dominated by the hot corrosion mechanism on higher alloys and weld overlays,
the latter two reasons, i.e., delayed availability of the sulfate and especially the reduction
of salt basicity from the acidic gases, would have played a more prominent role. These
two reasons would impact the corrosion performance of alloys significantly by
modification of the salt chemistry in the deposit. Consequently, a more dramatic
improvement was generally observed on the measured corrosion rates in Fig. 2 for the
higher alloys and weld overlays when the combustion mode was switched from air-firing
to oxy-firing.
CONCLUSIONS
The laboratory study involving realistic combustion test conditions revealed that
corrosion rates of the alloys and weld overlays exposed to the oxy-firing conditions were
not higher than those of the corresponding air-firing conditions. In fact, lower corrosion
rates were generally observed for the materials tested under the oxy-combustion
o
o
environments at 704 C (1300 F) with few exceptions, even though the SO2 and HCl
concentrations in the gas phase of oxy-combustion cases were three to four times of
those of air-firing.
Based on the extensive metallurgical examinations and SEM/EDS analyses performed,
a pattern of behavior has been concluded for the higher alloys and weld overlays
o
o
exposed to a wide range of coal environments at 704 C (1300 F). First, the classic hot
corrosion mechanism dominated the corrosion process under both air-firing and oxyfiring conditions, with the possible exception of the very low sulfur WY PRB coal. The
austenitic stainless steels and nickel-base alloys showed the initial formation of a Cr-rich
protective scale that was eventually penetrated by fused sulfate to permit much more
rapid attack via basic dissolution and fluxing of the initially protective oxide scales
formed.
An entirely different corrosion mechanism was identified for the low-Cr ferritic steel. Due
to a relatively low Cr content, the corrosion scale consisted of iron oxide and iron sulfide
formed under the relatively sulfidizing and oxidizing environments, with the sulfide phase
in direct contact with the HCl-bearing combustion gas at the base of the porous deposit.
As a result, the corrosion attack was governed by a cycling reaction of the Active
Sulfide-to-Oxide Mechanism, in which FeS reacted with HCl to form FeCl2 vapor,
followed by outward diffusion of FeCl2 into the porous deposit and re-precipitation as iron
oxide upon exposure to a higher partial pressure of oxygen. This proposed Active
Sulfide-to-Oxide Mechanism was responsible for the unusually high wastage rates of
T23 and would likely dominate the corrosion attack of other low-Cr steels also. In
addition, this mechanism has effectively elucidated the detrimental effect of coal chlorine
on superheater/reheater corrosion under both air and oxy-firing combustion conditions.
878
The superior corrosion performance of the materials studied under the oxy-firing
conditions was attributed primarily to higher CO2 concentrations in the combustion gas.
First, the higher CO2 concentrations increased the density of the combustion gas,
leading to reduced diffusivity of corrosive gases, such as SO2, HCl, and FeCl2. The
decrease in diffusivity would be primarily responsible for the improvement in the
corrosion performance of T23 when the combustion mode was changed from air-firing to
oxy-firing. Secondly, the initial amount of sulfate salt available in the oxy-firing deposit
was lower than that in the corresponding air-firing deposit due to the significant
formation of carbonate. The conversion of carbonate to sulfate would require some time
to complete, thus reducing the availability of sulfate needed to initiate hot corrosion.
Most importantly, CO2 and HCl gases are highly acidic in nature and would reduce the
basicity of fused sulfate once the initially protective oxide scale was penetrated. The
reduction in basicity could be achieved by CO2 and HCl reacting with the basic
components of the sulfate melt to form carbonate and chloride solutes, hence reducing
the local basicity of the liquid. With a reduced basicity, the basic solubility of metal
oxides and the slope of a negative solubility gradient were decreased, thereby reducing
the severity of the hot corrosion attack via basic dissolution and fluxing. The formation of
carbonate and chloride solutes in fused sulfate would take place only when the partial
pressures of O2 and SO3 are low, a condition existing at the scale/metal interface.
Because the concentrations of CO2 in the oxy-coal combustion gases are orders of
magnitude higher than those of HCl, the reduction in salt basicity from the former is likely
to be more significant than the latter.
ACKNOWLEDGEMENTS
The author would like to acknowledge the funding support of two U.S. Department of
Energy projects: DE-FC26-07NT43097 (Project Manager: Vito Cedro III) and DE-FG2601NT41175 (Project Manager: Patricia A. Rawls). Professor Robert A. Rapp served as a
technical consultant and contributed considerably to the success of this work.
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18.
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880
ABSTRACT
Oxyfuel combustion is considered as one of the most promising technologies to facilitate CO 2
capture from flue gases. In oxyfuel combustion, the fuel is burned in a mixture of oxygen and
recirculated flue gas. Flue gas recirculation increases the levels of fireside CO 2 , SO 2 , Cl and
moisture, and thus promotes fouling and corrosion. In this paper the corrosion performance of two
superheater austenitic stainless steels (UNS S34710 and S31035) and one Ni base alloy (UNS
N06617) has been determined in laboratory tests under simulated oxyfuel conditions with and
without a synthetic carbonate based deposits (CaCO 3 - 15 wt% CaSO 4 , CaCO 3 - 14wt% CaSO 4 1 KCl) at 650 and 720C up to 1000 hours. No carburization of the metal substrate was observed
after exposure to simulated oxyfuel gas atmospheres without deposit, although some carbon
enrichment was detected near the oxide metal interface. At 720C a very thin oxide formed on all
alloy surfaces while the weight changes were negative. This negative weight change observed is
due to chromium evaporation in the moist testing condition. At the presence of deposits, corrosion
accelerated and considerable metal loss of austenitic alloys was observed at 720C. In addition,
clear carburization of austenitic steel UNS S34710 occurred.
Keywords: oxyfuel combustion, corrosion, carburization, high temperature
INTRODUCTION
Fossil fuels are expected to remain the leading fuel sources in power generation for the
foreseeable future. The CO 2 emission will have a social and economical impact in energy
generation. Carbon dioxide capture and storage (CCS) is considering as a feasible technology for
reducing CO 2 emissions while satisfying the ever-growing energy demands [1]. The most costeffective and readily available option is to mitigate CO 2 emission by increasing the plant
efficiency. At the same time new technologies to CO 2 emissions reduction and CCS processes are
been developed. In these processes, CO 2 is captured from the cleaned products of combustion or
gasification. It has been estimated that CCS for base load power generation is likely to become
commercially available at around 2025. The oxyfuel combustion represents a favorable CCS
method among wide variety of potential CO 2 capture technologies. Oxyfuel combustion is a
process where fuel (fossil fuels or even co-firing of coal and biomass) is burnt using pure oxygen
instead of air as the primary oxidant. Since the nitrogen component of air is not heated, fuel
consumption is reduced, and higher flame temperatures are possible [2,3]. Compared to
conventional air-fired combustion, the oxyfuel process will use a combination of oxygen, with a
881
purity of more than 95 vol %, and recycled flue gas to combust the fuel. Flue gas recirculation is
used to balance combustion and control combustion temperature [2,4]. Produced flue gas consists
mainly of CO 2 and water vapour, which is after purification and compression ready for storage.
Other major gas components in flue gases are carbon monoxide, nitrogen from fuel and air
leakages, and possible enrichments of sulfur oxides and chlorine species due to flue gas
recirculation. Experiments in oxyfuel pilot plants have indicated that sulfur concentration can be
higher compared to air combustion [5]. The changes in the combustion gas chemistry will also
affect the chemistry and formation of deposits, with potentially increasing corrosion and internal
attack of the boiler components that are in contact with the combustion and flue gas environment
[6-8].
The corrosion mechanisms and life limiting factors in air-fired combustion have been extensively
studied over the past years. However, there is still relatively little experimental information
available about the effects of oxyfuel combustion on the boiler material performance. The
experiments of demonstration scale are on-going with current high temperature materials.
Typically the presence of sulfur strongly increases the corrosion rate, but the influence of sulfur
on corrosion can be complicated, as in the form of SO 2 it can also slow down corrosion. The
phenomenon is dependent on time, fireside environment, gas partial pressures and alloying
elements of the tube material [9-11]. In oxyfuel combustion the likelihood of the presence of
sticky deposits is increased [12,13]. Sulfation and carbonation of ash particles under oxyfuel
combustion is higher due to high SO 2 and CO 2 potential. There are indications that oxide scales
developing in O 2 /CO 2 /H 2 O atmospheres are not protective and internal carburization may occur
[10,14,15].
Limestone (CaCO 3 ) is used in oxyfuel circulating fluidized bed (CFB) boilers as absorbent for
capture of SO 2 . In oxyfuel combustion the CaO - CaCO 3 equilibrium comes close to the normal
operating temperature and the capture mechanisms may change from normal sulfation (CaCO 3
CaO - CaSO 4 ) to direct sulfation path (CaCO 3 - CaSO 4 ) due to high CO 2 concentration. In
certain components hard deposits may form during the simultaneous occurrence of calcination,
sulfation and recarbonation. Such a deposit may cause operational problems like plugging of gas
channels and/or corrosion of heat exchanger surfaces. The effects of corrosion and microstructural
changes, like carburization, may reduce mechanical properties such as creep and/or fatigue
strength and ductility, and thus the expected component life. Austenitic stainless steels are widely
used for high temperature applications such as nuclear power plants, boilers, superheaters and
chemical reactors. Ni based alloys can withstand harsh environments and exhibit high heat
resistance, and thus are in future used at least in some extent in certain energy generation
components. Previous studies have shown that the carburization of low alloyed base materials
occurs when CaCO 3 -based deposits are used, e.g. [16]. The results presented here are a part of the
study aiming to experimentally clarify the corrosion resistance of some austenitic and Ni base
alloys in simulated oxyfuel combustion conditions.
EXPERIMENTAL
Two superheater austenitic stainless steels (UNS S34710 and S31035) and one nickel base alloy
(UNS N06617) have been studied in laboratory tests under simulated oxyfuel conditions with and
without synthetic deposits up to 1000 hours, Table 1. Table 2 shows the chemical composition of
used materials. Rectangle shape specimens with dimensions of 15 x 15 x 2.5 mm were machined
from thick walled tubes. The samples were bright polished with SiC paper (P1200), washed with
deionized water and ultrasonically degreased in ethanol. Exposure testing was carried out in
horizontal Al 2 O 3 tube furnace. The test environments were prepared from premixed and/or pure
882
gases that were mixed based on flow rates and controlled using calibrated mass-flow controllers.
The flow rate of gases was 10 l/h. The carrier gas was passed through a humidifying unit
containing deionized water before the furnace, to add moisture to the gas mixture. In tests with
synthetic deposit, deposit covered the half of sample.
Table 1: Test matrix
Gas composition
T [C]
650
720
Used deposit
CaCO 3 - 15 CaSO 4 wt%
CaCO 3 - 14 wt% CaSO 4 -1 KCl
CaCO 3 - 15 CaSO 4 wt%
CaCO 3 - 14 wt% CaSO 4 -1 KCl
Material
S34710, S31035, N06617
S34710, S31035, N06617
S34710, S31035
S34710, S31035, N06617
S34710, S31035
S34710, S31035, N06617
Cr
18.3
22.3
Ni
11.7
24.9
Mo
0.23
Nb
0.92
0.5
Fe
bal.
bal.
N06617
23
bal.
9.2
Other
1.64 Mn, 0.33 Cu, 0.4 Si, 0.07 C
3.4 W, 1.5 Co, 2.9 Cu, 0.2 Si, 0.3
Mn, 0.24 N, 0.06C
12.7 Co, 1.2 Al, 0.4 Ti
After testing the samples were moulded in plastic after which the prepared and polished sample
cross-sections were analysed using optical and SEM/EDX microscopy to determine the oxide
layer thickness and metal loss as well as the elemental distribution in the oxides. The
carburization tendency was evaluated from etched cross sections using optical microscopy.
Corrosion behaviour of the materials was based on the estimation of the metal loss and depth of
internal material degradation. In addition to sample thickness loss, weight change measurements
were carried out for the specimens exposed without deposit.
RESULTS AND DISCUSSION
Table 3 summarises the mean values of sample thickness loss and depth of internal degradation
below formed oxide scale after 1000 h of exposure at 650 and 720C under 2%O 2 -29%H 2 O44%CO 2 -0.6%SO 2 -0.2HCl-N 2 gas with and without deposits. After 1000 h exposure at 650C
without deposit UNS S34710 showed more extensive oxidation than S31035. Uneven oxides with
a two layer nodule structure formed on the S34710 surface although locally a continuous scale
was found in some parts of the sample, Figure 1. Nodule formation has probably started at weak
points such as grain boundaries. This nodular growth would have continued until the nodules
grow together to form a continuous oxide covering the whole surface. With short exposure times
(168 and 500 h), only a very thin oxide film was observed on alloy S34710 surface. EDX analyses
showed an iron rich outer oxide layer and a mixed oxide inner layer mainly containing iron,
chromium and nickel. Measured weight change was positive, Figure 2. The oxidation rate of UNS
S31035 and N06617 alloys was almost negligible at 650C and only a very thin continuous Cr 2 O 3
film formed on the alloy surfaces. At 720C a thin oxide (~1 m) formed on all alloy surfaces,
Figure 1, and the weight changes were negative. This negative weight change observed is due to
chromium evaporation in moist exposure conditions; no spallation of formed scales was seen. It
has been shown, e.g. in [17], that under the moist test conditions evaporating metal hydroxides are
883
formed and thus the protective oxide scale formation is retarded or prevented. The scatter in
results at 720C (no linear weight loss) is probably due to the depletion of surface chromium
causing, at least temporary, diminishing of evaporation until new chromium is diffused to the
surface area. Figure 2 summarizes the weight change results of the exposures without deposit at
650 and 720C.
Table 3: Mean thickness loss of sample and depth of internal degradation area below oxide scale
after 1000 h exposure at 650 and 720C under simulated oxyfuel atmosphere with and without
deposits. *Internal degradation mostly through grain boundaries
650C
Material
Environment
Thickness
loss
Internal*
Thickness
loss
Internal*
S34710
Gas exposure
30 m
none
<1 m
none
with CaCO 3 15
wt% CaSO 4
300 m
~50 m
950 m
~150 m
with CaCO 3 14
CaSO 4 1 wt%
KCl
200 m
~30 m
400 m
~150 m
0.51 m
none
<1 m
none
with CaCO 3 15
wt% CaSO 4
400 m
~50 m
with CaCO 3 14
CaSO 4 1 wt%
KCl
300 m
~80 m
650 m
~150 m
Gas exposure
<0.5 m
none
<1 m
none
25
~20 m
S31035
N06617
Gas exposure
with CaCO 3 14
CaSO 4 1 wt%
KCl
a)
720C
b)
Figure 1: Example of oxides formed on UNS S34710 after 1000 h exposure in atmosphere
simulating oxyfuel combustions; Oxide growth at a) 650C and b) 720C
884
a)
b)
Figure 2: Weight change of UNS S34710, S31035 and N06617 after gas exposure testing at a)
650C and b) 720C without deposit
Corrosion was visible under deposits on both austenitic stainless steels at 650 and 720C. At
720C corrosion of Ni base alloy was also observed. More severe corrosion of austenitic steels
was observed with CaCO 3 - 15 wt% CaSO 4 deposit than with CaCO 3 - 14 CaSO 4 - 1 wt% KCl
deposit. In the case Ni alloy this could not be seen because Ni alloy was exposed only with KCl
containing deposit at 720C.
The oxide scale on UNS S34710 surface was continuous around the sample both under deposit
layer and above it (deposit covered only the half of the sample). Under the deposit layer the
formed oxide was some what thicker, and thus the loss of metal was higher. At 650C a two layer
oxide scale was observed. At 720C the oxide growth accelerated significantly and the outer layer
of the oxide was detached. Also the depth of the internal degradation area with chromium
depletion increased with increasing temperature. Figure 3 shows the EDX analyses of oxide
formed on S34710 surface with CaCO 3 - 15 wt% CaSO 4 deposit. Sulphur was detected inside the
oxide scale, and also at grain boundaries under the oxide. No chlorine was observed in the
corrosion products with the chlorine containing deposit. This is probably due to sample
preparation. In addition to oxidation, carburization by formation of grain boundary carbides in
S34710 steel was observed at both exposure temperatures with the both deposits, Figure 4.
Surface layer of whole sample was carburized; carburization occurred both in the gaseous
environment (in the part of sample above the deposit) and under the deposit. Carbonate based
deposits and different corrosion reactions on alloy surface have an effect on carburization due to
change of local CO 2 pressure and carbon activity at deposit alloy interface [5]. Corrosion
reactions occurring at material surface may change the nature of oxide scale from protective to
non-protective allowing carbon and other harmfull species to penetrate inside the material. The
results from the exposure with CaSO 4 - KCl deposit in simulated oxyfuel conditions did not show
carburization of S34710 steel [18]. Figure 5 presents the carbon content of S34710 surface at
different depths, determined with optical emission spectrometry (Leco TC-136). The depth of
carburization after 1000 h based on Leco measurement and metallography was from 200 up to
400 m depending on exposure temperature.
885
Figure 3: EDX analyses of oxide formed on S34710 steel after 1000 h exposure at 720C with
CaCO 3 15 wt% CaSO 4 deposit
a)
b)
Figure 4: Carburization of S34710 after 1000 h under CaCO 3 -15 wt% CaSO 4 deposit with
simulated oxyfuel conditions at a) 650C and b) 720C
886
Figure 5: Carbon content on S34710 under CaCO 3 15 wt% CaSO 4 deposit after exposure in
simulated oxyfuel conditions for 1000 h at 650C
The part of UNS S31035 samples covered with deposit suffered from accelerated corrosion.
Whereas only a thin oxide layer and some deeper pits through grain boundaries were detected in
the part of samples exposed to gaseous environment (above the deposit), Figure 6. It seems that
the deposit cannot destroy the formed Cr 2 O 3 film on the upper part of the samples, at least during
1000 h exposure testing. Figures 7 and 8 presents EDX analyses of S31035 alloy exposed to
CaCO 3 - 15 wt% CaSO 4 and CaCO 3 - 14 wt% CaSO 4 - KCl deposits. The temperature increase
accelerated corrosion, especially with CaCO 3 - 15 wt% CaSO 4 deposit, and the part of sample
covered with deposit was almost completely destroyed. Sulphur was detected in the oxide
structures and the internal degradation area below oxide scale. No carburization of S31035 steel
was detected by optical microscopy.
Figure 6: Oxide scale morphology on UNS S31035 after 1000 h exposure with CaCO 3 -CaSO 4 KCl deposit in oxyfuel conditions at 720C, under gas phase (left) and under deposit (right). A
schematic specimen between micrographs shows sectioning and positions of inspection
887
Figure 7: EDX analyses of the oxide scale on S31035 after 1000 h exposure at 720C with
CaCO 3 -CaSO 4 deposit. Sample tip almost totally corroded
Figure 8: EDX analyses of the oxides on S31035 after 1000 h exposure at 720C with CaCO 3 CaSO 4 -KCl deposit
Figure 9 shows the EDX analyses of N06617 alloy after 1000 h at 720C with the chlorine
containing deposit. Chromium oxide formed on the alloy surface was still thin, however below
oxide layer there was the internal degradation area where sulphur was detected. No chlorine was
observed.
888
Figure 9: EDX analyses of the oxide on N06617 after 1000 h exposure at 720C with CaCO 3 CaSO 4 -KCl deposit
CONCLUSIONS
The results imply that without a deposit, the oxidation rate under simulated oxyfuel conditions
(2%O 2 -29%H 2 O-44%CO 2 -0.6%SO 2 -0.2HCl-N 2 ) is very reasonable at 650C after 1000 h for
the tested materials. At 720C formed oxide thickness was also quite low, however negative
weight change was observed due to chromium evaporation and no spallation of formed scales was
seen. Chromium based oxides was observed on material surfaces. No carburization of the metal
substrate was observed after exposure to simulated oxyfuel gas atmospheres without deposit,
although some carbon enrichment was detected near the oxide metal interface. With extended
exposure time, the oxide scale properties may change to enable metal carburization.
With deposits the thicknesses of oxide scales and metal losses of the stainless grades increased
with increasing temperature. Some sulphur penetration was observed through grain boundaries in
chromium depletion area under oxide scales. At 720C oxidation rate was higher and the part of
the oxide scale, probably outer Fe-rich layer, had peeled off from austenitic stainless steels. UNS
S31035 steel corroded most, especially with CaCO 3 - CaSO 4 deposit, and the part of sample
covered with deposit was almost completely destroyed. Corrosion of the Ni alloy also increased at
720C, although the formed oxide after 1000 h was thin, some internal degradation was observed.
High Cr or total alloying does not guarantee corrosion resistance in severe conditions.
Modification of other properties like grain size may give additional protection against corrosion.
Exposure with the carbonate deposit resulted in corrosion and carburization by formation of grain
boundary carbides in the UNS S34710 steel. Earlier results [16] suggested that the critical Cr and
Ni content limits for carburization are around 20% under the applied gas and deposit
environments. Current results of S31035 grade support this observation. The limits may be
affected by the Cr/Ni ratio, extended time of exposure, and changes in the chemical and
thermodynamic equilibria of the surfaces due to gradual modification in alloys, its oxides and
889
deposits. The effects of corrosion and microstructural changes, like carburization, may reduce
mechanical performance such as creep and/or fatigue strength and ductility, and thus the expected
component life.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the financial support from VTT Technical Research
Centre of Finland, Tekes and EU-FP7 Energy MacPlus project (contract 249809). The authors
would also like to acknowledge the skilful assistance of T. Kinnunen, J. Veivo, T. Lehtikuusi, J.
Metsjoki and A. Kukkonen.
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[2] Oxy-fuel combustion for power generation and carbon dioxide capture (Ed. Ligang Zheng)
Woodhead Publishing Series in Energy (Cambridge, UK, 2011), pp. 1-9
[3] Hack, H., Fan, Z., Seltzer, A., Advanced Oxyfuel Combustion Leading to Zero Emission
Power Generation, Proc 35th International Technical Conference on Clean Coal & Fuel
Systems Clearwater, Clearwater, FL, June, 2010.
[4] Scheffknecht, G. et al,Oxy-fuel coal combustionA review of the current state-of-the-art,
Int. J. of Greenhouse Gas Control, Vol 5S (2011), pp. 1635.
[5] Kranzmann, A. et al, The challenge in understanding the corrosion mechanisms under
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[6] Hjrnhede, A. et al, Preliminary Experiences with Materials Testing at the Oxyfuel Pilot
Plant at Schwarzepumpe, Proc. 9th Liege Conference on Materials for Advanced Power
Engineering, Liege, Belgium. 201,0 pp. 1220-1235 .
[7] Wigley, F., Goh, B. Characterisation of Rig Deposits from Oxy-coal Combustion, 1st
Oxyfuel Combustion Conference, Cottbus, Germany. 2009.
[8] Stein-Brzozowska et al., Influence of Oxy-Coal on Fly Ash Transformations and Corrosion
Behavior of Heat-Exchangers, Proc. Oxyfuel Combustion Conference 2, Queensland,
Australia, September. 2011.
[9] Covino, B., Matthes, S., Bullard, S. Effect of Oxyfuel Combustion on Superheater
Corrosion, NACE Corrosion 2008, Houston, Texas, March. 2008. Paper No. 8456.
[10] Natesan, K., Rink, D.L. Corrosion Performance of Structural Alloys for Oxy-fuel
Combustion Systems, Proc 21st Fossil Energy Materials Conference, Knoxville, TN, May.
2007.
[11] Fryda, L. Sobrino, C., Cieplik, M., van de Kamp, W.L., Study on Ash Deposition under
Oxyfuel Combustion of Coal/Biomass Blends, Fuel, Vol. 89, 2010, pp. 1889-1902.
[12] Stein-Brzozowska, G., Maier, J., Scheffnecht, G. Deposition Behaviour and Superheater
Corrosion under Coal Fired Oxyfuel Conditions, IEAGHG Special Worksop on
SO 2 /SO 3 /Hg/ Corrosion Issue under Oxyfuel Combustion Conditions, London, January.
2011.
[13] Hnert, D., Schulz, W., Kranzmann, A. Corrosion of Steels in H 2 O-CO 2 Atmospheres at
Temperatures between 500C and 700C, ICPWS XV, Berlin, September. 2008.
[14] Piron Abellan, J., Olszewski, T., Penkalla, H.J., Meier, G.H., Singheiser, L., Quadakkers,
W.J., Scale Formation Mechanisms of Martensitic Steels in High CO 2 /H 2 O-Containing
Gases Simulating Oxyfuel Environments, Mater. High Temp., Vol. 26, No. 1 (2009), pp. 6372.
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[15] Sellakumar, K.M., Conn R., Bland, A. A Comparison Study of ACFB and PCFB Ash
Characteristics, Proc 6th International Conference on Circulating Fluidized Beds,
Wurzburg, Germany August. 1999.
[16] Pohjanne, P., Tuurna, S., Auerkari, P. Fireside Corrosion and Carburization of Superheater
Materials in Oxyfuel Combustion, NACE Corrosion 2012, Salt Lake City, UT, March.
2012, pp. 4969 4980.
[17] Saunders, S.R.J., Monteiro, M., Rizzo, F., The oxidation behaviour of metals and alloys at
high temperatures in atmospheres containing water vapour: A review, Prog. Mater. Sci.,
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[18] Tuurna, S., Yli-Olli S., Pohjanne, P. Corrosion and Carburization of Superheater Materials
in Oxyfuel Combustion, Proc. Baltica IX Int. Conference on Life Management and
Maintenance for Power Plant Components, Helsinki-Stockholm-Helsinki, June, 2013, pp.
527-537.
891
ABSTRACT
Using oxygen, rather than air, in coal-fired boilers has been studied for several years as a strategy
to reduce NOx and concentrate CO2 for capture. In combination with flue gas recirculation, higher
levels of CO2 are expected but increased H2O and SO2 levels also may occur. In order to
understand the role of substrate composition on corrosion, a combination of commercial and model
alloys were investigated with synthetic coal ash and gas compositions simulating air- and oxyfiring environments. Exposure temperatures ranged from 600-800C to cover current operating
temperatures up to advanced ultrasupercritical conditions. Using 500h exposures, no consistent
negative effect was found for switching to the oxy-firing environment with the same synthetic ash.
For model Fe-Cr alloys, 30%Cr was needed to form a thin protective reaction product across this
temperature range. Among the commercial stainless steels, 310-type stainless steel showed low
reaction rates with the maximum attack at 650C. At higher temperatures, the depth of attack on
Fe-base type 310 stainless steel was less than for Ni-base alloy 740. Initially, this difference was
attributed to the Al and Ti additions in alloy 740. However, cast and hot rolled model Ni-18Cr and
-22Cr alloys with various Al and Ti additions showed decreased metal loss with increasing Al and
Ti additions in the oxy-firing environment at 700 and 800C. As expected, metal loss was very
sensitive to Cr content. A second set of model alloys also examined the effect of Co and Mo.
INTRODUCTION
Burning coal with oxygen rather than air is one strategy to assist in large-scale carbon capture and
storage. One potential drawback for this approach is that the resulting CO2-rich combustion
environment may also contain higher levels of H2O and SO2 which could accelerate fireside
corrosion in the boiler. Thus, current and candidate boiler tube alloys have been extensively
examined in simulated laboratory testing [1-15]. However, because of the variations in coal
chemistry [16-19] and the various possibilities in implementing oxy-firing [20,21], there is
considerable variation in the experimental conditions being evaluated and disagreement over the
effect of oxy-firing on fireside corrosion rates. Among the many variables, temperature still
dominates, especially because of accelerated corrosion that occurs when the deposits melt. This
and other factors result in a bell-shaped curve of corrosion rate versus temperature with a
maximum attack at ~700C [18,22-24]. The temperature range being considered has expanded
significantly due to the interest in high-efficiency advanced ultra-supercritical (A-USC) conditions
of 760C/34.5 MPa (1400F/5000 psi) [25-27] resulting in fireside metal temperatures of ~800C.
Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States
892acknowledges that the United States Government retains a non-exclusive, paid-up,
Government retains and the publisher, by accepting the article for publication,
irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.
The current multi-year project has studied a broad range of commercial and model alloys and
temperatures from 600-800C using 500h isothermal exposures with specimens covered in one
synthetic coal ash under oxidizing-type gas conditions. No significant difference was found
between air- and oxy-firing conditions [10,14-16], despite the use of the worst case oxy-firing
conditions assuming hot gas recirculation [3]. Results presented here focus on the most corrosion
resistant candidates and also Ni-Cr model alloys to explore the role of alloy composition on the
corrosion behavior of precipitate-strengthened Ni-base alloys such as 740 and 282 [28,29]. This
class of alloys is needed to achieve the A-USC conditions. Model alloys were used to examine the
roles of Cr, Al, Ti, Co and Mo in fireside corrosion resistance at 700 and 800C.
EXPERIMENTAL PROCEDURE
Corrosion experiments with synthetic ash were conducted with rod specimens (6.0mm diameter x
~25mm long, 120 grit finish) or coupons (1.5 x 10 x 19mm). The specimens were covered with
9g of synthetic ash (30%Fe2O3-30%Al2O3-30%SiO2-5%Na2SO4-5%K2SO4) in a porous alumina
crucible. The rod diameter was measured at multiple locations before exposure. Representative
alloy compositions are shown in Table 1. The ash exposures were performed at 600-800C for
500h using gas mixtures intended to simulate combustions gases from conventional air-firing (N216%CO2-10%H2O-3%O2-0.15%SO2) and oxy-firing (CO2-5%N2-32%H2O-3%O2-0.45%SO2).
To create these environments with H2O, distilled deionized water was atomized into the carrier
gas. Prior to exposure, all specimens were ultrasonically cleaned in acetone and ethanol. The
loaded crucibles were heated and cooled to temperature in an Ar environment and oxidizing gas
was introduced when the tube furnace had reached temperature. Specimen mass changes were
measured and are reported elsewhere [15]. There was little correlation between mass change and
oxide thickness due to combinations of ash incorporation into the scale and scale spallation [10],
thus, characterization focused on metal loss and oxide thickness measurements measured on
metallographically polished cross-sections. Where there was relatively little metal wastage, ~40
oxide thickness measurements were made around the circumference using ImageJ software on
light microscopy images. These measurements also included internal oxidation. Where greater
attack occurred, ~12 diameters of the remaining sound metal were measured. The data were
plotted using box and whisker plots [30] where the box is defined by the 25%, median and 75%
values and the whiskers show the minimum and maximum values measured.
RESULTS AND DISCUSSION
Figure 1 summarizes oxide thickness results for rod specimens of three of the most protective
alloys examined: 310HCbN, 740 and Fe-30Cr after 500h exposures at 600-800C in air- and oxyTable 1. Chemical compositions (mass%) determined by inductively coupled plasma analysis
and combustion analysis.
Material
Ni
Fe
Cr
Mo W
Mn Si
Fe-30Cr
69.7 30.2
0.02
310HCbN
20.3 51.4 25.5 0.1 0.01 1.2 0.3
740
48.2 1.9
23.4 0.5 <
0.3 0.5
282
58.0 0.2
19.3 8.3 <
0.07 0.06
CCA617
55.9 0.6
21.6 8.6 0.09 0.02 0.1
21.8 < 0.02 < 0.01
N22CA2T 75.1 <
< indicates below the detectability limit of <0.01%
893
Al
Ti
<
0.8
1.5
1.3
1.1
<
0.01 0.05
2.0 0.08
2.2 0.06
0.4 0.05
1.9 <
Other
20ppm S
0.4Nb,0.3Co,0.27N, <10ppm S
20.2Co,2.1Nb, <10ppm S
10.3Co, <1ppm S
11.2Co, <10ppm S
0.01Na, <1ppm S
max.
75%
median
25%
min.
Figure 1: Box and whisker plots of oxide thickness after 500h in synthetic ash at 600-800C in
air- (open) and oxy-firing (shaded) conditions for 310HCbN, 740 and model alloy Fe-30Cr.
firing conditions. Unlike conventional austenitic and martensitic steels, these alloys did not show
a significant peak in attack at 700C [18,22-24]. Alloy 740 showed thicker reaction products in
oxy-firing conditions at 700 and 750C. Figures 2-4 show examples of the reaction products
observed in both environments at 650, 700 and 800C. At 650C, the reaction products were
similar in thickness and morphology in both environments for these three materials. Occasional
deeper pits were observed for 310HCbN (Figures 2a and 2d) and this is reflected in the
measurements in Figure 1. The internal oxidation observed for the 740 specimens (Figures 2c and
2f) is attributed to the Al and Ti in this alloy, Table 1. It is common to see internal oxidation of
low levels of such oxygen active elements in a chromia-forming alloy like 740 [31]. Figure 3
shows the oxides formed at 700C. Again, the reaction products were similar in the simulated airand oxy-firing environments. Alloy 740 formed the thickest oxides, especially in the oxy-fired
environment with deeper internal oxidation than at 650C. The Fe-30Cr sample showed a less
uniform attack than at 650C. In contrast, a relatively thin reaction product and smaller pits were
observed on the specimens of 310HCbN. Exposures at 700C are expected to produce the highest
894
310HCbN 20 m Fe-30Cr
b 10m
740
air-firing
internal oxidation
oxy-firing
epoxy
Figure 2. Light microscopy of polished sections after 500h at 650C in synthetic ash (a-c) air-firing and (d-f) oxy-firing; (a,d) 310HCbN, (b,e) Fe-30Cr, (c,f) 740
corrosion rates. It may be that after 500h these alloys are in an incubation period where the Crrich surface oxide is still protective. Longer exposures at this temperature could produce faster
corrosion rates. At 800C, subtle differences between the air- and oxy-firing reaction products
were observed, Figure 4. Slightly deeper oxide penetrations were observed on Fe-30Cr and
310HCbN in the oxy-firing environment. The morphology was slightly different for alloy 740
with elongated penetrations with the higher SO2 content, Figure 4f. As at lower temperatures, the
specimens of 310HCbN and especially Fe-30Cr with no Al and Ti show much less internal
oxidation than the alloy 740 specimens. While it is somewhat surprising that the higher CO2, H2O
and SO2 levels in the oxy-firing environment had a limited effect on the corrosion rate compared
to the air-firing conditions, these oxidants also are present in the air-firing environment. The
general finding for these conditions was that increasing their concentration in the gas had little
effect on the reaction rate after 500h. Perhaps associated changes in the ash composition with oxyfiring could lead to larger differences between these two environments. However, no information
is currently available on changes in the ash composition due to oxy-firing.
epoxy
310HCbN 10 m Fe-30Cr
b 10m
740
oxy-firing
air-firing
One hypothesis for the differences observed for alloy 740 compared to the Fe-base alloys is that
the Al and Ti added to alloy 740 to form precipitates for creep strength has a detrimental effect
Figure 3. Light microscopy of polished sections after 500h at 700C in synthetic ash (a-c) air-firing and (d-f) oxy-firing; (a,d) 310HCbN, (b,e) Fe-30Cr, (c,f) 740
895
310HCbN 10 m Fe-30Cr
b 10m
740
air-firing
oxy-firing
epoxy
Figure 4. Light microscopy of polished sections after 500h at 800C in synthetic ash (a-c) air-firing and (d-f) oxy-firing; (a,d) 310HCbN, (b,e) Fe-30Cr, (c,f) 740.
on fireside corrosion resistance. In order to study the effect of Al and Ti additions, a series of Ni18Cr and Ni-22Cr alloys with combinations of 1-2%Al and Ti were fabricated for testing. An
example composition is shown in Table 1 for the alloy designated N22CA2T. In this case,
parallelepiped coupons were used instead of rod specimens, as it was expected that the metal loss
would be minimal. Instead, Figures 5-8 show that the attack was very significant, especially for
the binary Ni-18Cr and 22Cr specimens and the Ni-18Cr-2Al-1Ti specimens. Coupons of 740 and
282 were included in these experiments for reference. Figure 5 shows the metal losses measured
along the sectioned coupon as a function of the nominal Al+Ti addition to the alloys after exposure
to the oxy-firing condition at 700C. Arbitrary 0.1% offsets were used around 1, 2 and 3% so that
the boxes would not lie on top of each other. The measured Al+Ti values were used for 282 and
740, Table 1. Rather than being detrimental, the Al and Ti additions reduced the rate of metal loss.
Not surprisingly, the metal loss was higher for the 18%Cr alloys but much lower for alloy 282 with
only 19.3%Cr. Figure 6 shows representative cross-sections to illustrate the results in Figure 5.
Specimens corners tended to be the most heavily attacked, often accounting for the maximum
metal loss in Figure 5 and supporting the use of rods for these experiments. The specific examples
Figure 5: Box and whisker plots of oxide thickness after 500h in synthetic ash at 700C in
oxy-firing conditions for various Ni-Cr model alloys.
896
epoxy
18Cr
400 m
22Cr
282
18Cr-2Al,1Ti
400m
740
22Cr-2Al,1Ti
Figure 6. Light microscopy of polished sections after 500h at 700C in synthetic coal ash and
oxy-firing conditions: (a) Ni-18Cr, (b) Ni-18Cr-2Al-1Ti, (c) alloy 282, (d) Ni-22Cr, (e) Ni-22Cr2Al-1Ti and (f) alloy 740.
with 2Al+1Ti additions show the reduction in metal loss with these additions with both 18 and
22Cr. The metal loss was much more pronounced on one side of the 740 specimen compared to
the other, Figure 6f.
Figure 7 shows the results for the same set of alloys after 500h at 800C in the oxy-firing gas
condition. The 18Cr model alloys and the alloy 282 specimen were fully consumed after this
exposure. It should be noted that while alloy 740 was specifically developed for this application,
alloy 282 was developed for less aggressive turbine applications [29]. Obviously, the lower Cr
content in these specimens was detrimental at 800C. The slight differences in metal loss reflect
differences in the starting ~1.5mm coupon thickness. For the 22Cr alloys, the attack was much
less but again the amount of metal loss was reduced in most cases with the additions of Al and/or
Ti. The one exception was the alloy with 2%Al which also experienced very rapid attack. This
result needs to be further explored. Similar to Figures 6d-6f, Figure 8 shows low and high
magnification images of the same materials after exposure at 800C. Compared to the results at
Figure 7: Box and whisker plots of oxide thickness after 500h in synthetic ash at 800C in
oxy-firing conditions for various Ni-Cr model alloys.
897
22Cr
740
epoxy
internal oxidation
40 m d
40m
Figure 8. Light microscopy of polished sections after 500h at 800C in synthetic coal ash and
oxy-firing conditions: (a-b) Ni-22Cr, (c-d) Ni-22Cr-2Al-1Ti and (e-f) alloy 740.
700C in Figure 6, the reduced attack is evident in the square corners on all but the Ni-22Cr
coupon. Figure 8 illustrates the point that Al and Ti additions, either in the model alloy or alloy
740, clearly create internal oxidation. However, this internal oxidation did not increase the metal
loss in the fireside corrosion environment compared to binary Ni-22Cr.
One potential benefit of adding Ti is shown in Figure 9, which compares the oxide thickness
formed in steam at 800C to that formed during the 700 and 800C oxy-fired exposure. For oxide
growth in steam at 800C, the addition of Ti increased the oxide thickness, both by incorporation
of Ti in the scale and increasing the scale growth rate [32]. This effect also has been observed in
Fe-Cr solid oxide fuel cell interconnects [33] and Ni-Cr alloys [34]. In contrast, the 2%Al addition
b
Figure 9: Box and whisker plots of oxide thickness for various Ni-Cr alloys after (a) 5,000h in
17bar steam at 800C and (b) 500h in synthetic ash at 700 and 800C in oxy-firing conditions.
898
reduced the scale thickness, Figure 9a. If this same effect occurs in the fireside corrosion
environment, then the thicker Cr-rich oxide with Ti doping may remain protective for a longer
exposure time before being dissolved by the ash. This would explain the benefit observed in
Figures 5-8. In contrast, the accelerated attack observed with 2%Al at 800C, Figure 7, could be
attributed to a reduction in the scale thickness. A beneficial role of Ti was suggested in a recent
fireside corrosion study of Ni-base alloys [35].
The dramatic difference observed between 282 and 740 in coupon exposures at 800C was
unexpected based on the results at 700C, Figures 5 and 6. Therefore, rod specimens of 282 and
740 were exposed under the same conditions to compare their performance, Figure 10. For
comparison, the results for 310HCbN and CCA617 (at 700C only) are shown for comparison.
The 282 rod exposed at 800C had much larger metal loss than 740 or 310HCbN. Even at 700C,
282 showed the most metal loss. These three Ni-Cr alloys are different in their Cr, Co and Mo
contents, Table 1. Both 282 and 617 have over 8%Mo, which was recently suggested to be
detrimental to fireside corrosion resistance [35].
In order to explore the effect of Co and Mo on fireside corrosion, a second set of Ni-Cr model
alloys was fabricated with 20%Cr, 0-20%Co and 0-8%Mo. The initial metal loss results from rod
specimens from these alloys is shown in Figure 11 as a function of the nominal alloy Co content.
(Note some negative values that need to be re-evaluated.) Arbitrary 0-1% offsets were used for the
model alloys so that the boxes are easier to see. The measured Co values were used for 282 and
740, Table 1. At 700C, the largest metal loss was for the 20%Co-0%Mo alloy, similar in
composition to 740 except for the Cr, Al and Ti contents (all of which should improve corrosion
resistance) but very different in performance. With 20%Cr and 20%Co, increasing the Mo content,
decreased the metal loss at 700C. The metal loss for the model 10%Co-8%Mo alloy was very
similar to that observed for alloy 282 and the Mo addition appeared to have a positive effect. At
800C, increasing the Co content appeared to have little effect on the metal loss. However, the
addition of Mo consistently increased the metal loss at this temperature. Thus, the 8%Mo in alloy
282 (and 617) may have a detrimental effect on fireside corrosion resistance at 800C. The higher
metal loss for 282 could be attributed to its lower Cr content than the model alloys. At 800C, the
median metal loss for 740 was similar to the model alloys. Unfortunately, this set of model alloys
does not provide a clear answer for alloy development to improve fireside corrosion resistance,
Figure 10: Box and whisker plots of oxide thickness after 500h in synthetic ash at 700 or
800C in oxy-firing conditions for various Ni-base commercial alloys.
899
Figure 11: Box and whisker plots of oxide thickness after 500h in synthetic ash at 700 or
800C in oxy-firing conditions for various Ni-Cr model alloys. The dashed lines connect the
median values (center line of box) for 0, 4 and 8%Mo.
especially because the Co and Mo effects are different at 700 and 800C.
CONCLUSIONS
Laboratory experiments with synthetic coal ash were used to simulate the complex corrosion
experienced on the fireside of a coal-fired boiler under air- and oxy-firing conditions. These initial
500h results at 600-800C suggest onluy minor differences in the reaction rates of the worst-case
oxy-firing conditions with higher CO2, H2O and SO2. Examples were shown for the most
protective alloys observed in these laboratory studies: Ni-base alloy 740, Fe-base 310HCbN steel
and a Fe-30Cr model alloy. Alloy 740 showed the most difference between the air- and oxy-fired
conditions, generally forming a thicker oxide with more internal oxidation, especially at 700800C. This difference was attributed to the Al and Ti in alloy 740. However, model Ni-18Cr and
-22Cr alloys with various Al and Ti additions exposed in oxy-firing conditions at 700 and 800C
demonstrated that Al and Ti additions are generally beneficial compared to binary Ni-Cr alloys.
This may be attributed to Ti accelerating the growth rate of the protective Cr-rich surface oxide.
These model alloys also demonstrated the well-known importance of Cr content on fireside
corrosion resistance. The 19%Cr content of alloy 282 likely explains its higher rate of metal loss
compared to alloy 740 (23%Cr), especially for exposure at 800C. A second set of model alloys
with 20%Cr, 0-20%Co and 0-8%Mo did not further clarify composition differences between alloys
740 and 282. However, the alloys with 8%Mo (like 282) did show more metal loss at 800C than
the alloys without Mo (similar to 740). While some work is still in progress, this project is nearing
completion as this study has not found a strong effect of oxy-firing on the fireside corrosion rate
and there is little interest in constructing an oxy-fired boiler in the U.S. at the present time.
900
ACKNOWLEDGMENTS
The author would like to thank G. Garner, M. Howell, T. Lowe, D. Harper, H. Longmire and T.
Jordan for assistance with the experimental work. P. F. Tortorelli and S. Dryepondt provided
helpful comments on the manuscript. The research was sponsored by the U.S. Department of
Energy, Fossil Energy Advanced Research Materials Program (V. Cedro, project monitor).
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902
ABSTRACT
A Japanese national project has been undertaken since Aug. 2008 with the objective
of developing an advanced ultra-supercritical power plant (A-USC) with a steam
temperature of 700C. Fe-Ni and Ni-based alloys, namely HR6W, HR35, Alloy617,
Alloy740, Alloy263 and Alloy141, were taken as candidate materials for piping and
superheater/reheater tubes in an A-USC boiler. Weldments of these alloys were
manufactured by GTAW, after which long term creep rupture tests were conducted
at 700C, 750C and 800C. Weldments of HR6W, HR35 and Alloy617 showed
similar creep strength as compared with these base metals. Weldments of Alloy740
tended to fail in the HAZ, and it is considered that voids and cracks preferentially
formed in the small precipitation zone along the grain boundary in the HAZ. The
creep strength of Alloy263 in weldments exhibited the highest level among all the
alloys, although HAZ failure occurred in the low stress test condition. A weld
strength reduction factor will be needed to avoid HAZ failure in Alloy740 and
Alloy263. Also, to prevent premature failure in weld metal, optimization of the
chemical composition of weld filler materials will be required.
INTRODUCTION
To improve thermal efficiency and reduce CO2 emissions in coal fired plants, a
Japanese national project has been undertaken since Aug. 2008 with the objective of
developing an advanced ultra-supercritical power plant (A-USC) with a steam
temperature of 700C. The target net thermal efficiency for the higher heating value
base is 46 to 48%. This is more than 10% higher than that of 600C class USC
boilers, meaning a drop of over 10% in CO2 emissions[1].
Although 9 to 12Cr steels such as P91, P92 and P122 having tempered martensite
structures with fine precipitates have been used for piping and headers in 600C
class USC boilers, these materials cannot be used in an A-USC boiler for these
applications, because their creep strength and steam/oxidation resistance are
903
Si
Mn
Ni
Cr
Mo
Ti
Nb
Co
Sol.Al Others
HR6W
bal.
HR35
0.83
0.0040 4.03
bal.
0.0044
11.75
1.27
20.06
0.93
0.0040
19.99
0.48
0.0049
1.24
904
Heat treatment
Manufacturing
process
Size
Soaking
treatment
HR6W
120024h
HR35
Alloy617
Alloy740
Plate
25T180W500L
Alloy263
180kgVIM
Forging (50t)
Soaking treatment
Hot rolling (25t)
Solution treatment
Solution treatment
12201h
12301h
11751h
117524h
Alloy141
11501h
11501h
10661h
this alloy[2]. HR35 was developed using strengthening of -Cr phase, a b.c.c.
structure consisting mainly of Cr with Ni and W, and other intermetallic phases for
piping applications[2]. Alloy141 was first developed as a 600-650C class steam
turbine material for parts such as blades and casing bolts[4]. Alloy 617 is a stable
austenitic solid solution alloy, already registered in ASME as SB-167 and in the
VdTV Materials Datasheet as 485,09.2001.
Welding Conditions
Test materials were covered with thin oxidation scale due to solution treatment,
which was removed by grinding of 1mm on both sides of the plate. Figure 1 shows an
example of the groove configuration applied in this test. Multi-pass gas tungsten arc
weldments were prepared on 23mm thick plates of each tested alloy. The weldments
were welded using matching filler metal, deposit chemical compositions shown in
Table 3. The multi-pass weldments were made at 140-175A and 10V under Ar
shielding gas at 25-30 liters per minute. There was no welding preheating, and the
maximum inter-pass temperature was controlled to within 200C. Post weld heat
treatment was not applied. The reasons that two types of filler materials were
adopted for each base metal shown in Table 3 were to evaluate weld quality and to
prevent premature fracture in the weld metal. Figure 2 shows an example of the
appearance of the HR6W weldment.
Remove oxidation scale by grinding
7.5
25 23
R2.5
1
905
Chemicalcomposition (mass%)
C
Si
Mn
Ni
Cr
Mo
Ti
Nb
Co
Al
Fe
Zr
HR35
Alloy 740
Alloy 263
Alloy 141
Auto
GTAW
19.95 6.90
0.67
0.56
0.002
0.037
HR6W
Alloy 617
Auto
GTAW
21.65 9.73
1.14
1.03
0.003
0.002
HR6W
Alloy 617
Auto
GTAW
21.40 8.82
1.36
1.60
0.003
0.001
HR35
Alloy 740
Alloy 263
Alloy 141
Manual
0.063 0.28 0.340 0.001 <0.001 49.40
GTAW
19.92 5.92
0.46
906
400
300
300
200
700
100
BM
BM
BM
Stress (MPa)
Stress (MPa)
400
BM
BM
BM
BM
750
BM
800 BM
70
200
700
BM
BM
750
BM
BM
100
800
70
103
104
Time to rupture (h)
50 2
10
105
103
104
Time to rupture (h)
(a) HR6W
400
100
700
HAZ
750
WM
BM
800
BM
WM
BM
70
200
HAZ
800
103
104
Time to rupture (h)
50 2
10
105
HAZ
HAZ
103
104
Time to rupture (h)
HA Z
750
200
300
700
WM
700
HAZ
WM
HAZ
Stress (MPa)
Stress (MPa)
400
WM
WM
WM
800
WM
HAZ
70
200
750
WM
100
BM
800
BM
BM
BM
BM
70
103
104
Time to rupture (h)
105
400
50 2
10
HAZ
HAZ
100
100
750
WM
70
50 2
10
300
HAZ
WM
WM
Stress (MPa)
Stress (MPa)
200
WM
300
HAZ
700
105
(b) HR35
400
300
BM
BM
BM
50 2
10
BM
105
50 2
10
103
104
Time to rupture (h)
105
Figure 3 Creep rupture test results for six types of Fe- Ni and Ni-based alloy weldments
907
(a)HR6W
All of the specimens ruptured at the base metal in gauge length. Figure 4 shows an
example of the optical microstructure. Intergranular fracture with grain distortion
was observed near the fracture portion. All of the ruptured specimens exhibited
intergranular fracture.
Comparing the extrapolated 105h creep rupture strength between weldment and
base metal[2], this weldment shows similar or higher extrapolated 105h creep
strength in base metal. Consequently, weld strength reduction factor (WSRF) is not
needed, but longer creep rupture tests are important to confirm the creep strength.
1mm
908
41MPa at 700C, 750C and 800C, respectively[6]. In the present study, the
extrapolated 105h creep strengths of the weldments are seen to exceed the reported
values for base metal at every test temperature.
(d)Alloy740
Weld metal failure occurred in the high stress test condition, and HAZ failure
appeared in the low stress test condition. In particular, the stress dependence of the
time to rupture (shown as the slope of the regression line) dramatically increased
according to the transient of the fracture portion from weld metal to HAZ. This
means that the creep strength of the HAZ is weaker than that of the base metal,
such that WSRF will be needed to avoid HAZ failure in piping. The reason for the
occurrence of HAZ fracture occurred will be discussed below.
(e)Alloy263
The weldment creep strength of Alloy263 is the highest among all the alloys at every
test temperature. However, HAZ failure appeared in the low stress test condition,
and the creep strength of weldments in the low stress condition is thus dependent on
that of the HAZ.
(f)Alloy141
Weld metal fracture was observed in the high stress test condition at 700C and
750C. It was considered that filler material D shown in Table 2 was weaker in
terms of creep strength than base metal.
DISCUSSION
Creep Strength of Weldments
Figure 5 shows the regression line of each test temperature in order to compare the
creep strength of the weldments. Three general levels of creep strength were
observed at 700C, i.e., a level associated with Alloy617, Alloy263, Alloy740 and
Alloy141; a level associated with HR6W; and level associated with HR35. The
maximum gap in 105h extrapolated creep strength among the three levels is
approximately 100MPa. Creep strength dropped in Alloy740 weldment, caused by
HAZ failure at 750C, leading to a lower estimate of extrapolated creep strength at
105h. Each creep regression line tended to converge toward time to rupture at 105h
at 800C. The slope of the creep regression line for HR6W is the smallest, and it is
possible that the HR6W weldment will show the strongest creep strength, over 2 x
105h, at this temperature.
Many weldments ruptured at the weld metal in the high stress test condition. Three
types of weld deposits designated by marks B, C and D as shown in Table 3 were
subjected to creep rupture testing in order to compare the creep strengths at 700C.
Creep rupture test results are shown in Fig.6. Creep strength in the weld deposit
indicated by mark B is obviously weak as compared to other weld deposits.
Furthermore, it is expected that weld deposit failure such as Alloy617, Alloy740,
Alloy263 and Alloy141 in weldments will occur in lower stress test conditions,
909
Stress (MPa)
300
400
Alloy
Alloy 141
740
Alloy
263
Alloy 617
200
300
HR35
Stress (MPa)
400
HR6W
100
70
200
100
70
50
102
103
104
Time to rupture (h)
50
102
105
103
104
Time to rupture (h)
(a) 700
105
(b) 750
400
Stress (MPa)
300
200
Alloy 740
Alloy 263
Alloy 617
100
HR6W
Alloy 141
HR35
70
50
102
103
104
Time to rupture (h)
105
(c) 800
400
Stress (MPa)
300
200
Filler material
100
70
50 2
10
B
C
700
103
104
Time to rupture (h)
105
910
because the extrapolated creep regression lines of the deposits adopted are weaker
at 700than those of the weldments shown in Fig.3(c)-(f).
The volume and density of precipitates in weld deposits are possibly related to
hardness, and Vickers hardnesses for all creep fracture deposits shown in Fig.6 were
measured. The maximum and minimum hardnesses are seen to be 338 and 309HV
respectively; there is no clear relationship between hardness and creep strength.
Optimization of the chemical composition of weld fillers will be necessary so as to
prevent premature weld metal failure.
HAZ Failure
HAZ failure was especially noticeable in the low stress test condition for the
weldments of Alloy740 and Alloy263. Figure 7 shows an example of the appearance
of a ruptured specimen and the cross-sectional macrostructure of Alloy740,
presenting typical HAZ failure. The un-fractured side HAZ and base metal in this
specimen were observed in order to investigate the HAZ fracture mechanism. Figure
8 shows the appearances of microstructures in base metal and HAZ crept at 750C,
130MPa, observed by FE-SEM (field emission-scanning electron microscope). Many
small particles and needle like precipitates were observed inside the grains. Figure 9
shows the high magnitude SEM microstructure of creep damage to the HAZ along
the grain boundary in the same specimen. The number of small particles (known as
') near grain boundary was small, appearing to be a precipitation free zone (PFZ) as
reported in this type of alloy[7]. Also, creep voids and/or preferential cracking was
observed along the grain boundary. The microstructures of the base metal and the
HAZ shown in Fig.8 (a) and (b) thus appear to be different, in view of the amount of
precipitation along the grain boundary. It is considered that the voids and cracks
preferentially formed in the small precipitation zone along the grain boundary in the
HAZ and weldment of Alloy740 tend to have failed in HAZ due to lack of creep
strength.
(a) Appearance
5mm
5mm
911
4m
(b) HAZ
4m
Figure 8 Base metal and HAZ microstructures of Alloy740 specimen crept at 750,130MPa
observed by FE-SEM
1m
Figure 9 SEM microstructure of creep damage HAZ along grain boundary in Alloy740
specimen crept at 750,130MPa
CONCLUSIONS
Fe-Ni and Ni-based alloys, namely HR6W, HR35, Alloy617, Alloy740, Alloy263 and
Alloy141, were used to evaluate the creep strength of the respective GTAW
weldments.
All of the HR6W specimens ruptured at the base metal, which showed intergranular
fracture with grain distortion. The creep strengths of the weldments show similar or
higher extrapolated 105h creep strength as compared to those reported for base
metal. The creep strengths of the HR35 weldments were the same as reported for
base metal, and all of the specimens ruptured at the base metal in gauge length.
Accordingly, weld strength reduction factor will not be needed in weldments of
HR6W and HR35. Alloy617 weldments tested at 750C and 800C in low stress test
condition were seen to rupture at the base metal, while HAZ failures were observed
in the case of testing at 700C. Extrapolated 105h creep strength of Alloy617
weldments exceeded the values reported for base metal at every test temperature.
Weld metal failures in Alloy740 weldments occurred in the high stress test
condition, with HAZ failure appearing in the low stress test condition. In particular,
912
the stress dependence of time to rupture (shown as the slope of the regression line)
dramatically increased according to the transient of the fracture portion from weld
metal to HAZ. It is considered that voids and cracks preferentially generated in the
small precipitation zone along the grain boundary in the HAZ, as well as the
weldment of Alloy740 tended to fail in the HAZ due to lack of creep strength. The
weldment creep strength of Alloy263 was the highest among all alloys at every test
temperature. However, as HAZ failure appeared in the low stress test condition, the
creep strength of the weldment in the low stress condition is dependent upon that of
the HAZ. Weld strength reduction factor will be needed to avoid HAZ failure in
Alloy740 and Alloy263. Weld metal fracture was observed in the high stress test
condition at every test temperature for Alloy141. It was considered that the filler
material applied was weaker in terms of creep strength than base metal.
Optimization of the chemical composition of weld filler will be necessary to prevent
premature weld metal failure.
The regression lines for each test temperature were investigated in order to compare
the creep strength of their weldments. Three levels of creep strength level at 700C
were observed. Each creep regression line tended to converge toward time to rupture
at 105h at 800C.
ACKNOWLEDGMENTS
The authors wish to acknowledge their colleagues Seiji Sasaki and Yusuke Ayukawa
for long term creep rupture tests, as well as Toshiyuki Imazato, Takahiro Shirane
and Naofumi Kimura for microstructural investigation.
REFERENCES
[1]M. Fukuda et al.: "Advances in Materials Technology for A-USC Power Plant Boilers",
Advances in Materials Technology for Fossil Power Plants, ASM International, (2010), p325
[2]H. Ogawa et al.: "Sumitomo's R&D activities for Advanced USC Boilers", VGB Powertech,
Vol.91, No.11(2011), p59
[3]R. Smith et al.: Nickel Alloys for the Next Generation of Advanced Steam Boilers, VBG
Materials and Quality Assurance Conference, March 10-11, Dortmund, Germany, 2004.
[4]H. Kamoshida et al.: "Low thermal expansion Ni-base Superalloy for 700C class steam
turbine plant (USC141)", Advances in Materials Technology for Fossil Power Plants, ASM
International, (2010), p373
[5]Y. Tanaka et al.: "Coal Ash Corrosion Properties of Ni-based Alloy for Advanced-USC
Boilers", Proc. of 6th International Conference on Advances in Materials Technology for
Fossil Power Plant, Aug 31-Sep. 3, 2010, Santa Fe, New Mexico, USA, (2010)
[6]ECCC Creep Data Sheet, (2005)
[7]Bechetti, Daniel Henry, "Microstructural Evolution and Creep Rupture Behavior of
INCONEL Alloy 740H Fusion Welds", Theses and Dissertations of Lehigh Univ.,
Paper 1247, (2013)
913
ABSTRACT
Precipitation, grain-boundary and sub-boundary hardening are the most important strengthening
mechanisms in creep resistant martensitic high chromium steels. In recent years, a design concept
for the stabilisation of the microstructure (precipitates, grain boundaries and martensitic lath
structure) by addition of boron and nitrides was developed. This so called MARBN steel
(MARtensitic steel strengthened by Boron and Nitrogen) combines boron strengthening (solid
solution strengthening) with nitride strengthening (precipitation strengthening). Welding trials
showed no uniform formation of a fine grained region in the heat affected zone HAZ, which is
considered critical for creep strength due to Type IV cracking. First creep test results of
crosswelds are very promising.
In this work, an improved MARBN steel was developed and investigated. Uniaxial creep tests of
base material as well as of welded joints have been carried out at 650C up to 25.000 hours at
different stress levels. The creep strength of base material and that of welded joints was analysed
and the evolution of damage was investigated using synchrotron micro-tomography and electron
back scatter diffraction in order to understand the creep damage mechanism.
The combination of long-term creep testing data with a 3-D damage investigation by using
synchrotron CT allows a completely new view on the basic failure mechanisms at elevated
temperatures in the heat affected zone of welded joints.
1. INTRODUCTION
Thermal power plants, especially coal fired power plants will continue to play a major role in the
electricity production of the future. Unfortunately, electricity production by coal combustion leads
to a relatively high CO2 emission and it is undeniable that this is a major factor in global
warming.[1] Therefore, big efforts are made to reduce CO2 emissions by increasing the net plant
efficiency of thermal power plants. In general, the efficiency can be increased by increasing the
temperature and pressure levels (up to 650C and 350bar) of the steam entering the turbines.[2-4]
However, these efforts lead to develop new steels with excellent creep properties and oxidation
resistance which can resist the harsher service conditions. Due to the low coefficient of thermal
expansion, high heat conductivity and the low price compared to Ni-based superalloys or
austenitic steels, by still acceptable creep strength, advanced martensitic 9% chromium steels have
914
been identified as a favoured group of materials for high temperature application in thermal power
plants.[2,5] The development of this group of steels has a long history especially in Japan and
Europe.[6-7] In recent years the design concept for advanced martensitic 9%Cr steels targets the
enhancement of long term microstructural stability during creep. The National Institute for
Material Science in Japan for example is following an extensive research program with the
concept of stabilising the microstructure by controlled boron and nitrogen addition. This so called
MARBN-concept (MARtensitic steel strengthened by Boron and Nitrogen) is one of the most
promising concepts for developing steels for future thermal power plant applications.[8-11]
1.1. MARBN concept
Recently, an advanced 9Cr steel with controlled addition of boron and very low amount of
nitrogen was developed at NIMS in Japan. First experimental investigations show not only
improved long term creep strength of the base material but also improved strength of welded
joints.[8-11]
1.1.1. MARBN concept Improvement of base material
Abe et al. investigated the effect of boron on the creep deformation behaviour of 9-12%Cr steels.
Creep tests of different boron containing 9Cr steels were performed at 650C and 80MPa. The
results showed that the addition of boron significantly decreases the minimum creep rate by
retarding the onset of the tertiary creep region, see Figure 1a. Additionally, scanning Auger
spectroscopy revealed that boron is enriched in M23C6 in the vicinity of prior austenite grain
boundaries (PAGBs) and reduces the growth and coarsening of M23C6 precipitates during service
and is therefore the main reason for a decreased minimum creep rate of boron containing 9Cr
steels (Figure 1b).[5,8]
Furthermore, the creep strength can be increased by adding nitrogen to form finely distributed
vanadium/niobium rich carbonitrides (MX) precipitates. It should be noted that boron is a strong
nitride former and therefore the boron/nitrogen ratio has to be kept in a certain range to avoid
formation of boron-nitrides.
Figure 1: Effect of boron on the creep life of 9Cr steels; a) Creep rate versus time curves at
650C and 80MPa and b) Schematic diagram showing the effect of boron for improvement of
creep life. [5]
915
Welded joints of martensitic 9-12%Cr steels are especially prone to premature cracking during
service. The most dominant failure mode of welded joints during creep exposure is categorised as
Type IV cracking and occurs in the fine grained heat affected zone (FGHAZ) of a welded joint.[4]
Today, Type IV cracking is the major end of life failure mechanism of 9-12%Cr steel welded
joints in thermal power industries and therefore it is of great concern all over the world. Figure 2
shows a typical Type IV failure (failure in the FGHAZ) in a common 9Cr steel crossweld (ASME
P92). The cracking mode is governed by creep cavitation, which leads to micro and macro
cracks.[11-17] The mechanism governing this failure is influenced by a combination of a very
unique microstructure and complex load conditions in this area and can be summarised and
simplified into three factors:
Uniform grain refinement in the heat affected zone close to the unaffected base material
Reduced boundary and sub-boundary strengthening in the FGHAZ (only few precipitates
are formed along the new grain- and sub grain-boundaries)
Multi axial stress conditions in the HAZ.
Figure 2: Characteristic Type IV failure of a P92 crossweld at 650C and 71,5MPa after 17.204
hours.
One key goal of this MARBN approach of NIMS was to suppress the FGHAZ in order to avoid
the Type IV cracking problem. Normally, the FGHAZ is formed where the material is exposed to
916
a peak temperature just above Ac3. Austenite grain growth is limited by the incomplete dissolution
of carbides (in this temperature range) and the fully austenitised material subsequently transforms
into martensite during cooling.[4] Abe et al. [5] showed that the grain boundary segregation of
boron reduces the interfacial energy of the grain boundaries and makes these grain boundaries less
effective as nucleation sites for the austenite phase. This leads to a martensitic reverse
transformation by shear.
2. EXPERIMENTAL
Together with NIMS a new MARBN steel concept was developed at the Institute for Materials
Science and Welding at Graz University of Technology. This concept combines stabilisation of
the microstructure (precipitates, grain boundaries, martensitic lath structure) by addition of boron
and nitride strengthening.
2.1. ALLOY DESIGN
In order to assist the selection of the most appropriate chemical composition, equilibrium
calculations using MatCalc [19] have been carried out. The MatCalc software is applied to
calculate equilibrium phase fraction diagrams of the alloys with a defined chemical composition.
The calculations were performed using the mc_steel15 database and MatCalc version 5.42 (rel
1.006). Figure 3 shows the equilibrium phase fraction diagram for the first trial melt (heat 1) with
the chemical composition shown in Table 1. The calculation of heat 1 indicates that the steel
should be free of delta ferrite at room temperature. Normalising at 1150C will dissolve most of
the precipitates formed during solidification (except NbC and M2B) and allow the homogenisation
of the elemental distribution by diffusion. During tempering at 770C, a uniform tempered
martensitic structure with precipitates is predicted to form.
Figure 3: Equilibrium simulation of Heat 1, representing phase fractions of different phases and
precipitates as a function of the temperature.
917
Si
Mn
Cr
Ni
Nb
Co
Al
Heat 1
0.074
0.29
0.44
9.26
0.06
2.84
0.21
0.056
2.95
<0.005
0.0120
0.013
Heat 2
0.090
0.30
0.51
9.26
2.92
0.20
0.050
2.88
0.004
0.0114
0.010
For homogenisation of heat 1, the ingot (110mm square) was forged to final dimensions of 50mm
square. The second melt was cast and rolled to 20mm thick plates. The exact chemical
composition in weight % (wt. %) for heat 1 and heat 2 is given in Table 1. The final quality heat
treatment for both heats consisted of normalising at 1150C for 1 hour followed by tempering at
770C for 4 hours. Light optical micrographs of the two heats reveal a tempered martensitic
microstructure. Compared to a conventional 9Cr material (P92), only very few BN for heat 1 and
no BN for heat 2 were detected by SEM and EDX.[17]
Figure 4: Boron content versus nitrogen content in martensitic steels: IWS TU Graz
developed steel in this work and NIMS 9Cr boron steel developed steel in [20].
918
2.3. WELDING
The material (heat 1) was welded by a gas tungsten arc welding process using a nickel based filler
metal (Nibas 70/2-IG). The reason for choosing this filler metal was to overmatch the base
material in order to avoid fracture in the weld metal. After the welding process the postweld heat
treatment was carried out at 740C for 4 hours.
2.4. CREEP TESTS
Uniaxial creep tests for heat 1 and heat 2 have been carried out at 650C at different stress levels.
Heat 1 was mainly tested in order to get first and important results on the creep behaviour of
welded joints. Furthermore, creep tests of the parent material (heat 2) are performed.
2.5. MICROSTRUCTURAL INVESTIGATIONS
Creep tested crosswelds of heat 1 are fully characterised by LOM, SEM, EBSD and Synchrotron
tomography. Results for heat 2 (parent metal) have to be analysed after completion of creep
testing.
2.6. SYNCHROTRON CT
In order to get a 3 dimensional picture of the void formation during creep exposure, synchrotron
micro-tomography experiments were carried out. The specimens for the micro-tomography (SRCT) scan were extracted from creep tested crossweld samples. The specimen extraction as well
as the Synchrotron experimental setup is described elsewhere.[21] A voxel size (a volume element
in 3D) with an edge length of 0.5m was achieved in order to reach a spatial resolution of 1m.
3. RESULTS:
3.1. WELDING TRIALS
Figure 5 shows a detailed view of the HAZ of a welded joint utilising a Ni-based filler metal. It
can be clearly seen that the fine grained zone in the HAZ was suppressed. Only a certain fraction
of small grains along the PAGB are formed. HAZ simulations showed similar results and
confirmed the suppression of a uniform fine grained region in the HAZ.
Figure 5: Micrographs of the welded joint of heat 1 with suppressed fine-grained zone in the
HAZ.
919
Figure 6: a) Creep testing results for heat 1 and heat 2 of the MARBN steel at 650C compared
to P91 and P92 base material and b) Cross-sections of the creep tested crossweld samples of
heat 1 with a change of the failure location.
3.3. MICROSTRUCTURAL INVESTIGATIONS
Microstructural investigations by LOM and SEM of crosswelds (heat 1) revealed that the failure
was caused by void nucleation along grain boundaries. Figure 7a shows a light optical micrograph
of a creep tested sample with a rupture time of 12.000 hours (80MPa). It can be clearly seen that
voids are formed along prior austenite grain boundaries in the HAZ. The crossweld sample with
the longest time to rupture (70MPa) showed a heavy void formation in the HAZ at a certain
distance from the fusion line, Figure 7b. It seems that these voids are formed along the PAGBs.
920
Figure 7: Light microscopy images of the void formation along former austenite grain
boundaries in the HAZ of the crossweld specimen a) failed after 12.900 hours at 80MPa at
650C and b) failed after 17.000 hours at 70MPa at 650C (unechted).
3.4. SYNCHROTRON CT
Figure 8 shows a 3D image of the specimen failed after 17.000 hours of creep testing at 650C
and 70MPa. This image clearly illustrates the inhomogeneous distribution of voids in the HAZ.
Additional EBSD measurements revealed that voids are formed along small grains located along
the large prior austenite grain boundaries and small grains that have formed in this MARBN steel
along the weld fusion line. The reason for the void formation along the fusion line has to be
investigated in more detail. The small grains, which are formed at a certain distance from the
fusion line are caused by the weld thermal cycle. Due to the rapid heating and cooling, only a few
precipitates are formed along these new grain boundaries and sub grain boundaries, reducing
therefore the creep strength in this zone. This and the reduced grain size are considered as the
main reasons for the reduced creep strength and the increased void formation in this area.
Figure 8: 3D micro-CT image of the crossweld sample failed after 17.200 hours of creep testing
at 650C with supporting EBSD measurements.
921
4. CONCLUSION
2 trial melts of a new alloying concept based on thermodynamic equilibrium calculations have
been produced. First welding trials for heat 1 (GTAW) were successfully applied on the new
material. It was shown that the weldability of this material is also very promising. No uniform fine
grained zone was observed after welding trials.
Ongoing uniaxial creep tests of base material show a superior creep strength compared to P92
material. The creep strength of the parent material is more than 20% higher than the creep
strength of P92. The addition of boron and nitrogen enhances the microstructural stability during
creep. Soluble boron stabilises the martensite microstructure and decreases the minimum creep
life. Adding nitrogen increases the precipitation hardening by forming finely distributed
vanadium/niobium rich carbonitrides. Compared to the parent material, the crossweld creep test
results of heat 1 are not fully satisfying. It was observed that the loss of creep strength at stress
levels below 100MPa is similar to that of conventional 9Cr materials. First synchrotron microCT
experiments together with light optical and EBSD investigations revealed an intense void
formation in a restricted area along small grains at PAGB in the HAZ as the main reason for creep
failures. The alloying concept of adding boron can suppress the formation of a uniform fine
grained zone but cannot suppress the formation of individual fine grains along PAGBs. Future
tasks are dealing with the improvement of the chemical composition of this alloying concept and
the application of advanced welding techniques in order to decrease the susceptibility to Type IV
cracking.
Acknowledgments
This work was sponsored by a KMM-VIN research fellowship 2012 (European Virtual Institute
on Knowledge-Based Multifunctional Materials AISBL) and by the European Union (directorategeneral for energy), within the project MACPLUS (ENER/FP7EN/249809/MACPLUS) in the
framework of the Clean Coal Technologies. The synchrotron radiation experiments were
performed with the approval of JASRI (Proposal no. 2011A1291).
REFERENCES
[1] World Energy Outlook 2010, International Energy Agency, Paris, France, 2010.
[2] Cerjak, H., The role of welding in modern power generation plants, Proc. of IIW Int. Conf.
on Achievements and perspectives in producing welded construction for urban environments ,
Bucharest, July 2003, pp. 127-136.
[3] Bhadeshia H.K.D.H., Design of Ferritic Creep-resistant Steels, ISIJ International, Vol.41
(2001), No.6, pp.626-640.
[4] Francis, J.A., Mazur, J., Bhadeshia H.K.D.H., Type IV cracking in ferritic power plant
steels, Mater. Sci. Technol., Vol.22, No. 12 (2006), pp. 1387-1395.
[5] Abe F., Tabuchi M., Tsukamoto S., Mechnism for Boron effect on microstructure and creep
strength of ferritic power plant steel, Energy Materials, Vol 4, No.4 (2012), pp166-175.
[6] Kern, T. U., Wieghardt, K., Kircher, H., Material and Design Solutions for Advanced Steam
Power plants, Proc 4th Advances in Materials Technology for Fossil Power Plants, Hilton
Head Island, SC, October. 2004, pp. 20-34.
[7] Masuyama, F., Alloy Development and Material Issues with Increasing Steam
Temperature, Proc 4th Advances in Materials Technology for Fossil Power Plants, Hilton
Head Island, SC, October. 2004, pp. 35-50.
922
[8] Horiuchi, T., Igarashi, T., Abe, F., Improved utilization of added B in 9Cr heat resistant
steels containing W, ISIJ Int., Vol. 42, (2002), p67.
[9] Abe, F., Okada, H., Wanikawa, S., Tabuchi M., Itagaki, T., Kimura, K., Yamaguchi, K.,
Igarashi, M., Materials for advanced power engineering 2002, Vol 3, , (2002) Julich
Germany, pp1297-1406.
[10] Kondo, M., Tabuchi, M., Tsukamoto, S., Yin, F., Abe, F., Suppression of Type IV failure in
high-B low-N 9Cr-3W-3Co-NbV steel welded joint, Proc 4th Advances in Materials
Technology for Fossil Power Plants, Hilton Head Island, SC, October, 2004, pp. 987-998.
[11] Albert, S. K., Kondo, M., Tabuchi, M., Yin, F., Sawada, K., Abe, F.,Improving the Creep
Properties of 9Cr-3W-3Co-NbV Steels and their Weld Joints by the Addition of Boron,
Metallurgical and Materials Transactions A, 36A, (2005), pp.333-343.
[12] Mayr, P., Evolution of microstructure and mechanical properties of the heat affected zone in
B-containing 9% chromium steels, Doctoral Thesis, Graz University of Technology, Graz,
2007.
[13] Mayr, P., Schlacher, C., Mitsche, S., Critical issues with creep-exposed ferritic-martensitic
welded joints for thermal power plants, Proc. of IIW Int. Conf. on Global Trends in
Joining, Cutting and Surfacing Technology, Chennai, July 2011, pp. 417-425.
[14] Masuyama, F., Matsui, M., Komai, N., Creep Rupture Behavior of Advanced 9-12%Cr steel
Weldment, Key Engineering Materials, Vols. 171-174, (1999), pp. 99-108.
[15] Abe, F., Tabuchi, M., Kondo, M., Tsukamoto, S., Suppression of Type IV fracture and
improvement of creep strength of 9Cr steel welded joints by boron addition, Int. J. Pres.
Ves. Pip., Vol. 84, (2007), pp. 44-52.
[16] Kondo, M., Tabuchi, M., Tsukamoto, S., Yin, F., Abe, F., Suppressing type IV failure via
modification of heat affected zone microstructures using high boron content in 9Cr heat
resistant steel welded joints, Science and Technology of Welding and Joining., Vol.11, No.
2, (2006), pp. 216-223.
[17] Mayr, P., Holzer, I., Mendez-Martin, F., Agero, A., Gonzalez, V., Baumgartner, S., Cerjak,
H., Experience with 9Cr3W3CoVNbBN Base Material and Crosswelds at 650C for
Implementation in USC Power Plants, Proc. of the 3rd Symposium on Heat Resistant Steels
and Alloys for High Efficiency USC Power Plants, Tsukuba, Japan, June, 2009.
[18] Abe, F., Tabuchi, M., Tsukamoto, S., Shirane, T., Microstructure evolution in HAZ and
suppression of Type IV fracture in advanced ferritic power plant steels, Int. J. Pres. Ves.
Pip., Vol. 87, (2010), pp. 598-604.
[19] Svoboda, J., Fischer, F.D., Fratzl, P., Kozeschnik, E., Modelling of kinetics in multicomponent multi-phase systems with spherical precipitates: I: Theory, Mater. Sci. Eng. A,
Vol. 385, (2004), pp. 166-174.
[20] Abe, F., Horiuchi, T., Sawada, K., High-temperature Annealing for Maximization of
Dissolved Boron in Creep-Resistant Martensitic 9Cr Steel, Materials Science Forum, Vols.
426-432, (2003), pp. 1393-1398.
[21] Schlacher, C., Sommitsch, C., Mayr, P., Gupta, C., Toda, H., Uesugi, K. Suzuki, Y., Creep
and damage investigation of improved 9%Cr steel, Trends in Welding research, Proceedings
of the 9th International Conference (2012), Chicago, pp. 376-381.
923
924
Induction
heating
Microstructural
condition
Specimen
numbers
8804
Condition 1
50-56
8850
Condition 2
43-49
8804
Condition 3
15-21
8850
Condition 4
29-35
3346
Condition 5
8-14
3611
Condition 6
36-42
3346
Condition 7
1-7
3611
Condition 8
22-28
Grain
fine
COST F
coarse
COST
FB2
fine
coarse
925
Figure 1: Low-temperature schedule applied to COST F specimens. Thermal cycles simulate the
impact of heat on the farther and fine-grained part of the heat-affected zone of the weld during
sequential deposition of weld beads.
Figure 2: High-temperature schedule applied to COST F specimens. Thermal cycles simulate the
thermal impact on the closer and coarse-grained part of heat-affected zone of the weld during
sequential deposition of weld beads.
926
Figure 3: Low-temperature schedule applied to COST F specimens. Thermal cycles simulate the
impact of heat on the more distant and fine-grained part of the heat-affected zone of the weld
during sequential deposition of beads.
Figure 4: High-temperature schedule applied to COST F specimens. Thermal cycles simulate the
thermal impact on the closer and coarse-grained part of heat-affected zone of the weld during
sequential deposition of weld beads.
MICROSTRUCTURES OF COST F AND COST FB2 MATERIALS
The heat treated specimens were prepared for examination using standard metallographic
techniques of grinding and polishing. Micrographs with magnifications of 1000 10000 were
taken in JEOL 6380 scanning electron microscope.
Microstructures of all specimens consist of phases resulting from hardening with various
proportions of bainite and martensite. Carbide precipitates were found in all microstructures. The
size of most of them did not exceed hundreds of nanometres. In some specimens (see below),
preferential precipitation of carbides on prior austenite grain boundaries can be observed.
Micrographs taken in SEM at magnifications above 10000 reveal that specimens exposed during
the welding cycle simulation to higher temperatures (above 1400 C) contain finer carbide
precipitates. Apparently they dissolve partially during short exposure to a high temperature. In
927
specimens exposed to lower temperatures, greater numbers of both finer a coarser carbides can be
found. The initial grain size prior to welding simulation has substantial impact on the grain size
of austenite, the decomposition of which leads to the resulting microstructure. The grain size has
a considerable effect on the nature of the decomposition process, on the ferritic phase
morphology and on its preferential orientation. Micrographs of the microstructures investigated
are shown in Figs. 5-12. Detailed description of the microstructures can be found below.
Figure 5: COST F - Initial fine grain - Low-temperature simulation of heat effects, 8804
condition 1.
The Fig. 5 shows fine-grained microstructure of upper bainite where fine and coarse carbides can
be found precipitated preferentially between individual bainite laths but also on prior austenite
grain boundaries. The size of the largest carbides is approx. 400 nm. From the creep behaviour
perspective, this type of microstructure is unfavourable.
Figure 6: COST F - Initial fine grain - High-temperature simulation of heat effects, 8850
condition 2.
928
There is fine-grained martensitic-bainitic microstructure depicted in the Fig. 6. The bainite with
the present morphology may be regarded as lower bainite. Carbide particles have precipitated in
ferrite matrix and are of small size. No signs of preferential precipitation of these particles on
boundaries of prior austenite grain were detected. This microstructure is favourable from the
creep behaviour viewpoint.
Figure 7: COST F - Initial coarse grain Low-temperature simulation of heat effects, 8804
condition 3.
Coarse-grained martensitic-bainitic microstructure with signs of chaotic orientation of acicular
ferrite in bainite matrix is shown in Fig 7. The carbides consist of very fine an also coarser
particles (max. size of approx. 200 nm) distributed uniformly within the material. They are
present within the ferrite matrix, on boundaries of bainite laths and on prior austenite grain
boundaries.
Figure 8: COST F - Initial coarse grain High-temperature simulation of heat effects, 8850
condition 4.
929
Figure 9: COST F B2 - Initial fine grain - Low-temperature simulation of heat effects, 3611
condition 6.
Fine-grained bainitic structure is shown in Fig. 9. Carbides precipitated within bainitic ferrite
matrix with uniform distribution. Some of their particles are fine and others coarse with sizes of
up to hundreds of nanometres. Carbides are dispersed within the ferrite matrix and, to a great
extent, on prior austenite grain boundaries as well.
Figure 10: COST F B2 - Initial fine grain - High-temperature simulation of heat effects, 3346
condition 5.
930
Figure 11: COST F B2 - Initial coarse grain - Low-temperature simulation of heat effects 3611
condition 8.
There is shown martensitic-bainitic microstructure with signs of acicular ferrite in Fig. 11.
Martensite laths within prior austenite grains form packets with preferential orientation. Finer as
well as coarser carbides are mostly distributed along edges of these laths.
Figure 12: COST F B2 - Initial coarse grain -High-temperature simulation of heat effects, 3346
condition 7.
Fig. 10 shows martensitic-bainitic microstructure with coarse prior austenite grains. The
microstructure exhibits well distinguishable preferential orientation of laths of hardening-type
phases within individual prior austenite grains. Preferential precipitation of carbides on grain
931
boundaries is visible. The carbides are very fine and dispersed within the ferrite matrix. However,
they are also found along lath and prior austenite grain boundaries to great extent.
SHORT-TERM (ONE-DAY AND ONE-WEEK) CREEP TESTS
The materials of interest in all their microstructural conditions were examined by short-term
creep tests at 600 C. Two or three specimens representing a particular material condition were
tested in servohydraulic machine for 24 hours in a split furnace. Strain was measured by means of
a high-temperature extensometer. Based on these results, three stress levels were identified for
each condition to be used in one-week creep tests with strain monitoring. Results of the test
included the time dependence of strain (or time to fracture) at 600 C and at various loading
levels for eight different microstructural conditions of COST F and COST FB2 materials. The
creep test specimen configuration is shown in Fig. 13.
932
Specimen
Temp.
Time to fracture
Strain upon
24/200 hrs
1_specimen_52
1_specimen_53
1_specimen_51
1_specimen_55
1_specimen_56
1_specimen_54
2_specimen_48
2_specimen_45
2_specimen_44
2_specimen_46
2_specimen_47
3_specimen_18
3_specimen_20
3_specimen_16
3_specimen_17
3_specimen_19
3_specimen_21
4_specimen_34
4_specimen_31
4_specimen_22
4_specimen_30
4_specimen_35
5_specimen_13
5_specimen_09
5_specimen_10
5_specimen_11
5_specimen_12
6_specimen_40
6_specimen_37
6_specimen_38
6_specimen_39
6_specimen_42
7_specimen_07
7_specimen_06
7_specimen_03
7_specimen_04
7_specimen_01
8_specimen_28
8_specimen_26
8_specimen_22
8_specimen_25
(MPa)
400
385
370
360
340
325
385
370
360
340
325
385
370
350
360
340
325
385
370
360
340
325
385
370
360
340
325
385
370
360
340
325
385
370
360
340
325
385
370
360
340
(C)
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
600
(hrs)
3.3
1.1
2.6
2.5
6.3
8.6
19.9
(%)
Condition_1
8_specimen_27
325
600
144.0
Condition_2
Condition_3
Condition_4
Condition_5
Condition_6
Condition_7
Condition_8
933
0.80
105.0
24.5
19.9
1.61
1.56
5.60
1.9
76.3
59.3
137.0
1.29
0.98
1.38
1.78
0.89
48.0
2.27
2.52
8.7
1.81
14.8
33.3
58.6
2.11
1.2
76.3
296.5
26.8
93.3
2.42
2.22
2.78
1.60
RESULTS SUMMARIZATION
For the purpose of comparison, the conditions of the materials were ranked on the basis of their
creep properties from the poorest to the best ones, as shown in Tabs. 3 and 4. The comparison
suggests that schedules 8804 and 3611 lead to poorer creep properties. In conditions denoted as 1,
6, 3 and 8, the impact of grain size can be observed. With coarser grain, materials in these
conditions exhibit better creep properties. Conditions 7, 2, 5 and 4 (with simulation of hightemperature spikes) do not allow straightforward comparison with regard to scatter in their
measured properties. Nevertheless, their creep properties are notably better than those of 1, 3, 6
and 8 conditions (with simulation of low-temperature spikes). High-temperature simulation of
welding schedules no. 3611 and 8804 results in more favourable microstructures from the creep
perspective. In this case, the effect of grain size was not distinct.
Table 3: Evaluation of materials conditions with respect to creep properties
Rank
(from poorer
to better creep
properties)
Microstr.
condition
5-8
Specimens failed at 360 MPa and 340 MPa. At 325 MPa, the second
largest strain was recorded
5-8
Specimens failed at 385 MPa and 360 MPa. At other levels, strain
values were among the smallest ones
5-8
5-8
934
Material
Grain
Induction Microstructura
heating
l condition
COST F
fine
8804
Condition 1
COST FB2
fine
3611
Condition 6
COST F
coarse
8804
Condition 3
COST FB2
coarse
3611
Condition 8
5-8
COST FB2
coarse
3346
Condition 7
5-8
COST F
fine
8850
Condition 2
5-8
COST FB2
fine
3346
Condition 5
CONCLUSIONS
Heterogeneous weld of turbine rotor materials was investigated in the current study. A critical
microstructure points were detected by means of the metallographic investigations. The FEM
calculations provided representative heating simulation regimes for the critical points that were
subsequently applied to the experimental materials. Simulation schedules 8050 and 3346 were
almost identical and the magnitudes of their temperature spikes were approx. 1400 C. Likewise,
simulation schedules 8804 and 3611 were almost identical with temperature spikes of approx.
1000 C. Specimens with a total of eight different microstructural conditions were prepared and
used for tension tests and short-term creep tests (24 hour and one-week tests). Seven specimens
for each microstructural condition were prepared, making the total of 56 specimens. Selected
specimens were examined by metallographic methods. Microstructures of all specimens consisted
of hardening-type phases with various proportions of bainite and martensite. Carbide precipitates
of various sizes were found in all microstructures. The size of most of them did not exceed
hundreds of nanometres. In some specimens, preferential precipitation of carbides on prior
austenite grain boundaries was observed. Micrographs taken in SEM at magnifications of 10000
reveal that specimens exposed to higher temperatures (above 1400 C schedules 8850 and
3346) during the welding cycle simulation contained finer carbide precipitates. It appears that
during the short exposure to this temperature, the particles partially dissolve. Coarser particles
which remain in the microstructure of specimens exposed to lower temperatures are likely to have
adverse effects on the materials creep properties.
Results of tension tests and creep tests suggest that it is the welding operation schedule and then
the grain size which have the most profound effect. In terms of welding schedules, the most
favorable ones were no. 8850 and 3346 but the impact of grain size is ambiguous. Schedules
3611 and 8804 lead to lower values of tensile and creep properties in specimens. In those
specimens, the impact of grain size is detectable. Specimens with coarser grain exhibit better
creep properties than the fine-grained ones. Further investigations are going to be performed in
order to provide deeper insight into the problematic discussed here.
ACKNOWLEDGMENTS
The paper was realized due to the support of project TA01020985 - Development and
modernization of turbine blades from the perspective of the reliability and service life increase
sponsored by Technology Agency of the Czech Republic and FR-TI2/080 - New Technologies of
Joining of Flow Turbine Components for Ultra Super Critical Parameters of Steam (2010-2012,
MPO/FR).
935
Si
0.2
Cr
9.0
Mo
1.0
Ni
0.2
V
0.2
Nb
N
0.04 0.04
Figure 1: Influence of PWHT on mechanical properties of P91 flux cored wire weld metal
937
All weld metal specimens of the modified P91 flux cored wire welded with shielding gas
Ar+25%CO 2 according to AWS A5.36 show corresponding results. Figure 2 compares the
mechanical properties at room temperature and tensile properties at elevated temperatures for a
PWHT of 760C (1400F)/2h according to AWS A5.36 to a PWHT of 760C (1400F)/4h.
Tensile properties are slightly lower with longer annealing time but still meet the requirements of
the standard, but impact toughness can be clearly increased. Therefore a PWHT of 760C
(1400F) for 4 hours is recommended to ensure good impact toughness.
Figure 2: Comparison of mechanical properties of all weld metal at ambient temperature and
elevated temperatures with PWHT 760C(1400F)/2h and 760C (1400F)/4h of modified P91
flux cored wire
Figure 3 shows the results of equilibrium calculation of the P91 flux cored wire weld metal with
precipitations of M 23 C 6 , MX, Laves phase and Z-phase evolving from MX particles. The phase
fraction at 600C (1112F) is given in table 3. The reduction of Ni has no influence on the
calculated phase fraction of the creep relevant precipitates.
Figure 3: Equilibrium calculation of P91 flux cored wire weld metal with MatCalc
Table 3: Equilibrium phase fraction of creep relevant precipitates at 600C (1112F)
M 23 C 6
2,07
Laves
0,71
Z-Phase
0,49
938
Nb, V (C,N)
-
Figure 4 shows the results of the Matcalc Caculation of the microstructure evolution during multi
layer welding, PWHT and service at 600C (1112F) up to 100,000 h. According to this
calculation MX particles precipitate already during multi layer welding, M 23 C 6 Carbides evolve
during PWHT and Laves phase occurs after few hours of service. The creep relevant precipitates
slightly coarsen during, while the number densitiy decreases. The phase fraction stays nearly
constant. As expected no Z-phase occurs up to 100.000 h.
Figure 4: Calculation of the microstructure evolution during multi layer welding, PWHT and
service of P91 flux cored wire weld metal at 600C (1112F) up to 100,000 h with MatCalc
Providing of creep rupture data which exceed 30,000 h is required for the TV approval. For this
purpose creep rupture tests have been started with the original flux cored wire some years ago. To
prove that the reduction of Ni does not downgrade the creep properties a short term specimen has
been supplemented. Figure 5 shows the creep rupture strength of P91 flux cored wire weld metal
specimens at 600C (1112F) compared to the creep rupture strength of the parent material
according to VdTV data sheet of P91. All ruptured specimens are clearly within the scatterband
of the base material and the last running specimen already exceeded the required running time.
939
Figure 5: Creep rupture tests of P91 flux cored wire weld metal at 600C (1112F)
Matching joint Grade 91
Table 4 shows the welding parameters for a 25 mm Grade 91 butt weld. Root and second pass
have been welded with stick electrode and intermediate and final pass have been performed with
flux cored wire. For FCAW of P91 the recommended heat control during welding and PWHT is
the same as for other welding processes (see Fig. 6). The mechanical properties at ambient
temperature of this matching joint and the microstructure of the weld metal after PWHT of 760C
(1400F)/4h are presented in table 5.
Table 4: Welding parameters for Grade 91 butt weld
second
pass
Thermanit Chromo 9 V
3.2
4.0
root pass
Filler metal
Diameter [mm]
Wire feeding rate [m/min]
Voltage [V]
Current [A]
Preheating/interpass
temperature
Welding position
Shielding gas
Soaking
PWHT
Base metal
23
126
205C
(400F)
23,5
154
PA (G1)
Ar+25%CO 2 , 16 l/min
260C (500F)/4h
760C (1400F)/4h
Grade 91
940
Figure 6: Heat control during welding and PWHT for P91 [3]
Table 5: Mechanical properties of Grade 91 butt weld at ambient temperature and
microstructure of the weld metal after PWHT 760C (1400F)/4h
Y.S. [MPa]
T.S. [MPa]
El. [%]
CVN@RT [J]
Hardness
[HV10]
490
708
32.5
31 (28)
206 - 251
Si
0.2
Cr
9.0
Mo Ni W V Nb
0.5 0.5 1.5 0.2 0.04
N
0.04
The mechanical properties of P92 flux cored wire weld metal are also strongly depending on
PWHT parameters. Figure 7 compares the mechanical properties of all weld metal samples
941
according to AWS A5.36 welded with shielding gas Ar+25% CO 2 at ambient temperature and
elevated temperatures up to 600C (1112F) for a PWHT of 760C(1400F)/2h and 760C
(1400F)/4h. The results are similar to the P91 flux cored wire weld metal. With longer annealing
time tensile properties are slightly lower but impact toughness is clearly improved. So also for the
P92 flux cored wire a PWHT of 760C (1400F)/4h is recommended. Even an annealing
temperature of 770C (1418F) can be considered.
Figure 7: Comparison of mechanical properties of all weld metal at ambient temperature and
elevated temperatures with PWHT 760C(1400F)/2h and 760C (1400F)/4h
Figure 8 shows the results of the equilibrium calculation of the P92 flux cored wire weld metal
with precipitations of M 23 C 6 , MX, Laves phase and Z-phase evolving from MX particles. The
phase fraction of creep relevant precipitates at 600C (1112F) is given in table 7. Compared to
the P91 flux cored wire weld metal the calculated phase fraction of M 23 C 6 and laves phase are
higher for equilibrium conditions at 600C and the amount of Z-phase is slightly lower.
Figure 8: Equilibrium calculation of P92 flux cored wire weld metal with MatCalc
Table 7: Equilibrium phase fraction of creep relevant precipitates at 600C (1112F)
M 23 C 6
2,49
Laves
1,0
Z-Phase
0,45
942
Nb, V (C,N)
-
Also for P92 creep rupture tests have been started some years ago. Figure 9 shows the results at
600C (1112F) up to 30,000h. All specimens are clearly within the -20% scatterband of the base
metal. Compared to the P91 flux cored wire weld metal the creep rupture strength of P92 flux
cored wire weld metal is about 20-30MPa higher.
Figure 9: Creep rupture tests of P92 flux cored wire weld metal at 600C (1112F)
Matching joint Grade 92
Table 8 shows welding parameters for a 20 mm Grade 92 butt weld. Root and second pass have
been TIG welded and intermediate and final pass have been performed with flux cored wire. For
FCAW of P92 heat control during welding and PWHT is the same as for P91 (see Figure 6), only
a higher annealing temperature might be considered. The mechanical properties of this matching
joint are presented in table 9.
Table 8: Welding parameters for Grade 92 butt weld
Filler metal
Diameter [mm]
Wire feeding rate [m/min]
Voltage [V]
Current [A]
Preheating/interpass
temperature
Welding position
Shielding gas
Soaking
PWHT
Base metal
root pass
second pass
Thermanit MTS 616
2.0
11
120
205C
(400F)
12
200
PA (G1)
Ar
943
Ar+25%CO 2 , 16 l/min
260C (500F)/4h
760C (1400F)/4h
Grade 92
Table 9: Mechanical properties at ambien temperature of Grade 92 butt weld and microstructure
of the weld metal after PWHT 760C (1400F)/4h
Y.S. [MPa]
T.S. [MPa]
El. [%]
CVN@RT [J]
Hardness
[HV10]
490
708
32.5
28 (23)
200 - 248
Mn
0.88
Cr
9.20
Mo
1.49
Co
0.98
Ni
0.17
V
0.21
Nb
0.06
N
0.020
B
0.011
In line with the base material development consumable manufacturers started the design of
matching welding consumables for shielded metal arc welding [8, 9]. Due to the fact, that the
importance of FCAW increases, also the development of a matching flux cored wire based on the
slag systems of P91 and P92 flux cored wires has been started. The chemical composition of the
all weld metal was kept close to the chemical composition of the base material. Care was taken by
establishing the Boron content due to the detrimental influence of high Boron contents on hot
cracking susceptibility and impact toughness [10].The actual chemical composition of all weld
metal is shown in table 11.
Table 11:Chemical Composition of CB2 Flux Cored Wire Weld Metal [wt%]
C
0.12
Si
0.2
Mn
0.9
Cr
9.0
Mo
1.5
Co
1.0
944
Ni
0.2
V
0.2
Nb
0.03
N
0.02
B
0.006
Creep rupture tests of cross weld specimens and weld metal at 625C (1157F) with terms up to
6,500h prove that the creep rupture strength of weld metal and cross weld specimens are within
the scatterband of the base material. The terms of the weld metal specimens are longer than the
cross weld specimen runtimes. They fractured in base metal and heat affected zone, respectively
(see Fig. 10).
Figure 10: Creep rupture tests of cross weld specimens and weld metal at 625C (1157F)
Welding Qualification Procedure and first industrial application
Welding is one of the most important steps of the steel casting process and FCAW is one of the
most common welding processes there. For new materials the qualification of the welding process
with appropriate filler metal is required. Therefore welding of CB2 cast components with Bhler
CB 2Ti-FD has been successfully qualified. The requirements of a tensile strength of 600MPa and
a minimum impact energy of 27J are met for base metal, weld metal and heat affected zone and
also the side bend tests are satisfactory. Figure 11 shows the macro sections for the welding in
position PA (1G) and PF (3G). The detailed results of the welding qualification procedure are
given in [11].
Figure 11: Macro sections for welding position PA (1G) right and PF (3G) left, respectively
945
With passing the welding procedure qualification the CB2 flux cored wire can be used for
welding of large scale CB2 cast components. Figure 12 shows an example of an IP inner casing
made of CB2 for service temperatures up to 620C (1148F).
Figure 12: IP inner casing made of CB2 manufactured at voestalpine foundry Linz for advanced
coal-fired steam turbines, approx. 35 to delivery weight
CONCLUSIONS
Flux cord wires for P91 and P92 with rutile slag systems offer good out-of position weldability
and meet the requirements of the standard. The requirement of Mn+Ni<1.0wt% for P91 and
Mn+Ni<1.2wt% for P92 are fulfilled. Creep rupture tests at 600C (1112F) exceeding 30,000h
prove that the creep rupture strength of the flux cored wire weld metal is in the scatterband of the
corresponding base metal. For the new 9Cr-1.5Mo-1Co cast steel CB2 a matching flux cored wire
has been developed and successfully qualified for welding thick section components by the
voestalpine foundries Linz and Traisen, Austria.
ACKNOWLEDGMENTS
The authors want to thank the Austrian Forschungsfrderungsgesellschaft (FFG) for the
financial support based on the contracts no. 821912 and 831995.
946
REFERENCES
[1] Posch, G., Baumgartner, S., Fiedler, M., GMA-Welding of creep resistant steels with flux
cored wires (FCAW): perspectives and limitations, Proceedings of the IIW International
Conference on Advances in Welding and Allied Technologies, Singapore 16-17 July, 2009,
pp.619-624
[2] Kimura, K., Sawada, K., Kushima, H., Toda, Y., Microstructural Stability and Long-term
Creep Strength of Grade 91 Steel, Energy Materials: Materials Science and Engineering for
Energy Systems, Vol. 4, No. 4 , 8th Charles Parsons Turbine Conference 2011, pp. 176-183
[3] Heuser, H., Fuchs, R., Hahn, B., Properties of matching filler metals for T91/P91,
Conference Proceedings: EPRI-RRAC Fifth International Conference on Welding and
Repair Technology for Power Plants, October 2002, 4-1
[4] Sonderegger, B., Charakterisierung der Substruktur in modernen Kraftwerkswerkstoffen
mittels der EBSD Methode, Thesis TU Graz 2005
[5] Abe, F., Alloy design of creep and oxidation resistant 9Cr steels for thick section boiler
components operating at 650C, Advances in Materials Technology for Fossil Power
Plants, Proceedings from the Fourth International Conference, October 2528, 2004, Hilton
Head Island, South Carolina, 2004, pp.202-216
[6] Abe, F., Horiuchi, T., Sawada, K., High-temperature annealing for maximization of
dissolved boron in creep-resistant martensitic 9Cr steel, Materials Science Forum 426-432,
2003, pp. 1393-1398
[7] Staubli, M., Hanus, R., Weber, T., Mayer, K.-H., Kern, T.-U., The European Efforts in
Development of new High Temperature Casing Materials COST536, Materials for
Advanced Power Engineering 2006, Proceedings Part II, pp. 855-870
[8] Braun, E., Cerjak, H., Caminada, St., Jochum, C., Mayr, P., Pasternak, J., Weldability and
Properties of new Creep Resistant Materials for use in Ultra Supercritical coal fired Power
Plants, Materials for Advanced Power Engineering 2006, Proceedings Part II, pp. 871-891
[9] Heuser, H., Jochum, C., Kreuzer-Zagar, D., Development of Matching Filler Metals for
Welding CB2 and first Experience, Proceedings of the 9th Lige Conference: Materials for
Advanced Power Engineering 2010, pp. 506-513
[10] Baumgartner, S., Posch, G., Mayr, P., Welding advanced martensitic creep resistant steels
with Boron containing filler metal, Welding in the World, Vol. 56, No. 7/8 2012, pp. 2-9
[11] Lochbichler, C., Schmidtne-Kelity, E., Baumgartner, S., Latest Developments of Cast
Materials and Welding Consumables for Coal-fired Steam Turbines Components / Nickelbase Alloy A625 and CB2 Steel for the A-USC Technology, Proceedings of PowerGen
2013, Vienna
947
948
INTRODUCTION
The 9%Cr-Mo-Co-B advanced ferritic heat-resistant steels can be used in the casings and valves
for 620 ultra-supercritical power plants due to their high creep strength at elevated temperature
and oxidation resistance [1]. The high creep strength is achieved by a dispersion of fine MX
carbonitrides along with M23C6 carbides which are effectively stabilized by boron [1-3].
However, there are problems of premature failure at welded joints of 9%Cr-Mo-Co-B steels and
failure occurs in the HAZ of the welds [4,5]. The thermal history and consequent morphology of
HAZ welds are extremely complex. Based on the microstructure, HAZ can be categorized as
coarse grain region (CGHAZ), fine grain region (FGHAZ) and intercritical region (ICHAZ)
[6-8].
The mechanisms responsible for failure of 9-12% Cr steels weld joint have been intensively
studied by Abe et al [9-11]. They investigated microstructures and creep strengths of simulated
HAZ specimens and weld joints for 9-12% Cr steels. It was found that failure occured in the
FGHAZ and was referred to as Type IV cracking. They concluded that the sparse M23C6 carbides
along prior austenite grain boundaries (PAGBS) and no lath martensitic distribution degrade the
creep strength of FGHAZ. Increasing soluble boron is proposed to suppress the formation of
FGHAZ, resulting in the removement of Type IV fracture.
In the present work, we made the effort to systematically investigate the creep rupture properties
of welded joints of advanced 9%Cr-Mo-Co-B steels. Microstructure observations have been
carried out for base metal (BM), weld metal (WM) and HAZ by means of optical microscopy,
SEM and TEM. The creep rupture properties and microstructures of welded joints of advanced
9%Cr-Mo-Co-B steels with different boron concentrations have been analyzed.
EXPERIMENT
The 9%Cr-Mo-Co-B steels with different boron concentrations are detailed in Tab. 1. Plates of 20
mm thickness were subjected to heat treatment and the parameters of normalizing and tempering
are shown in Tab. 2. The weldments were fabricated by SMAW using matching electrodes of
MTS 5Co1 and the post-weld heat treatment (PWHT) was applied. A cross-section of the welded
joint is shown in Fig. 1. The results of tensile and impact tests at room temperature are shown in
Tab. 3.
The rod-shaped specimens (6.4 mm in diameter and 25.6 mm gauge length) were used for creep
tests. The cross-weld creep tests were performed at 600~650 with the constant loading stresses
ranging from 100 MPa to 165 MPa. The microstructure of the creep specimens were observed by
optical microscopy, SEM and TEM.
949
Heat No.
Si
Mn
Cr
Mo
Ni
Co
Nb
H1
0.1
0.3
0.66
9.06
1.4
0.35
0.97
0.19
0.054
0.006
0.019
H2
0.11
0.28
0.69
9.23
1.47
0.33
0.98
0.23
0.059
0.009
0.020
Heat No.
Normalizing
Tempering
PWHT
H1
1100/6h
2730/12h
2730/8h
H2
1100/6h
2730/6h
2740/12h
Table 3 Results of cross weld tensile and impact tests at room temperature.
Rp0.2
Rm
El.
Fracture
MPa
MPa
location
H1
552
705
27.5
H2
588
748
19.5
Heat No.
WM
HAZ
BM
44
42
54
BM
33
37
40
950
Microstructures of HAZ
The microstructures of the H1 and H2 steel weld joints before creep are respectively shown in
Fig. 2. The HAZ of H1 steel is composed of CGHAZ, FGHAZ and ICHAZ. The size of the grains
in the FGHAZ is about 6 m (see Fig. 2a), which is much smaller than those in the CGHAZ
(50-60 m). The fine grains nucleate along the PAGBS in the ICHAZ (see Fig. 2b). The size of
the fine grains in the ICHAZ is less than 3 m. Granular bainite has been observed in the ICHAZ
(see Fig. 2e and f), where the lath boundaries disappear and the row of M23C6 carbides shows a
trace of original lath boundaries.
The HAZ of H2 steel welded joint consists of CGHAZ and ICHAZ. The microstructure of
CGHAZ is similar to that of H1 steel. FGHAZ is not found in the HAZ of H2 steel welded joint,
which indicates that the addition of large amount of boron can suppress the formation of FGHAZ.
The fine grains exist along the PAGBS in the ICHAZ (see Fig. 2c and d) and there is no bainite
microstructure in the ICHAZ.
TEM micrographys of ICHAZ in H2 steel are shown Fig. 3. The recovery of lath martensitic
microstructure occurs in some areas (see Fig. 3a and b). The new grain with lower dislocation
density was observed. An equilateral grain marked by the arrow in Fig. 3a with very lower
dislocation density was surrounded by un-equilateral fine substructures. The growth front of new
grain consisting of an arc of circle also been found (see Fig.3b). On the right side of the Fig. 3b, the
lath structures were maintained due to several rows of precipitated particles existing in the
boundary. The lath structure was kept perfectly with high density dislocations in some areas (see
Fig. 3c). It is well known that lath structure, dense dislocation and dispersive precipitated phase are
account for the high creep strength of martensite steels. The results of TEM observation suggest
that nucleation and growth of the new grain along with lower dislocation density degrade the creep
rupture strength of the ICHAZ.
The Vicker-Hardness HV10 measurement at room temperature across the weld joint was
performed after PWHT and the results are presented in Fig. 4. WM hardness are about 240
HV10~255 HV10. WM hardness is about 25 HV10 higher than the BM hardness of H1 steel (see
Fig. 4a). The hardness difference between WM and BM is slight for H2 steel (see Fig. 4b). The
hardness near the fusion boundary is the highest. The minimum hardness was measured in the
ICHAZ for H1 (198 HV10~205 HV10) and H2 steel welded joints (219 HV10~225 HV10).
951
Figure 2 Microstructures of the pre-creep welded joint. (a) and (b) FGHAZ and ICHAZ of H1 steel;
(c) and (d) ICHAZ of H2 steel; (e) and (f) bainite in the ICHAZ of H1 steel.
952
(a)
(b)
Figure 4 Hardness profiles of weld joints. (a) H1 steel weld joint; (b) H2 steel weld joint.
Creep rupture properties and microstructures
The results of creep tests performed on weld joints are shown in Figure 5. It is shown that the
creep rupture strength of H2 steel welded joint is higher than those of H1 steel welded joint. The
fractures occure in the HAZ for the both steel welded joints (see Fig. 6). The microstructures of
weld joints after creep tests are shown in Fig. 7. For H1 steel welded joint, the fracture occurs at
the bainite boundary in the ICHAZ (see Fig. 7a) and is typical of Type IV cracking. Zigzag line
formed by cracks are also found at the fine grain boundaries along PAGBS in ICHAZ (see Fig.
7b). The welded joint of H2 steel is fractured in ICHAZ and the failure is classified as a Type IV
facture. The creep crack and creep voids occur at the fine grain boundary along PABS in ICHAZ,
as shown in Fig. 7c and d.
The creep rupture behaviors of 9-12Cr% steel weldments have been studied by other researchers
[9-15]. They found that the failure generally occurs in the FGHAZ at lower stress. However, the
failure exists in the ICHAZ in our experiments. The hardness HV10 measurement at room
temperature across the weld joint was performed after creep tests and the results are presented in
953
Fig. 8. The lowest hardness was measured at the ICHAZ and the failure was observed at the
lowest hardness zone.
Figure 7 Microstructures of fractures after creep test at 650 and 100 MPa. (a) crack at the bainite
boundary; (b) crack at the fine grains boundary along the PAGBS in ICHAZ (H1 steel); (c) and (d)
zigzag crack at the fine grain boundaries along the PAGBS in ICHAZ (H2 steel).
954
(a)
(b)
Figure 8 Hardness profiles of weld joints after creep tests. (a) H1 steel weld joint; (b) H2 steel weld
joint.
To further investigate the degradation mechanism of ICHAZ, the distribution of precipitates has
been explored using SEM. The microstructures of welded joint for H1 and H2 steels after creep
tests are respectively given in Fig. 9 and 10. For H1 steel, particles mainly form along PAGBS
and at the fine grain boundary along PAGBS (see Fig. 9d and e). The size of precipitates
aggregating at the boundaries of ICHAZ is much larger than those of the FGHAZ, CGHAZ and
BM (see Fig. 9a, b and c). The EDS investigations have been carried out for the precipitates (see
Fig. 11), which shows that the precipitates are mainly M23C6 ((Cr,Mo)23C6) and Laves phase
((Fe,Cr)2Mo). The sizes of Laves phase are much larger than that of M23C6 carbides (see Fig. 9e).
955
Figure 9 SEM microstructures of welded joint for H1 steel after creep tests. (a) BM; (b) CGHAZ; (c)
FGHAZ; (d) and (e) ICHAZ.
Figure 10 SEM microstructures of welded joint for H2 steel after creep tests. (a) BM; (b) CGHAZ;
(c) and (d) ICHAZ.
Figure 11 EDS spectra of precipitates in the ICHAZ (a) Laves phase; (b)M23C6.
The distributions of M23C6 and Laves phase in the welded joints of H2 steel are similar to those
of H1 steel (see Fig. 10). The particles also majorly form along PAGBS and at the fine grain
956
boundaries along PAGBS (see Fig. 10c and d). The size of Laves phase of H2 steel ( about 1 m )
is less than those of H1 steelabout 3 m.
DISCUSSION
Creep voids are mainly observed near the coarse Laves phase in the vicinity of PAGBS (see Fig.
9d and 10c). It is implied that the Laves phase acts as nucleating sites for creep voids. The Laves
phase particles are precipitated during creep deformation because of the grain boundary
segregation of Mo. Laves phase grows at the cost of M23C6 carbides due to the segregation of the
alloying element, which results in the deterioration of strengthening effect of the alloying
elements [14]. Coarse Laves phase can lead to a further decline in the creep strength. With creep
damage accumulation in the ICHAZ, creep voids located closely began to grow, link to each
other and form the micro-crack. The micro-crack can easily connect to form the zigzag
macro-cracks, as shown in Fig. 7.
The granular bainite along the PAGBS in the ICHAZ of H1 steel weld joint forms due to the
segregation of alloying elements. The granular bainite hardness (158 HV10) is the lowest in the
weld joint, indicating the lower strength zone exits in the bainite. During the creep deformation,
the strain concentrates at the bainite boundary. Therefore, the creep voids nucleate easily at the
Laves phase particles in the vicinity of the bainite and fracture usually occurs at the bainite
boundary.
The addition of boron to 90 ppm (H2 steel) suppresses the formations of FGHAZ and bainite. The
grain boundary segregation of boron reduces the grain boundary energy and makes the
boundaries less effective as heterogeneous nucleation sites for austenite grain. On the other hand,
boron suppresses the coarsening of M23C6 carbides and degrades the segregation of alloying
elements [11]. It is assumed that the coarsening rate of the Laves phase is suppressed by boron,
which will be investigated by further work. The creep rupture strength is improved due to the
suppression of the FGHAZ and bainite as well as the reduction of the growth rate of Laves phase.
CONCLUSIONS
The creep rupture properties of welded joints for 9%Cr-Mo-Co-B steels with different boron
concentrations have been investigated. It is interesting to note that fracture appears in the ICHAZ,
which is different from the previous work where facture was found in the FGHAZ. The creep
rupture properties of 9%Cr-Mo-Co-B steels can be improved by increasing the content of boron
to suppress the formation of FGHAZ and bainite as well as decrease the coarsening rate of M23C6
carbides and Laves phase.
957
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[1] A. Pirscher, B. Scarlin and R. Vanstone, Material Development and Mechanical Integrity
Analysis for Advanced Steam Turbines, 5th International Conference on Advances in
Materials Technology for Fossil Plants, Marco Island, FLorida, October. 2007, pp. 338-352.
[2] S. Baumgartner, G. Posch and P. Mayr, Welding Advanced Martensitic Creep-Resistant
Steels with Boron Containing Filler Metal, Welding in the World, Vol. 56, No. 07-08 (2012),
pp. 2-9.
[3] A. Vrostkov, L. Falat, J. Kepic, P. Brziak and J. Pecha, Microstructure and Fracture of 9%
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Radhotm , May. 2010.
[4] D.J. Abson, J.S. Rothwell and B.J. Cane, Advances in Welded Creep Resistant 9-12% Cr
Steels, 5th International Conference on Advances in Materials Technology for Fossil Plants,
Marco Island, FLorida, October. 2007, pp. 790-808.
[5]
P. Mayr and H. Cerjak, The Heat Affected Zone of Boron Alloyed Creep Resistant 9%
Chromium Steels and Their Susceptibility to Type IV Cracking. 5th International Conference
on Advances in Materials Technology for Fossil Plants, Marco Island, FLorida, October.
2007, pp. 914-926.
[6] J.A. Francis, W. Mazu and H.K.D.H. Bhadeshia, Type Fracture in Ferritic Power Plant
Steels, Materials Science and Technology, Vol. 22, No. 12 (2006), pp. 1387-1394.
[7] J.A. Francis, H.K.D.H. Bhadeshia and P.J. Withers Welding Residual Stresses in Ferritic
Power Plant Steels, Materials Science and Technology, Vol. 23, No. 9 (2007), pp.
1009-1018.
[8] R.K Nanstad, D.E, McCabe, M.A. Sokolov, C. A. English and S. R. Ortner, Comparison of
Effects of Thermal Aging on the Propensity for Temper embrittlement on an RPV Submerged
Arc Weld HAZ, ORNL Letter Report, U.S. Nuclear Regulatory Commission Office of
Nuclear Regulatory Research under Interagency Agreement DOE 1886-N695-3W, December.
2001, pp. 3-31.
[9] F. Abe, M. Tabuchi and S. Tsukamoto, Suppression of Type Fracture and Improvement of
Creep Strength of 9Cr Steel Welded Joints by Boron Addition, Pressure Vessels and Piping,
Vol. No. 84 (2007), pp. 44-52.
[10] F. Abe, M. Tabuchi and S. Tsukamoto, Metallurgy of Type Fracture in Advanced Ferritic
Power Plant Steels, Materials At High Temperature, Vol. 28, No. 2 (2011), pp. 85-94.
[11] F. Abe, M. Tabuchi and S. Tsukamoto, Mechanisms for Boron Effect on Microstructure and
Creep Strength of Ferritic Power Plant Steels, Energy Materials, Vol. 4, No. 4 (2012), pp.
166-175.
958
[12] P. Mayr and H. Cerjak, The Impact of Welding on the Creep Properties of Advanced 9-12%
Cr Steels, Transactions of The Indian Institute of Metals, Vol. 63, No. 2-3 (2010), pp.
131-136.
[13] L. Falat, A. Vrostkov, V. Homolov and M. Svoboda, Creep Deformation and Failure of
E911/E911 and P92/P92 Similar Weld-Joints, Engineering Failure Analysis, No. 16 (2009),
pp. 2114-2120.
[14] Lei Zhao, Hongyang Jing, Lianyong Xu, Yongdian Han and Junjie Xiu, Experiment Study on
Creep Damage Evolution Process of Type Cracking in 9Cr-0.5Mo-1.8W-VNb Steel Welded
Joint, Engineering Failure Analysis, No. 19 (2012), pp. 22-31.
[15] S. K. Albert, M. Kondo, M. Tabuchi, F. Yin, K. Sawada and F. Abe, Improving the Creep
Properties of 9Cr-3W-3Co-NbV Steels and Their Weld Joints by the Addition of Boron,
METALLURGICAL AND MATERIAL TRANSACTIONS A, Vol. 36A, (2005), pp. 333-342.
959
ABSTRACT
In order to improve thermal efficiency of fossil-fired power plants through increasing steam
temperature and pressure high strength martensitic 9-12%Cr steels have extensively been used,
and some power plants have experienced creep failure in high temperature welds after several
years operations. The creep failure and degradation in welds of longitudinally seam-welded CrMo steel pipes and Cr-Mo steel tubes of dissimilar metal welded joint after long-term service are
also well known. The creep degradation in welds initiates as creep cavity formation under the
multi-axial stress conditions. For the safety use of high temperature welds in power plant
components, the complete understanding of the creep degradation and establishment of creep life
assessment for the welds is essential. In this paper creep degradation and initiation mechanism in
welds of Cr-Mo steels and high strength martensitic 9-12%Cr steels are reviewed and compared.
And also since the non-destructive creep life assessment techniques for the Type IV creep
degradation and failure in high strength martensitic 9-12%Cr steel welds are not yet practically
established and applied, a candidate way based on the hardness creep life model developed by the
authors would be demonstrated as well as the investigation results on the creep cavity formation
behavior in the welds. Additionally from the aspect of safety issues on welds design an
experimental approach to consider the weld joint influence factors (WJIF) would also be
presented based on the creep rupture data of the large size cross-weld specimens and component
welds.
INTRODUCTION
Since the first practical application of creep strength enhanced ferritic (CSEF) steel, Gr.91 in
1989 in the high energy piping of a thermal power plant, almost quarter of century has elapsed.
Conventionally, Cr-Mo steel such as Gr.22 would have been used in high energy piping and high
temperature tubing. However, some power plants constructed using CSEF steels have
experienced Type IV creep failure in martensitic fine grain heat affected zone (FGHAZ) of high
temperature welds after several year operations. The creep failure and degradation in welds of
conventional Cr-Mo steel pipes and tube after long-term service are also well known as Type III
creep failure in martensitic coarse grain heat affected zone (CGHAZ) of welds. In order to use
any material safely over the long term in a power plant, it is essential to be able to conduct life
and material conditions assessment as required by power plant operators. However, a suitable
creep degradation/life assessment technique and damage detection method have not yet been
developed for CSEF steels due to the complex features of degradation in the martensitic heat
affected zones of welds in comparison with conventional Cr-Mo steels whose CGHAZ also has
similar martensitic structures (Type IIII area). Therefore it is very interesting to understand the
Type IV creep degradation mechanism in martensitic FGHAZ of CSEF steels comparing with the
Type III creep failure in martensitic CGHAZ of conventional Cr-Mo steels in order to establish
960
degradation/life assessment for the welds of CSEF steels. In this study creep degradation and
initiation mechanism in welds of Cr-Mo steels and 9-12%Cr CSEF steels are reviewed and
compared to propose the degradation model in martensitic structures. And also the hardness
creep life model is applied to CSEF steel welds to conservatively assess the creep life.
Additionally from the aspect of safety issues on welds design an experimental approach to
consider the weld joint influence factors (WJIF) would also be discussed based on the creep
rupture data of the large size cross-weld specimens and component welds.
CREEP DEGRADATION IN WELDS
Microstructures and Creep Failure Mode
The conventional Cr-Mo steels are still extensively used in power plant components as welded
construction, and the microstructural phase of Cr-Mo steels varies with heat treatment conditions
however the CSEF steels basically are composed of single phase of martensite for any heat
treatment conditions practically applied. Table 1 shows microstructural phases for Cr-Mo steels
and CSEF steels after post weld heat treatment of sub-critical annealing or normalizing followed
by tempering, and creep failure mode experienced in actual power plant components. The
structural phase of base metal of Cr-Mo steels is ferrite and pearlite due to the normalizing or
annealing at the austenitizing temperature of around 900C. The weld metal and the CGHAZ
transform to martensite structure due to the rapid cooling from the higher temperature above
about 1200C to melting temperature after welding and then tempered by post weld heat treatment
(PWHT) at the sub-critical temperature for the stress relief. The dislocation density of this
martensite is easily reduced by tempering and high temperature service under stress loading to
form ferritic subgrain structures. The FGHAZ and intercritical heat affected zone (ICHAZ) of CrMo steels form the fine grained bainite structure from the recrystallized austenite due to the
relatively rapid cooling at the temperature slightly above Ac3 or intercritical temperature. And
the fine grained bainite changes to very fine ferrite grain and carbide structure after long-term
service at high temperature. On the other hand when normalizing followed by tempering is
applied to all of the welded components as a PWHT, the microstructure of the components
including welds is reset to the base metal structure of ferrite and pearlite. But in the weld metal
somewhat bainite structure is formed in the vicinity of fusion line by the inclusion of austenite
former element of Cu into the weld metal which is used as plating of sub-merged arc filler wire.
In case of CSEF steels tempered martensite structure is seen in any part of welded joint by both of
sub-critical annealing and normalizing followed by tempering due to the good hardenability of 912%Cr steels even under the slower cooling conditions such as air cooling, while the
microstructure of martensite sub-critically PWHTed vary depending on the welding heat cycles,
that is, maximum temperature heated forming the CGHAZ, FGHAZ, ICHAZ and tempered HAZ.
When the entire of the component is renormalized and tempered as PWHT, the microstructure of
any part of welded joint is reset to the almost homogeneous tempered martensite structure of asmanufactured material.
The creep failure modes experienced in the conventional Cr-Mo steels are Type III, Type IV and
fusion line failure. The fusion line failure in the longitudinally seam-welded hot reheat pipe
renormalized and tempered as PWHT is catastrophic and has been experienced at a number of US
power plants. The cause of failure has been investigated and discussed by a number of experts
[1]. The microstructure at the failure location is ferrite and bainite colonies formed in the
961
Table 1: Microstructural phases of Cr-Mo steels and CSEF steels after post weld heat treatment
weld metal slightly inside from fusion line, while the base metal and the weld metal along the
fusion line shows ferrite and bainite/pearlite. And the weld metal contained more bainite structure
which may probably be attributable to different carbon equivalents between both. The weld metal
has higher carbon equivalent than that in the base metal due to the relatively higher content of Mn
and Cu in spite of lower carbon content in the weld metal. Most of the precipitates in the ferrite
are M2C while almost all of precipitates in bainite are M6C. And precipitates along the grain
boundaries are composed of M23C6 and M6C, and the bainite boundaries show more precipitation
of M6C. Sincce it has been reported that the creep cavities formed during creep of Gr.22 with
martensite or bainite structure often nucleate adjacent to the M6C carbide [2]. The creep cavities
are observed at the grain boundaries between bainite and ferrite and within the bainite structure.
Based on the detailed microstructural observation it is speculated that creep cavities in the
bainaite boundaries and within the bainite colonies would be associated with precipitation of fine
MnS in addition to the M6C carbide precipitation [2]. The Type IV failure in Cr-Mo steels is
experienced in the FGHAZ of the longitudinally seam-welded thick section main steam pipe
welds sub-critically PWHTed after relatively long-term service, and appears as sub-surface
cracking in the wall of FGHAZ which is composed of very fine ferrite grains and coarsened
carbide after long term service. The creep cavities in this case are observed at the grain
boundaries between ferrite and carbide, and the macroscopic feature of the failure is the same as
that in the CSEF steels. As mentioned above the Type III failure in Cr-Mo steels is observed in
the martensitic CGHAZ of not only the longitudinal seam welded pipe welds, but also the
circumferential/attachment welds and dissimilar metal tube welds with austenitic steel. The Type
III failure in the martensitic CGHAZ of conventional Cr-Mo steels will be discussed comparing
with Type IV creep failure in the martensitic FGHAZ of CSEF steels in the following sections.
As indicated in the Table 1 the creep failure mode of CSEF steels is limited to the Type IV failure
which is observed only in FGHAZ and ICHAZ of the welds PWHTed at the sub-critical
temperature, but also sometimes in the FGHAZ formed in the weld metal.
Creep Degradation in Martensitic CGHAZ of Cr-Mo Steels
Creep damage in martensitic CGHAZ of Cr-Mo steel is categorized into the Type III failure
which initiates on the component surface area as a nucleation of creep cavity in the grain
boundaries. And the creep cavities are aligned in a direction normal to the primary stress under
not only the pure creep but also creep dominated creep-fatigue conditions. A typical Type III
failure with cavities is shown in Fig. 1, which is observed in the Gr.22 CGHAZ of dissimilar
962
metal weld joint of reheater tube with 304SS using 309SS weld metal. This welded joint (tube
size: 54 mm OD and 5 mm WT) was heat-cycled at 600C with holding time of 18 h for 350
cycles under the 12.7MPa internal pressure in the laboratory. The creep cavities were observed to
be aligned in the prior-austenite grain boundaries. According to the study on the carbide
precipitation behavior in CGHAZ of Cr-Mo steel during creep at the beginning and the first half
of creep life CGHAZ were thought to have contained rod like carbide of M7C3 and M23C6 in the
boundaries of tempered martensite lath, but the long-term service spheroidized the carbides, most
of which were identified to have become M6C carbide [3]. Fig.2 (a) shows scanning electron
micrograph (SEM) and EPMA results which indicate the evidence of the existing of sulfur with
molybdenum from M6C carbide in CGHAZ, and alloying and impurity elements were analyzed in
the region of grain boundaries with or without carbide by energy dispersive X-ray spectrometry as
shown in Fig.2 (b) which indicates that no chemical impurities were detected at the grain
boundary without carbides and the grain boundary with M6C showed the existence of sulfur while
the M6C carbide extracted by replica itself had no sulfur. The SEM structure in Fig.2 also gives
the creep cavitation behavior which is characterized as such as the cavities are always
accompanying with M6C carbide. As shown in Figs.1 and 2 the creep cavities were formed as
brittle manner without any deformation in the CGHAZ due to the multi-axial stress conditions,
and the M6C carbide is assumed to act as the nucleation site of creep cavities because the
segregation of sulfur decreases the interfacial energy between M6C and matrix [2]. Based on
these findings creep failure mechanism in martensitic CGHAZ of Cr-Mo steel under multi-axial
stress conditions is shown in Fig.3 [3].
Figure 1: Typical Type III failure in the Gr.22 CGHAZ of dissimilar metal weld joint with 304SS
using 309SS weld metal
In order to clarify the creep damage progress in martensitic CGHAZ of Cr-Mo steel cross-weld
creep tests using the standard uni-axial creep specimen machined from the wall of the dissimilar
metal welded joint tube of Gr.22/309SS/321SS in such a manner that the CGHAZ in Gr.22 could
be located at the center of the specimen were conducted. The specimens interrupted at the life
fraction of 0.63, 0.70, 0.80 and 0.88 in the creep tests at 600C and 78.4MPa were subjected to
measure the creep cavity number density in the martensitic CGHAZ. In addition to the above
mentioned pure creep test of Gr.22 CGHAZ structure in the dissimilar metal weld joint with
austenitic steel, welds in the wall of large diameter pipe (size: 313.6 mm OD and 26.15 mm WT)
963
made of Gr.22 which is tightly fitted by 304SS pipes to the outside and inside diameters of Gr.22
pipe were subjected at 600C to generate creep dominated creep-fatigue damage under the
constraint of strain due to the thermal stress caused by the thermal expansion difference between
both steels [4]. During the cyclic heating test until the occurrence of macro-cracks (1.0 of life
fraction) in CGHAZ of Gr.22 weld the cavity number density was measured in terms of the
number of cycles. Fig. 4 shows the relationship between the cavity number density and the life
fraction of pure creep or creep dominated creep-fatigue. The cavity number density in the
martensitic CGHAZ of Cr-Mo steel (Gr.22) increases with life fraction. The cavity generates
earlier in the creep-fatigue test than the creep test, but the number density in the creep test
significantly increases at the end of life.
Figure 3: Creep failure mechanism in martensitic CGHAZ of Cr-Mo steels under multi-axial
conditions
964
Figure 4: relationship between the cavity number density and life fraction in CGHAZ of Cr-Mo
steel (Gr.22)
Creep Degradation in Martensitic CSEF Steels
In the cross-weld creep rupture tests of CSEF steels using matching or overmatching filler metal
the location of failure is always seen in FGHAZ or ICHAZ of welds (Type IV failure) when tests
are performed under the condition of stress below the line from the point of 175MPa at 600C to
that of 125MPa at 650C [5]. That is, the Type IV failure in the CSEF steels takes place at higher
temperature and lower stress. Fig.5 shows sectional macrostructures of cross-weld creep rupture
specimens from the Gr.92 GTAW welded joint tested at the stresses of 70MPa, 100MPa and
125MPa at 650C. The Type IV failure is observed at these test conditions, however the rupture
ductility and the cavity formation differ at the stress conditions. At the higher stresses rupture
ductility becomes larger and the creep cavities number density is seemed to be smaller while the
specimen tested at the lower stress of 70MPa ruptured in brittle manner and cavity number density
is larger, and also the cavity size is smaller than that found in the specimens tested at higher stress
conditions. Fig.6 shows the sectional microstructures at the depth of 4 mm from the outer surface
of Gr.91 large-size cross-weld specimen ruptured at 5071 h at 650C and 57MPa. Rupture
occurred as typical Type IV failure in the FGHAZ. According to the results of the dimensional
measurement of the test specimen after rupture, overall, the cross-section maintained a regular
shape of 29.50.1 mm, and contraction of over 1 mm was seen only in the immediate rupture
vicinity, which was thought to have occurred at the time of rupture [5]. The test specimen after
rupture indicated that only the four outer surface layers were deformed. It can be seen that the
rupture here was ductile, and that the location shown was that of final rupture. From the figure, it
was thought that creep damage occurred internally, and the fracture surface runs along the weld
bead, corresponding to the FGHAZ with numerous creep cavities inside, indicating this to be the
point of initiation. Creep cavities at the rupture location grew to the size of the grains of the
martensite lath, and the shape is horned and irregular, while the cavities at the opposite side of the
heat affected zone appear to be round and growing towards shape seen at the rupture location.
F i g . 7 s h o ws a s c h e ma t i c i l l u s t r a t i o n o f t h e ma r t e n s i t i c s t r u c t u r e and str ess
965
Figure 5: Sectional macrostructures of cross-weld creep rupture specimens from Gr.92 GTAW
welded joint showing rupture ductility and creep cavitation
martensite lath become unstable to reduce the dislocation density due to the growth of M23C6
which is the only carbide observed in CSEF steels beside the MX carbonitride, Laves phase and Z
phase. The relationship between the maximum cavity number density in the FGHAZ and the life
fraction of the Gr.122 cross-weld large specimen was measured. Fig. 8 shows that creep cavities
start to form in the FGHAZ and ICHAZ at approximately 0.5 of life fraction while there are only
a few creep cavities observed in the CGHAZ and base metal until creep rupture, and the cavity
number density in the FGHAZ increases with creep life fraction [5]. The behavior of increasing
cavity number densities measured on the top and side of welds are different, and this must
originates in the small differences of stress distribution along the wall of welded joint.
Figure 7: Schematic illustration of creep degradation model for FGHAZ of CSEF steels
Figure 8: Relationship between creep cavity number density and creep life fraction of Gr. 122
large-size cross-weld specimen
967
Figure 9: Creep cavity morphology and cavity number density in X-groove welds of component
Figure 10: Hardness distribution in the X-groove welds of component ruptured at 650C and 66MPa of
hoop stress
968
It has already been reported that hardness measurement for Gr.91 base metal is a highly useful
technique for assessing the material conditions and creep life [6] and the hardness creep life
model has been proposed by an author of this paper [7]. And it is known that hardness
measurement of welds cannot be applied in the context of material condition or life assessment,
because the damaged area is in the very narrow soft zone (FGHAZ) as mentioned above, making
it difficult to distinguish the changes in hardness. It is comparatively easy to detect changes in the
hardness distribution for such welds, but it is difficult to detect and track changes in hardness at
specific locations, and a method is needed for life assessment technique based on these data.
Fig.11 shows the hardness ratio is shown as being linear against the creep life fraction for Gr.91
base metal and welds. However the hardness of the ruptured specimens is widely scattered
depending on the initial applied stress, excepting the welds, the hardness ratio can be expressed as
H/Ho = 0.98-0.15t/tR, where t/tR is creep life fraction. The minimum hardness in welds enabled
reliable creep life assessment regardless of the relatively small amount of hardness data due to
very narrow area of the heat affected zone. This fact suggests that if the minimum value is
determined using the limited measured data obtained from the welded joint of Gr.91 steel, the
maximum creep life fraction in the component can be accurately predicted [8]. As indicated
Figs.9 and 10, hardness measurement at a load of 9.8MPa was performed to collect data using the
welds in the hot reheat pipe component test rig [5]. Fig.12 shows the hardness distribution
measured along the five lines in the welds indicated in the figure, which traverse from weld metal
to base metal toward both side of large size cross-weld specimen. The data points measured were
then used for the analysis to predict the minimum value in the welds for conservative life
assessment of welded joint. The statistical procedure based on extreme value analysis to
determine the minimum hardness value is used as a double exponential distribution analysis. In
this process return period, T = S/s was defined as with S as the maximum number of penetration
depth points theoretically measurable in the soft zone, and with s as the number of data points
used. Fig.13 shows the relationship between hardness and reduced variate as a double
exponential plot. The data measured are plotted in good agreement with the line, showing that the
assumption in this probabilistic estimation is reliable, with the minimum hardness value predicted
as approximately 5 to 15 in HV lower than the minimum value measured. Therefore it is
recommended to use the predicted minimum hardness by the statistic procedure in order to
conservatively assess the creep life of CSEF steel welds.
Figure 11: Relationship between hardness ratio and creep life fraction for Gr.91 base metal and
welds creep tested at various conditions
969
Figure 12: Hardness traverse measured in the X-groove welds of Gr.91 along the five lines in the
wall from weld metal to base metal toward both side
Figure 13 Relationship between hardness and reduced variate as a double exponential plot to
estimate the minimum hardness in the welds
EFFECT OF WELD CONFIGURATION AND COMPONENT STRUCTURE ON LIFE
In addition to the internal pressure creep rupture tests using clam shell type seam-welded pipe
mentioned in the previous section the large-size cross-weld creep rupture tests were conducted for
the specimens with X- and U-grooves having 40 mm by 32 mm cross-sections at 650C and
66MPa [5]. The test results are listed in Table 2. The rupture locations were all in the FGHAZ,
and rupture times were longer in the uniaxial specimen and U-groove type cases. In the seam970
welded pipe internal pressure creep rupture tests, the rupture location was intrados of elbow.
These data can be used to know the effect of welding groove configuration in the uniaxial crossweld specimen and internal pressure component and Larson-Miller parameter (LMP) constants
(the best fit value for all data and the conservative value) on the creep life, which may be an
experimental approach to consider the weld joint influence factors (WJIF). The estimated
equivalent stress to cause the rupture and the predicted rupture time at 600C affected by welding
groove configuration, construction and LMP constants are summarized as follows,
Stress estimated:
X-groove = 1.05 x U-groove in the uniaxial cross-weld specimen
X-groove = 1.03 x U-groove in the internal pressure component
Internal pressure component = 1.1 x uniaxial cross-weld specimen (LMP constant = 31)
Internal pressure component = 1.2 x uniaxial cross-weld specimen (LMP constant = 20)
Rupture time at 600C predicted:
X-groove = 0.73 x U-groove in the uniaxial cross-weld specimen
X-groove = 0.85 x U-groove in the internal pressure component
Internal pressure component = 0.45 x uniaxial cross-weld specimen (LMP constant = 31)
Internal pressure component = 0.37 x uniaxial cross-weld specimen (LMP constant = 20)
Effect of LMP constant on rupture time:
Constant of 20 = 0.1 to 0.2 x Constant of 31
Although the effect of LMP constant is significant, the equivalent stress is increased by the Xgroove configuration, but the effect of the component construction on the stress increase is
approximately 20% larger than the groove configuration effect (at the intradose of elbow) to cause
the rupture. The hoop stress for the internal pressure test was 66MPa at 650C which was the
design stress for the base metal. This stress predicted the approximate rupture time of 400,000 h
(LMP constant: 20) for base metal at 600C, while the rupture time of the seam-welded
component at 600C and estimated stress of 72MPa was approximately 20,000 h (LMP constant:
20). If the WJIF is defined by the ratio of rupture time of welded component to that of base metal
component, the WJIF in this case is about 0.05. If the WJIF is defined as the ratio of the stress
that gives the same rupture time, the WJIF is approximately 0.6.
Table 2: Results of large-size cross weld creep tests and internal pressure creep tests of
longitudinally seam-welded pipe component made of Gr.91
971
CONCLUSIONS
The microstructures and failure modes in the post-weld heat treated welds (from weld metal to
base metal) of Cr-Mo steels and CSEF steels were classified and compared, and it was found that
Cr-Mo steels had a variety of microstructures depending on the maximum temperature heated
while the CSEF steels had the only tempered martensite structure which was creep-damaged by
the only Type IV failure. The creep degradation mechanism and the cavity initiation model for
the martensitic CGHAZ of Cr-Mo steels and martensitic FGHAZ of CSEF steels were proposed.
The creep softening of CSEF steels was a good index to assess the creep life by the proposed
hardness creep life model, and statistic procedure to estimate the minimum hardness value in the
welds which might give the conservative creep life prediction. Finally based on the creep data
obtained from the cross-weld creep tests and internal pressure creep tests of longitudinally seamwelded component the effect of welding groove configuration and component construction on the
creep life was discussed to consider the WJIF as an experimental approach.
REFERENCES
[1] Henry, J. F., Zhou, C. and Ward, C. T., Seam-Welded Steamline Piping: An Industry
Alvatross, Proc. EPRI/DOE Conference on Advances in Life Assessment and Optimization
on Fossil Power Plants, Orlando, FL., March, 2002
[2] Masuyama, F., Nishimura, N. and Takeda, Y., Carbide Changes and Sulphur Segregation in
Cr-Mo Steel during Creep, High Temperature Technology, Vol.8, No.4 (1990), pp. 257-260
[3] Masuyama, F., Life Assessment and Extension of Welded Structures for High Temperature
Components, Extending the Life of Welded Structures, Welding in the World, Vol. 32,
Pergamon Press, (Oxford, UK., 1993), pp. 51-64
[4] Masuyama, F., Nishimura, N. and Igari, T., Creep Damage Simulation Test and Creep Life
Assessment System for Elevated temperature Plant Components, ISIJ International, Vol. 30,
No.10 (1999), pp. 885-894
[5] Masuyama, F., Effect of Specimen Size and Shape on Creep Rupture Behavior of Creep
Strength Enhanced Ferritic Steel Welds, Int. J. PVP, Vol. 87, (2010), pp. 617-623
[6] Masuyama, F., Fujita, M. Maruyama, M. and Endo, M., Development of Creep Life
Assessment Technology for Mod. 9Cr-1Mo Steel, Proc. EPRI/DOE Conference on Advances
in Life Assessment and Optimization on Fossil Power Plants, Orlando, FL., March, 2002
[7] Masuyama, F., Hardness Model for Creep Life Assessment of High Strength Martensitic
Steels, Materials Science and Technology A, Vol. 510-511, (2009), pp. 154-157
[8] Masuyama, F., Creep Degradation in Welds of Mod. 9Cr-1Mo Steel, Int. J. PVP, Vo.83,
(2006), pp. 819-825
972
ABSTRACT
Qualifying welding procedures for repair of components in high temperature service requires
careful consideration of factors including identification of the materials involved, existing
mechanical properties and service operating parameters such as temperature, pressure and
environment. Selection of weld metals to match, under match or overmatch base material as well
as direct and indirect consequences on the heat-affected zone also require evaluation.
Application of post weld heat treatment and ramifications where dissimilar base materials are
involved are discussed plus the necessity of conducting tests at the operating temperatures and
conditions where information is not available from the literature. Each of these factors is
discussed and examples provided.
INTRODUCTION
Many factors enter into the qualification of welding procedures for high temperature service
(1000-15000F [538-8160C]). Welding procedures or weld filler metal chemical compositions
chosen for original fabrication and installation were usually selected to provide a deposit with
overmatching properties to compensate for dilution with the base metal. This may not always be
the case for repairs, since existing system materials, although providing adequate service, may
not be in their originally installed condition. Thus, alternate weld material choices may be
necessary to consider. This is especially true for temper bead type repairs that are conducted
without subsequent high temperature post weld heat treatments. HAZ concerns, however, can
only be addressed through control of the welding process and technique.
Welding procedure qualifications tested at room temperature with traditional tensile and bend
tests may not be adequate to assess high temperature behavior, especially dissimilar welds that
will experience cyclic loading.
BASE METALS
It is fundamentally important to know the composition and status of the existing base metals and
weldment. Knowledge of the operational history can offer clues to whether the material(s) has
been degraded in service or may have near original mechanical properties. Toughness usually is
not an issue for materials used in elevated temperature service, other than for start-up shut-down
concerns. However, corrosion of existing materials can severely affect wall thickness and can
prompt complete replacement of the materials involved. Several vendors offer portable devices
for nondestructively determining basic chemical composition while the best method is still
removal of actual material and subjecting to laboratory analysis.
973
WELD METALS
Weld metals are typically chosen to provide compatible as-welded chemistry and mechanical
properties. Within this criteria, weldments generally exhibit acceptable in service performance.
Matching strength properties can be obtained on low carbon steel materials via weld metal
selection or the application of post weld heat treatment. Post weld heat treatment is almost
always used to achieve properties on low alloy steel components.
Corrosion and oxidation characteristics of the base materials may also influence selection. Where
hardness in ferritic materials is of concern, weld metal with lower carbon levels and the lowest
tendency to harden upon cooling that meets all other requirements is normally selected. If high
temperature creep is a major consideration, then compromise may be required and minimum
carbon levels could be of significance.
Weld filler metals specified for use during new construction may not be the best choice for repair
applications. Service conditions such as high temperature operation may actually reduce the
properties of the base metals and weldment over extended periods of time. Most filler metals
within a given classification are formulated to exhibit minimum specified strength levels, even
after post weld heat treatment in many cases. When used in the as-welded condition, elevated
strength is typically observed. Some compositions may also result in as-welded deposits of
increased hardness. These factors become particularly important for repair applications where
traditional post weld heat treatments will not be employed on dissimilar weldment applications.
Weld filler metal options are shown in Table 1.
WELDMENTS & HAZ CONSIDERATIONS
The location of the failure or repair base metal, weld metal or heat-affected zone (HAZ)
should be determined. This will likely influence weld metal selection or choice of alternate
material where complete replacement is warranted. Behavior in prior service should be examined
to determine if the cause of the repair was due to inadequate creep strength or ductility.
Significant data from cross-weld creep tests is typically available. Less information is recorded
for all-weld-metal creep testing.
A transition of properties from base metals through the weld metal, whether in a similar or
dissimilar metal situation, is optimum. Superior weld metal strength with lower creep ductility
will only tend to force any problems into the HAZ or base materials. Two examples include the
soft zone (Type IV region) in creep strength-enhanced ferritic (CSEF) steels such as Grade 91;
or, 347H weld metal that strengthens with time and cracking in the HAZ is observed.
There is no matching alternate weld filler metal for joining Grade 91 that offers satisfactory
performance yet has a lower strength level matching the soft zone. However, the 16-8-2 alloy
family of filler metals have been effective in eliminating HAZ cracking issues in 347H base
materials.
974
Table 1
Welding Filler Metal Selection Table (Preferred filler metal is listed first) [1-4 ]
Grade
11
2
22
23
91
911
2
92
2
SS1
11
B2
B2, B3
B2
B2, B3
B2
22
B2
B35
B3,G(23)
B3,B9
B3,G(911)
B3,B9
P87,Ni
23
B2
B3,G(23)6
G(23)
G(23),B9
G(23),G(911)
G(23),B9
P87,Ni
91
B2
B3,B9
G(23),B97
B9
B9,G(911)
B9,G(92)
P87,Ni
911
B2
B3,G(911)
G(23),G(911)
B9,G(911)
G(911)
G(911),G(92)
P87,Ni
92
B2
B3,G(92)
G(23),B9,G(92)
B9,G(92)
G(911),G(92)
G(92)
P87,Ni
SS1
P873,Ni4
P87,Ni
P87,Ni
P87,Ni
P87,Ni
P87,Ni
SS
B2
P87,Ni
SS = Stainless Steel
B2 = 1.25Cr-0.5Mo
3
P87 = EPRI P87
4
Ni = ENiCrFe-2 or 3, ERNiCr-3
5
B3 = 2.25Cr-1.0Mo
6
G = Nonstandard composition. The desired grade is noted in parenthesis for each G
specification.
7
B9 = 9.0Cr-1.0Mo-V
2
975
Further, local thermal expansion mismatch may result in stress/strain conditions that are only
partially active in laboratory specimens made from sections of a complete pipe girth weld. Local
geometric features near the root of a dissimilar metal weld (DMW) girth weld can exhibit very
high local sustained load stress concentration factors leading to formation of shallow cracking at
the weld roots very early in life. Such geometric factors are typically not considered in laboratory
or traditional welding procedure qualification tests. Laboratory tests are normally static loaded
tests and do not consider the very complex cyclic and time dependent loading events that weld in
service may experience.
976
Differences in Strength
Large differences in strength between a low alloy steel, austenitic stainless steel and various
CSEF steels can be seen in terms of allowable stress and creep strength. Although the increase in
strength or CSEF steels creates a dramatic advantage in using these materials in design and
construction, it creates added complexity when choosing the correct filler material for a given
dissimilar metal weld. When a low alloy steel is welded to a CSEF steel or a CSEF steel is
welded to a stainless steel, the difference in creep strength of the alloys can cause stress to be
concentrated in the weaker component. In situations where one component might be in a creep
regime and the opposite component is not, this concentration could be especially damaging if the
proper filler material is not selected. The improper use of too strong a filler metal to join weaker
parent materials will cause the concentration of strain in the base metal. In the case of the weaker
base material being a CSEF steel, the difference in strength is highly related to the grain size and
therefore localized damage can be expected to occur in the fine grained heat-affected zone
(FGHAZ) or coarse grained heat-affected zone (CGCHAZ) of the weaker base material. The
ultimate result will be an unintentional and accelerated failure due to Type IV cracking.
Filler Metal Selection in Thick-section DMWs of Different Thicknesses
Transitions between conventional ferritic or stainless steels and CSEF steels can be made in
several ways. Outlining the proper approach to a transition between a CSEF steel and another
alloy is critical. An example were a transition was not properly planned was the welding of a
Grade 91 pipe (1.5in thick, 38mm) to a heavier wall thickness 1.25Cr-0.5MoV valve (3.0in,
76mm) with E9018-B3 (Grade 22) weld metal, as shown in Figure 2. Cracking developed in this
transition joint following less than 5,000 hours of operation, as shown in Figure 3. It was
determined that the combination of the E9018-B3 weld metal operating in its creep regime (the
Grade 91 pipe was not) and the formation of a carbon depleted zone in the E9018-B3 weld metal
adjacent to the fusion line caused the distinctive cracking, which was concentrated in the weld
metal along the fusion line. [5-6]
Figure 2.
1.5in. thick P91 pipe to 3in. thick 1-1/4Cr1MoV Valve Body Welded with E9018-B3. [5-6]
977
Figure 3. Cracking Observed in the carbon denuded zone at the P91 base metal [5-6]
The options for making welds between thick-section CSEF steels and low alloy steels (i.e. Grade
22) are described in Table 2. These examples are especially important as the welding or repair of
thick-section CSEF steels to low alloy grades typically involves a large change in thickness:
Typical DMW combinations and corresponding approaches are presented in Tables 1 and 2.
Weld filler metal selection possibilities for DMWs are shown in Table 1. Recommended PWHT
temperatures are included in Table 2. In most cases, use of the lower strength weld metal is
recommended. The temperatures shown, particularly where B9 weld metal is involved, are
selected to provide proper tempering of the weld metal. These temperatures may not necessarily
coincide with traditional code values and may require specific knowledge of the lower critical
transformation temperatures (A1) or special properties of the materials involved and additional
welding procedure qualifications.
DISCUSSION
In most cases, a variety of weld filler metal options exist within any alloy category and the actual
choice will be dependent on specific performance and ability-to-weld factors. Use of
conventional, off-the-shelf material manufactured to existing standards may be appropriate, or
special non-standard or proprietary filler metals may provide superior results. These factors as
well as availability of the chosen material affect selection decisions.
For example, if temperature and notch toughness are not major considerations, adequate strength
levels can usually be obtained by selecting weld metal with a strength level equal to or one
classification (10 ksi) less than matching weld metal (See Table 3). Some code restrictions may
apply, but latitude can generally be used for repairs via special procedure qualifications,
consideration of the repair as a partial joint penetration situation or by use of finite element
analysis techniques for identification of actual stress levels.
978
Table 2.
Recommended PWHT Temperatures (0F) for Dissimilar Welds and Repairs. [1-4]
Grade
11
22
23
11
1250+25F
1250+25F
1250+25F
22
1250+25F
1350+25F
23
Butter 11
1250+25F
91
911
92
SS
Butter 91
1325+25F;
1250+25F
Butter 911
1375+25F;
1250+25F
Butter 92
1375+25F;
1250+25F
Butter 11
(opt)
1250+25F
91
Butter 91
1325+25F;
1250+25F
911
Butter 911
1375+25F;
1250+25F
92
Butter 92
1375+25F;
1250+25F
SS
Butter 11
(opt)
1250+25F
Butter (opt)
1350+25F
1350+25F
1325+25F
1375+25F
1375+25F
1350+25F
1350+25F
1375+25F
1375+25F
1375+25F
(Note 8)
None
1325+25F
1375+25F
1400+25F
1375+25F
(Note 8)
1375+25F
(Note 8)
1375+25F
1375+25F
1375+25F
(Note 8)
1375+25F
1375+25F
(Note 8)
Butter 91
1375+25F
Butter 911
1375+25F
137525F
1375+25F
Butter 92
1375+25F
None
1375+25F
(Note 8)
Butter 911
1375+25F
1375+25F
Butter (opt)
1350+25F
1375+25F
(Note 8)
Butter 91
1375+25F
Butter 92
1375+25F
None
Notes:
1. The recommendations in the above table were developed from References 1-5.
2. The objective in dissimilar welding is to maintain properties while addressing
differences in the respective base metals, HAZs and PWHT temperatures. See
Table 2 for weld metals.
3. Buttering and multi-step PWHT is used where PWHT required for one base metal,
HAZ or weld metal is excessive for one or more of the others.
4. Where Butter is shown, Butter the indicated base metal, perform PWHT of the
butter at the temperature listed, then join the other material to the butter and perform
PWHT of the completed weldment at the second temperature.
5. T23 has shown tendencies toward reheat cracking from PWHT. This alloy was
originally designed to be used without PWHT. Thus, buttering may be required.
6. T23 should NOT undergo PWHT subsequent to bending operations or significant
loss in creep strength may result.
7. T24 typically does not require PWHT. Thus, buttering may be required.
8. Caution must be observed when selecting PWHT temperatures that will not
encroach on the AC1 of the lower temperature material.
9. Where B9 weld metal is used for buttering or joining, 1400+25F (7600C + 150C) is
the optimum heat treatment temperature, provided the AC1 is not exceeded.
The major differences between selected filler metal specification/classification minimum strength
requirements, typical as-welded results plus typical all weld metal properties in the stress relieved
condition are illustrated in Table 3. As alloy content increases, actual deposited properties also
increase. Of particular interest are the low alloy materials (E7018-A1, E8018-B2, E9018-B3,
ER80S-D2, ER80S-G( SGMo; DIN 8575; Wks. No. 1.5424), E9018-B3, ER90S-B3 and E9015B9. The elevated strength levels of these materials in the as-welded condition are representative
of what would exist in a temper bead or other repair scheme that would not see a subsequent post
weld heat treat.
979
Table 3.
Comparison of Selected All Weld Metal Specification Requirements with Typical As-Welded and
Stress Relieved Strength Properties [10-12]
Filler Metal
Specification
Requirements, ksi
Typical
As-Welded, ksi
Typical
Stress Relieved, ksi
Ultimate
Yield
Ultimate
Yield
Ultimate
Yield
E6013
62
50
74
64
E6018
67
55
68
57
E7018
72
60
87
79
831
741
E7018-A1
701
571
90
71
841
701
E8018-B2
802
682
118
103
951
791
E9018-B3
90
77
E9015-B9
90
77
ER70S-2
70
58
74
ER70S-6
72
60
946
ER80S-D2
80
68
ER80S-G
803
683
ER90S-B3
90
78
101
871
120
1005
60
756
851,6
711,6
110
79
1002
862
92
79
902
722
141
210
127
-
104
932
Stress Relieved @ 1150F for 1 Hour. 2 Stress Relieved @ 1275F for 1 Hour.
SGMo; DIN 8575, Wks. No. 1.5424 4 Stress Relieved @ 1375F for 1 Hour.
5
Stress Relieved @ 1400F for 1 Hour 6 GTAW Process
3
The typical values shown also suggest why test coupons and evaluations rarely fail in the weld
metal, except where truly matching base metals are involved or workmanship problems are
identified (slag, lack of fusion, etc.). Also, the chromium bearing filler metals (E8018-B2,
E9018-B3, ER80S-D2, ER90S-B3, etc.) do experience varying levels of air hardening in the aswelded condition that contribute to the higher observed strengths but also can result in single
digit elongation percentages. Such low ductility is not normally identified with these weld metals
because, as previously mentioned, fracture or failure generally occurs in the base metal or heataffected zone and those results are reported. Where tensile, toughness or creep rupture tests are
conducted on all weld metal samples, potential strength/ductility problems are normally
identified. Bend tests also provide go/no-go information, but can be misleading where code
acceptable indications that initiate from the edges are not carefully evaluated.
Even after traditional post weld heat or tempering treatments the weld metals exhibit significantly
greater yield strength, thus potentially forcing service induced failures into the heat-affected zone
or base metal. Given these as-welded or even post weld heat treated strength levels, use of a
carefully chosen under matching classification may be necessary to obtain weld metal
properties that match the base materials. The effects of overall restraint and adequate low
hydrogen controls must be observed plus other factors such as potential time at temperature from
subsequent heat treatments of other areas of the component, creep resistance, or corrosion
concerns must be considered. It is very important, from an overall repair filler metal selection
standpoint, to consider whether the strength and ductility of the weld metal has contributed to the
failure, has had little or no consequence, or may contribute to a future problem. [7-8]
Further review of Table 3 and consideration of an under matching approach suggests that many
980
temper bead-type repairs on the 80 ksi family of base metals may be able to be conducted with
70-series weld filler metals. Also, where repair cavities are minimal, very low strength weld
metals can provide adequate strength by minimizing preheat and taking advantage of fast cooling
rates, dilution with the higher strength base material(s) plus cavity aspect ratio advantages. [9]
Lower strength, more ductile weld metals can also be very useful in high restraint situations,
where distortion must be minimized, or when crack sensitive base metals are involved.
CONCLUSIONS
It is important to know the composition and status of the existing base metals, weldment and
operational history, if possible. For many repairs and even new construction, weld filler metal
properties should be chosen to match existing components or base material. This is especially
true where repairs to weldments that typically receive post weld heat treatment will be repaired
and remain in the as-welded condition. Factors including strength level, hardness, toughness and
creep resistance can all be addressed through careful selection of weld filler metal. In many
cases, selection of under matching weld filler metal may provide equivalent properties and
eliminate cracking tendencies or other problems associated when an overmatched condition
exists. Care must be observed to properly evaluate the effects and implementation of post weld
heat treatment as well as the fact that code rules for room temperature testing of welding
procedure qualifications may not be representative of actual service conditions.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
Fabrication and Installation Guideline for Fossil Power Plants. EPRI, Palo Alto, CA:
2010. 1017619.
Welding Filler Metals for Power Plant Engineering, 2008. Germany: Bohler
Schweisstechnik Deutschland GmbH.
Auerkari, P., Hakkila, J., Holmstrom, S., Nevasmaa, P., Rantala, J., and Salonen, J.
Creep Performance of Welded Pipe Material Made of 7CrMoVTiB10-10 (T/P24)
Steel. 9th Liege Conference: Materials for Advanced Power Engineering, September
27-29, 2010, Liege, Belgium. Forschungszentrum Julich GmbH, Germany: 2010, pp.
221-228.
Performance Review of P/T91 Steels. EPRI, Palo Alto, CA: 2002. 1004516.
Evaluation of Filler Materials for Transition Weld Joints Between Grade 91 to Grade 22
Components. EPRI, Palo Alto, CA: 2005. 1009758.
Henry, J., Investigation of a Leak in a Main Steamline Piping Joint: Causes and
Implications, Euroweld Conference, June 21-23, Columbus, Ohio
Imazato, T. and Komai, N. Effect of Tempering Times on Creep Strength in ASME
Gr.23 (2.25Cr-1.6W) Steel. Proceedings of the International Scientific Conference
Materials for Advanced Power Engineering, 2006, Liege, Belgium. Forschungszentrum
Julich GmbH, Germany: 20060, pp. 997-1009.
Allen, D. J., Brett, S. J., Buchanan, L. W., and Degnan, C. C. Influence of Weld
Structure on Cross-weld Creep Behavior in P23 Steel. 9th Liege Conference: Materials
for Advanced Power Engineering, September 27-29, 2010, Liege, Belgium.
Forschungszentrum Julich GmbH, Germany: 2010, pp. 500-513.
Patchett, B.M. and Bicknell, A.C.; Welding Engineering Report, Narrow Gap
Understrength Weld Metal, University of Alberta, Canada1995.
Project Files; W. F. Newell, Jr., PE; W. F. Newell & Associates, Inc., Mooresville, NC.
Correspondence: Bekkers, K.; Lincoln Smitweld (Ref. B7128KB/SP/TS) February 1996.
Correspondence: Dr. S. Dittrich; Thyssen Schweitechnik GmbH (Russia, et al)
981
units. Influence of trace yttrium on high and low temperature properties of 9Cr-1Mo steel have
been studied.
1 Experiment
1.1 Effect of different content yttrium element on the mechanical deposit metal of
9Cr1Mo steel
Electrode coating transition method has been applied to add certain amount of yttrium element
into the weld metal of 9Cr1Mo steel. Basic low hydrogen electrode coating and electrode has
been designed and prepared with different amount of yttrium oxidation.
The base metal of the test plate is 16Mn with the dimension 30010020mm,45O and V type
groove. A buffering layer has been welded on the groove before formal depositing The thickness
of buffering layer is not less than 3mm. The welding specification for the deposition layer is as
following: preheat treatment, small heat input , thin weld and low swing.
The ambient temperature for welding is 20. The electrode has been preheated for 1h under
350. The deposited weld metal is air cooled to 80 after welding and kept warm for 2hrs till
the structure of the deposited weld metal have been completely transferred into martensite.
Different yttrium content has been added into the coating and the tensile strength, percentage
elongation after fracture and impact toughness. The optimized yttrium could be determined based
on the test result.
1.2 Effect of optimized yttrium on phase transition point and diffusion hydrogen
content
1.3
Based on the optimized yttrium, comparison test has been performed between optimized yttrium
and commercial electrode B9015.
Mercury method has been used for the determination of diffusion hydrogen according to GB/T
3965-1995Methods for determination of diffusible hydrogen in deposited metal.
Phase transition points of deposited metal of optimized yttrium and E9015 have been measured by
differential scanning calorimetry with DSC 404C.
1.3 Properties test for weld joint with optimized yttrium
The composition and micro-structure between actual P91 welded metal and deposited metal are
different due to dilution transition. P91 pipe with 273mm25mm are welded with butt joint by
both commercial electrode and with adding optimized yttrium. The effect of optimized yttrium
has been studied by high temperature tensile, Charpy impact test, hardness test, SEM and XRD
analysis.
2 Results and Discussion
2.1 The definition of Relative Ratio of Yttrium
An index Relative Ratio of Yttrium (RRY) has been used to simplify the analysis. The definition
of RRY is the ratio between the weight percentage of yttrium in the coating of electrode. A basic
weight percentage of yttrium in the coating of electrode is 0.750%. That is if RRY is 1.0. So if
983
RRY is 1.5, the weight percentage of yttrium in the coating will be 1.125%, and if RRY is 2, the
weight percentage will be 1.50%.
2.2 Effect of RRY on the mechanical properties and micro-structures of deposited
metal
Fig. 1-4 shows the mechanical properties of yttrium relative ratio on the tensile strength,
percentage of area reduction, elongation. impact energy. It could be seen that with the increase of
RRY, the mechanical properties will increase to a maximum point. And with the continuously
increasing, a point of inflection will occur and most of the indexes will decrease.
984
Fig.4 Effect of yttrium relative ratio on impact absorb energy of deposited metal
The microstructures of deposited metal with different relative yttrium ratio are tempered
martensite. Fig. 5 shows the microstructure of deposited metal (RRY=1.5) is martensite.
985
The Ac1 of deposited metal with optimized yttrium is 856.4which is higher than the Ac1 of
base metal 810. The Ac1 of commercial electrode is 855.2. The diffusion hydrogen on the
deposited metal with RRY=1.5 is 2.19ml/100g and on the deposited metal of 2.35ml/100g.
2.4 Properties test for weld joint with optimized yttrium
Table 1 shows the tensile test result under room temperature.
Table 1 Tensile test result under room temperature
A
Item
RelN/mm2
RmN/mm2
%
RRY=1.0
E9015-B9
ASME SA335
715
700
620
585
575
530
18.5
19.2
17
375
364
21.0
24.0
600
294
304
29.0
26.0
625
280
266
29.0
28.5
Table 3 shows the hardness test result of weld joint welded by electrode with and without yttrium.
Table 3 Hardness test result
HBW
RRY1.5
E9015
Weld metal
254
255
Fusion line
244
251
HAZ
245
238
Measuring
position
Fig. 6 and 7 show the impact test result of weld metal and HAZ under different temperature.
986
987
c
Fig.8 SEM and XDR analysis of the weld metal
A second phase partial could be seen on the fractured surface of the welded metal impact surface.
The XDR analysis shows the different between the samples with ad without certain amount of
yttrium.
3 Discussion
988
(1)
Formula (1) shows that Re oxidation decomposes under high temperature. Yttrium oxidation
decomposes into yttrium atom under gas status and oxygen atom under gas status. During welding
process, the welding arc temperature reaches 3000 to 5000K, which could guarantee the above
reaction to reach into balance state. Yttrium atoms are absorbed into the welding arc and these
active atoms are ease to attached on the surface of the melted droplet and transferred into the
welding pool. And the coating of the electrode includes Mg, Al element, which have strong
affinity with oxygen, the following chemical reaction set off:
(2)
(3)
The first stage deoxygenation occurred and the oxidizing atmosphere in the arc decreases. The
transferring of yttrium is intensified.
In the welding pool, the following chemical reactions set off[12]:
(4)
The relationship between balancing constant of the reaction (4) and temperature is :
(5)
When
( here
is the balancing constant of concentration. i.e.
), the
reaction is from the left to the right. So the reacting temperature of reaction formula (4) is :
During shielded metal arc welding (SMAW), the temperature of the droplet reaches 30005000K, the yttrium oxidation absorbed into the droplet will decompose according to the reaction
formula (4). This means that in the droplet stage , the decomposition reaction of yttrium exists in
the droplet. The temperature of the welding pool is about 2100K, which is lower than the
temperature 2722.5K, so the above decomposition reaction could not go on.
The coating of the electrode includes titanium pigment , which is titanium dioxide. The
following reaction sets off in the low temperature welding pool:
6
10-6mm sized Y-Ti-O particles, which are embedded in the steel matrix. The finely dispersed
clusters are believed to give ODS alloys very high creep strength [13-15]. Fig.8(a) shows 10-6mm
size particle and the cavity remained in the impact fracture surface. The dispersed particles
989
contributes the improvement of the mechanical properties of the deposited metal and weld metal
of 9Cr-1Mo steel with yttrium transferred into.
3.2 Effect of yttrium on the content of diffusion hydrogen in the deposited metal
According to the relationship between the melt point and the sequence of atom[16],the surface
tension of yttrium is lower than iron, so the yttrium transferred into the weld pool decreases the
surface tension of the liquid metal. This l reduces the adsorption of hydrogen atom in the space of
the welding arc of of the liquid metal surface. So the amount of hydrogen atoms solutes into the
welding pool decreases and reduces the hydrogen in the weld metal[17].
4 Conclusions
1) Yttrium could be added into the weld metal of 9Cr1Mo steel by coating transition
method..and an optimized yttrium content for welded metal of 9Cr1Mo steel is could be
obtained by comprehensive properties measuring. the The optimized content of Relative
Ratio of Yttrium is 1.5,which is1.125% weight percentage .
2) The room temperature mechanical properties of the welding joint is in accordance with
ASME SA 335 P91, the low temperature impact energy and high temperature tensile strength
are higher than the commercial electrode.
3) Second phase particle has been found in the fractured surface of impact sample. And adding
yttrium could increase both the phase transition point is and decrease the diffusion hydrogen.
These will help to increase the low temperature properties of the welding joint with yttrium. .
REFERENCES
[1] Brinkman,C.R., Alexander,D.J.,Mazisaz P.J. [J].ASME/VGE International Power Plants
Conference Boston MA(USA),1990
[2] Xu Delu. Welding[J], 2006, (8):10
[3] Zhang Chunlei, HuPing. Guangdong Electric Power[J], 2010, 23(7):35
[4] Zheng Zhongfu, Chen Quan. Hot Working Technology[J], 2006,35(15):41
[5] Yang Hongquan,Zhang Zhaolin et al. Mechanical Manufacturing Digest: Welding Part [J],
2011, (6):33
[6] Zhang Yinghui,Zhong Zhiqiang, Chen Han.Noferrous Metals Science and Engineering [J],
2011, (2):32
[7] Zhao Yu-hua, Zhang Li, Huang Zhenwei, WU Baolin, et al. Foundry Technology[J], 2006,
(11):1214
[8] Guo Yonghuan,Fan Xiying, Wang Guangfeng.Journal of the Chinese Rare Earth Society[J],
2009,27 (2):32
[9] Zhang Wenyue,Zhang Zhi.Journal of the Chinese Rare Earth Society[J], 1995, (3):255
[10] Fan Xiying GUO Yonghuan
[11] Su Keng. Rare Earth Chemistry[M].Zhengzhou:Henan Science Press,1993
[12] Du Ting,Han Qiyong,Wang Changzhen, et al.The Physical Chemistry of Rare Earth Basic
Elements and Their Application in Material [M]. Beijing:Science Press,1995
[13] . M.K. Miller et al. Materials Science and Engineering: A[J]. 2003,(353):140
[14] S. Ukai, T. Nishida, T. Okuda and T. Yoshitake. Journal of Nuclear
Materials,[J].1998,(258):1745
[15] M.K. Miller, D.T. Hoelzer, E.A. Kenik, Russell.. Intermetallics[J]. 2005,(13):387
[16] Qu Ying. The Principle of Steelmaking[M]. Beijing: Metallurgical Industry Press,1994:54
990
[17] Zhang Zhiming, Shao Dechun, Li Zhonglin et al.Journal of Haerbin Institute of Technology
[J].1985,(6):136
991
APPLICATION OF EPRI P87 IN DISSIMILAR AUSTENITICMARTENSITIC WELDED JOINTS OF TEMPALOY AA-1 AND T92
STEEL GRADES
Michael URZYNICOK
ZELKOT, Koszcin, POLAND
Robert JACHYM, Krzysztof KWIECISKI
INSTITUTE OF WELDING, Gliwice, POLAND
Paola MARIANI
TenarisDalmine, Dalmine, ITALY
Yusuke MINAMI
TenarisNKKTubes, Kawasaki, JAPAN
ABSTRACT
Dynamic development of steels used in power engineering industry for the production of
boilers characterised by supercritical parameters poses new welding challenges. The introduction
of new combinations of alloying agents aimed at obtaining the best possible mechanical
properties, including creep resistance, affects the weldability of new steels. Each of the latter have
to undergo many tests, particularly as regards bending and welding, in order to enable the
development of technologies ensuring failure-free production and assembly of boiler systems.
Martensitic steels containing 9% Cr, used in the manufacturing of steam superheaters, are
characterised by good creep resistance and, at the same time, low oxidation resistance at a
temperature in excess of 600C. In turn, steels with a 12% Cr content are characterised by
significantly higher oxidation resistance, but accompanied by lower strength at higher
temperatures, which translates to their limited application in the production of boilers operating at
the highest parameters.
The niche between the aforesaid steels is perfectly filled by austenitic steels, the creep
resistance and oxidation resistance of which are unquestionable. This article presents experience
gained while welding dissimilar joints of advanced steels TEMPALOY AA-1 and T92, with the
use of EPRI P87, Inconel 82 and Inconel 617 filler metals. The tests involving the said steel
grades belong to the very few carried out in the world.
INTRODUCTION
The current and already steady tendency aimed at reducing power generation costs is
closely related to increasing the efficiency of power units in conventional power plants. An
increase in efficiency can be obtained by increasing key technological parameters i.e. steam
pressure and temperature. Today, obtaining higher parameters of steam boilers is possible only by
applying modern structural materials able to bear increased operational loads and ensure
sufficiently high resistance at higher temperatures.
Modern martensitic steels such as P92 (X10CrWMoVNb9-2), VM12
(X12CrCoWVNb12-2-2) or PB2 (X12CrMoCoVNbNB9-2-1) make it possible to design power
plant systems in which the temperature of superheated steam is 625C. An increase in steam
pressure and temperature has a direct effect on the operational conditions of boiler elements
(especially on superheaters). Martensitic steels are characterised by high creep resistance and
992
moderate oxidation resistance at high temperature (P92, PB2) or vice versa (VM12), therefore the
development of modern steels is focused on materials with austenitic microstructure [1-4].
Many years of research have led to the development of TEMPALOY AA-1 austenitic
steel by TenarisNKKTubes. This article shows possible combinations of welds in real-life
situation where a header is made out of P92 with connecting tubes of T92 welded to a
TEMPALOY AA-1 superheater coils. New EPRI P87 filler metal has been evaluated/tested along
with well known Inconel 82 and 617.
GENERAL CHARACTERISTICS OF TESTED STEEL
TEMPALOY AA-1 is an austenitic steel containing 18% Cr and 10% Ni alloyed with
niobium and titanium with addition of 3% Cu, the microstructure of which does not contain delta
ferrite. Factors which directly improve creep resistance are niobium and titanium carbides (Nb,
Ti)C present along grain boundaries as well as inside the grain.
In operating temperature range 600750C, the microstructure of the steel is
strengthened by Cr-rich carbides (M23C6). Addition of copper determines the precipitation of fine
and diffuse Cu-rich phase which significantly increases creep resistance.
Hot corrosion and steam oxidation resistance are conditioned by chromium content. The
metal loss of TEMPALOY AA-1 material due to hot corrosion is around 25% lower than that of
TP321H steel, while the oxidation resistance in the environment of fumes and boiler ash at a
temperature of 700C is similar for both . The performing of shot blasting on the internal surface
enables the formation of a stable Cr-rich layer which reduces further and substantially the steam
oxidation rate. There was no grain boundary corrosion observed on any of the TEMPALOY AA-1
test specimens.
Martensitic steel 9Cr-1Mo-0.25V-0.06Nb-0.1C designated as P/T91 was developed in
the USA in order to meet the needs of nuclear and conventional power engineering. In Europe the
steel is designated as X10CrMoVNb9-1.
Modifications of the chemical composition of grade 91 consisting in the reduction of
molybdenum content by approximately 0.5% and addition of 1.7% tungsten resulted in the
development of a steel whose creep resistance is by around 30% higher than that of P91 grade.
The steel obtained through the aforesaid modifications was designated as grade 92 or
NF616 or, otherwise as, X10CrWMoVNb9-2. Tungsten, similarly to molybdenum, is an element
enhancing solid solution strengthening as it increases recrystallisation temperature thus improving
long-term stability of matrix at higher temperature. Through stabilising carbides - limiting their
excessive growth at grain boundaries, a microaddition of boron used in P92 steel increases its
creep resistance [1-6].
OBJECT OF TESTS
The object which underwent tests was a welded joint with an outer diameter of 50.8 mm,
wall thickness of ca. 9 mm, made of TEMPALOY AA-1 (ASTM A213, UNS No. S30434) and
T92 (ASTM A213) tubes. The chemical composition of both steels is presented in Table I. The
tubes were welded with GTAW (Gas Tungsten Arc Welding) in 5G uphill position.
993
Table I. Chemical composition of welded steels acc. to Material Test Report (MTR)
Contents of chemical elements, %
Grade
Si
Mn
Cu
Ni
Cr
Mo
Ti
Nb
AA-1
0,09
0,32
1,42
2,75
10
17,7
n.d
n.d.
n.d.
0,17
0,20
n.d.
0,0019
T92
0,1
0,24
0,48
n.d.
0,3
8,58
0,42
0,42
0,21
<0,01
0,06
1,78
0,0027
Re, MPa
Rm, MPa
E., %
HV
246
540
60
120
(min. 205)
(min. 500)
(min. 35)
(max. 200)
646
788
32
250
(min. 440)
(min. 620)
(min.20)
(max. 265)
AA-1
T92
After welding, all joints were subjected to stress relief annealing at a temperature of 760C, for
approx. 30 minutes.
FILLER METALS FOR DISSIMILAR WELDING
The selection of a filler metal for welding depends on the chemical composition of the
base metal and operational conditions of joints. Consumables used in welding processes should
ensure the chemical composition and properties of the weld metal as similar as possible to those
of the base metal.
A filler metal grade EPRI P87 was designed having in view the production of dissimilar
joints between martensitic steels such as T91/T92 and austenitic steel e.g. Super 304H and
TEMPALOY grade series.
Previously applied Ni-based consumables (e.g. Inconel 82) were responsible for the
generation of a zone poor in carbon (the so-called white zone), whereas the use of, for instance,
alloy Inconel 617 was economically unjustified and gave rise to post-weld micro-cracks.
Owing to the optimally selected chemical composition of wire EPRI P87, dissimilar
joints made with the latter practically have no decarbonised zone. In order to limit the thermal
expansion of the weld metal it was necessary to reduce the content of manganese below 2%,
whereas to eliminate micro-cracks it was necessary to optimise the content of niobium and carbon
acc. to the relation of Nb:C>10 [7]. Table III presents the chemical composition of Metrodemanufactured solid wires EPRI P87.
994
Mn
Si
Cr
Ni
Mo
Nb
Ti
Co
Al
Fe
EPRI P87
0.11
1.55
0.16
8.52
rest
2.02
1.09
n.d.
n.d.
n.d.
38.8
Inconel 82
0.035
2.99
0.08
20.0
rest
n.d.
2.42
0.35
n.d.
n.d.
1.27
Inconel 617
0.06
0.3
0.3
22.4
rest
8.8
n.d.
0.4
11.2
1.22
0.5
SCHEDULE OF TESTS
Tests involved the production of dissimilar joints of steel TEMPALOY AA-1 with steel
T92, welded with Metrode-manufactured solid wires EPRI P87, Inconel 82 (ASME SFA 5.14
ERNiCr-3) and Inconel 617 (ASME SFA 5.14 ERNiCrCoMo-1).
The production of the aforesaid welded joints was followed by non-destructive tests i.e.
VT, PT and RT. The tests were carried out following the quality level B of the standard ISO
5817. After carrying out NDT tests, the test pieces were sampled for destructive tests.
The scope of destructive tests included:
static tensile test of welded joint,
bend test,
impact test,
macro- and microscopic metallographic tests,
hardness measurements.
creep test - ongoing
RESULTS OF TENSILE TESTS
The tests were carried out in order to determine the tensile strength (Rm) of a welded
joint and compare obtained results with the minimum required value of (Rm) for the base metal
(BM), which amounts to 500 MPa for steel TEMPALOY AA-1 (specified by an ASTM standard)
and 620 MPa for steel T92 (specified in the standard EN 10216-2). The minimum value was
marked with a red line in the graph (Figure 1). The static tensile test was carried out following the
requirements of the standard ISO 6892-1 by means of a testing machine Instron 4210, provided
with a computer-aided system of controlling and recording test results performed following the
requirements of the standard ISO 4136.
995
670
648
620
Rm [MPa]
631
621
570
520
470
420
EPRI P87
IN82
IN617
Filler metal
Figure 1. Tensile strength of butt joint of tube 50.8x9mm made of steel grade Tempaloy AA-1
and T92.
RESULTS OF IMPACT TESTS OF WELD METAL AND HAZ
Impact tests were carried out in order to determine the values of impact energy for the
Weld Metal (WM) and Heat Affected Zone (HAZ); they were performed at room temperature on
test pieces with a Charpy v-notch in the WM, HAZ and parent metal following the requirements
of the standards ISO 9016 and EN 10045-1.
The criterion in the standard EN 12952-6 specifies that the minimum impact energy of
test pieces of a typical section (10x10 mm) in HAZ should amount to 24 J at ambient temperature,
whereas the standard EN 10216-2 states that the minimum value of impact energy for the base
metal should be 27 J. In the related graph (Figure 2), the value of 27J is marked with a red line.
The impact energy values obtained for the weld and HAZ are higher than those specified
in the relevant standards. The tests were carried out on test pieces with a reduced section (5x10
mm), therefore the values shown in figures are, in fact, according to recommendations,
proportionally higher. Figure 2 presents average values from three measurements.
RESULTS OF IMPACT TEST
TEMPALOY AA-1 and T92
specimen size: 5x10mm
PM AA-1
HAZ AA-1
WM
HAZ T92
PM T92
120
100
80
92
77
77
65
61
60
40
92
97
87
77
60
54
35
58
45
33
20
0
EPRI P87
Inconel 82
Inconel 617
Filler metal
Figure 2. Impact energy of weld metal, HAZ and base metal in butt joints of tube 50.8x9 mm
made of steel grade Tempaloy AA-1 and T92.
996
Figure 3. Results of bend test view from root side and face side EPRI P87
Figure 4. Results of bend test view from root side and face side Inconel 82
Figure 5. Results of bend test view from root side and face side Inconel 617
997
Hardness (HV10)
Line A
Line B
290
280
270
260
250
240
230
220
210
200
190
180
170
160
150
1
10
11
12
13
14
15
Measurement point
Figure 7. Results of hardness measurements of butt joint welded with EPRI P87
Hardness arrangement for T92 + TEMPALOY AA-1
welded with Inconel 82
Hardness (HV10)
Line A
Line B
290
280
270
260
250
240
230
220
210
200
190
180
170
160
150
1
10
11
12
13
14
Measurement point
15
Hardness (HV10)
Line A
Line B
290
280
270
260
250
240
230
220
210
200
190
180
170
160
150
1
10
11
12
13
14
15
Measurement point
Figure 9. Results of hardness measurements of butt joint welded with Inconel 617
RESULTS OF MACROSCOPIC METALLOGRAPHIC TESTS
Macroscopic metallographic tests were carried out following the requirements of the
standard EN 1321. A criterion adopted for assessment was the quality level B according to the
standard ISO 5817, which was satisfied in case of the test joints. Figures 10, 11 and 12 presents
the results of macroscopic tests in the form of a photograph of the microstructure of a dissimilar
GTAW butt joint made of steel grade TEMPALOY AA-1 and T92 welded with EPRI P87,
Inconel 82 and Inconel 617.
Figure 10. Grade AA-1 and T92 welded with EPRI P87;
etchant: Nital; magnification 2x; quality level: B.
Figure 11. Grade AA-1 and T92 welded with Inconel 82;
etchant: Nital; magnification 2x; quality level: B.
Figure 12. Grade AA-1 and T92 welded with Inconel 617;
etchant: Nital; magnification 2x; quality level: B.
999
weld metal
electrolytic etching;
mag. 200x,
austenite
1000
weld metal
electrolytic etching;
mag. 200x,
austenite
Table VI. Grade AA-1 and T92 welded with Inconel 617
weld metal
electrolytic etching;
mag. 200x,
austenite
Figures 13, 14 and 15 show micrographs of the transition zone between the weld and T92. The
application of filler metal EPRI P87 made it possible to obtain a very narrow decarbonised zone,
if compared to Inconel 82 or Inconel 617. The narrower the decarbonised zone, the smaller the
1001
weakened zone of ferritic/martensitic material. Lower thermal expansion of filler metal EPRI
P87, if compared with e.g. Inconel 617, eliminates stresses generated during operation between
the weld metal and materials being welded, which also significantly affects the life of the joint.
1002
As measured under the microscope the carbon depleted zone for Inconel 82 is in some places over
18 times wider and for Inconel 617 over 24 times compared to EPRI P87 filler. In addition microhardness examinations were performed in the depleted zone. Figure 16 shows the results for EPRI
P87, figure 17 for Inconel 82 and figure 18 for Inconel 617.
Figure 16. Micro hardness test in transition zone between T92 and EPRI P87
Figure 17. Micro hardness test in transition zone between T92 and Inconel 82
Figure 18. Microhardness test in transition zone between T92 and Inconel 617
1003
The results are also given in tables VII, VIII and IX respectively.
Table VII. Micro-hardness test in transition zone between T92 and EPRI P87
Measuring point
1
2
3
4
5
6
7
HV 0,1
250
255
240
218
212
210
186
Table VIII. Micro-hardness test in transition zone between T92 and Inconel 82
Measuring point
1
2
3
4
5
6
7
HV 0,1
210
242
241
217
157
105
251
Table IX. Micro-hardness test in transition zone between T92 and Inconel 617
Measuring point
1
2
3
4
5
6
7
HV 0,1
203
224
207
272
242
219
226
186
172
214
242
255
238
We can conclude that for EPRI P87 and Inconel 617 hardness is on proper level while for Inconel
82 hardness level of 100 HV is too low and this area is considered to be the first to fail during
long-term work under high pressure and high temperature conditions.
CONCLUSIONS
On the basis of the aforesaid tests it was possible to come to the following conclusions:
1. Dissimilar joints made of steel grades TEMPALOY AA-1 and T92, GTAW welded in
5G uphill position are characterised by high quality, which is confirmed by the results of
destructive and non-destructive tests.
2. The application of filler metal Metrode EPRI P87 made it possible to obtain very good
results on a dissimilar welded joint and the OM investigations confirmed the absence of
welding micro-imperfections. The decarbonised/carbonised zone is very narrow, which
favourably affects the operational properties of the joint.
EPRI P87 is not yet included in the EN code thus its usage may be limited in European
projects. The results shown in this work and further advanced microstructural investigations
and creep tests will enable a more detailed knowledge of the welded joint properties and
their industrial usability.
ACKNOWLEDGEMENTS
The authors wish to thank TenarisDalmine, Italy and TenarisNKKTubes, Japan for providing
TEMPALOY AA-1 and T92, Metrode, UK for providing EPRI P87, Inconel 82 and Inconel 617
rods, ZELKOT, Poland for general idea of research and producing the welded joints and Institute
of Welding, Poland for all carried examinations.
REFERENCES
[1] Caminada S., Cumino G., Cipolla L., Venditti D., Di Gianfrancesco A., Minami Y., Ono T.:
Creep properties and microstructural evolution of austenitic TEMPALOY steels.
International Journal of Pressure Vessels and Piping 87 (2010)
[2] Urzynicok M., Kwieciski K., Szubryt M., Sania J.: Application of new GMAW welding
methods used in prefabrication of P92 (X10CrWMoVNb9-2) pipe butt welds. 9th Liege
1004
[3]
[4]
[5]
[6]
[7]
Conference on Materials for Advanced Power Engineering, September 27th - 29th, Liege,
Belgium, 2010
Urzynicok M., Kwiecinski K., Slania J., Szubryt M., Mariani P.: Comparison of SMAW and
GMAW Methods used in P92 Butt Welds. 1st Australasian International Welding, Inspection
and NDT (iWIN2013) Conference, 10-13 March 2013, Perth, Australia
Urzynicok M., Kwiecinski K., Szubryt M.: Testing butt joints in pipes made of VM12-SHC
martensitic steel, Welding International, iFirst article 2012, 1-6
Kwieciski K., Urzynicok M., omozik M.: Practical experience with welding new
generation steel PB2 grade assigned for power industry. Archives of metallurgy and
materials, Vol. 56, Issue 1, 2011
Jachym R., Kwieciski K., Urzynicok M., omozik M.: Properties of thickwelded similar and
dissimilar joints made of TEMPALOY A-3 steel assigned for power industry. 9th
International Conference on Trends in Welding Research, June 4-8 2012, Chicago IL, USA
Schingledecker J.: Update on EPRI P87 Filler Metal. Boiler Reliability Interest Group,
Baltimore 22.04.2010
ASTM A213 / A213M - 13: Standard Specification for Seamless Ferritic and Austenitic
Alloy-Steel Boiler, Superheater, and Heat-Exchanger Tubes
2. ISO 5817: Welding - Fusion-welded joints in steel, nickel, titanium and their alloys (beam
welding excluded) - Quality levels for imperfections
3. EN 10216-2: Seamless non-alloy and alloy steel tubes for pressure purposes with specified
elevated temperature properties
4. ISO 6892-1: Metallic materials - Tensile testing - Part 1: Method of test at room temperature
5. ISO 4136: Destructive tests on welds in metallic materials - Transverse tensile test
6. EN 12952-6: Water-tube boilers and auxiliary installations. Inspection during construction.
Documentation and marking of pressure parts of the boiler
7. ISO 9016: Destructive tests on welds in metallic materials - Impact tests - Test specimen
location, notch orientation and examination
8. EN 10045-1: Charpy impact test on metallic materials. Test method (V- and U-notches)
9. ISO 15614-1: Specification and qualification of welding procedures for metallic materials Welding procedure test - Part 1: Arc and gas welding of steels and arc welding of nickel and
nickel alloys
10. ISO 5173: Destructive tests on welds in metallic materials - Bend tests
11. ISO 9015-1: Destructive tests on welds in metallic materials - Hardness testing - Part 1:
Hardness test on arc welded joints
12. EN 1321: Destructive test on welds in metallic materials. Macroscopic and microscopic
examination of welds
1005
ABSTRACT
In recent years continuous and extensive research and development activities have been being
done worldwide on 700C A-USC (Advanced Ultra Super Critical) power plants to achieve
higher efficiency and reduce the CO2 emission. Increasing steam temperature and pressure of
such A-USC boilers under consideration require the adoption of Ni based alloys. In the Japanese
national project launched in 2008, Ni based alloy HR6W (45Ni-23Cr-7W-Ti, ASME Code Case
2684) is one of the candidate materials for boiler tube and pipe as well as Alloy617, Alloy263
and Alloy740H. The most important issues in A-USC boiler fabrication are the establishment of
proper welding process for thick wall components of these alloys and verification of the long
term reliability of their weldments. In our previous study, the weldability of HR6W was
investigated and the welding process for Ni based thick wall pipe was established with the narrow
gap HST (Hot wire Switching TIG) welding procedure originally developed by Babcock-Hitachi
K.K. In this paper, creep rupture strengths of HR6W weldment were verified by the long term test
up to 60,000 hours for tube and 40,000 hours for pipe. In Japanese national project, narrow gap
HST welding process was also applied to the welding test for the other Ni based candidate pipe
materials. Furthermore, as the practical A-USC boiler manufacturing trials, header mockup test
was conducted and qualified for HR6W.
INTRODUCTION
In recent years, the environmental restrictions on CO2 emission require advanced power plants
with higher efficiency. This has prompted a need to develop fossil fired power plants with higher
steam temperature and pressure conditions. Significant efforts on research and development of
advanced ultrasupercritical (A-USC) boilers with steam conditions of 700C or higher have been
made worldwide [1-4]. To achieve such advanced steam conditions, the application of Ni based
alloys with high creep rupture strength and corrosion resistance becomes essential. The most
critical issues to be settled are the development of materials for boiler thick wall pipes as well as
the establishment of the corresponding fabrication procedures.
1006
HST welding process [10]. Comparing with the common GTAW (Gas Tungsten Arc Welding)
process, narrow gap HST welding procedure combining the electrode oscillation technology with
the hot-wire system; can achieve higher efficiency especially for very thick wall components.
The thick wall components can be welded with narrow gap of only about 12mm groove width in
flexible welding position. As shown in Figure 2, comparing with the conventional SAW
(Submerged Arc Welding) and SMAW (Shield Metal Arc Welding) processes, one-pass-onelayer technology of narrow gap HST welding process with fewer weld layers and less deposited
metal offers higher welding efficiency. Furthermore, the low total heat input of narrow gap HST
welding also results in small heat distortion. Figure 3 shows the some examples of narrow gap
welding applied to conventional USC boiler components [10].
20mm
Conventional
SAW, SMAW
Narrow gap
Figure 2: Schematic comparison and typical macrostructure of narrow gap HST weldment
Header
Piping
Narrow gap HST welding was conducted for the butt welding in flat position successfully. Figure
4 shows the overall view of HR6W pipe after the welding. The non-destructive tests following
the welding process were done using both the radiographic inspection and the liquid penetration
examination. It was confirmed that there was no detective defects like crack, porosity or lack of
fusion. The results of side and root bend tests of weldment also demonstrated defect-free and
good ductility of the weld joint (Figure 5).
Figure 6 shows the macrostructure and microstructures on the cross section of the weldment. The
microstructure observation of the weld metal demonstrates a typical solidification microstructure
of Ni based alloy. There is no defect such as porosity or micro-crack detected in both of the weld
metal and the HAZ (Heat-Affected Zone) by the optical microscope inspection. There is no
extreme coarsening microstructure observed in the HAZ near the fusion boundary. Hardness
measurement was carried out on the cross section of the weld joint as shown in Figure 7. The
weld joint showed gradual increase in hardness from the parent metal towards the weld metal,
and there is no extreme hardening or softening zone.
Concerning the possible loss of strengthening elements of Al and Ti during the welding, the Al
and Ti contents in the weld metal were analyzed and compared with those of parent metal and
filler wire. Although dilution with the parent metal occurred, the oxidation loss of the alloy
elements in the consumable during the narrow gap HST welding procedure was proved to be
quite small [8-9].
Tensile tests of weld joint were conducted at room temperature, 700 and 750C. For the specimen
of weld joint, no failure occurred in the HAZ, fusion boundary or weld metal. All the specimens
ruptured at the parent metal [8-9].
According to the results of non-destructive tests, microstructure observation, bend test and tensile
test shown above, the narrow gap HST welding procedure was confirmed to be suitable for Ni
based pipe welding and the metallurgical integrity of the weldment was proved.
Table 1: Chemical compositions of tested pipe and weld consumable
(Wt%)
Si
Mn
Ni
Cr
Ti
Nb
Fe
Co
Al
Mo
HR6W pipe*
(OD355.5, WT37.5)
0.09
0.29
0.92
0.01
0.0003
44.64
22.83
6.87
0.09
0.18
Bal.
Filler wire
(Alloy617,1.0)
0.06
0.07
0.001
0.001
0.004
Bal.
20.20
0.46
0.16
10.23
0.86
8.52
Side
20mm
(OD355.5, WT37.5t)
Root
10mm
(B) Fusion boundary
100m
300
250
200
150
Weld metal
100
50
0
Weld bead
2mm
Parent metal
B Weld joint
A
B
1010
1,000
:Running
Stress (N/mm )
100
700C
750C
800C
HR6W
10
10
100
1,000
10,000
100,000
(1)
(2)
Mo
(2)
Ni
Ni
(1)
Ni
Si
(3)
Mo
Ni
Cr
Cr
Ni
CrFe Co
(3)
Cr
(4)
Cr
Fe Co
Ni
(4)
Cr
Fe
Mo
Cr Fe
Ni
Ni
Ni
Cr
Ni
Fe
5m
Figure 9: SEM BSE micrographs and EDS spectrums of long term crept HR6W weldment
(750C75N/mm2, 27kh)
1011
Alloy617
HR6W
HR35
10mm
Figure 10: Macrostructures of Narrow gap HST weldments of Ni based alloy pipes
(OD350, WT40)
Crept weldment specimens were analyzed to investigate the microstructure stability. Figure 9
shows the some typical SEM micrographs of long term ruptured creep specimen of weld joint at
750C. Comparing with the parent metal, the HAZ microstructures showed similar precipitation
morphology and distribution. It seemed that no degradation of microstructure occurred due to the
thermal cycle of welding. The predominant precipitates in both of the HAZ and the parent metal
of crept specimens were W, Cr, and Fe-rich particles, and precipitated both at grain boundaries
and intragranularly. According to our previous study [8], they were identified as the hexagonal
Fe 2 W type of Laves phase, with partial Cr and Ni content (14Cr-11Fe-5Ni-69W, wt %).
Although the other precipitates such as -Cr phase, -W phase (found in 700C crept specimen)
and fine M 23 C 6 carbides (found in crept specimens of 700C to 800C) were also identified in
long term crept specimens, Laves phase was the main precipitation strengthening phase.
Moreover, in both of the parent metal and the HAZ after the long term creep, SEM micrographs
revealed many fine particles smaller than 1m, although some of Laves phase grew up to an
equivalent diameter of several m. There were no distinct reductions in the number density after
long term creep up to about 27,000 hours at both of 700 and 750C. These microstructural
characterizations indicate that Laves phase precipitation is still in the growth stage and coarsening
process has not started, which demonstrates the superior microstructure stability of this alloy. The
good microstructure stability is considered to be the main metallurgical factor behind the alloys
good creep strength stability.
APPLICATION OF NARROW GAP HST WELDING PROCEDURE TO OTHER NI
BASED PIPES
In Japanese national project, besides of HR6W, welding tests of Ni based thick wall pipes (OD of
350mm, WT of 40mm) of HR35 (50Ni-30Cr-4W-Ti) and Alloy617 were also conducted with
narrow gap HST welding procedure. The filler wire of Alloy617 was used for both of these two
alloys as same as HR6W. The macrostructures of the cross section of the weld joints were shown
in Figure 10 representatively. Non Destructive Testing of radiographic inspection and the liquid
penetration examination, bending test as well as the microstructure observation of weldment
demonstrated no defects and imperfections. At present, the long term creep strength properties of
these weld joints are still under evaluation. The weld joint strengths for all of pipes were expected
to be comparable with those of parent metal.
MOCKUP TEST OF NI BASED ALLOY HEADER COMPONENT
As the practical trials of A-USC boiler manufacturing in Japanese national project, mockup test
of header components of HR6W were conducted, as shown in Figure 11-13. The superheater and
reheater headers were designed assuming steam conditions of 35MPa/700C/720C (main steam
1012
Figure 11: Narrow gap HST butt welding of superheater header pipe of HR6W
(OD558.8, WT138)
Figure 12: Stub-header socket welding and stub tube orbital welding of HR6W
pressure/main steam temperature/reheat steam temperature) class. From the viewpoint of practical
application, leg tube bending, narrow gap HST butt welding of thick wall pipes (superheater: OD
of 558.8mm, WT of 138mm, reheater: OD of 635mm, WT of 72mm), GTAW and SMAW for
socket joints and orbital GTAW of stub tubes were conducted. By the mockup test, the
fabrication capabilities with Ni based alloy section was demonstrated and verified. The detailed
tests and investigations on the mockup components are in progress.
CONCLUSIONS
In present paper, based on the previous study of establishment of narrow gap HST welding
procedure for Ni based thick wall pipe, the long term creep rupture strength of HR6W weld joint
and the metallurgical characteristics of crept weldment were investigated experimentally. The
welding tests on the other Ni based pipe materials and mockup fabrication of HR6W header were
also conducted. The main results are shown below.
1. The long term reliability of HR6W weld joint strength was confirmed by long term creep
rupture tests exceeding 60,000 hours for the tube and 40,000 hours for the pipe. Both of the weld
joints showed comparable creep rupture strength with the parent metal.
2. The microstructural characteristics of crept weldments were analyzed to investigate the
microstructural stability. There were no distinct microstructural degradation in both of the parent
metal and the HAZ after long term creep up to about 27,000 hours at both of 700 and 750C. The
good microstructure stability is considered to be the main metallurgical factor behind the alloys
good creep strength stability.
3. In Japanese national project, narrow gap HST welding procedure was also applied and verified
for the other candidate Ni based pipe materials. Narrow gap HST welding procedure has been
proved to be preferable for Ni based thick wall pipes for A-USC boiler components.
4. As the practical trials of A-USC boiler manufacturing in Japanese national project, mockup test
of header components of HR6W were conducted. The fabrication capabilities with Ni based alloy
section was demonstrated and qualified.
ACKNOWLEDGMENTS
The HR6W pipe with OD of 355.5mm was fabricated by Nippon Steel Sumitomo Metal
Corporation with a support by a grant from the Joint Research Program of Technological
Development of the Research Institute of Innovative Technology for the Earth (RITE). The other
HR6W, HR35 and Alloy617 pipes and HR6W tubes were produced by Nippon Steel Sumitomo
Metal Corporation with a subsidy from Cool Earth-Innovative Energy Technology Program
granted by Ministry of Economy, Trade, and Industry (METI) of Japan.
REFERENCES
[1] J. Shingledecker, H. Hendrix, J. Philips, J. Siefert, R. Purgert and P. Rawls, "U.S. Program
on Advanced UltraSupercritical Power Plant Materials The Economy of Using Advanced
Alloys", Proc IEA Clean Coal Centre Workshop: Advanced Ultrasupercritical Coal-fired
Power Plants, Vienna, Austria, September. 2012, Paper No. SESSION 4-4.
[2] J.L. Marion, O. Drenik, C. Frappart, F. Kluger, M. Sell, A. Skea, V. Rod and P. Walker,
"Advanced Ultra-Supercritical Steam Power Plants", Proc IEA Clean Coal Centre
1014
1015
ABSTRACT (074)
This paper summarizes recent efforts to improve creep performance in Grade 91 (Mod. 9Cr-1Mo,
ASTM A387) steel weldments via non-standard heat treatments prior to welding. Such heat
treatments offer a potential solution for minimizing Type IV failures in creep strength enhanced
ferritic (CSEF) steels. A lower temperature tempering (LTT, 650C) of the 9Cr steels prior to gas
tungsten arc welding (GTAW) resulted in improved creep-rupture life at 650C compared to the
samples tempered at a standard condition (HTT, 760C) before welding. From detailed
characterization of precipitation kinetics in the heat affected zone, it was hypothesized that M23C6
carbides in the fine-grain heat-affected zone (FGHAZ) in the LTT sample were fully dissolved,
resulting in re-precipitation of strengthening carbides during post weld heat treatment (PWHT).
This was not the case in the HTT sample since M23C6 in the FGHAZ was only partially dissolved
prior to welding, which caused coarsening of existing M23C6 after PWHT and premature creep
failure in the FGHAZ. However, it was also found that the LTT raised the ductile-brittle
transition temperature above room temperature (RT). Two different thermo-mechanical
treatments (TMTs); two-step tempering and aus-forging/aus-aging, of the modified 9Cr-1Mo
steels were attempted, in order to control the balance between creep properties and RT ductility,
through control of precipitation kinetics of the M23C6 carbides and/or MX carbo-nitrides. The
hardness map of the TMT samples after GTAW and PWHT were evaluated.
INTRODUCTION
Creep-strength enhanced ferritic steels containing 9-12Cr are now extensively used in coal-fired
boilers, heat-recovery steam generators, and piping systems in new high-efficiency fossil power
plants because of their excellent creep properties at elevated temperatures matched with
reasonable material costs [1,2]. The performance of CSEF steel components, however, does not
always meet expectations in many industrially relevant circumstances, and there have been
reports of numerous failures in the heat affected zone (HAZ) of CSEF steel weldments after only
a few years in service [3-6]. These failure locations are often traced back to the fine-grained heat
This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with
the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the
article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up,
irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow
others to do so, for United States Government purposes.
1016
affected zone (FGHAZ) of a weld, which experiences a weld thermal cycle with a peak
temperature just above the Ac3 temperature. It is a well-established fact that non-equilibrium
microstructures and their gradients in FGHAZ regions will significantly reduce creep strength [710]. Moreover, the grain size and orientation of the FGHAZ can lead to high tri-axial stress states
that may contribute to accelerated creep damage [11,12]. This combination of circumstances
leading to premature failure of welded components is discussed in the literature as Type-IV
failures in CSEF steels. Published literature also shows that the reduced creep strength of such
joints can be on the order of 40%, compared to the base metal for a given service life [13].
Therefore, minimizing Type IV failure is essential for improving the CSEF steel components
used in many industrial applications, especially at service temperatures above 550C [14].
Previously published work [15] indicated that modification of plate tempering and post weld heat
treatment (PWHT) procedures had the potential of minimizing behaviors contributing to Type IV
failures. The observations were based on testing a gas-tungsten arc weld (GTAW) made in Grade
91 (modified 9Cr-1Mo with V, Nb, and N, ASTM A387) plate using Grade 9 (9Cr-1Mo) filler
metal. The plates used for welding were normalized as usual but tempered at 621C (1150F)
rather than above the ASME Code specified minimum of 732C (1350F). (For reference,
contemporary practice for Grade 91 uses tempering temperatures of 760C and above). Pieces of
the weld made with these plates were then given a PWHT at temperatures of either 732C or
760C. Specimens of both PWHT pieces were then prepared for metallographic examination,
hardness testing, and creep-rupture testing. In creep-rupture testing at 593C, cross-weld
specimens from the 621C temper/760C PWHT coupon failed in the base metal with cup-cone
characteristics, indicating relatively high ductility. In contrast, cross weld specimens from the
760C temper/732C PWHT coupon failed in the HAZ region under the same temperature and
stress conditions. Shorter creep-life was also observed in the 760C temper/732C PWHT
coupons.
Current activities related to microstructure control in CSEF steels included reexamining previous
work, and additional creep testing of the modified 9Cr-1Mo steel weldments, with standard and
non-standard pre-weld tempering [16]. It was found that non-standard pre-weld tempering
conditions resulted in improved creep properties compared to the standard heat treated samples.
Detailed microstructure analysis through an in-situ X-ray diffraction study of the simulated HAZ
on modified 9Cr-1Mo samples revealed the potential improvement mechanism of the creep
properties using the non-standard material heat treatment [17,18]. This paper summarizes our
recent progress on characterization of the microstructure of the modified 9Cr-1Mo weldments;
consideration of the ductile-brittle transition temperature of the base metals imparted by the nonstandard heat treatment; and trial control of precipitation kinetics through two different types of
thermo-mechanical treatments in order to control the balance between creep properties and room
temperature ductility.
EXPERIMENTAL
A 25 mm thick plate of Grade 91 (modified 9Cr-1Mo) steel, with the chemistry shown in Table 1,
was used in the present study. Several small pieces (50-100 mm x 150-250mm x 25mm) were
sectioned from the hot-rolled plate sample [15]. The pieces were normalized at 1050C for 1h
under Ar cover gas, and then air cooled. Some pieces were tempered at several different
temperatures (600, 650, 700 {=non-standard}, 760, and 800C {=standard}) for 1.5-2h, and then
air cooled. After applying single-V or double-V shape GTAW with a matching 9Cr-1Mo filler
metal (the chemistry is also listed in Table 1), PWHT was conducted at 760 or 800C for 2-4h.
1017
Micro-Vickers hardness measurements were conducted on the cross-section of the welded 9Cr1Mo steels after PWHT, using a 300g load and automated stage motion measuring hardness in
50-100m steps on a traverse across the base metal, weld and heat affected zone. Sub-sized and
full-sized cross-weld tensile specimens (ASTM E8) with a cylindrical gage section were
machined and creep-rupture tested at 600-650C and 50-120MPa in laboratory air. V-notch
Charpy impact testing (ASTM E23) on samples machined from the mod. 9Cr-1Mo steel tempered
at 650C and 760C was conducted in a temperature range from -100C to 200C.
Microstructural characterization was conducted using an optical light microscope (OM) and a
scanning electron microscope (SEM).
Aus-forging/ aus-aging was also applied to the mod. 9Cr-1Mo steel plates for potential
enhancement of stable MX carbo-nitride precipitation prior to the martensitic transformation
[19,20]. The samples were heated to 1050C and held for 1h, followed by air-cooling to an
intermediate temperature in the range between 700C and 900C (just below or above Ac1/Ac3 at
~820C, and higher than MS at ~400C). Once the intermediate temperature was achieved a 510% thickness reduction was applied by forging. The plates were subsequently placed in a
furnace for 1 h at the same temperature that forging was performed, and then air-cooled to room
temperature (RT). The samples were then tempered at 760C for 2h. GTAW and PWHT at 760C
for 2h were performed and the HAZ hardness was evaluated.
Table 1: Chemical composition of the base and weld filler metal (Grade 91).
(wt%)
Base
Filler
Fe
Bal.
Bal.
C
0.08
0.08
Mn
0.27
0.41
Si
0.11
0.31
Cr
8.61
8.62
Mo
0.89
0.92
Ni
0.09
0.15
V
0.21
0.24
Nb
0.07
0.08
N
0.06
0.04
B
<0.001
<0.001
FGHAZ, as shown in the OM picture. These results indicate that the improvement of creepproperties is somehow associated with the microstructural changes in the FGHAZ through the
non-standard heat treatment.
Figure 1. Larson-Miller parameters (LMP) of cross-weld 9Cr-1Mo steels with standard or nonstandard pre-weld heat treatment, followed by GTAW and PWHT, plotted as a function of creep
stress. Creep tests were conducted in a range of 593-650C and 62-172MPa [15]. The LMP
curve of the base metal is also drawn for comparison purpose.
hardness traverse was conducted at room temperature the test results may be relevant to the
observed improvement in the high temperature creep properties of the materials.
Figure 3. Cross sectional microstructure of the mod. 9Cr-1Mo steel after (a) standard (HTT) or
(b) non-standard (LTT) pre-weld heat-treatment + GTAW + PWHT, together with super-imposed
hardness color maps measured across the base metal, heat affected zone, and weld metal.
Detailed analysis of the precipitation kinetics was attempted through an in-situ X-ray diffraction
study of the HAZ simulated mod. 9Cr-1Mo samples at SPring-8, Japan. The detail experimental
procedure is described elsewhere [17,18]. The study revealed that the standard heat treated
sample showed incomplete dissolution of M23C6 at the FGHAZ during welding, and it caused
coarsening of the residual M23C6 after PWHT in the FGHAZ area, which would not contribute to
the high temperature strength. On the other hand, the non-standard heat treated sample exhibited
less M23C6 formation (not fully tempered) which allowed complete dissolution of the M23C6
during welding, and then redistribution of fine M23C6 during PWHT. The fine distribution of the
carbides may contribute to the higher temperature creep resistance. Based on the results, the
potential microstructure evolution at the FGHAZ during welding and PWHT are hypothetically
proposed via illustration in Figure 4. It should be emphasized that MX carbo-nitrides were also
detected in the diffraction study, and they showed almost no change in volume fraction during the
HAZ simulated heat treatment. This indicates that MX is very stable and it could be utilized for a
source of high temperature creep resistance at the FGHAZ through a proper control.
Figure 4. Schematic illustration showing microstructure evolutions during welding and PWHT of
the mod. 9Cr-1Mo steel with HTT and LTT conditions [17,18].
1020
Lower temperature tempering caused the ductile-brittle transition temperature (DBTT) of the base
mod. 9Cr-1Mo steel to increase above RT. Figure 5 shows the impact absorbed energy measured
by Charpy impact testing of the mod. 9Cr-1Mo steel with standard and non-standard tempering
(for 2h at 760 and 650C, respectively), plotted as a function of test temperature. The HTT
sample showed a DBTT of approximately -50C, whereas the LTT sample was approximately
80C. Longer time tempering (24h) at 650C did not significantly improve the ductility. This
indicates that the LTT base metal could be easily broken during installation at a factory or in the
field if mishandled. The high DBTT could be due to high amount of residual C in solution in the
martensitic matrix thereby decreasing the toughness of the material. On the other hand, a drastic
improvement was observed when the second tempering (760C for 2h) was applied to the LTT
sample. This result indicates that there is a potential solution to control both creep properties and
RT ductility; use LTT for refining M23C6 carbides, and add the second-step tempering to return
the DBTT to below RT.
Figure 5. Charpy impact test results of the mod. 9Cr-1Mo steels applied standard (HTT) and
Non-standard (LTT) tempering. The results of the longer-time tempered sample (650C/24h) and
two step tempered sample (650C/2h + 760C/2h) are also plotted.
Two-Step Tempering
Based on the discussion in the precious section, two-step tempering (650C/2h + 760C/2h) was
evaluated in the mod. 9Cr-1Mo steel sample. Figure 6 shows the cross-sectional OM micrograph
and the hardness color map of the first trial two-step tempered sample after GTAW and PWHT. It
exhibited a distinct weak zone at FGHAZ similar to the standard heat treated sample shown in
Fig. 3a, indicating that the current two-step tempering condition did not achieve the desired
control of the M23C6 size to allow the complete dissolution during welding. Preliminary SEM
observation also confirmed that relatively coarse M23C6 was present in the base metal prior to
welding. More experimental trials are required to further optimize the first and second tempering
conditions to achieve both the carbide refinements and fully tempered conditions.
1021
Figure 6. (a) OM micrograph showing a cross-sectional view of the mod. 9Cr-1Mo steel with two
step tempering applied GTAW and PWHT, and (b) the hardness color map corresponding to the
area with a broken line.
Aus-Forging/ Aus-Aging
Klueh et al. [19,20] reported a breakthrough concept for improving creep properties of 9-12Cr
CSEF steels through a thermo-mechanical treatment (TMT) with aus-forging and aus-aging. This
process enhances the formation of the stable MX carbo-nitrides at austenitizing temperatures by
applying hot-work (e.g. rolling or forging) to introduce dislocations which act as nucleation sites
for the MX. Following forging, aus-aging resulted in a dense MX precipitation before the
austenite matrix transformed to martensite. The resulting material exhibited almost two to three
orders of magnitude longer creep life at 650C and 138MPa [19]. Since MX precipitates were
stable and would not be dissolved into the matrix at the FGHAZ during welding as discussed in
the previous section [17,18], the aus-forging/ aus-aging could be worth trying for a potential
improvement of high temperature creep properties at the FGHAZ.
Figure 7 shows the CCT/TTT combined diagram of the modified 9Cr-1Mo steel made in the
current study. The samples were heated to 1050C, aus-forged 5-10% and aus-aged at 700C,
800C, and 900C, followed by air-cooling to RT. It should be noted that the aus-forging/ ausaging temperatures were selected to be higher than the than MS (400C). Similar heat treatment
without aus-forging was also made for comparison purpose. It was found that there was a C-curve
of the ferrite formation with a nose around 700C and 1h when no forging was applied, and the
curve sifted toward higher temperature and shorter time by applying aus-forging. The SEM back
scatter electron images of the sample processed at 800C and 700C (7b and 7c) clearly showed
the transition of the microstructure from martensite to ferrite.
Figure 8 shows the hardness color maps of the aus-forged/ aus-aged samples at 900C and 800C
with the standard tempering at 760C/2h, followed by GTAW and PWHT. The sample processed
at 900C (8a) showed almost the same hardness distribution as the standard heat treated sample
with a distinct hardness dip at the FGHAZ. On the other hand, the sample processed at 800C
(8b) exhibited very high hardness in the base metal together with much less hardness reduction at
HAZ. Although it is still difficult to estimate the high temperature creep properties from the RT
hardness test results, the 800C aus-forged / aus-aged sample reveals a processing window with
significant promise in potentially improving the creep properties, when compared with standard
heat treated samples. Property screenings of the TMT samples, as well as optimization of the
thermo-mechanical treatment, are currently in progress.
1022
Figure 7. (a) CCT/TTT combined diagram showing the experimental heat history of aus-forging
and aus-aging, together with the estimated the C curves of ferrite formation with and without
aus-forging; (b) and (c) SEM-back scattered electron images of the aus-forged/ aus-aged
sampled processed at 800 and 700C, respectively.
Figure 8. Hardness color maps of TMT samples after GTAW and PWHT showing the hardness
distribution across the weld metal and the base metal; (a) TMT processed at 900C and (b) at
800C prior to the welding.
CONCLUSIONS
Significant improvement of creep properties of the modified 9Cr-1Mo (Grade 91) steel weldment
was observed by applying non-standard pre-weld heat treatments (lower temperature pre-weld
tempering), compared to the standard heat treated sample weldment. Controlling M23C6
refinement after PWHT at the FGHAZ is the key for improving the creep properties, although
lower temperature pre-weld tempering sacrifices the room temperature ductility of the base metal.
Two different thermo-mechanical treatments, two-step tempering and aus-forging/aus-aging,
were attempted to control the refinement or dense dispersion of M23C6 and MX, respectively.
Optimization of the processing routes is currently in progress.
1023
ACKNOWLEDGMENTS
The authors thank Mr. Tom Muth for his review and comments on this manuscript, and Dr. Pete
Tortorelli for his thoughtful supports on the project. Research sponsored by the U.S. Department
of Energy, Office of Fossil Energy, Fossil Energy Advanced Research Materials Program, under
contract DE-AC05-00OR22725 with UT-Battelle, LLC. ORNL's Shared Research Equipment
(ShaRE) User Program, sponsored by the Office of Basic Energy Sciences, the U.S. Department
of Energy, is also acknowledged.
REFERENCES
[1] Cole, D.G., Design of Heat-Resistant Steels for Small Power Plant Doctoral Dissertation,
University of Cambridge, UK, (2000)
[2] Abe, F., Precipitate design for creep strengthening of 9% Cr tempered martensitic steel for
ultra-supercritical power plants Science and Technology of Advanced Materials, Vol 9.
(2008) p.013002
[3] Shibli, I.A., Performance of P91 Thick Section Welds Under Steady and Cyclic Loading
Conditions: Power Plant and Research Experience, OMMI, Vol. 1, No. 3 (2002), pp. 1-17.
[4] Henry, J.F., Combined Cycle Journal, First Quarter (2005) p.8.
[5] Shibli, I.A., Coleman, K., www.ommi.co.uk/etd/ETD-EPRI-%20P91%20Failures.pdf
[6] Berte, F.J., Combined Cycle Journal, Second Quarter (2007) p.52.
[7] Francis, J.A., Mazur, W., Bhadeshia, H. K. D. H., Mater. Sci and Technol. 22 (2006) p.1387.
[8] Abe, F., Tabuchi, M., Mater Sci and Technol., 9 (2004) p. 22.
[9] Hirata, H., Ogawa, K., Weld. Int, 19 (2005) p.37.
[10] Hirata, H., Ogawa, K., Weld. Int, 19 (2005) p.118.
[11] Albert, S.K., Matsui, M., Watanabe, T., Hongo, H., Kubo, K., Tabuchi, M., Int. J. Press.
Vessel. Pip., 80 (2003) p.405.
[12] Li, D., Shinozaki, K., Kuroki, H., Mater. Sci. Technol. 19 (2003) p.1253.
[13] Otoguro, Y., Matsubara, M., Itoh, I., Nakazawa, T., Nucl. Eng. Des., 196 (2000) p.51.
[14] Yaguchi, M., Matsumura, T., Hoshino, K., Evaluation of Long-term Creep Strength of
Welded Joints of ASME Grades 91, 92 and 122 Type Steels, Proceedings of the ASME
2012 Pressure Vessels & Piping Conference, PVP 2012, July 15-19, 2012, Ontario, Canada,
PVP2012-78393.
[15] Brinkman, C.R., Sikka, V.K., Horak, J.A., Santella, M.L., Long-Term Creep-Rupture
Behavior Of Modified 9cr-1mo Steel Base And Weldment Behavior, ORNL/TM-10504,
1987.
[16] Santella, M.L., Improving The Performance Creep Strength-Enhanced Ferritic Steels,
Proceedings of the 25th annual conference on fossil energy materials, Portland, OR; 26-28th
April 2011. Available at: www.ornl.gov/sci/fossil/proceedings.shtml.
[17] Yu, X., Multi-Scale Characterization of Heat-Affected Zone in Martensitic Steels, Doctor
of Philosophy Dissertation. Columbus, Ohio: The Ohio State University, 2012.
[18] Yu, X., Babu, S.S., Terasaki, H., Komizo, Y., Yamamoto, Y., Santella, M.L., Acta
Materialia, vol. 61 (2013) p. 2194-2206.
[19] Klueh, R.L., Hashimoto, N., Maziasz, P.J., Scripta Materialia, 53 (2005) pp. 275-280.
[20] Klueh, R.L., Hashimoto, N., Maziasz, P.J., J. Nuclear Materials, 367-370 (2007) pp. 48-53.
1024
ABSTRACT
The use of high-nickel superalloys has greatly increased among many industries. This is
especially the case for advanced coal-fired boilers, where the latest high temperature
designs will require materials capable of withstanding much higher operating
temperatures and pressures than current designs. INCONEL alloy 740H (UNS
N07740) is a new nickel- based alloy that serves as a candidate for steam header pipe
and super-heater tubing in coal-fired boilers. Alloy 740H has been shown to be capable
of withstanding the extreme operating conditions of an advanced ultra-super-critical (AUSC) boiler, which is the latest boiler design, currently under development.
As with all high nickel alloys, welding of alloy 740H can be very challenging, even to an
experienced welder. Weldability challenges are compounded when considering that the
alloy may be used in steam headers, where critical, thick-section and stub-to-header
weld joints are present. This paper is intended to describe the proper procedures
developed over years of study that will allow for ASME code quality welds in alloy 740H
with matching composition filler metals.
INTRODUCTION
In todays world, the use of high-nickel superalloys has greatly increased, as people are
developing ways to increase productivity and output. For the electrical power generation
from coal, this increase has meant upgrading from a conventional power boiler to an
Ultra-Super-Critical boiler (USC). In the future even higher efficiency is expected from
advanced ultra-super-critical boilers which are now under development. These A-USC
boilers will require the use of materials that are capable of withstanding operating
temperatures and pressures which are well beyond the capabilities of the special steels
that are currently being used in USC boilers.
INCONEL alloy 740H (UNS N07740) is a candidate for use as A-USC steam header
pipe and super-heater tubing. Extensive research and development has shown that alloy
740H is capable of withstanding the extreme operating conditions of an A-USC boiler. As
with all high nickel alloys, welding can be very challenging even to an experienced
welder. This paper is intended to show that with proper procedures and knowhow, ASME
1025
code quality welds utilizing alloy 740H can be made with matching composition filler
metals.
Alloy 740H is a nickel-base, precipitation hardenable superalloy that offers a unique
combination of high strength and creep resistance at elevated temperatures along with
resistance to coal ash corrosion, oxidation, carburization and sulfidation. Alloy 740H is
derivation of NIMONIC alloy 263. With its higher content of chromium (24.5%), alloy
740H offers a significantly improved resistance to high temperature corrosion. Alloy 740H
is age hardened by the precipitation of a second phase, gamma prime (). By balancing
the hardener content (niobium, aluminum and titanium), alloy 740H exhibits good thermal
stability in addition to high strength.
Alloy 740H was developed specifically to operate under the demanding service
conditions encountered in advanced ultra-supercritical coal fired boilers. The alloy was
originally designated as the material for boiler tubes in the superheater section of the AUSC plant but was then adapted for use as the steam header pipe to which the boiler
tubes are connected. Consequently, welds will be required to connect sections of the
large header pipes and also to attach the boiler tubes to the header
Base Metal Preparation
The single most important issue when it comes to making a quality weld on alloy 740H is
cleanliness. If one starts out with unclean material, achieving a quality weld will be
difficult if not impossible. With alloy 740H tubing, when it is received by the customer,
most likely it will be in the solution treated condition. In this condition, (unless it has been
machined) there will be a thin layer of oxide on the material surface. This oxide layer
needs to be removed from the areas where welding is to be done. Abrasive skim grinding
is the best way of removing it in the field. In fabricating shops, pickling with an acid
solution or machining can be used as well.
The amount of material that requires cleaning depends solely on the weld joint design
and product form. For plate material, both top and bottom surfaces need to be cleaned.
For the tubing and piping products, both the outside (O.D.) and inside (I.D.) surfaces will
need to be cleaned. Typically, material up to 1.5 (38.1mm) away from the weld joint is
cleaned. Once the surface oxide and/or other surface contaminates have been removed,
methanol or other suitable solvents are recommended to remove any residual grinding
dust or shop dirt from in and around the weld joint.
Joint Design
As with all welding projects, using the proper weld joint design is a crucial part of having
a project run smoothly. Many different joint designs may be used when joining
alloy 740H products. Examples of some of the joints commonly used are shown
in Fig. 1. The same basic designs are used for all welding processes.
However, modification of the designs may be required to allow adequate
access to the joint. This is normally accomplished by either increasing the root
gap or increasing the included angle. The most economical joint is that which
requires the minimum of preparation, requires the least amount of welding
consumables and welding time while still resulting in the deposition of a code
quality weldment.
1026
60
V-Groove
1/16
(1.6mm)
60
Double
V-groove
1/16
(1.6mm)
15
UGroove
3/16-5/16
(4.8-7.9mm)
R
3/32
(2.4mm)
15
Double
U-Groove
3/16-5/16
(4.8-7.9mm)
R
3/32
(2.4mm)
(6.3mm)
J-Groove
37.5
3/32
(2.4mm)
The joint design for heavy wall (3 thick) steam header piping is dependent on the
welding process being used to carry out the circumferential girth welds. All heavy
section circumferential girth welds to date have been done utilizing a Narrow
1027
groove, compound angle joint design with the hot-wire Gas Tungsten Arc
Welding (HWGTAW) process (See Fig. 5). As seen in Fig. 6, Narrow groove
refers to a 1 side wall and single pass layers.
Figure 6: Photograph Illustrating 1 Narrow Groove Joint Design with Single Pass
HWGTAW Utilizing matching 740H Filler Metal. Macro Sample Taken from 14 O.D.
Header Pipe
As shown in Fig. 6, 30 single passes were all that was needed to fill the 3 thick weld joint
with a 1 bevel. At the time this paper was being written, evaluation of the weldment was
still ongoing. During the installation of each weld pass on this particular weldment, each
pass was examined for proper tie-in to the side walls, proper tie-in to previous weld
beads, and oxide accumulation. If the oxide accumulation was enough to pose a lack-offusion (LOF) threat, skim grinding with an abrasive wheel was used to remove the layer
of oxide. Although the photograph in Fig. 7 illustrates a completed 740H weldment, it is a
1028
good representation of when a weld bead should be skimmed with a grinder to remove
the oxide layer.
Figure 7: Photograph Illustrating Excessive Oxide Build-Up on a 740H Weld Bead. Weld
Should be Skimmed with a Grinder to Ensure Proper Tie-In with Subsequent Beads.
Welding Parameters
To weld alloy 740H materials, parameters similar to those used for stainless steels are
recommended. Although the parameters mentioned in Table 1 are a good starting point,
every operator has his or her preference as to the way he or she likes to weld. These
parameters can be tailored to each operators preference as long as the heat input is not
drastically increased and the quality of weld being deposited is not compromised.
INCONEL Alloy 740H Welding Parameters
Manual GTAW
Manual P-GMAW
Hot-Wire GTAW
DCEN
DCEP
DCEN
Miller Dynasty
Power Source
Miller Axcess 350
AMI Model 415
DX-300
Process
Manual GTAW
Manual PGMAW
Hot-Wire GTAW
Amperage
110-180
130-160
110-270
Voltage
12-17
24-32
9-15
Shielding Gas/Flow 75/25 Argon,/Helium 75/25 Argon,/Helium 75/25 Argon,/Helium
cfh
cfh
cfh
Rate
@ 30
@ 40
@ 40
Wire Speed (ipm)
2% Thoriated
250-400 ipm
100-175 ipm
Tungsten 1/8
w/.045 wire
w/.045 wire
Travel Speed (ipm)
~8-12
~8-12
4-12
Heat Input (kJ/in)
18-36
25-38
16-30
Interpass Temp.
<350F
<350F
<350F
Note** Parameters listed above are intended to be used as a starting point.
Table 1: Welding Parameters Used for INCONEL Alloy 740H Welding
Parameter
wire process is the most common selection of the two; typically used for manual GTA
welding, it is also used for automatic. GTAW is performed with direct current and straight
polarity (DCEN).
Gases
The recommended shielding gases for INCONEL 740H are helium, argon, or a mixture of
the two. Additions of oxygen, carbon dioxide or nitrogen can cause porosity in the weld or
erosion of the electrode and should be avoided. With a preferred mixture of 75% argon
and 25% helium, welding travel speeds can be increased as much as 30% over those
achieved with 100% argon. The arc voltage for a given arc length is about 40% greater
with helium. Consequently, the heat input is greater. Since welding speed is a function of
heat input, the hotter arc permits higher speeds. The addition of helium to the shielding
gas mixture also helps with the wetting and tie-in actions of the weld metal to the base
metal and previously deposited weld beads.
Shielding gas flow rate is critical. Low rates will not protect the weld while high rates can
cause turbulence and aspirate air, thus, destroying the gas shield. For argon, 10 to 20
cu.ft./hr (0.28 to 0.57 cu.m./hr) is typical for manual welding. Helium should flow at 1-1/2
to 3 times the rates for argon to compensate for heliums greater buoyancy. The largest
gas cup practical for the job should be used. The cup should be maintained at the
minimum practical distance from the work.
Welding grades of argon and helium are produced to a very high degree of purity. Even
a small amount of air will contaminate the protective gas shield and cause porosity in the
weld. Shielding gas flow can be disrupted by drafts, wind, fans, and the cooling systems
of electric equipment. Air movement from such sources should be avoided. A gas lens
should be used on the torch to stabilize the gas column and provide more efficient
shielding. Contamination can also result from air picked up in the gas stream as it
leaves the torch or from inefficient distribution of the gas shield around the electrode and
joint.
Proper maintenance of equipment is essential. If the electrode extension cap or the gas
cup is loose, a venturi effect can be created that will draw air into the gas stream. The
O-rings in water-cooled equipment should be checked periodically. Even a small
leakage of air or water into the shielding can provide sufficient contamination to cause
porosity and weld oxidation and discoloration.
Electrodes
Tungsten electrodes or those alloyed with thorium may be used. A 2% thoriated
electrode will give good results for most welding applications. Although the initial cost of
the alloyed electrodes is greater, their longer life, resulting from lower vaporization and
cooler operation in conjunction with greater current-carrying capacity makes them more
economical in the long term. Regardless of the electrode used, it is important to avoid
overheating them at excessive current levels.
The shape of the electrode tip can have a significant effect on the depth of penetration
and the width of the bead, especially with welding current over 100 amps. The best arc
stability and penetration control are achieved with a tapered tip. For most work, the
vertex angle should be between 30 and 120 degrees with a flat land of about 0.015 in
(0.38 mm) diameter on the tip end. Larger angles (blunter tips) can be used to produce
narrower beads and deeper penetration.
1030
The tungsten electrode will become contaminated if it contacts the weld metal or the base
metal surface during the welding operation. If this occurs, the electrode should be
cleaned and reshaped by grinding. Chemical compounds that chemically react with the
electrode to point it are also available
Current
Direct current, straight polarity (electrode negative) is recommended for both manual and
automated welding. A high-frequency circuit for assistance in starting the arc and a
current-decay unit for slowly stopping the arc should also be used when GTA welding
alloy 740H. Contact starts and pull away arc stops are unacceptable techniques.
A high-frequency circuit eliminates the need to contact the work with the electrode to start
the arc. Contact starting can damage the electrode tip and also result in tungsten
inclusions in the weld metal. Another advantage of a high-frequency circuit is that the
starting point can be chosen before the welding current starts, eliminating the possibility
of arc marks on the base material.
Rough, porous, or fissured craters can result from an abrupt arc break. A current-decay
unit gradually lowers the current before the arc is broken to reduce the puddle size and
end the bead smoothly. For manual GTA welding, a foot pedal that controls the
amperage or torch with amperage controls built in are recommended for slowly decaying
the arc.
The torch should be held at nearly 90 degrees to the work. A slight inclination in the
forehand position is necessary for good visibility during manual welding. However, too
acute an angle can cause aspiration of air into the shielding gas. The electrode
extension beyond the gas cup should be as short as possible. However, it must be
appropriate for the particular joint design.
The arc length may be longer if filler metal is to be added but it should be the minimum
length practical for the diameter of filler metal to be used.
The size of filler metal used must be appropriate for the thickness of the material being
welded. The filler metal should be added carefully at the leading edge of the puddle to
avoid contact with the electrode. The hot end of the filler metal should always be kept in
the protective atmosphere during welding. A slight torch manipulation may be required
to ensure good tie-in to the side walls and previous weld beads.
Shielding of the weld root is usually required with gas-tungsten-arc welding. If a full
penetration weld is made without root protection, the underside of the weld bead will
likely be discolored (oxidized) and porous. Shielding can be provided by grooved backup bars or inert-gas backing. Consumable inserts or backing rings can also be used
when welding alloy 740H materials.
Whether welding alloy 740H material manually, automatic, cold-wire or hot-wire; it is
crucial that each weld bead deposited be examined for excessive oxide build-up, lackof-fusion indications or areas that may need to be skimmed with a grinder to ensure
proper tie-in with subsequent beads. Questionable weld beads should be liquid
penetrant inspected to verify weld quality. Proper deposition of the root pass is a critical
part of laying a solid foundation for a code quality weld. As with all high nickel alloys,
convex bead geometry is a must when welding alloy 740H [2]. Flat and concave bead
shapes are more prone to centerline weld bead cracking. Alloy 740H can be subject to
this type of cracking. Early experiences with welding parameter development have
1031
shown that concave weld beads deposited in alloy 740H weldments exhibited centerline
weld bead cracking. However, with proper parameters and convex weld beads,
centerline cracking is avoided.
As the 740H weld joint is being filled with multi-pass weld beads, the operator needs to
maintain an interpass temperature no greater than 350F (177C). The operator may
find it necessary to manipulate the weld torch slightly to ensure side walls and previous
weld beads are being properly penetrated. Both, manual and automatic welding
methods typically require some sort of torch manipulation when welding high nickel
alloys due to their sluggish nature. The need to manipulate the torch can be different
for each weldment being made. The knowledge, skill set and experience of the operator
plays a huge part in knowing when and how to apply it.
The final fill layer is typically skim ground to prevent any accumulated oxide from floating
to the surface of the subsequent cap layer. As shown back in Fig. 6, the cap layer
should not extend more than a 1/8 (3.17mm) on each side of the weld joint.
Gas Metal-Arc Welding
The GMAW process in the pulsed mode of transfer is a high deposition, moderate heat
input welding process often preferred by companies for heavy section welding in the
field and fabricating shops. When welding high nickel alloys such as 740H, it is highly
recommended that a liquid cooled welding torch be used. With most GMAW welding
torches, the liner is made up of a flexible carbon steel tube. A Teflon liner is preferred
over a steel liner. The Teflon liner allows for much smoother wire feeding with limited
restrictions. Reverse-polarity direct current (DCEP) should be used with the GMAW
process
Although the majority of welding done on 740H to-date utilized the GTAW process,
several heavy section (2 [50.8mm] thick) 740H weldments were done with the GMAW
process utilizing the pulsing transfer mode (PGMAW). The fast freeze action of the weld
puddle when using pulse, allows this process to be used for all welding positions. As
previously mentioned, the root pass is the most critical part of a quality weld. When
installing the root pass it is crucial that proper penetration and tie-in is being
accomplished. If ones attention is wandering, a weld containing LOF, incomplete
penetration and centerline cracking can very easily be deposited. Fig. 8, shows a typical
740H PGMAW two-bead root pass.
Figure 8: Photograph Illustrating the Two Bead Root Technique with PGMAW
1032
The two bead root technique is commonly used with the GMAW process on material
greater than 1 thick (25.4mm). Utilizing the two bead root technique allows for the joint
geometry to use a much lower degree of bevel (15-20 as opposed to 30). The lower
degree of bevel is mainly governed by the wider root opening (1/2, 12.7mm). The wider
root opening is needed to successfully deposit two convex weld beads with an
approximate 50% overlap. It is also necessary to allow for the wider cup/nozzle of the
GMAW torch.
With the two bead root technique, it is much easier to produce a convex weld bead. A
front-to-back shuffling action with the welding torch assists with producing a convex weld
bead which in turn aids in the resistance of centerline weld cracks. Figure 9 shows a
close-up of the completed root pass utilizing the front-to-back shuffling action. The
somewhat serrated appearance of the weld toe should be dressed with a grinder to
ensure adequate tie-in with subsequent weld beads. Leaving areas such as these
greatly increase the chances of an inadequate weld being deposited.
Figure 9: Photograph Illustrating Close-Up of Two Bead Root Technique Utilizing the
Front-To-Back Shuffling
During the fill layers using the PGMAW process, the same interpass cleaning and
temperature monitoring techniques must be adhered to as those of the GTAW process.
Depending on how well the material was cleaned/prepared for welding, the oxide build-up
will pretty much mimic the GTAW process. As previously mentioned, it is up to the
operator to judge when to remove oxide build-up. In case of uncertainty, it is better to
grind. As welding progresses and a questionable bead is deposited, a quick way to
reveal any surface indications is the use of liquid penetrant inspection (LPI). All
indications revealed by LPI should be ground out and re-examined to verify removal.
When preparing to deposit the cap layer, the previous layer needs to be skimmed to
ensure adequate tie-in with the cap layer and to minimize oxide floating to the cap layer.
Figures 10 and 11 show a completed 2 (50.8mm) thick 740H PGMAW weldment and a
full cross section macro.
1033
1034
Transverse side bends were sectioned from the qualification weldments and tested. Per
code requirements, bend tests are required to pass a minimum 4-T bend radius. Both
the GTAW and PGMAW weldments passed all four transverse side bends. Figures 1215 Show acceptable bend test for both welding processes.
1035
CONCLUSIONS
If followed, the above information regarding how to weld INCONEL alloy 740H should
provide adequate guidance to produce a code quality weld utilizing 740H materials. As
any skilled welder knows, a lot more can be said about welding high nickel alloys. This
guide is intended to be just as the title reads a practical guide on welding INCONEL alloy
740H. Should additional how-to information be needed on welding alloy 740H, one can
search the literature listed below or contact Special Metals research and technology
group directly.
1036
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
1037
ABSTRACT
Finite element (FE) modeling has been applied to a stress relaxation cracking (SRC) test in order
to evaluate the effects of changing sample geometry and material type. This SRC test uses
compressive pre-straining to create a tensile residual stress in modified compact-tension
specimens and has been used to test 316H stainless steel. The FE model is first used to verify that
sample integrity will not be compromised by modifying the geometry. The FE model is then
applied to candidate Advanced Ultra Supercritical nickel-base alloys 617, 740H, and 800. It is
determined that this stress relaxation test will be appropriate for these alloys.
INTRODUCTION
INCONEL Alloy 740H, a candidate superalloy for Advanced Ultra SuperCritical (AUSC) coalfired power plant construction, has recently been the subject of considerable research [1-11].
Remaining research includes an investigation of stress relaxation cracking, a cracking
phenomenon that raised concern during the development of Alloy 617 for the European AUSC
program [12]. Stress relaxation cracking typically occurs in service after many thousands of hours
(10,000 100,000 hours) and is, in general, due to the acceleration of creep by residual stress
[13-16]. SRC is typically associated with the heat affected zone (HAZ) of welds but weld metal
and regions of cold work are also susceptible [14, 17]. The thermal excursion associated with
welding leads to the development of residual stress on cooling and also significantly affects the
microstructure surrounding the weld. Strengthening precipitates (carbides or ) dissolve in the
HAZ and re-precipitate during heat treatment or service. The nature of this re-precipitation drives
SRC. Typically, strengthening precipitates re-precipitate in grain interiors, strengthening them
relative to the grain boundaries. This forces stress relaxation to be concentrated on grain
boundaries. Additionally, carbide precipitation on grain boundaries can consume the alloying
elements that might have formed strengthening precipitates near the boundary, further weakening
grain boundaries and immediately surrounding areas. As a result of this precipitate distribution,
SRC typically occurs intergranularly [14, 16-18].
While the terms stress relaxation cracking and strain age cracking (SAC) are often used
interchangeably and their mechanisms are similar, there is one major difference which merits
discussion. Unlike stress relaxation cracking, strain age cracking primarily occurs in superalloys
which harden very rapidly during aging. Due to this rapid hardening, SAC typically occurs during
heating or aging. The time required for SAC to occur is very short, especially when compared to
the thousands of hours required for SRC to occur and this is the main difference between SAC
and SRC. If it is not possible to heat large components to a stress relieving temperature quickly
enough, SAC will be very difficult to avoid. It is often necessary to use alloys that harden slowly
(e.g. 718) for welded construction in order to avoid strain age cracking. Stress relaxation cracking
occurs after much longer times and can be avoided with stress relieving heat treatments because
heating rate is less critical.
1038
Since alloys which harden very rapidly will crack due to SAC before reaching service, their SRC
susceptibility is somewhat irrelevant but alloys which can be aged without cracking are not
susceptible to SAC but may still be susceptible SRC. While this distinction is minor, it should be
kept in mind that SAC tests, which are meant to reveal failures that occur in a short time, will be
less useful when evaluating susceptibility to long-term cracking mechanisms such as SRC.
The long-term nature of SRC and the large time window within which it may occur make it very
difficult to predict and therefore it is particularly concerning. There are many different
approaches to SRC testing and most of them rely on an externally applied load to generate
cracking. A detailed explanation of many of these tests can be found in the SRC reviews by
Siefert and Tanzosh [14] and Dhooge and Vinckier [18]. Self-restrained testing approaches
include the Borland test [19] and compressively pre-strained compact tension specimens [13, 15].
Compressively pre-strained compact tension specimens are particularly interesting because they
have been well characterized in the recent past, and are easy to model, fabricate, and inspect.
Recent work has been done with this type of test examining SRC in 316H stainless steel [15]. In
this work, Turski, et al. accurately modeled the stress state after pre-straining and accurately
predicted the magnitude of damage due to SRC in a 4500 hour test. The aim of the present study
is to determine the feasibility of applying such a test to alloy 740H and other Ni-base alloys using
the finite element software Abaqus [20].
Alloys 617 and 800 were chosen for comparison with alloy 740H because they have both
demonstrated susceptibility to SRC [12, 17]. Alloy 617 is an AUSC candidate alloy but lacks the
high temperature strength of alloy 740H. This has consequences with respect to wall thickness,
maximum pipe inner diameter, and other design parameters [1]. Alloy 800 is another nickel-base
alloy that can demonstrate susceptibility to SRC and can be tested at a similar temperature as 617
and 740H. The compositions of these alloys are given in Table 1. Considering these compositions
with respect to the mechanism of SRC explained earlier, 316H is susceptible due to its high
carbon content. Alloys 617 and 800 have more carbon and are also hardened by a small amount
of and they are also susceptible to SRC. Alloy 740H, which has a similar carbon content as
316H, has the highest levels of forming elements and therefore the strongest precipitation;
however, it may not be the most SRC susceptible alloy because other factors such as creep
ductility play an important role the SRC mechanism [14, 16].
Table 1. Nominal compositions of alloys in this study in weight percent. All values are maxima.
Note that in alloy 740H, the H does not indicate high carbon as it does in 316H.
Ni
Cr
Co
Fe
Mo
Al
Ti
C
800 [21]
35
23
Bal
0.6
0.6
0.10
617 [22]
Bal
24
15
3
10
1.5
0.6
0.15
740H [23]
Bal
25
20
1.5
0.5
1.4
1.4
0.06
316H [16]
12
17
Bal
2.2
0.07
EXPERIMENTAL PROCEDURE
In order to evaluate the feasibility of using compressively pre-strained compact tension
specimens, the first step was to create a finite element model that matches the work done by
Turski, et al. [15]. This was done using alloy 316H. Once this model was established, it was used
to evaluate a modified sample geometry. The sample geometry was modified in order to
accommodate currently available material. The finite element model of the modified geometry
was then used to evaluate alloys 740H, 617, and 800.
1039
Following the work of Turski, et al., a 3D finite element model was created using the
approximate dimensions, properties, and procedure given in their publication. The sample
geometries used in this study is shown in Figure 1 below.
Figure 1. Sample geometries considered in this study. Note the different thicknesses.
Using the finite element software package Abaqus, rigid cylinders were used to compress a
compact tension specimen 2 mm. The compression was applied to a full 3D model using
boundary conditions to move each cylinder 1 mm towards each other. In order to observe residual
stresses, the y-direction boundary conditions of the cylinders were removed and a remote portion
of the sample was fixed. Residual stress and elastic strains in the crack opening direction (ydirection, S22, EE22) were recorded in order to compare with the results of Turski et al.
Triaxiality was taken to be the negative ratio of hydrostatic pressure to Mises stress, as defined by
Abaqus [24]. These three parameters were considered for a path along the mid-thickness and
quarter-thickness planes immediately behind the notch root. These paths are shown in Figure 2.
1040
Figure 2. The paths used to query the model for data shown on a meshed model of the modified
geometry.
Once a model that resembled the results of Turski, et al. was created, the geometry was modified
to that in Figure 1 and the same parameters were considered again. Upon discovering that this
modified geometry created a very similar stress state, it was used to consider alloys 740H, 617,
and 800. The material property data used for these models are given in Table 2. Turski, et al.
generated additional stress-strain data specifically for their study and this data were also used in
the present work.
Table 2. Material property data used for modeling. A more thorough stress-strain profile was
entered for 316H in the current study and the work by Turski, et al [15].
316H [15]
Alloy 617 [22]
Alloy 740 [23]
Alloy 800H [21]
800 C / 16 h
hot rolled
Mpa (ksi)
Mpa (ksi)
Mpa (ksi)
MPa (ksi)
204,000 (29,600)
211,000 (30,600)
221,000 (32,000)
196,500 (28,500)
0.27
0.3
0.3
0.337
250 (36.3)
322 (46.7)
720.5 (104.5)
445 (64.6)
UTS
895 (129.8)
734 (109.5)
1169 (169.5)
665 (96.4)
1041
Figure 3. Comparison of crack-opening residual stresses. Data from Turski, et al. is on the right
and data from the current work is on the left. Even though only the Original geometry should be
compared to the data from Turski, et al., there are strong similarities among all sets of data,
especially within the first half inch.
Figure 4. Comparison of elastic strain in the crack opening direction. Data from Turski, et al. is
on the right and data from the current work is on the left. As with the residual stress data, very
strong similarities can be seen, especially within the first half inch.
While the initial peaks are slightly smaller than the reported data [15], they are still rather
comparable and the magnitude and position of the other maxima and minima are accurate. Some
possible sources of error include an inexact duplication of the sample geometry and a different
mesh shape. At this point it was determined that the present model was sufficient to continue the
analysis.
After modifying the geometry in order to accommodate available material, residual stress, elastic
strain, and triaxiality were compared between the two models on both the mid-thickness and
quarter-thickness planes. Stress and strain data were shown above and triaxiality data is shown in
Figure 5 below.
1042
Figure 5. Triaxiality data for the original and modified sample geometries along both the midand quarter-thickness planes. As with the other data, good agreement can be seen, especially in
the first half inch behind the notch.
These graphs indicate that the geometry modification did not significantly change the residual
stress, elastic strain, or triaxiality, especially near the notch root. As expected, the profiles were
shifted to be narrower in the modified sample since the sample itself was shortened. Another
important point is that in both models, there are very minor differences between the midthickness and quarter-thickness profiles. This indicates that the profiles of these parameters are
constant for at least half of the sample thickness in both geometries. The quarter thickness plane
is particularly interesting because a somewhat constant depth of cracking was observed behind
the notch between the mid-thickness and quarter-thickness planes [15]. The fractographs that
report the cracking depth are shown in Figure 6. Based on the similarities of the magnitudes and
breadths of these parameters, it was concluded that the modified sample geometry is thick enough
to produce the same residual stress state that was observed by Turski, et al.
Figure 6. Fractographs from the work of Turski, et al. showing the depth of cracking behind the
notch. Notice how the maximum crack depth is somewhat constant over at least half of the
sample. Half of a 1 inch thick sample is shown here.
After accepting the modified geometry, other materials were modeled. The residual stress and
elastic strain levels were variable which should be expected due to the dependence of these
parameters on material properties. Triaxiality was found to be relatively comparable, especially
near the notch root. This is also expected since triaxiality is a ratio of stresses and is therefore less
subject to individual material properties. The slightly different profile for alloy 316H is likely due
to the material property data entered into the model. Several points along the stress-strain curve
were entered for only 316H because Turski, et al. specifically determined data for this purpose. It
is expected that this increased the resolution of the model and provided a level of accuracy that
1043
could not be achieved without such data. Residual stress, elastic strain, and triaxiality data are all
graphed in Figure 7. Data from the quarter thickness plane was omitted because in every case it is
very similar to the data from the mid-thickness plane.
Figure 7. Comparison of residual stress, elastic strain, and triaxiality as modeled for the alloys in
this study. Data is from the mid-thickness plane of the modified sample geometry.
While the similar levels of triaxiality indicate similar stress states, they do not describe the stress
magnitude. In order to evaluate the magnitude of these residual stress levels, the peak residual
stresses for each alloy were normalized by the stress required to cause rupture in 4000 hours at a
temperature near 750 C. A temperature closer to 550 C was considered for 316H because this
material was originally tested at 550 C [15]. Rupture stress was chosen as the normalization
parameter since SRC is so closely related to creep and a failure time of 4000 hours was chosen
based on the experiments by Turski, et al. which were 4500 hours long. It was found that for all
of the alloys studied here, the peak residual stress is approximately 4-7 times greater than the
stress required to cause rupture in 4000 hours near 750 C. The detailed data can be found in
Table 3. Since these alloys all exhibit a very similar level of triaxiality and will all experience a
similar residual stress level relative to their stress rupture strengths, it is concluded that such a test
for SRC would provide a reasonable comparison between these alloys.
Table 3. Data used to evaluate the residual stress levels calculated by the FE model. All of the
stresses correspond to failure after 4000 hours at the indicated temperature.
316H [25]
Alloy 617 [22]
Alloy 740 [23]
Alloy 800H [21]
800 C / 16 h
annealed
Mpa (ksi)
Mpa (ksi)
Mpa (ksi)
Mpa
T (C)
600
760
750
705
Rupture
190 (27.5)
124 (18)
214 (31)
55 (8)
Max 22
800 (98.7)
649 (94.1)
1036 (150.2)
362 (52.5)
Max/Rupture
3.6
3.7
4.8
6.6
1044
CONCLUSIONS
It is concluded that the sample geometry used by Turski, et al. can be modified to accommodate
available material without significant penalties in residual stress state or magnitude. It is further
concluded that the approach of compressively pre-straining compact tension specimens in order
to produce a tensile residual stress will produce the same residual stress state and relative level in
candidate AUSC nickel-base alloys. This tensile residual stress will be used to evaluate stress
relaxation cracking susceptibility. In future work, alloy 740H samples will be subjected to
thermal cycles before pre-straining in order to simulate an as-welded HAZ, postweld heat treated
HAZ, and fully aged base metal microstructures. The SRC susceptibility of these microstructures
will be compared to alloys 617 and 800, which are known to be susceptible to SRC.
ACKNOWLEDGEMENTS
The authors would like to thank Joe Dierksheide and Jim Tanzosh of Babcock and Wilcox for
financial support, Brian Baker, Ronnie Gollihue, and Jack DeBarbadillo of Special Metals for
material, and Professor Wei Zhang, Ryan Smith, and members of the OSU Welding and Joining
Metallurgy Group for helpful discussions.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
Baker, B.A., R.D. Gollihue, and J.J. deBarbadillo, Fabrication and Heat Treatment of
Weld Joints in Inconel Alloy 740H Superalloy Steam Header Pipe and Superheater
Tubing, in Welding and Repair Technology for Power Plants: Tenth International EPRI
Conference, D. Gandy, Editor. 2012: Marco Island, FL.
Evans, N.D., et al., Microstructure and phase stability in INCONEL alloy 740 during
creep. Scripta Materialia, 2004. 51(6): p. 503-507.
Sanders, J.M., et al., Elimination of Fissures in Thick Section Inconel Alloy 740 Welds, in
34th International Conference on Clean Coal & Fuel Systems. 2009: Clearwater, FL.
Shingledecker, J.P., N.D. Evans, and G.M. Pharr, Influences of Composition and Grain
Size on Creep-Rupture Behavior of Inconel Alloy 740. Journal of Materials Engineering
and Performance, 2012: p. in review.
Shingledecker, J.P. and G.M. Pharr, The Role of Eta Phase Formation on the Creep
Strength and Ductility of Inconel Alloy 740 at 1023 K (750 C). Metallurgical and Materials
Transactions A, 2012: p. 10.1007/s11661-011-1013-4.
Smith, G.D., B.A. Baker, and L.E. Shoemaker, The Development of Inconel Alloy 740 for
use as Superheater Tubing in Coal Fired Ultra Supercritical Boilers, in 4th Annual
Conference on Advances in Materials Technology for Fossil Power Plants. 2004, Special
Metals Corporation: Hilton Head, VA.
Tung, D.C. and J.C. Lippold, Weld Solidification Behavior of Ni-Base Superalloys for Use
in Advanced Supercritical Coal-Fired Power Plants, in Superalloys 2012, E.S. Huron, et
al., Editors. 2012, TMS: Champion, PA. p. 563 - 567.
Xie, X.S., et al., A New Improvement of Inconel Alloy 740 for Usc Power Plants.
Advances in Materials Technology for Fossil Power Plants, 2008: p. 220-230.
Zhao, S.Q., et al., Research and Improvement on Structure Stability and Corrosion
Resistance of Nickel-Base Superalloy INCONEL Alloy 740. Materials & Design, 2006.
27(10): p. 1120-1127.
Zhao, S.Q., et al., Microstructural stability and mechanical properties of a new
nickelbased superalloy. Materials Science and Engineering a-Structural Materials
Properties Microstructure and Processing, 2003. 355(1-2): p. 96-105.
1045
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
Bechetti, D.H., Microstructural Evolution and Creep Rupture Behavior of Inconel Alloy
740H Fusion Welds, in Materials Science and Engineering. M.S. Thesis. 2013, Lehigh
University.
Bader, M. Investigation of Behaviour of Alloy 617mod. in Energy Day. 2010. Rome.
Hossain, S., C.E. Truman, and D.J. Smith, Generation of Residual Stress and Plastic
Strain in Fracture Mechanics Specimen to Study the Formation of Creep Damage in Type
316 Stainless Steel. Fatigue and Fracture of Engineering Materials and Structures, 2011.
34: p. 654-666.
Siefert, J.A. and J.M. Tanzosh, Stress Relaxation Cracking Literature Review. EPRI
Conference Paper.
Turski, M., et al., Residual Stress Driven Creep Cracking in AISI Type 316H Stainless
Steel. Acta Materialia, 2008. 56: p. 3598-3612.
Lippold, J.C. and D.J. Kotecki, Weldability and Welding Metallurgy of Stainless Steels.
2005, Hoboken, N.J.: John Wiley & Sons.
Van Wortel, J.C., Prevention of Relaxation Cracking by Material Selection and/or Heat
Treatment Final Report. 2000, TNO.
Dhooge, A. and A. Vinckier, Reheat Cracking - Review of Recent Studies (1984-1990).
Welding in the World, 1992. 30: p. 44-71.
Spindler, M.W., The Use of Borland Specimens to Reproduce Reheat Cracking in Type
316H, in Int. Conf. on High Temperature Plant Integrity and Life Extension. 2004:
Robinson College, Cambridge University.
Abaqus Software. 2012, Dassault Systemes Simulia Corp.: Providence, R.I.
Inconel Alloy 800 Technical Bulletin. 2004, Special Metals.
Inconel Alloy 617 Technical Bulletin. 2005, Special Metals.
Inconel Alloy 740 Technical Bulletin. 2004, Special Metals.
Abaqus v6.12 Analysis User's Manual Vol. 1: Introduction, Spatial Modeling, Execution &
Output. 2012, Providence, R.I.
Whittaker, M.T., M. Evans, and B. Wilshire, Long-Term Creep Data Prediction for Type
316H Stainless Steel. Materials Science and Engineering A, 2012. 552: p. 145-150.
1046
and Alloy 740H) are required. Because most Fe-Ni base alloys and Ni base alloys have never
been applied to boiler piping, welding and other fabrication processes have to be developed.
Table 1 shows the schedule of their development in Japan. Since 2008, basic tests on the
candidate materials have been conducted to understand their mechanical properties and develop
welding and fabrication processes. Additionally, long term creep tests are ongoing to obtain the
creep rupture strength at 100,000 hours.
In this paper, the techniques used in the welding and the other fabrication processes are
introduced for boiler tubes and thick walled piping.
Tachibanawan
No.1
25,88 MPa
605/613C
600
25
24.1
20
500
450
538
593C
566C (Base)
~ ~
550
610C
31.0
STEAM TEMP.
30
620C
15
485
482
Hekinan No.3
25.0 MPa
543/596C
16.6
450
10
4.1
STEAM PRESS.
5
~
400
55
60
65
70
90
95 2000
in Japan
Alloy263
Alloy740H
SUPER304H
Alloy617
100
Gr.92
HR35
7
6
5
Gr.91
TP347HFG
550
600
HR6W
650
700
750
Temperature / C
800
850
Items
Fiscal 2008
Fiscal 2009
Fiscal 2010
System Design
Fiscal 2011
Fiscal 2012
Fiscal 2013
Study of Economy
Summarization
Material LongTerm
Characteristic
Evaluation
Plate Materials
Large Diameter Pipes (Ni-Based Alloys)
Large Diameter Pipes (Ferritic Steels)
(Creep Test on
Welded Joints)
Material
Characteristic
Evaluation
Welding and
Bending Tests
1.7DR
Hot bending
Cold bending
2.8DR
Alloy617
HR6W
HR35
Alloy263
Hot bending1.7DR
Cold bending2.8DR
1050
750 degree C
HR6WInterrupted
10
Lifetime ratio /
HR35
Alloy617
Alloy263
0.1
Alloy740/740H
Alloy263
Alloy617
HR35
HR6W
Alloy740/740H
10
Pre strain / %
15
20
Fig. 6 The effect of pre-strain on the creep properties of A-USC boiler tube materials
When the pre-strain is less than 5%, Alloy 740H shows the same lifetime as one of the samples
without pre-strain, but the ratio decreases to around 0.5 when the pre-strain is more than 7.5%.
The test result shows the same tendency reported by some researchers [8] and it is believed that
the amount of precipitation at grain boundary changes [9]. The lifetime ratio of Alloy 263 does
not change due to pre-strain. The ratio of Alloy 617 increases with pre-strain and reaches double
at 15% pre-strain. This is thought to be due to an increase of precipitation including Mo carbide at
the grain boundary instead of phase (Ni3Mo) decreasing. The ratio of HR6W and HR35 is more
than 10 when pre-strain is 5%, which corresponds to the results reported by Okada [10]. Increase
of creep strength by pre-strain corresponds to the previous test results of austenitic stainless steels.
Welding tests for small diameter tubes
Welding tests were performed to develop welding processes for the candidate alloys in an AUSC plant. Table 2 lists the test items for the candidate materials and their weld metals. Alloy 82
was applied to weld SAVE12AD, and Alloy 617 to HR6W, HR35 and Alloy 617.
Table 2 List of welding tests for A-USC boiler tubes
Materials
Filler metal
method
Microstruc
ture
Mechanical
properties
Creep tests
SAVE12AD
Alloy82
TIG
HR6W
WEL-AUTOTIG-617
TIG
HR35
WEL-AUTOTIG-617
TIG
Alloy617
WEL-AUTOTIG-617
TIG
Alloy263
Alloy740
TIG
Alloy740H
Alloy740
TIG
1051
Alloy 740H was applied to Alloy 263 and Alloy 740H. Figure 7 shows the welding process, and
Figure 8 shows the weld joints after welding.
Fig. 8 The appearance of weld joints for A-USC boiler candidate tubes
After welding, side bend tests, root bend tests, tensile tests and the Charpy impact test for bond
and HAZ were conducted. Long term creep tests are ongoing to obtain test results at 100,000
hours. All samples passed the bend tests. The tensile strengths of the bonds are the same or
greater than those of the base metals at room temperature and high temperature.
To determine stress relief (SR) after welding, microstructure observation, stress relaxation tests
and the Vickers hardness test were conducted. It was confirmed that residual stress was almost
zero by X-ray measurement after SR heat treatment.
1052
Pipe Size
Bending
angle
Bending R Mechanical
properties
HR35
35040
90
4DR
HR6W
51038
60
3DR
HR6W
35040
30
4DR
Alloy617
30572
30
4DR
1053
Creep tests
HR35(f350)
HR6W(f500)
Alloy617(f305)
HR6W(f350)
R.T.
750
600
500
400
300
200
100
0
As bended
1185
1195
1210
1220
Heat treatment Temperature / degree C
Fig. 11 Effect of heat treatments on the tensile properties of HR6W after bending
Welding tests for large diameter piping
The welding tests listed in Table 4 were conducted to develop a welding process for large
diameter and thick walled pipes. SAVE12AD (650C class ferritic steel), HR6W, HR35 and
Alloy 617 were tested. The weldability of Alloy 617, which contains a large amount of boron was
also evaluated. The difference in HR6W weld joints welded by TIG and SMAW was evaluated
for their weldability and mechanical properties. Ferritic weld metal was used to weld SAVE12AD
piping. All of the materials except Alloy 617 passed the side bend test after welding. Some hot
cracking was observed by optical microscopy of the cross section surface of the weld joints of
1054
Alloy 617. Figure 12 shows photos of the macrostructure of an Alloy 617 weld joint and an
HR6W weld joint. The weldability of HR6W weld joints by SMAW was also confirmed. Charpy
impact tests of HAZ and bond show sufficient ductility at more than 100 J and their tensile tests
show sufficient tensile strengths that are equal to or greater than those of the base metals.
Table 4 List of welding tests for A-USC pipes
Materials
Filler metal
Welding
method
Microstruc
ture
Mechanical
properties
Creep tests
HR6W
WEL-AUTOTIG-617
TIG
HR6W
WEL 117
Alloy617
SMAW
HR35
WEL-AUTOTIG-617
TIG
Alloy617High B
NIMONIC Filler
Metal 263
TIG
Alloy617
WEL-AUTOTIG-617
TIG
SAVE12AD
New ferritic
steel
TIG
Alloy617
HR6W
Fig. 12 Cross sections of the macrostructures of large pipes for A-USC boilers
To determine the SR condition for large diameter piping, the relaxation behavior of residual
stress was studied by the stress relaxation testing method. The microstructures of the piping were
also investigated after heat treatments. Below 850C, the stress was higher than 50 MPa at 0.1
hours by the stress relaxation tests. Above 900C, the stress decreased immediately and was less
than 50 MPa at 0.1 hours. From these test results, the SR condition has to be more than 900C.
Figure 13 shows the microstructure in HAZ of an HR6W weld joint which changes widely
depending on the heat treatment. Below 900C, no precipitation was observed, but needle-like
precipitations were found above 950C. These are thought to be Cr carbides based on EDX
analysis. The microstructure in the base metal was observed, but there was no change after one
heat treatment. In HAZ of an Alloy 617 weld joint, no of precipitation was found above 900C.
900C for 3 hours was selected as the SR condition based on these test results. Figure 14 shows
the residual stress of the weld joint of HR6W after being welded and after being annealed at
900C for 3 hours. Residual stress without heat treatment was around 240 MPa and the SR
treatment decreased stress to around 20 MPa.
1055
As weld
900C x 3h
950C x 3h
As weld
After SR
treatments
0
100
200
300
Residual stress /MPa
Fig. 14 Changes in the residual stress in HR6W weld joints with SR treatments
To study the effect of SR treatment on creep rupture strength, creep rupture tests were
conducted on the standard specimens and the actual thickness size specimens. Figure 15 shows
the geometry of the large specimen. The creep rupture test was conducted on the large specimen
for 10,000 hours. Figure 16 summarizes the creep test results of HR6W weld joints. SR treatments
had no effect, and all plots lie in the range of the test results of the base materials. The final test
duration will be 100,000 hours and the tests are currently underway. Long term creep tests are
underway for Alloy 617 and HR35 as well.
Fig. 15 Creep rupture specimen with actual thickness size made of HR6W weld joints
1056
f 6mm size
actual thickness size
4
3
Stress /MPa
700
2
100
750
800
9
8
7
6
5
4
10
100
1000
10000
100000
Time / h
1057
SUMMARY
Basic tests were performed for A-USC candidate materials such as HR6W, HR35, Alloy 617,
Alloy 263, Alloy 740H and SAVE12AD and good results were obtained for the following items.
- Ability to bend small diameter piping
- Weldability and appropriate SR condition for small diameter piping
- Ability to use high frequency induction heating and bending for large diameter
piping and appropriate PBHT conditions
- Weldability and appropriate SR condition for large diameter piping
- High creep strength in long term creep tests
- Ability to produce a mock-up
In the future, the test loop project will make progress by using the above information.
REFERENCES
[1] H. Umaki, I. Kajigaya, T. Kunihiro, T. Totsuka, M. Nakashiro and R. Kume :IshikawajimaHarima Engineering Review, Vol. 31, No. 5, pp. 339 (1991)
[2] http://www.enecho.meti.go.jp/policy/coolearth_energy/coolearth-hontai.pdf
[3] H. Semba, H. Okada, M. Igarashi and M. Yoshizawa: Proceedings of the 9th Liege
Conference (2010)
[4] http://www.meti.go.jp/meti_lib/report/2012fy/E002041.pdf
[5] http://www.smst-tubes.com/en/products-services/downloads/technical-datasheets/
[6] http://www.specialmetals.com/documents/Nimonic%20alloy%20263.pdf
[7] http://www.specialmetals.com/documents/Inconel%20alloy%20740.pdf
[8] J.P. Shingledecker and G.M. Pharr. Journal of Materials Engineering and Performance
(2012)
[9] K. Kubushiro, K. Nomura, S. Takahashi, M. Takahashi and H. Nakagawa. Advances in
Materials Technology for Fossil Power Plants Proceedings from the Sixth International
Conference (2010)
[10] H. Okada, H. Semba, S. Ishikawa, M. Yoshizawa. CAMP-ISIJ, Vol. 25, (2012)
1058
This paper illustrates that CF8C-Plus offers a viable alternative not only to common austenitic
steels but also to solid-solution strengthened nickel-based superalloys for power piping and
tubing through the analysis of full-scale extrusions. This paper builds on early scoping studies
which showed forged CF8C-Plus had comparable properties to the cast alloy [7,8].
MATERIALS AND PROCESSING
This investigation discusses the manufacturing and analysis of two heats of a wrought alloy
melted to the CF8C-Plus (ASTM A297, A351, and A703 HG10MNN) chemistry. CF8C-Plus is a
precipitation strengthened, fully austenitic stainless steel of the composition in Table 1. The first
proof-of-concept heat was a 400 lbs (188 kg) hot-topped ingot melted by Carpenter Technologies
(Reading, PA) and open-die forged at 1200 C to 5:1 and 12:1 reduction ratios [7,8]. The
extruded heats discussed in this paper build on the experiences of that first heat.
The second and third heats of CF8C-Plus were 1000 lbs (472 kg) and melted by Special Metals
(Huntington, WV). Wyman Gordons Burnaugh, KY facility extruded Heat HF8726C in one step
at 1190 C from a 267 mm diameter ingot with a 114 mm bored center to a pipe with a 154 mm
OD and 19 mm wall (a 5.3:1 reduction ratio); likewise heat HF87268 was extruded to a pipe with
a 133 mm OD and 13 mm wall (a 9.4:1 reduction ratio). Finally, both were solution heat treated,
like the Carpenter heat, at 1200 C for 1 hour and water quenched. Chemistry for the three heats
is reported in Table 1 and show good agreement with the specification requirements. The only
notable discrepancies are that, relative to the first heat from Carpenter, the newer heats were
leaner in Nb and contained little Cu and Co.
Table 1: Aim and actual chemistry for the CF8C-Plus heats in this investigation (weight %,
balance Fe).
HG10MNN
Target
Min
Max
Carpenter
Heat 011124
Special Metals
Heat HF8728
Special Metals
Heat HF8726C
Cr
Ni
Mn
Mo
Nb
Si
Cu
Co
19.5
12.5
0.3
0.9
0.45
0.09
0.25
0.3
--
--
--
19
20
12
13
3.5 0.25
4.25 0.45
0.8
0.9
0.4
0.5
0.08
0.1
0.2
0.3
-0.5
-0.3
-0.04
-0.01
0.032
0.002
0.006
0.3
0.09
0.08
0.3
0.82 0.41
first trials. Table 2 discusses some of the findings, such as grain size, for the extrusions with
additional data from the earlier report [7,8] and example micrographs are included in Figure 1. In
all conditions, forge work dramatically refined the grain structure, breaking up the as-cast
features such as dendrites and carbides, with higher levels of work further refining grain size.
Solution annealing at 1200 C fully recrystallized the microstructure; unfortunately, it also had
the consequence of producing some uncontrolled grain growth, particularly in the samples with
more hot work.
Table 2: Metallographic Grain Size and Structure Observations of Wrought CF8C-Plus.
Sample
Comments
011124
As-cast
011124 As-cast
+ 3h at 1200 C
011124 (5:1)
as forged
011124 (12:1)
as forged
HF8728 (9.4:1)
as extruded
HF8728 (9.4:1)
+ 1h at 1200 C
HF8728 (9.4:1)
+ 4h at 1260 C
ALA 500 m
HF8726C (5.3:1)
ASTM 8 (23 m dia.)
as extruded
HF8726C (5.3:1)
ASTM 7 (32 m dia.)
+ 1h at 1200 C
HF8726C (5.3:1)
ASTM 3 (124 m dia.)
+ 4h at 1260 C
ALA 300 m
Table 3: Room temperature tensile and impact data collected for the CF8C-Plus extrusions as
compared to previous data [4]. All values reported here are the averages of at least two tests.
Condition
Orientation
As-Cast
Transverse
283
545
37
42
32
Longitudinal
262
547
27
35
33
As-Cast
Transverse
+ 2 h at 1200 C Longitudinal
294
574
24
32
24
268
551
26
35
28
Forged 5:1
Transverse
+ 2 h at 1200 C Longitudinal
336
705
44
50
73
329
707
52
68
178
Forged 12:1
Transverse
564
806
37.5
Longitudinal
564
807
36.7
Forged 12:1
Transverse
342
713
47
+ 2 h at 1200 C Longitudinal
354
738
52
Special Metals Heat HF8728
61
93
66
197
Extruded 9.4:1
Longitudinal
384
763
44
61
not tested
Transverse
386
743
40
42
not tested
61
not tested
50
61
Extruded 5.3:1
Longitudinal
390
788
41
65
not tested
Transverse
368
728
41
45
not tested
333
731
44
60
not tested
332
707
45
55
73
absorbed several times the energy of the samples tested from cast product which is very
encouraging for the development and use of this alloy as toughness can be an important property
in heavy wall component life management.
Elevated Temperature Properties
Mechanical testing also included elevated temperature tensile and creep-rupture testing up to 760
C. In USC and AUSC power plant designs, elevated temperature properties are the most
important for developing usage models such as ASME stress tables and provide quick
benchmarks for alloy comparison and selection.
The tensile testing performed at elevated temperature is summarized in Table 4 including data
from the first heat [7,8]. As with room temperature data, these extruded parts show marked
improvement over the cast versions, though not as consistently. Many of the extrusion results are
over 25% improved over the cast version of the alloy. Figure 2, showing a plot of strength versus
temperature of the data in Table 4, illustrates the increased scatter in yield strength over the range
of temperatures examined, as compared to the tight performance band of the ultimate tensile
strength. Tensile ductility of the extrusions over these elevated temperatures was above but
relatively close to the as-cast average with the notable exception of the Carpenter heat, forged to a
12:1 reduction, remaining well above the other tests. The data also begins to provide a measure of
heat-to-heat consistency/variation and some quantification of the effect of work on behavior.
1063
Table 4: Elevated temperature tensile data collected for the CF8C-Plus extrusions as compared
to previous data [4]. All values reported here are the averages of two tests.
Condition
Orientation
As-Cast
Transverse
760
150
291
37
Longitudinal
760
145
302
33
As-Cast
+ 2 h at 1200 C
Transverse
760
148
279
26
Longitudinal
760
128
236
14
Forged 5:1
+ 2 h at 1200 C
Transverse
760
178
338
31
Longitudinal
760
169
351
30
Forged 12:1
+ 2 h at 1200 C
Transverse
760
185
338
37
Longitudinal
760
188
Special Metals Heat HF8728
338
45
Extruded 9.4:1
+ 1 h at 1200 C
Longitudinal
Extruded 5.3:1
+ 1 h at 1200 C
400
210
574
43
450
195
560
41
500
181
533
39
550
185
518
39
600
182
486
36
650
178
462
36
700
174
419
37
750
164
Special Metals Heat HF8726C
370
33
Longitudinal
400
216
585
36
450
188
566
39
500
183
544
37
550
176
513
35
600
173
490
34
650
185
475
35
700
183
419
33
750
165
375
30
Creep-Rupture Testing
The creep-rupture testing on these extrusions provides a first assessment for this alloys
application in power piping. Creep-rupture tests were performed over a range of temperatures and
stresses to accelerate simulated operational conditions. Tests were limited to the exact same
conditions as were used before, per Table 5. Due to the nature of these early, exploratory tests,
rupture lives for these conditions are relatively short by design but sufficient to provide data at
stress levels for preliminary design considerations. The data presented in Table 5 shows a
reduction in capability in the new extrusions compared to previous heats, both cast and wrought.
There is possibly a connection to grain size as this is known to have an effect and the extrusions
microstructures were indeed finer than had been seen before. Combining the data from the earlier
study and this one, there is a sensitivity of rupture capability to the amount of forge work. Both
the 011124 12:1 and HF8728 (9.4:1) failed sooner than the corresponding data showing less work
(011124 5:1 and HF8726C).
1064
a)
b)
Figure 2: Stress vs. temperature plots of the a) tensile yield strength and b) ultimate tensile
strength from testing performed on the extruded heats as compared to both the as-cast baseline
and the previous forgings. Room temperature data has been offset for illustrative purposes only.
Figures 3 and 4 illustrate the data set generated on these extrusions and compare it to previous
data sets. The new extrusions consistently fall short of expectations in rupture life. Whereas the
initial forging of CF8C-Plus was comparable to the as-cast data set, the new extrusions,
especially at low stresses, show a small debit compared to expected life. The values are still
positive ones as CF8C-Plus maintains a competitive edge over standard austenitic stainless steels,
but something has reduced the capability in these heats [7,8] and further investigation will be
necessary. Similarly, rupture ductility in the new data is showing different behavior (Figure 4).
While these ductility values are lower, they are well above zero; however, the trend towards
lower ductility at longer test times merits additional testing to examine ductility at >10,000 hours.
1065
Table 5: Creep Rupture data from the CF8C-Plus extrusions as compared to previous data [4].
Temperature
(C)
Stress
(MPa)
700
150
750
750
800
800
44.0
57
5.38E-04
140
219.9
100
1864.2
38.5
42
3.87E-03
33.0
48.5
1.68E-03
100
142.8
75
36.5
47.5
2.35E-02
1194.6
30.0
40.5
Carpenter 011124 12:1
1.49E-03
700
150
1572.9
37.0
59.5
1.71E-03
750
140
156.2
47.5
60
2.23E-02
750
100
1327.2
34.6
53
3.37E-03
800
100
136.0
37.0
55
3.58E-02
800
75
875.1
31.0
41
Special Metals HF8728 9.4:1
3.16E-03
700
150
989.7
13.0
15.5
7.77E-04
750
140
141.4
18.5
23
1.20E-02
750
100
642.0
12.5
20
3.49E-03
800
100
65.1
22.0
22
7.44E-02
800
75
303.1
15.0
18.5
1.23E-02
760
103
543.6
14.0
14.5
Special Metals HF8726C 5.3:1
1.03E-03
700
150
645.3
15.5
750
140
116.6
750
100
761.1
800
100
123.7
800
75
582.1
760
103
451.1
18.5
3.26E-03
20.0
22
6.57E-03
19.0
20.5
4.42E-03
24.5
26
2.48E-02
19.5
21.5
1.23E-02
21.0
24.5
9.83E-03
DISCUSSION
Using rupture capability as a benchmark, even with the slightly lower strength in the latest trials,
CF8C-Plus remains as strong or stronger compared to similar austenitic stainless steels. Figure 5
shows the rupture strength of a series of high temperature stainless alloys, many of which are in
high volume application in power generation tubing (note none of these alloys is currently
available in a pipe form). CF8C-Plus ranks among the top stainless steel performers offering
sufficient strength even to compete with much more expensive nickel-based superalloys in high
temperature applications, especially those in the power generation industry such as in boiler tubes
and pipes. Figure 6 compares CF8C-Plus to some of those superalloys and shows how it can be a
competitive material while forgoing high-cost constituents like nickel.
As noted earlier, there does seem to be some benefits as well as detriments to extensive work
developed by the extrusion process in comparison to the forging. The 9.4:1 extrusion resulted in a
finer grain size, albeit with a propensity for very large grains, which resulted in higher yield
strength, but the sacrifice to rupture properties was noted as well impacting rupture life as well as
1066
Figure 3: A graph of time to rupture for the extrusions as compared to fit curves of average cast
behavior as well as the data from the Carpenter heat.
1067
1068
ductility negatively. When examining the alloy for large-scale manufacturing, some optimization
of the process parameters for uniformly great properties is needed or the variation from different
processes will need to be accounted for.
CONCLUSIONS AND NEXT STEPS
This study, undertaken by EPRI, continues to build a database that shows wrought CF8C-Plus
provides acceptable microstructural and mechanical properties to be considered for the power
generation industry in pipe and tube applications. Following the 400 lb heat produced and forged
at Carpenter, the work described herein produced and characterized two full scale pipes that
mirror a wrought steam pipe or header. The pipes were extruded at Wyman Gordon and were
nominally 5.25 inch OD x 0.5 inch wall thickness and 6 inch OD x 0.75 inch wall (13.3 x 1.3 cm
and 15.2 x 1.9 cm), each about 1000 lbs. These heats were mechanically tested to quantify their
ranking with respect to other alloys already in use as boiler tubing.
The results from the mechanical properties generated out of these three heats compare well to the
as-cast version of CF8C-Plus, better than several similar austenitic stainless steels, and even
comparable to some solid solution strengthened nickel-based superalloys currently used in this
application. The advantage of having this competitive alloy available is that the manufacturing
cost of CF8C-Plus is about 25% that of nickel-based superalloys, largely due to alloy content. In
the power generation industry where a single installation can require many tons of high
temperature boiler tubing (>600 C), this cost differential can offer a great deal of flexibility.
A summary of the properties generated during this feasibility study are presented below:
Microstructure - The hot-deformation dramatically transformed the coarse, dendritic, as-cast
microstructure into a uniform recrystallized grain structure that is many times finer in size.
Additional forge work seems to correlate, not unsurprisingly, with finer grain sizes down to
ASTM 8. Some optimization of solution heat-treatment will be required.
Room Temperature Tensile Properties - The 0.2% yield strength of the hot-extruded material
is about 20% stronger than as-cast CF8C-Plus steel while maintaining comparable ductility to
the as-cast product (> 40%).
Elevated Temperature Tensile Properties - At 760 C, yield strength of these wrought
materials is 25% stronger than as-cast, again with tensile elongation over 25%, which is
similar to or slightly improved over as-cast CF8C-Plus steel.
Toughness - Room temperature Charpy impact energy of both hot-extruded pipes is about 50
ft-lb (transverse), which is much greater than the 20 ft-lbs found in as-cast CF8C-Plus steel.
Creep Rupture Properties - The creep-rupture data from the hot-extruded CF8C-Plus at 5.3:1
and 9.4:1 reductions is slightly below the as-cast average. The HF8728 and HF8726C heats
rupture ductility data are below the as-cast values. Both of these effects could be related to the
refined grain structure observed in these parts, but when compared to other equivalent boiler
alloys, the wrought CF8C-Plus exceeded the rupture strength of similar alloys.
The investigation into these extrusions continues with a characterization of a coarser grain size
like the one reported after 4 hours at 1260 C. Testing in this condition will illuminate the effect
of grain size on mechanical properties such as creep-rupture strength and provide a basis for
selecting appropriate heat-treatments. The production of additional, larger heats will exercise the
supply chain and provide the demonstration history necessary for an ASME Code Case such that
this alloy could be used for pressure retaining parts. Long-term mechanical testing beyond 10,000
hours is planned as process optimization proceeds.
1069
ACKNOWLEDGEMENTS
The authors would like to thank P. Maziasz for his development of cast CF8C-Plus and assistance
with earlier characterizations and L. Klingensmith and C. Nowill (Wyman Gordon Fittings and
Pipes) and J. deBarbadillo (Special Metals) for their deep knowledge of the processing techniques
that led to a successful extrusion and their invaluable assistance in the evaluation of these pipes.
REFERENCES
[1]
[2]
[3]
[4]
P.J. Maziasz and M.J. Pollard, High-Temperature Cast Stainless Steel, Advanced
Materials & Processes, ASM-International, Materials Park, OH, 161(10), 2003, pp. 57-59.
[5]
P.J. Maziasz, J.P. Shingledecker, N.D. Evans, and M.J. Pollard, New Heat-Resistant Cast
Stainless Steel CF8C-Plus Advanced Materials & Processes, ASM-International,
Materials Park, OH, 166(10), 2008, pp. 27-29.
[6]
P.J. Maziasz, J.P. Shingledecker, N.D. Evans, and M.J. Pollard, Developing New Cast
Stainless Steels with Improved High-Temperature Creep Resistance, (PVT-08-1047)
Journal of Pressure Vessel Technology (ASME), 131(5), 2009, pp. 1-7 (051404).
[7]
[8]
[9]
P.J. Maziasz and R.W. Swindeman, Selecting and Developing Advanced Alloys for CreepResistance for Microturbine Recuperator Applications, Journal of Engineering for Gas
Turbines and Power (Trans. ASME), 125, 2003, pp. 310-315.
[10] J.P. Shingledecker, M. Santella, D. Wilson, I. Wright. State of Knowledge for Advanced
Austenitics. EPRI, Palo Alto, CA: 2009. 1020241.
[11] Hastelloy X Alloy, Publication H3009A, Haynes International, Kokamo, IN, 1997.
[12] Inconel Alloy 617, Publication SMC-029, Special Metals Corporation, Huntington, WV,
March 2005.
[13] P.J. Maziasz and P. Jablonski, 3rd Quarterly Report National Laboratory Collaborative
Project on Cast Ni-Based Alloys for Casing Applications Sept. 2009, Consortium for
Advanced Ultra-SuperCritical Steam Turbine Materials Project.
1070
1071
need to melt steel under high pressure nitrogen atmosphere. Such dedicated and high-cost device
is not preferable for basic study. Therefore, solid state nitriding was applied as a nitrogen
introduction method into the steel. High nitrogen steels are obtained in laboratory by holding the
steel sheets in nitrogen atmosphere at high temperature. However, solid state nitriding needs the
diffusion of nitrogen from the surface of the specimen sheet. Diffusion limited nitriding takes
long time to manufacture the thick plate. Therefore, thin plate was nitrided in short period, and
the piling up of plate specimens and hot rolling ,so-caled Laminate rolling, shortened the
process duration and avoided the oxidation of the sheet specimens during the nitriding due to the
impurity of the atmosphere, oxygen.
Chemical composition and manufacturing process of the specimen
Table.1 shows chemical compositions of the parent steels for nitride specimens. Basic
composition was determined Fe-12(mass%)Cr-1(mass%)W-1.5(mass%)Co. In order to
analyze the effect of nitrides in ferritic creep resistant steel, steels C changed
nitriding time for 0, 3, 5 hours. In the case of steels VV, V amount was changed from
0.2 to 0.9%. Model steels were melted in laboratory through high frequency induction furnace in
a vacuum atmosphere, and cast into 50kg ingots. Ingots specimens were hot rolled to 5 mm thin
plate specimens. The length of the thin plate specimens were 150mm.1150oC holding in 1atm
nitrogen atmosphere produced the nitrided specimens. Nitriding time was 3 and 5 hours. After
nitriding, oxide scale was removed by machining. As shown in fig.1, these sheets were piled up
on depth-with direction and packed in a steel box by cap welding. After preheating at 1200 oC for
30minutes, the laminate rolling produced the thick plate specimen with 8mm thickness. The hot
rolling reduction ratio was over 80%. These plate specimens were normalized at 1000 oC for 1
hour and tempered at 720 oC for 2 hours. Fig.2 shows macrostructure and microstructure of steel
C3 by optical microscope.
Table 1: Chemical composition of the parent specimens for nitriding (mass%)
C1,2,3
VV1
VV2
VV3
Si
Mn
Co
Cr
0.009
0.0031
0.0037
<0.001
0.062
0.058
0.06
0.058
0.49
0.50
0.50
0.49
1.53
1.54
1.54
1.53
11.92
12.20
12.22
12.11
0.21
0.35
0.90
0.97
1.01
1.01
1.00
0.0106
0.0101
0.0106
0.0115
1072
(a)
(b)
1073
Figure 4Boundary transition type Nitrogen diffusion model in solid state nitriding
V1
V1
V1
0.0362
0.0213
0.0368
CMA= 0.9exp {1.7 ( - 1.659.0102 [%Cr] - 7.6104 [%Cr] 2 + 3.4 102 [%Mn]
- 2.59105[%Mn] 2 - 5.0104 [%Cr] [%Mn] )} (1473K)
(1)
1075
1076
(b)
(a)
Cr2N
Cr2N
(a)
(b)
Figure 8 : TEM images of microstructure
of steel C3
(a)Before heat treatment (b) After heat treatment
VN
VN
Figure 10: TEM images of microstructure of steel VV3
(a)Before heat treatment (b) After heat treatment
1077
sl 1
MbE
sin 2 cos
1
4 1
ln
0.6
r0
(2)
(3)
C3
VV3
0.445 m
1.612 m
0.804 m
0.816 m
0.456 m
0.636 m
C3
VV3
90.9 MP
20.1 MPa
135.3 MPa
53.1 MPa
1078
(a)
(b)
Initial
Long
time
C3
VV3
90.9
MP
20.1
MPa
135.3
MPa
53.1
MPa
(a)
(b) Magnified strain curves at
transition region up to 100ks
Figure 12 : Creep strain curves of CR1 and VV3 steels at 620, 100MPa
1 of C3 was shorter than VV3 in average. However, 2 of C3 is much higher than VV3. Cr2N in
steel C3 also precipitated in boundary. VV3 had higher threshold stresses than C3. These results
also meet the creep rapture test results. In spite of VV3 steel had full ferrite phase, creep strength
of VV3 was higher than C3 with the dual phase microstructure. Cr 2N was not detected by
extraction residue XRD analysis of steel VV3. Nucleation and growth rate of VN is much lower
than Cr2N. Therefore, the precipitation strengthening by VN was almost decided by the inter
space of aligned VN precipitation lines. Furthermore, the precipitation initiate slower than Cr 2N.
The creep strain curve difference is derived from the VN precipitation behavior.
Ti and Zr are expected to precipitate more stable nitride. Results and discussion on Ti and Zr
containing steel will be introduced by presentation as in the announcement.
CONCLUSIONS
High nitrogen steel was manufactured by solid state nitriding and Laminate rolling. According to
the nitride morphology analysis and creep test, the following results were obtained:
1.
2.
3.
4.
5.
6.
1079
REFERENCES
[1] A. Sieverts, Absorption of Gases by Metals, Zeitschrift fr Metallkunde, Vol. 21, (1929),
pp. 37-46.
[2] M. J. Hu, J. S. Pan, Y. J. Li, D. Ruan, Mathematical modeling and computer simulation of
nitriding, Materials science and Technology, Vol. 19,(2000),pp.547-550.
[3] T. Tsuchiyama, H. Ito, K. Kataoka, S. Takaki, Fabrication of ultrahigh nitrogen austenitic
steels by nitrogen gas absorption into solid solution, Metallurgical and materials
transactions A, Vol. 34 A, (2003), pp2591-2599
[4] Y. Imai, T. Matsumoto, K. Maeda, Structural Diagrams and Phase Reactions of Fe-Cr-N
Ternary System Science reports of the Research Institutes, Tohoku University. Ser. A,
Physics, chemistry and metallurgy 19, (1967) ,pp.35-49.
[5] Y. Hasegawa, The new metallurgical precipitation strengthening model of w containing
advanced high Cr ferrtic creep resistant steels,7th International Conference On Advances In
Materials Technology for Fossil Power Plants, October (2013) In Printing.
[6] D. J. Srolovitz, R. A. Petkovic-Luton, M. J. Litton, Diffusional relaxation of the
dislocation-inclusion repulsion, Philosophical Magazine A, Vol. 48, Issue 5, (1983), pp
795-809.
1080
ABSTRACT (#16)
Constricted steam oxidation resistance and finite microstructural stability limits the use of 9 - 12
wt.-% chromium ferritic-martensitic steels to steam temperatures of about 620 C. Newly
developed 12 wt.-% Cr steels are prone to Z-phase precipitation, which occurs at the expense of
the strengthening precipitates, and therefore suffer an accelerated decline in strength during longterm operation. While the concept of ferritic-martensitic chromium steels thus seems to hit
technological limitations, further improvement in steam power plant efficiency necessitates a
further increase of steam pressure and temperature. Furthermore increasing integration of
intermitting renewable energy technologies in electrical power generation poses a great challenge
for supply security, which has to be ensured on the basis of conventional power plant processes.
Besides improved efficiency for resource preservation, load flexibility, thermal cycling capability
and downtime corrosion resistance will play key roles in the design of tailored materials for
future energy technology. Under these preconditions a paradigm shift in alloy development
towards improvement of cyclic steam oxidation and downtime corrosion resistance in
combination with adequate creep and thermomechanical fatigue strength seems to be mandatory.
The steam oxidation, mechanical and thermomechanical properties of fully ferritic 18 - 24 wt.-%
chromium model alloys, strengthened by the precipitation of intermetallic (Fe,Cr,Si) 2 (Nb,W)
Laves phase particles, indicate the potential of this type of alloys as candidate materials for
application in highly efficient and highly flexible future supercritical steam power plants.
INTRODUCTION
Reliable energy supply is - among many others - one of the most important requirements modern
industrial societies are based on. Even under the prerequisite of a 10 % reduction of the German
energy consumption by 2050 [1], future scenarios for the coming decades predict an increase in
global energy demand. Moderate economic growth in OECD countries, but especially the rapidly
growing economies of the non-OECD - countries could thus account for almost a tripling of
global energy demand until 2050 [2]. The development of 9 - 12 wt.-% chromium ferriticmartensitic steels during the past few decades enabled a gradual rise in steam parameters and thus
an increase in the efficiency of steam power plants from about 31 % in the 1960s to greater than
43 % today [3]. In the course of this a reduction in specific CO 2 emissions per megawatt hour of
generated electricity by approximately one fourth was accomplished. For further improvement of
plant efficiency towards 50 % a further increase of steam parameters would be necessary [4].
Furthermore, only the combination of well known - efficiency improved - conventional processes
1081
and renewable energy technologies seems to be promising to tackle the uprising challenges.
Thermal power plants, either running on fossil or regenerative fuels, will continue to play a
significant role in future supply security backing the fluctuation caused by the integration of
intermitting renewable technologies.
The future trend to not only improved efficiency, but increased load flexibility, thermal cycling
capability and downtime corrosion resistance will pose new demands like resistance to
thermomechanical fatigue, cyclic oxidation and aqueous corrosion in the development of suitable
materials. Traditionally the material development for base load steam power plants was focused
on creep strength, with steam oxidation resistance as a subordinate goal. The strength potential of
state of the art ferritic-martensitic 9 wt.-% Cr steels cannot be adequately exploited, because of
their lack in steam oxidation resistance. Currently the application of these materials is constricted
to maximum temperatures of about 620 C [4]. Newly developed enhanced chromium (up to 12
wt.-%) steels like VM12, NF12 and HCM12 (T122) do exhibit superior steam oxidation
resistance. However these materials might be prone to Z-phase (Cr(V,Nb)N) formation, which
occurs at the expense of the strengthening finely dispersed MN-nitrides (M=V, Nb) and is
believed to cause an accelerated decline in creep strength during long-term application [5, 6].
The thermomechanical fatigue properties of these materials are still largely unknown. Due to the
comparatively low content of chromium the resistance to downtime corrosion is limited and
extensive conservation measures have to taken during wet or dry storage [7]. Austenitic stainless
steels and nickel-base alloys would provide sufficient creep, steam oxidation and corrosion
resistance. Due to their comparatively high coefficients of thermal expansion and low thermal
conductivity at application temperature [8] they do have disadvantages in thermal cycling
operation. Furthermore, high nickel contents along with the highly fluctuating nickel price cause
high investment and maintenance costs and make the application of these alloy classes
economically risky.
A new high-performance ferritic steel, which combines high creep, steam oxidation and corrosion
resistance with good thermomechanical fatigue resistance and low cost, would remedy this
situation. For several years the Institute for Microstructure and Properties of Materials (IEK-2) at
Forschungszentrum Jlich, Germany developed fully ferritic high chromium (22 wt.-%) steels for
application in high temperature fuel cell stacks [9, 10] in cooperation with Outokumpu VDM.
Commercial Crofer 22 H exhibits promising creep and thermomechanical fatigue properties in
the temperature range from 600 650 C without any further optimization done yet. The
performance of newly developed fully ferritic model alloys, designed on the technological basis
of Crofer 22 H, shows potential to compete with standard ferritic-martensitic 9-12 Cr and even
some austenitic steels in steam oxidation and mechanical strength in the temperature range from
600 to 650 C. The mechanical properties of these high-performance ferrites depend on both
chemical composition and thermomechanical treatment history. The present paper gives an
overview of the current development status and an outlook to future development.
EXPERIMENTAL
Materials
Because of limited availability of advanced model steels some of the mechanical testing and the
characterization of the impact of thermomechanical pre-treatment was accomplished utilizing
commercial, solution annealed (1075 C, 22 Min., air cooled) 12 mm Crofer 22 H plate
material, which was manufactured by Outokumpu VDM (formerly ThyssenKrupp VDM) by
conventional arc melting. The Crofer 22 model steel and the advanced materials (Tab. 1) were
produced by Outokumpu VDM by vacuum melting of approximately 10 kg ingots. The casted
blocks were annealed at 1080 C for 2 h, then hot-rolled (between 1050 - 980 C) to a final plate
1082
thickness of 16 mm and subsequently air cooled. The chemical compositions of all the steels
were measured by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and
are given in Tab. 1.
Table 1: Chemical compositions (wt.-%)
Alloy:
Cr
Nb
Si
Mn
La
Fe
Ti
Crofer 22 model
Crofer 22 H
0.002
0.007
0.011
0.015
22.38
22.93
1.91
1.94
0.52
0.51
0.25
0.21
0.44
0.43
0.017
0.082
R
R
0.037
0.07
22Cr2.25W0.5Nb
22Cr 2.45W0.6Nb
0.001
0.006
23.79
2.25
0.49
0.25
0.45
0.131
0.003
0.002
0.007
22.72
2.45
0.58
0.22
0.47
0.036
0.004
Crofer 18 model
0.001
0.005
18.17
1.95
0.51
0.25
0.45
0.132
0.057
creep testing were equipped with electrical five-zone furnaces (temperature accuracy: +/- 3 C).
In tensile testing type R (Pt/RhPt) thermocouples were attached to the specimens gauge length for
temperature control. Shielded temperature measuring rods (type R) in close vicinity to the
specimens were utilized in the creep experiments.
All specimens were heated to the designated testing temperature within 1.5 h and then held for 1
h before starting the testing machine (tensile) or applying dead weight loads (creep) for ensuring
thermal equilibrium and comparability of initial microstructure.
Inductive heating was applied in thermomechanical fatigue testing. Type R sling thermocouples
were utilized for temperature control and strain measurement was accomplished by an
extensometer directly attached to the gauge length of the samples. The tests were carried out in
total strain control, where
t = me + th . [1]
t : total strain, th : thermal strain, me : mechanical strain
Out-of-phase (OP) experiments with me = - th and me = - 1.8 th were carried out in the
temperature range from 250 to 650 C (no dwell times at T Min. and T Max. ) in air applying
heating/cooling rates of 10 Ks-1. The lifetime was evaluated by intersection of linear
approximations of the upper shelf- and the downhill-slope of the Max. line (cf. Fig. 3).
Steam Oxidation Testing
Discontinuous oxidation experiments were performed at specimens of the dimensions 20 mm 10
mm 2 mm, which were machined and subsequently ground down to a 1200 grit surface finish, in
horizontal furnaces. Sintered alumina was used for the reactor tubes and specimen containers.
This is important in testing atmospheres containing water vapor in combination with low
equilibrium oxygen partial pressure [11] to prevent contamination of the specimens by volatile
silicon containing species released by silica glass components of the experimental setup.
Discontinuous oxidation tests were carried out in simulated water steam environment (Ar50Vol.%H 2 O) at 600 C. The specimens were cooled to room temperature under Ar atmosphere for
weight change measurement in 250 h intervals.
RESULTS AND DISCUSSION
Initial Microstructure
The initial microstructure of the materials is characterized by a fully ferritic matrix with equiaxed grains in case of the solution annealed commercial material (Fig. 1a). The hot-rolled model
steels display elongated grains, aligned towards the rolling direction (cf. Fig. 1b). Few
comparatively coarse La 2 O 3 - (cf.: in Fig. 1) and Ti/Nb-C/MX-particles (cf.: in Fig. 1)
decorate the grains interiors (Fig. 1), which are merely free from small intermetallic particles.
Only very few small AB 2 Laves type precipitates with a chemical composition of 43.5 % Fe, 8 %
Cr, 1.5 % Si, 25 % Nb and 22 % W (wt.-%), which form during cooling after solution treatment
or hot-rolling, occasionally decorate the grain boundaries. The micrographs displayed in Fig. 1b
are representative for all the model steels.
1084
200 m
150
m
200 m
a)
b)
Fig. 1: Initial microstructures (OM) of (a) commercial (solution annealed) Crofer 22 H and (b)
the (hot-rolled) Crofer 22 model steel (representative for all the model steels)
Hardness
Table 2 contains the hardness testing results. The increased hardness of the ambient temperature
pre-deformed Crofer 22 H and the hot-rolled model steels is apparently caused by increased
dislocation density, because all the materials are free from hardening precipitates (cf. Fig. 1). The
impact of dislocation density on precipitation morphology and the resistance against
thermomechanical fatigue and creep will be demonstrated in the following.
Table 2: Hardness of the tested materials
Material:
Crofer 22 H
Crofer 22 H,
pre-deformed
Crofer 22 model
22Cr2.25W0.5Nb
22Cr 2.45W0.6Nb
Crofer 18 model
Hardness [HV0.1]:
197
237
226
218
223
216
Tensile Properties
The tensile testing results of commercial Crofer 22 H and the Crofer 22 model steel at ambient
temperature, 600 C and 700 C are summarized in Tab. 3.
Table 3: Tensile properties of solution annealed and pre-deformed Crofer 22 H and the Crofer
22 model steel at different temperatures
Temperature
[C]:
ambient
600
700
YS
[MPa]:
Crofer 22 H
solution
preannealed
deformed
311
426
128
84
-
1085
UTS
[MPa]:
Crofer 22
model steel
363
162
102
Crofer 22 H,
solution
annealed
498
332
147
Crofer 22
model steel
501
343
144
The hot-rolled model steel offers higher yield strength than the solution annealed commercial
Crofer 22 H at all temperatures, while the ultimate tensile strength values are in good
agreement. Both materials were still free from small, strengthening precipitates after tensile
testing at 600 C (time at temperature approximately 18 hours). Because of widely comparable
chemical compositions it can be assumed that the higher yield strength values of the hot-rolled
model alloy were caused by enhanced dislocation density only. By plastic pre-deformation the
room temperature yield strength of Crofer 22 H was increased to 426 MPa. No 600 / 700 C
tensile tests were performed with the pre-strained material.
The Impact of Initial Dislocation Density
Comparing the precipitate microstructure, creep and thermomechanical fatigue properties of
solution annealed / pre-deformed Crofer 22 H and the Crofer 22 model steel, the important role
of initial dislocation density becomes obvious.
Creep
Fig. 2 displays creep curves (600 C, 120 MPa) of the Crofer 22 H model alloy and Crofer 22
H in the solution annealed / pre-deformed state.
Fig. 2: Creep curves of the hot-rolled Crofer 22 model alloy and solution annealed / predeformed Crofer 22 H (600 C, 120 MPa, air, experiment marked with arrow: in progress).
Inserted micrographs show the particle morphologies after 100 hours (in case of solution
annealed Crofer 22 H after rupture at 106 h; SEM, inverted for better contrast, taken from
head sections of the creep specimens).
Apparently the thermomechanical pre-treatment history has a decisive influence on the creep
resistance: The solution annealed (1075 C, 22 Min., air cooled) commercial material (HV0.1:
197) failed after only 106 hours of testing. On the contrary the pre-deformed material (HV0.1:
237) showed a performance beyond the level of the hot-rolled trial alloy (HV0.1: 226), which
ruptured after 31134 hours. Considering yield strength and precipitate nucleation during creep
1086
this behavior can be explained as follows: In the cases of the hot-rolled model steel and the prestrained Crofer 22 H material enhanced dislocation density causes increased yield strength.
Consequently these two materials are loaded within its elastic regimes while solution annealed
Crofer 22 H is loaded into the plastic regime. Precipitation starts at about 25 hours at 600 C in
solution annealed Crofer 22 H. This approximately correlates with the onset of tertiary creep
(cf. Fig. 2) and it can be concluded that precipitation is too slow to unfold a beneficial effect.
Both the hot-rolled Crofer 22 model steel and pre-deformed Crofer 22 H are still well within
the transient stages of creep at this point in time. The micrographs inserted into Fig. 2 were taken
from (quasi stress-free) head sections of the creep specimens after 100 hours (in case of Crofer
22 H after rupture at 106 hours) of testing at 600 C. Interestingly the particles are comparatively
big and low in quantity in Crofer 22 H, whereas the hot-rolled and the pre-strained Crofer 22
H materials show a shift towards smaller mean particle diameter and higher number density.
Enhanced initial dislocation density can be considered to have a manifold impact on the
microstructural properties and thus the mechanical strength of such materials: First, enhanced
dislocation density gives a (short-term) strengthening effect itself. Second, it may boost
precipitation kinetics. Third, it changes the morphology of the Laves phase particles.
Thermomechanical Fatigue
P91
Crofer 22 H
Crofer 22 H, pre-deformed
400
400
Max.
200
0
b*
t*
t*
-200
Stress [MPa]
Stress [MPa]
Max.
t*
t*
Min.
-200
Min.
b*
200
-400
-400
1500
3000
4500
500
1000
1500
2000
a)
b)
Figure 3: Cyclic deformation curves of ferritic-martensitic P91 and solution annealed / predeformed Crofer 22 H with me = - th (a) and me = - 1.8 th (b). t*: terminated, b*: broken.
Pre-deformation prior to testing further extends the fatigue life of Crofer 22 H (Fig. 3a: me = th : Crofer 22 H, pre deformed: 4489 cycles, Fig. 3b: me = - 1.8 th : Crofer 22 H, pre
deformed: 1048 cycles). A closer look to the Min. and Max. graphs in Fig. 3a uncovers the effect
of cold deformation: Cyclic strain hardening is encountered in solution annealed Crofer 22 H in
the low temperature tensile regime of the first cycles (app. + 100 MPa), whereas the pre1087
deformed material exhibits cyclic softening in the high temperature compression regime
accompanied by only little strengthening in the tensile regime. This behavior may be explained
by deviating dislocation density evolution in the two materials during the TMF-cycle: In case of
pre-deformed Crofer 22 H the dislocation density was increased, to a level that the initially
solution annealed material obviously matches after the first couple of cycles, prior to the TMF
experiment (cf. Min. / Max. lines in Fig. 3a). Recovery by annihilation of stored dislocations
overcompensates the strengthening effect by newly created ones during the high temperature
compression phases. This leads to significant softening of the pre-deformed (approximately
80 MPa) and prevents further strengthening of the solution annealed material. Strengthening
of solution annealed Crofer 22 H increases during the high temperature compression regime,
while it remains almost the same during the low temperature tensile phases with me = - 1.8 th
(Fig. 3b). Higher tensile and lower compressive stresses in combination with reduced softening in
the high temperature compressive regime is encountered in case of the pre-deformed material.
Increased mechanical strain during cycling apparently - at least partly - counterbalances recovery.
Detailed examination of the microstructural changes, especially of precipitate evolution, during
TMF cycling focused on thermomechanical pre-treatment history is one of the main topics of
ongoing research.
Creep Properties of the Model Steels
Because of their comparatively low chromium contents of 9-12 wt.-% state of the art ferriticmartensitic steels only offer moderate high temperature steam oxidation and fireside corrosion
resistance. The strength potential of for example P92 cannot be fully utilized in power plant
processes for this reason.
Figure 4: Stress rupture plot of the ferritic model alloys in comparison to conventional ferriticmartensitic steels (600 C, air; data for P91, P92, E911 processed from ECCC data sheets 2005
[13], for VM-12 from [14])
The proposed fully ferritic high chromium materials offer supreme steam oxidation [11, 12] and
corrosion resistance at operating temperatures of 600 - 650 C in combination with promising
creep properties. The creep rupture performance of the hot-rolled Crofer 18 / 22 and advanced
1088
model alloys are depicted in Fig. 4. The Crofer 22 model alloy outbalances the extensively used
conventional 9 Cr steel P91 in creep performance up to testing durations of 30000 hours. Owing
to their increased tungsten and niobium contents the advanced model steels exhibit further
improved creep resistance in short- ( 15000 h) and medium-term durations (~ 44000 hours). In
particular, the 22Cr2.45W0.6Nb variant approaches the performance of the currently strongest
commercial 9 Cr steel P92 in short-term testing at comparatively high stress (145 MPa). The 120
MPa specimen is still within the secondary stage of creep with an elongation of 0.3 % after
43970 hours. To reduce the formation of the undesired, potentially embrittling, (Fe,Cr) -phase
the chromium content was decreased to 18 wt.-% in the Crofer 18 model steel. This
compositional change did not unfold negative effect on the creep performance so far (cf. Fig. 4).
At 600 C precipitation mainly takes place in between 20 and 300 hours in case of the advanced
model alloys. For example the mean equivalent circle diameter (ECD) of the Laves phase
precipitates in the 22Cr2.45W0.6Nb model steel is ~ 70 nm after 300 hours. Obviously the
(Fe,Cr,Si) 2 (Nb,W) Laves phase particles do only show moderate growth, which is demonstrated
by the SEM micrograph taken after 26086 hours of annealing at 600 C (cross section taken from
the head of the 120 MPa creep specimen, cf. micrograph inserted into Fig. 4: mean ECD of Laves
particles: ~ 85 nm). Apparently the strengthening (Fe,Cr) 2 (Nb,W)-particles do coarsen much
slower than it is reported for (Fe,Cr) 2 W and (Fe,Cr) 2 Mo-Laves phases in conventional 9 - 12 Cr
steels [15, 16].
1089
316
800
1000
100
LN
1
P9
10000
22Cr2.45W0.6Nb
22Cr2.25W0.5Nb
Crofer 22 model
600
625
310
P9
2
650
Temperature [C]
Figure 6: Rupture time / temperature chart (stress: 145 MPa) of conventional ferriticmartensitic, austenitic and the novel ferritic model steels (P91, P92, 310, 800H and 316 LN data
processed from [13]; experiment marked with arrow: in progress.
The shaded area indicates the target area for further alloy development.
Because of the well balanced property profile the outlined alloying philosophy should offer the
development potential to increase the efficiency, load flexibility and thermal cycling capability of
future power plants. Furthermore economic savings by avoiding conservation measures during
downtime may be reached.
Future work will comprise:
ACKNOWLEDGEMENT
The authors gratefully acknowledge the support of W. Lange, M. Braun, H. Reiners, H. Esser and
A. Moser in mechanical testing, V. Gutzeit and J. Bartsch in sample preparation and Dr. E.
Wessel and Dr. D. Grner for SEM investigations.
REFERENCES
[1] T. Klaus, C. Vollmer, K. Werner, H. Lehmann, K. Mschen: Energy Target 2050: 100
% Renewable Electricity Supply. In: 2050: 100 %, Publikation des
Umweltbundesamtes, http://www.umweltdaten.de/publikationen/weitere_infos/39970.pdf
[2] P. Grundy: Shell energy scenarios to 2050.
http://www.static.shell.com/static/public/downloads/brochures/corporate_pkg/scenarios
/shell_energy_scenarios_2050.pdf
[3] The Power Plant Process. In: The Niederaussem Coal Innovation Centre. November
2008, p. 8,
http://www.rwe.com/web/cms/mediablob/en/234504/data/2378/5/rwe-powerag/innovations/coalinnovation-centre/Brochure-The-Niederaussem-Coal-InnovationCentre.pdf
[4] R. Viswanathan, W. Bakker; Materials for ultra-supercritical coal power plants Boiler materials - Part 1; In: Journal of Materials Engineering and Performance
Volume 10, Number 1, 81-95, DOI: 10.1361/105994901770345394
[5] H. K. Danielsen, J. Hald; Behaviour of Z-Phase in 912%Cr steels; In: Energy
Materials: Materials Science and Engineering for Energy Systems, Volume 1, Number
1, March 2006, pp. 49-57
[6] H. K. Danielsen, J. Hald; Influence of Z-Phase on Long-term Creep Stability of
Martensitic 9 to 12 % Cr Steels; In: VGB PowerTech 5/2009, pp. 68 73
[7] GE Power & Water, Water & Process Technologies; Handbook of Industrial Water
Treatment, Chapter 11;
http://www.gewater.com/handbook/boiler_water_systems/ch_11_preboiler.jsp
[8] F. Richter; The Physical Properties of Steels, The 100 Steels Programme, Part I:
Tables and Figures; http://ebookbrowse.com/staehle-richter-pdf-d445273030
[9] J. Froitzheim; Interconnectors and their Interactions with Ni Base Anodes in Solid
Oxide Fuel Cells (SOFC), Schriften des Forschungszentrums Jlich, Reihe Energie &
Umwelt / Energy & Environment 16, URI: http://hdl.handle.net/2128/3615, ISBN: 389336-540-0, ISSN: 1866-1793
[10] J. Froitzheim, G.H. Meier, L. Niewolak, P.J. Ennis, H. Hattendorf, L. Singheiser, W.J.
Quadakkers; Development of high strength ferritic steel for interconnect application in
SOFC; In: Journal of Power Sources 178 (2008); pp. 163173
[11] In: Shreirs Corrosion. Editors: Bob Cottis, Mike Graham, Rob Lindsay, Stuart Lyon,
Tony Richardson, David Scantlebury, Howard Scott. Fourth Edition (2010), Vol. 1, S.
407-456
[12] I. G. Wright, R. B. Dooley; In: International Materials Reviews 55 (3), 2010, S. 129167
[13] ECCC Datasheets 2005
[14] J. Gabrel, W. Bendick, B. Vandenberghe, B. Lefebvre; Status and Development of
VM12 steel for tubular applications in advanced power plants; In: Energy Materials,
2006, Vol. 1, Nr. 4, pp. 218 222
1091
1092
ABSTRACT
The recently developed 12%Cr steel VM12-SHC is characterized by very good creep properties
at temperatures up to 620C. This new material development exhibits an excellent oxidation
resistance in steam atmospheres at the typical application temperature but also at temperatures up
to 650C. In comparison to the existing 9% Cr grades T/P91 and T/P92, VM12-SHC steel opens
due to its excellent oxidation behavior, new possibilities for its application as a heat exchanger
boiler component.
It was found that outside its application temperature range VM12-SHC also shows, as all 912%Cr steels, the appearance of the so called Z-phase. This effect was investigated to understand
its influence on creep properties of this class of ferritic/martensitic steels aiming at controlling the
microstructure stabilities for future grade developments.
Creep testing has been carried out in the temperature range between 525C and 700C. Selected
crept specimens have been investigated using light optical microscopy, SEM with EDX and
TEM. In this study, the oxidation behavior of a number of typical martensitic 9-12%Cr steels was
compared with the newly developed 12% Cr steel VM12-SHC. The compositions and
morphologies of oxide scales formed after 5000 h exposure steels in simulated steam
environments as function of temperature were characterized by light optical metallography and
scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX).
INTRODUCTION
The main driver for the further development of the power plant technology is the increase of the
operating efficiency, which on the one hand would help to limit the fuel consumption and
operating costs and on the other hand imply the reduction of CO2 emissions [1]. The
improvement of the efficiency in fossil-fired steam power plants can only be achieved by further
increase of steam parameters, namely pressure and temperature. The realization of elevated steam
parameters can accomplish by application and/or development of materials with improved
capabilities with regard to creep rupture strength and oxidation properties at higher temperatures.
Martensitic creep resistant 9-12%Cr steels are preferentially applied for constructions of thickwall components, because they combine high creep strength, good steam oxidation resistance,
good thermal conductivity, low thermal expansion coefficient in addition with high resistance
against thermal fatigue, good workability and low production costs. The increase of the
temperature application range up to 630C and beyond will require an improvement on the
oxidation resistance properties of the used materials [2]. Enhanced oxidation resistance can be
1093
implemented by an increase of chromium content from 9 to 12%. W modified 12%Cr steel grade
HCM12A represents the first attempt to develop steel grade with good creep properties and
oxidation resistance [3]. However, the microstructural instabilities related with the appearance of
the so called Z-phase led to a breakdown of the long-term creep properties resulting in creep
rupture strength below that of P92. Vallourec & Mannesmann developed a 12%Cr steel under the
designation VM12-SHC that combines good creep properties and excellent oxidation behavior of
a 12%Cr steel [4].
The aim of this paper is to describe the microstructure evolution and appearance of the Z-phase in
VM12-SHC, deliver explanations concerning the origin for the drop of the long-term creep
rupture strength of all martensitic steels and give alternative or new approaches to develop new
boiler grades, which should comprise excellent creep properties and good steam oxidation
resistance. In addition, the oxidation behavior of the VM12-SHC steel in simulated steam
environment will be presented laying special emphasis on scale growth mechanisms in the high
water vapour containing atmospheres.
EXPERIMENTAL
The chemical composition of the investigated VM12-SHC heat is given in Table 1. The heattreatment consists of two steps: normalization at 1060 C for 30 minutes followed by air cooling
and tempering at 780 C for two hours followed by air cooling. The creep experiments have been
carried out at 575 C, 600 C, 625 C and 650 C. Selected crept specimens were investigated
using light optical microscopy SEM, with EDX and TEM. Extracted carbon replicas were
prepared and investigated by TEM. The phase identification was done by means of EDS (Energy
Dispersive X-Ray spectroscopy), EELS (Electron Energy Loss Spectroscopy) and electron
diffraction (ED). The diameters and the number densities of different precipitates were evaluated
and analyzed according to [5].
Table 1: Chemical composition of investigated VM12-SHC heat
Chemical Composition (%)
C
Mn
Si
Cu
Cr
Mo
Ni
Co
Al
Nb
VdTV
Specification
0,10
0,14
0,15
0,45
max.
max.
max.
0,01
0,25
11,00
12,00
0,20
0,40
0,20
0,30
0,10
0,40
0,003
0,006
0,030
0,070
1,40
1,80
max.
0,02
0,40
0,60
0,02
1,30
1,70
0,03
0,08
Heat 1
0,112
0,36
0,017 0,001
0,47
0,05
11,49
0,29
0,28
0,29
0,0046
0,062
1,48
0,008
1,43
0,049
Additionally, oxidation specimens with dimensions of 20x10x2 mm3 were machined from a
VM12-SHC model alloy and ground to 1200 grit surface finish prior to exposure to steam.
Specimens of VM12-SHC steel were exposed at 550 C, 600 C and 650 C for 5 000 h in Ar50%H2O (concentration in vol.%). The mass changes of the oxidized specimens were
periodically measured every 250 h. After exposure, the steel microstructure and the oxide scales
formed were examined using light optical microscopy (LOM) and scanning electron microscopy
(SEM) with an energy-dispersive X-ray analysis (EDX). The metallographic preparation of the
oxidized specimens was obtained by first electroplating with nickel prior mounting in an epoxy
resin and subsequently, the specimens were conventionally grounded and polished. For
comparison reasons, published data on various 9%Cr steels, such as P/T91 and P/T92 steels and
various austenitic steels were collected and compared with the values obtained in this work.
1094
180
160
140
120
100
80
60
VM12-SHC
40
T91
20
0
T92
0
100
200
300
400
500
600
700
Temperature in C
Figure 1: ASME allowable stress values for VM12-SHC, T92 and T91.
Figure 2 shows the microstructure of the VM12-SHC steel after the heat-treatment
(1050C/30min, a.c. +780C/2h, a.c.). The microstructure consists of tempered martensite with
the absence of -ferrite.
20 m
TEM investigations showed that in the as-received state six different types of precipitates can be
observed: M23C6 chromium-rich carbides, MX vanadium nitrides and niobium carbides, M2X
chromium nitrides and boron nitrides (BN). Figure 3 shows exemplarily a zero loss peak image
and the corresponding RGB and niobium ratio images. Thus, by combining diffraction patterns,
EELS and EDS, the Cr-rich precipitates could be identified as M23C6, the V-rich particles as
MX(VN), and the Cr and V-rich particles as Cr2N (M2X).
a)
c)
b)
Figure 3: TEM images of VM12-SHC in as-received state (after heat-treatment), a) zero loss
peak image (ZLP), b) RGB image (red: vanadium; green: chromium; blue: nitrogen) and c) Nbratio mapping.
No Z-phase was detected in as-received state. However, after creep exposure Laves phase and
modified Z-phase particles were found (Figure 4). The discrimination between Z-phase and MX
carbonitrides was done by comparing V and Cr maps [6].
RGB: Red (V) Green (Cr) Blue (N)
Nb
b)
a)
c)
NbC
Cr2N
M23C6
200 nm
200 nm
VN
200 nm
Figure 4: TEM images of VM12-SHC after creep at 625C for 17487h, a) zero loss peak image
(ZLP), b) RGB image (red: vanadium; green: chromium; blue: nitrogen) and c) Nb-ratio
mapping.
Figure 5 shows the balance between the elements Nb, Fe+Cr and V in modified Z-phase and MX
in creep specimens tested at 575C, 600C and 625C. Modified Z-phase particles as well as MX
particles contain small amounts of Fe (1-3 at%). The chemical composition of MX and modified
Z-phase particle does not show a significant temperature or load dependence.
1096
100
As-received
575C / 17487h
80
25
600C / 24639h
Z-phase
40
%
[at
Nb
[at
%
60
50
e
+F
Cr
625C / 17487h
75
20
MX
100
0
20
40
60
80
100
V [at%]
Figure 5: Ternary diagram of as-received and crept specimens at 600C and 625C.
Further, it was found that the number of modified Z-phase precipitates increased with increasing
temperature and exposure time, whereas the number density of MX precipitates at the same time
significantly decreased (Figure 6).
1,0E+20
650C
1,0E+19
1,0E+18
1,0E+17
10
As-received
100
1000
10000
100000
Figure 6: Evolution of the number density of MX precipitates during creep exposure at 650C.
Much work has been done to indentify the cause for the loss of the long-term creep rupture
strength of 9-12%Cr steels. Basic understanding of the mechanisms behind the drop of creep
properties has been established [3, 6-8]. Very recently, it was shown that the formation of the
complex nitride, the so called modified Z-Phase Cr(V,Nb)N, might be responsible for the
deterioration of the long-term creep properties at elevated temperatures. Hence, the MX particles
transform increasingly during exposure to thermodynamically more stable Z-Phase [8]. The Zphase grows rapidly and consumes the surrounding MX strengthening particles. Since the Zphase emerges as a large particle due to its rapid coarsening, its strengthening effect is considered
as negligible.
As the driving force for Z-phase formation is directly related to the steel Cr content [11], the
number density of Z-phase will increase with increasing the Cr content in the steel, imposing a
1097
Stress [MPa]
steeper drop of creep rupture strength in a stress versus rupture time diagram (Figure 7). This is
also the reason, why all available 11% Cr steels that rely on MX carbonitride strengthening,
failed to reach the T/P92 creep strength level.
Increasing Cr content
12Cr
9Cr
Time [h]
Figure 7: Schematic illustration of the effect of Z-phase formation on creep rupture strength of
MX strengthened heat-resistant steels
However, the possibility to develop ferritic/martensitic steel grades with creep strength beyond
that of currently strongest commercially available boiler grade T/P92 are not completely
exhausted. New alloying design approaches disclose opportunities to develop steel grades with
improved creep properties.
All ferritic/martensitic 9-12% Cr boiler steel grades are characterized by a metastable
microstructure, which will evolve during thermal exposure. The microstructure change/instability
(precipitate coarsening, change in dislocation density, recovery etc.) explains the decrease in
creep rupture strength, which is common for all steels of this class. Once the microstructurerelated strengthening effects completely disappear, the inherent creep strength will remain [10].
By retardation of the microstructural changes the drop in the creep rupture strength can be
delayed to longer times, which are not relevant for the application. The stabilization of the
microstructure usually involves different types of precipitates. The main microstructure
stabilizers in 9-12% Cr steels are the finely and homogeneously throughout the matrix
dispersed MX carbonitrides (M: V, Nb; X: C, N) and M23C6 carbides (M: Cr, V, W, Mo), located
at prior austenite grain boundaries, martensite block, packet and lath boundaries. Since the Zphase formation preferentially occurs at PAGB (prior austenite grain boundaries) leaving MX
denuded zone at and around them, the recovery of the martensitic microstructure will
preferentially occur in this area [11]. The weakened PAGB are susceptible to creep void
formation resulting in intergranular fraction (grain boundary sliding). This instability of MX
particles eliminates possibilities to develop high Cr martensitic steels relying mainly on
strengthening by MX particles.
Therefore, novel alloying concepts for development of new stronger martensitic heat-resistant
steels involve:
Use of Z-phase as strengthening particle
1098
Retardation of Z-phase formation by reducing the driving force for Z-phase formation
(limitation of Cr content, removal of Nb)
Low C concept
Using strengthening effect of B.
Steam oxidation
To illustrate the differences in oxidation behaviour of the 9-12% Cr steels in Ar-50%H2O, the
scale growth rate of VM12-SHC compared to various commercial 9%Cr steels and austenitic
grades at various temperatures are shown in Figure 8.
2
Super304H
P/T91
P/T92
Save25
-1
Compilation
T9 type steels
-2
HR3C
-3
Super304H
shot blasting
-4
-5
VM12-SHC
0,8
0,9
1,1
1000/T, K
1,2
1,3
1,4
Figure 8: Scale growth rate kp of VM12-SHC steel versus reciprocal temperature during steam
oxidation compared with various 9%Cr [12] and austenitic steels [13].
Substantially higher mass gain values are frequently found for the 9% Cr steels at all
temperatures. Much lower oxidation rates were found for the 12%Cr VM12-SHC steel. This
material tends to show the typical bell-shape temperature dependence, which has been
previously described by other authors [15]. The oxidation rate at the lowest temperature of 550
C is qualitative similar than that of the 9%Cr T/P91 and T/P92 steels. This indicates that at the
lowest temperature, the chromium content in the alloy is not substantial important. At
temperatures >600 C, the scale growth rate of VM12-SHC steel is much lower than that
observed for several austenitic grades [13].
Figure 9 shows the metallographic cross sections for the studied steels after 5000 h discontinuous
exposure in Ar-50%H2O at various temperatures. The cross sections confirmed the gravimetric
data in Figure 8, showing that the lowest temperature, the same type of scales (Figure 9b)) that
are formed on VM12-SHC steel, tend to be formed on the 9%Cr steels [15, 16]. The scales
differed mainly in respect to the morphology and relative amount of the formed oxide phases.
They consisted of a thick multiphase iron-rich oxide scales, an inner layer formed beneath the
1099
original metal surface, which consisted of Fe3O4 and Fe,Cr- rich spinel. The outer layer consists
of Fe3O4 and Fe2O3. A gap is formed within the outer scale, however spallation of the outer scale
was not observed.
a)
b)
Fe2O 3
Ni- coating
Ni- coating
Fe3O 4
Fe3O 4 + (Fe,Cr) 3O 4
Cr-rich oxide
Fe-rich oxide
c)
Ni- coating
Fe-rich oxide
Cr-rich oxide
Figure 9: Metallographic cross sections of oxide scales formed on VM12-SHC steel after 5000h
discontinuous oxidation in Ar-50%H2O at a) 550 C b) 600 C and c) 650 C.
During exposure, some of the tested specimens tended to form local bucking, which occurred in
the outer part of the scale. Buckling of the external scale was found to repeat during exposure. It
is expected that these layers are prone to spallation upon repeated cooling of the specimens [17,
18].
During exposure at 600 C, very thin chromium-rich oxide scale was formed on the 12%Cr steel
VM12-SHC and just few iron-rich nodules were locally formed. This steel exhibits an abnormal
temperature dependence of the oxidation rates, which tend to decrease when the temperature is
increased above 600 C. At 650 C similar scale growth rates than those at 600 C were found.
To understand the temperature dependence of the oxidation rates for this type for steels, it is
important to note that at the lowest exposure temperatures the oxidation rate are hardly affected
by the chromium content in the steel. In other words, the oxidation rates of 9%Cr and 12%Cr
steels are qualitatively very similar. However, with increasing the exposure temperature, the
chromium diffusion toward the inner part of the scale is significantly improved and a continuous
chromia layer can be formed. Chromium becomes gradually more enriched in the inner region of
the scale and as consequence, the thickness of the inner layer is dramatically reduced and the
1100
internal oxidation zone, formed at the lower exposure temperature, tends to vanish. This
behaviour has been already observed by other authors [14, 19], where chromium was found only
in the inner region of the oxide scale and at temperatures <600 C hardly any chromium
enrichment was found. At these low temperatures chromium can be considered as virtually
immobile. The chromium found in this layer forms due to internal oxidation of chromium and/or
due to the oxidation of the chromium carbides present in the steel microstructure [17]. At higher
temperatures, chromium diffusion is substantially promoted and then tends to be present in form
of chromium-rich spinel bands. The result of this strong chromium enrichment in the inner scale
is that the oxidation rates are significantly reduced.
CONCLUSIONS
Because the 9%Cr steels are not able to provide a sufficient oxidation resistance at temperatures
beyond 620C, several attempts have been undertaken to develop a 12%Cr steel grade with
improved oxidation properties while keeping the excellent creep strength of grade 92. So far all
attempts to reach the long-term creep strength of T/P92 have failed.
VM12-SHC is a recently developed 12%Cr steel exhibiting superior oxidation properties and
good creep strength. During exposure in Ar-50%H2O the typical 9%Cr steels does not form a
chromium rich oxide scale at any of the operation temperatures. The high chromium VM12-SHC
steel exhibits much lower oxidation rates at all temperatures, comparable to those of some
austenitic steels. At temperatures below 600 C, the diffusion of chromium in the 12%Cr steel
VM12-SHC is very low, which lead to similar oxidation rates than that of the 9%Cr steels.
The long-term creep properties of VM12-SHC steel, however, do not reach the level of T/P92.
The TEM investigation on VM12-SHC creep specimen has been carried out to increase the level
of understanding about the mechanisms behind the degradation of creep properties. It was fond
that during the creep exposure the complex nitride (Cr,V,Nb)N forms, the modified Z-phase. At
the same time the number density of MX precipitates decrease. This result confirms the recent
finding from other researchers that the microstructural instabilities responsible for the drop in the
long-term creep properties arise from the formation of Z-phase, which consumes the surrounding
MX precipitates.
The development efforts for new steel grades with improved creep properties did not stop and
some very interesting concepts have been presented very recently. Particularly small additions of
B in amounts beyond 100ppm have proved to improve significantly the long-term creep
properties of 9-12%Cr steels. Another promising approach includes the use of Z-phase as
strengthening particle.
ACKNOWLEDGEMENTS
The authors are grateful to Prof. W.J. Quadakkers (Forschungszentrum Jlich GmbH) for
carrying out the oxidation experiments on VM12-SHC and further specimens characterization
and to Dr. Mendez Mrtin (formerly IWS at TU Graz, now at University of Leoben), who
performed the TEM investigations on VM12-SHC steel.
1101
REFERENCES
[1] Dieulin, A.; Landier, C.; Subanovic, M.; Knezevic, V.; Cini E.; Schneider A.: V&Ms
innovative contribution to meet the challenges of present and future conventional power
plants; VGB PowerTech 11/2011
[2] Hald, J.: Development status and future possibilities for martensitic creep resistant steels,
Proceedings of the 9th Liege Conference: Materials for Advanced Power Engineering 2010,
pp. 55-66
[3] Cipolla, L.; Danielsen, H. K.; Venditti, D.; Nunzio, P. E. D.; Hald, J.; Somers, M. A.:
Conversion of MX nitrides to Z-phase in a martensitic 12% Cr steel, Acta Materialia 58
(2010), S. 669-679
[4] Vandenberghe, B., Lefebvre B., Gabrel, J;; Vaillant, J.C.: Development of a new 12%Cr
steel for tubes and pipes in power plants with steam temperatures up to 650C, La Revue de
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[5] Sonderegger, B.: Modications of stereological correction methods for precipitate parameters
using transmission microscopy, Ultramicroscopy (2006) vol. 106, pp. 941-950
[6] Kota Sawada, K.; Kushima, H; Kimura, K: Z-phase Formation during Creep and Aging in
9-12% Cr Heat Resistant Steels, ISIJ International (2006), Vol. 46, pp. 769-775.
[7] Golpayegani, A.; Andren, H.; Danielsen, H.; Hald, J.: A study on Z-phase nucleation in
martensitic chromium steels, Materials Science and Engineering A 489 (2008), pp. 310-318.
[8] Danielsen, H. K. and Hald J.: Behaviour of Z phase in 912%Cr steels, Energy Materials
(2006) Vol. 1(1), pp. 49-57.
[9] Danielsen, H.K.; Hald, J.: A thermodynamic model of the Z-phase Cr(V, Nb)N, Calphad
31, 2007, pp. 505-514.
[10] Kimura, K; Toda, Y; Kushima, H; Sawada, K.: Creep strength of high chromium steel with
ferrite matrix, International journal of pressure vessels and piping 87 (2010), pp. 282-288.
[11] Kimura, Sawada, K.; Kushima, H: Assessment of long-term creep strength of grade 91
steel, Proceedings of the 9th Liege Conference: Materials for Advanced Power engineering
2010, pp. 162-171
[12] Zurek, J.; De Bruycker, E.; Huysmans, S. and Quadakkers, W.J., Steam oxidation of 912%Cr steels: critical evaluation and implications for practical application, Prococeedings
of the 9th Liege Conference: Materials for Advanced Power Engineering 2010, pp. 11581167.
[13] Quadakkers, W. J. et al., Shreirs Corrosion, Volume 1: Basic Concepts, High Temperature
Corrosion, Elsevier 2010, pp. 407-456
[14] Quadakkers, W.J.; Ennis, P.J.; Zurek, J. and Michalik, M., Steam oxidation of ferritic steels
- laboratory test kinetic data, Materials at High Temperatures, 22, 47-60 (2005).
[15] Zurek, J.; Wessel, E.; Niewolak, L.; Schmitz, F.; Kern, T-U.; Singheiser, L. and Quadakkers,
W.J., Effect of alloying additions in ferritic 9-12%Cr steels on the temperature dependence
of the steam oxidation resistance, Corrosion Science, 46, 2301-2317 (2004).
[16] Ehlers, R.J.; Young, D.J.; Smaardijk, E.J.; Tyagi, A.K.; Penkalla, H.J.; Singheiser, L. and
Quadakkers, W.J., Enhanced oxidation of the 9%Cr steel P91 in water vapour containing
environments, Corrosion Science, 48, 3428-3454 (2006).
[17] Pirn Abelln, J.; Olszewski, T.; Penkalla, H.J.; Meier, G.H.; Singheiser, L. and Quadakkers,
W.J, Scale formation mechanisms of martensitic steels in high CO2/H2O-containing gases
simulating oxyfuel environments, Materials at High Temperatures, Volume 26, Number 1,
March 2009 , pp. 63-72(10).
[18] Pirn Abelln, J.; Olszewski, T.; Meier, G. H.; Singheiser, L. and Quadakkers, W. J., The
oxidation behaviour of the 9%Cr steel P92 in CO2- and H2O-rich gases relevant to oxyfuel
1102
1103
ABSTRACT
Precipitation of Z-phase, Cr(V,Nb)N, is known to negatively affect creep properties of 9-12%Cr
steels for power plant applications as it dissolves finely distributed MX particles, (V,Nb)N,
especially in high Cr steels. As the Z-phase precipitates slowly as large particles, this causes a net
drop in precipitation strengthening.
Two model alloys containing 9 and 12%Cr, but otherwise having similar composition, were
produced in order to quantify the difference in Z-phase precipitation speed at different Cr levels.
The nitride precipitation behavior was followed at different temperatures using TEM and XRD,
allowing for a quantification of the Z-phase precipitation. The Z-phase was found to precipitate
20-50 times faster in the 12%Cr steel compared to 9%Cr steel in the temperature range 600650C.
The transformation of MX into Z-phase was followed in a Ta containing alloy without V or Nb. In
this alloy the Z-phase precipitates very quickly, and thus appears as finely distributed particles
which have the same strengthening effect as MX particles. Investigations using atomic resolution
microscopy showed how Cr diffuses from the matrix into the TaN MX particles and gradually
transforms them both chemically and crystallographically into Z-phase CrTaN particles.
INTRODUCTION
9-12%Cr steels
9%Cr martensitic steels are extensively used in fossil fired steam power plants because of their
high creep and fatigue strength, oxidation resistance and moderate cost. Current 9%Cr steels
allow operating temperatures of up to 600C, but any increase in temperature would necessitate a
higher Cr content for oxidation resistance. Thus many 11-12%Cr steels have been in development
in order to raise steam temperature up to 650C, in order to increase the overall efficiency of the
power plants. However, the high Cr content has caused microstructure instabilities, causing the
creep strength to drop drastically during long term service.
The 9-12%Cr steels rely on precipitation strengthening for their long term creep strength. The
primary beneficial precipitates of these steels are the MX type (V,Nb)N particles, which
precipitate as finely distributed small particles during tempering and are considered to have a low
coarsening rate at high temperatures. However they are not thermodynamically stable, and they
will slowly be replaced by similar Cr rich nitride, the Z-phase, Cr(V,Nb)N.
1104
Z-phase
The Z-phase has long been known to precipitate in austenitic steels in its Nb form, CrNbN. It was
first described in 1950 [1], although its crystal structure was first properly described in 1972 [2].
Contrary to the Z-phases usually seen in 9-12%Cr martensitic steels, the CrNbN precipitated very
rapidly in low carbon austenitic steels as small and finely distributed rodlike particles, which were
credited with beneficial strengthening effects. In 1981 these CrNbN Z-phases were identified in
ferritic steels, however they formed as large granular particles in contrast to the austenitic steels
[3]. Z-phase investigations in ternary systems at high temperature showed the presence of both
CrNbN and CrTaN type precipitate types [4], but failed to identify any V variant of the nitrides,
possibly because of the high temperatures used.
Figure 1: Comparison of three different 10-12%Cr steels at 600C. X19 was the first martensitic
steel where Z-phase was found. [6]
V-containing Z-phase was first found in austenitic steels in 1985 with the composition Cr(V,Nb)N
[5], and in 1986 the Cr(V,Nb)N was also observed in a 11%Cr martensitic steel, X19 [6].
Although the X19 steel showed the same drop in creep strength, see Fig. 1, as more recent
experimental high Cr martensitic steels, no connection was drawn between the appearance of Zphase and the breakdown of X19. The detrimental effects of the Cr(V,Nb)N Z-phase in 9-12%Cr
martensitic steels was first properly described in 1996 [7], where it was stated that the Z-phase
was the thermodynamically stable nitride in 11-12%Cr martensitic steels. Furthermore it was
concluded that precipitation of Cr(V,Nb)N Z-phase would dissolve the beneficial (V,Nb)N, and
thus cause a breakdown in long term creep strength. Nickel was assumed to have an accelerating
effect on the Z-phase precipitation.
Authors work
In 2006 many different 9-12%Cr steels were investigated for Z-phase content [8], and the
presence of Z-phase could be verified in all of them if exposed for high temperatures (600-650C)
at long times, usually 10.000h would be enough. The amount observed was of course dependent
on temperature and exposure time, but there was also a very clear trend towards 11-12%Cr having
very high Z-phase amounts, while in the 9%Cr steels the Z-phase content was significantly lower.
This was in good correspondence with creep data, which showed breakdown in creep strength for
11-12%Cr steels after some thousand hours of exposure at 650C, see Fig. 1, at the same time that
massive Z-phase precipitation occurred. Although Z-phase was observed in 9%Cr steels, the
1105
precipitation was much slower, and only small amounts could be observed, even at very long
exposure times. This showed that the Z-phase was the most thermodynamically stable nitride in all
9-12%Cr martensitic steels for power plant applications. However, the precipitation speed in
9%Cr steels is so slow that the creep strength would remain unaffected within the lifetime of a
power plant.
Thermodynamics
In order to create a thermodynamic model of the Z-phase, experiments were carried out at
elevated temperatures to find a solution temperature. As Z-phase precipitation proceeds slower at
temperatures above 650C in 12%Cr steels, samples where Z-phase already had replaced MX
were used. Above 800C the Z-phase would be replaced by re-emerging MX precipitates. Thus
the solution temperature of Cr(V,Nb)N Z-phase in martensitic steel was around 800C, much
lower than its CrNbN counterpart in austenitic steels [8]. A thermodynamic model was created
using the experimental data from both martensitic and austenitic steels [9], and verifies the
importance of Cr for Z-phase, see Fig. 2. This model is now incorporated in the ThermoCalc
databases from version TCFE6 and onwards. The thermodynamic model can be used to estimate
the Z-phase precipitation speed by using driving force calculations, which is the difference of free
energy in a system with and without Z-phase (with MX if no Z-phase is present). By varying the
chemical composition it is possible to observe which elements influence the precipitation speed.
Cr is seen as the most influential element, which verifies the experimental results. This is perhaps
not surprising when considering the main difference between (V,Nb)N MX and Cr(V,Nb)N Zphase is Cr. Elements that reduce the Cr matrix content will also influence the driving force, such
as C forming chromium containing M 23 C 6 . Unexpectedly, Co is seen to increase the driving force
of Z-phase as it reduces the Cr affinity of the matrix. On the other hand, Ni was not predicted to
have any effect on the precipitation speed of Z-phase.
1106
CrVN
As only Cr(V,Nb)N type Z-phases had been reported in 9-12%Cr martensitic steels, several Nbfree 11-12%Cr X20 steels were investigated in order to verify a CrVN variant [8]. Specimens
with exposure up to 150,000h hours at 600C were investigated, and although CrVN Z-phase was
observed they did not appear in large amounts, and the VN MX precipitates were still extensively
present. This can also be reflected in the creep curves of X20, which do not suffer breakdowns as
similar Nb-containing steels do, see Fig. 1. These results were verified in model alloys with XRD
measurements [10], thus it seems that Nb acts as a catalyst for the precipitation of Z-phase, greatly
enhancing the precipitation speed in 9-12%Cr steels. The thermodynamic model does not show
any large driving force gradient as a function of Nb content, thus there does not seem to be a
thermodynamic reason for the slower precipitation in Nb-free steels.
Figure 3: The double layered tetragonal crystal structure of Z-phase (purple: Ta, Nb or V, green:
Cr, small orange: N). The Z-phase (tetragonal) and corresponding MX (cubic) unit cells are
drawn in bold lines. [16]
Crystal structure
The MX has a NaCl type crystal structure, where the metallic atoms are arranged in an fcc lattice
and the lattice parameter depends on the chemical composition. NbN and TaN have a
significantly larger lattice parameter than VN, around 0.439 nm compared to 0.413 nm. The
crystal structure of Z-phase is tetragonal [2] with the c lattice parameter being 0.739nm and a
lattice parameter depending on the chemical composition [7,11] , being 0.286nm for vanadium
containing Z-phase. The crystal structure can be described as a double layered structure with
alternating layers of MX and Cr, see Fig. 3. While CrNbN and CrTaN have been found to be
strictly tetragonal, the V-containing Z-phase crystal structure is less well defined, as both cubic
and tetragonal diffraction patterns can be obtained from the same particles [11,12]. This cubic
crystal structure has been verified by electron diffraction and XRD measurements to have a lattice
1107
parameter around 0.404nm, corresponding to the MX layers in Z-phase, see Fig. 3 [12,13]. The
dual cubic/tetragonal crystal structure is believed to be connected with the nucleation process of
Z-phase, see below, as the V-containing Z-phase have a much slower precipitation rate than their
Nb and Ta counterparts. Another nitride that can appear in these steel is M 2 X, (Cr,V) 2 N, which
has a chemical composition close to Z-phase, but it has an unrelated hexagonal crystal structure,
with lattice parameters of a=0.481nm and c=0.448nm.
EXPERIMENTAL
Three different model alloys were used for this work, all 80kg ingots produced by vacuum
induction melting, compositions are given in table 1. All the alloys were normalized at
1050C/1h, the 12CrVNbN and 9CrVNbN were tempered at 750C/2h while the 12CrTaN was
tempered at 720C/24h.
Table 1: Composition of the alloys used in this work in wt%, balance Fe.
12CrVNbN
9CrVNbN
12CrTaN
Cr
11.85
9.11
11.79
C
0.0048
0.0040
0.005
V
0.183
0.207
-
Nb
0.76
0.80
-
Ta
0.39
N
0.061
0.059
0.033
W
2.90
Co
7.30
Ni
1.29
1.27
0.50
Mn
0.32
0.34
0.48
Si
0.40
0.41
0.30
For determination of the precipitated phases present in the 12CrVNbN and 9CrVNbN alloys, XRay powder Diffraction was applied, using a Bruker D8 Advance powder diffractometer equipped
with Cu-radiation. In order to avoid interference from matrix reflections, the precipitates were
extracted from the bulk by electrolysis in an acidic solution of 5% HCl in 95% ethanol, dissolving
the matrix while gathering the precipitates by sedimentation. Some of the very small MX
precipitates may not have been fully recovered by the sedimentation process.
The 12CrTaN alloy was designed for extremely fast Z-phase precipitation, which takes place
already during tempering. The transformation process was examined on carbon extraction replica,
with High Angle Annular Dark Field (HAADF) using a FEI Titan 80-300ST TEM with CEOS
CESCOR probe spherical aberration corrector.
RESULTS
Precipitation rate
The 12CrVNbN and 9CrVNbN alloys are identical except for the Cr content, and were designed
to study the nitride evolution as a function of time and temperature. They do not contain any C, W
or Mo as not to precipitate non-nitride particles, such as carbides or Laves phase, which could
interfere in XRD measurements. After short term heat treatments both alloys contained only M 2 X
and MX nitrides. Two separate populations of MX nitrides could be identified, (V,Nb)N and
(Nb,V)N. Thus lattice parameters of both precipitate types are in between those of VN and NbN.
Figure 4 (left column) shows XRD powder diffraction of thermal aging of the 12CrVNbN alloy at
three different temperatures. For graphical representation the spectra use the highest intensity
peak of M 2 X as reference points (except for 600C/30,000h), as M 2 X was the most stable
1108
precipitate amongst the nitrides. The main feature is that with time Z-phase peaks replace the MX
peaks. The main Z-phase peak (tetragonal) at 2 angle = 40 is visible after 300h at 650C. As the
V-rich MX transform into Z-phase, a gradual shift in VN peak position towards a lower lattice
parameter corresponding to the cubic Z-phase takes place. At 600C, the M 2 X peaks are replaced
with time by new peaks corresponding to an A13 crystal structure (same as -manganese) which is
believed to belong to the -nitride, a chromium and iron rich nitride usually found in austenitic
steels [14].
Figure 4: XRD spectra of nitride evolution in 12CrVNbN (left) and 9CrVNbN (right). [14]
The results from the thermal aging of the 9CrVNbN alloy are shown in Fig. 4 (right column). The
{200} (V,Nb)N peak has been used as a reference point as it does not overlap with other peaks.
Note there is a peak overlap between Cr 2 N and (Nb,V)N, as lattice parameters for MX are
1109
slightly lower compared to the 12CrVNbN alloy. There are also fewer Cr nitrides as the Cr
content is lower. As Z-phase precipitation was expected to be slower, longer annealing times were
used. The peak position of VN has only barely started to move to the cubic Z-phase positions for
the 20,000h samples.
Figure 5: TTP curves of the amount of MX transformed into Z-phase estimated from Rietveld
data. [14]
A rietveld refinement [14] was done in order quantify how much of the MX was transformed into
Z-phase. When plotting this data into a TTP curve, accurate information can be obtained on the Zphase precipitation speed. Comparing 12CrVNbN and 9CrVNbN shows the Z-phase to precipitate
considerably faster in the 12%Cr alloy at all temperatures, see Fig. 5. Presence/no presence TEM
measurements of Z-phase from literature [15] indicate both 9%Cr and 12%Cr steels have fastest
Z-phase precipitation at 650C. However in the current work, the Z-phase at precipitates fastest at
650C for the 12CrVNbN while in 9CrVNbN it is fastest at 600C. This does correspond well
with the thermodynamic model, which predicts Z-phase to be stable up to higher temperatures for
higher Cr contents, see Fig. 2. Thus an increase in Cr is expected to raise the TTP curve to higher
temperatures. As no data was available from temperatures lower than 600C, the 9CrVNbN TTP
curve in Fig. 5 is based on an estimate that the precipitation will be slower at 550C. These results
might indicate that the Z-phase content in 9%Cr steels could be underestimated if accelerated tests
at 650C are used. As the model alloys do not contain C, they have a higher Cr content in the
matrix compared to commercial alloys. The matrix Cr content would correspond to that of 10%Cr
and 13%Cr commercial alloys containing 0.1%C.
Nucleation
The 12CrTaN alloy was investigated in as tempered condition with HAADF on carbon extraction
replicas, where Cr atoms appear very dark in comparison to Ta atoms which are 3.5 times heavier.
The N and C atoms are not visible. The investigations showed both MX and Z-phase precipitates,
including particles in the course of transforming. Figure 6 shows the transformation process from
cubic TaN into tetragonal CrTaN. The TaN precipitates can be recognised as a Ta fcc structure of
monotonous brightness, some Cr will be uniformly distributed in the Ta fcc lattice. During the
transformation, Cr double layers develop inside the TaN crystal structure, corresponding to the Zphase crystal structure which consists of alternating TaN double layers and Cr double layers. The
layers appear very dark compared to the Ta-rich MX and almost always appear as double layers.
EDS measurements confirm areas containing dark layers are Cr rich.
1110
Figure 6: Different stages during transformation of MX into Z-phase, from the beginning of
formation of Cr layers (top left) to fully transformed Z-phase (bottom right). [16]
As follows from the images in Fig. 6 the transformation from TaN to CrTaN is accomplished by
an ordering of the Cr atoms, which are incorporated from the matrix into the particles, as double
layers along the {001} planes in TaN. These double layers continue to develop until a regular Zphase crystal structure has formed. Figure 6 (bottom left) shows an area where a regular double
layered structure has formed and is in contact with a primarily homogenous MX, with occasional
Cr double layers. At the interface between tetragonal and cubic crystal structures the atomic
structure is continuous, illustrating the orientation relationship. Defects inside the double layered
CrTaN structure can be seen close to the interface, where some of the layers are changing contrast
from bright to dark, indicating a change in composition of the layers. Such defects are common in
the developing double layered structures, with occasional single or triple layers being present, see
Fig. 6 (top right).
1111
Figure 7: When Cr layers form they are parallel in some particles (left) and perpendicular in
others (right). The sketch shows the three perpendicular planes the Cr layers can for on a MX
type unit cell. [16]
The formation of Cr double layers in TaN was observed to vary from precipitate to precipitate. A
small particle at the onset of transformation in Fig. 7 (left) shows some alternating bright and dark
double layers, implying that the center of this particle consists of Z-phase crystal structure with a
thickness of three unit cells; the remainder is MX. In other particles the Cr double layers were
found to be perpendicular to each other, with layers changing directions at 90 angles, Fig. 7
(right). This is consistent with the orientation relationship, implying that the tetragonal Z-phase
can develop along all three mutually perpendicular {001} MX planes. Generally for the precipitates
with perpendicular Cr double layers, it was difficult to get all TaN regions in the particle in focus
at the same time with atomic resolution. Figure 6 (bottom left) shows an example of this, where
only small scattered regions of the TaN crystal structure are found to be in the zone axis. This
may indicate that the presence of a Cr double layer in an otherwise homogeneous TaN particle
causes a slight lattice distortion, as the Cr double layers are slightly thinner than the
corresponding MX double layers [2].
Z-phase strengthened steels
When using a Cr content of 11-12% needed for oxidation resistance, the Z-phase will precipitate
and remove the crucial strengthening effect of the MX precipitates. Thus it has not been possible
to produce martensitic steel with both long term creep strength based on MX and oxidation
resistance based on Cr at 650C. A new concept was tried out in this work, where the Z-phase was
to be used as the strengthening nitride agent instead of MX [17]. In normal V-containing steels the
transformation rate of MX to Z-phase is relatively slow, thus the Z-phase has plenty of time to
consume nearby MX precipitates during growth, leading to a coarse distribution of large Zphases. If a fast transformation rate could be obtained the fine MX precipitates would
immediately be replaced by fine Z-phase precipitates, and thus the growth process could be
avoided altogether, see Fig. 8. The finely distributed Z-phase would act as a strengthening agent
as seen in austenitic steels, where they are thermally stable with a low coarsening rate. Thus if the
1112
coarsening rate of Z-phase in martensitic steels also was low, a steel based upon Z-phase nitride
strengthening could be obtained. This could be combined with a high Cr content for oxidation
resistance, in fact a high Cr content would be necessary to obtain a fast transformation.
Figure 8: An illustration of a slow V-based Z-phase precipitation (top) and a fast Nb based
precipitation (bottom). [17]
Figure 9: CrTaN precipitates from the 12CrTaN alloy, exposed at 650C for 1000h (left) and
38000h (right). It shows the Z-phase to have a relative high coarsening rate compared to MX
type precipitates in 9-12%Cr steels.
In order to obtain a very fast transformation, V-free compositions with Nb or Ta were used, in
order to promote CrNbN and CrTaN type Z-phases. The C content was kept very low, as C would
stabilize the MX type Nb(N,C) or Ta(N,C) carbonitrides, the Z-phase is believed to be a more
pure nitride [18]. The best result obtained was the Ta-containing steel shown in table 1, which
1113
showed a very fast Z-phase formation rate. The Z-phases in this steel precipitate as very small
precipitates already during tempering, which provided initial creep strength higher than
commercial grades such as P92. Unfortunately the coarsening rate of both CrNbN and CrTaN
type Z-phases were found to be higher than (V,Nb)N type MX at temperatures of 600-650C, see
Fig. 9. Thus the long term creep strength of the Z-phase strengthened steels cannot compare to
that of P92 at these temperatures.
Figure 10: The interface between steel matrix (not in focus) and CrTaN Z-phase (in focus). The
crystalline planes of the Z-phase are visible, but stop a few nanometers before the interface.
Interface effects
Investigating the CrTaN and CrNbN in thinfoils, an interface layer a few nanometers thick
between the Z-phase nitrides and the steel matrix could be observed. Upon closer investigations
this interface layer was shown to be amorphous, that is the crystalline nature of the nitride stopped
shortly before reaching the steel matrix, see Fig 10. Darkfield investigations of SAED and FFT of
atomic resolution imaging confirmed that the interface between the nitride and matrix was
amorphous. Since the precipitate particles were completely embedded inside the steel matrix, this
was not an influence of sample preparation. The steel matrix in Fig. 10 is set not to be in focus on
purpose, as the steel structure is present below and above the nitride. Carbon extraction replicas
showed the nitrides contained amorphous shells which crystallized during beam exposure in the
TEM. No Fe content was found within these amorphous shells.
As the interfacial energy governs the coarsening rate, the appearance of the amorphous layer
would explain why the Z-phase has such a high coarsening rate compared to the MX. The
crystallization of the interface in carbon extraction replicas where the matrix has been removed
indicates that the amorphous layer is an interface effect. Such interface effects could also be
responsible for the slow transformation of VN into CrVN, as VN has a good baker-nutting
1114
orientation relationship with the matrix compared to (V,Nb)N, while there is not much difference
between Cr(V,Nb)N and CrVN lattice parameters.
CONCLUSIONS
Z-phase precipitation in 9-12%Cr steels is very detrimental to the creep strength as it replaces
otherwise beneficial MX precipitates. XRD measurements of model alloys show the precipitation
speed of the Z-phase to be very dependent on the Cr content and temperature. The Z-phase
precipitation is fastest at 650C for 12%Cr steel and at 600C for 9%Cr steel. 12%Cr steels
precipitate Z-phase 20-50 times faster than 9%Cr steels, depending on the temperature.
Z-phase was attempted to be used as a strengthening agent instead of MX. Atomic resolution
imaging showed that the precipitation of Z-phase is actually a transformation from MX. Cr
diffuses into MX precipitates changing them chemically and crystallographically into Z-phases.
By using specific chemical compositions a very fine distribution of Z-phase could be obtained.
However the Z-phases coarsened very quickly, and are thus not suitable for strengthening
purposes. The high coarsening rate stems from an unfavorable interface with the matrix, which is
manifested as a several nanometer thick amorphous interface layer covering the entire nitride.
ACKNOWLEDGMENTS
Financial support from the Danish Research Council for Independent Research: Production and
Technology Sciences (grant 10-093690) is gratefully acknowledged.
REFERENCES
W.O. Binder, ASTM STP, Vol. 110, (1950), pp. 146-164.
Jack D. H. and Jack, K. H., J. Iron Steel Inst., Vol. 209, (1972), pp. 790792.
Kurosawa F. et al, J. Japan Inst. Metals., Vol. 45, (1981), pp. 63-67.
Ettmayer P. et al, Monatsh. Chern., Vol. 102, (1971), pp. 858-863.
Andren H. O. et al, Stainless steel 84, The Institute of Metals, London, (1985), pp. 91-96.
Schnabel E. et al, Stahl und Eisen, Vol. 107, (1987), pp. 691-696.
Strang A. and Vodarek V., Mater. Sci. Technol., Vol. 12, (1996), pp. 552-556.
Danielsen H. K. et al, Energy Mater. Vol. 1, (2006), pp. 49-57.
Danielsen H. K. et al, Computer Coupling of Phase Diagrams and Thermochemistry, Vol.
31, (2007), pp. 505-514.
[10] Cipolla L. et al, Scripta Materialia, Vol. 63, (2010), pp. 324-327.
[11] Danielsen H. K. et al, Scripta Materialia Vol. 63, (2010), pp. 324-327.
[12] Danielsen H. K. et al, Metall. Mater. Trans. A, Vol. 37A, (2006), pp. 2633-2640.
[13] Cipolla L. et al, Acta Materialia, Vol. 58, (2010), pp. 669-679.
[14] Danielsen H. K. et al, Metall. Mater. Trans. A, Vol. 44A, (2013), pp. 2445-2452.
[15] Sawada K. et al, ISIJ Int., Vol. 47, (2007), pp. 73339.
[16] Danielsen H. K. et al, Scripta Materialia, Vol. 66, (2012), pp. 261-264.
[17] Danielsen H. K. et al, VGB PowerTech, Vol. 5, (2009), pp. 68-73.
[18] Karlsson L. et al, Mater. Sci. Tech., Vol. 1, (1985), pp. 337-342.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
1115
EFFECT OF COPPER ADDITION ON THE TOUGHNESS OF NEW ZPHASE STRENGTHENED 12% CHROMIUM STEELS
Fang Liu, Hans-Olof Andrn
Department of Applied Physics, Chalmers University of Technology, SE-412 96
Gteborg, Sweden
Contact author, fang.liu@chalmers.se
ABSTRACT
Two Z-phase strengthened test steels with similar chemical composition were studied. The main
difference in composition is the addition of 1 wt% Cu into one of the steels (referred to as ZCu). Mechanical testing was performed. The impact strength is very different: 3 J vs. 46.3 J, for
the original and the Z-Cu steel, respectively. In the original steel that contains no Cu, much more
Laves-phase (Fe2(W,Mo)) precipitates had formed along the prior austenite grain boundaries than
in the steel with Cu addition. This is believed to be the reason for the difference in impact
strength. Furthermore, the Cu addition also influenced the morphology of Laves-phase
precipitates; fine rod-shaped instead of coarse equiaxed Laves-phase particles were observed in
Z-Cu steel in comparison to the original steel. No partitioning of Cu into the Laves-phase
particles was detected by using atom probe tomography (APT). The main function of Cu seems to
be the formation of Cu precipitates that act as nucleation site for Laves-phase.
KEYWORDS: precipitation strengthening, creep resistant steels, Laves-phase, precipitate
morphology, APT.
1. INTRODUCTION
Todays best martensitic 9-12% chromium steels are successfully applied in steam power plants
up to 600-620C/300 bar. To apply these steels at 650C/350 bar, which is believed to be the
ultimate service environment for this type of steels, both creep and corrosion properties have to
be improved compared to the state-of-the-art materials. At present the most widely used
martensitic 9-12%Cr steels contain only approximately 9 wt% Cr, which is too low in terms of
corrosion resistance at 650C. It is well established that at high temperatures the corrosion
resistance of a steel is proportional to its Cr content: the higher the Cr content, the better the
corrosion resistance [1].
There have been several recent trials by adding e.g. Co, W and B to the steels, in combination
with a higher Cr content (11-12 wt% vs. 9 wt% for todays most widely used commercial steels).
Nevertheless, all of them turned out to be failures [2]. They suffered a dramatic loss of creep
strength after ~10,000 hours, which is mainly attributed to precipitation of a complex nitride
known as Z-phase ((Nb,V)CrN) at the expense of the fine and densely distributed MX
precipitates [3, 4]. Z-phase is thermodynamically more stable at this temperature, but since it
nucleates very slowly it tends to form few and coarse precipitates that give very little contribution
to creep strength [5].
Together with Hald and Danielsen from the Technical University of Denmark, we are trying to
develop a new generation of martensitic steels aiming for 650C: the Z-phase strengthened steels.
These new steels are expected to have good corrosion resistance, which is attributed to a high Cr
1116
content (up to 12 wt%). Good creep resistance would be expected, if densely distributed fine Zphase precipitates can be formed during heat treatment and if they coarsen slowly during service.
We have prepared and studied several test alloys. We have verified the feasibility of the basic
alloy design concept using Z-phase as strengthening precipitates [6] in 9-12%Cr martensitic
steels. On-going creep testing shows that the steels have good creep resistance after more than
10,000 hours. In these steels there are often W and/or Mo additions for solid solution
strengthening. After certain thermal exposure W/Mo can form Laves-phase (Fe2(W,Mo))
precipitates. Depending on their size and coarsening rate, phase formation can be either beneficial
or detrimental for the creep property [7].
In the present paper, we focus on two new Z-phase strengthened test steels. They are similar in
chemical composition (Table 1), with the main difference lying in the addition of 1wt% Cu in one
of the steels. The emphasis was put on understanding the effects of Cu on Laves-phase formation
and the underlying mechanisms.
2. EXPERIMENTAL
2.1. Materials
Two Z-phase strengthened test steels with similar chemical composition were prepared. One steel
is without Cu addition, and the other with 1 wt.% Cu addition. They are referred to as steel Z and
Z-Cu, respectively. Their chemical composition is listed in Table 1 in both wt% and at%. Steel Z
was austenitized at 1050C for 1 hour and then tempered at 720C for 6 hours. Steel Z-Cu was
austenitized at 1050C for 1h and then tempered at 700C for 7 hours. Mechanical testing was
carried out on as-tempered steels. The microstructure of steel Z aged at 650C for 1000 hours and
steel Z-Cu aged at 650C for 300 and 1000 hours was studied.
Table 1. Chemical composition of the test Z-phase strengthened steels: steel Z and Z-Cu (in both
at% and wt%; Fe in balance).
Cr
Ta
Mo
Ni
Co
Cu
Mn
Si
Z (wt%)
11.79
0.005
0.004
0.39
0.033
2.90
0.50
7.30
0.48
0.30
Z (at%)
12.84
0.02
0.02
0.12
0.13
0.89
0.48
7.01
0.49
0.6
Z-Cu(wt%)
11.96
0.005
0.007
0.36
0.058
2.46
0.21
1.03
6.49
1.0
0.56
0.29
Z-Cu (at%)
13.00
0.02
0.04
0.12
0.23
0.76
0.12
0.99
6.22
0.89
0.58
0.58
1117
polished samples were etched with Villelas reagent. This reagent consists of 45 ml glycerol, 45
ml nitric acid and 30 ml hydrochloric acid.
2.3 Atom Probe Tomography (APT)
APT is the only tool that can yield chemical composition of individual atoms with sub-nanometer
spatial resolution. Atoms are ionized from the surface of the sharp end (<50 nm) of a specially
fabricated specimen, which is exposed to a high electric field superimposed with high frequency
electric or laser pulses. The ionized atoms are detected by a position-sensitive detector. The
chemical identity of each ion is determined from its mass-to-charge ratio, which is measured
based on the flight time. All the data is recorded in time sequence, and can be used to reconstruct
the atoms in 3-dimensional images afterwards [8].
2.3.1 Sample preparation using two-stage electropolishing
The steels were cut into small rods (~ 8 0.25 0.25 mm3) by a low speed saw. The rods
underwent a two-step electropolishing procedure in order to obtain APT samples with a final tip
radius of less than 50 nm. First a thin neck was produced in 10% perchloric acid in methanol by
using an ElectroPointerTM equipment that uses an electrolyte drop suspended by a platinum wire
loop. Then fine polishing was made in a bath of 2% perchloric acid in 2-butoxyethanol until the
lower part of the rod dropped off.
2.3.2 Sample preparation using lift-out technique in a FIB/SEM
In order to make site-specific APT analysis of selected features, e.g. rod-shaped Laves-phase
precipitates, we used an in-situ lift-out technique to prepare APT samples. An FEI Versa 3D Dual
Beam workstation, which is a combined Focused Ion Beam instrument (FIB) and a SEM, was
used. The details of the procedure was reported in ref. [9].
2.3.3 APT operation parameters
APT analysis was carried out in an Imago LEAP 3000X HR local electrode atom probe
instrument. Optimized APT acquisition parameters for the steels have been reported previously
[10]. The specimen temperature during analysis was in the range of 60-70 K. To avoid premature
specimen failure pulsed laser mode was used, with a pulsing frequency of 200 kHz and a laser
energy of 0.3 nJ. The acquired data were further analyzed by using the IVASTM 3.4.1 software
developed by Imago. Note that all the concentrations are given in atomic percent unless
otherwise stated.
3. RESULTS
3.1 Mechanical testing
In the as-tempered condition, both materials have good tensile strength (Rp0.2 around 800 MPa)
and ductility (elongation at fracture >15%). However, their impact toughness is remarkably
different, despite that both steels have very similar chemical composition. In Charpy V-notch
tests steel Z showed very poor impact behavior, on average only 3 J was absorbed, while for ZCu, the impact energy absorption was 46.3 J.
1118
3.2 SEM
After tempering both steels exhibit a martensitic/ferritic microstructure, containing prior austenite
grains and laths. SEM backscattered electron micrographs (Fig. 1(a) and (c)) show clearly the
prior austenite grain boundaries, which give bright contrast in the images. It is worth noticing that
both samples are polished but without any etching. The contrast in backscattered electron
imaging arises mainly from the difference in atomic number: bright contrast indicating regions
with heavier atoms. Thus the prior austenite boundaries are decorated by some heavy elements.
Further EDX analysis revealed W enrichment in the regions.
Images with higher magnifications (Fig. 1(b) and (d)) show more detail in these regions. There
are W-enriched Laves-phase precipitates (Fe2(W,Mo)) forming along prior austenite grain
boundaries and also inside the grains. Overall in steel Z (Fig. 1(b)) Laves-phase precipitates are
larger in size but fewer in number as compared to steel Z-Cu. However, in steel Z-Cu (Fig. 1(d))
precipitates on the grain boundary regions are much fewer; on the other hand there is a large
number of very small precipitates inside the grains. They are so small that they only give rather
faint grey contrast in the image. We believe that the preferential precipitation of Laves-phase
particles along prior austenite grain boundaries are responsible for the poor impact strength for
steel Z. Cu (~1wt%) and/or Mo addition in steel Z-Cu can modify Laves-phase nucleation and
distribution.
Figure 1. SEM backscattered electron micrographs of (a) and (b) steel Z; (c) and (d) steel Z-Cu
in the as tempered condition. Laves-phase precipitates (bright particles) decorate prior austenite
grain boundaries in both steels. Their sizes are larger in steel Z.
1119
Two different types of Laves-phase morphology can be identified in steel Z-Cu aged for 300 h
(Fig. 2 (a)): the normal equiaxed (indicated by thick arrows), which is the only type observed in
the steel Z, and the elongated rod-shaped (indicated by thin arrows), which are basically absent in
the steel Z. In steel Z aged for 1000 hours (Fig. 2 (b)) largely only the equiaxed type of
morphology was observed, while in Z-Cu aged for 1000 hours there are a large number of
elongated rod-shaped Laves (Fig. 2(c)). Interestingly, they are aligned in certain directions, which
suggests that there is a certain preferential crystallographic orientation relationship between these
Laves-phase precipitates and the steel matrix.
Figure 2. SEM backscattered electron micrographs of (a) steel Z-Cu aged for 300 h; two types of
morphology: equiaxed (indicated by thick arrows) and elongated (indicated by thin arrows). (b)
steel Z aged for 1000 h, mainly equiaxed type morphology. (c) Z-Cu aged for 1000 h, a large
numbers of elongated type of Laves particle.
The morphology difference is also believed to related to the Cu addition. In order to understand
the process of Laves-phase precipitation, Cu behavior, and if there is any connection between Cu
and Laves particles, for instance Cu partitioning to Laves or segregations of Cu to the interface
between Laves and the steel matrix, APT analysis was performed.
1120
Ni
Co
Cr
Mo
Cu
Si
Mn
78.8
1.0
6.3
12.2
0.23
0.05
0.24
0.59
0.56
(a)
1121
(b)
Figure 3. (a) Reconstruction of an APT dataset obtained from steel Z-Cu aged for 300 h. It
contains a part of an elongated Laves-phase on the top. The dark red and magenta dots represent
W and Fe atoms, respectively. For visual clarity only 5% of Fe and 30% of W atoms are shown.
The box size is: 80 80 56 nm3. (b) Part of the mass spectrum of the Laves-phase particle
only. The dashed red lines indicate the position of Cu isotopes in the spectrum. Their height
corresponds to the abundance of the two isotopes. No Cu was found in the Laves-phase.
Chemical composition of the elongated Laves-phase was obtained using APT. The results are
displayed in Table 3. It has the basic chemical formula of (Fe,Cr,Co)2(W,Mo,Si). This volume of
Laves-phase contains no Cu.
Table 3. APT results from an elongated Laves-phase particle in steel Z-Cu aged for 300 h (in
at%).
Fe
Ni
Co
Cr
Ta
Si
Mn
Mo
Cu
43.0
26.2
0.34
0.52
4.0
18.6
0.55
0.27
0.34
2.68
0.75
2.8
Mn
Ni
Fe
Co
Si
98.07
1.19
0.62
0.08
0.03
0.007
1122
In order to obtain accurate chemical information across the Cu/matrix interface, we used the socalled proxigram (proximity histogram), an embedded function in the APT reconstruction
program. Here we explain how this function works. To get the chemical composition across an
interface, we can take a volume, e.g. a cylinder, which includes the interface, which is often
defined by the continuous surface with the same concentration for certain element, the so-called
iso-concentration surface. Then we calculate the concentration data along the height. It is very
important that the direction of the height of cylinder is perpendicular to the interface plane, in
order to avoid smearing of the interface concentration. However, since the interfaces are usually
irregular, it is often impossible to define just one volume, which covers the entire interface and
simultaneously has the height perpendicular to the entire interface. What the proxigram algorithm
does is to create a very small cylinder, make it move over the entire interface, while changing its
position to ensure that it is perpendicular to the interfaces, calculate the concentration and finally
integrate it over for the entire interface. In this way, a composition profile over the interfaces with
much less smearing is obtained.
Figure 4 (a) shows APT reconstruction of a volume with a Cu-rich particle, and only Cu atoms
are displayed. The size of the Cu-rich particle is larger than 30 nm, since only part of the particle
was in the analyzed volume. Figure 4 (b) shows such a proxigram across the Cu/matrix interface.
Ni concentration is lower compared to the surrounding matrix, while Mn concentration is higher.
Interestingly, there are two concentration peaks at the interface region; in addition they do not
occur at the same position relative to the interface. The Ni peak resembles a classical peak when
diffusion occurs between two phases, while the peak of Mn is more likely to indicate the
occurrence of interfacial segregation.
(a)
1123
(b)
Figure 4. (a) Reconstruction of an APT dataset obtained from steel Z-Cu aged for 300 h. The
orange dots represent Cu atoms. The size of the particle is larger than 30 nm. The box size is 100
100 72 nm3. (b) Proxigram across the Cu/matrix interface. Note the Ni and Mn peak in the
concentration profile at the interface region.
4. DISCUSSION
There have been extensive studies on Cu additions to high-strength steels, where due to its low
solubility in ferrite Cu tends to form precipitates, which can act as one of the major hardening
agents. In these steels Cu precipitates are often observed to undergo several stages of phase
transformation, from metastable body-centered cubic (bcc) structure to intermediate 9R structure
and gradually into face-centered cubic equilibrium structure of pure Cu [11]. In 9-12%Cr steels,
Cu addition can effectively avoid the formation of delta ferrite, which is detrimental to the
mechanical properties of the steels. In addition, Cu precipitates may provide nucleation sites for
Laves-phase formation [12].
In fact the improved toughness in Z-Cu steel by Cu addition is, most likely, related to suppression
of preferential precipitation of embrittling Laves-phase along prior austenite grain boundaries of
the steel in the as tempered condition [13]. Laves-phase tends to nucleate heterogeneously along
boundaries. Other types of precipitate like M23C6 can greatly influence on nucleation process of
Laves, and subsequently on number density and size of Laves-phase particles. It takes a long time
for the precipitation of Laves-phase to reach its volume equilibrium [14]. O. Prat et al. reported
approximately 1.5 years at 650C in a 9%Cr steel [7].
Since there was no Cu partitioning into the Laves-phase found, it is expected that Cu precipitates
may have similar effect on Laves-phase as M23C6. Cu tends to precipitate out very quickly, and
form nano-sized precipitates at grain/lath boundaries and dislocations. On one hand Cu nanoparticles may occupy the possible nucleation sites, which otherwise can be occupied by Lavesphase. On the other hand, since Cu precipitates much more rapidly than Laves-phase, Cu particles
can provide a large number of new potential nucleation sites for Laves-phase. A large number of
Laves-phase particles can be formed on Cu particles, and thus leading to a much denser
distribution of Laves-phase particle. However, Z-phase, the major precipitates in steel Z, dose not
have such effect on Laves-phase.
1124
With regard to the morphology of the Laves-phase, it is speculated that there is crystallographic
orientation between Cu particles, most probably in coherent bcc structure, and the -ferrite
matrix, and subsequently between Cu particles and Laves particles that nucleated upon them.
These Laves-phase particles may then grow along certain direction, which is more energetically
beneficial. Ku et al. also reported rod-shaped morphology [12] in a Cu-containing 9%Cr steel.
Furthermore, they showed a Cu particle connected to a Laves-phase. Besides Cu addition, heat
treatment is also essential for the morphology since probably only Cu particles with certain
crystallographic structure can introduce Laves-phase with certain orientation relationship. Further
investigation on heat treatment conditions and in detailed TEM study are planed.
Another possibility is that the exchange of 0.12 at% (of a total of 0.89 at%) of W for Mo might
change the lattice parameter of Laves-phase somewhat, decreasing the elastic part of the
interfacial energy and thus facilitating nucleation, assuming then that nucleation occurs in a
coherent fashion relative to the matrix or Cu particles. Also the chemical part of the interfacial
energy could possibly be affected by the change in Laves-phase chemistry, but it seems unlikely
that this could be a large effect.
SUMMARY AND CONCLUSIONS
An addition of alloying element Cu has a significant influence on the behavior of Laves-phase. It
reduces Laves-phase formation along prior austenite grain boundaries, thus improving the
toughness of the steel. It also changes the morphology of Laves-phase precipitates from rather
coarse equiaxied to densely distributed rod-shaped. The later morphology is stable at least up to
1000 hours. The formation of this type of morphology is believed to be due to the nucleation of
Laves-phase upon nano-sized Cu precipitates, since Cu does not partition into Laves-phase.
ACKNOWLEDGEMENTS
Lennart Johansson of Siemens Industrial Turbomachinery, Finspong, Sweden, is thanked for
performing heat treatments and mechanical testing. Dr Hilmar Danielsen of the Technical
University of Denmark and Prof. John Hald of DONG Energy and the Technical University of
Denmark is thanked for many helpful discussions. Financial support by the Swedish Energy
Agency, KME the Consortium for Materials Technology in Thermal Energy Processes, as well
as the Research Foundation of VGB in Germany is grateful acknowledged.
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Morris J.W.Jr., Guo Z, Krenn CR, Kim Y-H. "The limits of strength and toughness in
steel". ISIJ International (2001);41:599.
[14]
Httestrand M, Andrn H-O. "Microstructural development during ageing of an 11%
chromium steel alloyed with copper". Materials Science and Engineering A - Structural
Materials Properties Microstructure and Processing (2001);318:94.
1126
ABSTRACT
The addition of boron without the formation of any boron nitrides during normalizing heat
treatment at high temperature minimizes the degradation in creep strength of both base metal and
welded joints of 9Cr steel at 650 oC and long times. The enrichment of soluble boron near prior
austenite grain boundaries (PAGBs) by the segregation is essential for the reduction of coarsening
rate of M23C6 carbides in the vicinity of PAGBs, enhancing boundary and subboundary hardening,
and also for the production of same microstructure between the base metal and heat-affected-zone
(HAZ) in welded joints, indicating no Type IV fracture in HAZ. Excess addition of boron and
nitrogen promotes the formation of boron nitrides during normalizing, which reduces the soluble
boron concentration and accelerates the degradation in creep rupture ductility at long times. 9Cr3W-3Co-VNb steel with 120 - 150 ppm boron and 60 - 90 ppm nitrogen (MARBN) exhibits not
only much higher creep strength of base metal than Gr.92 but also substantially no degradation in
creep strength due to Type IV fracture at 650 oC. The pre-oxidation treatment in Ar gas promotes
the formation of protective Cr2O3 scale on the surface of 9Cr steel, which significantly improves
the oxidation resistance in steam at 650 oC.
INTRODUCTION
Advanced ultra-supercritical (A-USC) power plants with steam temperature of 700 oC or above
require 9 to 12Cr martensitic steels in order to minimize the requirement of expensive nickel-base
superalloys [1]. Nickel-base superalloys are candidates for the highest temperature components
of A-USC power plants, while 9 to 12Cr martensitic steels can be used for the next highest
temperature components. The maximum allowable temperature of Creep Strength Enhanced
Ferritic (CSEF) steels Grades 91, 92 and 122 is 610 to 620 oC. Expansion of the maximum
allowable temperature up to 650 C is highly desirable for next-generation ferritic steels. Critical
issues for the development of ferritic steels for 650 oC boilers are the improvement of oxidation
resistance as well as long-term creep rupture strength, including welded joints. In particular, the
degradation in creep strength due to Type IV fracture in welded joints is serious for CSEF steels
at temperatures above 600 oC. The purpose of the present paper is to make clear the alloy design
philosophy for 9Cr-boron steel to achieve long-term safety in terms of long-term creep strength,
ductility, resistance to Type IV cracking and oxidation resistance at 650 oC, beyond Grades 91, 92
and 122.
1127
EXPERIMENTAL PROCEDURE
0.08C-9Cr-3W-3Co-0.2V-0.05Nb (in nominal) steel with different boron concentrations of 0, 48,
92 and 139 ppm was used to investigate the effect of boron on creep strength of 9Cr boron steel
base metal [2]. Nitrogen was not added to the steel to avoid the formation of boron nitrides (BN)
during normalizing heat treatment at high temperature. Although no nitrogen was added to the
steel, residual nitrogen was analyzed to be 10 to 30 ppm. Residual Al was also as low as 30 to 50
ppm. The 9Cr-3W-3Co-0.2V-0.05Nb steel with 140 ppm boron but different nitrogen
concentrations was used to investigate the effect of nitrogen on creep strength of 9Cr-boron steel
[3]. The steels were basically prepared by vacuum induction melting to 50 - 100 kg ingots. Creep
tests for the base metal were carried out at 650 oC for up to about 9 x 104 h, using specimens of 10
mm in gauge diameter and 50 mm in gauge length. The welded joints were prepared by means of
multi-layered Gas Tungsten Arc (GTA) welding [4]. The simulated heat-affected-zone (HAZ)
specimens were also prepared.
IMPROVEMENT OF LONG-TERM CREEP STRENGTH OF BASE METAL BY BORON
Figure 1 shows the creep rupture data for 9Cr-3W-3Co-0.2V-0.05Nb steel with different boron
concentrations at 650 oC. Nitrogen was not added to the steel. The base steel with no boron (0
ppm boron) exhibits a loss of creep rupture strength at long times above about 1000 h at 650 oC.
With increasing boron content, however, the time to rupture significantly increases at low stresses.
The creep rupture strength of the present 9Cr steel with 139 ppm boron (residual nitrogen
concentraion : 34 ppm) is evaluated to be 80 MPa at 650 oC and 105 h. The long-term creep
rupture strength of the present 9Cr steel with 92 ppm boron is roughly the same as T/P92 [5],
while that of the present 9Cr steel with 48 ppm boron is roughly the same as T91 [6].
200
9Cr-3W-3Co-0.2V0.05Nb-0.08C
Stress ( MPa )
T/P92
650oC
100
80
60
40 1
10
0 ppm B
48 ppm B
92 ppm B
139 ppm B
T/P92
T91
2
10
T91
10
10
Time to rupture ( h )
10
1128
The addition of boron also improves the creep rupture ductility at 650 oC and long times as shown
in Fig.2 for the reduction of area, although the reduction of area is roughly the same among the
steels containing 48 to 139 ppm boron. This suggests that the localization of creep deformation
near prior austnite grain boundaries (PAGBs) is less pronounced by the addition of boron. The
reduction of area after long-term creep rupture testing is in order of 9Cr-boron steel => T91 >
T/P92. The improved reduction of area is advantageous to the creep-fatigue life, because the
creep-fatigue life is proportional to the reduction of area in creep rupture test, namely,
proportional to the creep ductility but not proportional to the creep strength [7].
Reduction of area ( % )
100
80
60
40
20
0 1
10
9Cr-3W-3Co-0.2V0.05Nb-0.08C
650oC
0 ppm B
48 ppm B
92 ppm B
139 ppm B
T/P92
T91
2
10
10
10
Time to rupture ( h )
10
of atom-probe tomography (APT) and found that boron was enriched in M23C6 carbides, which
was more significant in the vicinity of PAGBs than inside grain, the same as the present results.
8
9Cr-3W-3Co-VNb-0.0139B
Aged for 10300h at 650oC
10
15
20
25
30
650oC, 120MPa
104
103
102
10
0.08C-9Cr-3W-3Co-0.2V-0.05Nb-0.014B
(b)
Boron ( mass % )
(a)
Nitrogen ( ppm )
100
10
10-1
Time to rupture ( h )
105
10-2
1000
BN
100
Solid solution
1050 - 1150 oC
P122
P92
10
Boron ( ppm )
10-3
1
Nitrogen ( mass % )
Fig.4 (a) Effect of nitrogen on time to rupture and minimum creep rate of 9Cr steel with 140 ppm
boron and (b) composition diagram of boron and nitrogen for 9 to 12Cr steels.
1130
formation of boron nitrides of several m size in the present steel containing 140 ppm boron and
650 ppm nitrogen and in Gr.92 after normalizing.
Excess addition of boron and nitrogen degrades the creep rupture ductility as well as the creep
strength at 650 oC and long times, as shown in Fig.6. The degradation in reduction of area is
significant in the present steel containing 300 and 650 ppm N, where a large amount of BN
formed during normalizing. On the other hand, the present steel containing nitrogen less than 100
ppm exhibits the enough reduction of area, similar as T91.
(a)
(b)
(c)
1m
10m
Fig.5 Boron nitrides in (a) present 9Cr steel with 140 ppm boron and 650 ppm nitrogen,
(b) and (c) Gr.92, after ductile fracture at room temperature.
Reduction of area ( % )
100
80
60
40
20
15 ppm N
34 ppm N
650oC
9Cr-3W-3Co-0.2V0.05Nb-0.08C
15 ppm
34 ppm
79 ppm
300 ppm
N
N
N
N
79 ppm N
300 ppm N
650 ppm N
T91
650 ppm N
T / P92, 462 ppm N
T/P92
0 1
10
10
10
10
Time to rupture ( h )
10
10
650oC, 120MPa
Creep rate ( 1 / h )
10-1
(a)
-2
10
-3
10
-4
10
-5
10
0.0015N
0.0079N
0.030N
0.065N
-6
10
10-7 -1
10
10
10
10
10
Time ( h )
10
containing 79 and 650 ppm nitrogen after tempering, Fig.7(b). Dissolved nitrogen can precipitate
as fine MX carbonitrides during creep at 650 oC. Indeed, very fine vanadium-rich MX
carbonitrides were observed to have precipitated in the steel containing 79 ppm nitrogen during
aging for 1000 h at 650 oC [3]. The fine MX carbonitrides precipitated during creep effectively
decreases the creep rates in the transient region and also stabilize the martensitic microstructure
by retarding dislocation recovery. The difference in onset time of acceleration creep between the
two steels containing 15 and 79 ppm nitrogen is due to the microstructure stabilization due to
distributions of fine MX carbonitrides. The addition of excess nitrogen of 300 and 650 ppm
reduces soluble boron available for microstructure stabilization by the formation of BN during
normalizing. This is a reason why the onset of acceleration creep takes place at earlier times in
the high nitrogen steels containing 300 and 650 ppm than in the low nitrogen steel containing 79
ppm.
9Cr-3W-3Co-0.2V-0.05Nb steel with 140 ppm B
After tempering
(b)
Fig.7 (a) Effect of nitrogen on creep rate versus time curves of the steels and
(b) dissolved and precipitated nitrogen concentrations in the steels after tempering.
Suppression of Type IV fracture in welded joints
The addition of boron and nitrogen without any formation of BN during normalizing heat
treatment causes no grain refinement and no Type IV fracture in HAZ of 9Cr steel welded joints,
Fig.8 [11-12]. Soluble boron is essential also for the suppression of Type IV fracture.
The 9Cr-3W-3Co-0.2V-0.05Nb steel containing 130 ppm boron consists of coarse grains of
roughly 200 to 300 m after the thermal cycle to a peak temperature of 950 oC, just above the AC3
temperature, which is substantially the same as that of base metal, as shown in Fig.9 [13], where
GBs are traced so that grain size is clearly identified. Fine grains form along GBs of coarse
grains but are limited only in the vicinity of GBs. Fe7W6 phase precipitates at GBs of fine
grains during PWHT. Inside the grains, the martensitic microstructure substantially consists of
blocks but laths are not clearly seen, Fig.10(a). Not only PAGBs but also block boundaries are
covered by enough precipitates, suggesting enough boundary and sub-boundary hardening,
substantially the same as the base metal.
1132
The AC3 simulated-HAZ specimens of Gr.92 exhibits the fine-grained microstructure, where very
few M23C6 carbides are formed along PAGBs, Fig.10(b) [14]. Inside the grains, Gr.92
10
Nitrogen ( ppm )
100
1000
10
100
P122
10
-3
10
-4
10
Solid solution
P122
P92
1050 - 1150 oC
10
P92
Large BN
Small BN
No BN
-3
Boron ( ppm )
Boron ( mass % )
BN
-2
No grain refinement
& no Type IV fracture
Grain refinement &
Type IV fracture
1
10
-2
Nitrogen ( mass % )
10
-1
Fig.8 Grain refinement and Type IV fracture in 9 to 12Cr steel welded joints.
Base metal
Fig.9 Optical micrographs of 9Cr-boron steel containing 130 ppm boron: base metal
and after thermal cycle to a peak temperature of 950oC (near AC3) and subsequent PWHT.
consists of equiaxed subgrains with low density of dislocations and sparse distributions of large
carbides. These results suggest that the boundary and subboundary hardening is significantly
reduced in Gr.92 after the AC3 thermal cycle. The degradation in creep life of Gr.92 after the AC3
thermal cycle is not caused by the grain refinement but that the reduction of boundary and
subboundary hardening is the most important. Diffusive / transformation takes place in Gr.92
during heating, while at first fine grains form at grain boundaries in the 9Cr-boron steel by
diffusive transformation and then martensitic / transformation takes place inside the grain [13].
Using a binding energy of 62.7 kJ mol-1 [15] reported for type 316 stainless steel, segregation of
boron at grain boundaries is evaluated to be several % at a temperature of 950 C, near Ac3, while
the boron concentration inside the grain is substantially unaffected, Fig.11.
We think that boron retards the diffusive / transformation during heating, because the grain
boundary segregation of boron reduces grain boundary energy and makes the boundaries less
1133
effective as heterogeneous nucleation sites for phase. This indicates that boron retards the
diffusive / transformation during heating. On the other hand, the nucleation of phase by
lath & block
PAGB of original
microstructure
(a)
9Cr-3W-3Co0.2V-0.05Nb
with 90 ppm B
(b) Gr.92
PAGB
of HAZ
1m
10
10
(a)
= 0.3 nm
104
3
10
10
10
600
CGB
Concentration of boron
Fig.10 SEM and TEM micrographs of (a) 9Cr-3W-3Co-0.2V-0.05Nb steel with 90 ppm B and
(b) Gr.92, after thermal cycle to 950 oC (near AC3) and subsequent PWHT.
d = 50 m
Ci = 100 ppm
B = 62.7 kJ mol-1
Within grain
Grain boundary
C0
800
1000
o
Temperature ( C )
CGB
CGB
(b)
(a)
Ci
C0
Distance
1200
Boron concentration
Retardation effect
by boron
0.5
%
20
ppm
100
ppm
Inside grain
Initial boron = 100 ppm
M23(CB)6
(b)
Inside grains
Nucleation of
Retardation effect
by boron
Nucleation of
9Cr-boron steel suggest that driving force for diffusive / transformation during heating is a little
bit larger near GBs than the retardation effect by boron, Fig.12(a). The martensitic
/ transformation inside the grain suggests that the retardation effect of diffusive /
transformation by boron is larger inside the grain than the driving force for diffusive /
transformation, Fig.12(a). The soluble boron concentration in the matrix is estimated to be about
20 ppm as shown in Fig.12(b), by assuming the initial boron concentration is 100 ppm, the
enriched boron concentration in M23C6 carbides is 0.5% (500 pmm) as can be seen from Fig.3,
and the mole fraction of M23C6 carbides is 0.0016 by thermo-calc. We think that the soluble
boron concentration of 20 ppm in the matrix can retard the diffusive / transformation and hence
the martensitic / transformation takes place inside the grain during heating.
C0
Fig.12 (a) Schematic drawing of driving force for / transformation during heating and
(b) boron concentration distribution inside grain.
Alloy design of MARBN : high strength and no Type IV fracture
Based on the suppression of Type IV fracture using boron and the improvement of long-term
creep strength of base metal using both boron and fine MX nitrides without any formation of BN
during normalizing, a 9Cr-3W-3Co-0.2V-0.05Nb steel containing 120-150 ppm boron and 60-90
ppm nitrogen was alloy-designed. The steel is denoted MARBN, which means MARtensitic 9Cr
steel strengthened by Boron and fine MX Nitrides. As already decribed, the addition of boron as
low as 40 ppm is enough to suppress the Type IV cracking in welded joints (Fig.8). However, the
maximum creep strength of welded joints is limited by the creep strength of base metal and the
increase in boron concentration improves long-term stability of base metal (Fig.1). Therefore, the
addition of boron higher than 100 ppm is recommended. At a boron concentration of 120-150
ppm, the nitrogen concentration should be less than 100 ppm to avoid the formation of BN at
normalizing temperature. The optimum nitrogen concentration is 60-90 ppm from a point of view
of creep strength (Fig.4).
Figure 13 shows the creep rupture data for the base metal and welded joints of MARBN at 650
C, together with those for the 9Cr-3W-3Co-0.2V-0.05Nb steel containing 139 ppm boron and 34
ppm nitrogen (Fig.1) and P92. MARBN exhibits a little bite higher creep rupture strength of base
metal than the 9Cr steel containing 139 ppm boron and 34 ppm nitrogen, which results from the
nitrogen effect. It should be noted that MARBN exhibits not only much higher creep rupture
strength of base metal than P92 but also substantially no degradation in creep rupture strength of
welded joints compared with the base metal.
o
1135
300
Stress ( MPa )
650oC
200
MARBN
100
80
60
50
1
10
MARBN :
9Cr-3W-3Co-0.2V-0.05Nb steel
with 120 - 150 ppm B and
60 - 90 ppm N
2
10
10
P92
4
10
Time to rupture ( h )
10
Fig.13 Creep rupture data for base metal and welded joints of MARBN, P92 and 9Cr-3W-3Co0.2V-0.05Nb steel containing 139 ppm boron and 34 ppm nitrogen at 650 oC.
Improvement of oxidation resistance by pre-treatment
The formation of protective Cr-rich oxide scale is achieved by several pre-treatments, such as the
pre-oxidation treatment in argon gas at 600 to 700 oC [14-15]. The long-term stability of Cr2O3
scale formed by the pre-oxidation treatment has been examined for the three steels, MARB1 with
100 ppm boron, MARB2 with 200 ppm boron and MARN with 0.05 % nitrogen but no addition
of carbon in steam at 650oC, after the pre-oxidation treatment in Ar gas at 700 oC for 50 h, Fig.14.
The formation of thin scale of Cr-rich oxides, having a thickness of less than 0.1 m, is achieved
by the pre-oxidation treatment. For the three steels MARB1, MARB2
Steam at 650oC
Time ( h )
Fig.14 Weight gain of the steels in steam at 650 oC. MARB1 and MARB2: 9Cr-3W-3Co- 0.2V0.05Nb with 100 and 200 ppm boron, respectively, MARN : Low-carbon of 30 ppm C.
1136
and MARN, the oxidation resistance in steam is significantly improved by the pre-oxidation
treatment. The thin scale of Cr-rich oxides is stable during oxidation test in steam at 650 oC for a
long time exceeding 20,000 h.
Comprehensive test program on the 9Cr-boron steel for getting approval is now being promoted
by Nippon Steel & Sumitomo Metal Corporation (NSSC), on the base of cooperation between
NSSC and some universities and institutes in Japan. Test results are presented in this conference
by a companion paper [18].
Conclusions
1) The addition of boron and nitrogen to 9Cr-3W-3Co-VNb steel without any formation of BN
during normalizing heat treatment improves the long-term creep strength of base metal and
suppresses the Type IV cracking in HAZ of welded joints at 650 oC. The addition of boron also
improves the creep rupture ductility.
2) The addition of excess nitrogen of 300 and 650 ppm to the 9Cr steel with 140 ppm boron
causes the formation of large amount of BN during normalizing, which significantly reduces
soluble boron and accelerates the degradation in creep rupture ductility.
3) The enrichment of soluble boron near PAGBs by the segregation is essential for the reduction
of coarsening rate of M23C6 carbides near PAGBs, which enhances boundary and subboundary
hardening near PAGBs, and also for the change in / transformation behavior in HAZ of
welded joints during heating, which produces approximately the same microstructure between
HAZ and base metal. The enhancement of boundary and subboundary hardening by fine
distributions of M23C6 carbides along boundaries retards the onset of acceleration creep, which
effectively decreases the minimum creep rate and increases the creep life.
4) 9Cr-3W-3Co-0.2V-0.05Nb steel with 120-150 ppm boron and 60-90 ppm nitrogen
(MARBN) exhibits not only much higher creep rupture strength of base metal than P92 but also
substantially no degradation in creep strength due to Type IV fracture in HAZ of welded joints at
650 oC.
5) The formation of protective Cr-rich scale is achieved on the surface of 9Cr steel by preoxidation treatment in argon gas at 600 - 700 oC. This significantly improves the oxidation
resistance of 9Cr steel in steam at 650 oC.
References
[1] Fukuda, M., Saito, E., Tanaka, Y., Takahashi, T., Nakamura, S., Iwasaki, J., Takano, S. and
Izumi, S., Advanced USC Technology Development in Japan, Proc. of 6th Intern. Conf. on
Advances in Materials Technology for Fossil Power Plants, Eds. By D. Gandy, J.
Shingledecker and R. Viswanathan, August 31 - September 3, 2010, Santa Fe, New Mexico,
USA (2010)325-341.
[2] Horiuchi, T., Igarashi, M. and Abe, F., Improved Utilization of Added B in 9Cr HeatResistant Steels Containing W, ISIJ International, 42 (2002) S67-S71.
[3] Semba, H. and Abe, F., Alloy design and creep strength of advanced 9%Cr USC Boiler
steels containing high concentration of boron, Energy Materials, 1 (2006) 238-244.
[4] Abe, F. and Tabuchi, M., Microstructural and Creep Strength of Welds in Advanced Ferritic
Power Plant Steels, Sci. Technol. Welding and Joining, 9 (2004), 22-30.
[5] NIMS Creep Data Sheets No.48A, Tokyo, Tsukuba: National Institute for Materials Science
(2012).
1137
[6] NIMS Creep Data Sheets, Atlas of Creep Deformation Property, No.D-1, Tokyo, Tsukuba,
National Institute for Materials Science (2007).
[7] Kimura, M., Kobayashi, K. and Yamaguchi, K., Creep and fatigue properties of newly
developed ferritic heat-resisting steels for ultra super critical power plants, Materials Science
Research International, 9 (2003), 50-54.
[8] Abe, F., Nakazawa, S., Araki, H. and Noda, T., The Role of Microstructural Instability on
Creep Behaviour of a Low Radioactivation Martensitic 9Cr-2W Steel, Metall. Trans., 23A
(1992), 469-477.
[9] Liu, F., Fors, D. H. R., Golpayegani, A., Andren, H. O. and Wahnstrom, G., Effect of boron
on carbide coarsening at 873 K (600 oC) in 9 to 12 pct chromium steels, Metallurgical and
Materials Transactions A, 43A (2012) 4053-4062.
[10] Sakuraya, K., Okada, H. and Abe, F., BN type inclusions formed in high Cr ferritic heat
resistant steel, Energy Materials, 1 (2006) 158-166.
[11] Tabuchi, M., Kondo, M., Watanabe, T., Hongo, H., Yin, F. and Abe, F., Improvement of
Type IV cracking resistance of 9Cr heat resisting steel weldment by boron addition, Acta
Metall Sin 17 (2004) 331-337.
[12] Abe, F., Tabuchi, M., Kondo, M. and Tsukamoto, S., Suppression of Type IV fracture and
improvement of creep strength of 9Cr steel welded joints by boron addition, International
Journal of Pressure Vessels and Piping 84 (2007) 44-52.
[13] Shirane, T., Tsukamoto, S., Tsuzaki, K., Adachi, Y., Hanamura, T., Shimizu, M. and Abe, F.,
Ferrite to austenite reverse transformation process in B containing 9%Cr heat resistant steel
HAZ, Sci. Technol. Welding and Joining, 14 (2009) 698-707.
[14] Liu, Y., Tsukamoto, S., Shirane, T. and Abe, F., Formation Mechanism of Type IV Failure
in High Cr Ferritic Heat-Resistant Steel-Welded Joint, Metall. Mater. Trans. A, (2013) DOI:
10.1007/s11661-013-1801-0.
[15] Karlsson, L. and Norden, H., Non-equilibrium grain boundary segregation of boron in
austenitic stainless steels II Fine segregation behavior, Acta Metall., 36 (1988) 13-27.
[16] Kutsumi, H., Itagaki, T. and Abe, F., Improvement of Steam Oxidation Resistance for
Ferritic Heat Resistant Steels, Proc. of 7th Liege Conference on Materials for Advanced Power
Engineering 2002, edited by J. Lecomte-Beckers et al., Liege, Belgium (2002), 1629-1638.
[17] Okubo, H., Muneki, S., Hara, T., Kutsumi, H. and Abe, F., Improvement of oxidation
resistance of 9% Cr steel for A-USC by pre-oxidation treatment, Proc. of the 34th MPA
Seminar, MPA, Stuttgart, October 9 and 10 (2008), CD-ROM.
[18] Yonemura, M., Hasegawa, Y., Igarashi, M., Tabuchi, M. and Abe, F., A new developed 9%
Cr steel with high boron content achieving the long-term microstructural stability and the
optimized mechanical properties for 625 oC USC power plant boiler, Proc. of this conference.
1138
ABSTRACT
Inflection is observed at 50% of 0.2% offset yield stress, that is HALF YIELD, on the relation
between stress and creep rupture life of creep strength enhanced ferritic steels with tempered
martensitic microstructure. Similar shape is generally recognized on the ferritic steels with
martensitic or bainitic microstructure, in contrast to ferritic steels with ferrite and pearlite
microstructure, as well as austenitic steels and superalloys except for several alloys. Ferritic steel
with martensitic or bainitic microstructure indicates softening during creep exposure, however,
hardening due to precipitation takes place in the ferritic steels with ferrite and pearlite
microstructure and austenitic steels. This difference in microstructural evolution is associated with
indication of inflection at half yield. Stress range of half yield in the stress vs. creep life diagram
of creep strength enhanced ferritic steels is wider than that of conventional ferritic creep resistant
steels with martensitic or bainitic microstructure. As a result of wide stress range of boundary
condition, risk of overestimation of long-term creep rupture strength by extrapolating the data in
the high-stress regime to the low-stress regime is considered to be high for creep strength
enhanced ferritic steels.
INTRODUCTION
Increase in steam parameter of temperature and pressure is required for fossil fired power plant,
since energy efficiency of the plant is improved by the increasing steam parameter and, therefore,
it is effective to reduce fuel consumption and emission of carbon dioxide gas considered to be a
greenhouse gas. Development of higher strength creep resistant materials is desired to improve
energy efficiency of the plant. On the other hand, creep rupture life of materials decreases with
increase in temperature. In order to ensure the safety and reliability of the plant with the high
energy efficiency, precise assessment of long-term creep strength property, such as 100,000 hours
creep rupture strength is fundamental to the materials used for high temperature components.
Modern thermal power plants with Ultra Supercritical (USC) steam condition have been achieved
with the introduction of creep strength enhanced ferritic (CSEF) steels. CSEF steels have also
been applied for heat recovery steam generator (HRSG) of combined cycle power plant.
However, remarkable strength drop in the long-term was reported on CSEF steels [1-3], and
region splitting analysis method was proposed in order to improve the accuracy of long-term
creep rupture life prediction [4]. According to region splitting analysis method, creep rupture data
in the high- and low-stress regimes is analyzed independently, which is divided by 50% of the
0.2% offset yield stress at the temperature, hereinafter referred to as HALF YIELD. Accuracy of
creep rupture life prediction of the CSEF steels is improved by region splitting analysis method in
contrast to a conventional analysis with use of whole dataset from short-term to long-term. On the
1139
basis of the reevaluation of long-term creep rupture strength with region splitting analysis method,
allowable stress of CSEF steels regulated in the Interpretation for the Technical Standard for
Thermal Power Plant in Japan was revised [5]. Creep rupture strength of welded joints of the
CSEF steels has also been evaluated by means of region splitting analysis method, and weld
strength reduction factors of the steels have been proposed [6]. In the present paper, in order to
ensure the reliability and availability of region splitting analysis method, creep rupture strength
property has been investigated on a wide variety of materials from a viewpoint of relation between
stress versus time to rupture curve and HALF YIELD, and role of HALF YIELD on creep life
prediction has been discussed.
INFLECTION OF STRESS-CREEP RUPTURE LIFE CURVE
Creep rupture life of the ASME Grade 122 type (a) pipe, (b) plate, (c) tube steels and (d) dual
phase tube steel containing delta ferrite is plotted against a ratio of stress to 0.2% offset yield
stress at the temperature, hereinafter referred to as yield ratio and shown in Figure 1. Inflection is
recognized on the relation between yield ratio and time to rupture at the HALF YIELD for all the
steels regardless of temperature. A slope of the curves changes from gentle in the high-stress ratio
regime to steeper in the low-stress ratio regime with decrease in stress ratio. It should be noted
that an extrapolation of the creep rupture data in the high-stress ratio regime above HALF YIELD
to the low-stress ratio regime below HALF YIELD causes overestimation of long-term creep
rupture life.
Figure 1: Creep rupture life of the ASME Grade 122 type (a) pipe, (b) plate, and (c) tube steels,
and (d) dual phase tube steel containing delta ferrite plotted against a ratio of stress to 0.2%
offset yield stress [7].
1140
Magnitude of plastic strain observed during tensile test at 600 and 650C of the same steels as
shown in Fig.1 is plotted against yield ratio and shown in Figure 2. Tensile test was conducted
under a constant strain rate of 5 x 10-5 s-1 (0.003/min), in accordance with Japanese Industrial
Standard (JIS) [8]. In the low-stress regime below yield ratio of about 0.5, no plastic strain is
observed, and plastic deformation starts when the applied stress increases beyond about 0.5 of
yield ratio at both 600 and 650C for all the steels studied. This observation indicates that elastic
limit of the steels is about 0.5 of yield ratio under strain rate of 5 x 10-5 s-1. Similar result on
elastic limit that corresponds to about 0.5 of yield ratio under the same strain rate has also been
obtained on ASME Grade T91 steel by means of stress abrupt change test at 600 and 650C [9].
Strain rate of 5 x 10-5 s-1 (0.003/min) is slightly lower than that regulated in ASTM standard,
which is 0.005 0.002/min [10]. Since yield stress depends on strain rate, HALF YIELD is also
influenced by difference in strain rate employed for the evaluation of 0.2% offset yield stress. It
has been confirmed on ASME Grade T91 steels that, however, difference in strain rate for the
evaluation of 0.2% offset yield stress in accordance with JIS [8] and ASTM [10] regulations does
not affect the results of creep rupture life analysis for low-stress regime below HALF YIELD
[11].
Figure 2: Magnitude of plastic strain of the ASME Grade 122 type pipe, plate, and tube steels
plotted against a ratio of stress to 0.2% offset yield stress at (a) 600 and (b) 650C [7].
1141
Schematic illustration on stress dependence of microstructural change during creep exposure and
its effect on creep rupture strength are described in Figure 3 [4]. Recovery at the vicinity of prior
austenite grain boundary is promoted mainly by concentrated internal strain introduced by
martensitic transformation in addition to a rapid diffusion rate and faster coarsening of
precipitates on grain boundary. With increase in applied stress, however, recovery within grain is
also accelerated and locally recovered region at the vicinity of prior austenite grain boundary
easily extends toward grain interior with the assistance of high external stress above elastic limit.
Consequently, creep strength in the high-stress regime is significantly lowered with increase in
applied stress, and the boundary of high- and low-stress regimes is found to be comparable to
HALF YIELD [4]. According to the above results, creep strength should be evaluated for highand low-stress regimes independently with a boundary of HALF YIELD, and the validity of that
has been demonstrated on Grade T91 steel as shown in Figure 4 [4].
Figure 5: Stress versus time to rupture curves of the 0.5Cr-0.5 Mo steel tubes [12].
Figure 6: Stress versus time to rupture curves of the normalized and tempered 2.25Cr-1Mo steel
plates [12].
1143
In comparison with the creep rupture strength of 0.5Cr-0.5Mo steels (Fig.5) and normalized and
tempered 2.25Cr-1Mo steels (Fig.6), a relatively large heat-to-heat variation of creep rupture
strength is observed in the low-stress regime of 9Cr-1Mo steels (Fig.7). Long-term creep strength
of high chromium ferritic steel is influenced by an effective nitrogen concentration which is free
from AlN and TiN [13]. A large heat-to-heat variation of creep rupture strength in the low-stress
regime of 9Cr-1Mo steels is supposed to be derived from the concentration of effective nitrogen.
Figure 7: Stress versus time to rupture curves of the 9Cr-1Mo steel tubes [12].
Bainitic and Tempered Martensitic Steels
Creep rupture strength of quenched and tempered (QT) 2.25Cr-1Mo steel plates is shown in
Figure 8 [12], in the same manner as Fig.5. In contrast to normalized and tempered 2.25Cr-1Mo
steels (Fig.6), stress dependence of time to rupture of quenched and tempered 2.25Cr-1Mo steels
is different in high- and low-stress regimes. Slope of the relation between stress and time to
rupture in the low-stress regime (< YS/2) is steeper than that in the high-stress regime (> YS/2).
Figure 8: Stress versus time to rupture curves of the quenched and tempered 2.25Cr-1Mo steel
plates [12].
1144
Creep rupture strength of 1Cr-1Mo-0.25V turbine rotor steels with bainitic microstructure, and
quenched and tempered 12Cr-1Mo-1W-0.3V steels [12] are shown in Figures 9 and 10,
respectively in the same manner as Fig.5. Stress dependence of time to rupture of 1Cr-1Mo0.25V, and 12Cr-1Mo-1W-0.3V steels is similar to that of quenched and tempered 2.25Cr-1Mo
steels shown in Fig.6. Slope of the relation between stress and time to rupture in the low-stress
regime is steeper than that in the high-stress regime, and inflection of the relationship is
recognized at HALF YIELD. Relatively large heat-to-heat variation of creep rupture strength is
observed on 12Cr-1Mo-1W-0.3V steels in the long-term, and it is also considered to be caused by
the influence of effective nitrogen [13] similar to 9Cr-1Mo steels (Fig.7).
Figure 9: Stress versus time to rupture curves of the 1Cr-1Mo-0.25V turbine rotor steels [12].
Figure 10: Stress versus time to rupture curves of the quenched and tempered 12Cr-1Mo-1W0.3V steels [12].
1145
Inflection of stress vs. time to rupture curve at HALF YIELD is observed on three ferritic steels of
quenched and tempered 2.25Cr-1Mo steel, 1Cr-1Mo-V steel, and 12Cr-1Mo-1W-0.3V steel.
Commonality of those three steels which indicate inflection at the HALF YIELD is initial
microstructure, that is tempered martensitic or bainitic microstructure. The initial microstructure
of the other steels which do not indicate inflection at the HALF YIELD is ferrite and pearlite or
ferrite. Ferritic steel with martensitic or bainitic microstructure indicates softening during creep
exposure, however, hardening due to precipitation takes place in the ferritic steel with ferrite and
pearlite microstructure. It has been supposed that HALF YIELD is comparable to an elastic limit
of tempered martensitic microstructure [7, 9], therefore, microstructural change during creep
exposure is promoted by the assist of stress in the high-stress regime above HALF YIELD. This
difference in microstructural evolution during creep exposure is associated with indication of
inflection at HALF YIELD.
Austenitic Steels and Superalloys
Creep rupture strength of TP304H at 700C is shown in Figure 11. A linear relationship between
stress and time to rupture in a double logarithmic scale is observed in the high-stress regime.
Creep rupture strength variation, however, increases in the low-stress regime, since some data
plots indicate large drop in creep rupture strength. Long-term creep rupture strength of the steels
was controlled by concentration of effective nitrogen which is free from AlN and TiN similar to
9Cr-1Mo steels [14]. Although it is interest that heat-to-heat variation of creep rupture strength
due to effective nitrogen is appeared prominently in the low-stress regime, inflection of stress vs.
time to rupture curve is not recognized on TP304H at the HALF YIELD.
Creep rupture strength of Alloy 800H at 700, and 800C is shown in Figure 12. Good linear
relationship between stress and time to rupture in a double logarithmic scale is observed and no
indication of inflection at HALF YIELD is recognized. Creep rupture strength has been
investigated on all austenitic steels and superalloys of NRIM/NIMS Creep Data Sheets, and no
identifiable correlation was observed on every austenitic steels, as well as superalloys except for
several alloys. Details on the superalloys are future work.
Figure 11: Stress versus time to rupture curve of the TP304H steels at 700C [12].
1146
Figure 12: Stress versus time to rupture curve of the Alloy 800H at 700 and 800C [12].
TEMPERATURE DEPENDENCE OF HALF YIELD
From the observation on creep rupture strength of wide variety of creep resistant steels and alloys,
it has been revealed that an inflection of relation between stress and creep rupture life at HALF
YIELD is a common feature of ferritic steels with bainitic and tempered martensitic
microstructures. Remarkable overestimation of long-term creep rupture strength of CSEF steels
was caused by conventional evaluation method which analyze whole dataset from short-term to
long-term, since the overestimation is considered to be caused by an inflection of stress vs. time to
rupture curve at HALF YIELD. However, such inflection of stress vs. time to rupture curve at
HALF YIELD is observed on not only CSEF steels, but also conventional ferritic steels with
bainitic and tempered martensitic microstructures. Similar problem of overestimation of long-term
creep strength was not recognized on the conventional steels. In this section, difference between
CSEF steels and conventional bainitic and tempered martensitic steels is discussed.
Temperature dependence of 0.2% offset yield stress of CSEF steels and conventional bainitic and
tempered martensitic steels are shown in Figure 13 [12]. 0.2% offset yield stresses of the
conventional steels are higher than those of CSEF steels from room temperature to the elevated
temperatures, especially on 1Cr-1Mo-0.25V and 12Cr-1Mo-1W-0.3V steels. Relatively lower
yield strength of CSEF steels is caused by higher tempering temperature in order to obtain higher
stability of microstructure during creep exposure at the elevated temperatures.
HALF YIELD of the steels in the range of temperatures corresponds to creep test data shown in
Figs.8-10 for the conventional steels is described in Figure 14, together with those of CSEF steels.
For the CSEF steels, HALF YIELD is described up to 700C, since it is the temperature range of
interest for CSEF steels. A trend of decrease in HALF YIELD with increase in temperature is
almost the same for all the steels investigated. On the other hand, range of HALF YIELD from the
lowest temperature to the highest temperature of CSEF steels is wider than those of the
conventional steels. Main purpose to use time-temperature parameter such as Larson-Miller
parameter for extrapolation of experimental creep test data is compensation of temperature,
therefore, creep test data obtained at higher temperature is considered to correspond longer creep
rupture strength at the same stress and lower temperature. From this point of view, experimental
creep test data obtained in the high-stress regime should not be extrapolated to the low-stress
regime across the boundary condition of HALF YIELD, because creep deformation mechanism in
1147
the low-stress regime below elastic limit is considered to be a different from that in the high-stress
regime above elastic limit [4, 15, 16]. Narrow stress range of HALF YIELD of conventional
steels is advantageous to reduce a risk to extrapolate high-stress regime data to low-stress regime.
In contrast to conventional steels, higher creep strength of CSEF steels provides wider stress
range of HALF YIELD, therefore, it increases a risk to extrapolate high-stress regime data to lowstress regime.
Figure 13: Temperature dependence of 0.2% offset yield stress of the steels [12].
Figure 14: Temperature dependence of 50% of 0.2% offset yield stress of the steels in the range
of creep test temperature [12].
Difference between conventional steels and CSEF steels are schematically illustrated in Figure 15.
Colored area indicates a practical experimental range of creep test for both type steels. For the
conventional steels, creep test data in the high-stress regime is obtained at the temperatures of T1,
T2 and T3, and those data may be extrapolated to the long-term in the low-stress regime.
However, the wrong extrapolation from high-stress regime to low-stress regime across the HALF
YIELD is limited to narrow stress range in the higher stress levels. On the other hand, creep test
data in the high-stress regime is obtained at all the temperatures from T1 to T5 for CSEF steels,
because of prolonged creep rupture life obtained by stabilized microstructure. Since a lot of creep
test data is obtained in the high-stress regime for CSEF steels, conventional life prediction method
with whole dataset provides a remarkable overestimation in the low-stress regime.
1148
Figure 15: Schematic illustration on the range of experimental creep test for (a) conventional
ferritic steels with bainitic and/or tempered martensitic microstructures and (b) creep strength
enhanced ferritic steels.
CONCLUSIONS
Inflection of stress vs. time to rupture curves at HALF YIELD was observed on not only creep
strength enhanced ferritic steels, but also conventional bainitic and tempered martensitic steels,
and it was supposed to be a common feature of those steels. Stress range of HALF YIELD in the
practical creep test condition of the conventional steels is limited to narrow stress range in the
higher stress level, therefore, a risk of overestimation of creep rupture life due to extrapolating the
high-stress regime data to the low-stress regime is relatively small. On the other hand, stress range
of HALF YIELD in the practical creep test condition of CSEF steels is wider than that of
conventional steels, as a result of improved creep strength property. Consequently, a risk of
overestimation of long-term creep rupture life of CSEF steels by extrapolating creep test data
obtained in the high-stress regime to the low-stress regime is high.
ACKNOWLEDGEMENTS
The creep tests were performed as a part of NRIM/NIMS Creep Data Sheet project. The author is
grateful to all the members participated in the NRIM/NIMS Creep Data Sheet project for their
sincere efforts.
1149
REFERENCES
[1] Foldyna, V., Kubo, Z. Jakobov, A., and Vodrek, V., Development of Advanced High
Chromium Ferritic Steels, Microstructural Development and Stability in High Chromium
Ferritic Power Plant Steels, Strang, A., and Gooch, D. J. eds., The Institute of Materials,
(1997), pp. 73-92.
[2] Strang, A., and Vodarek, V., Microstructural Stability of Creep Resistant Martensitic 12%
Cr Steels, Microstructural Stability of Creep Resistant Alloys for High Temperature Plant
Applications, The Institute of Materials, London, (1998), pp. 117-133.
[3] Kimura, K., Kushima, H., and Abe, F., Heterogeneous Changes in Microstructure and
Degradation Behaviour of 9Cr-1Mo-V-Nb Steel During Long Term Creep, Key Engineering
Materials, 171-174 (2000), pp. 483-490.
[4] Kimura, K., Kushima, H., and Abe, F., Degradation and Assessment of Long-term Creep
Strength of High Cr Ferritic Creep Resistant Steels, Proc. Int. Conf. Advances in Life
Assessment and Optimization of Fossil Power Plants, Orland, FL, March, 2002.
[5] Kimura, K., and Takahashi, Y., Evaluation of Long-term Creep Strength of ASME Grades
91, 92, and 122 Type Steels, Proc. PVP2012, Toronto, Canada, PVP2012-78323, July,
2012.
[6] Yaguchi, M., Matsumura, T., and Hoshino, K., Evaluation of Long-term Creep Strength of
Welded Joints of ASME Grades 91, 92, and 122 Type Steels, Proc. PVP2012, Toronto,
Canada, PVP2012-78393, July, 2012.
[7] Kimura, K., Kushima, H., Sawada, K., and Toda, Y., "Region Splitting Analysis on Creep
Strength Enhanced Ferritic Steels," Proc. CREEP8, San Antonio, TX, PVP2007-26406, July
2007.
[8] Japanese Industrial Standard, Method of elevated temperature tensile test for steels and heatresisting alloys, JIS G 0567:1998.
[9] Kimura, K., Sawada, K., Kubo, K., and Kushima, H., Influence of Stress on Degradation
and Life Prediction of High Strength Ferritic Steels, Proc. PVP2004, San Diego, CA,
PVP2004-2566, July, 2004.
[10] ASTM Standard, Standard Test Methods for Elevated Temperature Tension Tests of Metallic
Materials, ASTM International, E21-09, 2009.
[11] Kimura, K., Sawada, K., and Kushima, H., Strain Rate Dependence of Yield Strength and
Long-term Creep Strength Evaluation of ASME Grade 91 Steel, Proc. PVP2009, Prague,
Czech Republic, PVP2009-77484, July, 2009.
[12] NRIM/NIMS Creep Data Sheets, No.4B (1986), No.9B (1990), No.10B (1998), No.11B
(1997), No.19B (1994), No.20B (1994), No.27B (2000), No.36B (2003), No.48A (2012),
No.51A (2013), No.D-1 (2007).
[13] Abe, F., Heat-to-heat variation in long-term creep strength of some ferritic steels, Int. J.
Pressure Vessels Piping, 87 (2010), pp.310-318.
[14] Miyazaki, H., Tanaka, H., Murata, M., and Abe, F., Effects of Minor Elements on the
Long-Term Creep Rupture Time of SUS 304 HTB Stainless Steel, J. Japan Inst. Metals, 66
(2002), pp.1278-1286.
[15] Kimura, K., Sawada, K., Kushima, H., and Kubo, K., Effect of stress on the creep
deformation of ASME Grade P92/T92 steels, Int. J. Mat. Res., 99 (2008), pp.395-401.
[16] Kimura, K., Sawada, K., Kushima, H., and Toda, Y., Microstructural Stability and Longterm Creep Strength of Grade 91 Steel, Energy Materials, 4, 2012, pp.176-183.
1150
1151
ABSTRACT
An approach to phase analysis called multiphase separation technology (MPST) has been
developed to determine phase chemistries of precipitated particles with sizes visible under
SEM/EPMA observations based on the data from the conventional EDS measurements on bulk
steel/alloy material samples. Quite accurate results from its applications have successfully been
demonstrated by comparisons of SEM/EPMA - EDS + MPST with some other currently
available means, for instance, chemical extractions (CA), TEM-EDS, AP-FIM and Thermo-Calc.
etc. Applied examples regarding the relations of change in phase parameters including type,
composition, volume fraction, size and distribution of the precipitated particles with material
qualities, creep rupture lives, property stabilities, property recovery and boiler tube failures for
some advanced heat resistant steels (P92, Super304H, HR3C, TP347HFG (H)) are given through
the use of the SEM/EPMA - EDS + MPST in this contribution. Examples on phase
quantifications
of
some
nickel
base
superalloys
(Nimonic263,
Inconel
740
and
Rhenium-containing alloys) are also shown to reveal the feasibility of its use in determining
phase chemistries of precipitated particles under different measurement conditions. Practical
applications of this combined technology to the material quality control and assessments,
processing parameter improvements, as well as fracture/failure analyses of high temperature
components have shown that this technology is quite convenient and effective when used for
microstructural analysis purposes during R&D, manufacturing and operating processes.
KEYWORDS
Phase chemistry analysis, multiphase separation technology (MPST), precipitates, phase stability,
material quality, creep-rupture life, boiler tube failure
INTRODUCTION
With a growing need of high efficiency and low carbon dioxide emission power generations, the
increasing grades of steels and alloys developed for high temperature components equipped in
the generation sets are meeting the challenges corresponding to the generation capacities from
ultra-supercritical to advanced ultra-supercritical level based on the operating temperature and
pressure. Correspondingly, the high temperature properties of the materials are directly
determined by the microstructures consisting of matrix and precipitates formed after they
experience standard heat treatments and during generation service. Usually, the microstructural
characterization of the high grades of materials includes not only the morphology, size, volume
fraction and distribution of the precipitates, but also their chemistries related to the other phase
parameters mentioned. However, the difficulty is that when the phase chemistries of the
precipitated particles are measured under a currently available and widely used instrument, for
example SEM/EPMA - EDS, qualitative/semi-quantitative results are usually received. The
reason for this phenomenon is that when an electron beam hits the surface of the particle
1152
measured, it will produce a characteristic X-ray region in the bulk steel/alloy material sample,
leading to the measurement result being the chemistry of a multi-phase mixture consisting of the
particle and its surrounding matrix. In other words, to accurately separate the multiphase mixture
into the individual phases in chemistry is difficult through the current measurement technology.
But to know the chemistry of the precipitates is very important and helpful in order to
understand the as-received status and the variation in microstructure and property during/after
forming, heat treatment, testing and operating of the steel/alloy materials. The problem can be
satisfactorily resolved through a so called multiphase separation technology (MPST) developed
in the past decade [1-9]. The purpose of this paper is to show some applied examples to reveal the
difference in phase chemistry in as-received samples from different manufacturing sources and
in creep ruptured/failed pipe/tube samples from different testing/operating conditions. The
general content of this work deals with the following: as-received quality related to phase
chemistry, change of Cr concentration of GB Precipitates with creep rupture time, property
breakdown with phase chemistry changes, property recovery with changing phase stability, and
boiler tube failures with phase changes of precipitates.
VERIFICATION EXAMPLES
First of all is to show some examples to see the feasibility and accuracy of SEM/EPMA-EDS +
MPST when it is applied for verifications and then to use this combined technology for the
quantitative determination of phase chemistries of precipitated particles in bulk steel/alloy
samples investigated. Numerous related verifications have been made for their practical uses.
Here, only a few of them are present as typical examples. Some verification examples of the
combined technology for the samples experiencing chemical measurements from one of the
following means are presented, for example, CA (Chemical Analysis, Fig. 1), TEM-EDS
(Transmission Electron Microscopy - Energy Dispersive Spectrum, Fig. 2 and Fig. 3) and
AP-FIM (Atom Probe-Field Ion Microscopy, Fig. 4), and TC (Thermodynamic Calculations, Fig.
5), respectively. All the results shown indicate that this combined technology makes it possible
to accurately quantify the phase chemistries based on the measurements on bulk steel/alloy
material samples under SEM/EPMA - EDS conditions. It should be explained that each of the
verification examples shows the comparison of the results from one of the currently available
means, for example, CA (Fig. 1 - GH163 ~ Nimonic 263), TEM-EDS (Fig. 2 - Inconel 740) and
AP-FIM (Fig. 4 - a Re-containing single crystal superalloy) and TC (Fig. 5 - P92 and HR3C),
with those from firstly using the above measured/calculated result to form a two phase mixture
by lever rule and then using the MPST to chemically separate the mixture into the individual
phases. In addition, results shown in Fig. 3 (TP347HFG) are from both TEM-EDS and
EPMA-EDS + MPST, respectively, which used the same samples under the same test conditions.
It is indicated that quite good agreement has been achieved according to the verification results.
1153
60
40
50
10
(a)
CA
MPST
30
20
10
0
Ni
Cr
Ti
Co
Al
8
6
4
2
0
Mo
(b)
CA
Alloying element
MPST
Fig. 1 Comparison of the element content (a) and volume fraction (b) of from chemical
analysis (CA) [10] with that from firstly using the CA result to form a two phase mixture (/) and
then using the MPST to chemically separate the mixture into the individual phases (, ) on a
GH163 ( ~ Nimonic 263) sample
60
50
80
50
40
30
30
20
20
10
10
Ni
Ti
Al
Co
Nb
Co
Ti
Ni
(b)
TEM-EDS
MPST
60
40
10
70
(a)
TEM-EDS
MPST
70
Volume fraction, %
80
6
4
2
0
Alloying element
'
Phase
Fig. 2 Comparison of the element content (a) and volume fraction (b) of and from TEM-EDS
[11]
with that from firstly using the EDS result to form a two phase mixture (/, /) and then
using the MPST to chemically separate the mixture into the individual phases (, , ) on an
Inconel 740 sample
EPMA-EDS+MPST
TEM-EDS
100
(a)
100
80
60
40
20
0
150 / 2426(S1)
(b)
60
40
20
0
150 / 8837(S2)
EPMA-EDS+MPST
TEM-EDS
80
150 / 2426(S1)
150 / 8837(S2)
Fig.3 Comparison between the results from TEM-EDS and from EPMA-EDS + MPST for Cr
(at.%) in M23C6 (a) and Nb (at.%) in MX (b) of two 650-creep-ruptured TP347HFG samples [2]
(S1: 150MPa/2426h, S2: 150MPa/8837h), respectively
1154
80
(a)
AP-FIM
FIM-AP+MPST
60
20
10
Ni
Al
Co Nb Ta W
(b)
70
70
60
50
40
30
20
10
0
Cr Mo Re Hf
AP-FIM
Alloying element
MPST
Fig. 4 Comparison of the element content (a) and volume fraction (b) of from AP-FIM with
that from firstly using its result to form a two phase mixture (/) and then using the MPST to
chemically separate the mixture into the individual phases (, ) on a Re-containing Ni-base
2.0
1.6
80
80
1.2
0.8
60
0.4
0.0
40
M23C6
M23C6
Laves
Phase
40
20
20
0
100
Cr
Fe
Mo
Cr
Fe
TC
MPST
60
600 (b)
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
80
60
M23C6
M23C6
40
Phase
40
20
20
100
60
100
2.4
80
600 (a)
2.8
Volume fraction, %
TC
MPST
100
Volume fraction, %
Cr
Fe
Alloying element
Fe
Cr
Nb
Alloying element
Fig. 5 Comparison of the element content and volume fraction of M23C6 and Laves phase for P92
(a) and of M23C6 and Z phase for HR3C (b) from thermodynamic calculation (TC) with that from
firstly using the TC result to form a two phase mixture (M23C6 / Laves phase + matrix for P92,
M23C6 / Z phase + matrix for HR3C) and then using the MPST to separate the mixture into the
individual phases (M23C6, ,Laves phase, matrix for P92 and M23C6, Z phase, matrix for HR3C)
APPLIED EXAMPLES TO SOME PRACTICAL PURPOSES
As-received quality related to phase chemistry
The following example gives the evidence that the microstructural quality of as-received P92
pipes can be examined through the application of EPMA/SEM EDS + MPST [5]. Fig. 6 shows
the chemical compositions of heat treated P92 pipe samples from different manufacturing
sources, which were determined by EPMA-EDS measurements. Figs. 7(a) through 7(e) are
photographs of their corresponding microstructures. It should be noted that the W content in pipe
sample D was remarkably higher than that in the samples from other pipe manufacturers. In
addition, sample D did not experience a complete tempering after normalizing treatment, which
might be the cause that Cr content in M23C6 of this pipe sample was much lower than the other
1155
samples, as shown in Fig. 8. It is known from a dynamic point of view that Cr content in M23C6
particles in P92 after a complete heat treatment would affect its growth rate in the later
testing/generation service. The other example is that the formation and coarsening of Laves
phase particles could be promoted along the boundaries between the delta-ferrite and its
surrounding martensite matrix in P92 if the steel sample contains a certain amount of
delta-ferrite even though it did not experience tempering at a temperature much higher than its
precipitation start temperature [1], as shown in Fig. 9. A related quantitative result is also given in
Fig. 10.
10
A
B
C
D
Weight percent, %
8
6
4
2
0
Cr
Mo
Mn
Ni
Si
Nb
Alloying element
Fig. 7 Backscattered electron images of as-received P92 samples from different manufacturers
1156
10
Cr
Mo
W 8
50
40
30
4
20
10
0
60
Pipe sample
Fig. 8 Concentration of Cr, Mo and W in M23C6 of as-received P92 samples from different
manufacturers
Fig. 9 Backscattered electron images of P92 samples subject to ageing at 700 (a) and 750
1.2
(a)
Cr 700
Cr 750
Mo 700
Mo 750
W 700
W 750
0.20
0.16
0.12
0.8
0.08
0.4
0.0
0.04
1000
3000
Ageing time, h
5000
0.00
1.6
(b)
Mo 700
Mo 750
Cr 700
Cr 750
W 700
W 750
0.10
0.05
0.00
1000
3000
Ageing time, h
5000
Fig. 10 Partitioning of Cr, Mo and W to M23C6 (a) and Laves (b) in the P92 samples aged for
1,000, 3,000 and 5,000h, respectively
Another example is for the as-received quality of an austenitic steel. Phase chemistry
distributions of precipitates in as-received Super304H samples from two manufacturing sources
designated as S and W
[5]
sample W is much higher than that in sample S, and also the Nb (Cr) content of the secondary
MX particles in sample W is obviously lower (higher) than that in sample S. As a result, an
excessive amount of un-dissolved primary MX particles with coarser sizes actually acted as
possible sources of cracking and the secondary MX particles with a lower Nb content
corresponding to a lower phase stability did not benefit high temperature properties. All the
above can be revealed by the present EPMA/SEM EDS + MPST technology.
Change of Cr concentration of GB precipitates with creep rupture time
The distributions of Cr content in grain boundary precipitates of two groups of creep-ruptured
Super304H samples designated with S and W, respectively, are typically characterized by some
of the stress levels corresponding to different rupture lives after creep-rupture tests at 700
[3]
as shown in Fig. 11 (a). It is seen from this figure that the Cr content of grain boundary
precipitates determined by the EPMA/SEM EDS + MPST increased with decreasing stress
level and increasing creep-rupture time for the bulk steel samples. Fig. 11 (b) reflects the change
of external stress level and Cr content distribution parameter Ka with creep-rupture time,
respectively, where Ka is the value of enclosed area of the curve with the fs (apparent fraction)
axis in the coordinate system of Cr content (at. %) vs. fs. It is clear from the figure that the
externally applied stress level decreased and the value of Ka increased with increasing
creep-rupture time, respectively. This phenomenon indicates that the lower the stress level
applied, the longer the rupture time experienced, and accordingly the higher the Cr concentration
in the grain boundary precipitates acquired in the ruptured samples. On the other hand, a
relatively higher stress level corresponded to a relatively smaller change of Cr concentration in
the grain boundary precipitates for group S samples after the two groups of samples experienced
an equivalent length of testing time. It is explained that the variation of Cr concentration in the
grain boundary precipitates is directly related to the phase stability of ruptured Super304H tube
samples.
80
70
200
Stress, MPa
90
500
400
300
(a)
S-180MPa/523h
W-160MPa/732h
S-130MPa/4109h
W-130MPa/4823h
S-120MPa/8688h
W-110MPa/12139h
100
60
50
40
30
20
10
0.0
0.2
0.4
0.6
0.8
fs
104
100
90
80
70
60
50
40
30
20 1
10
1.0
(b) 10
103
Ka
110
abd
102
102
103
104
101
105
Rupture time, h
Fig. 11 (a) Cr content distribution in grain boundary precipitates in the 700 creep ruptured
Super304H samples, which was determined by EPMA-EDS measurements and by MPST after
the measurements, respectively (S / W), (b) Stress / Cr content distribution parameter (Ka) for
GB precipitates vs. creep rupture life
1158
[4]
shown in the stress vs. rupture time plot, the whole set of stresses used in the investigation could
be divided into two sets, i.e. higher-stress shorter-rupture time and lower-stress longer-rupture
time regions, respectively. The latter region corresponded to an evident increase of Mo and Cr
(W for Laves) partitioning to coarser and clustered Laves and M23C6 particles, leading to a
corresponding decrease of that to martensite matrix. This elemental migration behavior
promoted the coarsening of grain boundary precipitates, and meanwhile caused the degradation
of martensite matrix.
Property recovery with changing phase stability
The pipe material used in this investigation is P92. Its W content (wt. %) just reached the
corresponding lower limit from ASME standard, and creep rupture life and ultimate tensile
strength at 650 did not reach the lower limit of the related standard. The purpose of the related
work was to find the cause and to see if this condition could be improved through changing the
phase stability of precipitates. The entire improvement procedure was guided by a relevant heat
treatment making a change of the factor, step by step, established to access the phase stability of
precipitates in the tested samples shown in Fig 12, which was based on the results of
EPMA-EDS + MPST. Eventually, the ultimate tensile strength at 650 reached a value 2.5%
higher than the lower limit required by the related standard.
Fig. 12 Ultimate tensile strength at 650 vs. phase stability factor before and after reheat
treatments for P92
1159
Fig. 13 Backscattered electron images of un-failed (a) and failed (b) Super304H tube samples
after generation service at 598.7 and 24.08MPa for 12,000h
90
100
EPMA-EDS
EPMA-EDS+MPST
80
100
M23C6
70
60
50
40
30
20
0.0
Measured
0.2
0.4
0.6
(a)
0.8
1.0
fs
90
EPMA-EDS
EPMA-EDS+MPST
M23C6
80
70
60
50
40
Measured
Measured
(b)
30
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
fs
Fig. 14 Cr content distribution in grain boundary precipitates of un-failed (a) and failed (b)
Super304H tube samples after generation service at 598.7 and 24.08MPa for 12,000h
1160
Volume fraction, %
2.5
(a)
M23C6
phase
3.0
2.0
1.5
1.0
0.5
0.0
un-failed
failed
1.0
0.8
(b)
M23C6
phase
0.6
0.4
0.2
0.0
un-failed
failed
Sample
Sample
Fig. 15 Volume fraction and normalized size fraction of precipitates of un-failed and failed
Super304H samples after generation service at 598.7 and 24.08MPa for 12,000h
Using the same assessment mean as the previous case to examine the phase stability of
precipitates
in
the
failed
T91
tubes
(540/17.2MPa/3.8104h
for
tube
and
540/17.2MPa/3.510 h for tube B), the phase parameters (the Cr concentration, the volume
fraction and the normalized size fraction of M23C6) of both failed and un-failed tube samples
differ from each other, remarkably, which indicates that the existing difference in phase stability
between them might be the cause of the material degradation. Equivalent temperatures
corresponding to tubes A and B with respect to the boiler service conditions are estimated based
on the results from the EPMA-EDS + MPST and a thermodynamic calculation, which shows
that some 750 was reached for both failed and failed positions of tube A and for failed
positions of tube B (relevant figures are omitted due to the page limit). Therefore, overheat
generation service are considered as the possible cause for the failure of the T91 tubes.
CONCLUSION
Examples for the applications of the EPMA-EDS + MPST technology to practical uses of some
advanced heat resistant steels and Ni-based superalloys are given in this investigation:
to compare the main differences in quality of as-received materials from different sources,
to compare the phase stability of pipe/tube materials on as-received, tested and operated
statuses,
to make evaluations for the rationalities of alloying additions and processing parameters,
and also for the degree of microstructural evolution after testing/ generation service based
on the chemical composition, volume fraction and normalized size fraction of precipitated
phases, and
All the above have successfully been demonstrated in correctness and efficiency.
1161
REFERENCE
[1] Z.F. Peng, L.S. Cai, F.F. Peng et al, Effect of Delta-ferrite on The Composition and Volume
Fraction of Precipitates in P92 Steel Aged at 700 and 750, Acta Metallurgica Sinica
(Chinese version), Vol. 48, No. 11 (2012), pp. 1315-1320.
[2] Z.F. Peng, Y.Y. Dang, F.F. Peng, Effect of Carbon and Niobium Contents on Phase
Parameters and Creep Rupture Time at 650 for TP347HFG Steel, Acta Metallurgica
Sinica (Chinese version), Vol. 48, No. 4 (2012), pp. 450-454.
[3] Z.F. Peng, L.S. Cai, Y.Y. Dang et al, A Brief Introduction to Alloy Phase Chemistry
Determination under EPMA/SEM-EDS Conditions and its Applications, Materials Science
Forum, Vol. 706-709 (2012), pp, 2450-2455.
[4] Z.F. Peng, L.S. Cai, F.F. Peng et al, Effects of Variation of Phase Chemistry on Multi-region
Stress Rupture Properties at 625 for P92 Steel, Proceedings of the 6th International
Conference on Advances in Materials Technology for Fossil Power Plants, Santa Fe, USA,
September. 2010, pp. 667-678.
[5] F.F. Peng, Z.F. Peng, F.Y. Chen, Evaluating USC Boiler Steel Quality Based on Alloy
Stability, Electric Power Construction, Vol. 31, No. 1 (2010), pp. 11-14.
[6] Y.G. Zhou, Z.F. Peng, Effect of (Ti+Al)/Nb Value in , and Phase Mixture on Volume
Fraction of Phases in IN718 Alloy, Materials and Heat Treatments, Vol. 38, No. 18 (2009),
pp. 5-8.
[7] Y.G. Zhou, Z.F. Peng, F.Y. Chen et al, Microstructure and Typical Elements Distribution of
IN718 Alloy after Aging Treatment, Heat Treatment of Metals, Vol. 34, No. 6 (2009), pp.
19-24.
[8] Z.F. Peng, Z.G. Yang, G.Z. Yan et al, A New Method for Accurate Quantifications of Alloy
Phases in Superalloys under EPMA/SEM-EDS Conditions, Proceedings of the 11th
National Annual Symposium on Superalloys, Shanghai, China, May. 2007, pp. 666-669.
[9] G.Z. Yan, Z.F. Peng, An Optimization algorithm and its application for predicting elementsl
concentrations of sublattices of phase in Ni base superalloys, Acta Metallurgica Sinica
(Chinese version), Vol. 41, No. 3 (2005), pp. 251-254.
[10] Y. Liu, Z.F. Peng, Y.Y. Ren et al, An Approach to Phase Amount Calculation, Acta
Metallurgica Sinica (Chinese version), Vol. 38, No. 2 (2002), pp. 131-134.
[11] N.D. Evans P.J. Maziasz, R.W. Swindeman et al, Microstructure and phase stability in
INCONEL alloy 740 during creep, Scripta Materialia, Vol. 51 (2004), pp. 503507.
1162
ABSTRACT
25Cr-20Ni-Nb-N (Tp310HCbN) steel is a promising austenitic steel for applications in
superheater tubes in coal fired thermal power plants due to the high creep strength and oxidation
resistance. In this work, the microstructural evolution of this material during heat treatment and
thermal ageing has been investigated. The investigations were carried out by Light Optical
Microscopy (LOM), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy
(TEM) and Energy Dispersive Spectroscopy (EDS). Besides, equilibrium and Scheil calculations
were carried out using the thermodynamic software MatCalc to analyse the stable phases and the
solidification process, respectively. Precipitation calculations during solution annealing and
subsequent ageing at 650 and 750C were performed to predict the phase fraction and precipitates
radius up to 10.000h ageing time.
SEM and TEM investigations of aged specimens revealed the presence of six different
precipitates: M23C6, Cr2N, sigma, Z-phase, eta-phase (Cr3Ni2Si(C,N)) and Nb(C,N). These
precipitates were predicted and confirmed by MatCalc simulations. The calculated phase fraction
and mean radius show good agreement with experimental data. Finally, simulations of different
Cr-, C- and N-content in Tp310HCbN were performed.
1. INTRODUCTION
The increasing demand of electrical energy in Europe and the world can be met by a number of
strategies; one of them is the increase of the efficiency of coal fired thermal power plants.
Currently, the worlds mean efficiency of coal-fired power plants is approximately 30%, in
Germany an efficiency of 38% is reached. This higher level is achieved by steam temperatures of
600C and steam pressures of 285bar. An increase of the steam state to 700C/350bar will
increase the efficiency up to 50% and correspondingly lead to a drop in Co2 emissions that is of
utmost importance to reduce global warming [1]. Such conditions require materials with
enhanced creep strength and corrosion resistance such as austenitic steels.
This work focuses on the material 25Cr-20Ni-Nb-N commonly known as Tp310HCbN which is
used for superheater tubes in fossil fired, black liquor recovery and refuse fired boilers [2]. This
steel is an advancement of the 25Cr-20Ni (AISI310) with additional amount of Nb and N to
promote the formation of fine NbCrN (Z-phase) which leads to a higher creep strength. The high
Cr-content gives an excellent oxidation resistance. The main precipitates observed in previous
investigations by SEM, TEM, EDS and diffraction pattern in Tp310HCbN at 650C for 500h and
1163
3000h are Cr-rich M23C6 and NbCrN (Z-phase). The M23C6 was found in grain interior but mainly
at grain boundaries [3]. SEM, TEM, EDS and XRD observations of long term aged Tp310HCbN
at 650C for 5400h and 25000h show M23C6 and Cr-, Ni-, Si-rich M6C precipitates at grain
boundaries and NbCrN inside grains [5]. Investigations of Tp310HCbN at 750C/500h reveal
M23C6, NbCrN, sigma and Nb(C,N) precipitates. NbCrN and Nb(C,N) are found to nucleate
intragranularly whereas M23C6 nucleate intragranularly as well as at grain boundaries. It is found
that some of the M23C6 precipitates at grain boundaries are transformed into sigma phase [4].
TEM observations of aged specimens in the temperature range of 600-750C for 3000h reveal
fine NbCrN and no sigma phase [2]. Limited information about the microstructure of the
Tp310HCbN steel at high temperature (750C) is available and no precipitates calculation of
solution annealing and ageing has been performed before. The purpose of this work is to present
an investigation (SEM, TEM, EDS) of long term aged samples (up to 3000h at 650C and 750C)
and to supplement these experimental investigations with solidification and precipitation
calculations carried out with the thermo-kinetic software MatCalc [6].
2. EXPERIMENTAL
The austenitic steel was prepared by melting, casting and hot rolling. The dimensions of the
samples were 10x10x2mm and the chemical composition is presented in Table 1.
Table 1: Chemical composition (wt%) of Tp310HCbN
Cr
24.7
Ni
20.6
C
0.062
Fe
51.9
Si
0.38
P
0.017
Nb
0.44
Mn
1.2
S
<0.001
O
0.016
N
0.182
The samples were solution annealed at 1200C for 12min. Afterwards, the samples were aged at
650C and 750C for 1000 and 3000h. For the microstructure characterization, LOM, SEM and
TEM were used. The chemical compositions of the precipitates were determined by EDS. The
scattering for the determination of heavy elements (like Cr, Nb, Ni) is approximately 2-5%. All
LOM and SEM samples were prepared by mechanical grinding, polishing and electrolytic
etching. For the electrolytic etching, a 10% solution of oxalic acid in distilled water at 3 volts for
10 to 60s was used. For evaluating the distribution of precipitates size with SEM, the samples
were prepared by mechanical grinding and polishing only, and no etching. Plate samples for TEM
carbon replicas were etched with a solution of 40% HCl and 20% HNO3 in distilled water at 60C
for 10s.
Thermodynamic calculations have been carried out with the thermo-kinetic software MatCalc
(version 5.52) including the iron database (version 2.00 prebeta 012).
3. RESULTS
3.1. SAMPLES AGED AT 650C
Samples aged at 650C for 1000h and 3000h reveal seven different precipitates: Z-phase, M23C6,
Cr2N, Nb(C,N), eta (Cr3Ni2Si(C,N)), Al- and Si-oxide. Sigma-phase was not found in samples
aged up to 3000h at 650C. Al-oxide (1) and Z-phase (2) are presented in Fig. 1(A). Z-phase is
found at grain boundaries and within grains as well. Its average diameter is 2.40m and 3.02m
in 1000h and 3000h aged samples, respectively. Figure 1(B) presents one of the TEM images
with sample condition of 650C/3000h. Precipitates 1, 3 are Si-oxide with a mean diameter of
65nm. The precipitates 2 and 4 are identified as Nb(C,N) and with a mean diameter of 212nm.
1164
Figure 1: SEM image of 650C/1000h (A) and TEM image of 650C/3000h (B) aged
Tp310HCbN sample. A-1: Al-oxide; A-2: Z-phase; Spectrum 1, 3: Si-oxide; Spectrum: 2, 4:
Nb(C,N)
3.2. SAMPLES AGED AT 750C
Samples aged at 750C for 1000h and 3000h reveal eight different precipitates: Z-phase, M23C6,
Cr2N, Nb(C,N), eta (Cr3Ni2Si(C,N)), sigma, Al- and Si-oxide. Sigma (1) and Z-phase (2) are
presented in Fig. 2(A). Sigma is found at grain boundaries (especially at triple points of grains)
and its mean diameter is 1.73m. Z-phase is found at grain boundaries and inside the grains. Its
mean diameter is 2.52m. It should be mentioned that Z-phase has an irregular shape, which
appears in form of clusters. A TEM micrograph of the specimen aged for 1000h at 750C taken
from a carbon extraction replica is shown in Fig. 2(B). The large precipitates in Fig. 2(B-1) are
Nb(C, N) with a mean diameter of 145nm.
Figure 2: SEM image of 750C/1000h (A) and TEM image of 750C/1000h (B) aged
Tp310HCbN sample. A-1: Sigma; A-2: Z-phase; B-1: Nb(C,N)
The compositions of different phases in the Tp310HCbN samples aged at 650 and 750C
measured by TEM are listed in Table 2.
1165
Table 2: Composition (wt%) of different phases in Tp310HCbN samples aged at 650 and 750C
Ageing
Temp /C
650
Ageing
Time /h
1000
3000
1000
750
3000
Phase
M23C6
Eta
M23C6
Nb(C,N)
Cr2N
M23C6
Nb(C,N)
Cr2N
Z
M23C6
Nb(C,N)
Cr
min
46.0
46.2
71.3
18.7
54.2
38.1
24.6
67.6
5.6
55.8
0.5
Nb
max
50.5
47.7
88.8
40.6
73.0
93.7
49.1
77.1
7.1
79.8
28.2
min
0
0.7
0
17.9
6.7
0
10.6
0
53.8
0
19.2
Ni
max
3.6
2.8
5.8
58.3
26.2
30.9
61.0
21.6
66.0
29.9
95.8
min
1.2
35.8
0.7
0.1
2.0
0
0
0.7
16.9
0
0
max
13.8
47.3
7.0
0.9
15.1
5.2
1.4
3.4
30.4
2.7
1.4
1166
1167
Figure 4: Evolution of phase fraction and mean radius of precipitates during ageing at 650C
3.3.4. PRECIPITATION CALCULATION AT 750C
The precipitation calculation at 750C predicts five different precipitate types: M23C6, sigma,
Nb(C,N), Z-phase and Cr3Ni2Si(C,N). The phase fractions and mean radii of these precipitates are
shown in Fig. 5. The phase fractions and mean radii of precipitates aged at 750C are similar to
the ageing at 650C. The phase fraction of M23C6 at grain boundaries and interior is 0.001 and
0.01, respectively. The mean radius of M23C6.gb (at grain boundaries) is about 400nm and
M23C6.ig (inside grains) about 100nm after 10000h. Sigma phase shows a rapid increase of phase
fraction and radius which are 0.03 and 2500nm after 10000h, respectively. Cr3Ni2Si(C,N) phase
fraction and mean radius increase with increasing ageing time and show good agreement with
experimental data. Nb(C,N) and Z-phase show similar phase fractions after 10000h which are
about 0.001.
1168
Figure 5: Evolution of phase fraction and mean radius of precipitates during ageing at 750C
3.3. MICROSTRUCTURE OPTIMIZATION OF 25CR-20NI-NB-N (TP310HCBN)
One of the main results of the experimental investigations and precipitates calculation are that
sigma phase is a dominant phase at the grain boundaries. It grows fast with increasing ageing
temperature and time. Sigma phase is a well-known intermetallic phase, which has a detrimental
effect on creep properties when it precipitates at grain boundaries and little effect when it
precipitates inside grain [11]. Since sigma phase nucleates mostly at grain boundaries in
Tp310HCbN, the goal of the optimization was to reduce the phase fraction of this phase. Table 3
and 4 present the influence of different C-, N-, Cr-contents in Tp310HCbN on the phase fraction
and mean radius of precipitates. The total phase fraction (without sigma phase) and total mean
radius of each composition is presented in the last column of the Table 3 and 4, respectively. The
increase/decrease of the phase fraction and mean radius related to the initial Tp310HCbN is
presented in percent. It was predicted that a lower Cr-content of 22% will reduce the sigma phase
fraction up to 100%, whereas a higher Cr-content of 26% will increase the sigma fraction up to
786%. To avoid sigma phase a C-content larger than 0.08% and N-content larger than 0.25% is
necessary. The highest increase of total phase fraction of 68% is achieved by low Cr-content and
high N-content. Additionally, low Cr- and N-contents lead to a much smaller precipitates means
radius up to -44%, see Table 4.
1169
M23C6.gb
0.00075
0.00180
139%
0.00024
-68%
0.00170
131%
0.00026
-65%
0.00090
20%
0.00038
-49%
M23C6.ig
0.011
0.010
-12%
0.012
2%
0.008
-30%
0.016
35%
0.011
-7%
0.012
3%
NB(C,N)
0.0015
0.0022
45%
0.0035
128%
0.0013
-15%
0.0016
8%
0.0015
-3%
0.0014
-5%
Z
0.0013
0.0009
-29%
0.0014
7%
0.0015
17%
0.0010
-20%
0.0016
25%
0.0010
-21%
Cr3Ni2Si(C,N)
0.0016
0.0091
463%
0.0023
39%
0.0027
68%
0.0006
-65%
0.0076
368%
0.013
725%
Sigma
0.018
0
-100%
0.16
786%
0.037
110%
0.0037
-79%
0.14
678%
0.00032
-98%
(no sigma)
0.017
0.024
45%
0.019
14%
0.015
-9%
0.019
14%
0.022
33%
0.028
68%
Table 4: Mean radius (nm) of precipitates in different Tp310HCbN compositions (wt%) at 650C
after 10000h
Tp310HCbN
22%Cr
26%Cr
0.05%C
0.08%C
0.14%N
0.25%N
M23C6.gb
467
406
-13%
391
-16%
487
4%
434
-7%
393
-16%
396
-15%
M23C6.ig
71
66
-7%
80
13%
71
0%
72
1%
84
18%
68
-4%
Nb(C,N)
30
27
-10%
40
33%
29
-3%
26
-13%
31
3%
30
0%
Z
12
11
-8%
12
0%
12
0%
12
0%
13
8%
11
-8%
Cr3Ni2Si(C,N)
699
212
-70%
732
5%
712
2%
653
-7%
766
10%
443
-37%
Sigma
1374
0
-100%
550
-60%
1342
-2%
1351
-2%
854
-38%
1209
-12%
(no sigma)
256
144
-44%
251
-2%
262
3%
239
-6%
257
1%
190
-26%
4. DISCUSSION
The calculated radius of M23C6.gb at grain boundaries at 650/750C ageing temperature is higher
than the experimental measured radius, whereas the calculated radius of M23C6.ig inside the grain
is smaller. However, the investigated radius of M23C6 is a mean value of all M23C6 (no distinction
between grain boundaries and grain interior was made). If this is considered, the prediction of
M23C6 radius is in good agreement with the experimental investigated radius. The mean radii of
Nb(C,N) are predicted smaller than the experimental ones. This can be explained by the
production process of the material, which comprises cooling from the liquid state and afterwards
hot rolling, which is not considered in the calculation. The equilibrium calculation shows that
Nb(C,N) is stable in the temperature range between 1000 and 1400C where hot rolling is
performed. So during the production process Nb(C,N) is able to nucleate and grow. The
subsequent solution annealing was not able to dissolve these Nb(C,N) and they remain stable in
the matrix.
It was shown that the sigma phase fraction is strongly dependent on the C-, N- and Cr-contents in
Tp310HCbN. Increasing C-, N-content and decreasing Cr-content leads to a lower sigma phase
fraction. A higher C- and N-content binds more solid solution elements such as Cr, which leads to
1170
more Cr-nitrides and -carbides. An example for this case is Tp310HCbN with an increased Ccontent of 0.08% where the higher C-content gives a higher M23C6.ig phase fraction inside grain
and a lower sigma phase fraction as can be seen in Table 3. Furthermore, Table 3 shows that a
Cr-content of 22% would decrease the sigma phase fraction by up to 100%, but it has to be
mentioned that Cr is essential for the corrosion resistance and a lower Cr-content results in lower
corrosion resistance. It has to be noticed that a higher C-content of 0.08% decreases the phase
fraction of large M23C6.gb (r~470nm) and Cr3Ni2Si(C,N) (r~700nm) precipitates. These are the
type of particles that are expected to have a negative influence on the creep ductility and are
known to be harmful for the room temperature ductility. Similar applies for a higher N-content
but with lower effect.
So the most promising chemical compositions for optimizing Tp310HCbN and reducing the
sigma phase fraction are achieved by higher amounts of C (0.08%) and N (0.25%).
CONCLUSIONS
Microstructure investigation and thermodynamic calculations of austenitic steel 25Cr-20Nr-Nb-N
(Tp310HCbN) were carried out for thermally aged samples. For the investigations SEM, TEM
and LOM techniques were performed. The experimental investigations are summarized as
follows.
Eight different precipitates were found: M23C6, Cr2N, sigma, Z-phase, eta-phase
(Cr3Ni2Si(C,N)), Nb(C,N), Al- and Si-oxide.
The observed particle sizes of sigma, M23C6, Z and eta (Cr3Ni2Si(C,N)) increased with
temperature and ageing time. Sigma mainly forms at grain boundaries. M23C6 was
initially observed at grain boundaries, but after longer ageing times also at twin
boundaries and slip bands. Z-phases were observed at grain boundaries, twin boundaries
and within the matrix.
Thermo-kinetic calculations were performed using the software MatCalc. Equilibrium, Scheil as
well as precipitates calculation at 650C and 750C were carried out. The calculation results are
summarized as follows:
All experimentally investigated phases were predicted by the equilibrium calculation.
Scheil calculations give primary Z-phase during the solidification process, which is in
good agreement with the experimental investigation where large (~2m) Z-phase was
found in all investigated samples.
The primary Z-phase has to be considered separately in the kinetic calculation by
introducing an effective system where primary Z-phase is subtracted from the initial
composition. When including this effect, the calculations show a good agreement with
the experimental results.
The optimization of chemical composition of Tp310HCbN was performed by varying
the C-, N- and Cr-content. It was found out that a higher C-, N- and lower Cr-content
reduces the sigma phase fraction.
With this calculation, a basis was created for the precipitation strength calculation in order to
optimize the Tp310HCbN by additionally modifying the chemical composition and heat
treatment.
ACKNOWLEDGMENTS
This investigation was sponsored by the European Union (directorate-general for energy), within
the project MACPLUS (ENER/FP7EN/249809/MACPLUS) in the framework of the Clean Coal
Technologies.
1171
REFERENCES
[1] Aschenbrenner, N., Kohlekraftwerk strebt 50 Prozent Wirkungsgrad an, June. 2008,
http://www.innovations-report.de
[2] Yagi, K., Merckling, G., Kern, T.-U., Irie, H., Warlimont, H., 25Cr-20Ni-Nb-N steel,
SpringerMaterials - The Landolt-Brnstein Database, Vol. 2B
[3] Chengyu, C., Hongyao, Y. and Xishan X., Advanced Austenitic Heat-Resistant Steels for
Ultra-Super-Critical (USC) Fossil Power Plants, InTech (2011), pp. 192-197
[4] Fang, Y., Zhao, J., Li, X., Precipitates in HR3C steel aged at high temperature, Acta
Metallurgica Sinica, Vol. 46, No. 7 (2010), pp. 844-849
[5] Yin, Z., Cai, H., Liu H., Performance on New Heat-resistant Steel HR3C in the Ultrasupercritical Units After Service at High Temperature for 25 000 Hours, Proceedings of the
CSEE, Vol. 31, No. 29 (2011), pp. 103-109
[6] Svoboda, J., Fischer, F.D., Fratzl, P., Kozeschnik, E., "Modelling of kinetics in multicomponent multi-phase systems with spherical precipitates: I: Theory," Mater. Sci. Eng. A,
Vol. 385 (2004), pp. 166-174
[7] Kozeschnik, E., Rindler, W., Buchmayr, B., "Scheil-Gulliver simulation with partial
redistribution of fast diffusers and simultaneous solid-solid phase transformations," Int. J.
Mater. Res., Vol. 98, No. 9 (2007), pp. 826-831
[8] Sonderegger, B., Kozeschnik, E., "Generalized nearest neighbour broken-bond analysis of
randomly oriented coherent interfaces in multicomponent fcc and bcc structures,"
Metallurgical and Materials Transactions A, Vol. 40, No. 3 (2009), pp. 499-510.
[9] Sonderegger, B., Kozeschnik, E., "Size dependence of the interfacial energy in the
gerneralized nearest-neighbor broken-bond approach, " Scripta Materialia, Vol. 60 (2009b),
pp. 635-638
[10] Sonderegger, B., Kozeschnik, E., "Interfacial Energy of Diffuse Phase Boundaries in the
Generalized Broken-Bond Approach," Metallurgical and Materials Transactions A, Vol. 41,
No. 12 (2010), pp. 3262-3269
[11] Sourmail, T., "Precipitation in creep resistant austenitic stainless steels," Materials Science
and Technology, Vol. 17 (2001), pp. 1-14
1172
ABSTRACT
The Creep Strength Enhanced Ferritic steel grade 91 is widely used for both retrofit applications
and primary construction on high temperature power plant. Although to date most structural
integrity issues with this material have been associated with welds, as the operating hours of these
plants accumulate, there will be a growing need for remanent creep life assessment of the base
material. Arguably this is already the case for aberrant grade 91 material entering service in an
incorrectly heat treated condition. In these circumstances the strength may fall below the
normally accepted lower bound of the creep strength range and some indication of actual strength
may be required.
One strategy to address potential base material failure is to use small scale sampling of individual
components, followed by small scale creep testing, to investigate the current creep strength
present. The data can be compared with the equivalent data produced for well characterised
material known to be at the lower bound of the creep strength range.
This paper describes a methodology for using the impression creep data obtained to provide both
creep strength ranking and an estimate of absolute creep strength for individual grade 91
components. This will enable appropriate judgements to be made by plant operators on repair/run
decisions. For those components remaining in service, it allows for the weakest items to be given
priority for early re-inspection at future outages. The ultimate goal is to identify base material
creep damage development at as early a stage as possible and well in advance of failure in
service.
INTRODUCTION
The Creep Strength Enhanced Ferritic steel grade 91 is used extensively for both retrofit
applications on aged power plant and the primary construction of new plant. The plant operating
conditions for grade 91 components vary. In the UK for example, the earliest applications, retrofit
headers, have tended to operate at ~580C, pipework and headers on early CCGTs typically at
540C, and pipework and headers on current CCGT plant at 565C.
Although the structural integrity issues which have arisen to date with this material have tended
to be associated with welds, as the operating hours of these plants accumulate, there will be a
growing need to address the base material. Arguably this is already the case for aberrant grade 91
material entering service in an incorrectly heat treated condition, where normal properties cannot
be guaranteed and the creep strength may fall below the normally accepted lower bound.
1173
In these circumstances some indication of actual creep strength may be required for life
assessment purposes. One strategy which has been successfully applied to older low alloy
CrMoV pipework systems, is small scale sampling, followed by small scale impression creep
testing, to investigate the current creep strength present [1][2]. In that case the creep strength of a
given sample is compared with the spread of strength obtained from a range of pipework systems,
effectively placing it within the material scatter band.
In the case of grade 91 systems where, as yet, fewer impression creep data are available, an
alternative strategy is proposed. The data can instead be compared to equivalent data produced
for well characterised grade 91 material of known creep strength. The approach can provide both
creep strength ranking and an estimate of absolute creep strength for individual grade 91
components, enabling appropriate judgements to be made by plant operators on repair/run
decisions. For those components which can be justified for further service, the creep strength
ranking allows for the weakest items to be given priority for early re-inspection at future outages.
Targeting inspection in this way should enable base material creep damage development to be
identified at as early a stage as possible and well in advance of failure in service.
MATERIALS
The three grade 91 materials studied in this exercise are detailed in Table 1. Two were tested in
the as-received condition, representative of normal material encountered in service. The third,
also initially in the as-received condition, was given an artificial heat treatment to deliberately
produce a non martensitic, fully ferritic, condition typical of aberrant material encountered in
service. The microstructure of this material is shown in Fig.1.
Table 1: Materials
Material
Bar 257
Manufacturing History
Section 1m long x 257mm OD solid forged
bar material surplus to a retrofit header
contract.
Normalisation for 5.5 hours at 1040C + air
cool + 12 hours tempering at 760C + air
cool.
Microstructure
Tempered
Martensite
Hardness
204HV
2328-75776
Tempered
Martensite
195HV
RWE Simulated
Ferrite
151HV
1174
These three particular materials were chosen because significant amounts of uniaxial data were
available to compare with the impression creep data, and because they had been shown to display
a range of creep strength, with one (Bar 257) lying at the lower end of the scatter band for the
normal martensitic microstructural condition.
The impression creep test [1][2] does not result in a specimen failure, but instead produces a near
linear strain rate which mirrors that in a conventional test. The conventional uniaxial data
comprised both creep test data, for which the minimum creep strain rates (MCR) were available,
and creep rupture data, for which only the rupture lives were available. In order to be able to
compare both with the impression creep tests the Monkman Grant relationship was used to
convert from strain rate to estimated creep life, as necessary. This was considered justified
because it had been earlier demonstrated that the strain rate in the impression test reflects that in a
conventional uniaxial creep test at the same stress and temperature [3]. This shown in Fig.2 for
Bar 257, where the uniaxial MCR obtained at a range of stresses at 600C by three different test
laboratories are compared to the impression creep strain rates. Both sets of results are compared
with the expected strain rates derived from grade 91 uniaxial rupture data [4] and the Monkman
Grant relationship.
1175
Figure 2. Uniaxial (MCR) and impression creep strain rate data for material Bar 257 compared
to the Monkman Grant derived MCR lines for mean and lower bound grade 91 (Cipolla 2005)
material at 600C.
The data show good agreement between uniaxial and impression creep strain rates and also place
Bar 257 close to the lower bound for grade 91, particularly at stresses >100MPa.
The Monkman Grant relationship used for Fig.2 is that derived by Parker from data produced by
Spigarelli, Kimura and Ellis [5]:
The conventional creep test results available for the three chosen materials are compared with this
equation in Fig.3, where they show reasonable agreement. While it would be possible to improve
the fit by modifying the equation, that would represent the Monkman Grant relationship for these
three specific materials, whereas the equation above is supported by a larger amount of
supporting data and can be regarded as more generally applicable.
1176
Figure 3. Monkman Grant plot for the three tested materials, compared to the Parker line.
It should be borne in mind that the intention is to apply this approach in future to grade 91
materials sampled on site. The corresponding uniaxial data would not generally be available and
a general equation of this type would be needed.
In the present work the same approach has been extended to the other two materials, one (232875776) stronger and one (RWE Simulated) weaker than Bar 257. Fig.5 shows impression creep
results for all three materials compared to the strain rates expected for mean and lower bound
grade 91. The correct relative creep strength is reproduced.
As a further exercise the Monkman Grant relationship can be used to convert each impression
creep result into an estimated rupture life. In Fig.6 the rupture lives derived in this way are shown
with actual creep lives measured for these materials by the conventional uniaxial tests. Again
there is good agreement, with the relative strength ranking being the same for each type of data.
Each life shown in Fig.6 can be represented in relation to mean grade 91 strength by dividing the
stress during the test by the stress required to produce failure at the same life in mean grade 91
material.
Relative Creep Strength = (tf)
/ (tf
Figure 4. Impression creep tests on three grade 91 materials of differing creep strength
compared to the Monkman Grant derived MCR lines for mean and lower bound (Cipolla 2005)
material at 600C.
Figure 5. Creep lives estimated from impression creep tests and the Monkman Grant relationship
for the three materials shown in Fig.5 compared to actual uniaxial lives obtained at 600C.
1178
2328-75776 Uniaxial
2328-75776 Impression
2328-75776 All tests
0.9339 + 0.0609
0.9136 + 0.0615
0.9201 + 0.0515
0.603 + 0.0203
0.6112 + 0.0386
0.6064 + 0.028
Fig.6. Creep strength at 600C in terms of stress / stress for the same life in mean grade 91.
1= RWE Simulated, 2 = Bar 257, 3 = 2328-75776.
This confirms that, on average, Bar 257 is close to mean-20% (ie lower bound), with 2328-75776
a little lower than mean, and RWE Simulated close to mean-40%. Significantly there is very little
difference between the strength obtained by uniaxial testing and that derived from the impression
creep testing.
1179
DISCUSSION
Although small scale sampling and impression creep testing has been successfully applied to
CrMoV steam pipework systems in the UK, in extending these techniques to grade 91, certain
differences between the two steels need to be considered. In the case of CrMoV, the UK power
stations of concern shared the same operating conditions, and sampling across a number of plants
allowed a database of impression creep results, representative of the population as a whole, to be
built up. In the case of grade 91 the situation is more complicated in that, as mentioned in the
introduction, this material is used at a wide range of operating conditions.
For CrMoV it also proved possible to adopt a single impression creep test condition as the basis
of comparison which gives usable impression creep strain rates over the range of strength present.
The range of grade 91 creep strength encountered however is likely to wider than that for
CrMoV. For example the predicted rupture life for CrMoV at typical steam pipework
operating conditions of 568C and 40MPa is less than 4, whereas the prediction for grade 91 at
typical retrofit header operating conditions of 580C and 76MPa is ~16, and much wider if
allowance is made for aberrant material to be present. This makes the choice of a single test
condition, usable over the entire strength range, less viable.
Against this background the use of the strain rate plot illustrated in Fig.5 is considered the best
approach to adopt. This allows grade 91 tested over a wide range of stress level to be compared.
Impression creep data obtained at relatively high stress on stronger material and at lower stress on
weaker material can be shown together.
In addressing base material failure as an end of life structural integrity issue the plant operator is
confronted with a large number of largely indistinguishable items. In these circumstances random
inspection will be relatively ineffective at detecting creep damage unless the inspection sample
size is large or the damage is widespread. Small scale sampling surveys covering different parts
of a header or sections of a pipework system can allow targeting by identifying the weakest items
present for priority in subsequent inspection programmes. Items showing current, ie at the time of
sampling, creep strength within the scatter band for new material will present the least structural
integrity risk. Items with creep strength below the lower end of the scatter band can be given
greater attention.
The discovery of aberrant material presents possibly the greatest challenge to plant operators with
grade 91 systems. While removing such material from service might be considered an obvious
response, this may not always be immediately practical and structural integrity justification for a
period of further operation, until replacement can be organised, may be required. Small scale
sampling and impression creep testing potentially allows this to be achieved.
1180
CONCLUSIONS
[1] The test programme carried out has demonstrated that impression creep testing of grade 91
can be successfully used to place a given material in the creep strength scatter band and to
rank different materials in order of creep strength.
[2] Estimates of creep rupture life can be derived from the impression creep strain rates using a
Monkman Grant relationship, with the lives being consistent with those obtained directly by
conventional rupture testing.
[3] The estimates of current creep strength obtained from small scale in situ sampling of grade
91 components can be used to prioritise them in terms of inspection as part of a long term
life management strategy.
[4] This approach may be particularly useful in the case of aberrant, incorrectly heat treated
grade 91, where creep strength will be likely to fall below the normal lower bound.
ACKNOWLEDGEMENTS
The impression creep tests for all materials shown in this report were carried out at Nottingham
University for RWE npower. The author would also like to thank RWE npower for their
agreement to include some previously unpublished uniaxial and impression creep data for this
paper.
REFERENCES
[1] S.J.Brett, Small Scale Sampling and Impression Creep Testing of Aged CrMoV Steam
Pipework Systems. 2nd International ECCC Conference: Creep & Fracture in High
Temperature Components Design & Life Assessment, EMPA, Switzerland, April 21 23,
2009.
[2] S.J.Brett, Small Scale Sampling and Impression Creep Testing Applied to Aged CrMoV
Steam Pipework Systems. EPRI International Conference on Advances in Condition and
Remaining Life Assessment for Fossil Power Plants Coal, Gas and HRSG, Hilton Head
Island, South Carolina, October 17- 19, 2012.
[3] S.J.Brett, Application of Impression Creep Testing. Presentation at Practitioners Meeting
held at Nottingham University, UK, March 8, 2011.
[4] L.Cipolla and J. Gabrel, New Creep Rupture Assessment of Grade 91. ETD Conference:
Industry and Research Experience in the Use of P/T91 in HRSGs/Boilers, IOM3, London,
December 7-8, 2005.
[5] J. Parker, EPRI, private communication.
1181
Li Shuxue[2]
1182
1183
1184
situation
[3-5].
Then,
1185
transverse
and
longitudinal
1186
Main
failure
Life prediction method
mechanism
Aging factor correction LM
High
method Proposed by Xi'an
temperature
Thermal Power Research
creep
Institute of China [6].
Fatigue/creep
interaction
Low cycle
fatigue
Abrasion and
corrosion
1187
module allows special users to download, edit, upload and preserve the
word reports. It brings convenient daily work for users.
4 Conclusion
Risk Management and Life Prediction System is developed based
on basic theory of risk assessment and life prediction basic principle and
combined with actual requirement of electric power enterprise and
supervision institution. It can realize risk assessment and management
for boiler important components. According to the results, reasonable
and effective inspection plan and repair strategy was put forward to
achieve lower accident rate and minimum loss and optimal safety
investment benefits. Therefore, maintenance optimization can be
achieved on the basis of pursuit unification of safety and economy of
special equipment.
5 References
[1] Editorial board. Thermal Power Plant Metal Material Handbook[M].
China Electric Power Press, 2000.
[2] YU XiaoHong ZHANG LaiBin, WANG ZhaoHui, etc. Reliability life
analysis of the equipment based on new weibull distribution parameter
estimation method. Journal of Mechanical Strength[J]. 2007,29(6):932
[3] DL/T 302-2011, Equipment maintenance analysis guideline for
power plant [S]. Beijing: China Electric Power Press, 2011
[4] ASME. Risk-Based Inspection Development of Guidelines, Volume3,
Fossil Fuel-Fired Electric Power Generating Station Application [R],
Washington, D.C. 1994
1188
1189
1190
BACKGROUND
Time-dependent inelastic deformation resulting from stresses at elevated
temperatures is known as creep [1,2]. Creep is often the life-limiting design
consideration in high temperature components. Engineering applications also
often involve components that experience cyclic loads during service. The term
creep-fatigue (C-F) refers to conditions that involve cyclic deformation and
damage in conjunction with time-dependent deformation and damage due to
creep.
The practice of conducting laboratory experiments to characterize a materials
creep-fatigue response is common in the scientific community for the past
years. Because of the large number of experimental variables involved during
laboratory C-F testing that can introduce variability in the data, it is beneficial to
code the best practices in a standard test method. To respond to this need, the
ASTM (American Society for Testing and Materials) Task Group on Creepfatigue Crack Formation (E08.05.08) with global support enabled by EPRI
(Electric Power Research Institute) developed a new standard E2714 in 2009
[3]. Specifically, this standard deals with and is limited to the formation of
macroscopic cracks in a specimen that was initially un-cracked, to a size
detectable by a technique stated in the standard.
A voluntary round-robin (RR) program began in 2009 with the primary objective
of conducting C-F tests to characterize the number of cycles required for crack
formation of an elevated temperature material. This RR also included pure
fatigue and creep tests that were expected to be conducted as per existing
ASTM standards E606 [4] and E139 [5], respectively for completeness with
regard to characterizing the test material. With the test results obtained from this
RR, a measure of precision and bias and specifically inter- and intra-laboratory
variability within the results was derived and successfully balloted through the
ASTM process. This paper describes the results of this round-robin. Even
though previous RR studies have been conducted under low-cycle fatigue (LCF)
loading conditions at elevated temperatures [6,7,8], none have been conducted
under conditions with hold time.
TEST MATERIAL
The test material chosen for this RR is the modified 9% chromium (Cr)-1%
molybdenum (Mo) steel that is designated by the ASTM as grade P91 steel
wherein the prefix P denotes piping application. All the P91 specimens used for
the current RR were obtained from a retired pipe donated by EPRI, Charlotte,
USA. The pipe material was re-normalized to ensure consistency with the
original tempered martensitic/ferritic microstructure of these steels. The physical
dimensions of the pipe section were as follows: outer diameter: 482 mm, wall
thickness: 47.5 mm and a length of approximately 1 m. The pipe was cut along
its length to obtain approximately 3 equal sections. The 3 cut segments were
respectively labeled as sections 1, 2 and 3 and only the cut Section 2 was used
for the current RR. All RR participants were given their choice of either receiving
machined specimens or specimen blanks that they would use for machining
specimens. A comprehensive collection of all the specimen drawings and
1191
machining layouts, along with other test matrix details, used for the current RR
is provided in a recent EPRI report and publication [9]. It was stipulated that all
of the test specimen geometries must comply with the guidelines recommended
by the test standard E2714-09. The chemical composition of P91 steel used in
the RR testing in weight% is given in Table 1.
Table 1: Chemical composition of test material (in weight %).
C
Si
Mn
Ni
Cr Mo
As
Nb
Al
Cu
Sb,
Fe
Sn
0.11 0.31 0.45 0.011 0.009 0.19 8.22 0.94 0.005 0.21 0.07 0.006 0.16 0.039 0.001 Bal.
Tensile tests and creep deformation and rupture tests on P91 steel were
0
conducted at 625 C to fully characterize the material. The creep deformation
and rupture tests were conducted as per the recommended guidelines
prescribed by the ASTM standard E139 [5]. The test durations varied from as
low as few days to as high as a few months. The test parameters were finalized
by using a model based on the Larson-Miller parameter (LMP). These results
clearly showed that the creep characteristics of the RR material compare
favorably with data from the literature.
ROUND-ROBIN TEST RESULTS
The RR participants were requested to send their completed test results to the
University of Arkansas (UA) for further data analysis. UA along with EMPA in
Switzerland were responsible for the post-test inspection and optical microscopy
analysis of the tested specimens. All the test results from all the participants are
shown in Fig. 1.
1192
1.5
Average endurance
for 30 min. tests
0.5
0.5% (0 min. hold)
1% (10 min. hold)
0 min. hold Avg. Line
0
100
1% (0 min. hold)
1.5% (10 min. hold)
10 min. hold Avg. Line
1000
N 2% (cycles)
Figure1: Creep-fatigue endurance plot containing all the round-robin test data
0
for P91 steel at 625 C.
The RR participants were requested to determine 2% load drop as the end-oflife criterion for C-F crack formation and record their interpretation of C-F
endurance for each completed test using the method described in the ASTM
standard. The stress-strain response and stress-relaxation response during hold
times were also recorded and reported as part of the participant reports. The
RR participants were randomly coded and each was assigned an arbitrary
identification number from 1 to 15. A total of 32 tests were completed by 10 RR
participants under three strain ranges of 0.5%, 1% and 1.5% without hold time
at 625C while following the test procedure prescribed in the C-F test standard.
In addition, 46 tests were completed with a hold time of 10 and 30 minutes
under strain ranges of 1% and 1.5% by 11 participants.
Plots of maximum and minimum stress (max and min, respectively) vs. cycles
obtained under cyclic testing without hold time consistently showed that P91
steel undergoes significant cyclic softening. The magnitude of peak stress
decreases as loading cycles increase during the initial cycles followed by a
linear softening stage for considerably longer duration before softening
accelerates again, marking the onset of crack formation [3]. The endurance
results presented for discussion in this section are based on 2% percent
deviation in the maximum stress from the extended linear softening phase, as
reported by the RR participants.
All test results for C-F crack formation under the condition of no hold time are
provided in Fig.2. The standard deviations in the mean values are also
presented if there had been more than one test conducted at any given strain
amplitude by any of the RR participants. The number of cycles for C-F crack
formation decreases with increasing strain amplitude. In addition to this obvious
1193
result, several significant observations can be made from the results. (1) At the
lowest strain range, the resistance heating method seems to result in lower lives
as compared to radiation heating but significantly higher compared to the one
test performed with induction heating. At the other strain ranges, no biases in
lives were detected that could be associated with the heating methods. (2)
Specimens from one of the locations in the pipe appear to yield the highest lives
at all the 3 strain ranges. (3) It appears that considerable scatter exists in the
endurance data for a given strain range but on the basis of the information
provided by the participants, there is no basis for eliminating any data from
being considered. Further, the scatter observed was comparable or less than
those reported in the earlier round-robins [6,7,8] (4) As part of analysis, we
developed a method for analytically determining the 2% stress drop point. The
differences between the average trends and the 95% confidence interval from
this method versus those reported by the participants are both shown in the
plot. The difference between the two approaches for estimating lives is
marginal. For more details, refer to reference [9]. The metallography results will
be considered later in the paper.
1.5
0.5
Participant # 1
Participant # 7
Participant # 11
Avg. Line_Stand.
0
100
Participant # 3
Participant # 8
Participant # 14
95% CI_Stand.
Participant # 4
Participant # 9
Avg. Line_Part.
Participant # 6
Participant # 10
95% CI_Part.
1000
10000
N 2% (cycles)
0
Figure 2: Creep-fatigue endurance plot for P91 steel at 625 C containing the
round-robin data from tests conducted at different strain range with no hold
time. The 95% confidence interval is provided considering C-F endurance data
as per both the Participants assessment (CI_Part.) and Analytical method
(CI_Stand.).
Next we focus on the results obtained from cyclic tests conducted with hold time
10 and 30 minutes at the maximum (tensile) peak strain during loading,
Figures 3 and 4. It is expected that under such loading conditions, the C-F
endurance is still dominated by fatigue with creep deformation contributing
somewhat marginally to the accumulated damage. It was observed that P91
1194
steel qualitatively shows similar cyclic softening behavior in the presence of hold
time as in tests without hold time. Also, the C-F lives were on the average
shorter under the hold time conditions. Increasing the hold time for the same
strain range was found to further decrease the C-F life. Although these
observations were not noted in all of the RR tests, the majority of the test results
followed this trend. In the tests conducted by RR participants 4, 6, 9, 10 and 11,
the introduction of hold time led to approximately equal or higher C-F lives
compared to tests with no hold time. This indicates that perhaps the effects of
creep are small on the life of the specimens with the scatter in the data masking
the effects due to hold time under the adopted conditions.
Considerable scatter in the mean C-F endurance for a given strain range arises
by including the test results corresponding to some of the data. These tests
indicate the possibility of being potential outliers and the reasons, if any, will be
discussed later based on post-test metallographic inspection. These results
correspond to tests conducted by participants 4, 9, and 11 who also reported
significantly different C-F endurances for the zero hold time tests. This raises
the possibility of issues with the test set-up and/or practices for participants 4
and 9 that consistently persisted during the RR testing. This deserves further
examination using metallography and post-test analyses.
Besides the problems encountered with data contributed by participants 4 and
9, there were additional issues that are identified among the reported results
that merit further discussion. For 1% strain range tests with 10 minute hold time,
the participants reported excellent repeatability but the reproducibility among the
various participants was not as good. Participant 11 reported considerably
reduced C-F endurance in both their tests. Participant 6 had significant
repeatability scatter in the tests conducted at 1% strain range with either 10 or
30 minutes hold. Participant 4 reported increasing C-F endurances in both their
tests with the introduction of hold time, as compared with LCF tests conducted
in their laboratory. Participant 8 had a standard deviation of ~ 40% as a
percentage of the mean C-F endurance in the 2 tests conducted at 1% strain
range, as compared with that of < 1% for 2 tests conducted at 1.5% strain range
(both with hold time) in the same facility. The results from Participant 8 reported
considerably reduced C-F endurances at 1.5% strain range with 10 minute hold.
Post-test inspection and metallographic results will provide more definitive
insight into these trends.
1195
1.5
0.5
Participant # 1
Participant # 6
Participant # 10
95% CI_Part.
0
100
Participant # 2
Participant # 7
Participant # 11
Avg. Line_Stand.
Participant # 3
Participant # 8
Participant # 15
95% CI_Stand.
Participant # 4
Participant # 9
Avg. Line_Part.
1000
N 2% (cycles)
10000
0
Figure 3: Creep-fatigue endurance plot for P91 steel at 625 C containing the
round-robin data from tests conducted at different strain ranges and 10 minutes
hold time. The 95% confidence interval is provided considering C-F endurance
data as per both the Participants assessment (CI_Part.) and Analytical method
(CI_Stand.).
2
1.5
0.5
Participant # 6
Participant # 15
Participant # 9
95% CI_Part.
Participant # 11
95% CI_Stand.
0
100
10000
1000
N 2% (cycles)
0
Figure 4: Creep-fatigue endurance plot for P91 steel at 625 C containing the
round-robin data from tests conducted at different strain ranges and 30 minutes
hold time. The 95% confidence interval is provided considering C-F endurance
data as per both the Participants assessment (CI_Part.) and Analytical method
(CI_Stand.)
1196
POST-TEST INSPECTION
Before the tested specimens were mechanically sectioned for metallography
and further optical microscopic examination, high resolution digital photographs
of the as-tested specimens were obtained for the records and are reported
elsewhere in detail [9] with only a few select examples here such as in Fig.5.
Visual inspection of these specimens was carried out and prominent
characteristics of the specimen morphology and the presence of any geometric
instability (or bulging) were carefully noted. The main features from these visual
and digital observations are summarized as follows:
1) Pure LCF (no hold time) test specimens show multiple crack initiation
sites characteristic of transgrannular failure and no significant bulging.
2) All C-F (hold time) test specimens showed limited crack branching, but
bulging becomes more pronounced with increasing hold time.
3) Bulging was much more noticeable for tests conducted with induction
heating as compared to tests conducted using resistance furnaces
under the same test condition. This is indicative of localized hot spots
and perhaps non-uniform temperatures in the specimen during
induction and radiation heating.
4) Oxidation and specimen dimensions may also play a vital role in the
formation of bulges; Specimens tested by Participant 11 (that have
comparatively smaller diameters) do not show any indication of bulging
even on 30 minute hold time tests.
5) Specimen location does not seem to play any role on the type and
morphology of C-F crack(s) for any of the tests.
6) In several tests conducted by Participant 6, the fatal cracks originate at
the ceramic bead applied to avoid extensometer slippage. The thermal
expansion mismatch between the metal and the ceramic may have
influenced the test results in these cases.
7) One of the participants (Participant 2) used both induction and
resistance heating systems and reported variations in cycles to failure;
however, no visible differences existed in the external appearance of
the tested specimens.
The test specimens were then mounted onto transparent specimen holders
followed by two rounds of grinding and polishing to reveal the microstructure.
These specimens were then examined primarily using an optical microscope
and scanning electron microscopic analyses followed, if warranted.
Rather than at inclusions and/or other internal microstructural features, cracks
predominantly formed on specimen surfaces and propagated normal to the
loading direction with secondary branching of cracks in specimens tested under
C-F loading with a hold time. The surfaces of almost all the primary cracks that
propagated and opened due to plastic/creep deformation were covered with
thick oxide layers although the thickness of these layers seemed to vary
significantly for specimens tested under similar conditions but by different
participants. These observations resemble those of Fournier et al. [10].
Creep damage, normally associated with grain and lath boundary cavitation, is
not visible in any of the chemically unetched metallographic specimens. Thus,
1197
these specimens were etched using chemical etchants that are known to
preferentially etch these boundaries. Since 1% strain range is the only test
condition under which three different hold times (0, 10 and 30 minutes) were
employed, it is the most suitable for such examination. The specimens were
taken from three different RR participants all using resistance heating method
system. It was clearly seen that creep damage was present in the specimens
tested with 30 minute hold time but not in specimens tested with 0 minute hold
time. There is evidence of some cavitation damage in the 10 minute hold time
tests. These examinations indicate that creep might be actively involved in
enhancing deformation micromechanisms with increasing hold times, but does
not seem to contribute significantly to damage for hold times less than 30
minutes.
Few Specimen
Photographs
Participant # 6
t = 1%
th = 0 seconds
Resistance heating
47.72 mm
Participant # 4
t = 1.5%
th = 600 seconds
Induction heating
44.37 mm
Participant # 15
t = 1%
th = 1800 seconds
Resistance heating
41.36 mm
1198
heating method can contribute to systematic biases in the C-F life, with
resistance heating associated with comparatively lower C-F lifetimes. This may
be more the case for ferritic materials and something to keep in mind during C-F
testing. Also, additional studies to investigate the differences due to heating
methods must be undertaken.
DISCUSSION
To formulate the precision and bias statements needed for supporting the C-F
test standard, statistical analyses of the reported RR data were performed.
These analyses provide a measure of the inter- and intra-laboratory variability
also termed as the reproducibility and the repeatability, respectively. Statistical
analyses performed are as per the guidelines prescribed in the ASTM standard
E691-09 [11].
Repeatability and reproducibility are statistical measures indicative of the intraand inter-laboratory variability, respectively in the test results obtained among
the different laboratories while following the test procedure prescribed in the C-F
test standard E2714-09. Formally, repeatability limit (r) means that two test
results obtained within one laboratory shall be judged not equivalent if they
differ by more than the r value for that material; r is the interval representing
the critical difference between two test results for the same material, obtained
by the same operator using the same equipment in the same laboratory.
Reproducibility limit (R) means two test results shall be judged not equivalent if
they differ by more than the R value for that material; R is the interval
representing the critical difference between two test results for the same
material, obtained by different operators using different equipments in different
laboratories.
The potential sources of uncertainty in the test results are expected from
hardware related issues such as the accuracies of strain and force transducers,
temperature measurement and control, type of heating systems employed and
machine alignment, along with inherent microstructural variability within the
nominally homogeneous test material. Additional factors such as load-cell
calibration and/or bending misalignment might also contribute to further
uncertainty. All these issues are highlighted in the test standard and the
recommended test practices are detailed to minimize these effects. The RR
data from this study provides an ideal opportunity to quantify the uncertainties
that are expected due to these factors. The influence of specimen size on the CF endurance has not been systematically investigated even for sizes that fall
within the recommended test specimen configurations. Hence, a small number
of tests were conducted to investigate if there is any systematic bias of
specimen size on C-F lives of specimens.
(a)
1199
Participant # 15
Resistance heating
Participant # 2
Induction heating
N 2% = 400 cycles
(c)
N 2% > 1039 cycles
1200
results from those shown earlier in Figure 2. It can be readily seen that the
overall scatter reduced considerably.
Table 2: A measure of mean creep-fatigue endurance is defined as the C-F life
corresponding to 2% load drop and the standard deviation in the data. The intraand inter-laboratory variability is also computed and presented as per both
assessment procedures.
Participants Assessment
Analytical Method
Test Condition
Strain Amp.
(hold time)
Mean N 2%
Std. Dev.
(cycles)
Repeatability/
Reproducibility
Std. Dev. (cycles)
Mean N 2%
Std. Dev.
(cycles)
Repeatability/
Reproducibility
Std. Dev. (cycles)
0.25%
5920 474
547 / 612
5938 499
523 / 621
0.5%
911 174
47 / 177
880 180
47 / 183
0.75%
491 68
40 / 74
489 71
37 / 75
0.5%
(10 min. hold)
741 235
51 / 238
753 244
51 / 246
0.75%
(10 min. hold)
457 97
18 / 98
479 102
27 / 103
0.5%
(30 min. hold)
697 203
82 / 211
672 207
44 / 210
To quantify the reduction in scatter before and after excluding few invalid test
results, the variability factor ratio of maximum to minimum C-F life obtained
from the 95% CI bands was calculated for the different test conditions. For
LCF tests, the variability factor reduced from 10, 3 and 2 to 3, 3 and 2 for the
strain ranges of 0.5%, 1% and 1.5%, respectively. For 10 minute hold time
tests, the variability factor reduced from 4 and 3 to 3 and 3 for the strain ranges
of 1% and 1.5%, respectively. The variability factor remained at 5 for the 30
minute hold time tests at 1% strain range, as none of the test results from this
condition could be excluded from the data set.
1201
1.5
0.5
Participant # 1
Participant # 7
Participant # 14
95% CI_Stand.
Participant # 3
Participant # 9
Avg. Line_Part.
100
Participant # 4
Participant # 10
95% CI_Part.
1000
Participant # 6
Participant # 11
Avg. Line_Stand.
10000
N 2% (cycles)
1202
Average
Repeatability
Standard
Deviation, Sr
Reproducibility
Standard
Deviation, SR
Repeatability
Limit, r
Reproducibility
Limit, R
0.25/5/7
3957.5
488.9
1902.8
1368.9
5328
0.50/7/13
869.8
105.8
207
296.3
579.5
0.75/6/11
491.5
82.3
84.0
230.5
235.3
Table4- Statistics from all tests conducted at 0.5% with hold times of 10 and 30
minutes
Hold
Time/No.
of Labs/
No. of
Tests
Average
Repeatability
Standard
Deviation, Sr
Reproducibility
Standard
Deviation, SR
Repeatability
Limit, r
Reproducibility
Limit, R
10/8/19
740.8
143.7
266.3
402.3
745.8
30/4/10
696.3
163.8
247.3
458.5
692.4
Table 5- Statistics from all tests conducted at 0.75% with hold time of 10
minutes
Hold
Time/No.
of Labs/
No. of
Tests
Average
Repeatability
Standard
Deviation, Sr
Reproducibility
Standard
Deviation, SR
Repeatability
Limit, r
Reproducibility
Limit, R
10/7/14
456.7
47.1
102.9
132.0
288.2
1203
ACKNOWLEDGEMENTS
The authors wish to acknowledge the financial support of Electric Power
Research Institute (EPRI) for the material donated for the inter-laboratory study
and for heat-treating and machining of the specimen blanks used in the roundrobin testing. The contribution of the following individuals and their affiliating
organizations is also gratefully acknowledged for resources devoted to testing
as part of the round-robin. Dr. Laura Carroll, Idaho National Laboratory, Idaho
Falls, USA, Dr. Yukio Takahashi, CRIEPI, Japan, Dr. R. Sunder, BiSS,
Bangalore, India, Dr. Alfred Scholz, Technical University of Darmstadt,
Germany, Dr. David Knorr, General Electric, Schenectady, USA, Dr. Richard
1204
Neu, Georgia Tech., USA, Dr. Jonathan Tsang, NRC, Canada, Dr. Mike
Spindler, EDF Energy, UK, Dr. Stefan Bereta/Dr. Mauro Filippini, Politecnico di
Milano, Italy, Dr. Brad Lerch, NASA, USA and Dr. Warick Payten, ANSTO,
Australia.
REFERENCES
1. Evans, R. W. & Wilshire, B., Introduction to Creep (Institute of Materials,
London, England, 1993).
2. Ashby, M., Shercliff, H. & Cebon, D., Materials: Engineering, Science,
Processing and Design (Elsevier, New York, USA, 2007).
3. ASTM E2714-09, Standard Test Method for Creep-Fatigue Testing, Annual
Book of ASTM Standards, Vol. 03.01, ASTM International, West
Conshohocken, PA
4. ASTM E606 - 04e1 Standard Practice for Strain-Controlled Fatigue
Testing, Annual Book of ASTM Standards, Vol. 03.01, ASTM International,
West Conshohocken, PA.
5. ASTM E13906, Standard Test Methods for Conducting Creep, CreepRupture, and Stress-Rupture Tests of Metallic Materials, Annual Book of
ASTM Standards, Vol. 03.01, ASTM International, West Conshohocken,
PA.
6. Scholz, A., Results of a low cycle fatigue inter-laboratory comparison on
1CrMoNiV rotor steel at elevated temperature. Materials at High
Temperatures 27 (2), 117-125 (2010).
7. Thomas, G. B. & Varma, R. K., in Review of BCR/VAMAS Low Cycle
Fatigue Intercomparison Programme, Chapter 8, Harmonization of Testing
Practice for High Temperature Materials, edited by Loveday, M. S. &
Gibbons, T. B. (Elsevier Applied Science, London, UK, 1992), pp. 155-185.
1205
context, remaining life assessment procedures are used only to ascertain that failures will not
occur between such intervals. Periodic checks to ensure the validity of the initial approach are
essential. In this sense, remaining life assessment should be viewed as an on-going task, rather
than a one-time activity.
A phased approach, in which the initial level includes non-incursive techniques followed by other
levels of actual plant monitoring, then followed by nondestructive inspections and destructive
tests would be the most logical and cost effective approach. In Level I, assessments are
performed using plant records, design stresses and temperatures, and minimum values of material
properties from the OEM. Level II involves actual measurements of dimensions, temperatures,
simplified stress calculations and inspections coupled with the use of minimum material
properties from the OEM. Level III involves in-depth inspection, stress levels, plant monitoring,
and generation of actual material data from samples removed from the component (destructive
testing). The degree of the detail and accuracy of the results increases from Level I to Level III,
but at the same time, the cost of the assessment also increases. Depending on the extent of the
information available and the results obtained, the analysis may stop at any level or proceed to the
next level as necessary.
In evaluating the failure criteria or remaining life, one needs to understand the various failure
mechanisms that can occur. In turbomachinery components, the failure criteria can be governed
by one or a combination of the following failure mechanisms:
Erosion Corrosion
Embrittlement /High Temperature
Corrosion
Mechanical (foreign objective) Damage
Creep/stress rupture
In assessing remaining life of components due to creep, such as blade attachments or high
stressed areas in the steam end of a steam turbine, generally crack initiation is used as the criteria.
In design, traditionally one has used a Larson-Miller (LM) plot to assess the stresses and metal
temperature against the creep rupture data.
Generally the OEM will apply a safety margin to these values and generate a lower bound design
curve. Most of the data generated for the grade of material is based upon creep rupture tests done
at 3X104 hours and with few data at 105 hours. Consequently, the data for longer hours is
extrapolated with no effect of notch ductility or environment embrittlement.
For crack initiation as the fracture criteria, history based calculation methods are often used to
estimate life.
Methods For Crack Initiation Due To Creep
For the analytical method, one must have accurate operating history of the components which
may consist of temperature, applied loads, changes in operation, such as shut downs or variation
in speed or pressure. A simplistic estimation of the creep life expended can be made by assessing
the relaxed long-term bore stresses and rim-stresses against the standard rupture data using the
life fraction rule. The life fraction rule (LFR) states that at failure:
ti
=1
(1)
tri
1207
where: ti is the time spent at a given stress and temperature and tri is the rupture life for the same
test conditions.
Metallographic Examination
Metallographic techniques have been developed that can correlate changes in the microstructure
and the onset of incipient creep damage, such as triple point cavitation at the grain boundaries.
For this technique, measurements by replication technique are taken on crack sensitive areas that
are subjected to the higher temperatures and stresses. These areas are generally indicated by
experience and analysis of previous damages.
The creep damage measured by replication is classified into four damage stages:
In applying this approach Neubauer, et al., classified the stages into five stages which are
Undamaged, Stage A, Stage B, Stage C, and Stage D. These stages were corresponded roughly
to expended life fractures (t/tr) values of 0.27, 0.46, 0.65, 0.84 and 1 respectively using the
conservative lower bound curve. Consequently, the remaining life can be calculated using the
relationship as shown in Equation (2):
trem = t
tr
1
t
(2)
Figure 4. Example of Load Displacement Curve from CDR Tests at 1200F and 2 mils/in/hr.
An example of how the environment can affect the notch sensitivity of the material is indicated
by Figure 5. This example illustrates the effect of air exposure on IN738.
1210
Figure 5. Constant Displacement Rate Tests Comparing Crack Growth Resistance in Heat
Treated and Oxygen Embrittled Specimens.
One major objective to this framework has been that effects of very long time exposures that
could influence stress rupture life will not be accounted for. However, Woodford (1993) believes
that such effects, i.e., precipitation of embrittling phases and grain boundary segregation of
harmful elements, are expected to influence the fracture resistance rather than creep resistance.
The authors company has utilized this methodology to generate data for high temperature
materials and weldments. Current methods are being developed for miniature specimens taken
from serviced blades. From these data, it is envisioned that establishment of a set of minimum
performance criteria which will enable repair/rejuvenation/replacement decision to be made.
Creep/Fatigue Analysis
Components that operate at a higher temperature where creep growth can occur, the hold/creep
time intervals between each fatigue cycle must be assessed. This is done by utilizing the latest
computer software and high temperature creep/fatigue data to perform the analysis (Dowson,
1995, 1994).
The following equation is applied when considering Creep-Fatigue Crack Growth:
n
da
q
C
C c [ C t (t)] f ( K ) f
(3)
h
dt
Creep
Fatigue
Where: h is the hold time in each cycle (which is 368 hours in this case).
The creep crack driving force is consisted of two parts, which is based on Sexenas relations
considering the rate of growth of the creep zone in front of the crack (Saxena, 1986) as modified
by Bloom and Malito (Bloom 1992).
2/ [(1 p)(m 1)]
C(t)
[C*]
t
Ch*( )
C*
En 1 t
(n 1)(p 1)
t
Primary Creep
Secondary Creep
1211
(4)
If the material/component is operating in the creep mode, one must perform a creep-fatigue
analysis instead of fatigue only. Generally a rule of thumb is that if only low cycle fatigue crack
growth is counted and creep is not, then the calculated lifetime is about 10 times longer than the
real life. Utilizing computer software, a more accurate remaining life assessment can be achieved
for materials operating in the creep regime under cyclic loading (Figure 6).
Comparation of Low Cycle Fatigue and
Creep-Fatigue Assessments with the Real Life
C ra c k D e p th [in c h ]
0.22
0.2
0.18
0.16
Low Cycle Fatigue
Real Life
Creep-Fatigue
0.14
0.12
0
500
1000
1500
Cycles
2000
2500
Figure 6. Compares Low Cycle Fatigue and Creep-Fatigue Crack Growth to the Real Crack
Growth.
Embrittlement
Trends toward increasing size and operating stresses in components, such as large turbinegenerator rotors, require higher hardenability steels with increased strength and fracture
toughness. However, higher hardenability steels especially those containing nickel and
chromium are usually much more susceptible to a phenomena called temper embrittlement. The
term temper embrittlement refers to a shift in the brittle-to-ductile transition temperature when
steels/rotor shafts are heated or cooled slowly through the temperature range 660F to 1060F.
This shift in the brittle-to-ductile transition temperature can be reversed by heating at a
temperature of 1100F or higher then fast cooled. Consequently, when examining rotor or
casings that have been in service and operated within this temper embrittlement temperature
range, the property toughness becomes an important criteria.
Evaluation of Toughness
Due to the advancement of fracture mechanics, it is now become possible to characterize
toughness in terms of critical flaw size ac. The definition of ac depends on the conditions under
which final rapid fracture occurs following the initial phase of sub-critical crack growth. At rotor
grooves and rotor bores where final fracture is likely to occur at low temperatures during startstop transients, ac is dictated by linear elastic fracture mechanics. ac is given by an expression of
the form
KIC = M ac
(5)
1212
where: KIC is the fracture toughness of the material or critical stress intensity for fracture, M is a
constant to a given flaw size and geometry and is the nominal applied stress.
There have been various nondestructive and relatively destructive tests involving removal of very
small samples to determine toughness of rotors. These techniques investigated include eddycurrent examination, analytical electron microscope, secondary ion mass spectroscopy (SIMS),
compositional correlations, Auger electron spectroscopy, chemical etching, use of single Charpy
specimen and small punch tests. The techniques that show the most promise and have currently
been applied in service application are:
(6)
where: FATT is expressed in F and the correlation of all the elements are expressed in weight
percent. According to this correlation, the elements P, Sn, and As increase temper embrittlement
of steels, while Mo, P and Sn interaction decrease the temper embrittlement susceptibility.
All available 10,000 hour embrittlement data are plotted in Figure 7 as a function of calculated
FATT using Equation (9), (Newhouse, et al. 1972). A good correlation is observed between
calculated and experimental FATT. The scatter for this data is approximately 30F for 750F
exposure and 15F for the 650F exposure.
Figure 7. Correlation between compositional parameter N and the shift in FATT of NiCrMoV
steels following exposure at 650F and 750F for 8800 hours.
1213
Other correlations for determining the temper embrittlement susceptibility of steel, such as the J
Factor proposed by Watanabe and Murakami (1981) and X Factor proposed by Bruscato (1970),
are widely used.
These factors are given by:
J = (Si + Mn) (P+Sn) 104 (7)
Figure 8. Correlation Between Charpy FATT and Small Punch Transition Temperature.
Case study 1
30MW Tenth Stage Disk Rim Restoration
During operation the rotor experienced a hard axial rub ten years ago, which resulted in contact
between the stationary nozzle diaphragm and the tenth stage disk blade rim. At that time the
tenth stage disk rim rub was cleaned up by grinding followed by an NDT which is unknown. The
unit then ran and was down in 2012 for a routine maintenance cycle.
The rotor was cleaned and NDT (wet magnetic particle) was done, which revealed three to four
linear indications on the tenth stage traversing radial from the rim periphery towards the main
body of the shaft. The largest linear indication was about one inch in length. The linear
indication was probably due to the rub incident that occurred ten years ago. The indications were
probably hidden due to the transfer of material from the nozzle diaphragm. No further
indications were found on the rotor.
1214
A decision was made to remove the defective tenth stage rim and replace with a weld buildup
using the automatic submerged arc welding process. Chemical analysis and mechanical testing
was performed on the removed tenth stage disk rim to determine the material property data
(Tables 2 & 3).
%C
0.3
%Mn
0.6
Material
ASTM
A470
Grade B Class 4
Weld Deposit
%P
0.007
Yield
Strength
107,546 psi
81,600
Table 2: Chemistry
%S
%Si
0.007
0.27
%Ni
2.55
Table 3: Mechanicals
Tensile
Elongation
Strength
125,910 psi 18.7 %
111,200
25.2
%Mo
0.54
%Cr
0.62
Reduction of
Area
54.6 %
Hardness
269 HB
66.9
229
Weld tests were performed to determine filler material with optimal matching mechanical
properties for the tenth stage base material. The results indicated that the weld deposit was lower
than the base material for yield and tensile strength after post weld heat treatment (PWHT) (Table
3). Due to the yield strength being lower than the base material, a defect tolerant design concept
was applied.
A detailed linear-elastic 2D finite elemental analysis (FEA) at 4032 rmp was performed on the
disk root (Figure 9).
1215
The authors company acceptance standard for a detectable defect is a surface indication of
0.060 long using MPI. For low cycle fatigue 7000 cycles would be required to propagate the
indication (Figure 10).
Figure 10. Number of Cycles for Crack Propagation for Low Cycle Fatigue
If one utilizes high cycle fatigue where the Kth (threshold stress intensity factor range) for R =
0.8 will be 2ksiin. Using computer software it was found that for a length of 0.07 the crack did
not grow.
Also shown in Fig. 11 is the critical crack size is not exceed for a KIC of 50ksiin.
Figure 11. The Critical Crack Size is not Exceeded for a KIC of 50ksiin
The disk rim was successfully restored and the analysis/testing results showed the welded disk
rim will have an acceptable low cycle fatigue life and long term reliability of the rotor for high
cycle fatigue.
1216
Case Study 2
Background
The authors company was asked by the end user to assist them in the assessment of the
remaining life of a 44 MW H.P. steam turbine casing. The objective of the assessment was to
propose recommendations on the steam turbines casing reuse and long term serviceability. This
is a Westinghouse steam turbine that has operated for 50+ years at inlet conditions 950FTT and
1250 PSIG.
Field Inspection of HP Casing
The entire casing was magnetic particle inspected (MPI), which revealed multiple crack
locations. Nondestructive examination (NDE) of the casing revealed 90 plus indications. The
indications ranged in size from to 13 in length. The casing was polished at the inlet and
exhaust temperature locations. Each location was etched and replications were taken to observe
the microstructures under an optical microscope. Microstructure deteriorations, such as carbide
precipitation at grain boundaries and bainite degradation, were evident. However, the casing did
not show any creep voids at any of the locations examined. Positive Material Identification
(PMI) analysis indicated that the material was a 1Cr-Mo alloy (ASTM A217 GR. WC6).
Microstructure Deterioration of the HP Casing Material
Figure 12. Compared Microstructures from Inlet Casing with Reheat-Treated Material
Replicas of the service exposed areas showed profound carbide precipitation at grain
boundaries, and the extent of the precipitation increases with exposure to higher
temperatures. Replicas of the service exposed areas also showed carbide precipitation inside
the proeutectoid ferrite phase.
Evidence of microstructure degradation of the bainite phase was noticed in the replicas, due
to the transformation of cementite (M 3C) into different carbides (M 2C and M7C3).
No creep voids were evident.
Hardness tests were done at the replica locations and were found to be on average 122 BHN
(Brinell Hardness Number) at the inlet and 136 BHN at the exhaust. The expected hardness
value of a non-service 1Cr-Mo alloy is in the range of 169 200 Brinell. This represents
1217
This
1218
REFERENCES
[1] Neubauer, E. and Wadel, V., 1983, Rest Life Estimation of Creep Components by
Means of Replicas, Advances in Life Prediction Methods, Ed., Woodford, D.A., and
Whitehead, J.E., (New York: ASME), pp. 307-314.
[2] Viswanathan, R. and Gehl, S.M., 1991, A Method for Estimation of the Fracture
Toughness of CrMoV Rotor Steels Based on Composition, ASME Transaction, Journal
of Engineering Mat. and Tech., Vol. 113, April, pp. 263.
[3] Woodford, D.A., 1993, Materials and Design, Vol. No. 4, p. 231.
[4] Woodford, D.A., 1993, Test Methods for Accelerated Development, Design and Life
Assessment of High Temperature Material Materials & Design, Vol. 14, pp. 231-242.
[5] Pope, J.J. and Genyen, D.D., 1989, International Conference on Fossil Power Plant
Rehabilitation, ASM International, pp. 39-45.
[6] Dowson, P., 1994, Fitness for Service of Rotating Turbomachinery Equipment, 10th
Annual North American Welding Research Conference, Columbus, Ohio, October 3-5.
[7] Dowson, P., 1995, Fracture Mechanics Methodology Applied to Rotating Components
of Steam Turbines and Centrifugal Compressors, Third International Charles Parson
Turbine Conference, Materials Engineering in Turbine and Compressors, Vol. 2, pp.
363-375.
[8] Saxena A., 1986, Creep Crack Growth under Non-Steady-State Conditions, Fracture
Mechanics: Seventeenth Volume, ASTM STP 905, Philadelphia, Pennsylvania, pp. 185201
[9] Bloom, J.M., and Malito, M.L., 1992, Using Ct to Predict Component Life, Fracture
Mechanics: Twenty-Second Symposium (Volume 1), ASTM STP 1131, Philadelphia,
Pennsylvania, pp. 393-411
[10] Newhouse D.L., et al., 1972, in Temper Embrittlement of Alloy Steels ASTM STP
499, pp. 3-36.
[11] Watanabe, J. and Murakami, Y., 1981, Prevention of Temper Embrittlement of CrMo
Steel Vessels by the Use of Low Si Forged Steels, American Petroleum Institute,
Chicago, IL, p. 216.
[12] Bruscato, R.M., 1970, Welding J, Vol. 35, page 148S.
[13] Baik, J.M., Kameda, J., and Buck, O., 1983, Scripta Met., Vol 17, p. 1143-1147.
[14] Foulds, J.R., Jewett, C.W., and Viswanathan, R., 1991, Miniature Specimen Test
Technique for FATT, ASME/1EEE Joint Power Generator Conference, Paper No. 91
JPGC PWR-38, ASME, New York.
1219
Krzysztof Cieszyski
1220
membrane walls for USC and A-USC boiler units [2]. In order to avoid problems which
existed up to middle of 2011 with the T24 grade steel [3], it is necessary to perform
detailed investigation of the microstructure and properties of the steel applied in the
boiler construction, butt (tube-tube) and fillet (tube-fin) welded joints in particular.
Investigation on 12Cr2MoWVTiB steel, which is intended for pressure elements of the
boilers, in particular for the membrane walls, is the first part of a procedure to qualify
this material for power generation application.
Research on weldability of T24 steel conducted in RAFAKO S.A. resulted in searching
for a "new" material for membrane walls. "New" material should fulfil very important
conditions. Welding technology and welding process must be easy and without post
welded heat treatment (PWHT). One of the candidates for "new" material to be applied
for boiler membrane walls is 12Cr2MoWVTiB steel grade. The following article presents
the results of investigations jointly performed in RAFAKO S.A. and AGH University of
Science and Technology. To our knowledge this kind of investigation on
12Cr2MoWVTiB steel was performed in Europe for the first time.
2. EXPERIMENTAL DETAILS
The chemical composition (in wt%) of 12Cr2MoWVTiB steel provided by manufacturer
according to the Chinese standard [4] is shown in the Table 1.
Table 1. Chemical composition of the steel investigated (wt%) [4].
Steel
Mn
Si
Cr
Mo
Ti
12Cr2MoWVTi
B
0.080.15
0.450.65
0.450.75
1.62.1
0.50.65
0.30.55
0.280.42
0.080.18
B
0.0020.008
The tube (6 mm wall thickness), was delivered after normalization at 1020-1060 C for
30 min., air cooled followed by tempering at 760-790 C for 3 hours, air cooled.
According to Chinese standard given in Ref. [4], mechanical properties of
12Cr2MoWVTiB steel after such treatment are as follows: R0.2 = 345 MPa (min.), Rm =
540-735 MPa, A = 18%. The limit of yield strength at temperature of 600 C is equal to
274 MPa and creep rupture strength (600 C/100 000 h.) is 92 MPa.
Figure 1 shows long-term creep rupture strength in 100 000 h for steels and alloys
designated for membrane walls [5]. It is shown that 12Cr2MoWVTiB steel has better
strength than those of T23 and T24 steels. It should be noted that the best strength has
T92 steel, but for this steel PWHT is needed. Ni-base alloys, like DMV 617 and DMV
617 mod., are much more expensive. Beside that, there is a high possibility of hot cracks
occurrence during welding process.
1221
1222
investigation was carried out using thin foils prepared by conventional double-jet
electropolishing with a Tenupol and A3 electrolyte from Struers cooled down to 15 C
and under 32V polarisation. Phase identification was conducted by selected area electron
diffraction supported by the JEMS software [6] and EDX spectrometry. Image analysis
and quantitative metallography were performed using AnalySIS 3.2 software.
3. RESULTS AND DISCUSSION
3.1. Welded joints
Butt welded joints
Welding process of butt joints was made at following conditions:
welding procedure 141 (TIG - manual method)
welded position - PC, PH
dimensions of welded tube - 42,4 x 6,0 mm
welded wire material: UNION IP23, diameter - 2 mm and 2,4 mm
average amperage for grain layer of approx. 110A
number of passes 3-4
maximal temperature of inter-pass was not exceeding 280 C
protective gas - argon
Butt welded joints were performed with and without PWHT. Detail of welded joint and
welding process is shown in Fig. 2 given below.
1223
a)
b)
c)
Figure 3. Fillet joints welding process: a) preassembling the tubes with the bending wall
fins b) preheating of preassembled membrane wall elements c) membrane wall after
completed joining process.
1224
Figure 4. Results of impact test for 12Cr2MoWVTiB steel grade - butt welded joints.
As shown in Fig.4, the average values of samples after PWHT are higher than these of
samples without PWHT. The distribution of impact energy of 12Cr2MoWVTiB steel
with- and without PWHT is not acceptable (energy of some samples of welded joints is
below the normative minimum).
Hardness test results of 12Cr2MoWVTiB welded joints are shown in Figures 5-7.
1225
Figure 5. Results of hardness test for 12Cr2MoWVTiB steel grade - butt welded joints
without PWHT.
Figure 6. Results of hardness test for 12Cr2MoWVTiB steel grade - butt welded joints
with PWHT.
1226
Figure 7. Results of hardness test for 12Cr2MoWVTiB steel grade - fillet welded joints.
Hardness test values across both butt- and fillet welded joints of 12Cr2MoWVTiB steel
grade are good enough. Test results for butt- and fillet welded joints presented above
indicate that welding procedure applied to this steel is acceptable.
3.3. Macro- and microstructure
Figures 8 a, b show microstructures of the as-received tube cross-section, as seen by LM
(Fig. 8a) and SEM in secondary electron (SE) imaging mode (Fig. 8b). It consists of
ferritic grains (labelled as F in Fig. 8b) and some small bainitic areas (labelled as B)
between the ferritic grains as well as various precipitates.
F
B
20 m
a)
2 m
b)
1227
Detailed microstructure analyses were conducted by TEM. Fig. 9 shows the typical
microstructure of 12Cr2MoWVTiB steel revealed by TEM in bright-field imaging. It
shows grains of ferritic matrix with fine precipitates of VC carbides.
1 m
a)
b)
Figure 10. Macrostructure of butt welded joints without PWHT a) PC and b) PH
position
1228
a)
b)
c)
Figure 11. TEM image of the microstructure of butt welded joints without PWHT: a)
base material (tube),
b) Heat affected zone (HAZ) c) weld
a)
b)
Figure 12. Macrostructure of butt welded joints with PWHT a) PC and b) PH position
a)
b)
c)
Figure 13. TEM image of the microstructure of butt welded joints with PWHT: a) base
material (tube), b) Heat affected zone (HAZ) c) weld
1229
a)
a)
b)
b)
c)
Figure 14. Macrostructure of fillet welded joints and microstructure of a) base material
of tube b) base material of fin c), HAZ from tube side, d) weld, e) HAZ from fin side.
4. CONCLUSIONS
12Cr2MoWVTiB steel grade might be a good candidate for boiler membrane walls
designated for USC and A-USC power plant. Literature data shows that long-term creep
rupture strength in 100 000 h is very high - the best of ferritic/martensitic steels available
for membrane walls. As-received 12Cr2MoWVTiB steel exhibits a microstructure of
ferritic grains with some bainitic areas between them. The steel is strengthened by VC
carbides precipitated on dislocations within the grains. Some M23C6 and M6C carbides
precipitated at the grain boundaries are also present. Preliminary results of mechanical
tests and microstructure analyses of welded joints are satisfactory. Hardness of butt- and
fillet welded joints is good enough to comply the requirements for welding procedure.
1230
Microstructure of butt- and fillet welded joints do not reveal welding voids or
discontinuously of the material. However, to obtain a certificate for a welding procedure,
good results of the impact test are mandatory. To fulfill this requirement, some changes
of weld wire materials or butt weld procedures are necessary. RAFAKO S.A. is in the
process to complete these requirements.
ACKNOWLEDGEMENTS
The study was supported by the EIT KIC InnoEnergy project on New Materials for
Energy Systems (NewMat). Valuable contribution of Mrs Krystyna Poska-Ninik and
Adam Gruszczyski, MSc. (AGH-UST) for sample preparation and SEM investigation is
kindly acknowledged.
REFERENCES
[1] Xie X. et al,: Proceedings of 6th International Conference on Advances in
Materials Technology for Fossil Power Plants, 31.08-3.09, 2010, Santa Fe, New
Mexico, USA, D. Gandy et al. (eds), ASM International, 2010, p.30.
[2] Procedings of 9th Liege Conference on Materials for Advanced Power
Engineering, Liege, Belgium, 27-29.09.2011, J. Lecomte-Beckers, Q.
Contrepois, T. Beck, B. Kuhn (eds), Forschungszentrum Juelich, 2011.
[3] Nowack R., Gotte Ch., Heckmann S.: Qualitatsmanagment bei RWE am Beispiel
des Kesselwerkstoffs T24, VGB 11/2011, ISSN: 1435 3199, pp. 40-44.
[4] National Standard of the People's Republic of China - GB 5310 2008
[5] EN 10216-2 2009 and VdTUV data sheet
[6]
Stadelmann
P.:
JEMS
Java
Electron
Microscopy
Software,
http://cimewww.epfl.ch/people/
[7] Fudali S., Hajda J., Kucubaa A.: Assessment of base material, welded metal
deposit and manufacturing process of gas-tight membrane walls made of
7CrMoVTiB10-10 steel grade, Proceedings of Internal VGB Workshop,
7.07.2011, Stuttgart, upublished
[8] Cieszyski K., Osuch W., Kaczorowski M., Czyrska-Filemonowicz A.:
Microstructure of 12Cr2MoWVTiB steel for power generation application,
Inynieria Materiaowa, in press
[9] Cieszyski K., Osuch W., Kaczorowski M., Fudali S., Czyrska-Filemonowicz A.:
Microstructure and properties of 12Cr2MoWVTiB steel for power generation
application, KMM-VIN 1st Industrial Workshop on Materials for Energy,
10.07.2013, Madrid, unpublished (poster presentation)
1231
The availability of welding consumables in the form of solid wires as well as access to
modern welding equipment enabled GMAW, and in particular, pulse current-based to be used on
welding of higher temperature materials [2, 4].
GENERAL CHARACTERISTICS OF P92 STEEL
Martensitic steel 9Cr-1Mo-0.25V designated as P/T91 was developed in the USA in
order to meet the needs of nuclear and conventional power engineering. In Europe the steel is
designated as X10CrMoVNb9-1.
The modifications of the chemical composition of P91 steel consisting in the reduction
of molybdenum content by approx. 0.5% and addition of 1.7% tungsten resulted in the
development of steel whose creep resistance is by approx. 30% higher than that of P91 grade.
The steel obtained through the aforesaid modifications was designated as P92 or NF616 or,
otherwise as, X10CrWMoVNb9-2. Tungsten, similarly to molybdenum, is an element enhancing
solid solutions as it increases recrystallisation temperature thus improving long-term stability of
matrix at higher temperature. Through stabilising carbides a microaddition of boron used in P92
steel increases its creep resistance and limits excessive liberation of carbides on grain boundaries
[5].
The chemical composition of steels with 9% Cr content is presented in Table 1; the
comparison of mechanical properties of such steels is presented in Table 2.
Table 1. Comparison of chemical composition of 9%Cr steels according to EN 10216-2 [6]
Grade
P91
P92
E911
PB2*
C
0.080.12
0.070.13
0.090.13
0.135
Si
0.20.5
Mn
0.3-0.6
<0.5
0.3-0.6
0.10.5
0.3-0.6
0.076
0.31
Cr
89.5
8.59.5
8.59.5
Mo
9.28
Chemical composition, %
Nb
Co
Others
0.85-1.05
0.06-0.1
0.18-0.25
N=0.03-0.07
0.3-0.6
0.04-0.09
0.15-0.25
1.5-2
0.9-1.1
0.06-0.1
0.18-0.25
0.9-1.1
1.51
0.053
1.33
0.19
N=0.03-0.07
B=0.0005-0.005
N=0.05-0.09
B=0.0005-0.005
N=0.026
B=0.0091
450
440
450
601
630
620
620
754
19
19
19
19
SUBJECT OF INVESTIGATION
The subject of investigation included butt-welded joints of pipes (OD x WT 219.1 x
31.75mm) made of X10CrWMoVNb9-2 (P92) steel. The heat analysis of the steel as delivered is
presented in Table 3, whereas its mechanical properties are detailed in Table 4.
1233
0.15
0.22
0.45
9.14
0.4
0.16
1.97
Others
B-0.002
N-0.039
666
805
23
252
Nb-0.055
Ni-0.11
KV, J
118
WELDING CONSUMABLES
Properly selected welding consumables are decisive for obtaining required joint
properties. Their role is to ensure that the chemical composition of the weld and its mechanical
properties will be as close to those of the parent metal as possible. Table 5 presents welding
consumables while welding test joints [5, 7].
Table 5. Welding consumables used for P92 steel grade
Method
SMAW
GMAW
GTAW
Filler metal
Diameter
Manufacturer, designation
Welding consumables used with P92 steel (X10CrWMoVNb9-2)
E ZCrMoWVNb 9 0.5 2 B 4 2 H5
3.2; 4
Bhler Thyssen Thermanit MTS 616
G ZCrMoWVNb 9 0.5 1.5
1.2
Bhler Thyssen Thermanit MTS 616
W ZCrMoWVNb 9 0.5 1.5
2.4
Bhler Thyssen Thermanit MTS 616
WELDING PROCESS
Today the most widespread method of producing butt-welded joints of headers is Gas
Tungsten Arc Welding of the root combined with filling performed with a covered electrode.
GTAW was applied in the research for comparison-related purposes; the other method was
GMAW with double pulse current.
Prior to welding the joints were prepared as shown in Figure 1a. The welding process
involved the production of a root run and filling runs as shown in Figure 1b. Pure argon was used
as a backing gas. The test joints were produced in 1G rotating position [1-3].
a)
b)
Figure 1. Joint preparation diagram: weld groove geometry (a), weld run sequence (b)
1234
The scope of mechanical tests included the static tensile test of the welded joint (samples
R1 and R2), bend test (samples GB1GB4 side bend tests), impact tests (samples S1S6
notch cut in the weld; samples H1H6 notch cut in HAZ), macroscopic examination (sample
MA), microscopic examination (sample MA), hardness measurements (sample MA) and
fractographic examination from impact tests.
WELDING TIME MEASUREMENT
During the production of all joints related welding times were measured for comparative
purposes. The measurements were performed so that it would be possible to assess the total time
necessary for the production of a welded joint. The final result is then composed of welding time,
time for inter-run cleaning of welds, electrode exchange time as well as time for removing
splinters and slag.
375
350
Time [min]
300
250
200
149
150
100
50
0
GTAW/SMAW
GTAW/GMAW
Welding process
1236
732
728
720
Rm [MPa]
670
620
570
520
470
420
GTAW/SMAW
GTAW/GMAW
Welding process
Weld metal
HAZ
146
146
132
140
120
100
87
80
60
46
37
40
20
0
GTAW/SMAW
Welding process
GTAW/GMAW
Line B
280
Hardness (HV10)
270
260
250
240
230
220
210
1
Measurement point
1238
10
11
12
13
14
15
Hardness arrangement
welding process GTAW/GMAW
Line A
Line B
280
Hardness (HV10)
270
260
250
240
230
220
210
1
10
11
12
13
14
15
Measurement point
Figure 10. Macrostructure of butt welded joint; methods: SMAW (left), GMAW (right)
RESULTS OF MICROSCOPIC METALLOGRAPHIC TESTS
The microscopic examination, which was performed according to standard EN 1321, did
not reveal any microcracks and confirmed the presence of proper microstructure in all the zones
of the joints made of P92 martensitic steel. Figure 11 contains microscopic examination areas
(marked). Table 6 presents the results of microscopic examination in the form of photographs and
description of the structures present in the characteristic areas of the welded joint.
1239
parent metal
area 1,
mag. 500x,
etch. FeCl3
tempered martensite
tempered martensite
tempered martensite
tempered martensite
tempered martensite
tempered martensite
HAZ
area 2,
mag. 500x,
etch. FeCl3
weld
area 3,
mag. 500x,
etch. FeCl3
The topography of fractures of welds welded with method GMAW following the impact
test are presented in figure 12a), whereas the HAZ fractures are presented in figure 12b). Figures
13a) and 13b) present the fractures of the weld and HAZ welded with SMAW respectively.
The fractographic analysis and microanalysis of the chemical composition of precipitates
in the weld welded with the covered electrode reveals that the joint was produced properly and
should meet the requirements of operation at higher temperature. The aforesaid fact is confirmed
by impact energy values, which for the weld and HAZ amounted to 49J and 87 J respectively.
Also the hardness of the joint, which did not exceed 280 HV, confirms the correctness of the
applied technology.
During fractographic examination both MC carbides and MX carbonitridies were found.
Both precipitates were analyzed with chemical microanalysis and it was found that chromium
carbides and tungsten carbides were present in weld and HAZ. During fractographic examination
both MC carbides and MX carbonitridies were found. Both precipitates were analyzed with
chemical microanalysis and it was found that chromium carbides and tungsten carbides were
present in weld and HAZ.
a)
b)
b)
Both NDT and DT confirmed high quality butt-welded joints made of P92 steel in
workshop conditions.
Theres over 50% time advantage while using Gas Metal Arc Welding compared to
Shielded Metal Arc Welding
The application of GMAW method reduces impurities and increases the comfort of
welders work.
Base on the performed examinations it can be concluded that weld properties in service
temperature will meet the standard requirements.
1242
ACKNOWLEDGEMENTS
The authors of the article wish to express their thanks to ZELKOT, Poland for the idea of this
research and welding of pipes, TenarisDalmine, Italy for providing the pipes used for the
investigations, BHLER Schweitechnik, Deutschland for providing the covered electrodes and
solid wires used for welding P92 steel and Institute of Welding, Poland for all carried
examinations.
REFERENCES
[1] Urzynicok M., Kwieciski K., Szubryt M., Sania J.: Application of new gmaw welding
methods used in prefabrication of P92 (X10CrWMoVNb9-2) pipe butt welds. 9th Liege
Conference on Materials for Advanced Power Engineering, September 27th - 29th, Liege,
Belgium
[2] Urzynicok M., Kwiecinski K., Slania J., Szubryt M., Mariani P.: Comparison of SMAW and
GMAW Methods used in P92 Butt Welds. 1st Australasian International Welding, Inspection
and NDT (iWIN2013) Conference, 10-13 March 2013, Perth, Australia
[3] Kwieciski K., Urzynicok M., omozik M.: Practical experience with welding new
generation steel PB2 assigned for power industry. 9th Liege Conference on Materials for
Advanced Power Engineering, September 27th - 29th, Liege, Belgium
[4] Urzynicok M., Kwiecinski K., Szubryt M.: Experience in the welding of martensitic steel
VM12-SHC, Welding International, iFirst article 2011, 1-6
[5] Urzynicok M., Szubryt M.: A new approach to welding collector pipes performed with
16Mo3 grade steel, Welding International, Volume 25, Issue 8, 2011
[6] EN 10216-2+A2. Seamless steel tubes for pressure purposes. Technical delivery conditions.
Non-alloy and alloy steel tubes with specified elevated temperature properties
[7] Heuser H., Jochum C., Alloy design for similar and dissimilar welding and their behaviors.
1st International Conference Super-High Strength Steels. Rome, (2-4.11.2005).
ISO 5817: Welding - Fusion-welded joints in steel, nickel, titanium and their alloys (beam
welding excluded) - Quality levels for imperfections
2. EN 10216-2: Seamless non-alloy and alloy steel tubes for pressure purposes with specified
elevated temperature properties
3. ISO 6892-1: Metallic materials - Tensile testing - Part 1: Method of test at room temperature
4. ISO 4136: Destructive tests on welds in metallic materials - Transverse tensile test
5. EN 12952-6: Water-tube boilers and auxiliary installations. Inspection during construction.
Documentation and marking of pressure parts of the boiler
6. ISO 9016: Destructive tests on welds in metallic materials - Impact tests - Test specimen
location, notch orientation and examination
7. EN 10045-1: Charpy impact test on metallic materials. Test method (V- and U-notches)
8. ISO 15614-1: Specification and qualification of welding procedures for metallic materials Welding procedure test - Part 1: Arc and gas welding of steels and arc welding of nickel and
nickel alloys
9. ISO 5173: Destructive tests on welds in metallic materials - Bend tests
10. EN 1321: Destructive test on welds in metallic materials. Macroscopic and microscopic
examination of welds
1243
punch tests, FEA has been used to obtain the relationship between the central vertical
displacement and the in-plane tensile strain at the centre of the specimen [3], resulting in a
temperature independent curve of strain versus displacement.
Through the introduction of a vertical displacement probe, vertical displacements as a function of
position on the sample and time have been measured. This data provides much greater
understanding of the specimen deformation. Having displacement data at a series of measurement
points facilitates the calculation of strains across the sample. The probe can also be used during a
test to provide time dependent data from small punch creep tests. The measured displacement data
have been used in conjunction with FE analysis to determine a set of calibration curves for
inferring strain at any given vertical displacement and a series of creep tests conducted comparing
the small punch test to conventional creep data.
EXPERIMENTAL
Small Punch Test
A mechanical test rig has been developed to perform small punch creep tests under controlled
atmospheres whilst measuring the deformation of the small punch specimen. Figure 1 shows a
schematic representation of the small punch test. The small punch specimen is a disc, nominally 8
mm in diameter, with a thickness of 0.5 mm. The load is applied with a Si3N4 ceramic ball of
radius 1.2 mm and the disc is clamped with a thermocouple in the recess of the face of the clamp.
The sample is located above a 3.4 mm diameter hole. The thermocouple allows the temperature to
be accurately controlled throughout the test. Further details of the test method are provided in
NPL Report DEPC-MPE 029 [11].
3 demonstrate that the probe functioned as required and produced the necessary measurement
data, although a hysteresis in the probe measurements was observed, caused by frictional effects
on the probe as it was dragged across the specimen. Modification of the controller software so
that the probe now bounced across the surface produced a much better result, Fig. 4.
Figure 2 Cross sections from interrupted small punch tests to examine the punch shape on P92
material at room temperature, crosshead displacements are shown on the right hand side of the
figure.
Figure 3 Probe output as it traverses a ball bearing (a) compared to optical profilometery
values obtained with a confocal microscope (b).
Vertical Displacement, mm
0
-0.2
-0.4
-0.6
-0.8
-1
0
200N
400N
600N
800N
1kN
0.5
Position, mm
Figure 4 Room temperature run of prototype NPL small punch rig, with probe bounced across
the surface.
1246
Small punch tests were carried out on specimens of P92 at four different temperatures (room
temperature, 400C, 600C and 650C) over a range of applied loads. Vertical displacement data
were obtained at regular intervals as the probe traverses the measurement region of the lower
surface, see Fig. 5. The experimental data produced from this series of tests is shown in Fig. 6. At
the highest temperatures, where greater deformation is occurring at high loads, the measurement
profile is not as smooth. At these temperatures there is also less consistency between the profiles
obtained as the probe is scanned from left to right and from right to left. This is due to
acceleration in the creep rate occurring leading to a large deformation during the scan.
Deformed shape
z
x
2.75 mm
Measurement region
Vertical Displacement, mm
-0.2
-0.1
-0.15
-0.3
-0.4
-0.5
-0.6
0
400N
600N
800N
1kN
-0.2
Position, mm
-0.3
-0.35
0
(b)
600C
-0.1
-0.2
-0.3
-0.4
200N
300N
400N
500N
-0.5
-0.6
-0.7
-0.8
0
400N
500N
600N
700N
-0.25
(c)
400C
-0.05
-0.1
(a)
Vertical Displacement, mm
RT
Position, mm
Vertical Displacement, mm
Vertical Displacement, mm
Position, mm
650C
-0.2
-0.4
-0.6
-0.8
-1
-1.2
-1.4
(d)
Position, mm
300N
400N
500N
600N
Figure 6. Experimental data from small punch tests carried out at (a) room temperature (b)
400C (c) 600C and (d) 650C.
1247
400C
800
Load, N
600
400
Exptal
200
FE prediction
0
0
0.1
0.2
0.3
Displacement, mm
0.4
1248
Vertical Displacement, mm
Experimental
FE
FE Shifted
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
-0.8
0
Position, mm
(1)
lnew is known from the experimental measurement positions (0, 0.1375 etc.), but loriginal is unknown,
see Fig. 9. This required information can be obtained with the help of FEA.
Figure 9. Schematic showing unknown starting positions for the measurement points.
To facilitate the calculation of loriginal and hence the x-direction strain, as described above, the
movement of nodes during the analysis has been investigated. FEA has been used to find the
1249
initial x-location of the measurement points at final positions of x=0, 0.1375 mm etc. These initial
x-positions were then used to calculate the loriginal values required in equation (1). Figure 10 shows
comparisons between the FE predicted strains and the strains calculated from experimental data
using equation (1), for small punch tests at room temperature and 600C. The method presented
here shows good correlation between the FE predicted strains and the experimental strains
calculated based on knowledge of specimen deformation from an FE analysis. A disadvantage of
this method is that it is time consuming and would require a new FE analysis to be run for each
new experimental test i.e. when a new load is applied.
Room Temp 1kN load
0.15
0.2
0.15
Strain
0.1
Strain
0.05
0.1
0.05
0
-0.05
-0.1
0
-0.05
FE predictions
Calculated values
-0.1
Position, mm
1
2
FE predictions
Calculated values
Position, mm
Figure 10. Comparison of FE predicted strain and calculated experimental strain based on FE
deformations for a room temperature test with 1kN applied load (a) and a test at 600C with
500N applied load.
CALIBRATION CURVES
The availability of experimental vertical displacement data at a series of measurement position
means a set of calibration curves can be generated. These curves can be used to map the strain
across the sample for tests at any temperature and applied load. To obtain the necessary data,
predicted FE strains were output at nodes along the radius on lower surface of the specimen
during the analysis. At each increment of the analysis these were interpolated to give strain at the
measurement positions. Data obtained from an analysis at 600C and 500N applied load is shown
in Fig. 11. Measurement position 0 is at the centre of the specimen, with subsequent positions
being at 0.1375mm increments outwards along the radius. Similar sets of curves were obtained
from analyses at room temperature, 400C and 650C.
Calibration curves for each measurement position were then created by plotting strain versus
vertical displacement for all four temperatures. Examples of theses curves, obtained from FE
analyses with 500N applied load, are shown in Fig. 12. It was found that the correlation between
the curves at different temperatures improved as you moved further away from the centre of the
specimen, with smaller displacements observed in lower temperature tests. Figure 13 shows
calibration curves at a measurement position of 0.55 mm, for analyses with (a) an applied load of
500N and (b) higher loads for the room temperature, 400C and 650C cases. The calibration
curves sit on top of each other, with the only difference being an increase in displacements with
increased loads.
1250
0.15
Predicted strain
0.1
0
0.1375
0.275
0.05
0.4125
0.55
0.6875
0
0
0.2
0.6
0.4
0.825
0.9625
1.1
-0.05
1.2375
1.375
Vertical Displacment, mm
-0.1
Figure 11. Strain versus vertical displacement for each measurement position
Measurement position '0.1375'
0.08
-0.01
0.06
0.1
0.2
0.3
RT
-0.02
0.04
Strain
Strain
RT
400C
600C
650C
0.02
0.2
0.4
Vertical Displacment, mm
600C
-0.04
650C
-0.05
-0.06
0
0
400C
-0.03
-0.07
0.6
Vertical Displacment, mm
Figure 12. Calibration curves at measurement positions 0.1375 mm and 1.1 mm from the centre
of the specimen.
Measurement position '0.55'
Measurement position '0.55'
0.15
0.2
400C
0.05
600C
(a)
0.2
0.4
400C 700N
600C 500N
0.05
650C 700N
0.6
-0.05
Vertical Displacment, mm
RT 1000N
0.1
650C
0
-0.05
0.15
RT
Strain
Strain
0.1
0.5
1.5
Vertical Displacment, mm
(b)
Figure 13. Calibration curves at measurement position 0.55 mm with (a) 500N load and (b)
varying applied loads.
1251
CREEP ANALYSIS
In the small punch creep test a fixed load was applied to the punch and the specimen allowed to
creep. Probe traces were taken at regular intervals producing a series of displacement curves at
known times. Initial attempts at modelling the creep behaviour using FEA were unable to
accurately predict the creep response of the specimen due to a lack of parameters for the creep
models. Time constraints prevented further investigation of the model. Instead standard FE
analyses were used to model the experimental data by running analyses with increased loads.
Figure 14 shows the results from FE analyses run to produce curves that match the initial
deformed shape from an 83N load, and the curve after 3 hours creep. The FE predicted curve with
83N applied load matches the initial experimental curve well. The experimental curve after 3
hours creep was found to be replicated by an FE curve using an applied load of 160N. The
corresponding strain versus displacement plots are shown in Fig. 15, where longitudinal strain in
the x-direction was calculated from the experimental data using FE predictions to understand
movement of the measurement positions as detailed previously.
0.02
Vertical Displacement, mm
0.5
1.5
2.5
-0.02
-0.04
-0.06
-0.08
-0.1
Position, mm
Figure 14. FE analyses producing deformed profiles matching the initial load and after 3 hours
creep curve.
0.06
exptal at time=0
0.05
Experimental test:
Load to 83N
Creep for 3 hours
0.04
Strain
0.03
0.02
0.01
0
0.5
1.5
2.5
-0.01
-0.02
Position, mm
1252
A series of FE analyses were run at increasing loads to replicate all the experimental creep curves
at known times. This provided a set of strain versus measurement position plots, similar to Fig.
15, where each load represents a specific time during the creep test. These curves were then
converted into curves of strain versus time for different measurement positions on the sample, see
Fig. 16. The curves from most measurement positions show a compressive strain. This is also
observed in the early part of the calibration curves (Fig. 12) corresponding to the lower loads such
as those needed to replicate the creep curves.
This work indicates that it is possible to use a standard non-creep FE model to predict the strain in
the sample during a small punch creep test. This suggests that the calibration curves presented
here could be used in conjunction with experimentally measured vertical displacements after a
given creep time period, to obtain the strain across the sample at that time instance. This would
allow data similar to that shown in Fig. 16 to be obtained, and hence the calculation of creep
strain rates becomes possible.
0.06
0.04
Strain
0.02
0
-0.02
Measurement position, mm
-0.04
-0.06
0.12
0.28
0.4
0.56
0.68
0.96
1.21
50
100
time (hours)
150
200
Figure 16. FE predicted variation of strain with time for a small punch creep test at 650C with
83N applied load.
CONCLUSIONS
A prototype small punch test rig has been designed to extend the range of data output during a
small punch test. The use of a probe bouncing over a measurement region on the underside
surface of the specimen has enabled vertical displacements to be recorded at a series of fixed
measurement positions. This is in contrast to the current standard small punch test where
displacement is only measured at the centre of the specimen. The new technique leads to much
greater understanding of material deformation during the test. Because the displacement data are
obtained at fixed measurement positions, the deformation of a single point is not tracked during
the test i.e. the movement of a single point on the untested sample to its final position on the
deformed surface is not measured. This means that to obtain the actual longitudinal strain, further
information on the sample deformation is required. This information has been obtained through
following the movement of nodes in FE analyses. This method is laborious and requires FE
analyses run for each separate test set-up i.e. temperature and applied load, but by running a
whole series of these analyses to match all experimental configurations, a set of calibration curves
have been determined. This series of curves allow the strain profile across any sample to be
1253
inferred from the experimentally measured vertical displacements. Near the centre of the
specimen the curves are temperature dependent, but away from the centre the curves are
temperature independent.
The calibration curves are based on measured vertical displacements obtained on initial
application of a load. The measurement probe is also able to obtain displacement data at set time
increments during a small punch creep test. The initial creep work presented here has looked at
obtaining creep strains from this data, in conjunction with standard non-creep FE analyses. It has
shown that creep strain versus time data can be obtained which would allow calculation of creep
strain rates.
Future work will include the use of a creep model in the FE analyses to explore whether
deformation under creep loading gives the same strains as static loading, allowing the calibration
curves to be used to determine strains. Longer term creep tests are planned and calculation of
creep strain rates for these tests will support the aim of relating small punch creep tests to fullscale uniaxial creep tests.
REFERENCES
[1] S.-H. Song, R.G. Faulkner, P.E.J. Flewitt, P. Marmy and L.-Q. Weng, Small punch test
evaluation of neutron-irradiation-induced embrittlement of a Cr-Mo low-alloy steel Mater.
Characterization, 2004, 53, 35-41.
[2] E.N. Campitelli, P. Sptig, J. Bertsch and C. Hellwig, Assessment of irradiation-hardening
on Eurofer97 and Zircaloy 2 with punch tests and finite-element modeling Mat. Sci. Eng. A,
2005, 400-401, 386-392.
[3] S.R.J. Saunders, J.P. Banks and M. Wright, Measurement of Ductile Brittle Transition
Temperature of Coatings Using the Small Punch Test NPL Report MATC(A)60, 2001.
[4] B. Roebuck, L. Brown, J. Banks, R. Brooks and M. Evans, Miniaturised Testing NPL
Report DEPC-MPE 042, 2007.
[5] B.J. Kim, Y.B. Sim, J.H. Lee, M.K. Kim and B.S. Lim, Application of small punch creep
test for Inconel 617 alloy weldment Proceedings of 11th International Conference on the
Mechanical Behavior of Materials (ICM), Como, Italy 2011, pp 2579-2584
[6] L.J. Brown, J.P. Banks and J.W. Nunn, NPL Good Practice Guide No. 105 Measurement of
Ductile:Brittle Transition Temperature in Coatings
[7] T. Wei, D.G. Carr, E. Budzakosha, W. Payten, R.P. Harrison and M.I. Ripley, Assessment
of the Fracture Toughness of 6061 Aluminium by the Small Punch Test and Finite Element
Analysis Materials Forum, 2006, 30, 39-44.
[8] J.D. Lord, B. Roebuck, R. Morrell and T. Lube, Aspects of strain and strength measurement
in miniaturised testing for engineering metals and ceramics Mater. Sci. Technol., 2010, 26, (2),
127-148.
[9] L.O. Bueno, V.L. Sordi and L. Marino, Constant load creep data in air and vacuum on
2.25Cr-1Mo steel from 600C to 700C Mater. Research, 2005, 8, (4), 401-408.
1254
[10] D.T. Blagoeva and R.C. Hurst, Application of the CEN (European Committee for
Standardization) small punch creep testing code of practice to a representative repair welded P91
pipe Mat. Sci. Eng. A, 2009, 510-511, 21-223.
[11] S. Osgerby and J.P. Banks, Experimental Aspects of Small Punch Testing at Elevated
Temperatures NPL Report DEPC-MPE 029, 2006.
1255
Ultrasonic thickness gauging techniques have commonly been used to measure oxide scale
thickness for many years. Commercial 20 MHz longitudinal wave ultrasonic transducers can
measure down to a minimum oxide thickness of approximately 250 m. By using normal
incidence shear wave transducers that limit can be reduced to 125 m [6]. The methodology used
for this work demonstrated oxide layers as thin as 65 m could be measured ultrasonically.
EXPERIMENTAL PROCEDURE
Specimens were manufactured using a pin in collar design to ensure close mating surfaces
between the alloys. Several combinations of power plant materials were used, specifically the
nickel-based INCONEL alloys 617, 740, 939, 738 and P92 ferritic-martensitic steel, only a subset
of these are reported here. Once manufactured the samples, comprising of a pin and collar section,
were exposed to a flowing steam environment at atmospheric pressure at a number of different
temperatures and times (Table I). The feed water to the steam furnaces was controlled such that
the water was deionized and deaerated to a level of dissolved oxygen of approximately 15 ppb.
After the exposure was completed the oxide thicknesses were measured by ultrasonic techniques,
after which the specimens were finally examined using destructive metallographic techniques for
optical microscopy measurements. The detailed procedure is described below.
Specimen Design
The specimen design used for this work is shown in Figure 1. The specimens were constructed
via the insertion of a pin into a collar placing the external surface of the pin and the internal
surface of the collar into close contact, with the gap tolerancing controlled by raised pips on the
pin as shown in Figure 1. The pin and collar surfaces were produced with a ground finish to
provide a standardised surface finish and to facilitate accurate metrology of the oxide thickness
after exposure. The specimens were manufactured using different combinations of ferriticmartensitic steels and Ni-based alloys as indicated in Table 1. For the purposes of this paper the
focus will be on the IN738-P92 specimens. The aim of using such a design was to promote oxide
jacking between the two mating surfaces, a feature required for a separate task of the funding
project, and to provide a challenging geometry for the assessment of the ultrasonic measurement
technique.
Exposure Procedure
The specimens were exposed to flowing steam inside a horizontal tube furnace. The water was
forced via a positive gas pressure into the furnace, through a metallic pipework system to prevent
any oxygen ingress through polymeric materials.
The samples were placed into the hot furnace which had been previously profiled, and left in the
flowing steam environment for a set number of hours at appropriate temperatures (see Table 1) to
allow the oxides to form and grow on both the exposed pin and collar surfaces. After the exposure
periods, the specimens were gradually removed from the furnace to avoid thermal shock and
carefully stored prior to subsequent preparation and examination. Once the steam oxidation
exposure was completed, the samples were measured ultrasonically and subsequently sectioned
and prepared by means of standard metallographic techniques.
1257
1258
AARJ
AARK
AARL
001
002
003
004
001
002
003
004
001
002
003
004
Pin
Materials
Collar
T [C]
IN738
P92
650
IN740
P92
650
P92
P92
650
Time [h]
500
1000
2000
3000
500
1000
2000
3000
500
1000
2000
3000
thickness on these calibration specimens was varied by exposing the specimens for different times
in an atmosphere of 100% flowing steam at 650 C. For each exposure time, two specimens were
produced, one for non-destructive evaluation (NDE) and the other for destructive optical
thickness measurements.
Figure 3 shows the correlation between the ultrasonic time-of-flight measurements compared with
the optical thickness measurements of the oxide scale. The slope of this provides a calibration
value for the oxide velocity of 5472 ms-1 (typically ~6000 ms-1 is quoted for oxide scales [3]).
Some inconsistency can be expected due to spatial averaging effects and sample-to-sample or
point-to-point variations between optical measurements and ultrasonic determinations of oxide
thickness.
1260
surfaces, but this proved too problematic due to the increased signal attenuation through either
thicker metallic volumes or from irregularly finished surfaces.
Figure 4 Section of a pin and collar sample indication measurement locations, (a) for
light microscopy and (b) for ultrasonic NDE.
Figure 5 shows the basic methodology of the technique. The time difference between the initial
return from the metal/oxide interface (t1) and the much larger return from the oxide/air interface
(t2) equates to the time taken to travel across the oxide and back, i.e. double the thickness/path
length (2d). As described for the ultrasonic calibration measurements previously, by using
samples of known oxide thicknesses which are independently measured using an alternative
technique such as microscopy, this process can be used to determine the oxide velocity.
Conversely, once the oxide ultrasonic velocity is known the measured time difference can be used
to ascertain the thickness of the oxide layer. Further details about the method and the calibration
process are described elsewhere [10].
1261
1262
Figure 7 shows the optical oxide thickness measurements as a function of exposure time for the
specimens with an IN738 pin in a P92 collar. The dashed lines represent the optical thickness
measurements of the discrete spinel and magnetite layers grown on the P92 collar surface. The
solid line represents the total oxide thickness, the sum of both oxide layers. A typical optical
micrograph of the double oxide layer formed between the pin and the collar is shown in Figure 8.
Figure 7 Oxide thickness as a function of time for the IN738 Pin / P92 Collar specimens.
Ultrasonic and optical oxide thickness measurements are presented together for comparison in
Figure 9. The filled points are the individually measured total oxide thicknesses, considering both
spinel and magnetite layers, determined by optical microscopy. The unfilled points represent the
mean value of the total oxide thickness within each of the three subdivided regions. Each of these
regions correlates approximately with the three areas over which the ultrasonic measurements
were performed as shown in Figure 4. The crosses indicate the ultrasonic thickness averages from
each region. Thus both the optical and ultrasonic mean values should be directly comparable. In
the first two regions, the ultrasonic measurements were slightly lower but are within the range of
the optical results. For the third area, the ultrasonic thickness perfectly matched the optical
measurements.
Figure 8 Oxide scale in the interface of an IN738 Pin / P92 Collar sample (AARJ001)
exposed for 500 h at 650 C
1263
Figure 9 Ultrasonic and optical thickness measurements for an IN738 Pin / P92 Collar
specimen after 500 h steam exposure at 650 C (AARJ001).
The results obtained from an IN738 Pin / P92 Collar specimen after 1000 h steam exposure were
represented in a similar way in the graph in Figure 10. Here the filled points represent only the
spinel thickness, the filled squares depict the total oxide thickness including the magnetite layer,
and the unfilled points are the mean values of the spinel thickness for each of the three divisions.
The ultrasonic results showed good agreement with the measured spinel oxide thickness in all
three regions, corresponding to approximately half of the total oxide thickness, maintaining the
conventional 1:1 ratio of spinel to magnetite thickness [11-13]. Further examination of
micrographs taken from the cross-section of the specimen showed that there was a discontinuity
between the inward growing Fe-Cr spinel and outward growing magnetite layer, as shown in
Figure 11. The presence of this gap resulted in only the spinel thickness being measured
ultrasonically. The fracture of the magnetite scale could be produced during the exposure period
due to the internal stresses caused by the oxide growth and the more brittle nature of the magnetite
in comparison to the spinel.
Figure 10 Ultrasonic and optical oxide thickness measurements for an IN738 Pin / P92
Collar specimen after 1000 h steam exposure at 650 C (AARJ002).
1264
Figure 11 Oxide scale in the gap of an IN738 Pin / P92 Collar sample (AARJ002), exposed
for 1000 h at 650 C
Similar results for this material combination were obtained after 3000 h exposure, as can be seen
in Figure 12. Later optical analysis of the sample showed that it had a wider collar opening at the
open end than the other specimens, which resulted in the unconstrained growth of the oxide
exhibiting higher internal porosity of the magnetite and hence an indistinct ultrasonic signal from
which quantitative measurements could not be made. The distributed porosity acts as multiple air
interfaces which produce small back reflections at many depths and locations rather than the
strong coherent signal from a single oxide or air interface plane. Optically, the oxide thicknesses
along the first millimeter down from the collar surface had much higher values (see the initial
points in Figure 12). For the other two regions there was good agreement between both
techniques.
Figure 12 Ultrasonic and optical oxide thickness measurements for an IN738 Pin /
P92 Collar specimen after 3000 h steam exposure at 650 C (AARJ004).
1265
A similar set of comparative measurements have been performed for the AARK series of
specimens consisting of IN740 Pin and P92 Collars. Once again there was good agreement
between the optically measured oxide thickness and the ultrasonic data, with a similar trend as
described previously.
CONCLUSIONS
A non-destructive technique, which uses the intrinsic physical property of the speed of sound in a
material, has been used to measure the oxide thickness of steam grown oxides on internal
contacting surfaces. This method was able to successfully measure the oxide thickness even given
the extremely challenging pin and collar specimen geometry.
Ultrasonic inspection is typically used in industry for inspection of both remnant metal thickness
and bore oxide scale thickness, but the limited resolution may be a concern with the increased use
of austenitic and superalloy materials. It has been demonstrated that improved resolution in the
thickness measurement of oxide scales by ultrasonic methods can be obtained with accurate
measurements becoming possible down to an oxide thicknesses of 65 m. Previous practical
limits of around 100 to 250 m have been quoted in the literature depending on the nature of the
transducer being used for the measurement. This work has shown that higher measurement
resolution is possible. Measurements of oxide thickness in the range that spallation normally
occurs for ferritic - martensitic 9-12 %Cr alloys are obtainable, these tend to be in the order of
200 to 300 m.
It has also been shown that the ultrasonic technique is susceptible to microstructural and
morphological features in the oxide. This is a characteristic of this measurement method and
cannot be overcome, so when examining an area it would be better to use a larger diameter
transducer to improve the spatial averaging or to measure in several places in a localised area and
use an average thickness value. The geometry (small size and tight radius of curvature) of the
specimens used in this work prevented such an approach.
Ultrasonic measurements of oxide thickness agreed very well with optical measurements where
there was no integral discontinuity in the oxide scale. In these instances, the measurement
correlated with the thickness of the Fe-Cr spinel layer since fracture of the interface between this
layer and the magnetite layer was often seen to occur.
Considering the tight radius and difficult geometries used in this work, the use of ultrasonic
transducers to make higher resolution measurements of the oxide thickness has been demonstrated
and should be even simpler to apply to large scale items such as the large bore pipework and
tubing used in power plants.
To summarise, it has been shown
The speed of the ultrasound wave has been measured and calibrated for steam grown
oxides on a 9%Cr martensitic alloy, giving a value of 5472 ms-1, a figure somewhat
lower than that usually quoted.
It has been demonstrated that improved resolution is possible by using appropriate
transducers, amplifiers and analyses techniques.
Ultrasonic measurements of oxide thickness agree well with optical measurements
provided there is no discontinuity in the oxide scale, where this occurs the measurement
1266
correlates with the thickness of the Fe-Cr spinel layer, as it is at this interface with the
magnetite layer where fracture was seen to occur.
Considering the tight radius and difficult geometries used in this work the use of
ultrasonic transducers to make higher resolution measurements of the oxide thickness has
been demonstrated and should be easier to apply to large scale items such as pipe work
and tubing in plant.
ACKNOWLEDGMENTS
The authors are grateful to Jim Banks and David Laing, and would like to acknowledge funding
from the Department of Business Innovation and Science for the work reported in this document.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
1267
standard conditions (UNS7718) is about 650C. Therefore a new heat treatment was developed to
increase the high temperature behaviours of the IN718 and his microstructural stability to target
the AD700 goal and a prototype disk was produced [3]. After the optimisation of the heat
treatment, by mechanical and short term creep tests, a long term creep program was launched in
order evaluate the creep resistance of the new modified heat treatment, as well as, microstructural
analysis to investigate the alloy stability.
The aim of this paper is to present the results of this test programme that are discussed in
relationship with the microstructure evolution in the service conditions.
2. Material production
One ton billet produced by Electric Arc Furnace, followed by Argon-Oxygen Degassing refining
and double VAR (Vacuum Arc Remelting) remelted by Foroni Metals, has been forged by
Societ delle Fucine using a 12.600 ton press, following a procedure designed by model
simulations in order to promote recrystallisation. Figure 1 shows the billet before during the
forging steps and the prototype forged disk having the following final dimensions: diameter
850mm and thickness 350mm [3].
Figure 1: IN718 billet before forging and the prototype disk after forging
Table 1 shows the chemical analysis of IN718 billet compared with that of the standard
UNS7718; the trace elements are the following: Pb <0.2, Bi <0.1, Se<1.0, Sn<10, Ag <
1.0 (values in ppm).
C
Standard
UNS7718
Foroni
Billet
Ni
50
<0.0 8 55
Fe
Bal
Cr
Mo
17
21
2.8
3.3
Co
<1
<0.1
<
0.1
Nb
Ti
Al
Zr
4.8
5.5
0.7
1.2
0.2
0.8
<
0.006
0.9
0.5
0.004
Mn
<
<
0.35 0.35
<
0.15 0.15
0.0005
1269
Si
<
0.015
0.008
0.001
927-1010
720/8/FC
620/8/air
>1035
>1240
>10
1000/2/water
718/8/FC
621/8/air
1135
1403
20.4
74
1065/1/air
760/8/FC
650/12/air
1120
1335
27.0
80
Table 2: Heat treatment conditions and mechanical properties (FC = Furnace cooling)
To evaluate the microstructural stability and the mechanical behaviour after standard and
modified heat treatment (HT), aging tests were carried out at 700 and 750C up to 10200 h: the
tensile strength slightly decrease after aging (Figure 4). It is important to take into account that
aging at 750C for 3000 h, according with Larson Miller Parameter (LMP), is equivalent to
60.000 hours at 700C [7].
1270
a
B
Figure 2: Microstructure after standard heat treatment: a) conventional HT; b) modified HT
1271
Comparison with literature data was not possible because the only available data are at very high
stress [9].
Figure 5: Isothermal curves of smooth and notched specimens (yellow point are test still
running)
1,E-02
650C
700C
750C
1,E-03
y = 2E-07x1,3756
R = 0,8832
1,E-04
1,E-05
y = 3E-36x11,567
R = 0,9738
y = 2E-12x3,0698
R = 0,9871
1,E-06
50
500
Stress (MPa)
1272
The material with new heat treatments is not affected by notch effect: in fact in figure 8 it is
possible to appreciate that the master curves are very similar.
The creep behaviours of IN718 mod superalloys have been compared with ORNL data from
literature on standard material [11]. The modified treated material shows the same creep
resistance at 650C, but a relevant increase of the rupture time at the highest temperatures,
especially at 750C, as showed in figure 9. The modified treated material shows at 100MPa the
same rupture time of the standard material, but with an increase of 46C in term of service
temperature (circle in the figure 9).
Furthermore the creep ductility showed by the IN718 with the modified heat treatment, appears
interesting, in terms of elongation and reduction of area to rupture, that increase with the
temperature and the test time. The figures 10 shown the elongation to rupture and the reduction of
area versus time to rupture (tr), giving evidence that the physiological evolution of in -phase
doesnt reduce ductility of the material with the modified treatment. This behaviour was just
observed in literature [12] and was related to the effect of particle to guide crack advance in a
zigzag path resulted in absorbing strain energy and increasing plasticity. Further analyses in order
to confirm this mechanism are still in progress.
Figure 7: 2012 creep data assessment with current smooth test running (red symbol)
1273
Figure 8: Comparison of master curves of IN718 Mod smooth and notched specimens
(the yellow points on the right are the specimens still running over 93.000 hours)
1274
a)
b)
Figure 10: Creep Ductility of IN718 Mod: a) elongation and b) reduction of area vs
rupture time (yellow point is test still running)
5. Microstructural evolution
In order to understand the reasons of these better behaviours the modified treated material TEM
investigation have been performed on both treated materials in aged conditions. Figures 11
shown a comparison of the microstructure evolutions after 3000hours at 700C and 750C for the
modified treated material: at this magnification, on the specimen aged at 700C only can be
recognised, being too finer to be observed. At 750C fast coarsening of both and phases is
well evident, as well as the formation of the large plates, due to transformation. Figures 12
the microstructure after 3000 hours at 750C for the standard treated material shows a reduced
amount of phase, if compared with the microstructure of material, in the same ageing
1275
conditions, when is treated with new heat treatment. (figures 11b and 12), giving evidence of the
effect of the new heat treatment to reduce the transformation kinetics of into phase.
Quantitative analyses on aged specimens have been carried out to define the evolution of the
main phases [13]. The measured of , and sizes gave evidence that all the phases in the
standard treated material shown faster growing compared with the modified treatment. After
3,000h at 750C, the measured precipitate size distribution shows that particles coarsening is
rather similar both heat treatments, growing up to 80nm; particles grow up close to
micrometric dimension after 5.000-10,000 h and then they decrease.
a)
b)
Figure 11: IN718 Mod treated material: TEM image on thin foil after 3.000 hours of
aging: at 700C; b) at 750C
Figure 12: IN718 standard treated material: TEM image on thin foil after 3.000 hours of
aging at 750C
Quantitative analyses on aged specimens have been carried out to define the evolution of the
main phases. The measured of , and sizes are respectively reported in the figures 13, 14
and 15, where the 750C temperature and aging time have been transformed in 700C and time
1276
1277
a)
b)
c)
Figure 16: IN718 mod microstructures of aged specimens by light microscopy:
a) 650C 25355h; b) 700C 25860h; c) 750C 33206h
a)
b)
c)
Figure 17: IN718 mod microstructures of aged specimens by SEM: a) 650C
25355h; b)
700C 25860h; c) 750C 33206h
With investigations at higher magnification it was possible to identify the phases in the specimens
aged at 700C for 25.860 hours, shown in figure 18: the presence of Niobium reach round shape
carbides and acicular phase, as well as, between the -phase particles still the presence of
some small particles: that means that the transformation to it is not jet completed in these
ageing conditions.
Figure 18: SEM images of the crept specimen at 700C after 25.860 hours: a) MC Nb
rich particles; b) phase; c) phase
1278
a
c
Figure 21: TEM images of the crept specimen after 33.206 hours at 750C: a) -phase;
b) -phase
1279
Figure 22: TTP diagram for IN718 proposed by Thomas and Co [15]: red star indicates
the position of the experimental specimen aged 33.206 hours at 750C.
Figure 23: Orowan climb of a dislocation on a particle in the specimen after 33.206
hours at 750C
1280
1281
5. W. D. Cao and R. L. Kennedy: improving stress rupture stress rupture life of alloy 718 by
optimizing Al, Ti, P and B contents: Superalloys 718, 625, 706 and various derivatives: TMS
2001, edited by F.A. Loria
6. C. Slama, G. Cizeron, Etude du comportement structural de lalliage NC 19 Fe Nb (Inconel
718), Les editions de Physique, 1997.
7. M. Sundararaman, P. Mukhopadhyay, S. Banerjee: Precipitation and Room Temperature
deformation of Inconel 718 Superalloy 718, 625, 706 and Various Derivates, Ed. Loria, 1994
8. A. Di Gianfrancesco and Others: Mechanical and microstructural qualification of a prototype
IN718 forged disk IFM2003 Kobe Japan 2003, pag. 471
9. A. Di Gianfrancesco & others: Mechanical and microstructural qualification of a prototype
IN718 forged disk: ECCC Conference, Zurich CH 22-24 April 2009
10. R.W. Hayes, Creep deformation of Inconel 718 in the 650C to 760C temperature regime,
Superalloy 718, 625, 706 and Various Derivates, Ed. Loria, 1991
11. Creep data validation and assessment procedures: ECCC Recommendations Volumes 2005
12. C. R. Brinkman, M. K. Booker, and J. L. DingCreep and Creep-Rupture Behavior of Alloy
718"; Superalloy 718, 625, 706 and Various Derivates, Ed. Loria, 2001
13. Z. Yun et al., Superalloys 718, 625, 706 and various derivatives; TMS, ed. Loria, 1997, p.
229.
14. J. Dong, X. Xie, Z. Xu, S. Zhang, M. Chen, J. Radavich: TEM study on microstructure
behaviour of Alloy 718 after long term exposure at high temperature: Superalloys 718, 625,
706 and various derivatives; TMS, ed. Loria, 1994, p. 649.
15. A. Thomas, M. El-Wahabi, J.M. Cabrera, J.M. Prado: High temperature deformation of
Inconel 718; Journal of Materials Processing Technology 177 (2006) 469472
1282
1283
Ingot making
(VIM & ESR)
Forging
Heat treatment
Machining &
inspection
EXPERIMANTAL PROCEDURE
Specimen collecting
The specimens were collected from the positions denoted by the black squares in Fig. 3. The
subscripts of each black square are the specimen designations. Because the lengths of the trial
rotors are not equal, the specimen collecting positions are described by X n , which is the distance
from the bottom side normalized by the rotor length. Table 1 lists the chemical composition of the
specimens, except MA1. No significant difference was observed between the first and second
trials, surface and center, bottom and top, indicating that the chemical composition of the trial
forgings, as a whole, was quite homogenous.
1st trial
2154
1077
MA1
FA1
JA1
DA1
AA1
Bottom
(0.07)
Center
Top
(0.93)
Middle
(0.50)
2nd trial
Surface
Top end
160
CA1
Bottom end
877
160
1760
880
160
CA2
AA2
Bottom
(0.09)
MA2
FA2
JA2
DA2
Surface
Top end
910
Bottom end
160
Center
Unit: mm
Top
(0.91)
Middle
(0.50)
Bottom
Middle
Top
Trial
Si
Mn
Ni
Cr
Al
Ti
Nb
Fe
AA1
1st
0.012
0.01
0.02
<0.005
<0.001
40.9
15.5
1.39
1.52
2.03
38.4
0.0027
0.002
O(ppm)
7
AA2
2nd
0.009
0.01
0.02
<0.005
<0.001
41.2
15.5
1.28
1.51
2.07
38.2
0.0029
0.002
11
CA1
1st
0.011
0.01
0.02
<0.005
<0.001
40.9
15.5
1.40
1.53
2.02
38.3
0.0025
0.002
CA2
2nd
0.010
0.01
0.02
<0.005
<0.001
41.7
15.5
1.25
1.53
2.02
37.8
0.0027
0.003
10
JA1
1st
0.009
0.01
0.02
<0.005
<0.001
41.2
15.6
1.43
1.48
1.98
38.1
0.0024
0.002
JA2
2nd
0.010
0.01
0.02
<0.005
<0.001
41.9
15.4
1.25
1.51
1.98
37.8
0.0027
0.002
11
MA2
2nd
0.009
0.01
0.02
<0.005
<0.001
41.9
15.4
1.24
1.53
1.97
37.7
0.0026
0.002
11
DA1
1st
0.009
0.01
0.02
<0.005
<0.001
41.0
15.6
1.29
1.48
2.00
38.5
0.0025
0.002
DA2
2nd
0.027
0.01
0.02
<0.005
<0.001
41.3
15.5
1.26
1.58
2.09
38.1
0.0033
0.002
FA1
1st
0.010
0.01
0.02
<0.005
<0.001
41.1
15.6
1.28
1.54
2.01
38.4
0.0024
0.003
FA2
2nd
0.013
0.01
0.02
<0.005
<0.001
41.8
15.4
1.23
1.48
1.97
38.0
0.0026
0.003
specimens were also collected from each position except MA1, were carried out at room
temperature. The specimens for the Charpy impact tests had a longitudinal notch 2 mm deep, and
the dimensions of the specimen were 10 10 55 mm. Creep rupture test specimens were taken
from the positions of CA1, JA1, FA1, CA2, MA2, and FA2. The test temperature of the creep test
was 700 C, and the stresses were 333, 294, and 245 MPa.
The permeability of the ultrasonic wave was evaluated by measuring the minimum detectable
flaw size (MDFS) in the radial ultrasonic inspection test.
RESULTS AND DISCUSSION
Microstructure
Figure 4 shows the micrographs of the trial forgings. The micrograph of the MA1 specimen
was taken by the SUMP method. On the first trial, the grain size numbers of the bottom and top
sides were 1.2 - 1.3, and no difference was observed between the center and surface. The grain
size number of the surface in the middle portion (MA1) is roughly the same as those of the bottom
and middle, however, it is greater than the grain size number of the center (JA1). The white area
observed in JA1 corresponded to the dendrite structure. On the other hand, the grain size numbers
of the second trial forgings were larger than those of the first one in every specimen, indicating
that the grain was refined in the second trial. In particular, the grain size number of the JA2 was
2.3 larger than that of the JA1; that is, the grain at the center in the middle portion was most
refined. No mixed-grain structure was observed in any specimen of the both trial forgings. Fig. 5
shows the distribution of the grain size number of the trial forgings. X n of the bottom, middle, and
top portion of the first and second trial rotors are almost equal, so the relative position of the
specimen can be regarded as the same. From Fig. 5, it can be stated that the grains at the center
were more refined than those of the surface.
Minimum Detectable
Flaw Size, MDFS / mm
1st trial
3.7 ~ 4.8
2nd trial
1.6 ~ 1.9
200 nm
200 nm
200 nm
(a) Center
RT
RT
1st trial
(b) Surface
1st trial
2nd trial
2nd trial
700 C
700 C
Figure 7 0.2% proof stress of trial forgings; (a) center, (b) surface
(b) Surface
(a) Center
RT
RT
1st trial
1st trial
2nd trial
2nd trial
700 C
700 C
(b) Surface
700 C
1st trial
1st trial
2nd trial
700 C
RT
2nd trial
RT
(a) Center
700 C
1st trial
1st trial
2nd trial
2nd trial
700 C
RT
RT
(b) Surface
1st trial
1st trial
2nd trial
2nd trial
Figure 11 Charpy absorbed energy of trial forgings; (a) center, (b) surface
Creep properties
The relationship between creep stress and time to rupture of the trial rotors are shown in Fig.
12. The previous data are also shown in the figure. Except for a few data, the times to rupture of
the second rotor are short compared to those for the first trial. Generally, because the grain
boundary works as the sink of dislocation and vacancy or the fast diffusion path in the high
temperature deformation, the vicinal area of the grain boundary is apt for deforming easily. Thus,
the short rupture time of the second trial can be interpreted as being the result of grain refinement.
However, provided that the grain size number ranges from -1 to 3, the times to rupture would be
plotted in the area between the broken lines[8]. Thus, the results acquired in this work are
considered proper. Although the grain is refined in the second trial, the 105 h creep rupture
strength at 700 C would be sufficiently higher than 100 MPa.
1289
Now, the time to rupture of JA1 is shorter than the other specimens of the first trial. Especially,
it ruptured immediately under a high stress condition of 333 MPa. Because the size of the
gamma-prime particles of JA1 is larger than those of CA1 and FA1, the strengthening mechanism
of the precipitated hardening alloy[9] implies that the difference in the time to rupture can be
attributed to the difference in the size of the gamma-prime particles.
Test temperature: 700 C
Ongoing test
Previous work 3)
1st trial
2nd trial
CA1
CA2
JA1
MA2
FA1
FA2
[3]
[4]
[5]
[6]
[7]
[8]
[9]
Conference on Advances in Materials for Fossil Power Plant, Macro Island, FL, October.
2007, p. 3B-04.
S. Imano, J. Sato, K. Kajikawa and T. Takahashi, Mechanical Properties and
Manufacturability of Ni-Fe base Superalloy (FENIX-700) for A-USC Steam Turbine Rotor
Large Forgings, Proc EPRI 2007 5th International Conference on Advances in Materials for
Fossil Power Plant, Macro Island, FL, October. 2007, p. 3B-03.
A. Diwo, B. Donth, N. Blaes, D. Bokelmann, Y. Yoshioka, S. Miyashita and T. Kubo,
Largest Steam Turbine Rotor Ever Manufactured From a Nickel Base Alloy, Proc
IFM2011 18th International Forgemasters Meeting, Pittsburgh, PA, September, 2011, pp.
224-228. pp. 213-219.
T. Takahashi, S. Ohsaki, K. Kajikawa, T. Kure, S. Imano, J. Sato, E. Saito and H. Doi,
Manufacturability of Ni-Fe base, Superalloy FENIX-700 for A-USC Steam Turbine Rotor
Large Forgings, JSW Technical Review, Vol. 61, (2010), pp. 7-16. (in Japanese)
T. Takahashi, S. Ohsaki, S. Imano, E. Saito and M. Takeyama, Mass Effect on the
Precipitation of and the Tensile Properties of Ni-Fe Base Superalloy FENIX-700 for AUSC Turbine Rotor Shafts, Netsushori, Vol. 51, No. 5, (2011), pp. 289-294. (in Japanese)
K. Takasawa, S. Ohsaki, T. Takahashi, S. Imano, J. Sato and E. Saito, Proc IFM2011 18th
International Forgemasters Meeting, Pittsburgh, PA, September, 2011, pp. 224-228.
S. Ohsaki, T. Takahashi, S. Imano, J. Sato and E. Saito, Proc EPRI 2010 6th International
Conference on Advances in Materials for Fossil Power Plant, Santa Fe, NM, August. 2010,
pp. 361-372.
M. Takeyama, Fundamentals of Physical Metallurgy for High-temperature Materials
Microstructure Control and Design, 194th Nishiyama Memorial Lecture, Tokyo, (2008), pp.
3-23. (in Japanese)
1291
1292
To increase the steam temperature of the power boiler, creep-resistant steel for high
temperature application is necessary. In addition, the length of heavy-wall steam pipe may be
longer than 100 m so as to transport the high-temperature steam from the boiler to steam
turbine in such a large volumetric plant. Therefore, the thermal-stress-induced fracture might
occur due to the start-and-stop of the plant and the controlled elevation of the steam
temperature.
Small thermal expansion coefficients of ferritic steel can avoid thermal stress fracture.
Therefore, the ferritic creep-resistant steel is always applied to the piping system. However, the
creep strength of ferritic steel is relatively low compared with those of austenitic creep-resistant
steels due to the high diffusion rates of transition elements in ferritic steels.
Moreover, in these two decades, new W-containing ferritic creep-resistant steels were
developed and applied in boilers with steam temperatures above 600C. The research on creepstrength increase in W-containing ferritic steels is ongoing, aiming the extremely high material
temperature above 650C.
However, the reason why the creep strength of W-containing steels is higher than that of the
steels without W as well as the decisive metallographic strengthening factor has not been
clarified yet. For example, the strengthening mechanism by W addition is attributed to the
solute dragging effect, the stabilization of the M23C6-type carbide through the solution in it, and
the transition element delay effect. There are no hypotheses that explain the strengthening
mechanism by W theoretically. In other words, no studies could explain the creep strengthening
mechanism by the W introduction to ferritic steels.
In this study, the new hypothesis of strengthening mechanism by W in ferritic creep-resistant
steel is proposed, which explains the strengthening mechanism by Cr in the ferritic creepresistant steel, by focusing the grain boundary precipitation, similar precipitation morphology
for both elements.
1. Experimental Procedure
To analyze the effect of W and Cr in ferritic creep-resistant steels, creep strengths and
microstructures were precisely analyzed in model steels with the chemical compositions as
indicated in Table 1. Model steels contain approximately 511% Cr with 2% W to extract the
effect of Cr content for C1C6 in Table 1. Model steels also contain approximately 0.53% W
with 9% Cr to extract the effect of W content.
Commercial ferritic creep-resistant steels contain Nb and V to enhance creep strength. Model
steels contain neither Nb nor V to avoid the strengthening effect of such intragranular fine
precipitates as NbC or VN.
1293
Figure 2: Sampling part of thin foil for the TEM analysis in the creep-suspended and
creep-ruptured specimens.
Creep rupture strength and creep strain curves were measured by the creep test from 600C to
700C. Microstructure development was analyzed using a transmission electron microscope
(TEM). The creep-suspended and -ruptured in the parallel gauge part of the creep specimen are
shown in Fig. 2. The precipitation morphology change and microstructure development with
creep time were analyzed with reference to creep life to understand the metallographic
strengthening factor of the model steels.
The types of precipitates in steels were qualified by the X-ray diffraction analysis on the
extracted residue and the structure was decided by the TEMelectron energy dispersive
spectrometry (EDX) analysis.
The extracted residue from the block specimen was analyzed separately for the precipitation
quantification.
1294
2. Experimental results
2.1 Effect of Cr content on the creep-rupture life
Fig. 3 shows the creep lives of C steels depending on the Cr content. The increase in Cr
content tends to increase the creep lives of C steels. In case of excess Cr, i.e., above 11%, the
Figure 3: Creep-rupture lives of specimens C2, C4, and C6 with increasing Cr content.
creep lives decrease when the applied stress is 80 MPa at 650C and 5060 MPa at 700C. The
microstructures of the specimens are martensite. Therefore, the differences of creep lives were
due to the Cr-content variation.
Figure 4: TEM micrographs of specimens C2, C4, and C5. All C steels consist of the tempered
lath martensite microstructure independent of the Cr content.
Fig. 4 shows the dislocation microstructure of steels C2, C4, and C5 before the creep tests. The
microstructure consists of martensite lath, block, and prior austenite grain boundary. It contains
dislocation at the lath interior. Precipitates on the high-angle grain boundary are also observed.
The microstructure of all C steels seems to be almost similar. Therefore, the creep strength
difference is small for short-time creep tests. This agrees well to the creep lives in Fig. 3.
Figure 5: Comparison of the TEM images between creep-ruptured C4 and C6 at 700C and at
a stress of 60 MPa in the creep test condition.
1295
Fig. 5 compares the TEM images of the creep-ruptured specimens of C4, 9.33 mass% Crcontaining steel, and C6,11.46 mass% Cr-containing steel. C4 ruptured at 295 h, while C6
ruptured at 238 h. The initial applied stress is 60 MPa in both specimens. In the TEM image of
C6, the block width is wider and the precipitation size is larger compared with that of C4. In the
C6 specimen, obvious block boundary migration and disappearance can be observed.
Therefore, the microstructure recovery of C6 was much advanced compared with that of C4
despite the shorter creep exposure time. The advanced microstructure recovery of C6 might
have resulted in the shorter creep life.
In Fig. 5, all precipitates were identified as M23C6-type carbide according to the TEMEDX
analysis and the X-ray diffraction qualification of the extracted electrolytic residue of the
specimen. Therefore, the precipitation size and site seemed to relate to the creep life. While the
M23C6-type carbide was aligned and fine, the creep life may tend to be long.
2.2. Effect of W content on the creep-rupture life
Fig. 6 shows the initial microstructure images of varying W-content specimens, W1, W4, and
W5, by TEM. Initial dislocation microstructures are tempered lath martensite for all specimens.
These microstructures seem to be independent of the W content and similar. The
microstructures consist of prior austenitic grain boundary, block boundaries with precipitates,
and lath boundaries without precipitates.
Figure 6: TEM images of specimens W1, W4, and W5 having different W content. The
initial microstructures of W steels are independent of the W content.
M23C6-type carbide is the precipitate. In case of W6, the W content is 3.05%. Therefore, 2.0%
W precipitates at the grain boundary as Fe2W-type Laves phase [1], according to the
equilibrium phase diagram at 600C. Laves phase precipitation may have increased the number
density of the grain boundary precipitation.
brought forward. Therefore, the optimum W content may exist. According to the commercial
W-containing steel design, the optimum content of 9 mass% Cr steel is approximately 2 mass%.
W precipitates at the high-angle grain boundary; in addition, the precipitation initiation period
and the initiation of the creep strain rate decrease in W-containing 9 mass% Cr steel almost
meet. On the other hand, the time to reach minimum creep rate is shortened by the W-content
increase. This tendency is also observed in the relation between Cr content and its creep life. Cr
and W precipitate almost at the high-angle grain boundary. Fine Cr carbide at the lath interior
will disappear for long-term creep. Therefore, W and Cr possibly have the same effect on the
creep-strength increase through the same mechanism.
3Discussions
3.1. Possible creep strengthening mechanism by the coarse precipitates on the
grain boundary
According to the experimental results, Cr and W possibly increase the creep rupture strength
through the precipitation strengthening mechanism. These results can also be explained as
follows: Cr and W addition increases the precipitates in the specimen, and the precipitates
restrict the dislocation motion for creep exposure up to optimum Cr or W content. Excess W
and Cr accelerate the precipitation and initiation of coarsening. To understand the results
correctly, the new strengthening hypothesis, precipitation strengthening, by examining
precipitates at the high-angle grain boundary is proposed. Intragranular precipitates restrict the
dislocation motion and creep deformation, as well known [3]; the dislocation motion restriction
by the precipitates at the grain boundary has not been studied yet because the grain boundary is
convinced to be a dislocation sink. Therefore, the precipitates at the grain boundary cannot trap
temperatures. Precipitates themselves at the grain boundary are coarse compared with ordinary
intragranular precipitates, MX-type precipitates. Therefore, such precipitates will not restrict
the dislocation motion by the Orowan mechanism. Integrating the conventional concept on
precipitates at grain boundary, the precipitation strengthening effect by the grain boundary
precipitation is almost denied. This conventional concept does not explain the experimental
results in Section 2. Fig. 9 shows the microstructure developments with creep deformation. At
the transition creep period, (a), the narrow block boundary and subgrain microstructure are
dominant. However, the block width increases with creep deformation at (b), minimum creep
rate period, and at (c), acceleration creep period, as indicated by white bidirectional arrows in
the photographs. Finally, the block boundary almost disappears or turns to the grain boundary
with a different character such as the packet or subgrain boundary. Here only the block
boundary moves during creep deformation that is affected by the lath and subgrain
microstructure disappearance. Packet and prior austenitic boundaries never move except the
large deformation by the rupture. The block boundary with low misfit angle preferentially
moves due to the low energy of atom relocation by boundary movement. The block boundary
with high misfit angle is difficult to move due to the high energy of atom relocation. Therefore,
the block boundary with relatively small misfit angle moves with the microstructure recovery,
leaving the precipitates at the prior boundary position. This concept is the block boundary
extension model through boundary migration. In this model, mobile boundary is restricted as
the boundary with small misfit angle between adjacent crystals. The boundary escape stress
from the left precipitate is negligible due to the small attraction energy between the coarse
precipitate and grain boundary. Precipitates at the grain boundary, Fe2W and M23C6, will not
move together with block boundary migration. These are left behind boundary migration and
form the intragranular precipitation lines, as confirmed in Fig. 10. When the dislocation passes
through the interparticle space in a direction perpendicular to the precipitation line, the
dislocation is first trapped by the precipitates and then bulges to the motion direction. This
escape stress of dislocation can be estimated by eq. (1) due to the absorption reaction between
the precipitates and dislocation. This equation is well known as Srolovitz formula [4], the
modified Orowan formula. The threshold stress of the dislocation motion is inversely
proportional to the averaged interparticle space .
Figure 10: Typical residual aligned precipitation lines after block boundary migration
1299
The interparticle surface space decides the threshold stress using eq. (1).
(1)
th = A
MbE 1 L
+ 0.7
ln
4 (1 ) r0
where is the Poissons ratio; M is the Taylors factor; E is the Youngs modulus; r0 is the
of the aligned precipitates with the dislocation motion resistance, as calculated by eq. (1). After
overcoming the residual aligned precipitation line, dislocation initiates glide again to the
precipitation line. If there is a small amount of other dislocations or rare fine M23C6 particles,
the dislocation motion will be a viscous glide. Therefore, the dislocation motion can be
assumed viscous always.
The deformation length of steel, , relates to the dislocation glide distance X as eq. (2). Here,
is the dislocation density. Dislocation glide distance can be assumed as interresidual aligned
precipitation line, and the block width as WB. Therefore, X in eq. (2) can be replaced by WB.
(2)
= bx = bWB
The creep stress glides the dislocation. Therefore, eq. (2) is differentiated by time, as shown in
eq. (3).
(3)
2
dW
b B
M2
dt
Creep strain rate is expressed by the effective internal creep stress e and diffusion coefficient
D at high temperatures, as shown in eq. (4) [5].
m
(4)
th D
= 0
2
E b
= e + th ,
where M and
are constants for each temperature and stress for a material and m is the stress
magnitude of creep deformation. Combining eqs. (3) and (4), creep deformation threshold
stress, th , is expressed as eq. (6).
1
(6)
2 b 3 dWB m
th = E
2
0 DM dt
If all precipitates react with the dislocation as incoherent particles, the threshold stress of the
dislocation overcoming the interparticle space, th , is expressed by eq. (1). Integrating eqs. (1),
(3), (4), and (6), the relationship among creep stress, effective internal creep stress, and creep
threshold stress can be expressed by eq. (7).
1
(7)
MbE
= A
4 (1 )
2 b 3 dW B m
ln + 0.7 + E
2
dt
r0
0 DM
Therefore, the second term on the right-hand side of eq. (7) is the effective internal creep stress.
1301
Time (h)
3
100
200
7.6 1012
7.6 1012
2.5
2.6
e = 0.22MGb
Fig. 12 indicates the image of residual aligned precipitates and its precipitation strengthening
mechanism as the microstructure model after block boundary migration, long-term creep
deformation.
The block width extension rate was expressed as eq. (9), modified from eq. (8). The
precipitation strengthening by the aligned precipitation line appears after block boundary
migration. Therefore, the coarsening of precipitates for long-term creep extends the space of
residual precipitation line, according to eq. (9)
(9)
dW B
MbE 1 L
1 DM 2
= [{ A
[ln + 0.7] } ] m 0 3
dt
E
4 (1 ) r0
2 b
Conclusions
Cr and W effect on the creep strength of W-containing ferritic steels are studied using the new
strengthening hypothesis by the examining the residual aligned precipitates consisting of W and
Cr.
1. Cr-content increase resulted in the creep-life extension up to 10 mass%. Cr content more
than 11% decreased the creep life for 2 mass% W containing steel.
2. W-content increase decreased the creep deformation rate with creep time. However, it
shortened the time to reach the minimum creep rate.
3. Therefore, optimum Cr and W contents may result in the highest creep rupture strength.
4. To understand the effect of W and Cr contents on creep strength, the precipitation
strengthening hypothesis by the precipitates at the block boundary must be introduced.
5. The residual aligned precipitation line is supposedly the obstacle for the dislocation motion
at the interparticle space of the aligned precipitates.
6. The new hypothesis occurs after block boundary migration, long-term creep.
7. On the basis of the hypothesis, the creep strength was expressed as the summation of
threshold creep stress and effective internal creep stress.
8. According to the experimental data of microstructure recovery, the effective internal stress
decreases with creep deformation and vanishes. Finally, the creep deformation mechanism of
ferritic creep-resistant steel may transit from the viscous dislocation gliding mode to the
microstructure recovery driven type mode.
REFERENCES
[1] Y. Hasegawa. T. Muraki, and M. Ohgami, A Grain Size Dependence of a Creep
Deformation of Tungsten Containing High Chromium Ferriric Creep Resistant Steel, J.
Soc. Mat. Sci. Japan, Vol. 52, (2004), pp124-133.
[2] K. Hamada, K. Tokuno and T. Takeda, Dispersion hardening effects of Nb-V precipitates
in Mod.9Cr-1Mo steels, Nuclear Eng. Des. Vol.139, (1993), pp 277-281.
[3] D.J.Srolovitz, R.A.Petkovicluton, M.J.Litton Diffusional relaxation of the dislocationinclusion repulsion, Philosophical Magazine A, Vol. 48, Issue 5, (1983), pp 795-809.
[4] R.W. Lund and W.D. Nix, Acta Mtall., High temperature creep of Ni-ZOCr-2Th02
single crystals vol.24, (1976), p469.
[5] K. Maruyama and H. Nakajima, Materials Science at high temperature strength, published
by Uchida Rokakuho Publishing, (1997), p. 164.
1303
ABSTRACT
In power plants operated at elevated temperatures, the operating life of structural materials
increases. Therefore, it is very important to be able to predict creep strength in long term above
100,000 h. Furthermore, it has been reported that the in the long term, the actual creep strength is
lower than the predicted life. Although this problem has been analyzed, the reasons remain
unclear. In this study, a fracture energy model is used to evaluate the mechanisms of the creep
strength reduction for martensitic steels. In the model, changes in fracture energy with rupture
time are expressed by a power law. The energy density rate is calculated using stress, rupture
elongation, and rupture time. The model indicates two mechanisms of creep strength reduction.
One is the increase in rupture elongation, which leads to reduction in creep strength with
ductility; the other is the decrease in reduction of area, which leads to reduction in creep strength
with brittleness. Difference between the two mechanisms affects creep-fatigue strength. The
study also shows that the equation based on the fracture energy model for creep-fatigue life can
be obtained by a parallel translation of that for creep.
INTRODUCTION
In power plants operated at elevated temperatures, the operating life can exceed 100,000 h.
Structural materials in such plants include low Cr steel in old power plants and 9%12% Cr steel
in newer plants. Recently, it has been reported that the actual creep strength is lower than the
predicted long-term life [1]. Precise prediction of creep strength is necessary for design because
few experimental tests have been performed in the long term. Abrupt decrease in creep strength
in the long term is a concern and therefore investigation of this phenomenon is particularly
important.
To predict creep strength, it is essential to understand the mechanism of creep rupture
mechanism. In the absence of experimental data, creep strength has been quantitatively
extrapolated to the long term. Such extrapolations are usually based on time-temperature
parameters [2-4]. In such methods, the creep-rupture mechanism in the long term is presumed to
be the same as that in short term. However, the rupture mechanism depends on temperature and
stress, and the rupture mechanism in the long term may differ from that in the short term.
Nagae has proposed a fracture energy model for evaluating long-term life. This model has been
used to determine creep-rupture life in an austenitic stainless steel [5]. Creep-rupture life from the
model was compared with that obtained using the LarsonMiller parameter and they were found
to be in agreement under limited conditions. In addition, the fracture energy model has been used
to predict creep-fatigue life in modified 9Cr-1Mo steel [6].
In this study a fracture energy model is proposed and used to evaluate the creep rupture
mechanism and creep strength reduction for Grade 91, and Grade 92 steels. In addition, the
1304
difference in creep-fatigue strength is discussed on the basis of the differences in the creeprupture mechanisms.
EVALUATION METHOD
Fracture Energy Model
Fracture energy may decrease with increasing creep time. In austenitic stainless steels, creep
fracture mode varies from transgranular to intergranular fracture. This is observed using the socalled fracture mechanism maps [7]. The loss of creep-rupture strength in T91 steel is due to
preferential recovery of the lath microstructure in the vicinity of prior austenite grain boundaries
[8-9]. This phenomenon is related to localized deformations. In addition to localized
deformations, coarsened particles result in abrupt reduction in fracture energy because of low
boundary strength or high localized stress.
The reduction in fracture energy is presumed to be expressed by the following power law.
=
(1)
Here, is the time to rupture, A and n are parameters of the material, and is the mean energy
density rate (= ), where is the initial stress and is the rupture elongation. From (1),
we can derive an expression for the creep-rupture curve as follows,
(1)
= 1 1
(1)
(2)
= 1
(3)
(4)
Creep strength depends on rupture elongation and the exponent n. The change in fracture energy
for creep-fatigue is expressed in the same way as for creep, but the mean energy density rate is
different. In creep-fatigue, the mean energy density rate is calculated from the following
equation.
Here is the energy density (= area of the hysteresis loop at half of failure cycles) and
is the time per cycle.
When n is less than unity, (1) shows that the fracture energy decreases with increasing time to
rupture. An abrupt reduction in fracture energy by coarsening of particles results in an abrupt
decrease in n.
Creep Data
We have analyzed creep and creep-fatigue data for modified 9Cr-1Mo steels; the data were
acquired by the Japan Atomic Energy Agency. In addition, we also analyzed creep data in the
Creep Data Sheet published by the National Institute for Materials Science [10-11]. Data for
the modified 9Cr-1Mo steels, T92, and P92 were selected. Hereafter, the modified 9Cr-1Mo
steels are referred to as Grade 91, while T92 and P92 are referred to as Grade 92.
1305
10
Gr.91(823K)
Gr.91(873K)
Gr.91(923K)
Gr.91(973K)
0.1
0.01
0.001
0.0001
0.00001
10
100
1000
10000
Time to rupture / h
(a) Grade 91
1306
100000
1000000
10
Gr.92(823K)
Gr.92(873K)
Gr.92(923K)
Gr.92(973K)
0.1
0.01
0.001
0.0001
0.00001
10
100
1000
10000
Time to rupture / h
100000
1000000
(b) Grade 92
Figure 1: Relationship between energy density rate and time to rupture for (a) Grade 91 and (b)
Grade 92 steels at selected temperatures.
Table 1: Parameters A and n for Grade 91 and 92 steels at various temperatures.
Grade 91
823K
873K
A
75.6
63.0
n
0.92
0.87
923K
55.9
0.82
973K
36.5
0.82
A
78.7
68.2
45.7
128.5
40.8
76.2
Grade 92
n
0.92
0.89
0.89
0.65
0.87
0.65
In contrast, the abrupt decrease in fracture energy due to the decrease in exponent n is related to
the reduction of area. Figure 2 shows the relationship between stress and reduction of area. In
Grade 91, reduction of area is higher than that in Grade 92. The reduction of area in Grade 92 is
significantly lower particularly in the long term. The large decrease in reduction of area
corresponds to the decreased exponent n and is related to localized deformations. Grades 91 and
92 have martensitic lath structures and particles such as carbides and MX carbonitrides, and
Laves phases. Lee et al. reported that cavity formation at coarse particles of Laves phase triggers
brittle intergranular fractures and that a ductile to brittle transition occurs when the Laves phase
1307
reaches an average diameter of 130 nm in Grade 92 [12]. However, Laves phases also precipitate
in Grade 91 [13]. Therefore, there is no clear reason for the decrease in reduction of area
decreases in Grade 92.
According to the fracture energy model, there are two types of mechanisms for the reduction in
creep strength. One is for Grade 91, where there is an increase in rupture elongation at a constant
value of n and then the creep strength decreases with ductility. The other is for Grade 92, where
there is a sudden decrease in n and then the creep strength decreases with brittleness. Although
the change in n for Grade 92 seems unclear within limited data, the decrease in reduction of area
clearly results in the abrupt decrease in n due to sigma phases austenitic stainless steels [5].
Figure 3 shows creep-rupture curves for Grades 91 and 92. The creep strength of Grade 92 is
higher than that of Grade 91. The tendency for creep strength reduction seems to be similar in
both steels at high temperatures, but the creep-rupture mechanisms differ, as described above.
Reduction of area / %
100
Gr.91(823K)
Gr.91(873K)
Gr.91(923K)
Gr.91(973K)
Gr.92(823K)
Gr.92(873K)
Gr.92(923K)
Gr.92(973K)
10
10
100
1000
Stress / MPa
Figure 2: Relationship between stress and reduction of area for Grade 91 and 92 steels at
various temperatures.
The creep strength reduction in both steels is estimated with good agreement from (2). Figure 4
shows an example of the relationship between rupture elongation and stress at 973 K. The
changes in rupture elongation for Grades 91 and 92 are different. The rupture elongation for
Grade 91 slowly decreases and becomes almost constant with decreasing stress. Presuming a
constant rupture elongation in Grade 91, the creep strength at higher temperatures is estimated, as
indicated by the solid lines in Fig.3. For Grade 91, the constant rupture elongation is about 34%
at 973 K. Precipitation hardening and creep resistance become weak by the coarsening of Z
phases and disappearance of MX carbonitrides [14-15], so the rupture elongation probably
increases in lower stress region because creep deformation is easy. In contrast, for Grade 92, the
rupture elongation continues to decrease. Presuming a low value of n and decreased rupture
elongation in Grade 92, the creep strength at higher temperatures is estimated, as indicated by the
dotted lines in Fig.3. The slopes for Grades 91 and 92 are 0.22 and 0.21, respectively.
1308
Therefore, although the creep-rupture mechanisms differ, the slopes of creep strength reduction
are similar.
Gr.91(823K)
Gr.91(873K)
Gr.91(923K)
Gr.91(973K)
Gr.92(823K)
Gr.92(873K)
Gr.92(923K)
Gr.92(973K)
Stress / MPa
1000
100
10
10
100
1000
10000
100000
1000000
Time to rupture / h
Figure 3: Creep rupture curves for Grade 91 and 92 steels.
Rupture elongation / %
100
10
Gr.91(973K)
Gr.92(973K)
1
20
Stress / MPa
1309
200
1310
Moreover, the reduction of area abruptly decreases in weld joints of Grade 91 [18], which is wellknown as Type IV cracking. Creep-fatigue life for weld joints will be estimated to decrease
abruptly.
10
0.1
0.01
0.001
Gr.91(823K)
Gr.91(873K)
Gr.91(823K, Creep-fatigue)
Gr.91(873K, Creep-fatigue)
0.0001
0.00001
10
100
1000
10000
100000
1000000
Time to rupture / h
Figure 5: Prediction of creep-fatigue life from creep life by the fracture energy model for Grade
91 steel.
Table 2: Parameters A and n for creep-fatigue in Grade 91 steel [6].
823K
873K
A
4.15*103
2.25*103
n
0.91
0.85
CONCLUSIONS
According to the proposed fracture energy model, there are two types of mechanisms for the
reduction in creep strength. One is the reduction in creep strength with the increase in rupture
elongation with constant value of the exponent n. The other is the reduction in creep strength due
to decrease in reduction of area with abrupt change in the exponent n. The difference in the creeprupture mechanism results in differences in creep-fatigue life.
1311
The relationship between the time to failure and the energy density rate for creep-fatigue can be
easily obtained by a parallel translation of the relationship for creep. From long-term creep data,
it is estimated that due to the change in the exponent n for creep results in an abrupt decrease in
creep-fatigue life for Grade 92 steel and weld joints of Grade 91 steel.
REFERENCES
[1] Kushima, H., Kimura, K., Abe, F., Degradation behaviour and long-term creep
deformation, Tetsu-to-Hagane, Vol.85 (1999), pp.841-847 (in Japanese).
[2] Larson, F. R., Miller, J., A time-temperature relationship for rupture and creep stresses,
Trans. ASME, Vol.74 (1952), pp.765-771.
[3] Manson, S. S., Haferd, A. M., A linear time-temperature relation for extrapolation of creep
and stress-rupture data, NACA TN 2890, (1953).
[4] Orr, R. L., Sherby, O. D., Dorn, J. E., Correlations of rupture data for metals at elevated
temperatures, Trans. ASM, Vol.46 (1954), pp.113-118.
[5] Nagae, Y., Asayama, T., Extrapolation of creep strength by fracture energy for 316FR
stainless steel at 823K, Proc of ASME 2013 Pressure Vessels & Piping Division
Conference, Paris, France, July. 2013, PVP2013-97807.
[6] Nagae, Y., Evaluation of creep-fatigue life based on fracture energy for modified 9Cr-1Mo
steel, Materials Science and Engineering A, Vol.560 (2013), pp.752-758.
[7] Ashby, M. F., Gandhi, C., Taplin, D. M. R., Fracture-mechanism maps and their
construction for F.C.C. metals and alloys, Acta Metallurgica, Vol.27 (1979), pp.699-729.
[8] Suzuki, K., Kumai, S., Kushima, H., Kimura, K., Abe, F., Heterogeneous recovery and
precipitation of Z phase during long term creep deformation of modified 9Cr-1Mo steel,
Tetsu-to-Hagane, Vol.86 (2000), pp.52-59 (in Japanese).
[9] Kimura, K., Sawada, K., Kushima, H., Creep rupture ductility of creep strength enhanced
ferritic steels, Proc of ASME 2010 Pressure Vessels & Piping Division Conference,
Bellevue, Washington, July. 2010, PVP2010-25297.
[10] NRIM Creep Data Sheet, No.43 (1996).
[11] NIMS Creep Data Sheet, No.48 (2002).
[12] Lee, J. S., Armaki, H. G., Maruyama, K., Muraki, T., Asahi, H., Causes of breakdown of
creep strength in 9Cr-1.8W-0.5Mo-VNb steel, Materials Science and Engineering A,
Vol.428 (2006), pp.270-275.
[13] Hald, J., Creep strength and ductility of 9 to 12% chromium steels, Mater High Temp,
Vol.21 (2004), pp.41-46.
[14] Sawada, K., Kushima, H., Kimura, K., Tabuchi, M., TTP diagrams of Z phase in 9-12% Cr
heat-resistant steels, ISIJ International, Vol.47, No.5 (2007), pp.733-739.
[15] Sawada, K., Kushima, H., Tabuchi, M., Kimura, K., Microstructural changes of T91 steel
during creep under low stress, 9th Liege Conference:Materials for Advanced Power
Engineering 2010, Liege, (2010), pp.172-177.
[16] Lefebvre, D., Ellyin, E., Cyclic response and inelastic strain energy in low cycle fatigue,
Int. J Fatigue, Vol.6, No.1 (1984), pp.9-15.
[17] Takahashi, Y., Gandy, D., Creep-fatigue behavior of grade 92 steel and its predictability,
Proc of ASME 2011 Pressure Vessels & Piping Division Conference, Baltimore, Maryland,
USA, July. 2011, PVP2011-57976.
[18] Takahashi, Y., Tabuchi, M., Evaluation of creep strength reduction factors for welded
joints of HCM12A (P122), Proc of ASME 2006 Pressure Vessels & Piping Division
Conference, Vancouver, BC, Canada, July. 2013, PVP2006-ICPVT-11-93488.
1312
1313
ABSTRACT
9-12%Cr martensitic-ferritic steels continue to be developed for target temperatures of 650C.
This paper reviews the performance of two experimental European steels against the performance
of the better known grade 92 alloy. It comments on the problem of type IV cracking and the effect
of welding variables on cross-weld creep performance. Preliminary results from an on-going
creep test programme are presented in context, and the findings compared with published data.
The author acknowledges the VALID project partners, contributors and funding body: Air
Liquide Welding, Metrode, Polysoude, E.ON New Build & Technology Ltd, UK, Doosan,
Centrica Energy, SSE, Tenaris, TU Chemnitz, The University of Nottingham, The Open
University and UK TSB.
INTRODUCTION
The poor cross-weld creep strength of welded joints compared with that of the parent material has
become a major concern for many operators who have installed creep strength enhanced ferritic
(CSEF) materials without adequate provision for the lower creep performance of welded joints.
Unfortunately, it seems that the detrimental impact of welding on cross-weld creep strength is
worse for the more recent steels, i.e. the weld strength factor (WSF) describing the rupture stress
of weldments relative to parent material [1],[2], see Figure 1.
Failures in welded components operating between 550 and 600C are often located in the heat
affected zone (HAZ) produced by welding. In particular, it is the inter-critical (IC) and finegrained (FG) regions of the HAZ that are known to be creep-weak. Microstructural degradation
of this region leads to void nucleation. Void growth and linkage culminates in distinctive type IV
cracking. The threshold for such cracking is a function of temperature and stress[3] and the type
IV shortfall negates to a large extent the advantages of such steels. In ASME I 2008 weld
strength reduction factors (WSRF) for CSEF steels have been implemented via the efficiency
factor E. At temperatures above 482C the material thickness requirement for seam-welded
constructions has effectively doubled due to the introduction of these factors; see Figure 2.
Researchers have been investigating compositions and heat treatments that improve both the
parent and cross-weld creep rupture strength of such steels, with some outstanding results
particularly for MARBN (martensitic boron nitrogen) steels invented by Japanese researchers
[4],[5]. A short review of the technology and presentation of data from an on-going independent
study of MARBN-type steels is made in the present paper.
UK collaborative project VALID
An on-going project involving those acknowledged in this paper is currently underway. The main
objectives of the investigations involved in this project are:
1) To demonstrate the cross-weld creep strength of selected experimental creep-resistant
steels to industry.
2) Identify and clarify possible benefits in cross-weld creep strength to be gained through
welding process and procedure considerations
3) Develop and demonstrate advanced welding processes for CSEF steels.
Creep rupture test results available from the on-going programme of work are presented and
discussed with reference to published data in this paper.
1314
Parent/Weld Metal
specimen rupture
Threshold
Stress
03D&KRXUV
03D &KRXUV
Type IV
shortfall
Figure 2 Schematic showing the calculated pipe thickness (t) according to ASME I 2007 and
2008, highlighting the difference that a weld strength reduction factor (included in the
efficiency term, E) makes for seam-welded vessels; (P = 5MPa, T = 572C, y = 0.7, C = 0, D
= 864mm). See ASME section 1, PG27.2 for further details of equation terms
1315
Type IV Cracking
Type IV cracking is defined as cracking towards the outer edge of the visible HAZ (Figure 3) [6],
and is understood to be a creep cracking mechanism that occurs after long durations. Types I-III
are associated with fabrication issues and occasionally long term creep-related cracks. By
characterization of the microstructure local to such cracks and by studying the creep rupture
strength of homogeneous simulated HAZ specimens, investigators have identified the type IV
region as the ICHAZ, or more commonly, the FGHAZ [7][8][9][10]. In these regions the thermal
cycle peak temperature is above Ac1 and Ac3 respectively (heating to within the intercritical and
austenitic phase fields). Creep voids nucleate and coalesce in the Type IV region to form local
damage that results in cracking and eventual failure, with a remarkably low total strain to failure.
Understanding the type IV cracking mechanism in detail is not straightforward, but is key to
solving the problem effectively. The key microstructural factor responsible for poor creep
performance in the FGHAZ has been the distribution of M23C6 precipitates. The tempered parent
microstructure features M23C6 precipitates mainly at the prior austenite grain boundaries (PAGB),
and the lath and block boundaries, that make up the martensitic structure. These precipitates
provide grain boundary hardening, and can prevent the recovery and growth of sub-grains and
impede dislocation movement, more so than that associated with Orowan interaction [11]. The
welding thermal cycle associated with the FGHAZ typically features temperatures between 900
and 1100C during welding [12]. The rapid cycle allows re-austenitisation at the peak
temperatures without complete dissolution of the boundary precipitates, despite the temperature
being above the thermodynamic dissolution temperature for M23C6. This results in a
microstructure consisting of precipitates at old boundary positions and at newly-formed
boundaries without any such precipitates or strengthening [13], as shown in Figure 4. The new
boundaries are considered weak, allowing recovery, sub-grain growth and softening to proceed
more quickly [14][15]. Furthermore, there is evidence to suggest that the fine MX precipitates in
the FGHAZ coarsen more quickly during high temperature service, further reducing the creep
resistance of this location[16]. Sawada et al, have measured sub-grain size and the dislocation
density in parent steel and FGHAZ for the creep resistant steel grade E911 [17]. Their study
showed that the initial sub-grain size in the FGHAZ was larger, and that the sub-grains grew more
quickly over the first 10,000hrs at temperature (600C). This was accompanied by a similar trend
in the reduction of dislocation density, i.e. the dislocation density was initially lower in the
FGHAZ and decreased more rapidly in the same time period. It was also reported that Z-phase
(Cr(V,Nb)N) precipitated rapidly and grew faster in the FGHAZ. Z-phase forms by dissolution of
MX particles, and hence reduces further the resistance to dislocation movement [18].
WM
60MPa,
630
C, 6290
hours
80MPa,
630
C,
6290
hrs
Weld metal
Parent HAZ
HAZ
Parent
II
IV
III
Figure 3 Type IV cracking as defined by location [6] and appearance in a 9Cr1MoVN steel.
1316
FGHAZ
900-1000 C
Parent
FGHAZ welding
thermal cycle
main differences: increased B (approx. 0.008%), no W and 1%Co addition [34][35]. At the end of
the COST action, a pipe form of FB2 named PB2 was produced and welded [36]. The on-going
VALID project will produce the first published PB2 creep-test data.
The benefit of B is reported to be related to its combination with M23C6 precipitates, which appear
to retard their coarsening. Hence, the precipitates remain effective for a longer, delaying the onset
of tertiary creep [37][38]. Boron segregates to grain boundaries during austenitising; during
tempering, B at the boundaries is incorporated into the precipitating carbides, giving M23(C,B)6
precipitates [4][39].However, the more extraordinary benefit that B may be able to provide is in
resistance to Type IV cracking. Cross-weld creep strength equal to or close to that of the parent
has been reported for steels containing controlled amounts of B and N [4][5]. Control of the B
and N content, together with increased normalizing temperatures are required to generate the
optimum microstructure without coarse BN precipitates. The other notable feature is the apparent
lack of a FGHAZ despite undisputable evidence that transformation takes place during the
welding thermal cycle [40][41][42][43]. Such alloys are known as MARBN (martensitic boron
nitrogen) steels, and were originally developed at the National Institute for Materials Science
(NIMS) in Japan. They contain nominally 9%Cr, 3%Co and 3%W and hence the classification
9Cr3W3CoVNbBN is commonly used to describe the family. More recently the same concept has
been investigated in Europe at TU Graz, Austria [42], to produce a steel called NPM1 with a
similar composition to those investigated in Japan. A new similar heat called NPM4 has been
tested in the welded condition within the VALID project, in order to assess independently any
benefits in creep strength of the steel to industry.
MATERIALS INVESTIGATED
Grade 92 pipe material from a single heat with an outer diameter (OD) of 406.4mm and a
thickness of 33mm was obtained. The compositional analyses are shown in Table 1. The
normalising and tempering temperatures were 1070C and 780C, respectively.
A sample of PB2 pipe, OD = 218mm, thickness = 31mm was obtained with the composition
shown in Table 2. The austenitising and tempering treatments were 1100C and 780C
respectively.
An experimental melt of NPM4 (MARBN type steel) was made in a vacuum induction furnace
and an ingot 125x125mm cross-section was cast. This ingot was then hot-rolled into a number of
plates with the dimensions: 140x195x20mm. NPM4 represents a refinement of the alloy strategy
employed to produce NPM1. Details of the NPM4 heat have been reported in [44]. Two plate
samples were received at TWI, and are referred to as plates A and B. Both plates were subjected
to a quality heat treatment as follows:
1.
2.
The chemical compositions obtained at TU Graz and TWI are shown in Table 3 alongside the
composition for a MARBN steel developed in Japan called MARBN130 here for ease of
reference [4]. The tempered martensitic microstructure microstructure of Plates B is illustrated in
Figure 5. The prior-austenite grain size was measured to be 110m (This compares to 255 m
reported previously for NPM1[42]). Results for Plate A were not available at the time of writing
Some segregation was identified in the central region of the plates, and efforts were therefore
made to remove the affected areas to provide material suitable for welding.
1318
Table 1 Compositional analyses for the P92 investigated including specification requirements
Heat analysis
Element % wt
C
Mn
0.070.300.13
0.60
0.104
0.518
Product analysis
0.11
0.53
0.016
0.001
0.28
8.7
0.38
0.2
Parent sample
0.11
0.55
0.02
0.008
0.31
8.55
0.47
0.23
Al
0.02
0.01
0.008
B
0.0010.006
0.0016
0.01
0.231
W
1.52.00
1.875
Zr
0.40
Nb
0.040.09
0.069
Ti
Heat analysis
N
0.030.07
0.0496
Ni
ASTM spec.
A335/A335M-11
0.001
0.002
Product analysis
0.0487
0.22
0.01
0.077
1.9524
0.0021
0.002
0.0001
Parent sample
0.055
0.24
0.01
0.09
1.97
0.002
ASTM spec.
A335/A335M-11
Si
0.020
0.010
0.50
0.019
0.001
0.267
Cr
8.509.50
8.68
Mo
0.300.60
0.372
V
0.150.25
0.2
Element, % (m/m)
C
Si
Mn
Cr
Mo
Ni
Al
Melt
0.135
0.076
0.31
0.0058
0.001
9.28
1.51
0.15
0.007
0.19
Product
Parent
specimen
0.129
0.092
0.32
0.007
0.000
9.3
1.53
0.14
0.01
0.19
0.12
N
0.07
O
0.33
Sn
0.009
Nb
0.003
Co
9.63
W
1.73
0.13
Melt
0.026
0.004
0.053
1.33
0.0091
Product
Parent
specimen
0.025
0.004
0.054
1.21
0.083
0.033
1.28
<0.01
0.004
<0.01
0.023
0.0025
<0.01
<0.01
As*
Sb*
0.0006
<0.01
Table 3 Compositional analyses for NPM1 and NPM4 (Heat 1910) and MARBN130
Sample
NPM1
(TU Graz)
NPM4
(TU Graz)
NPM4
(TWI)
MARBN130
Element, %
C
Si
0.074
0.29
Mn
0.44
P
-
S
-
Cr
9.26
Mo
-
Ni
-
As*
-
B
0.012
0.090
0.30
0.51
0.001
0.003
9.26
0.011
0.10
0.33
0.51
0.011
0.009
9.41
0.04
0.04
0.03
0.012
0.074
Al
0.29
Sb*
0.44
Se*
Sn
Co
2.95
2.88
9.28
V
0.21
0.20
W
2.84
2.92
N
0.013
0.010
O
-
0.013
Nb
0.056
0.050
<0.01
<0.005
3.16
0.18
3.13
0.007
0.01
2.91
0.2
3.03
0.002
0.045
NPM1
NPM4
0.004
(TU Graz)
Plate A
<0.01
0.04
(TWI)
MARBN130
*Not UKAS accredited
1319
0.2
Bi*
<0.0
1
Figure 5 Micrographs of parent NPM4 Plate B microstructure after quality heat treatment.
WELDING AND QUALIFICATION
Details of welding and qualificationss for P92 are reported in [45]. Five different welding
processes were employed, and three variations of heat input and resulting HAZ width was used.
The PB2 was welded using three different processes: reduced pressure electron beam (RPEB),
Flux cored arc (FCAW) and narrow gap tungsten inert gas (NGTIG) welding. Qualifications are
reported in [45].
The NPM4 was welded using RPEB in the HV (2G) position. Inspection of the HAZ region
confirmed that the parent prior austenite grain size had been maintained, although the edges were
much less defined than in the parent steel, Fig. 6. Vickers hardness mapping was carried out using
a 1kg load. The parent material hardness ranged from 230-260HV1kg. The softest region was
towards the edge of the visible HAZ (210 - 230HV1kg).
All welds for each material type were subjected to the same post-weld heat treatment (PWHT)
temperature and soak duration, i.e. 760C / 4hrs.
Figure 6. a) Low magnification image of HAZ region in NPM4; b) high magnification image of
HAZ region.
1320
Figure 7 All creep rupture test results collected in the VALID project at the time of writing
Figure 8 Larson-Miller plot showing performance of NPM4 tested within VALID at 675C
together with data obtained from [47] and [5] for other 9Cr3W3CoVNbBN steels tested at 650C
1322
What is more difficult to comprehend are the differences between cross-weld tests carried out for
NPM1 and those carried out for NPM4. (The latter performed significantly better in long-term
tests according to the Larson-Miller plot shown in Figure 8). It is proposed that the key to the
improvement shown for NPM4 cross-weld specimens is mainly a consequence of the reduced N
content of NPM4. Figure 9 shows the solubility limit for BN in a similar 9Cr3W3CoVNbBN type
steel for a normalising temperature of 1150C determined by Sakuraya et al. to have the equation:
Log[%B] = -2.45 log[%N]-6.81
(1)
Above the line (high N concentration) coarse BN precipitates are likely to form and below it the
size and number of BN will be considerably reduced. The compositions of NPM1 and NPM4 are
seen to be on different sides of the line, with NPM4 lying on the side where fewer coarse BN
would be expected. This indicates that more boron would be available in solution to combine with
other precipitates in a beneficial manner. The determination of the line was achieved by direct
observation of precipitates on fracture surfaces for different heats of steel, and agrees well with a
more recent thermodynamic analysis [48]. Secondary factors may be the more vertical fusion line
associated with the RPEB weld and a more rapid welding thermal cycle, which are likely to
provide minor benefits over a multi-pass weld process.
The composition of PB2 and P92 are also plotted in Figure 11, showing that the compositions are
non-ideal in terms of soluble boron, and the lack of an austenite memory effect (suppression of
grain refinement) leads to a less optimised arrangement of precipitates in the HAZ. On-going
testing of PB2 material in the VALID project will determine whether or not the PB2 heat has any
advantage over P92. The on-going testing of P92 welded with different processes and parameters
will highlight possible benefits to be gained by alteration of the welding procedure.
NPM4
NPM1
PB2
MARBN130
P92
spec
.
Figure 9 Plot of B and N composition for steels examined in this paper. The solubility line
described by equation (1) for BN precipitates at 1150C derived by Sakuraya et al. [41] is also
included.
1323
CONCLUSIONS
The 9Cr3W3CoVNbBN steel, NPM4, demonstrates exceptional cross-weld performance in
comparison with other data for steels of this type reported previously. The improvement is
attributed to a more optimised quality heat treatment and composition particularly with regard to
maximising soluble boron and minimising coarse BN precipitates.
The cross-weld creep rupture strength of 9Cr3W3CoVNbBN steels reviewed is at least
comparable to the parent creep rupture strength of P92 over the test durations reported. It
therefore appears to be an alloy concept worth further exploration and scaling-up in order to
identify true potential in pipe or pressure vessel form.
PB2 has a less optimal B and N content and heat treatment compared to the 9Cr3W3CoVNbBN
steels according to the theories connecting these factors to creep performance. However, there is
insufficient data at present to comment fully on its performance. On-going work will seek to
clarify its potential, particularly compared to the cast and forged products (CB2 and FB2), which
are currently finding a market.
ACKNOWLEDGEMENTS
Verified Approaches to Life Management & Improved Design of High Temperature Steels for
Advanced Steam Plants VALID is a project is managed by TWI Ltd, and is partly funded by
the UK TSB. The authors acknowledge the project partners: Air Liquide Welding, Metrode,
Polysoude and TWI process groups, for supplying weldments; E.ON New Build & Technology
Ltd, UK and Doosan for performing the creep tests, as well as Centrica Energy and SSE for their
contribution as end users. Additional contributors to the project are also acknowledged: Tenaris,
TU Chemnitz, The University of Nottingham and The Open University. The support of Dr David
Abson, formerly of TWI, who helped edit this document, is also gratefully acknowledged.
REFERENCES
[1]
K. A. and M. K. Schubert J, Determination of weld strength factors for the creep rupture
strength of welded joints, in Int Conf on Creep and Fracture in High Temperature
Components Design & Life Assessment Issues, 2005.
[2]
[3]
K. Bell, An analysis of published creep rupture data for modified 9%Cr steel
weldments, 1997.
[4]
F. Abe, High performance creep resistant steels for 21st century power plants, in Proc.
1st Conf. on Super high strength steels, 2005, p. Paper 84.
[5]
[6]
[7]
[8]
[9]
F. Abe, R&D of advanced ferritic steels for 650uC USC boilers, in Proc. Int. Workshop
on The innovative structural materials for infrastructure in 21st century, 2000, pp.
119129.
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
1325
[19]
[20]
T. H. Hyde, W. Sun, A. A. Becker, and J. Williams, Effect of weld angle and axial load
on the creep failure behaviour of an internally pressurised thick walled CrMoV pipe
weld, International Journal of Pressure Vessels and Piping, vol. 78, pp. 365372, 2001.
[21]
D. W. J. Tanner, W. Sun, and T. H. Hyde, The effect of weld fusion zone angle in a
cross-weld specimen under creep, in 12th International Conference on Creep and
Fracture of Engineering materials and Structures, 2012, no. May, p. B40.
[22]
[23]
F. Abe and M. Tabuchi, Microstructure and creep strength of welds in advanced ferritic
power plant steels, Science and Technology of Welding, vol. 9, no. 1, pp. 2230, 2004.
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
V. K. Sikka, Method for welding chromium molybdenum steels, U.S. Patent 4, 612,
0701986.
1326
[32]
[33]
[34]
[35]
J. S. Rothwell and D. J. Abson, Performance of weldments in advanced 9%Cr steel FB2', Materials at High Temperatures, vol. 27, no. 3, pp. 253264, 2010.
[36]
[37]
[38]
H. O. Andren and A. Golpayegani, Creep Resistant High Boron 9-12% Chromium Steels
for Steam Power Plants, New Developments and Applications of High Strength Steels,
vol. 1, pp. 265272, 2008.
[39]
[40]
R. W. Fountain and J. Chipman, Solubility and Precipitation of boron nitride in ironboron alloys, Trans. Metall. Soc. AIME, vol. 224, pp. 599605, 1962.
[41]
[42]
P. Mayr, Weldability of modern 9%C steels for application in USC power plants, TU
Graz, 2007.
[43]
[44]
1327
[45]
M. Consonni and J. S. Rothwell, Welding of high temperature Grade 92 and PB2 steel
with advanced arc processes, in 66th IIW International Conference, 2013, p. Under
preparation.
[46]
[47]
P. Mayr, C. Schlacher, and S. Mitsche, Critical issues with creep exposed ferriticmartensitic welded joints for thermal power plants Chennai.pdf, in International
Conference of the IIW, 2011, pp. 417 425.
[48]
P. Mayr, F. Mendez Martin, I. Holzer, A. Agero, V. Gonzlez, S. Baumgartner, and H.H. Cerjak, Experience with 9Cr3W3CoVNbBN base material and crosswelds at 650C
for implementation in USC power plants., in Proc. of the 3rd Symposium on Heat
Resistant Steels and Alloys for High Efficiency USC Power Plants, 2009, On CDROM.
1328
ABSTRACT
A new 9%Cr steel with high boron levels (boron steel) has been developed by optimization
studies on steels and alloys that are applicable to advanced ultra-super critical power plants
operated at steam conditions of 700C and 30 MPa and above. The composition and heat
treatment condition of boron steel was optimized by the initial hardness, tensile strength, yield
strength, and Charpy impact values on the basis of the fundamental investigation with the
stability of the long-term creep strength. Creep testing of boron steel was conducted at
temperatures between 600 and 700C. The creep rupture strength at 625C and 105 h is estimated
to be 122 MPa for the present 9% Cr steel with high boron by Larson-Miller parameter method.
Furthermore, physical properties as a function of temperature, metallurgical properties, tensile
properties, and toughness were examined to evaluate the applicability of the steel for a 625C
USC power plant boiler. It was also confirmed that the steel has good workability for such an
application by the flaring and flattening tests with tube specimens having an outer diameter of
approximately 55 mm.
INTRODUCTION
A new 9%Cr steel with high boron levels (boron steel) has been developed by optimization
studies on steels and alloys that are applicable to advanced ultra-super critical power plants
operated at steam conditions of 700C and 30 MPa and above. Also, a fundamental investigation
into the creep degradation and failure mechanisms of high Cr ferritic steels based on MARBN [1]
in the national R&D project on Fundamental Technology for Steel Materials with Enhanced
Strength and Functionality were conducted. It has been recognized that the developed ferritic
steel has a creep rupture strength of 100 MPa at 650C for 100,000 h, and its weldment has an
excellent creep rupture strength with 0.7 and above of weld strength reduction factors.
However, in real, the development of steel that can be utilized over 625C is extremely important
in the present coal-fired electricity generating plant, because there are problems such as CO 2
1329
exhaust and electric power supply that are more serious than nuclear power generation in Japan.
Therefore, boron steel was optimized and examined on the basis of the fundamental investigation
with the stability of long-term creep strength for applications to a 625C USC power plant and a
replacement of the present boiler tube. Furthermore, boron steel was confirmed in terms of
applicability for actual power plant through the new concept that the exposure trial test is
replaced by the internal pressure creep test.
The most important aspect is to realize defect-free tubes and pipes of 9% Cr steel with high boron
and to confirm long-term reliability at elevated temperature. In this paper, physical and,
mechanical properties, welding, and internal pressure creep properties were examined to evaluate
the applicability of the optimized boron steel for a creep rupture strength of 100 MPa at 625C
for 100,000 h.
EXPERIMENTAL PROCEDURE
Chemical composition
The chemical composition of four typical heats is given in Table 1. The chemical composition of
tubes (Heats 5 and 6) are same as those of plates (Heats 2 and 1), respectively.
Table 1: Chemical composition of plates (mass%)
No.
Heat 1
Heat 2
Heat 3
Heat 7
C
0.081
0.071
0.097
0.068
Si
0.27
0.19
0.20
0.18
Mn
0.51
0.50
0.50
0.51
Cr
8.96
8.92
8.94
8.95
V
0.20
0.20
0.20
0.18
Nb
0.051
0.051
0.051
0.053
W
2.82
2.74
2.70
2.71
Co
2.80
2.43
2.43
2.79
B
0.013
0.013
0.013
0.014
1330
Heat treatment
The heat treatment condition of boron steel was optimized by initial hardness, tensile strength,
yield strength, and Charpy impact values at room temperature on the basis of the fundamental
investigation with the stability of long-term creep strength as follows:
(i) Vickers hardness is approximately 220 at 10 kg
(ii) Charpy impact value is above 80 J/cm2 at 20C
(iii) Tensile strength is 660700 MPa
(iv) Yield strength is approximately 500 MPa
Consequently, the typical heat treatment was optimized as follows:
Normalization: 1100C 4h / air cooling
Tempering: 790C 4h / air cooling
Microstructure
Figure 2 shows the typical microstructure of Heat 2 after tempering at 790C for 4 h. The
structure is composed of tempered martensite.
1331
Figure 3: Crystal orientation map (a) and boundary map (b) using SEM-EBSD.
MECHANICAL PROPERTIES
Tensile properties
Yield and tensile strength values, elongation and reduction of area at room and elevated
temperatures are plotted with minimum values of P92 [2], which are shown by broken lines in
Figure 4. Although Heat 7 has slightly high strength, the elastic properties of boron steels are
similar to those of P92.
Tensile strength
Reduction of Area
Elongation
Yield strength
Gr.92
Gr.92
1332
Crystallinity (%)
Impact test
Transition temperature
625
600
650
675
700
1333
600
625
650
675
700
1334
700
675
650
600
Youngs modulus
Thermal expansion
Thermal expansion was measured by the
extension rod method. As shown in Figure
11, the thermal expansion is similar to
those of P92 [2] until 600C. It gradually
differs at a higher temperature since the
curve of P92 has shelving with temperature
elevation.
1335
Shear modulus
Thermal conductivity
Thermal conductivity is the product of density, specific heat, thermal diffusivity, which were
measured by Archimedes method, adiabatic scanning calorimetry, and laserflash method,
respectively. The typical density is 7.890 g/cm3 at room temperature. As shown in Figure 12, the
thermal conductivity of boron steel increases with temperature elevation.
CCT DIAGRAM
Figure 13 shows the complete CCT diagram of Heat 2. Depending on the chemical composition,
the Ac 1 temperature was found to be between 820 and 830C, and the Ac 3 temperature around
900C. The ferrite nose, observed in P92, was not observed in the CCT diagram of boron steel.
1000
Ac3:908
900
Ac1:833
800
Temperature ()
700
600
500
Ms
400
300
Vickers
Hardness
200
1 Kgf
No.6
397
No.8
No.7
No.12
392
386
100
1
10
Mf
No.9
100
1000
388
No.10
No.11
398
No.13
397
10000
No.14
395
100000
Figure 14 shows the microstructure of the slowest cooling condition, No.14 in CCT diagram. The
structure is composed of martensite.
Figure 14: Microstructure of the slowest cooling condition, No.14 in CCT diagram
MACHINABILITY
Flattening test
The flattening test of tube (Heat 5) was performed
on the Japanese Industrial Standards, JIS G3458.
The outer diameter, H, of the pressed tubes was
calculated by the following equation:
=
(1 + )
T: thickness of tube
D: outer diameter of tube
E: constant parameter, 0.08
1337
o
625oC 600 C
650oC
675oC
700oC
P92 625 oC
P92 650 oC
P92 675 oC
p (D t )
2t
where P, D, and t are the stress, outer diameter, and thickness, respectively.
Figure 19 shows the stressrupture time
curve of the internal pressure creep test.
Open marks show the creep data of
boron steel, while filled marks show
those of Gr.91, Gr.122 and Gr.92. The
solid lines show the LMP curves of
uniaxial creep test results for the
650
welded joints of 9% Cr steel with high
boron shown in Fig. 18. Uniaxial creep
strength of the base metal of boron steel
were almost equal to the internal
700
675
pressure creep strength of the welded
joint of boron steel, regardless of one or
two seam welds. Furthermore, the
internal pressure creep test results on
the creep strength enhanced ferritic
steels (CSEFS), such as Gr.91, Gr.92,
and Gr.122, were inferior to that of
boron steel.
Figure 19: Stressrupture time curve of
Figure 20 show the tubes of boron steel
internal pressure creep test
and Gr.122 that have been already
ruptured. Regarding the damage
location of ruptured steel, a crack was observed in the base metal in boron steel, which was crept
at 650C with 150 MPa corresponding to 43 MPa as hoop stress and ruptured for 435 h. On the
other hand, a crack was observed in the interface of weld metal/base metal in Gr.122 at 650C
with 100 MPa corresponding to 27 MPa as hoop stress and ruptured for 2556 h. The
demonstration test was advanced successfully. The internal pressure creep test results for welded
tubes of the 9% Cr steel with high boron shown in Fig.19 completely coincide with the uniaxial
test results for welded joints shown in Fig. 18 and also for base metal shown in Fig.6, indicating
highly resistant to Type IV damage in welded joints. We are now continuing long-term internal
pressure creep tests.
1339
Figure 20:Weldments after internal pressure creep test. Boron steel, Heat 2
(a) and Gr.122 steel (b)
CONCLUSION
New 9% Cr steel with high boron levels (boron steel) was evaluated on the basis of a fundamental
investigation with the stability of long-term creep strength. Tubes and plates with a good
adjustment of the chemical composition and heat treatment condition were produced without any
trouble. The creep rupture strength at 625 C and 105 h is estimated to be 122 MPa for the
present 9% Cr steel with high boron by Larson-Miller parameter method. Furthermore, physical,
mechanical, and tensile properties as well as toughness at room and elevated temperatures were
similar to those of Gr.92. By the flaring and flattening test, it was also confirmed that the tube
specimens of boron steel has good workability for such an application. The creep strength of
welded joint is similar to that of base metals. The internal pressure creep test results for welded
tubes of the 9% Cr steel with high boron completely coincide with the uniaxial test results for
welded joints and also for base metal, indicating highly resistant to Type IV damage in welded
joints. We are now continuing long-term internal pressure creep tests.
ACKNOWLEDGMENT
This work was conducted as a part of research activities of Fundamental Studies on
Technologies for Steel Materials with Enhanced Strength and Functions by Consortium of the
Japan Research and Development Center for Metals (JRCM) and Research and Development
Program for the Innovatively High Strength and High Performance steels. Financial support
from New Energy and Industrial Technology Development Organization (NEDO) is greatly
acknowledged. The authors would like to express their sincere gratitude to Prof. Fujimitsu
Masuyama and Dr. Masatsugu Yaguchi of the Central Research Institute of Electric Power
Industry, Prof. Hideharu Nakashima and Dr. Masatoshi Mitsuhara of Kyushu University, Prof.
Yasuharu Shirai and Dr. Kazuki Sugita of Kyoto University, Prof. Yoshinori Murata of Nagoya
University, Prof. Koichi Maruyama of Tohoku University for their sincere collaborative activities
to the ASME code application in the NEDO project.
REFERENCE
[2] T92 data package for ASME, 1st edition (1994), and 2nd edition (1998).
[3] R. W. Swindeman, Private communication, Task Group on Data Analysis, Section II on
Materials, ASME Boiler and Pressure Vessel Code Committee (2012).
1340
ABSTRACT
In order to develop an Fe/Ni dissimilar-weld rotor structure for an Advanced Ultra Super
Critical turbine, fundamental studies on the metallurgical properties of Fe/Ni welds are needed. In
the work reported in this paper, we studied the microstructure evolution and creep rupture
properties of Fe/Ni weld joints with different compositions. Investigation of thermally aged Fe/Ni
diffusion couples revealed that Fe-based ferritic steel and Alloy 617 weld joints with a large
difference in Cr content showed strong C diffusion at the weld interface. This decreased the creep
rupture life of the weld joint, caused by coarsening of a martensitic structure near the interface.
Analysis using Fe/Ni diffusion couples and thermodynamic calculations suggested that the
driving force of C diffusion is the chemical potential gradient at the interface, and the difference
in Cr content between Fe and Ni accelerates the C diffusion.
1. INTRODUCTION
To improve the efficiency of coal-fired power generation plants, research and development of
700 C-class Advanced Ultra Super Critical (A-USC) generation systems is underway in the US,
Europe, and Japan15). In the national project in Japan, five years of fundamental research on
boiler and turbine materials (Phase I: 20082012) has been completed57). For the next four years,
demonstration plants will be developed to confirm manufacturing processes and system reliability
(Phase II: 20132016).
To realize highly efficient turbine rotors, the weld structure is important for minimizing
material costs while maintaining efficiency. A welded rotor consists of a high-strength Ni-based
superalloy for high-temperature sections and a commercial Fe-based ferritic heat-resistant steel
for low-temperature sections5,6). The weld section of the A-USC rotor must exhibit suitable
mechanical properties at high-temperature, such as creep and fatigue behavior. There have been a
few studies of the microstructure and creep behavior in Fe/Fe or Ni/Ni similar welds812);
however, there have been almost no fundamental studies on Fe/Ni dissimilar welds.
In this study, we investigated the microstructure evolution and creep properties of
representative Fe/Ni dissimilar weld joints. Based on our findings, we determined an alloy
composition suitable for A-USC weld rotors. Various combinations of Fe and Ni diffusion
couples were prepared to investigate the effect of material composition on microstructure
evolution. Creep rupture tests using Fe/Ni weld joints were also conducted to investigate the
effect of microstructure evolution on creep properties.
1341
2. EXPERIMENTAL PROCEDURE
2.1 Manufacturing Fe/Ni Diffusion Couples
Table 1 shows the nominal compositions of Fe-based ferritic heat-resistant steels and an Nibased superalloy used for the diffusion couples. For the ferritic steels, we selected CrMoV steel,
2.25Cr steel, 9Cr steel and 12Cr steel, which are commercially used in conventional rotors, tubes
and pipes. The major difference in the composition of the four steels was the Cr content, which
ranged from 1 to 11 wt.%. As a Ni-based alloy with good weldability and creep rupture strength,
we selected ASTM UNS N06617 (InconelAlloy 617referred to as Alloy 617 below).
Figure 1(a) shows an example of a manufactured Fe/Ni diffusion couple. It was
manufactured by welding 5 to 10 layers of the Alloy 617 weld metal on top of a ferritic steel
block. In order to clearly understand the influence of the material composition on the
microstructure, welding was purposely performed to minimize the heat input and dilution of the
ferritic steel blocks.
To investigate the change in microstructure with aging, diffusion couples were thermally aged
at 640 C for 300 h and 1000 h. The microstructure of the Fe/Ni weld sections was observed by
scanning ion microscopy (SIM) and transmission electron microscopy (TEM). The composition
of the weld sections was analyzed by X-ray microprobe analysis (EPMA) and energy dispersive
X-ray spectroscopy (EDX).
Table 1 Nominal compositions of Fe-based ferritic steels and an Ni-based superalloy
used in the diffusion couples.
Alloy
Fe-based
Ni-based
CrMoV Steel
2.25Cr Steel
9Cr Steel
12Cr Steel
Alloy 617
Weld Metal
Fe
bal.
bal.
bal.
bal.
Ni
0.5
0.7
0.8
Nominal Compositionwt.%
Cr
Co
Mo
V
Al
Ti
1.1
1.2
0.3
2.3
1.0
0.3
9.0
0.9
0.2
10.5
1.0
0.2
-
bal.
23.0
12.5
9.0
1.2
0.6
Nb
0.03
0.04
0.07
C
0.30
0.10
0.07
0.14
0.10
1342
Weld Metal
(Alloy 617)
Weld Metal
(Alloy 617)
Ni-based Alloy
(TOS1X)
Fe-based Steel
(CrMoV)
Fe-based Steel
(CrMoV)
b
Figure 1 Examples of manufactured Fe/Ni diffusion couple and weld joint,
showing (a) CrMoV steel/Alloy 617 diffusion couple and (b) CrMoV/Alloy
617 (Weld metal)/TOS1X weld joint.
1343
2.25Cr/Alloy 617
9Cr/Alloy 617
12Cr/Alloy 617
As-Welded
CrMoV/Alloy 617
640/300h Aged
50
100m
m
Figure 2 SIM images of as-welded (a-d) and 640 C/300 h aged (e-h) Fe/Alloy 617
diffusion couples: (a,e) CrMoV steel/Alloy 617, (b,f) 2.25Cr steel/Alloy 617, (c,g) 9Cr
steel/Alloy 617, (d,h) 12Cr steel/Alloy 617. Top: Alloy 617; Bottom: Ferritic steel blocks.
2.25Cr/Alloy 617
9Cr/Alloy 617
12Cr/Alloy 617
As-Welded
CrMoV/Alloy 617
640/300h Aged
100
100m
m
Figure 3 EPMA analysis of C of as-welded (a-d) and 640 C/300 h aged (e-h) Fe/Alloy
617 diffusion couples:(a,e) CrMoV steel/Alloy 617, (b,f) 2.25Cr steel/Alloy 617, (c,g) 9Cr
steel/Alloy 617, (d,h) 12Cr steel/Alloy 617. Top: Alloy 617; Bottom: Ferritic steel blocks.
1344
Figure 4 shows EPMA quantitative analysis of the C distribution at the weld sections of
CrMoV steel/Alloy 617 (a) and 12Cr steel/Alloy 617 (b) diffusion couples with and without aging.
The as-welded specimen of CrMoV steel/Alloy 617 had a 0.2 wt.% difference in C content at the
interface, which was not clearly identified in the mapping analysis. This suggests that CrMoV
steel and Alloy 617 contain nominal compositions of C at the interface in the as-welded state.
However, for the aged specimen of CrMoV steel/Alloy 617, the C content of CrMoV steel
decreased by 0.2 wt.%, and that of Alloy 617 increased rapidly to 1.4 wt.%, which is much higher
than the initial content. The decrease in C content of the CrMoV steel and the increase in C
content of Alloy 617 suggests that C diffused at the interface from the CrMoV steel side to the
Alloy 617 side.
The as-welded specimen of 12Cr steel/Alloy 617 (b) also had a small difference in C content.
However, in contrast to the above-mentioned CrMoV/Alloy 617, it did not exhibit strong
diffusion of C at the interface with aging. From the mapping and quantitative analysis of C at the
weld interface, a combination of ferritic steel and Alloy 617 with a large difference in Cr content
tends to show higher C diffusion than that with a small difference in Cr content.
(a)
C Content wt.%
1.5
As-Welded
640/300h Aged
1.0
Alloy 617
0.10wt.%C
CrMoV Steel
0.30wt.%C
0.5
0
(b)
C Content wt.%
1.5
1.0
0.5
0
-200
Alloy 617
0.10wt.%C
12Cr Steel
0.14wt.%C
-100
100
200
1345
Figure 5 shows TEM bright-field images of as-welded (a) and 640 C/1000 h aged (b)
specimens of CrMoV steel/Alloy 617 diffusion couples. For the as-welded specimen, Alloy 617
and CrMoV showed austenitic and fine martensitic structures, respectively. However, for the
aged specimen, fine precipitates with a particle size less than 100 nm were found in Alloy 617,
and the martensitic structure of CrMoV steel was coarsened. Moreover, a thin film-like phase
with a thickness of 500 nm to 1 m appeared along the CrMoV steel/Alloy 617 interface. The
results of TEM-EDX composition analysis of the precipitates observed in the aged specimen are
listed in Table 2. Fine particles found in the Alloy 617 austenite region (A) contained Fe, Cr, Mo,
and Ni and had similar Cr and Mo content as coarse carbides found in the CrMoV martensite
region (B). Taking into account that the Alloy 617 region showed a large increase in C content,
the observed precipitates are likely be carbides. The thin film-like phase contained 94.7 at.% of
Fe, which suggests that this phase may be recrystallized -Fe. The microstructural changes in the
CrMoV steel with aging, such as coarsening of the martensitic structure and formation of -Fe
near the Fe/Ni interface, are the results of a large decrease in C content.
As-Welded
640/1000h Aged
ACr,Mo Carbides
C-Fe
Cr,Mo23C6
500 nm
Figure 5 TEM images of CrMoV steel/Alloy 617 diffusion couples: (a) as-welded
and (b) 640 C/1000 h aged. Top: Alloy 617; Bottom: Ferritic steel blocks.
Table 2 TEM-EDX composition analysis of precipitates observed in
microstructure of 640 C/1000 h aged CrMoV steel/Alloy 617
diffusion couple.
Point
A
Composition at.%
Cr
Mo
Fe
Ni
45.5
16.8
23.1
10.4
Co
Predicted
Phases
4.1
Cr,Mo-Carbides
57.3
1.9
32.7
8.1
(Cr,Mo)23C6
94.7
3.1
2.2
-Fe
1346
1000
(a)
100
10
18.5
19
19.5
Larson-Miller
20
20.5
21
21.5
Parameter103C=20
1000
(b)
100
10
23
24
25
Larson-Miller
26
27
Parameter103C=25
(b)
Alloy 617
CrMoV
Steel
Creep
Voids
1mm
(c)
Alloy 617
12Cr Steel
1mm
1348
Alloy 617
Carbides
Shear Stress
Shear Stress
CrMoV
Steel
Creep
Voids
Alloy 617
Shear Stress
Shear Stress
12Cr
Steel
J M
Darkens example, we calculated the chemical potential of C(c,) for the as-welded and
640 C/300 h aged samples of CrMoV/Alloy 617 shown in Figure 4. The c of CrMoV steel and
Alloy 617 at the interface were obtained from a thermodynamic equilibrium calculation using
ThermoCalcTM software. The calculation showed that the chemical potential gradient of C (c)
between CrMoV steel and Alloy 617 decreased with thermal aging (from 32.2 kJ/mol to 21.6
kJ/mol). This result confirms that the driving force of C diffusion is the chemical potential
gradient. According to this diffusion mechanism, the alloy of Fe and Ni should be carefully
selected to reduce the chemical potential gradient.
Figure 9 shows c of the four ferritic steels and Alloy 617 used in this study, together with
16,17)
. According to this estimation, the
other representative Fe- and Ni-based heat-resistant alloys
Cr content had a strong influence on c for the Fe-based and Ni-based alloys. Combinations like
CrMoV steel and Alloy 617, in which the difference in Cr content between Fe and Ni is relatively
large, are much more likely to exhibit C diffusion. Thus, the combinations with a small difference
in the Cr content, such as 12Cr steel and Alloy 617, are suitable candidates for rotor weld
sections.
20
S45C
CrMoV
12Cr
2.25Cr
15Cr
9Cr
-20
SUS316
SUS310S
SUS304
CCrMoV/617
-40
Alloy 82
-60
Fe-base Ferritic Steel
Fe-base Austenitic Steel
Ni-base Alloy
-80
Alloy 617
Alloy 625
-100
0
10
15
20
25
30
Cr Content wt.%
Figure 9 Chemical potential of C (c) of representative Fe-based
ferritic and austenitic steels and Ni-based superalloys, obtained by
thermodynamic equilibrium calculation.
1350
4. CONCLUSIONS
In this study, we investigated the microstructure evolution and creep rupture properties of
Fe/Ni weld joints for A-USC turbine rotors. The following conclusions were obtained:
1.
2.
3.
For the aged specimens of CrMoV steel/Alloy 617 and 2.25Cr steel/Alloy 617, a large
increase in the C content in Alloy 617 and decrease in the ferritic steel occurred near the weld
interface. Due to C diffusion, the martensitic structure was coarsened in the CrMoV steel,
and very fine precipitation of carbides was observed in Alloy 617.
The creep rupture of the Fe/Ni weld is mainly caused by the shear stress between the alloys.
In the case where C diffuses at the interface, the rupture is caused by coarsening of the
martensitic structure near the interface.
The behavior of C diffusion in this study can be explained by the chemical potential gradient
of C (c). According to the calculation of c and the diffusion couple experiments,
combinations of Fe/Ni in which the difference in Cr content between Fe and Ni is relatively
small are suitable candidates for rotor weld sections.
ACKNOWLEDGMENTS
This work was conducted as a part of the A-USC national project in Japan, funded by the
Ministry of Economy Trade and Industry.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
1351
strengthening" (GBPS) mechanism [10,11]. And the sufficient oxidation resistance to sustain the
creep strength under severe environment of steam condition is also needed to realize the A-USC
power plant. It was found that the Fe-20Cr-30Ni-2Nb steel exhibits superior steam oxidation
resistance to the existing steels at 973 K [12], whereas the steam oxidation resistance under
constant stress and its effect on the creep strength, in particular GBPS mechanism by TCP Laves
phase should be important issues.
In this study, in order to indentify whether the grain boundary TCP Laves phase can increase the
creep rupture strength at 1073 K under steam atmosphere, we have examined creep properties of
the present steels with different area fractions of TCP Laves phase on grain boundary () at 1073
K under air and steam atmospheres.
EXPERIMENTAL PROCEDURES
The chemical composition of our studied steels were Fe-20Cr-30Ni-2Nb at.% and that with 0.03
at.% B. Hereafter, the former and the latter are expressed by base steel and B-doped steel,
respectively. The addition of boron is to intentionally increase the area fraction of Laves phase on
grain boundaries (), based on our previous result [9]. These steels were prepared by vacuum
induction melting and hot-forged into rods with a diameter of 12 mm at 1553 K. Subsequently,
they were solution treated at 1473-1523 K/2 h to adjust the grain size to about 150 m. The
solution treated steels were pre-aged at 1073 K to control . Their microstructures were observed
by using a scanning electron microscope (SEM). We have measured the length of grain
boundaries covered by Laves phase particles and the total length of grain boundaries on the
mechanically polished samples, which can give a quantitative value of . The total length of
measured grain boundaries was more than 1000 m for each specimen. The creep tests were
conducted at 1073 K /70 MPa in air and steam atmospheres. In particular, creep test in steam
atmosphere was conducted by using our originally designed creep test machine. Its schematic
illustration is shown in Fig. 1. All components of extensometers, waterproof differential liner
valuable transducers and a creep test specimen were shielded by a quartz tube chamber, which
enables us to measure the precise creep elongation under steam atmosphere. Water was pumped
up at 4.0 x 10-3 l / min and then changed to steam by pre-heaters, followed by steam flowing into
Figure 1: (a) Appearance of the creep test machine used in this study and (b) its schematic
illustration.
1353
the chamber. Note that bubbling water in the storage tank can keep a constant amount of dissolved
oxygen in flowing water. We have observed microstructures of different microscopically strained
regions in the gage portion of creep ruptured specimens. The macroscopic strain was determined
by measuring the area reduction for the gage portion of the ruptured specimens.
RESULTS
Microstructure prior to Creep Test
In order to control the area fraction of grain boundary Laves phase (), the steels were
intentionally aged at 1073 K, where only the Fe 2 Nb Laves phase precipitates [8, 9]. Figure 2
shows back scattering electron images (BEIs) showing microstructures of the base and B-doped
steels aged at 1073 K for 240 h and 1200 h. In the base steel aged for 240 h, there are precipitates
of Fe 2 Nb Laves phase with a length of about 1 m on grain boundaries ( = 43%). In grain
interior, the plate-shaped Laves phase with a length of about 1 m precipitates homogenously.
After 1200 h, the precipitates of Laves phase cover a half area of grain boundaries ( = 52%),
whereas the precipitation morphology of Laves phase within grains slightly changes. In B-doped
steel aged for 240 h, a large part of grain boundaries is covered by precipitates of Laves phase (
= 80%). increases to 89% after 1200 h. The morphology of the Laves phase precipitated in
grain interior is coarser than that observed in the base steel. Its precipitation density becomes
lower after 1200 h aging.
Figure 2: Microstructures of (a, b) base and (c, d) B-doped steels aged at 1073 K for (a, c) 240 h
and (b, d) 1200 h.
Creep Properties
Figure 3 shows (a) creep rate/time curves and (b) creep rate/strain curves of the solution treated
base and B-doped steels at 1073 K/70 MPa in air and steam atmospheres. Base steel exhibits a
minimum creep rate of 1.1 x10-3, which is independent of the atmosphere. Its rupture life (t r ) and
rupture strain () under air are almost same to those under steam atmosphere. In B-doped steel,
1354
the creep rate decreases to about 2 x 10-4 /h after loading till 1 h, but increases and then keeps
constant creep rates of 8.5 x10-4 in air and 5.0 x10-4 h in steam atmosphere, followed by creep
acceleration. t r under air (293 h) is lower than t r under steam (376 h) ,whereas r under air (0.31)
is higher than r under steam (0.25).
Figure 3: (a) Creep rate/time curves and (b) creep rate/strain curves of base and B-doped steels
(as solution treated) at 1073K/70 MPa.
Figure 4 shows (a) creep rate/time curves and (b) creep rate/ strain curves of the pre-aged (1073
K/240 h) base and B-doped steels at 1073 K/70 MPa in air and steam atmospheres. In all
specimens, the creep rate gradually decreases after loading and then almost keeps a constant rate
in transient creep stage, followed by creep acceleration. These creep curves in steam have a close
overlap with the curves in air. The base steel with = 43 % exhibits a minimum creep rate of 1.6
x 10-3 /h ,which is much higher than one (7.0 x10-4 /h) of the pre-aged B-doped steel with =
80 %. The B-doped steel with = 80 % shows high t r of 825 h, which is more than three times
higher than t r of the base steel with = 43 % (255 h). This clearly indicates that increasing to
80% can substantially increase the creep resistance, resulting in the extension of creep rupture
time. Both steels exhibit large r of about 0.6, which demonstrates that covering grain boundaries
by Laves phase dose not reduce the creep ductility. All data on creep properties of the present
steel (including base and B-doped steels pre-aged at 1073 K/1200 h) at 1073 K/70 MPa are
summarized in Table 1.
Figure 4: (a) creep rate/time curves and (b) creep rate/strain curves of base and B-doped steels
(pre-aged at 1073K/240 h) at 1073K/70 MPa.
1355
Table 1: Creep rupture time and strain of base and B-doped steels tested at 1073 K /70 MPa.
Figure 5: (a, b) Appearances of creep ruptured specimens of base steel with =43% (pre-aged
at 1073 K/240 h) , (c) corresponding macroscopic strain in their gauge portion and (d, e)
optical micrographs of gauge portion of these specimens: (a, d) tested in steam, (b, e) tested
under air.
1356
steam exhibits a slightly smaller creep elongation than that under air. Their macroscopic strains
become higher by approaching the rupture surface and reaches to 0.75 in maximum (Fig. 5 (c)).
The optical micrographs indicates numerous inner cavities and their associated cracks along grain
boundaries in the creep ruptured specimens. It is noteworthy that the ruptured specimens in steam
shows a higher number of cavities than one under air. It is also obvious that the number of voids
and cracks becomes higher by approaching the rupture surface, which indicates higher cavity
density at higher creep strain.
Figure 6 show BEIs showing (a,b) the surface regions and (c,d) the inner microstructures in creep
ruptured specimens of base steel with = 43 %. A number of cavities and their associated cracks
are observed along grain boundaries perpendicular to stress axis. The cavities are often
surrounded by intergranular oxides underneath the specimen surface. The intergranular oxides
with a width of several tens micrometers are present and grow over 200 m in depth (Fig. 6 (a,b)).
Its depth is lager under steam atmosphere than one under air. On the surface of -Fe grains, the
oxide scale with a mean thickness of 10-20 m is formed, whereas the delamination of oxide scale
locally occurs by creep deformation. Inner microstructure of the crept specimen (Fig. 6 (c,d))
shows slight lower , comparing with microstructures of the steel before creep test (Fig. 2 (a)),
there is scarcely a change in microstructure after the creep test under air and steam atmospheres.
Figure 6: BEIs showing (a, b) the surface of creep ruptured specimens and (c, d) microstructure
of the base steel with = 43% (pre-aged at 1073 K/240 h) in (a, c) steam and (b, d) air
atmospheres. Macroscopic strains of these specimens under steam and air atmospheres are
0.60 and 0.70 , respectively.
1357
Figure 7 shows (a, b) stereographs of creep ruptured specimens of B-doped steel (pre-aged at
1073 K/240 h) with = 80 % in (a) steam and (b) air atmospheres, together with (c) the
corresponding macroscopic strain and (d, e) optical micrographs of the gauge portion in these
specimens. The ruptured specimen of B-doped steel tested in steam exhibits dark green colored
surface with local rusty colored areas (Fig. 7 (a)), as well as the base steel. In the B-doped steel,
the macroscopic strain becomes higher by approaching the rupture surface. These ruptured
specimen shows a localized necking (Fig. 7 (c)), comparing with base steel (Fig. 5 (a-c)) . The
optical micrographs (Fig. 7 (d, e)) indicates that the ruptured specimens of B-doped steel with =
80 % include the inner cavities and their related cracks, whereas their densities are much lower
than those in base steel with = 43 %. It is likely that the number of cavities in steam is almost
same to that in air.
Figure 7: (a, b) Appearances of creep ruptured specimens of B-doped steel with =80% (preaged at 1073K/240 h) , (c) corresponding macroscopic strain in their gauge portion and (d, e)
optical micrographs of gauge portion of these specimens: (a, d) tested in steam, (b, e) tested in
air.
Figure 8 show BEIs showing (a-d) the surface regions and (e, f) the inner microstructures in creep
ruptured specimens of the B-doped steel with = 80 %. The cavities and their associated cracks
are scarcely observed in the specimens, even at highly strained regions. The intergranular oxides
are present on the specimen surface, whereas their depth is about 100 m on even the highly
strained surface (Fig. 8(a, b)), which is much smaller than that in base steel with = 43% (Fig.
6(a, b)). The depth of intergranular oxide in steam is slightly larger than that in air. Note that the
oxide scale with a mean thickness of 10-20 m is also formed on -Fe grains in B-doped steel, as
well as base steel. There is scarcely a change in microstructure after the creep test in air and steam
(Fig. 6(c, d)), comparing with microstructures of both steels before creep test (Fig. 2(c)). B-doped
steel exhibits high above 70% even after the creep test.
1358
Figure 8: BEIs showing (a, b) the surface of creep ruptured specimens and (c, d) microstructure
of B-doped steel with = 80 % (pre-aged at 1073 K/240 h) in (a, c) steam and (b, d) air
atmospheres. Macroscopic strains of these specimens in steam and air are 0.49 and 0.70 ,
respectively.
Figure 9 shows changes in (a, c) the depth of intergranular oxide and (b, d) the width of
intergranular oxide on the specimen surface as a function of macroscopic strain () in creep
ruptured specimens of (a) base steel and (b) B-doped steel under both atmospheres. In the base
steel with = 43% in air, the depth of intergranular oxide is almost constant of about 100 m at
below 0.6 and increases to about 300 m at higher than 0.6. In steam, the depth of intergranular
oxide is almost constant at lower than 0.4, whereas it significantly increases at higher and
reaches to more than 400 m (Fig. 9 (a)). The same trend can be recognized in the width of
intergranular oxide on the specimen surface (Fig. 9 (b)). In the B-doped steel with = 80%, in air,
the depth of intergranular oxide is almost constant of about 100 m independent of , whereas it
increases at higher than 0.4 in steam atmosphere. The depth is limited to about 200 m in
maximum, which is much smaller than one of base steel with = 43 %. The width of intergranular
oxide is also constant at lower than 0.4 and it increases to more than 200 m at higher . Both
depth and width in steam atmosphere is larger than that in air, which is independent of . These
results demonstrate that steam atmosphere enhances the growth of intergranular oxides on the
specimen surface at higher creep strain above 0.4, which can be suppressed by increasing .
1359
Figure 9: Change in (a,c) a depth of the intergranular oxide and (b,d) a width of the
intergranular oxide on the surface as a function of macroscopic strain in creep rupture
specimens of (a,b) base steel with = 43 % and (c, d) B-doped steel with = 80 %.
DISCUSSION
Effect of Grain Boundary Laves Phase on Creep Properties
The present creep test of the pre-aged steels with different demonstrates that the pronounced
extension of creep rupture time (t r ) by increasing in steam atmosphere as well as air (Table 1).
One of the important findings in this study is that an increasing from 43 % to 80 % can reduce
by one half the creep rate in the transient stage (Fig. 3, Fig. 4), resulting in a significant increase
in the creep rupture life. This importantly indicates that GBPS mechanism [10-11] by stable Laves
phase could work at 1073 K even in steam atmosphere. And it is also noteworthy that the preaged steels exhibit large creep rupture strain ( r ) of about 0.6 under both atmospheres, which is
independent of . This clearly indicates that Laves phase on grain boundaries could not reduce the
creep ductility. In the present study, all creep rupture times are limited below 1000 h. Thus,
further creep tests beyond 1000 h should be needed to identify the effect of GBPS mechanism by
Laves phase on long-term creep strength above 973 K. They are under testing at lower stress level
of 50 MPa.
Effect of Steam Atmosphere on Creep Properties
Another important finding in this study is that steam atmosphere gives a slight effect on the creep
rupture life and the minimum creep rate, but a few percent reduction in the creep ductility (Table
1). This ductility loss would be related to the intergranular oxidation on the specimen surface of
1360
the present steel during creep (Fig. 6 (a,b), Fig. 8 (a,b)), in particular highly strained surface ( >
0.4). Considering that the creep acceleration stage starts at of about 0.4 (Fig. 3 (b), Fig. 4 (b)),
the intergranular oxidation into the inside of the specimens would be enhanced by steam, in
particular in the creep acceleration stage. They presumably enhance the crack propagation along
grain boundaries at a late stage of creep, resulting in the ductility loss of the steel by steam.
However, the intergranular oxidation accelerated by steam atmosphere can be suppressed by
sufficiently covering grain boundaries by stable Laves phase (increasing above 80 %) (Fig. 9).
This represents that Laves phase on grain boundaries would reduce the environment effect on
creep properties of the present steel. Such inhibiting the intergranular oxidation by Laves phase
on grain boundaries would be associated with the formation of voids and cracks (connecting each
other) along grain boundaries during creep. Optical micrographs of the ruptured specimens (Fig. 5
(d,e), Fig. 7 (d,e)) clearly indicate that increasing can inhibit the formation of voids and their
associated cracks. These results can be understood on the basis that in creep acceleration stage,
localized deformation around grain boundaries without precipitates of Laves phase might
accelerate the formation of voids, which connects each other and makes it cracks propagating
along grain boundaries to the surface of specimens, thereby extensively enhancing the
intergranular oxidation. To confirm this speculation, further quantitative analyses for the local
deformation and the void formation along grain boundaries should be needed. They must await
future research to understand a role of Laves phase on grain boundaries in creep deformation
under steam atmosphere.
Based on above results, it can be summarized that the stable Laves phase sufficiently covering
grain boundaries can increase the creep long-term creep rupture strength and suppress the
intergranular oxidation during creep even in steam atmosphere. Therefore, GBPS mechanism is a
key strengthening mechanism for use of innovative advanced ultra-super critical (A-USC) thermal
power plant to be operated above 973 K.
CONCLUSIONS
Creep of a novel austenitic heat resistant steel of Fe-20Cr-30Ni-2Nb (at.%) strengthened by
grain boundary Laves phase at 1073 K under steam and air atmospheres (t r < 1000 h) has been
examined. The conclusions are as follow:
(1) Sufficiently covering grain boundaries by stable Laves phase ( > 80 %) can increase the
creep resistance without a loss of creep ductility at 1073 K, resulting in the significant extension
of creep rupture life in steam as well as air. The creep rupture strain slightly decrease by steam
atmosphere.
(2) The intergranular oxidation and its related crack propagation along grain boundaries would be
enhanced by steam atmosphere at higher creep strain than 0.4 in the creep acceleration stage. Its
effect can be suppress by increasing .
(3) Grain Boundary Precipitation Strengthening is a key mechanism to not only improve the
creep long-term creep rupture strength and but reduce the environment effect on creep properties
in steam atmosphere.
ACKNOWLEDGMENTS
This study was supported by the Grant-in-Aid (JY220215) on Advanced Low Carbon Technology
Research and Development Program (ALCA), Japan Science and Technology Agency (JST).
1361
REFERENCES
[1] Viswanathan, R., Bakker, W. Materials for Ultrasupercritical Coal Power Plants-Boiler
Materials: Part 1 J. Mat. Eng. Per., Vol. 10 (2001) pp. 81-95.
[2] Viswanathan, R., Bakker, W. Materials for Ultrasupercritical Coal Power Plants-Turbine
Materials: Part II J. Mat. Eng. Per., Vol. 10 (2001) pp. 96-101.
[3] Masuyama F., History of Power Plants and Progress in Heat Resistant Steels ISIJ
International, Vol. 41 (2001) pp. 612-625.
[4] Viswanathan R., Shingledecker J.,"Effect of Creep in Advanced Maetrials for Use in
Ultrasupercritical Coal Power Plants", Proceedings of ECCC Creep Conference, Zurich,
April 2009, pp. 31-43.
[5] Takeyama M., Gomi N., Morita S., Matsuo T., Phase Equilibria and Lattice Parameters of
Fe 2 Nb Laves Phase in Fe-Ni-Nb Ternary System at Elevated Temperatures Mater. Res. Soc.
Symp. Proc. Vol. 842 (2005) pp. 461-466.
[6] Hasebe Y., Hashimoto K., Takeyama M., "Phase Equilibria among -Fe /Fe 2 Nb(TCP)
/Ni 3 Nb(GCP) Phases in Fe-Ni-Nb Ternary System at Elevated Temperatures" J. Japan Inst.
Metals Vol. 75, No. 4 (2011) pp. 265-273.
[7] Hasebe Y., Hashimoto K., Matsuo T., Takeyama M., "Assessment of the Phase Equilibria
among -Fe/ Fe 2 Nb/ Ni 3 Nb Phases in Fe-Ni-Nb Ternary System at Elevated Temperatures"
Mater. Res. Soc. Symp. Proc Vol. 1295 (2011) pp. 171-176.
[8] Takeyama M., "NOVEL CONCEPT OF AUSTENITIC HEAT RESISTANT STEELS
STRENGTHENED BY INTERMETALLICS" Materials Science Forum Vols. 539-543
(2007) pp. 3012-3017.
[9] Kurata K., Takata N., Matsuo T., Takeyama M., "Effect of Grain Boundary Fe 2 Nb Laves
Phase on Creep Resistance of Fe-20Cr-30Ni-2Nb Austenitic Heat Resistant Steel" Report of
the 123rd Committee on Heat-Resisting Materials and Alloys, Japan Society for the
Promotion of Science, Vol. 49 (2008) pp. 379-389.
[10] Tarigan I., Kurata K., Takata N., Matsuo T., Takeyama M., "Novel Concept of Creep
Strengthening Mechanism using Grain Boundary Fe 2 Nb Laves Phase in Austenitic Heat
Resistant Steel" Mater. Res. Symp. Proc. Vol. 1295 (2011) pp. 317-322.
[11] Tarigan I., Takata N., Takeyama M., "Grain Boundary Precipitation Strengthening
Mechanism by Fe2Nb Laves Phase in Creep of Fe-20Cr-30Ni-2Nb Austenitic Heat Resistant
Steel" Proceedings of the 12th International Conference on Creep and Fracture of
Engineering Materials and Structure (JIMIS 11) (CD-ROM), Kyoto, May 2012.
[12] Yamashita M., Ueda M., Kawamura K., Takeyama M., Maruyama T." High Temperature
Steam Oxidation of Fe-20Cr-30Ni-2Nb Austenitic Heat Resistant Steel Strengthened by
intermetallic Compounds", Report of the 123rd Committee on Heat-Resisting Materials and
Alloys, Japan Society for the Promotion of Science, Vo. 50 No. 2 (2009) pp. 267-276.
1362
ABSTRACT
Prediction of long-term creep strength is an important issue for industrial plants operated at
elevated temperatures, although the creep strength of high Cr ferritic steels depends on their
microstructural evolution during creep. The state of microstructure in metallic materials can be
expressed as numerical values based on a concept of system free energy. In this study, in order to
evaluate long term creep strength of 9Cr ferritic steel containing B, change in the system free
energy during creep of the steel is evaluated as the sum of chemical free energy, strain energy and
surface energy, which are obtained by a series of experiments, i.e., chemical analysis using
extracted residues, X-ray diffraction, and scanning transmission electron microscopy. The system
free energy decreases with creep time. Change in the energy is expressed quantitatively as a
numerical formula using the rate constants which depend on applied stress. On the basis of these
facts, long term creep strength of the steel can be evaluated at both 948K(675oC) and 973K(700
o
C).
INTRODUCTION
High Cr heat resistant ferritic steels are used for large scale components in fossil power plants
because of their low coefficient of thermal expansion. However, they have the disadvantage of
premature failure in long-term creep [1,2]. Thus, accurate estimation of the long-term creep
rupture life of the materials is required.
The microstructure of high chromium heat resistant ferritic steels consists of the martensite phase
as the matrix containing MX carbonitride, M23C6 carbide, Laves phase, and Z phase, etc. The
creep strength of high chromium heat resistant ferritic steels strongly depends on their
microstructure, so it is very important to estimate quantitatively the change in the microstructure
with creep time. System free energy [3] is the total energy showing the state of microstructure in
materials, including not only the energy based on chemical composition of each phase but also the
energy arisen from the morphology of each phase, such as grain size, precipitation size, and
dislocation density, etc. According to the concept of system free energy, the microstructure of
materials changes from the initial state to the equilibrium state along the direction in which the
system free energy decreases effectively. In fact, it is reported that the microstructural change of
1363
Ni-based superalloys and the morphological change of the Laves phase in high Cr and high W
ferritic steels can be explained by this concept [4,5]. In this study, long term creep strength of an
advanced heat resistant ferritic steel is evaluated on the basis of the system free energy concept.
EVALUATION OF SYSTEM FREE ENERGY IN ADVANCED HIGH Cr STEEL
For high Cr heat resistant steels, the system free energy (Gsys) is employed as the sum of the
chemical free energy (G0), elastic strain energy (Estr), and interfacial energy (Esurf), and is
expressed by the following equation,
(1)
Specimen
An advanced heat resistant ferritic steel (9Cr-0.08C-2.5W-0.1Mo-2.5Co-0.2V-0.02N-0.005B0.05Nb) is used in this study. The steel was austenitized at 1373K for 1h followed by air cooling
and then tempered at 1053K for 1h. Tensile creep tests were conducted at 948K by applying
stress of 80MPa and at 973K by applying stress of 60MPa. After both creep-ruptured and
suspended creep, the gauge and grip portions of specimens were analyzed by a series of
experiments so as to obtain the system free energy of each specimen.
Chemical Free Energy
The chemical free energy of the steel used in this study is expressed by the following equation,
MX
MX
23C6
G0 =G0bcc M bcc
+ G0M 23C6 M M
+ G0Laves M Laves
,
f + G0 M f
f
f
(2)
where G 0i is the chemical free energy for i phase, M fi is mole fractions of i phase, i.e., the
martensite phase, MX carbonitride, M23C6 carbide, and the Laves phase. The mole fraction of
each phase is estimated on the basis of quantitative analysis by using the extracted residue. The
chemical free energy for each phase is calculated using the sublattice model [6] based on the
thermodynamic data-base of Thermo-Calc (Ver. Fe-6). For the calculation of both mole fraction
and the chemical free energy of each phase, the chemical composition of each phase is required.
Chemical compositions of both MX carbonitride and the Laves phase formed in the early stage of
creep are similar to their equilibrium values at creep temperatures. However, it is reported that
the chemical composition of M23C6 carbide changes with creep time [7], hence we consider that
this compositional change occurs from the equilibrium value at tempered temperature to one at
creep temperatures, and it is calculated by the following equation,
t
as
e
n
mM
= mM C + mM C (1- exp(-kM C t )) .
23C6
23 6
23 6
23 6
(3)
Here, t is creep time (h), m (Cr, Fe, and Mo, etc.) is metal elements in M23C6
t
carbide, m M 23C6 ,
as
e
mM
and m M 23C6 are mole fractions at time t, as tempered and in the
23C6
equilibrium state, respectively. n and k M 23C 6 are constants estimated from the change in Cr
amounts in M23C6 carbide with creep time [8].
1364
=
Estr
b 2
4
R
Vm ,
r0
ln
(4)
where is the dislocation density, Vm is the molar volume of the steel, is the shear modulus, b is
the magnitude of the Burgers vector, and r0 is the radius for the dislocation core. In this study, =
8.01010 N/m2 and b = 0.248nm, both as values of pure iron, and r0 = 5b is used [9]. R is the
outer cut-off radius for calculating the elastic strain energy of the dislocation, and R = 104 b is
used in this study. The dislocation density of each specimen is measured by profile analysis of Xray diffraction based on a modified Williamson-Hall plot and modified Warren-Averbach analysis
[10]. The martensite phase is strictly a body-centered tetragonal lattice. However, in heat
resistant ferritic steels, the c/a value of the martensite is almost unity because of their very low
carbon content. Therefore, X-ray diffraction peak profiles can be analyzed by the body-centered
cubic lattice.
Interfacial Energy
The interfacial energy is expressed by the following equation,
Esurf = A Vm .
(5)
Here, A is the interfacial area per unit volume. In high chromium heat resistant ferritic steels, the
interfacial energy that we need to consider incorporates the energies due to boundaries in the
martensite structure (matrix) itself such as lath block and packet, and boundaries between the
matrix and precipitates, i.e., MX carbonitride, M23C6 carbide, and the Laves phase. is the
interfacial energy density, the value is 0.85J/m2 for precipitates [11] and 0.10J/m2 for matrix [12].
It is reported that the interfacial energy is very small compared to that between the matrix and
precipitates [13], the latter one is estimated in this study. The interfacial energy arisen from of
precipitates is estimated by using the size of each precipitate obtained from extracted carbon
replica images taken by a scanning transmission electron microscope (STEM) equipped with
energy dispersive X-ray spectroscopy (EDX). Nb and V rich precipitates are regarded as MX
carbonitride, Cr-rich precipitates are regarded as M23C6 carbide, and Mo-rich precipitates are
regarded as the Laves phase, judging from the chemical compositions based on the Thermo-Calc
data-base.
RESULTS AND DISCUSSION
Chemical Free Energy
Figure 1 shows the change in the amounts of precipitates (MX carbonitride, M23C6 carbide, and
the Laves phase) with creep time. The amount of MX carbonitride scarcely changes, whereas the
amounts of both M23C6 carbide and the Laves phase increase during creep, and the increasing
1365
rates in both phases are found to be faster in the gauge portion as indicated by solid line than in
the grip portion as indicated by broken the line. Fig. 2 shows the change in the chemical free
energy calculated using the data on the amounts of precipitates. The chemical free energy
decreases monotonically with creep time. The decreasing rate is also faster in the gauge portion
than in the grip portion, according to the time dependence of the amounts of precipitates. This
result indicates that the applied stress accelerates the decreasing rate of the chemical free energy.
Thus, the change in chemical free energy can be expressed by the following equation,
=
G0
C0
k0 ( ) t + 1
+ G0e .
(6)
Here, C0 is a constant and G0 is the chemical free energy in equilibrium state. k0() is a rate
constant depending on the applied stress, . Solid lines in Fig. 2 are regression lines calculated by
Eq. (6). Fig. 3 shows the relationship between the rate constant of the chemical free energy and
the applied stress.
C str
k str ( ) t + 1
+ Estr .
(7)
Here, Cstr is a constant and Estr is the elastic strain energy in the equilibrium state. kstr() is a rate
constant depending on the applied stress, . Fig. 5 shows the relationship between the rate
constant of the elastic strain energy and the applied stress.
1366
Fig.3 Dependence of the rate constant of the chemical free energy on applied stress.
1367
Interfacial Energy
Figure 6 shows the change in the mean diameter of precipitates with creep time. The size of MX
carbonitride scarcely changes, whereas those of M23C6 carbide and the Laves phase increase
during creep. Fig. 7 shows the change in the interfacial energy estimated based on the size of each
precipitate. The interfacial energy in the gauge portion decreases with creep time, whereas that in
the grip portion increases at first and then decreases with creep. This increase of the interfacial
energy is mainly due to increasing amounts of the Laves phase, as shown in Fig. 1. The interfacial
energy decreases in the long term because of precipitates coarsening. Then, the change in the
interfacial energy can be expressed by the following equation,
Esurf =
Csurf
k surf t + 1
'
Csurf
'
k surf
t +1
(8)
Here, Csurf and Csurf are constants, and k surf and k surf are rate constants. These rate constants
'
'
Fig.5 Dependence of the rate constant of the elastic strain energy on applied stress.
System Free Energy
From Eqs. (6)-(8), the change in the system free energy can be expressed by the following
equation,
'
C
Csurf
C0
Cstr
surf
e
+ Gsys
Gsys =
+
+
.
(9)
k0 ( ) t + 1 k str ( ) t + 1 k surf t + 1 k ' t + 1
surf
Here, Gsys is the system free energy in the equilibrium state. Fig. 8 shows the change in the
e
system free energy with creep time. In the figure, experimental values are indicated by open and
closed marks and lines are calculated by Eq. (9). The system free energy decreases with creep
time, and the decreasing rate depends on the applied stress, indicating that the rate of
microstructural change during creep is accelerated by the applied stress. From Eq. (9), the
microstructural state of the steel at an arbitrary creep time can be obtained quantitatively, and the
1368
effect of the applied stress of the microstructural change appears through the rate constants (k0,
kstr ).
1369
P=
r
e
Gsys
Gsys
as
Gsys Gsys
(10)
as
Here, Gsys is the system free energy as tempered state. P = 1 means the values of the parameter
as tempered state, and P = 0 means the value in the equilibrium state. Fig. 9 shows the
relationship between the rupture parameter, P, and the applied stress. This figure shows that the
steel having a microstructural state corresponding to a P value has the endure stress giving the
stress in Fig. 9. For instance, a steel of the microstructural state of P=0.6 at 973K will show an
endure stress of about 75MPa. Also, the time becoming P=0.6 at 75MPa can be calculated using
Eq. (9), resulting in obtaining the rupture time at 75MPa. In this way, we can obtain a stressrupture curve of the experimental steel, as shown in Fig. 10. This figure indicates that long-term
creep strength can be evaluated by the system free energy.
1370
ABSTRACT
The use of the bainitic creep strength enhanced ferritic steel T/P23 has increased over the last
decade in a wide range of applications including headers, superheater and reheater tubing and in
waterwall tubing. Many issues have been reported in weldments of this material, such as hydrogen
induced cracking, reheat cracking and stress corrosion cracking. In order to help characterize high
temperature cracking phenomena, including reheat cracking, a limited number of laboratory creep
crack growth tests are being conducted as part of an ongoing project. Tests were run on as-welded
sections with the test specimen crack-tip located in select zones of the weldment. Test
temperatures are intended to bookend the range of applications from a waterwall condition of
~482C (900F) to the superheat/reheat condition of 565C (1050F). This paper describes the
results of some early testing at 482C (900F). The tests provided useful insight into the cracking
susceptibility of the material at this temperature with respect to not only time-dependent cracking,
but also fatigue crack growth and fracture toughness. The paper includes details of the test
method and results, as well as findings from post-test metallographic examinations of the tested
specimens.
INTRODUCTION
Grade 23 is a bainitic/martensitic steel belonging to a relatively new class of materials known as
creep strength enhanced ferritic (CSEF) steels. This material is currently being utilized across a
large range of applications from thin to thick section power plant components and additionally
over a range of temperature regimes. In the low end of the use range, waterwall panels for
supercritical plants are expected to operate at ~450C (842F) while supercritical
superheater/reheater tubing and replacement headers may operate at temperatures approaching
580C (1076F). The utilization of Grade 23 over a relatively large operational range makes it
unique and challenging with regard to understanding the material behavior for component
integrity and life management.
A recent failure in T23 material near a tube to tube butt weld in the roof tubing section of a
supercritical boiler highlighted the need to characterize the response of weldments of this material
to operating stresses, including where there exist flaws (flaw tolerance). This particular section of
the boiler was designed to operate at maximum conditions of 480C (896F) and 30.5 MPa (4424
psi). An independent failure investigation provided to EPRI suggested that the failure (~10k hours
of operation) was a result of reheat cracking in the heat-affected zone (HAZ) near the tube to tube
butt weld. However, details of the investigation and related sample material to develop a root
1372
cause failure evaluation were not available. What was clear, however, was that the failure
occurred in a relatively short time frame following installation and appeared to be brittle, having
occurred at least in part by crack (flaw) growth during service. Thus, a need to predict the inservice growth of pre-existing flaws created by reheat or any other form of cracking became
apparent, given that dozens of similar tube to tube butt welds in the roof tubing would likely need
a life assessment plan for further non-destructive evaluation or eventual replacement with planned
outages.
At issue then, and as would be the case for a structure with indications or expectations of flaws, is
the tolerance of the weldments for flaws under anticipated operating conditions. In the case of
Grade 23, the experienced susceptibility to damage and failure likely due to weldment flaws (e.g.,
[1-3]), in addition to the roof tube failure that initially prompted this study, makes a flaw tolerance
assessment directly relevant to managing the integrity of the welded structure. In a broad effort to
begin addressing the flaw tolerance of Grade 23 weldments, both for thin and thick sections, EPRI
has initiated a Grade 23 weldment crack growth project with the first phase intended to mainly
examine time-dependent (creep) crack growth behavior. A published literature search for the
creep crack growth behavior of Grade 23 weldments revealed only one potentially useful
reference [4] with data at 565C (1049F) and lacking sufficient detail to enable extrapolation to
other exposure conditions. Following is a description of the findings from creep crack growth
tests conducted on side-grooved, subsize compact tension, C(T), specimens removed from a tube
weldment sample taken from the failed roof tube section. Effort was made to remove test
specimens so as to provide at least portion of the crack front within the HAZ.
EXPERIMENTAL PROCEDURE
Material and Specimen Configuration
An ex-service tube to tube butt weld section was provided by the utility as shown in Figure 1. The
tubing was nominally of 63.5 mm (2.5 inches) outside diameter and 7.1 mm (0.281 inches) wall
thickness. The as-received material base metal chemical composition was determined and is given
in Table 1. From this weldment, two subsize compact tension, C(T), specimens were wire
electrical-discharge machined (EDM) from the weld with the specimen notch being located near
the fusion line of the weldment as visible at the outside tube surface (i.e. the cap of the weldment).
The tube after EDM is shown in Figure 2. The nominal dimensions of the two nearly identical
specimens are shown in Figure 3. The specimen configuration and dimensions followed that of the
ASTM standard E1457 for measurement of creep crack growth [4], except that due to the
available material being limited by the size of the tubular component, the planar dimensions (e.g.,
width, W) were proportionately reduced to about 40% of the standard C(T) test specimen (W20
mm compared with the standard geometry W of 50 mm). The thickness, B, of the specimens was
nominally W/4.
Note that the single-V weld groove shape with a larger weld metal width at the outside surface is
such that the as-removed specimen would expectedly have a varying crack front weldment zone
location through its thickness at the fusion line or HAZ at the outside tube surface changing to
within unaffected base metal at the inside tube surface. The limitation of being able to locate the
entire crack front in a given weldment zone was recognized. Nevertheless, the need to
characterize the cracking response motivated this preliminary testing.
1373
Figure 1: Ex-service tube to tube butt weld utilized for creep crack growth testing
Table 1: Chemical Composition of As-received T23 Tube Base Metal in Weight %
C
Mn
Si
Cr
Mo
Cb (Nb)
0.052
0.33
0.002
0.001
0.22
2.24
0.12
1.54
0.23
0.042
Al
Ni
Ti
Cu
As
Sb
Sn
Ti/N
0.0061
0.002
0.0014
0.03
0.003
0.01
.0046
0.00053 0.0018
0.49
BN
mm
5.1
3.9
24.4
25.3
20.2
16.3
5.1
3.9
5.1
4.1
in.
0.201
0.153
0.960
0.995
0.796
0.643
0.199
0.154
0.201
0.161
Figure 3: Nominal dimensions for extracted subsize compact tension crack growth specimens as
shown in Figure 2.
Testing
Two tests were conducted. The first, a conventional creep crack growth test, consisted of static
loading at 482C (900F) of a fatigue pre-cracked specimen. The static loading, however,
involved periodic increases in load with crack length monitoring through the hold period
associated with each load level. The second test consisted of 1 Hz cyclic loading at 482C
(900F) of a similarly pre-cracked specimen. This test comprised six phases of loading, switching
between a low R-ratio (minimum-to-maximum load) of 0.1 typical of fatigue and a high R-ratio of
0.95 approaching a near-constant (static) load exposure typical of a creep crack growth test.
Again, crack length was monitored through each phase of the test. The test was designed to
develop a calibration for the DC electric potential drop (EPD) crack length monitoring system,
but also provided useful fatigue and creep cracking information as well as indications of material
fracture toughness at 482C (900F) that are discussed here.
Test 1
Following machining, the specimen was fatigue pre-cracked at room temperature on a servohydraulic frame up to a crack length of 4.585 mm (0.1805 in.) under an applied stress intensity
factor range, K, of 26.92 MPam (24.5 ksiin) and R-ratio of 0.1. The final pre-crack length
was determined from surface measurements taken using dye penetrant. Following pre-cracking,
the specimen was tested at 482C (900F) under constant load over a time period of ~520 hours
while monitoring the crack mouth opening displacement (COD). An attempt was made to
simultaneously measure the EPD in conjunction with the COD, but this system was incompatible
with the software on the creep frame equipment and was shown to be inaccurate. The load was
initially set at 1334 N (300 lbf) and periodically increased throughout the duration to an ultimate
load of 3379 N (760 lbf), after which the test was discontinued. The test loads correspond to an
approximate applied stress intensity factor, K, initially of 9.9 MPam (9 ksiin) increasing to the
ultimate level of about 51.6 MPam (47 ksiin). Following testing, the specimen was mounted,
polished and etched in Villellas for examination of the crack in the plane nearest to the cap or
face of the weld. Indications of crack extension were made and quantified using the measured
COD.
1375
Test 2
As noted above, the second test was conducted at 482C (900F) and primarily designed to
develop a calibration of the EPD system for monitoring crack growth for ongoing tests. This
specimen was fatigue cracked over six phases defined on the basis of a change in R-ratio.
Although this test was used principally for calibration, useful information was obtained on the
crack growth rate, fracture toughness and modes of crack advance. As such, the findings from this
test are reported in this paper. All of the cracking was conducted at 482C (900F) at 1 Hz, using
an R-ratio (minimum-to-maximum load ratio) periodically switching between 0.1 (fatiguedominant) and 0.95 (creep-dominant). The applied maximum stress intensity factor (Kmax) varied
from a low of about 7.7 MPam (7 ksiin) to about 77 MPam (70 ksiin). The total test
duration comprised about 306,000 cycles or 85 hours, split between the fatigue-dominant mode
for 5,400 cycles or 1.5 hours and the creep-dominant mode for 300,600 cycles or 83.5 hours.
Fatigue pre-cracking was conducted at room temperature to a crack length of about 9.91 mm
(0.39 in.). The test was conducted to full specimen fracture, and the broken halves were post-test
examined via light optical microscopy (LOM), laser microscopy and scanning electron
microscopy (SEM).
RESULTS
Test 1
The test output data are plotted in Figure 4, shown as test load and COD versus time. The test was
terminated following exposure at a final load of 3379 N (760 lbf), and one face of the tested
specimen was metallographically examined. Figure 5 through 7 are metallographic views of the
post-test specimen surface corresponding to the tube near-outside diameter region where the crack
front would be nearest the fusion line in the HAZ. At the time of this writing, examination of the
opposite surface of the specimen with the crack expected to be in the base material was not
complete.
Figure 4: Test load and crack mouth opening displacement (COD) versus time for Test 1 at
482C (900F)
1376
Figure 5: Mounted, polished and etched creep crack growth specimen face with crack-tip closest
to the fusion line.
Figure 6: Metallographic views of the crack of Figure 5 with inset showing the near-final cracktip region.
1377
B
Figure 7: Higher magnification views of the crack-tip region of Figure 6 of the specimen tested
at 482C (900F) showing intergranular cracking.
1378
While the COD response exhibited some scatter, the generally monotonic increase with time (and
load) provided a means to estimate crack advance. Given the uneven crack front and varying
crack growth rate from one side of the specimen to the other, no rigorous estimates of crack
advance can be made. However, to gain preliminary quantitative insight into the rate of crack
advance, the measured COD changes were used to infer compliance changes and consequent
crack length increase using the expression correlating crack size with crack mouth opening
compliance per ASTM E399 [6]. Two factors permit use of this elastic correlation as an
approximation: (a) plane strain dominant elastic conditions are predicted based on the remaining
ligament size for applied K up to about 33 MPam (30 ksiin) (applicable through about twothirds of the test period); and (b) estimates of creep deformation that would contribute to the COD
for these test conditions were small enough to be neglected. The correlation between estimated
compliance changes using the COD and crack advance was empirically adjusted to match the
initial crack size (pre-crack length) and final crack size as measured on the surface with crack
path nearest the fusion line in the HAZ. Smooth curve approximations to the COD response were
used to facilitate the computations.
Figure 8 summarizes the estimated crack size-time results applicable to the near-surface and nearfusion line, HAZ crack front. Superimposed on the graphic is the applied K. A correlation
between the crack growth rate, da/dt, and K could not be made due to the apparent scatter in the
estimates. However, indications are that crack growth rate in the HAZ varies over the range,
1.78E-3 to 1.78E-2 mm/h (7E-5 to 7E-4 in/h), for the range of applied K of 9.9 MPam (9 ksiin)
to 51.6 MPam (47 ksiin).
Figure 8: Inferred near-surface, HAZ crack size versus time for Test 1 at 482C (900F) shown
with the applied stress intensity factor superimposed.
The key findings from Test 1 are:
Even at a temperature as low as 482C (900F) where creep strain is expected to be low
for the material, the Grade 23 weldment, particularly in the HAZ, exhibited timedependent crack growth. The growth is accompanied by limited plastic and inelastic
strain.
1379
The time-dependent crack growth rate, as inferred via the COD measurements and
empirically benchmarked against the initial and final observed crack size, showed
significant scatter and could not be correlated against the applied stress intensity factor,
K. However, growth rate was estimated to be in the range, 1.78E-3 to 1.78E-2 mm/h
(7E-5 to 7E-4 in/h), for the range of applied K of 9.9 MPam (9 ksiin) to 51.6 MPam
(47 ksiin).
The cracking mode appeared to vary, showing a transgranular appearance in the early
phase, followed by a mixed transgranular and intergranular mode, culminating in a
predominantly intergranular mode that is striking in the appearance of the damage ahead
of the crack-tip (Figure 6 and Figure 7).
The varying cracking mode did not show an apparent correlation with the material zone,
since the specimen surface crack propagation appeared confined to a single HAZ region.
Test 2
A second test, conducted at 482C (900F) on a specimen nearly identical to that of Test 1 and
intended to calibrate the EPD system for crack length, provided useful data on fatigue cracking,
time-dependent creep cracking, and time-independent (fracture toughness) behavior. The test was
conducted in six phases for which data were recorded, for a total time of approximately 85 hours,
with each phase defined on the basis of the periodic change in the applied R-ratio. As noted
earlier, two R-ratio levels were used: R=0.1, representing a dominantly fatigue loading mode; and
R=0.95, representing a condition approaching a static, creep-typical application. The entire test
was run at a frequency of 1 Hz and conducted to specimen fracture (separation into two halves).
Table 2 summarizes the six phases of testing and the basic ranges of parameters for each phase,
including the maximum applied stress intensity factor and crack size. Crack size ranges in the
table are from post-test measurements on the fracture surface that were feasible due to the
markings associated with the R-ratio changes. The crack front in this case did not exhibit much
variability across the specimen thickness (the standard deviation of eight measurements made
across the thickness was <5% at the end of each of Phases 1 through 6). Crack extension
following Phase 6 was by relatively rapid ductile tearing for which no data were gathered. The
test data were analyzed in two separate sets one representing dominant fatigue (R=0.1), and the
other approaching conditions of creep (R=0.95).
Table 2: Test 2 Loading Conditions at 482C (900F)
Time
Applied Kmax
Initial Crack Size Final Crack Size
Phase R-ratio Cycles
[h] [MPam (ksiin)]
[mm (in.)]
[mm (in.)]
7.3 to 40.8
9.88
9.98
1
0.1
1501
0.42
(6.7 to 36.6)
(0.389)
(0.393)
~ 64.9
9.98
10.67
2
0.95
190,965
53
(~ 59)
(0.393)
(0.42)
26.6 35.8
10.67
11.0
3
0.1
1,882
0.52
(29.3 39.3)
(0.42)
(0.433)
63.2 64.6
11.0
11.61
4
0.95
5,784
1.6
(69.4 71)
(0.433)
(0.457)
31.5 43.9
11.61
12.17
5
0.1
2,015
0.56
(34.6 48.3)
(0.457)
(0.479)
53.5 57
12.17
12.395
6
0.95
103,546 23.8
(58.8 62.6)
(0.479)
(0.488)
1380
Figure 9: Crack growth data from Test 2 at 482C (900F) for the R=0.1 fatigue-dominant
Phases 1, 3 and 5 of Table 2. The inter-phase jumps in crack length reflect growth during the
R=0.95, creep-typical Phases 2, 4 and 6.
Polynomial curve-fits were made for each of the three phases of Figure 9. The first phase
exhibited a threshold, apparent from the data and a third-order curve-fit (regression
coefficient=0.9) seen in Figure 10. The threshold, occurring around 700-800 cycles, corresponds
to an applied stress intensity factor range, K, of about 9.9 MPam (9 ksiin). The data of Phase
3 showed a generally linear behavior with a constant crack growth rate, and the data from Phase 5
conformed to a second-order polynomial. The fits to both Phases 3 and 5 had regression
coefficients >0.99.
Figure 10: Crack growth data from phase 1 of Test 2 at 482C (900F) showing the apparent
threshold, highlighted by a third-order polynomial curve-fit.
1381
The curve-fits from each of the three phases were used to compute the cyclic crack growth rate,
da/dN. Figure 11 graphically summarizes the results. A Paris power law fit was made to the data
between K of about 16.5 and 38.5 MPam (15 and 35 ksiin) with regression coefficient of
0.91. Observations made from the R=0.1, 482C (900F), fatigue crack growth data and analysis
are:
The uniformity of the crack front across the specimen thickness, going from the near
fusion line at one face to the base metal at the other, suggests that the material fatigue
crack growth response under these test conditions did not vary as a function of material
microstructure from HAZ to unaffected base metal.
The da/dN-K behavior appeared qualitatively consistent with that seen for low alloy
steels.
The data exhibited an apparent K threshold at about 10 MPam (9 ksiin).
A power law Paris regime was identifiable, and a curve-fit to this region between about
16.5 and 38.5 MPam (15 and 35 ksiin) K yielded:
o da/dN (mm/cycle) = 1.06E-6 (K)1.4 for K in MPam; or
o da/dN (in./cycle) = 4.774E-8 (K)1.4 for K in ksiin
The deviation from Paris behavior appeared at K values approaching 44 MPam (40
ksiin). Indeed, a review of the cracking mode via post-test specimen metallographic
examination (described below) showed that this deviation coincides with a transition to
significant plasticity and to the onset of relatively rapid ductile tearing.
The crack growth behavior provides a means of assessing component flaw tolerance
under fatigue loading conditions.
Figure 11: Crack growth rate inferred from curve-fits to the crack length-cycles data. Note the
apparent threshold, the linear logarithmic Paris regime, and the apparent deviation from Paris
behavior approaching 44 MPam (40 ksiin).
1382
Figure 12: Crack length data for the three phases of testing at R=0.95, approaching the static
creep test condition.
Figure 13 graphically summarizes the Phase 6 ductile tearing crack growth rate versus applied
Kave (average of Kmax and Kmin). The behavior does not conform to a power law. The ductile
tearing crack growth rate curve may be approximated by a linear fit with a regression coefficient
of 0.98:
da/dt (mm/h) = 2.93E-3 (Kave) for K in MPam; or
da/dt (in./h) = 1.154E-4 (Kave) for K in ksiin
Over the narrow Kave data range for this phase of 59 to 61 MPam (53.7 to 55.5 ksiin), the crack
growth rate varied between about 4.1E-3 mm/h (1.6E-4 in/h) and 9.4E-3 mm/h (3.7E-4 in/h).
1383
Figure 13: Ductile tearing crack growth rate for Phase 6 of Test 2 at 482C (900F) versus the
average applied stress intensity factor, Kave.
Fracture Toughness
Test 2 also provided some indications of the fracture toughness of the material at 482C (900F).
Figure 14 shows a photograph of one face of a broken half of the specimen alongside a
macrograph of the fracture surface. The indicated onset of tearing occurred at an approximate
crack length of about 11.94 mm (0.47 in.), evidently accompanied by significant plasticity and
deformation of the specimen. This onset roughly coincides with the start of Phase 6 (R=0.95) of
testing and occurred under an applied Kmax of about 58.8 MPam (53.5 ksiin). While it remains
unclear as to why such tearing did not occur earlier in the testing period where this level of K max
was exceeded, the documented onset of tearing at this applied K level indicates that the material
fracture initiation toughness is likely to be less than 60 MPam (55 ksiin). The crack-tip
location corresponding to this estimate was mostly within unaffected base metal and need not
represent the toughness of the HAZ. The HAZ fracture initiation toughness, based on the
experience with weldments and on the limited damage observations from Test 1, may well be
lower. The inferred level of material fracture initiation toughness at 482C (900F) is lower than
what may be expected for this class of alloy.
Fracture Modes
The fracture surface examination, including close-up views of various locations on the surface of
the specimen remnant seen in Figure 14, provided indications of the cracking mode in various
phases of the load cycle.
1384
Figure 14: Photograph of the Test 2 broken specimen half along with a macrograph of the
fracture surface illustrating the onset of plasticity and ductile tearing.
The following observations are noteworthy:
The crack path through all of the loading cycle appeared to be within base metal, so
properties relevant to the weldment HAZ cannot be inferred.
The onset of ductile tearing roughly coincided with the beginning of Phase 6 (last
R=0.95 phase).
The onset of significant plasticity as evidenced by the specimen thickness reduction
roughly coincided with the beginning of Phase 3; i.e., a major portion of the monitored
crack advance for which the data were analyzed was accompanied by increasing
plasticity.
Figure 15 show select fractographs. The representative modes visible for Phases 1, 3
and 6 show that the fatigue cracking mode was flat and in case of Phase 3, shows
evidence of secondary brittle cracks.
1385
Figure 15: Macrophotograph of the Test 2 fracture surface. Close-up fractographs of the
identified regions corresponding to (a) Phase 1 fatigue R=0.1; (b) Phase 3 fatigue R=0.1; (c)
Phase 6 tearing R=0.95.
SUMMARY
This effort, although limited as the first phase of a broader project aimed at evaluating the crack
growth behavior of Grade 23 weldments, produced some useful insights meriting a summary:
The first of two tests of a tube to tube weldment conducted under static loading
conditions showed evidence of intergranular time-dependent cracking in the weldment
heat-affected zone at the test temperature of 482C (900F). Given the low expected
global creep at this temperature, the evidence highlights the risk of this form of cracking
under conditions that need not be associated with creep as conventionally defined and
expected.
The HAZ intergranular time-dependent cracking phenomenon at 482C (900F)
appeared morphologically consistent with that of reheat cracking. The observation
suggests that reheat cracking may well occur at this temperature. The base metal
chemistry showed a level of Ti lower than the minimum required by the current ASME
Code Case specification, and it is not clear to what extent this lower Ti content
contributed to this form of time-dependent cracking.
Given that the constraints on the tube to tube weldment specimen configuration resulted
in a crack front that could not be uniformly located in the HAZ, inferences relating to
creep crack growth rate of the HAZ could not be made. However, preliminary estimates
based on crack size measurements near the specimen face with crack front closest to the
fusion line gave a rate of 1.78E-3 to 1.78E-2 mm/h (7E-5 to 7E-4 in/h) for the range of
applied K of 9.9 MPam (9 ksiin) to 51.6 MPam (47 ksiin).
The second test conducted under cyclic loading conditions to represent fatigue
dominance (R=0.1) and creep dominance (R=0.95) had the crack front mostly within
base metal, so no firm conclusions can be drawn regarding the behavior of the HAZ.
1386
However, the fatigue-dominant, R=0.1 test data showed that the Grade 23 material had
an apparent fatigue crack growth threshold of about 10 MPam (9 ksiin) and a power
law Paris regime at 482C (900F) given by:
o da/dN (mm/cycle) = 1.06E-6 (K)1.4 for K in MPam; or
o da/dN (in./cycle) = 4.774E-8 (K)1.4 for K in ksiin
The observed onset of ductile tearing at 482C (900F) suggests a material fracture
initiation toughness likely to be less than 60 MPam (55 ksiin) at this temperature,
lower than would be expected for this class of steel.
Fractographs show regions of fatigue crack growth to be flat with evidence of areas of
secondary brittle appearing cracks.
The exercise provided potentially useful data for input to a component integrity analysis
based on flaw tolerance. Subsequent work will include a description of the application of
such laboratory crack growth data to field application.
ACKNOWLEDGEMENTS
J. Roselle, Innovative Test Solutions, Inc., is acknowledged for conducting the testing and
providing the raw crack growth data.
REFERENCES
[1] Fishburn, J. D., Henry, J. F., and Zhou, G. Service Experience with T23 Material.
Proceedings of the 9Cr Materials Fabrication and Joining Technologies, July 10-11, 2001,
Myrtle Beach, SC.
[2] Park, K., Kim, S., Chang J., Lee, C. Post-weld heat Treatment Cracking Susceptibility of
T23 Weld Metals for Fossil Fuel Applications. Materials and Design 34 (2012), pp. 699706.
[3] Fuchs, R., Hahn, B., Heuser, H., Affect of inexpert working of heat resistant steels to the
serviceability, in Proceedings of the Sixth International Conference on Welding and Repair
Technology for Power Plants, Sandestin, FL, EPRI, 2004.
[4] Di Gianfrancesco, A. et al. Applications of Advanced low-Alloy Steels for New HighTemperature Components. Contract No RFSR-CT-2003-00037, 2009. Luxembourg, 2009.
[5] Standard Test Method for Measurement of Creep Crack Growth Times in Metals, ASTM
E1457-07 in Annual Book of ASTM Standards, Vol. 03.01, ASTM, West Conshohocken,
PA, 2010.
[6] Standard Test Method for Linear-Elastic Plane Strain Fracture Toughness KIc of Metallic
Materials, ASTM E399-09 in Annual Book of ASTM Standards, Vol. 03.01, ASTM, West
Conshohocken, PA, 2010.
1387
1388
Before De-Scaling
After De-Scaling
Figure 3 shows the appearance of circumferential cracking on tubes and fins. The thermal
fluctuations that occur as a result of slag removal and operating changes etc. create alternating
stresses in boiler tubes that lead to cracks[3].
1389
Leakage
Leakage
NOx combustion environment in a Japanese coal fired supercritical boiler, a field test on Alloy
622 weld overlay panels has continued since in 2006. In order to develop a fundamental
understanding of the high temperature corrosion behavior of Alloy 622 weld overlay, gaseous
corrosion testing and mechanical tests related to aging were carried out.
EXPERIMENTAL PROCEDURE
Sample Panel in Field Testing
The Alloy 622 weld overlay sample panel consists of 16 tubes with 2500mm height, and overall
dimensions of 710mm x 3000mm. The material composition of the tube to be examined was
1.25%Cr-0.5%Mo steel (equivalent to SA-213T11), with tube diameter of 28.6mm. The tubes are
rifled, and nominal tube thickness at the bottom of the rib is 5.7mm. Sample panel welding
employed Alloy 622 filler metal wire measuring 1.2mm in diameter. Table 1 shows the chemical
composition of the Alloy 622 filler wire used to produce the weld overlay samples in this study. A
gas shielded metal arc welding (GMAW) overlay machine deposits weld beads from the fin and
then moves to the tube section to achieve a uniform coverage of the sample panel. Each weld bead
was overlapped by the subsequent weld bead to ensure full coverage with no missed spots. The
Alloy 622 weld overlay sample panel was placed in the front wall above the burners in the
Japanese supercritical boiler.
Table 1 Chemical composition of Alloy 622 weld wire(Weight%)
Wire rod
deposite metal
Si
Mn
Cr
Mo
Cu
Co
Fe
Ni
0.003
0.04
0.15
0.01
0.001
21.2
13.4
0.05
1.0
0.05
4.6
3.0
Bal.
2.5
3.5
Bal.
AWS Code
20.0 12.5
2.0
0.015 0.08 0.50 0.02 0.010
0.50 2.5 0.35
(ER NiCrMo-10)
22.5 14.5
6.0
Corrosion Testing
Two alloys, Type 309 stainless steel and Alloy 622, were selected for corrosion testing as weld
overlay materials. Low alloy steel tube SA-213T11 (1.25%Cr-0.5%Mo), being widely used as
waterwalls, in coal fired boilers, was used as the reference sample. Welding samples were
prepared using automatic MIG welding. Weld wire from each material was deposited onto
1.25%Cr-0.5%Mo steel tube using a single pass overlay. Each corrosion specimen was machined
from the overlay welded tube, so that all of the 1.25%Cr-0.5%Mo steel tube base metal was
removed. Corrosion specimen dimensions were 10x10x2mm. All specimens were measured and
cleaned in ethanol prior to corrosion testing. The corrosion specimens were kept in Al2O3
crucibles. Figure 5 shows a typical set of samples prior to exposure. Argon gas was used to flush
the test chamber several hours before injection of the corrosion gas. The furnace was heated to the
test temperature of 500C or 650C.The gas used for corrosion testing represented a typical low
NOx combustion environment, with sulfidizing gas composition of 960ppmH2S-6.6%CO2.5%H2-13.4%CO2-71%N2.
1391
In this study, the corrosion tests were performed for 200 hours at 500C and at 650C
respectively. After corrosion testing, the specimens were immersed in 18%NaOH-3%KMnO4
solution and then de-scaled using 10% ammonium citrate aqueous solution. The specimens were
weighed before and after the exposure period, and each specimen was measured to assess the
corrosion rate. The chemistry of a weld overlay is strongly dependent upon the wire chemistry,
welding method, weld bead sequence and other factors. There will be some dilution in chemistry
for the weld overlay, and the typical chemistry dilution from the wire is 10-20%. The chromium
range for Alloy 622 weld overlay metal is 20 to 22%, meaning that the overlay Cr content is about
18 to 20%Cr.
Test specimen
Figure 5 Corrosion test specimens and typical set of samples prior to exposure
Fatigue Testing of Aged Tubes
Low cycle fatigue tests were performed in a push mode on the aged overlay welded tubes. As
shown in Figure 6, a four point bend test machine was used in order to study low cycle fatigue
strength on the overlay welded tubes. In this test, cyclic tensile stress was applied on the surface
of the overlay welded tubes. The tubes were heated to 500 using the heating coil as shown in
Figure 6 and were tested up to failure. In this test, cycles to failure (Nf) was defined as a point at
which the tensile load measured by means of a load cell decreased rapidly. Crack initiation
behaviors on the overlay welded tube surface were also checked.
50mm
150mm
a) Size of test specimen
Heating Coil
b) Photograph of fatigue testing
1392
Figure 8 Installed sample panel after four years exposure and de-scaling
1393
10mm
Figure 10 Corrosion test specimens after de-scaling treatment
1394
4.0
3.5
3.5
4.0
3.0
2.5
2.0
1.5
1.0
0.48
0.5
0.17
0.0
2.9
3.0
2.5
2.0
1.5
1.0
0.5
0.04
0.35
0.05
0.0
(a) 500C
(b) 650C
Figure 11 Corrosion rates resulting from corrosion testing in a sulfidizing atmosphere consisting of
960ppmH2S-6.6%CO-2.5%H2-13.4%CO2-71%N2 for 200hr at 500 and at 650
Fatigue Testing of Aging Tubes
The fatigue strength of overlay welds gradually decreased with a long time used, as shown in
Figure12, with aging specimens. The applied stress on the tubes, however, is comparatively small,
so that the overlay welded tubes have sufficient fatigue strength in terms of practical use, based on
the results of the fatigue test in Figure12. Tube appearances after the fatigue test are also shown in
Figure13.
:1%Cr Bare Tube
Overlay Welded (As Weld)
:Overlay Welded (PWHT)
Aging 6001000h
Aging 6003000h
PWHT + Aging 7001000h
(MPa)
1000
2000
()
at 500
500
Actual
Stress
100
103
Require
of Cycle
104
105
106
107
1395
Crack
1396
ABSTRACT
Current nondestructive examination (NDE) technology detection capabilities limit our ability to
detect stress corrosion cracking (SCC) damage until it has progressed significantly. This work
describes the continued development of an in-situ monitoring technique to detect and characterize
mechanical damage caused by SCC, allowing the detection of the incipient stages of damage to
components/piping. The application of this study is to prevent failures in the primary cooling loop
piping in nuclear plants. The main benefit to the industry will be improved safety and component
lifetime assessment with fewer inspections. The technique utilizes high resolution fiber optic
strain gages mounted on the pipe outside diameter (OD). This technique has successfully detected
changes in the residual stress profile caused by a crack propagating from the pipe inside diameter
(ID). The gages have a resolution of < 1 . It has been shown experimentally for different crack
geometries that the gages can readily detect the changes of approximately 10-60 caused on the
OD of the pipe due to crack initiation on the ID. This paper focuses on the latest in the
development of the technology. Details of the previous work in this effort may be found in
References 1 through 3. A short summary is provided in this paper. The main recent development
was the full scale accelerated SCC cracking in boiling magnesium chloride (MgCl2) experiment.
In conjunction with experimentation, both 2D and 3D finite element (FEA) models with thermal
and mechanical analyses have been developed to simulate the changes in residual stresses in a
welded pipe section as a SCC crack progresses.
INTRODUCTION
Background and Motivation
One of the biggest challenges for the nuclear power industry is SCC in aging materials as plants
continue to run beyond their original design lifetimes. This occurs in structural materials of
pressurized water reactors (PWR) and boiling water reactors (BWR) primarily in the sensitized
heat affected zones (HAZ) of welds. Current NDE technology is limited in its ability to detect
1397
SCC cracks in their incipient stages. Previous laboratory-based studies undertaken by EPRI
suggest that component lifetime in the field is more often governed by the initiation and growth of
short SCC than by the growth of long (deep) cracks [4]. SCC is especially dangerous as it can
propagate rapidly once initiated with little or no change in external environment. The inspection
interval for each individual weld may be as long as 10-15 years of operation. This is likely
sufficient time for a through wall crack to form from an initiation point that currently is too small
to detect. The purpose of this work has been to develop a real time in-situ technique to allow the
earliest possible detection of incipient stage damage to components/piping. This is achieved by
monitoring the change in residual stress on the pipe OD as an ID SCC crack initiates, using highly
sensitive fiber optic strain gages. The technique has gone through proof of concept [1-3], and this
work now presents the results from the most realistic damage simulations (both experimental and
modeling based) to date. The main benefit to EPRI members will be improved component lifetime
assessment with fewer inspections.
DISCUSSION
Overview of Monitoring Technology Development to Date
A more complete description of the various stages and experimental methods may be found in
References 2 through 4. Firstly, a proof of concept study was conducted on a flat welded plate. A
crack front was simulated by electrical discharge machining (EDM) that introduced a linear
advancing crack front from the weld root towards the crown. A second experiment set used an
EDM electrode to simulate a more realistic semielliptical crack front progressing through a
circumferential weld in a pipe section. These experiments both showed that there was a
measureable and distinct strain response to crack initiation and propagation, independent of
temperature change, on the weld crown side (OD for the pipe) of a crack initiated on the opposite
side. In an effort to correlate strain response with crack depth, the initial portion of the data for
each semielliptical crack front experiment was taken and normalized to remove the time
component. Figure 1 shows the strain response data for the central strain gage for the first 5 mm
of cut for each of the normalized data sets.
Figure 1: Normalized Strain versus Depth Correlation Elliptical EDM Crack Experiment.
It can be seen that the relationship between cut depth and strain response is approximately linear
for the first 3 mm. Experimental limitations prevent constant cut rate beyond this depth. With
1398
further data sets it may be possible to develop a semi-quantitative relationship between crack
depth and strain response for a single crack. The presence of multiple, interacting, or branched
cracks will likely make this significantly more challenging. The experiments were limited in their
ability to accurately simulate an SCC crack, as the cracks produced were not branched, and they
did not follow the path of the sensitized region in the HAZ. There were also some equipment
limitations that prevented a constant crack growth rate. However, it was considered sufficient to
prove the concept that changes in residual stress could be used to monitor for crack initiation.
Full Scale Boiling MgCl2 Accelerated SCC Experimental Method
This experiment represents the most realistic simulation of SCC cracking to date. The specimen
used was, as in the semielliptical EDM experiments, a 12-inch OD 304L pipe section with a
1-inch wall thickness, and a height of 22 inches. There was a single V-groove circumferential
weld half way along its length. The experimental method is based on ASTM G36 - 94(2013):
Standard Practice for Evaluating Stress-Corrosion-Cracking Resistance of Metals and Alloys in a
Boiling Magnesium Chloride Solution [5]. This standard uses small test coupons (approximately
0.5-1.0 inch2) immersed in boiling MgCl26H2O in a 1-liter Erlenmeyer flask. The boiling
magnesium chloride test is applicable to wrought, cast, and welded stainless steels and related
alloys. It is a method for detecting the effects of composition, heat treatment, surface finish,
microstructure, and stress on the susceptibility of these materials to chloride stress corrosion
cracking [5]. The boiling MgCl2 solution reacts with the stainless steel to achieve chloride stress
corrosion cracking in an accelerated time frame. The experimental method employed here uses a
scaled up specimen in the form of the entire pipe section, and an accordingly scaled up volume of
corrosive media.
Figure 2 shows a diagram of the experimental set up with an image of the as-built apparatus.
Eighteen fiber optic strain gages (SG) and six temperature compensation (TC) gages were evenly
spaced around the OD of the pipe spanning the weld.
experiment. The external thermocouple records fluid temperature at a rate of 1 Hz. The boiling
solution is maintained until through wall cracking is observed or significant cracking is observed
in the strain responses. Additional MgCl26H2O powder is added as necessary to counteract any
evaporative fluid losses.
Full Scale Boiling MgCl2 Accelerated SCC Results & Discussion
The experiment ran for a total of 12 days before the heater failed, causing the MgCl2 solution to
solidify. Importantly, the solution in contact with the weld and HAZ area on the ID remained
molten throughout the experiment. The apparatus was disassembled and the ID surface of the
weld inspected using dye penetrant (DP) to check for indications of cracking around the weld.
Figure 3 shows the results of the DP inspection. Indications of cracking were evident in the HAZ
regions both above and below the root of the weld pass around almost the entire circumference of
the pipe ID.
1400
The SG and TC data were processed and analyzed upon completion of the experiment. Strain
events that were independent of temperature events were identified, and are summarized below:
Figure 6 shows strain and temperature data for a select time period near the beginning of
the run. There is a strain event indicated on all of the SGs simultaneously at time stamp
105.5x103 s. There are no corresponding temperature responses. This is the first large
strain change. The response is characterized by a sharp change in slope for a response of
approximate magnitude of approximately 50 . This is similar to the EDM experiments.
The strain change measured on all gages simultaneously and to similar magnitude. This
is the likely initiation point of one or multiple SCCs.
1401
Figure 7 shows strain and temperature data for a subsequent time period. The plot shows
a divergence of SG10 (green) and SG18 (brown) from the baseline strain. This is a more
gradual slope change, followed by a steady strain response. SG10 and SG18 are
approximately opposite each other around the pipe OD, suggesting that a single cracking
event puts one side of the pipe into compression and the other into tension. Given that
this is a gradual slope change compared to that observed in Figure 6, this is likely the
strain response to steady state crack growth. There are some thermal events also shown
on the plot. The drop in temperature likely closed up the SCC crack as indicated by the
sharp strain increase in SG10. There is a gradual decrease in temperature throughout the
time period, which corresponds to the gradual increase in baseline strain. The data shows
interaction of multiple initiating and growing cracks. Unlike the previous EDM tests, it
will likely be very challenging to relate strain responses for multiple cracks to location
and length. However, sharp changes in slope in the strain response may still be
distinguished and flagged as a crack initiation/growth event for further inspection.
Multiple other examples of steady state growth were found in the data.
Figure 8 shows strain and temperature data for a subsequent time period. The event at
time stamp approximately 320-325x103 s shows a sudden strain increase, followed by
steady state, then a similar sharp decrease (a hat shaped profile). The magnitude was
largest at SG10, but was registered on all the other gages. The event could have been a
pop when the crack progressed through a localized region of lower toughness, and then
arrested once it progressed through this region, perhaps passing from HAZ to weld metal
or weld bead to weld bead. The hat shaped profile strain event was observed several
times after this as the experiment progresses. There is a continued increase in strain over
the baseline at SG1 and SG2 as crack progresses. A possible explanation for the resetting
of the stress is local deformation at the crack tip.
1404
With the initial 3D analysis complete, a sensitivity study needs to be done to discover how much
detail can be removed or needs to be added to retain sufficient accuracy to be used to analyze the
effects of SCC. These initial results show that more fidelity is needed in the HAZ. This will be
accomplished by extending the fine detailed mesh in the weld zone out further through the HAZ.
Tetrahedral elements will be kept away from the areas of interest. The model will be further
reduced by taking advantage of the axial symmetry and processed as a half model. Stress
distribution changes due to cracking can then be introduced by freeing boundary constraints along
the symmetry line thus simulating crack propagation.
Other possible areas to explore to reduce computing time would include combining multiple
passes into a single lumped pass, taking advantage of lateral symmetry, or applying single weld
passes at once instead of simulating a moving welding arc.
CONCLUSIONS AND FURTHER WORK
In summary there are three distinct types of strain/cracking event that have been detected in this
experiment:
Initiation of SCC cracking in the form of an approximately 60- spike in strain in all
gages, similar to that observed in previous EDM experiments.
Steady state crack growth indicated by a gradual and sustained divergence from the
baseline strain.
Start/stop or pop crack growth characterized by hat shaped strain profiles as a crack
progresses through a localized region of lower toughness, and then arrested once it
progressed through this region.
It is also evident from the complexities of crack interaction observed in this more realistic
simulation of SCC that it would be highly challenging to correlate crack depth and location
around the circumference with strain response. However, sharp changes in slope in the strain
response may still be distinguished and flagged as a crack initiation/growth event for further
inspection.
The main conclusions from the initial results of the weld simulation model were:
1405
We have successful developed and documented a procedure for analyzing weld residual
stresses using the ANSYS finite element software package. A complete set of input
macros have been written to allow for easily changing the parameters such as weld and
piping dimensions, number of weld beads, heat input, meshing of the model, and solving.
Comparative studies can now be efficiently solved and analyzed.
The axial and hoop stresses did not produce smooth patterns or believable results due to
mesh coarseness in the HAZ and the stiffness of the tetrahedral elements.
A sensitivity study should be performed to ascertain the level of detail that can be
removed or needs to be added to retain sufficient accuracy to be used to analyze the
effects of SCC.
A greater degree of fidelity is required in the HAZ. This will be accomplished by
extending the fine detailed mesh in the weld zone out further through the HAZ.
Tetrahedral elements will be kept away from the areas of interest.
The model will be further reduced by taking advantage of the axial symmetry and
processed as a half model.
Once fidelity has been improved, stress distribution changes due to cracking may then be
introduced by freeing boundary constraints along the symmetry line thus simulating
crack propagation.
This experiment has confirmed that it is possible to generate real SCC cracks on a large scale.
They can be detected using fiber optic strain gages monitoring the change is residual stress on the
OD of a pipe section as a result of ID initiated SCC cracks. The strain events are all characterized
by an abrupt change in strain with respect to time. Such an abrupt change is unlikely to be due to
external events in a plant. In order to automate cracking event detection, data could be analyzed
by taking a running average of the data to reduce noise, then taking its first derivative. The sharp
changes of slope associated with strain events will then be flagged in a first derivative of strain
response vs. time plot. The results of this and future large scale SCC experiments will then be
used to calibrate the weld simulation model. This model may then be used and adapted to simulate
a variety of damage mechanisms and geometries.
REFERENCES
[1] Jackson, B., Interim Status Update: EDM Crack Simulations, (2010) EPRI Project Status
Report AES 10067465-2-1.
[2] Jackson, B. et al, Detection of Incipient SCC Damage in Primary Loop Piping using Fiber
Optic Strain Gages, (Orlando, FL, 2011) EPRI Conference: Welding and Fabrication
Technology for New Power Plants and Components.
[3] Jackson, B. et al, Detection of Incipient SCC Damage in Primary Loop Piping using Fiber
Optic Strain Gages, (Columbus, OH, 2011) MS&T2011.
[4] Hickling, J. et al, Status Review of Initiation on Environmentally Assisted Cracking and
Short Crack Growth, (2005) EPRI Report 10117888.
[5] Standard Practice for Evaluating Stress-Corrosion-Cracking Resistance of Metals and
Alloys in Boiling Magnesium Chloride Solution, (2013) ASTM G36-94.
[6] Materials Safety Data Sheet (MSDS) for Magnesium Chloride Hexahydrate (MgCl26H2O),
CAS# 7791-18-6, ACC# 13365, Revised 8/20/2000.
1406
ABSTRACT
Low thermal expansion precipitation strengthening Ni-base superalloy, Ni-20Cr-10Mo-1.2Al-1.6Ti
alloy (USC141TM), was developed for 700oC class A-USC steam turbine material by Hitachi, Ltd and
Hitachi Metals, Ltd. USC141 is usually solution treated and then aged to increase high temperature
strength for turbine blades and bolts. As the estimated 105h creep rupture strength at 700oC is about
180MPa, USC141 could also be expected to apply for boiler tubes. On the other hand, this alloy seems
to be only solution treated to apply for boiler tubes because tubes are usually jointed by welding and
bended by cold working and thus tube alloys should have low hardness before welding and bending
and should be used as solution treated. In this study, the creep properties of USC141 as solution
treated was evaluated, and the results and microstructures after creep tests were compared with those
as aged. As a result, USC141 as solution treated exhibited almost as same creep rupture properties as
that as aged because precipitation at grain boundaries and in grains gradually increased at testing
temperatures around 700oC. Furthermore seamless tubes of USC141 were produced and various
properties including creep properties are now being evaluated.
Keywords ; Ni-base superalloy, A-USC, boiler, creep, solution treatment, microstructure
INTRODUCTION
High efficiency coal-fired thermal power plants are required in order to reduce CO 2 emission which
affects global climate change and 700oC class advanced ultra super critical (A-USC) power plants are
being developed. In A-USC power plants, materials for steam turbine blades and bolts, boiler tubes,
main steam pipes, and so on are exposed at 700oC or higher. Although current main materials for USC
power plants are ferritic heat resistant steels, they do not have enough high temperature strength and
oxidation resistance at temperatures higher than 600C. In the temperature range of 600 - 700C
austenitic stainless steels are already used today for superheater and reheater applications. Only Nialloys have enough high temperature strength for material temperatures above 700C and will
therefore be used for A-USC power plants. Low thermal expansion Ni-base superalloy, USC141, has
been developed for A-USC steam turbine and bolt materials [1]. In addition, USC141 showed low
segregation tendencies and it can be cast to a large remelted ingot without freckle segregation for AUSC applications [2].
For turbine and bolt applications, USC141 is used after solution treatment and 2-step aging treatment
to precipitate phase in austenite grain and Cr carbide along grain boundary and obtain high tensile
strength, high creep rupture strength, and good creep rupture ductility. On the other hand, for boiler
1407
tube application, it should be used as solution treated because high creep rupture strength as well as
good weldability and cold bending property are required. Although microstructure of USC141 as
solution treated does not have precipitates as a strengthening phase, operating temperature of 700oC
class A-USC is comparable to the aging temperature of USC141 and phase can precipitate and
strengthen the alloy during operation of boiler. Furthermore, low thermal expansion property of
USC141 is expected to result in high thermal fatigue strength and to be easily jointed with ferritic
steels by welding. In this study, creep rupture strength and microstructural change of USC141 as
solution treated were investigated in order to apply USC141 for boiler tubes, compared with USC141
after aged.
EXPERIMENTAL PROCEDURES
Table 1 shows the typical chemical compositions of USC141 used in this study. Forged bars of
USC141 were solution treated at 1066oC for 4 hours and cooled in air. Tube material of USC141 of
which outer diameter was 44.5mm and wall thickness was 10mm as solution treated was also prepared.
Creep rupture test was carried out at 650, 700, 750, 800, and 850oC. Optical microstructure and
scanning electron microstructure were observed before and after creep test. Microstructures of some
specimens were also observed and analyzed with electron probe micro analyzer (EPMA) and
transmission electron microscope (TEM). Solution treatment and aging treatment are described as
(ST) and (Ag) respectively.
Table 1 Typical chemical compositions of USC141 (mass%)
C
Cr
Mo
Al
Ti
Ni
0.03
20
10
1.2
1.6
bal.
RESULTS AND DISCUSSION
Initial microstructure of bar material
Figure 1 shows the initial microstructure of USC141 bar as solution treated at 1066oC for 4 hours
observed with optical microscopy and FE-EPMA. Grain size number in ASTM was 5.5. No
precipitates such as carbides and metallic compounds were observed along austenite grain boundaries
although a small amount of undissolved carbides remain in austenite grains. precipitates were not
observed in the specimen as solution treated. In comparison with microstructure as solution treated,
scanning electron microstructure of bar material after 2-step aging is shown in Figure 2. The solution
treatment condition of aged specimen was the same as that of specimen as solution treated, and the
first aging was carried out at 850oC for 4 hours cooled in air to room temperature and the second aging
was carried out at 760oC for 16 hours and cooled in air. In the aged specimen, M 23 C 6 type Cr carbides
were observed along austenite grain boundaries and undissolved carbides were also observed in
austenite grains. A large amount of small precipitates were also observed in austenite grains in the
aged specimen.
1408
(a)
(b)
2m
50m
(b)
(c)
2m
50m
200nm
1409
1000
1000
(b)
Stress (MPa)
StressMPa
(a)
600_(ST)+(Ag1)+(Ag2)
650_(ST)+(Ag1)+(Ag2)
700_(ST)+(Ag1)+(Ag2)
750_(ST)+(Ag1)+(Ag2)
800_(ST)+(Ag1)+(Ag2)
650_(ST)
700_(ST)
750_(ST)
100
10
100
1000
10000 100000
100
800_(ST)
17
18
Time to ruptureh
19
20
21
22
23
24
25
26
(T+273)(20+Logt)/1000
Figure 3 Creep rupture strength of USC141 bar compared with that after 2-step aging.
(a)Creep rupture strength as a function if rupture time,
(b)Creep rupture strength as a function of Larson-Miller parameter.
1410
analyzed with EDS of TEM and it contained 29.4at%Ni, 22.9at%Cr, and 47.7at%Mo. From this TEM
analysis, this phase was identified as phase ((Ni, Cr) 7 Mo 6 ).
From the observation of microstructure and the EPMA analysis of USC141 bar as solution treated
before and after creep rupture test, it is found that the microstructure of USC141 bar as solution
treated changed in austenite grains as well as at austenite grain boundaries during creep rupture test.
There were no precipitates except for a small amount of undissolved M 6 C type carbide in austenite
grains as well as at austenite grain boundaries before creep rupture test. However, M 23 C 6 type carbide,
phase, and phase precipitated gradually at austenite grain boundaries while particles precipitated
in austenite grains gradually during creep rupture test. It is thought that this precipitation during creep
rupture test increased the creep rupture strength of USC141 bar as solution treated up to the creep
rupture strength of that after 2-step aging. It took about 250 and 4,000 hours at 750 and 700oC
respectively. At not lower than 800oC, creep rupture strength of USC141 bar as solution treated
became the same level as that after 2-step aging within about 10 hours.
Tr=525.0h
Tr=2765.3h
Tr=12176.6h
Tr=16385.0h
Tr=5911.2h
200nm
Figure 4 SEM images of particles in austenite grains USC141 bar as solution treated
after creep rupture test at 700oC.
Tr=1032.8h
Tr=2440.1h
Tr=8180.4h
200nm
Figure 5 SEM images of particles in austenite grains USC141 bar as solution treated
after creep rupture test at 750oC.
1411
100
90
700_(ST)
80
750_(ST)
70
60
50
40
30
20
10
0
0
10
15
20
25
30
Time to rupture1/3h1/3
Tr=525.0h
Tr=2765.3h
Tr=5911.2h
Tr=16385.0h
5m
Figure 7 SEM image around austenite grain boundaries after creep rupture test at
700oC of USC141 bar as solution treated.
Tr=1032.8h
Tr=2440.1h
Tr=8130.4h
5m
Figure 8 SEM image around austenite grain boundaries after creep rupture test at
750oC of USC141 bar as solution treated.
1412
25
Mol %
20
15
10
M23C6
M6C
0
600
700
800
900
1000
1100
Temperuture
BSE
Cr
Mo
Ni
Al
1m
Ti
1413
(a)
(b)
(c)
500nm
Figure 11 TEM bright(a) and dark(b) field images and electron beam
scattering pattern(c) of phase in USC141 bar as solution treated after
creep test at 700oC for 2765.3h.
1414
(a)
(b)
5m
100m
1000
(a)
(b)
Stress (MPa)
StressMPa
1000
100
Bar
Tube
(ST)
(ST)
100
650_(ST)
700_(ST)
750_(ST)
800_(ST)
700_tube(ST)
750_tube(ST)
800_tube(ST)
850_tube(ST)
650
700
750
800
850
10
10
100
1000
10000 100000
Time to ruptureh
10
17
18
19
20
21
22
23
24
25
26
27
(T+273)(20+Logt)/1000
Figure 14 Creep rupture strength of USC141 tube compared with USC141 bar
as solution treated.
(a)Creep rupture strength as a function of rupture time,
(b)Creep rupture strength as a function of Larson-Miller parameter.
CONCLUSIONS
(1) Creep rupture strength of USC141 bar as solution treated with grain size No.5.5 is almost as same
as that after 2-step aging. The creep rupture strength at 700oC for 100,000 hours for USC141 bar as
solution treated and after 2-step aging is estimated at 180MPa, which is much higher than 100MPa.
(2) phase in austenite grains and M 23 C 6 , phase, and phase at grain boundaries as solution
treated precipitated during creep test of USC141. It is thought that this microstructural change during
creep test for a long time was able to increase the creep rupture strength up to the same strength level
as USC141 bar after 2-step aging.
1415
(3) Creep rupture strength of USC141 tube as solution treated with grain size No.2-3 is a little higher
than that of USC141 bar. This is due to the same precipitation behavior of USC141 bar as solution
treated during creep test, as well as its larger grain size than bar.
REFERENCES
[1] T. Ohno, A. Toji, T. Uehara, G. Bao, J. Sato, S. Imano, Development of low thermal expansion
nickel base superalloy for steam turbine applications, 5th International Conference of Advances in
Materials Technology for Fossil Power Plants, 2007.
[2] H. Kamoshida, S. Imano, E. Saito, T. Uehara, T. Toga, T. Nonomura, Low thermal expansion
superalloy for 700C class steam turbine plant (USC141), 6th International Conference of Advances in
Materials Technology for Fossil Power Plants, 2010.
1416
1417
Cr
9
Mo
1
C
<0.15
Si
0.25-1
Mn
0.3-0.6
P
<0.03
S
<0.03
Oxidation experiments were performed using a vertical furnace, which has been
described elsewhere [6]. Samples were set in the furnace hot zone by suspending them in an Al2O3
crucible. The reaction tube was purged with oxidizing O2, CO2, or CO2-O2 mixed gas several
times prior to each oxidation test. The samples were heated at a rate of 10C/min to the oxidation
temperature of 700C in a flowing oxidizing gas stream with a flow rate of 150cm3/min. After the
oxidation test, samples were furnace cooled in the same oxidizing gas stream with a flow rate of
50cm3/min. Laboratory air, CO2 (>99.5 vol.%, H2O<0.012vol.%), and CO2-0.6, 1, 2, 3 vol.%O2
gas mixtures were used for the oxidation tests.
RESULT AND DISCUSSION
Oxidation Kinetics
Figure 1 shows the oxidation kinetics of Fe-9Cr-1Mo steel at 700C in different atmospheres. In
air, Fe-9Cr-1Mo steel oxidized very slowly at least until 100h of oxidation, but it was oxidized
faster in CO2. In CO2, the oxidation rate was relatively slow for the first 25h of oxidation, but
rapidly increased after further oxidation. The oxidation behavior of steel in CO2-O2 mixtures fell
between that of O2 and CO2. The incubation period before rapid oxidation occurs was observed
in CO2-O2 mixtures and the period became shorter with decrease in O2 content in the atmospheres.
1418
Surface morphologies
Figure 2 shows surface appearance of the samples oxidized at 700C for 25h in air, CO2, and
CO2-O2 mixtures. Fe-rich oxide nodules were observed to develop on all samples oxidized in
atmospheres with CO2. The number of nodules decreased with increasing O2 content in the gas
mixture. The areas where nodules were not formed were very smooth and showed interference
color, indicating that thin protective Cr2O3 scale was developed. The same smooth surface
appearance was observed on the steel oxidized in air. With longer oxidation, nodules grew
laterally larger in size and connected with each other. The surface of the steel oxidized in CO2
was completely covered by these nodules, but the areas with interference color remained on steels
oxidized in CO2-O2 mixtures.
Figure 2. Surface appearance of alloy after oxidation test in different atmospheres for 25h.
As shown in Figure 3, the number of nodules formed on the steel in different CO2-O2
mixtures increased initially up to 9 h, but then decreased with further oxidation. This decrease in
the number of nodules was due to their lateral growth and merging. After 25 h the surface of the
steel oxidized in CO2 was completely covered by these nodules (see Figure 2).
1419
Figure 3. Change in the number of nodules with oxidation time in different CO2-O2 mixtures.
Formation and growth of these nodules was the cause of increasing mass gain in CO2 containing
atmospheres, and introducing oxygen into the atmospheres prevented the formation of nodules.
Cross-sectional microstructure
Figure 4 shows the cross-sections of steel oxidized in CO2 at 700C for 25 h [2]. The nodules
were confirmed to consist of a thick duplex oxide scale. Outer and inner oxide layers were
confirmed to be Fe3O4 and FeCr2O4, respectively. The oxide scale formed on nodules free areas
was too thin to observe by SEM. An internal carburization zone was found to develop below
nodules, and growth of the internal carburization zone was confirmed to follow parabolic kinetics.
1420
The oxidation mass gain decreased with increasing oxygen content in the atmosphere. This
was because the number of nodules decreased with increasing oxygen content.
Nodules grew larger with oxidation time, but the number of nodules was independent of
oxidation time.
Existence of intrinsic defects in the initially formed protective Cr2O3 scale and gas
permeation via intrinsic defects is proposed to explain the dependence of the number of
nodules on oxygen content in the gas mixtures.
ACKNOWLEDGMENTS
Support for this work was provided by ISIJ Research Promotion Grant (2011-2012).
REFERENCES
[1] B.J.P. Buhre, L.K. Elliott, C.D. Sheng, R.P Gupta, T.F. Wall, Oxy-fuel combustion
technology for coal-fired power generation, Progress in Energy and Combustion Science,
Vol. 31, No. 4 (2005), pp. 283-307.
[2] K. Kaya, S. Hayashi, and S. Ukai, High-temperature oxidation behavior of 9Cr Ferritic-steel
in carbon dioxide, ISIJ international, submitted.
[3] M.R. Taylor, J.M. Calvert, D.G. Lees, and D.B. Meadowcroft, The Mechanism of Corrosion
of Fe-9Cr Alloys in Carbon Dioxide, Oxidation of Metals, Vol. 14, No. 6 (1980), pp. 499516.
[4] C.S. Giggins and F.S. Pettit, Corrosion of Metals and Alloys in Mixed Gas Environments at
Elevated Temperatures, Oxidation of Metals, Vol. 14, No. 5 (1980), pp. 363-413.
[5] D.J. Young, High Temperature Oxidation and Corrosion of Metals, Elsevier (Oxford, UK,
2008), pp. 353.
[6] C. Matsukawa, S. Hayashi, High-temperature carburization behavior of HASTELLOY X in
CH4 gas, Corrosion Science, Vol. 53, No. 10 (2011), pp. 3131-3138.
1421
ABSTRACT
Six types of solution treated Ni-based alloy plates having a thickness of 25mm, namely Alloy 617,
Alloy 263, Alloy 740, Alloy 141, HR6W (45Ni-23Cr-7W) and HR35 (50Ni-30Cr-4W-Ti) for
advanced-USC boilers, were subjected to corrosion testing. In addition, three types of
conventional ferritic and five types of conventional austenitic stainless tubes were also tested to
compare their corrosion properties. Hot corrosion tests were conducted in order to assess the
effects of temperature, material composition and coal ash composition on hot corrosion. The
maximum average metal loss and the maximum corrosion rate were observed under 700C test
conditions. Cr content in the materials played an important role in the corrosion rate, with higher
Cr content materials tending to show lower rates. However, Ni-based alloy materials showed
slightly greater corrosion rates than those of stainless steels having equivalent Cr content in the
over-700C test condition. It was considered that rich Ni in the alloys easily reacted with sulfur,
thus forming corrosion products having low melting points, such that corrosion was accelerated.
The concentration of Fe2O3 and NiO in the synthetic coal ash was also observed to affect the
corrosion rate.
INTRODUCTION
To improve the thermal efficiency and reduce CO2 emissions in coal fired plants, a Japanese
national project for developing an advanced ultra-supercritical power plant having a 700C steam
temperature has been conducted since Aug. 2008[1]. The application of Ni-based alloy tube for
the superheater and reheater in the highest temperature zone is indispensable, given the
requirements for creep strength and corrosion resistance. As the maximum temperature of the
tubes in this zone will reach up to 750C, coal ash corrosion resistance must be considered in
selecting the tubing materials. Evaluation of the coal ash corrosion properties of candidate Nibased alloy materials for the advanced-USC boiler was carried out in this study, as compared with
those of conventional ferritic and austenitic stainless steels. In a previous study, the effects of
temperature, Cr concentration and SO2 concentration on hot corrosion were reported[2]. The
present study is mainly concerned with the effect of coal ash composition on hot corrosion.
1422
EXPERIMENTAL PROCEDURES
Table 1 shows the chemical composition of candidate alloys and steels for comparison. The
candidate alloys are Ni-based alloys, namely Alloy 617, Alloy 263, Alloy 740, Alloy 141, HR6W
(45Ni-23Cr-7W) and HR35 (50Ni-30Cr-4W-Ti). The steels for comparison are three types of
conventional ferritic and five types of conventional austenitic stainless steels.
Table 1 Chemical composition of candidate alloys and comparative steels
Chemical composition (mass%)
Ni-based
alloys
Ferritic
steels
Austenitic
stainless
steels
Comparative steels
Candidate alloys
Alloy
Fe
Cr
Ni
Mo
Co
Others
Alloy141
20.2
66.7
10.0
Ti, Al
Alloy263
20.2
50.9
5.9
20.0
Ti
Alloy617
22.0
55.3
9.0
11.8
Al
22.8
23.1
45.3
7.1
25.1
49.2
0.5
20.1
Ti, Nb, Al
HR35
14.8
29.8
50.3
4.0
T22
96.0
2.1
1.0
T91
89.3
8.4
0.9
HCM12
84.3
11.8
1.1
1.0
TP347HFG
67.6
18.3
11.3
Nb
SUPER304H
68.7
18.4
8.4
Nb
XA704
65.9
19.1
9.9
2.1
NF709R
49.0
22.3
25.4
1.4
HR3C
53.5
24.3
20.1
HR6W
Alloy740
The samples were cut from the respective materials, sized 14 x 14 x 3mm. Three samples for each
material and each condition were polished using #600 emery paper. The corrosion tests were
carried out at 650C, 700C, 750C and 800C for 100h in SO2-bearing gaseous environments,
with a coating containing alkali sulfate applied to the sample surface, so as to simulate fire-side
coal ash deposition. Table 2 shows the conditions of the high temperature corrosion test regime.
The target compositions of synthetic flue gas were (0.2 or 1.0)SO2+2.6O2+14CO2+10H2O+bal.N2
(vol.%), to evaluate coal fuel with each sulfur content, respectively. Gas flow through the test
chamber was at a rate of 200cc/min. The typical composition of synthetic coal ash for corrosion
testing was 1.5molNa2SO4 + 1.5molK2SO4, 1.5molNa2SO4 + 1.5molK2SO4 + 1.0molFe2O3 and
1.5molNa2SO4 + 1.5molK2SO4 + 1.35molNiO [3, 4, 5], and the amount of synthetic ash coating
was 60mg/cm2.
The sample mass was determined before and after exposure to the simulated coal ash corrosion
conditions. After the corrosion tests, the ash deposits and oxide scale on two samples for each
material and each condition were removed by boiling first in 18% NaOH+3%KMnO4 and then in
10% (NH4)3C6H5O7. The mass change was used to calculate the average weight and the average
thickness. The cross-sectional structure of one sample with oxide scale was observed to determine
the corrosion behavior.
1423
650
700
750
800
Time (hours)
100
100
100
100
100
100
100
100
100
SO2(Vol.%)
0.2
0.2
1.0
0.2
1.0
0.2
1.0
1.0
0.2
Synthetic ash
Alloy141
Alloy263
Alloy617
HR6W
Alloy740
HR35
T22
T91
HCM12
TP347HFG
SUPER304H
XA704
NF709R
HR3C
Austenitic
stainless
steels
Ferritic
steels
Ni-based
alloys
Test
condition
Temperature Dependence
Figure 2 indicates the relationship between the test temperature and average metal loss. It is
known that the corrosion rate in this condition reveals a bell-shaped curve with peak temperature
between 650C and 750C [6, 7]. The average metal loss in this study as a function of temperature
also produces a bell-shaped curve with a maximum rate occurring around 700C. It is assumed
that the corrosive alkali iron tri-sulfate that is formed at just above the melting temperature
accelerates the metal loss. The corrosion reaction is as follows:
3Na2SO4Fe2O33SO32Na3Fe(SO4)3
2Na3Fe(SO4)36Fe3/2FeS3/2Fe3O4Fe2O32Na2SO43/2SO2
(1)
(2)
On the other hand, at higher temperatures corrosive alkali iron tri-sulfate decomposes into simple
sulfates with higher melting temperatures. It is therefore considered that the average metal loss
decreases at over 750C. Moreover the average metal loss increases in higher SO2 content gas
because the amount of the alkali iron tri-sulfate increases.
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
1.0%SO2
Ash A
TP347HFG
HR3C
Alloy740
SUPER304H
T22
HR35
T91
HR6W
0.2%SO2
Ash A
T22
T91
SUPER304H
TP347HFG
HR6W
Alloy740
HR35
650
HR3C 700
750
Temperature
1425
800
HR35
Alloy617
NF709R
HR6W
HR3C
Alloy740
HCM12
T91
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
T22
Figure 3 shows the relationship between the chromium content and average metal loss in
0.2%SO2. The average metal loss decreases with increasing chromium content. It was found that
Cr content in the materials played an important role in relation to the average metal loss, with
higher Cr content materials tending to show lower average metal loss. Ni-based alloys showed a
slightly greater metal loss than for austenitic stainless steel having the same Cr content at 700C
test conditions, but there was no difference at 650C. The reason for this is considered to be that
Ni-based alloys easily form a Ni compound whose melting temperature is about 650C[8, 9]. The
corrosion rate is rapid at just above the melting temperature, such that the average metal loss of
Ni-based alloys is slightly greater than for austenitic stainless steels at 700C[2].
Ferritic
steels
650100h
0.20%SO2
Ash A
Austenitic
stainless steels
Ni-based
alloys
Ferritic steels
SUPER304H
Alloy141
TP347HFG
XA704
Alloy263
700100h
0.20%SO2
Ash A
Ferritic steels
Alloy141
TP347HFG
SUPER304H
Alloy263
Ni-based alloys
XA704
10
15
20
25
Cr contents (mass%)
30
35
Figure 3 Relationship between chromium content and average metal loss under gas condition of
0.2%SO2
Coal Ash Composition Dependence
Figure 4 and Fig. 5 illustrate the effect of coal ash composition on average metal loss. Figure 4
shows the effect of Fe2O3 in synthetic ash on average metal loss at 750C. In the case of ash A,
containing Fe2O3, both Ni-based alloy and austenitic stainless showed a greater average metal loss
than in the case of ash B, which does not contain Fe2O3.
1426
XA704
Ferritic steels
HR35
Alloy617
NF709R
HR6W
HR3C
Alloy740
HCM12
T91
T22
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
Austenitic NiFerritic
stainless based
steels
steels
alloys
Austenitic stainless
steels (Ash A)
SUPER304H
TP347HFG
Ash A
With Fe2O3
Ni-based
Alloys (Ash A)
Alloy141
Alloy263
750100h, 0.2%SO2
Ash B
Without Fe2O3
Ni-based
Alloys (Ash B)
10
15
20
25
30
35
Austenitic stainless
Cr contents (mass%) Steels (Ash B)
Figure 4 The effect of Fe2O3 in synthetic ash on average metal loss at 750C
Alloy141,Alloy263 and Alloy617 showed greater average metal loss than for austenitic stainless
steel having the same Cr content in the test condition of ash B.
HR35
Alloy617
NF709R
HR6W
HR3C
Alloy740
HCM12
T91
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
T22
Figure 5 presents the effect of Fe2O3 and NiO in synthetic ash on average metal loss at 650C. In
the case of changing the additive ash from Fe2O3 to NiO, added to Na2SO4 + K2SO4, austenitic
stainless steel tends to show a greater average metal loss than for Ni-based alloys.
Austenitic NiFerritic
stainless based
steels
steels
alloys
650100h, 0.2%SO2
SUPER304H
Ferritic steels
Austenitic stainless
TP347HFG
XA704
10
15
20
25
Cr contents (mass%)
30
Ash A
With Fe2O3
Ash C
With NiO
35
Ni-based
alloys (Ash A)
Ni-based
alloys (Ash C)
Figure 5 Effect of Fe2O3 and NiO in synthetic ash on average metal loss at 650C
Corrosion Behavior
Figure 6 shows the cross-sectional EPMA analysis after corrosion testing of Alloy 141
(750C100h, 0.20%SO2, ash A and ash B). Due to the effect of Fe2O3 in ash, the surfaces that
were tested using ash A and ash B become uneven. The corrosion products were composed of two
layers with respect to the test condition of ash A. Cr, Fe, S, K and O were detected in the outer
layer, and it was thus considered that Cr oxide such as Cr2O3 and corrosive alkali iron tri-sulfate
1427
had formed. Ni, Mo and S were also detected in the inner layer of the corrosion products,
considered to represent Ni sulfide. In the case of Ni-based alloys tested using ash B, Alloy 141,
Alloy 263 and Alloy 617 show a slightly greater corrosion rate because these alloys contain Mo,
which easily reacts with sulfur[10]. It is difficult to clarify the difference between the cases with
1428
SO2+1/2O2 SO3
SO3
M : Fe,Cr
Fe2O3
Cr2O3
Metal
Na3M(SO4)3
Fe
Fe
FeS M3O4M2O3
CrS
2Na3M(SO4)3+6Fe
3/2MS+3/2M3O4+M2O3+2Na2SO4+3/2SO2
3Na2SO4+M2O3+3SO3
Na3M(SO4)3
Na3M(SO4)3
Cr2O3
NiO
Na2CrO4
Ni3S2
Ni Mo Ni
MoS2
Na2SO4+9/2Ni+1/2Cr2O3+3/4O2
3Na2SO4+M2O3+3SO3
Na2CrO4+3NiO+12Ni3S2
Na3M(SO4)3
(b) Ni-based alloys
1429
CONCLUSION
The average metal loss as a function of temperature produces a bell-shaped curve with the
maximum average metal loss occurring around 700C. It is considered that the corrosive
alkali iron tri-sulfate that is formed at just above the melting temperature accelerates the
average metal loss. At higher temperatures, however, corrosive alkali iron tri-sulfate
decomposes into simple sulfates with higher melting temperatures.
The average metal loss decreases with increasing chromium content in the materials.
Ni-based alloys showed a slightly greater average metal loss than for austenitic stainless
steel having the same Cr content under 700C test conditions, due to formation of Ni-Ni3S2
eutectic with a low melting point of about 650C.
In the case of ash containing Fe2O3, both Ni-based alloy and austenitic stainless steel showed
a greater average metal loss than in the case of ash without Fe2O3. It is assumed that the
melting point of ash containing Fe2O3 is at a lower temperature than for ash without Fe2O3.
When the synthetic ash composition is changed from Fe2O3 to NiO, austenitic stainless steel
tends to show a greater average metal loss than for Ni-based alloys. It is considered that the
melting point of the complex compound is lowered, because Fe2O3 is formed from Fe
contained in the metal, and that Fe2O3, Na2SO4, K2SO4 and NiO will then exist at the metal
surface.
1430
REFERENCES
[1]
[2] Yasuhiro Tanaka et al., " Coal Ash Corrosion Properties of Ni-based Alloy for AdvancedUSC Boilers ", Prof. of 6th International Conference on Advances in Materials Technology
for Fossil Power Plant, (2010), pp.303-311.
[3]
[4]
[5] N.Yamanouchi et al, "Corrosion of ferritic stainless steels in simulated coal fired boiler
environments", Compos. Corros. Coat. Adv. Mater. (1989), pp.371-376.
[6] L.Paul and G.Clark, "Coal ash corrosion resistance of new high chromium and chromiumsilicon alloys", Paper05456, CORROSION2005, NACE, Houston, TX, 2005.
[7]
[8]
[9] Y.B.Gabriel et al., "Corrosion problems in power plants" Corrosion Reviews, 9, Nos.3-4,
(1990), pp.207-234.
[10] H.Makiura et al., "Effect of Nb, Ti, and Mo on the hot corrosion behavior of 18Cr-10Ni
steels", High Temperature Corrosion of Metals and Alloys, (1983), pp.623-630.
1431
ABSTRACT
The current study proposed a new method that utilizes digital image correlation (DIC) techniques
to measure in-situ full field strain maps of creep resistant material welds. The stress-rupture test is
performed in a GleebleTM thermal mechanical simulator. This technique successfully captured a
significant difference in the local creep deformation between two Grade 91 steel welds with
different pre-welding conditions (standard and non-standard). Strain contour plots exhibited
inhomogeneous deformation in the weldments, especially at the heat-affected zone (HAZ).
Standard heat-treated specimens had significant creep deformation in the HAZ. On the other hand,
non-standard heat treated specimens showed HAZ local strains to be 4.5 times less than that of the
standard condition, after a 90-hour creep test at 650C and 70 MPa. The present study measured
the full field strain evolution in the weldments during creep deformation for the first time. The
proposed method demonstrated a potential advantage to evaluate local creep deformation in the
weldments of any creep resistant material within relatively short periods of time.
INTRODUCTION
Due to the heavy use of fossil fuels, the worldwide annual emission of greenhouse gas from fossil
fuel combustion is over 5.4 billion tons [1]. A reduction of CO 2 emission can be achieved by
improving power plant efficiency through an increase in steam temperature and pressure. The
pressure and temperature combination are referred to as steam parameters. For example, an
increase in steam parameters from typical 538C and 24.1 MPa to 650C and 34.3 MPa can
reduce the energy required by 6.5%, resulting in a commensurate decrease in coal use, and hence
a reduction of CO 2 emission [2]. Due to its excellent high temperature creep resistance, creep
strength-enhanced ferritic (CSEF) steels (9-12% Cr) are widely used from 600C to 650C as
tubing and piping in fossil fired power plants to accomplish increased efficiency. In addition, for
the last decade, researchers around the world are trying to develop Ultra Advanced Supercritical
(U-ASC) materials (stainless steels, Nickel based superalloy), which are aimed at increasing the
efficiency of coal-fired power plants by increasing the operating temperature and pressure to
760C and 35 MPa [3].
The performance of fossil power plant materials however, does not always meet expectations.
Nickel based superalloy welds can suffer a significant creep strength reduction [ 4, 5]. The
reduction of creep strength is related to the formation of a precipitate free zone in the weld
[6, 7]. ,For CSFF steels There have been reports of numerous failures in the HAZ of after only a
few years in service [8, 9, 10, 11]. These failure locations are often traced back to the finegrained heat affected zone (FGHAZ) of a weld, which experiences a weld thermal cycle with a
1432
peak temperature just above the A c3 temperature. It is a well-established fact that non-equilibrium
microstructures and their gradients in FGHAZ regions will significantly reduce creep strength
[12, 13, 14, 15]. Moreover, the grain size and orientation of the FGHAZ can lead to high triaxial stress states that may contribute to accelerated creep damage [16,17]. This combination of
circumstances leading to premature failure of welded components is discussed in the literature as
Type-IV failures in CSEF steels. Published literature also shows that the creep strength
reduction of such joints can be on the order of 40% compared to the base metal [18] for the same
service life. The implications of such failures include disruptions of electrical supply, increased
cost of electricity, and the potential for failure, endangering the safety of power plant personnel.
Previous research by the current authors showed by applying non-standard tempering (low
temperature tempering, LTT) on Grade 91 steel before welding, Type IV failure could be
mitigated [19]. The constant creep rate of the non-standard tempering sample were 2.5 times
lower than that of standard tempering sample when tested at 70MPa and 650C. A detailed
synchrotron X-ray diffraction study of the HAZ simulated heat-treated samples revealed that the
improvement in creep strength was related to the microstructure evolution at FGHAZ [19]. There
are many methods proposed to mitigate Type IV failures [30-38], however, the mechanism of
Type IV failure is still not clear. One of the difficulties in understanding Type IV failure is that
local strain rates can only be estimated by HAZ simulation and followed creep testing [29]. The
real strain distribution, which plays an important role in a cross-weld specimen, can hardly be
measured during stress-rupture testing.
Digital image correlation (DIC) has been developed and used to measure full field displacement
of an object for the last three decades [ 20]. DIC has been used to measure residual stress
[21, 22, 23, 24] , study fatigue [25] and high temperature tensile behavior[26, 27]. This paper
presents a novel approach to measuring local deformation in the weldments during creep testing
and addresses some of the shortcoming encountered in DIC methods. A GleebleTM thermal
mechanical simulator was used to control stress and temperature during creep testing. A 3D
camera system was used to capture the optical images of the sample surface that was coated with a
high contrast radom dot pattern. Later the patterns on the sample surface were correlated to one
another and strain was calculated as a function of time.
EXPERIMENTAL
Steels and Welding
The chemical composition of ASTM Grade 91 (heat number 30176) is shown in Table 1. After
initial thermo-mechanical processing, the steels were normalized at a temperature of 1050C for 1
h, and then air cooled to room temperature. Two tempering temperatures were investigated in the
current study: 760C (standard) and 650C (non-standard). The samples were tempered in a
furnace for 2 hours, followed by air-cooling to room temperature. These two conditions are
designated as HTT (higher pre-weld tempering temperature: 760C) and LTT (lower pre-weld
tempering temperature: 650C) throughout the text. These two base materials were used for
welding and simulated weld thermal cycling experiments.
Two 25.4 mm plates, in the HTT and LTT conditions, were machined on the edge with an angle
of 37.5 to make a double-V groove. The grooved plates were pre-heated in a furnace that was
set 120C. Gas tungsten arc welding (GTAW) with argon shielding gas was performed on the
plates with one root pass and six fill passes. Inter-pass temperature was kept under 350C.
1433
Welding current, voltage and speed were 260A, 8V and 2.5mm/s respectively. A 9Cr-1Mo filler
wire with 1.6mm in diameter was used. The welded plates were post-weld heat treated (PWHT) in
a furnace at 760C for 2 hours, followed by air-cooling to room temperature. The treated plates
were sectioned and machined for creep tests.
Table 1: Chemical composition of the base and weld filler metal (Grade 91).
(wt%)
Base
Filler
Fe
Bal.
Bal.
C
0.08
0.08
Mn
0.27
0.41
Si
0.11
0.31
Cr
8.61
8.62
Mo
0.89
0.92
Ni
0.09
0.15
V
0.21
0.24
Nb
0.07
0.08
N
0.06
0.04
B
<0.001
<0.001
Figure 1. System setup for full field strain measurement during creep deformation
RESULT AND DISCUSSION
Strain Maps Comparison
3D full field strain maps of the ROI and the corresponding sample images are shown in Fig. 2. e xx
is the strain along the direction of the load (the horizontal axis). In order to identify different
1434
regions, optical macrographs on the polished and etched surface after testing show the highly
deformed regions are in the HAZ. HTT strain maps clearly shows two distinct regions with high
strain values after 90 hours of creep. On the other hand, no significant strain localization is
observed in the LTT sample. The corresponding optical macrograph indicates the creep
deformation is localized in the HAZ (Fig. 2). Detailed microstructural examination in this region s
required in future work to obtain a full understanding of the mechanism affecting the
microstructure.
Figure 2. Full field strain maps (e xx ) obtained using DIC showing deformation of HTT and LTT
cross-weld sample after 90 hours creep deformation
In order to understand the local strain development as a function of time, four circular ROIs were
further selected on each strain map (A1-A4 and B1-B4 as shown in Fig.2). Four circular regions
0.5 mm in diameter depicted in the figure represent the left HAZ, weld metal, right HAZ and base
metal. Strain vs. time is shown in Fig. 3. For the HTT sample, there is very little creep
deformation observed in the weld metal and the base metal, whereas creep deformation in the left
and right HAZ is significant with almost the same strain rate (4.510-8/s) in the range of current
testing. For the LTT sample, no obvious creep deformation is observed in the base metal, but
slight deformation is seen in the weld metal. The reason for the deformation of weld metal in the
LTT sample is unknown and needs to be further investigated. Though the strain map of the LTT
sample in Fig. 2 does not show the apparent difference in local deformation at the HAZ, high
strain rate of HAZ is still observed (1.010-8/s). Previous stress-rupture tests have shown that
creep life of the HTT sample is approximately 5 times lower than that of LTT sample [19].
Surprisingly, the strain rate HAZ of the HTT sample is approximately 5 times higher than that of
LTT, indicating that the local strain rate at the HAZ could be associated with creep life of the
cross-weld specimens. Further detailed studies of the local deformation characteristics are
currently in progress.
The strain (e xx ) traverse plots along the lines A1-A4 and B1-B4 after 90 hours of creep were
shown in Fig. 4. Clearly, the two peaks of the HTT strain plot are due to the significant creep in
the the HAZ. The width of the peak is approximately 4mm, which is larger than the measured
width of the HAZ which is approximately 2mm [29]. As a result, this high strain rate region may
include both FGHAZ and ICHAZ. On the other hand, the spike in the LTT strain traverse plot is
just above the noise level. The width of the peak in the LTTcurve is also approximately 4mm.
1435
1436
Figure 5. Creep curve comparison between LTT and HTT cross weld samples
1437
In conventional stress-rupture tests, the overall strain of the cross-weld specimen is composed of
the deformations from weld metal, HAZ and base metal, due to the microstructure gradient in the
weldments. Usually, the creep resistance at the HAZ of CSEF steels, especially the
FGHAZ/ICHAZ, is very low, because of its weakened microstructure but the local creep
deformation can hardly be separated by using the conventional creep testing. The current study
successfully proved that the Gleeble and DIC system can map the full strain field with a resolution
of 200m, and the local strain rate can be correlated to the corresponding microstructure. Another
advantage of the 3-D camera method is to obtain the local strain rate distribution within a
relatively short test period. For example, it took thousands of hours to see the difference between
the LTT and the HTT samples at the same creep test condition used in the current study [19].
However, the current system focused only on the secondary creep regime, so that it could easily
differentiate the local strain rates of the HTT and LTT samples after only 90 h of testing. There
are many factors that affect the creep performance of the weldments of CSEF: weld metal strength
[30]; fusion welding process, joint design [31,32]; solid state welding design [33]; base metal
composition [34, 35, 36, 37]; base metal heat treatment [19, 30] etc. Evaluation of the effects of
these welding processes or material compositions on creep properties will involve tens of
thousands of hours of stress-rupture testing. The current stain mapping system could significantly
reduce the total test time.
The present study used Grade 91 steel as an example and shows the advantage of the Gleeble and
DIC system to measure full field strain distributions during creep. The same approach can also be
used to evaluate other heat resistant alloy welds for creep performance.
CONCLUSIONS
A GleebleTM thermal mechanical simulator and a DIC system has successfully been used to
measure in-situ full field strain maps of cross-weld Grade 91 steel samples. The spatial resolution
of the strain map is about 200m. Results show creep deformation is mostly concentrated in the
HAZ. Local strain rate for the HAZ, weld metal and base metal was plotted as a function of time.
The HTT sample showed significant deformation in the HAZ compared to the LTT sample. The
present measuring system, which has the advantage of evaluating creep performance of the weld
in a short period of time, can also be used to evaluate weld creep performance of other creep
resistant alloys.
ACKNOWLEDGMENTS
The authors acknowledge the materials from U.S. Department of Energy, Office of Fossil Energy,
Fossil Energy Advanced Research Materials Program, under contract DE-AC05-00OR22725 with
UT-Battelle, LLC. Mr. Tom Muth is thanked for his review and comments on this manuscript.
REFERENCES
[1] Cole, D.G.. Design of Heat-Resistant Steels for Small Power Plant Doctoral Dissertation,
University of Cambridge, UK, (2000)
[2] Abe, F. Precipitate design for creep strengthening of 9% Cr tempered martensitic steel for
ultra-supercritical power plants Science and Technology of Advanced Materials, Vol 9.
(2008) pp. 013002
1438
1439
[26]X. Chen, N. Xu, L. Yang, D. Xiang High temperature displacement and strain measurement
using a monochromatic light illuminated stereo digital image correlation system Meas. Sci.
Technol. 23 (2012) 125603
[27]B. Pan1, D.Wu, Z.Wang Y. Xia High-temperature digital image correlation method for fullfield deformation measurement at 1200 C Meas. Sci. Technol. 22 (2011) 015701
[28] Correlated Solutions, West Columbia, South Carolina. <www.correlatedsolutions.com>.
[29] X. Yu, Multi-Scale Characterization of Heat-Affected Zone in Martensitic Steels PhD
dissertation, The Ohio State University, 2012
[30] P. Mayr, S. Mitsche, H. Cerjak, S. Allen The Impact of Weld Metal Creep Strength on the
Overall Creep Strength of 9% Cr Steel Weldments Journal of Engineering Materials and
Technology APRIL 2011, Vol. 133 / 021011-1
[31] J. A. Francis, G. M. D. Cantin, W. Mazur and H. K. D. H. Bhadeshia Effects of weld
preheat emperature and heat input on type IV failure Science and Technology of Welding and
Joining 2009 VOL 14 NO 5 436-442
[32] S. K. Albert, M. Tabuchi, H. Hongo, T. Watanabe, K. Kubo M. Matsui Effect of welding
process and groove angle on type IV cracking behaviour of weld joints of a ferritic steel Science
and Technology of Welding and Joining 2005 VOL 10 NO 2 149-157
[33] G grant, J, Darsell, B. Jonsson, F. Rave, D. Chandrasekaran, J. Merta, C. Widner, M. West,
B. Jasthi, I. Markon Joining Technologies for Coal Power Applications The 26th Annual
Conference on Fossil Energy Materials, Pittsburgh, Pennsylvania April 19, 2012
[34] S. K. Albert, M. Kondo, M. Tabuchi, F. Yin, K. Sawada, F. Abe Improvi ng the Creep
Properties of 9Cr-3W-3Co-NbV Steels and their Weld Joints by the Addition of Boron
METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 36A, FEBRUARY
2005333-343
[35] Tsukamoto, S., Liu, Y., Shirane, T., Tabuchi, M., Abe, F., Improvement of Microstructure
Stability during Creep in High Cr Ferritic Heat Resistant Steel HAZ Trends in Welding Research
Proceeding of 9th International Conferenc, Chicago, 2012
[36] K. Sawada, M. Taneike, K. Kimura and F. Abe, Effect of Nitrogen Content
on Microstructural Aspects and Creep Behavior in Extremely Low Carbon 9Cr
Heat-resistant Steel, The Iron and Steel Institute of Japan(ISIJ) International, Vol. 44(7), 2004,
pp. 1243-1249.
[37] M. Ohgami, H. Minura, and H. Naoi, Creep Rupture Properties and Microstructures of a
New Ferritic W Containing Steel, Proceedings of the Fifth International Conference on Creep of
Materials, Lake Buena Vista, Florida, 18-21 May, 1992, pp. 69-73.
1440
ABSTRACT
This work concerns a study into the design of creep resistant precipitation hardened austenitic
steels for fossil fuel power plants using an integrated thermodynamics based model in
combination with a genetic algorithm optimization routine. The key optimization parameter is the
secondary stage creep strain at the intended service temperature and time, taking into account the
coarsening rate of MX carbonitrides and its effect on the threshold stress for secondary creep. The
creep stress to reach a maximal allowed creep strain (taken as 1%) at a given combination of
service temperature and time is formulated and maximized. The model was found to predict the
behavior of commercial austenitic creep resistant steels rather accurately. Using the alloy
optimization scheme three new steel compositions are presented yielding optimal creep strength
for various intended service times up to 105 hours. According to the evaluation parameter
employed, the newly defined compositions will outperform existing precipitate strengthened
austenitic creep resistant steels.
1. INTRODUCTION
Creep resistant steels are widely used in fossil fuel power plants owing to their great properties at
demanding conditions: elevated temperatures, high loads and long service times. During such
conditions, the creep strain evolves and shows three stages: primary, secondary/steady and tertiary
creep. Among these three stages, the secondary/steady stage is the most important one as it
accounts for the largest part of creep life [1]. During secondary stage, the creep rate is constant
and inversely proportional to the creep life according to the Monkman-Grant relationship [2],
Moreover, in industry, the stress that produces a creep rate of 10-7/ hour (or 1% strain for 105
hours) is taken as the maximum allowable stress.
Design of new creep resistant alloys by a traditional trial and error method is time consuming and
expensive. Computational methods have been considered as an alternative way to design novel
alloy in recent years. Computational thermodynamics [3-5], artificial neural networks (ANN) [6,
7] and ab initio calculations [8-10], have been developed to predict the optimal alloy composition
for specified use conditions, and to guide and accelerate costly experimental alloy development
programs. More recently, a thermodynamics based model in combination with genetic algorithm
(GA) was developed and successfully applied to the design of novel Ultra High Strength (UHS)
stainless steel grades for room temperature application [11-14]. This alloy design approach was
further extended to the design of heat resistant precipitates strengthened steels [15], and focused
on the high temperature strength evolution by taking into account the development of precipitates.
1441
However, in the latter approach, the creep strain during use itself, which essentially determines
the creep failure, was not considered. The creep strain can be estimated by using constitutive
equations which correlate the strain (rate) to the stress and the temperature. Some constitutive
models have been developed based on experimental observations of strain-stress behavior [16].
Other models attempt to link creep behavior with microstructural parameters, such as interparticle spacing [17, 18], leading to microstructure associated constitutive equations. These
constitutive equations can be used either as an assessment of creep rupture life at a given stress, or
for the prediction of the creep strength for an intended life time.
In the present work, the genetic alloy design approach of high temperature steels is further
developed by introducing a new (secondary creep) strain based optimization criterion and taking
the coarsening of the TiX carbonitrides and its effect on the creep threshold stress as the main
strength determining microstructural parameter. The model is validated against experimental data
for various commercial creep resistant steel grades. Using the alloy optimization scheme, three
new steel compositions are presented yielding optimal creep strength at 1% allowed strain for
various intended service times (10, 103, 105 h).
Remember that you should not re-state material that is readily available in the archival literature.
Simply summarize it, and then add a reference or two.
2. MODEL DESCRIPTION
2.1 Design methodology
In line with the chains model proposed by Olson [19], the design methodology presented here
follows the direction from performance to properties, microstructures and eventually to the
composition & processing conditions. The method relies on two key conversions, the translator
for the correlation from mechanical properties to desirable microstructures, and the creator to
link desirable microstructures to alloy composition/heat treatments employing established
metallurgical principles [20]. In the present work, the translator needs to translate the required
properties for creep resistant steels, such as high strength, good stability and decent oxidation or
corrosion resistance, into desirable microstructures using known microstructure-property
relationships. The tailored microstructure is chosen to be an austenitic matrix with MX
carbonitride precipitates. Compositional and microstructural details of such steels are reported in
our previous study [15]. Then, the creator should link the tailored microstructural features to a
specific composition and related heat treatment parameters via employing various go/no-go
criteria, which involve thermodynamic and kinetics calculations. All qualified solutions are then
ranked according to a properly chosen optimization factor,. Considering the large space of the
pre-defined compositional domain, a Genetic Algorithm is employed to make sure the space is
searched effectively and efficiently.
In the previous design study of heat resistant precipitation strengthened steels [15], the maximum
precipitation strengthening contribution of MX carbonitrides at the intended time of use was
considered as the optimization criterion. While the method yielded interesting suggestions for
optimal compositions, it can be argued that precipitate coarsening rate is an indirect optimization
parameter. Hence, it may be more appropriate to take the creep strain development itself as the
direct optimization parameter.
1442
Creep behavior can be divided into diffusional and dislocation creep depending on the service
temperature and applied stresses. According to Harnold and Ashbys deformation map for 316
austenitic stainless steel [21], advanced austenitic creep resistant steels will undergo dislocation
creep at the intended service condition i.e. a service temperature of 650 C and an applied stress
higher than 60 MPa. For this type of creep mechanism various failure models have been
proposed. Some researchers focused on the rupture due to void, grain boundary wedge
accumulation and tried to correlate the damage with the rupture strength and hence to design
austenitic and ferritic creep resistant steels [22-24] accordingly. Alternatively, others focused on
the strain damage [25] and investigated effects of stress and temperature on strain rate and
accumulated strain, especially in the secondary/steady stage [1, 26]. Our work will follow the
latter approach, and the choice of equations to describe strain-stress and other new the model
features are presented in the following.
Based on numerous experimental results involving various types of pure metals and precipitate
free alloys [1], a power law equation of dependence of strain rate upon applied stress has been
proposed and is now commonly accepted for estimating the strain rate during the steady stage [1]:
ss C exp(Q / RT )(
=
)n
(1)
where ss is creep rate of steady stage. C is a constant, Q is activation energy, R is gas constant, T
is temperature, is applied stress, G is shear modulus, component n is a constant normally
ranging from 4 to 6. However, in the case of precipitate strengthened alloys the creep rate is not
properly described by equation 1 and a threshold stress th has been introduced [27]. If the
applied stress is lower than the threshold stress, the strain rate is negligible and can be ignored.
When it reaches the threshold stress, the strain rate will increase significantly with further increase
of the applied stress. Thus, for precipitate strengthened alloys, equation (1) is reformulated as,
=
ss C exp(Q / RT )(
th
G
)n
(2)
In equation (2), the component n will again be in the range 4 to 6. In our further analysis a fixed
value for n, n=5, is imposed. According to Ref. [1], the threshold stress can be expressed as,
th = Gb / L
(3)
where, is a constant, G the shear modulus and L the average inter-particle spacing. For general
dislocation climb, varies from 0.004 to 0.02, for local climb, =0.19 [1]. According to the
detachment model [28] is not a constant but changes with the mechanism of dislocations passing
the particle. However, as a first order approximation can be taken as being constant and equal
for alloys with a common dislocation-precipitate interaction mode. In this work, the dimensionless
factor is taken as a constant, = 0.02. The validity of this assumption will be tested and
demonstrated in the results section using a range of experimental alloys.
In precipitation strengthened creep resistant steels, the precipitates evolve in time and hence the
inter-particle spacing increases and threshold stress decreases with service time due to the
coarsening of precipitates [29, 30]. According to LSW law [31, 32] the evolution of particle size
with time can be expressed as
1443
=
L r/ =
fp
r03 + Kt / f p
(4)
in which fp, K and r0 are the equilibrium volume fraction, coarsening rate and critical nuclei radius
of the strengthening precipitates (TiX carbonitride in the current study) at the service temperature,
respectively and t is time. r0 can be expressed as
r0 = 2 / Gv
(5)
9( xip ximp ) 2
mp
i =1 xi Di / RT
n
K = 8 Vm p /
(6)
where is matrix-precipitate interfacial energy, Vmp is the molar volume of precipitate. and t is the
exposure time at the high temperature. x is the equilibrium interface mole fraction of the MX
carbonitride forming elements on both the matrix (m) and the precipitate (p) side of the interface.
R is gas constant, T is the service temperature and D is the corresponding diffusion coefficient. In
the present work, the interfacial energy is arbitrarily set at a fixed value of 1 J/m2 irrespective of
the precipitate size. This is a slight simplification but allows illustrating the effect of precipitate
coarsening more easily. All thermodynamic information including fp, Gv, xip, ximp, Di and Vmp are
calculated by employing Thermo-Calc coupled with TCFE6 and Mob2 databases.
The creep strain during the secondary stage therefore can be calculated by integrating equation (2)
over time, while taking into account that the threshold stress is time dependent, as shown in
formula (7):
=
ss dt =
C1 exp(Q / RT )(
Gb f 5
th 5
) dt =
) dt
C2 (
3
G
(r03 + Kt )
(7)
C2 =
C2 is a constant for a certain temperature.
C1 exp( Q / RT )
G5
(8)
We are aware of the fact that the threshold stress not only depends on the initial size, coarsening
rate and volume fraction of TiX carbonitride (equation (4)), but also changes with applied
stress/creep rate [29]. In the current model, this second order effect has not been taken into
account as there is not enough experimental data for precipitation hardened austenitic steels of
different compositions available to numerically include the effect in the optimization process in a
proper manner.
From equation (7), it can be deduced that, for a certain creep strain , a higher volume fraction of
precipitate f and/or a smaller initial size r0 and/or a smaller coarsening rate K will result in a
1444
higher allowable stress (i.e. in a higher creep strength). Since equation (7) is only suitable for
the secondary stage, the selected strain level should be located within secondary creep range.
According to the literature, the maximum strain for the secondary stage is up to around 1% for
MX carbonitride strengthened austenitic heat resistant steels. Once it enters the tertiary stage,
creep rate increases dramatically and the sample fails rapidly. This is also in agreement with the
practical rule that the stress leading to 1% strain for the intended service time should be used as
the allowable stress in its design. As a result, in this work we chose the maximal stress for a given
combination of time and temperature to reach 1% strain as the optimization parameter. At given
temperature, time and strain, for a given steel composition, the applied stress can be determined
by solving equation (7) and be further optimized by the genetic algorithm. The actual algorithm
and the positions of various go/no-go criteria (to be explained in the next section) are indicated in
Fig. 1.
Figure 1 Alloy design strategy and criteria evaluation of high strength austenitic heat resistant
steels.
2.3 Defining the go/no-go criteria
For MX carbonitride precipitation strengthened steels, the size, density and spatial distribution of
precipitates together influence the threshold stress and affect the creep strength. In order to
achieve the most desirable combination of threshold strength and stability of TiX carbonitrides, a
proper heat treatment scheme is necessary. A typical heat treatment of precipitation strengthened
1445
MIN
MAX
Cr
Ni
Ti
Mo
Cu
Taus
0,01
15.00
8.00
0,01
0,10
0,01
0,01
1000
0,15
25.00 25.00
1.00
3.00
5.00
0,15
1446
1250
Fe
Tage=Tser
Service/coarsening time
and strain
Bal.
650
10h-1%, 103h-1%,
105 h -1%
A Genetic Algorithm is applied as the optimization scheme, taking into account 8 variables (7
alloying elements and the austenitization temperature) while setting 32 equally spaced levels
between minimal and maximal values for each variable, yielding in total 328 candidate solutions.
The composition and heat treatment parameters are coded in a 40 (5x8) bits binary string. More
details of the genetic algorithm used can be found in a previous publication [11]. The calculation
time to find the optimal solution in each design round is usually around 2 weeks using a high-end
PC.
3. VALIDATION AND APPLICATION
3.1 Validation against reported experimental data
First of all, we like to reproduce experimental creep data at a fixed temperature of 650 C for a
well-known creep steel 321H [35] and to justify the use of the time to reach 1% strain as the
appropriate creep resistance indicator. The experimental data are shown in Fig. 2. Figure 2a
clearly shows that the time to reach 1 % strain (indicated by dashed line) forms a substantial and
more or less constant fraction of the total creep life time, irrespective of the imposed stress level,
in accordance with the Monkman-Grant relationship [2]. Taking the composition of 321H and
calculating the initial precipitate size (equation) and the coarsening rate (equation 6) and inserting
the appropriate values into the final creep strain equation (equation 7) the time to reach 1% creep
strain was calculated. The calculated time to reach 1% strain (using a value of C2 = 2.23*1047 as
the calibration factor) is compared to the experimental value in Fig. 2b and a very good agreement
over the entire stress range of 53-216 MPa is obtained.
Figure 2 a) Actual creep strain evolution with time at various stress levels for 321H after [35]. b)
model predictions for the time to reach 1% strain versus the experimentally determined time to
reach 1% strain at various stress levels
Secondly, in Fig. 3a the relationship between the experimental life time (creep rupture time) at
fixed temperature of 650 C and the applied stress is plotted for 5 commercial precipitation
hardened austenitic creep steels. The compositions of the 5 steel grades are listed in table 2.
1447
Table 2 : Chemical compositions of the 5 commercial steels presented in Fig. 3 (in mass%)
16-13Nb
321H
347H
NF709
TEMPALOY-1
C
0,07
0,07
0,08
0,04
0,12
Cr
16
18,5
18,5
22,29
18
Ni
11
11
11
24,87
10
Ti
Mo
Nb
0,7
0,3
0,02
0,08
1,42
0,64
0,23
0,1
0,18
Mn
1
1
1
0,97
1
Si
0,5
0,5
0,4
0,4
0,6
It is clear that the compositions of all 5 steel grades are well within the final compositional space
to be explored in this optimization (see table 1) except for the N level for NF 709, which is only a
little greater than the maximum value set. For all alloys except TEMPALOY A-1, there is only
one type of MX carbonitride (as is assumed in the present design study). For TEMPALOY A-1,
there are two types of MX (TiX and NbX) carbonitrides, and the coarsening behavior of each of
them are completely different. Therefore, the time-stress curve of TEMPALOY A-1 crosses that
of the other grades.
In Fig. 3b, the calculated stress for these 5 steel grades to reach 1% strain after 104 hours service
at 650 C is compared to the experimental rupture stress values. There is a very good
correspondence. As is to be expected the rupture stress is slightly greater than the predicted stress
for 1% strain for the same service time, since the rupture strain is normally greater than 1%. For
other service times the prediction of the relative ranking of the 5 steel grades is equally good,
albeit that the relative behavior of TEMPALOY A-1 sometime deviates a bit due to the role of its
NbX carbonitrides, which are not taken into account in the model. It should be noted that the
same C2 value (calibrated by using data from 321H) was used for all 5 steel compositions,
suggesting that in the optimization over the composition domain defined in table 1, the use of a
constant calibration factor C2 is likely to be an acceptable simplification.
Figure 3 (a) Experimental rupture time dependence of (applied) stress for various existing
commercial steel grades [35, 36]. (b) Comparison of experimental rupture stress and the
calculated stress to reach 1% strain in 104 hours .
The very good agreement between predicted and experimental data for industrial grades
demonstrated in Figs. 2 and 3 should give some credibility to the predictions to be made with the
model for steel compositions not yet explored experimentally.
1448
Taus
Strain
tservice(hr)
Alloy 1 0,015 16,29 24,45 0,23 0,10 1,05 0,06 1.00 0.50
Cr
Ni
Ti
Mo
Cu
Mn
Si
650
1250
1%
10
Alloy 2 0,019 16,29 22,81 0,20 0,10 0,89 0,064 1.00 0.50
650
1161,3
1%
103
Alloy 3 0,051 17,58 17,87 0,17 0,10 0,10 0,055 1.00 0.50
650
1178,5
1%
105
In order to visualize the differences in time dependent behavior of the three alloys, the stresses
leading to 1 % strain as a function of time are plotted in Fig. 4. The Figure clearly indicates that
each steel grade outperforms the other two grades at its designed lifetime (indicated by arrows)
which demonstrates the effectiveness of the GA optimization procedure as such. Alloy 1 designed
for 10 h shows the fastest reduction in allowed stress as a function of the service time. Alloys 2
and 3 almost have more or less the same degradation behavior, and the maximal stresses for short
time services are only slightly lower than that of alloy 1. Nevertheless, the maximum imposable
stresses decrease much more slowly than that for alloy 1, and have a much higher value at a
service time of 103 h and beyond. The predicted relative strength of alloys 2 and 3 at the
intended service times of 103 and 105 hours are in their intended mutual position, but the
difference in absolute value is small.
Figure 4 The calculated stress of 1% strain versus time to reach 1% strain for the three alloys
designed to give optimal strength at 0, 10 and 105 hour at 650 C respectively.
1449
3.3 The comparison of designed alloys and existing commercial steel grades
To show the predicted improvement in maximum allowed stress for the two new alloys (alloys 2
and 3), the maximum allowable stresses and the experimentally determined creep strength values
at both 104 and 105 hours are plotted in Fig. 5. As shown in Fig. 5, the experimental allowable
stresses for the 5 reference steels can be well predicted using equation (7) the fixed C2 value
presented earlier. Given the excellent agreement between predictions and experimental data for
the commercial steels, we conclude that the newly designed alloys 2 and 3, with intended service
lifetimes of 103 and 105 hours are likely to have substantially higher creep strength values than the
currently existing precipitation hardened austenitic steels.
Figure 5 comparison of predicted and experimental maximal allowable stress values for
experimental steel grades [35, 36] (at either 104 or 105 hours) as well as the calculated allowable
stress and resulting predicted resulting allowable stress for alloys 2 and 3 (see legenda)
4. CONCLUSIONS
A strain based computational model for the design of creep resistant steels, which takes into
account the coarsening of TiX carbonitride precipitates and its effect on threshold stress, was able
to reproduce the properties of existing precipitation hardened austenitic creep resistant steels with
very good accuracy. The wider exploration of the compositional domain involving 7 alloying
elements and an adjustable austenisation temperature, led to the definition of new alloy
compositions predicted to have substantially better properties at 650 C (both for short, medium
and long service times) than the existing commercial steel grades.
ACKNOWLEDGEMENT
This work was carried out with financial support from the Chinese Scholarship Council (CSC) as
well as internal TU Delft funding.
1450
REFERENCES
.
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data
sheet,
National
institute
for
materials
science,
http://smds.nims.go.jp/creep/index_en.html
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1452
Author Index
A
B
Babu, S. ..........................................482, 1016
Baker, B. ........................................215, 1025
Banks, J. .........................................753, 1244
Bao, H. .................................................... 171
Barnard, P. ............................................... 565
Bartscher, M. ........................................... 400
Baumgartner, S. ....................................... 936
Bal, C. .................................................... 914
Beck, T. ................................................. 1081
Bhutani, O. ................................................ 53
Birks, S. ................................................... 491
Blaes, N. .................................................. 448
Bo, Z. ...................................................... 537
Bokelmann, D. ........................................ 448
Boohaker, C. ........................................... 832
Bosko, D. .............................................. 1397
Brett, S. ................................................. 1173
Budano, S. ............................................... 304
F
Fangfang, P. ........................................... 1151
Fangyu, C. ............................................. 1151
Farooq, M. ............................................. 1163
Feng, X. ................................................... 573
Feng, Z. ................................................. 1432
Folkov, E. .............................................. 924
Foulds, J. ............................................... 1372
Fry, A. ......................... 400, 753, 1244, 1256
Fu, R. ....................................................... 265
Fudali, S. ............................................... 1220
Fujii, S. .................................................. 1363
Fujita, Y. ................................................ 1341
Fukuda, M. ................................................ 24
C
Calderini, M. ........................................... 304
Caron, J. .................................................. 120
Caruso, M. ............................................... 847
Cernuschi, F. ........................................... 400
Chetal, S. ................................................... 53
Chi, C. ............................................... 98, 265
Christof, ................................................ 1163
Cieszyski, K. ....................................... 1220
Clausen, S. ............................................... 400
Coda, E. ................................................... 881
Coline, B. .............................................. 1163
Crocker, L. ............................................ 1244
Cronin, M. ............................................. 1397
Cui, Z. ......................................................... 1
Czyrska-Filemonowicz, A. .................... 1220
G
Gaal, B. .................................................... 847
Gandy, D. ...................... 382, 482, 667, 1059
Ganta, R. .................................................. 832
Gao, Z. ..................................................... 948
Gee, M. .................................................... 400
Gevelmann, G. ......................................... 549
Gollihue, R. ................................... 215, 1025
Gong, X. .................................................. 948
Goodstine, S. ........................................... 832
Gu, Y. ...................................................... 596
Gururaja, U. ............................................. 254
1453
L
Lai, X.-H. ................................................. 276
Leese, R. .......................................... 143, 491
Li, M. ......................................................... 98
Lin, F. ......................................... 98, 265, 351
Lin, S. ....................................................... 690
Lippold, J. ...................................... 573, 1038
Liu, F. ..................................................... 1116
Liu, X. ........................................................ 98
Liu, Y. .................................................... 1127
Liu, Z. ...................................................... 171
Lochbichler, C. ......................................... 936
Lodeiro, M. ............................................ 1256
Lombardi, P. .................................. 304, 1268
Longari, N. ............................................... 304
Lu, Q. ..................................................... 1441
I
Igarashi, M. .................................... 744, 1329
Imano, S. .............................. 202, 1283, 1407
Ishiguro, T. .............................................. 627
Ishikawa, K. ............................................. 468
Iwasaki, J. .................................................. 24
Izumi, S. .................................................... 24
1454
N
Nagae, Y. .............................................. 1304
Nagai, S. .................................................. 690
Nakagawa, H. ........................................ 1047
Nakagawa, K. .......................................... 777
Nakagawa, R. ........................................ 1006
Nakamura, J. ........................................... 732
Nakano, M. .............................................. 321
Narasimhachary, S. ............................... 1190
Narayana Rao, M. ................................... 254
Neri, S. .................................................... 304
Neuschaefer-Rube, U. ............................. 400
Newell, W. .............................................. 973
Nicholls, J. ............................................... 400
Nie, L. ..................................................... 948
Nishimoto, S. ................................... 468, 504
Nishiura, T. ........................................... 1292
Novy, Z. .................................................. 924
Nurmela, A. ............................................. 679
S
Sabau, A. ................................................. 821
Saito, E. ........................................... 24, 1283
Saito, N. ........................................... 190, 903
Sakai, T. ................................................... 702
Santella, M. .................................... 131, 1016
Sarver, J. .................................................. 765
Sato, N. .................................................... 202
Sato, T. ........................................ 1006, 1292
Sawada, K. ............................... 293, 607, 637
Saxena, A. ............................................. 1190
Schlacher, C. ............................................ 914
Schmidtne-Kelity, E. ............................... 936
Schneider, A. ......................................... 1093
Schnitzer, R. ............................................ 936
Scholz, A. ................................................ 180
Schraven, P. ................................... 167, 1407
Schuler, M. .............................................. 936
Seraffon, M. ............................................. 753
Shi, K. ...................................................... 351
Shimada, A. ........................................... 1006
Shingledecker, J. ...... 41, 131, 230, 821, 1059
Shinozaki, I. ........................................... 1071
Shioda, Y. .............................................. 1363
Shuxue, L. ............................................. 1182
Siefert, J. ................................ 482, 513, 1372
Singheiser, L. ......................................... 1081
Sania, J. ................................................ 1232
Smith, J. ................................................... 382
Smith, R. .................................................. 482
Sommitsch, C. ......................................... 914
Spaltmann, D. .......................................... 400
Srivastava, S. ........................................... 120
Stam, A. ..................................................... 74
Steiner, J. ................................................. 573
Stojan, V. ............................................... 1163
Stolzenberger, C. ......................................... 9
Strader, K. ............................................... 573
Subanovi, M. ................................ 648, 1093
Sumiyoshi, Y. ............................................ 24
Sun, R. ......................................................... 1
Suzuki, A. ................................................ 371
Suzuki, S. ................................................. 333
Swaminathan, V. ..................................... 382
Szubryt, M. ............................................ 1232
O
Oechsner, M. ........................................... 180
Ogata, T. .................................................. 702
Ohkuma, Y. ........................................... 1047
Ohno, T. ................................................ 1407
Oinuma, S. ............................................. 1341
Okajima, T. ............................................. 468
Osuch, W. .............................................. 1220
P
Parker, J. ........................... 596, 615, 667, 714
Patel, S. ................................................... 215
Patra, A. .................................................. 254
Paura, M. ................................................. 304
Penttil, S. ............................................... 791
Piedra, E. ............................................... 1256
Pike, L. .................................................... 120
Pint, B. .....................................360, 803, 892
Podany, P. ............................................... 924
Pohja, R. .................................................. 679
Pohjanne, P. ............................................. 791
Prchlik, L. ................................................ 459
Pschirer, J. ............................................... 832
Purdy, D. ............................................... 1059
Purgert, R. ................................................. 41
Putschoegl, A. ......................................... 281
Q
Quadakkers, W. ..................................... 1081
1455
X
Xiaoli, L. .................................................. 537
Xie, X. ................................................ 98, 265
Xu, S. ....................................................... 171
Xu, W. .................................................... 1441
Xu, X. ....................................................... 615
Xueyuan, X. ............................................. 537
Y
Yaguchi, M. ..................................... 690, 702
Yamagata, R. ............................................ 586
Yamaguchi, T. .......................................... 960
Yamamoto, R. .......................................... 468
Yamamoto, Y. .............................. 1016, 1432
Yamashita, H. .......................................... 744
Yamashita, M. .......................................... 815
Yamauchi, T. ............................................ 333
Yamazaki, S. ............................................ 690
Yang, G. ........................................... 171, 948
Yang, H. ..................................................... 98
Yang, H.-C. .............................................. 276
Yang, J. .................................................... 982
Yang, J.-B. ............................................... 276
Yang, W. .................................................. 276
Yang, X.-C. .............................................. 276
Yang, Y. ................................... 143, 171, 982
Yao, Z. ............................................... 98, 424
Yaojun, L. .............................................. 1182
Yli-Olli, S. ........................................ 791, 881
Yonemura, M. ................................ 744, 1329
Yongqiang, J. ........................................... 537
Yoshida, H. .............................................. 333
Yoshimi, K. .............................................. 732
Yoshioka, Y. .................................. 436, 1341
Yu, H. ......................................................... 98
Yu, Q. ......................................................... 98
Yu, X. ........................................... 1016, 1432
YuFeng, Z. ............................................... 537
U
Ueda, M. ........................................ 815, 1352
Ueda, S. ................................................... 333
Uehara, T. .............................................. 1407
Ukai, S. .................................................. 1417
Uno, K. .................................................... 468
Unocic, K. ........................................ 131, 360
Urzynicok, M. ................................ 992, 1232
V
van der Zwaag, S. .................................. 1441
Vnsk, K. ....................................... 791, 881
Venditti, D. ............................................ 1268
Vitek, P. ................................................... 459
1456
Subject Index
10-ton class A-USC Turbine Rotor, 1283
1291
0.2% proof stress, trial forgings,
1288(F)
A-USC turbine rotor production process,
1284(F)
Charpy absorbed energy, 1289(F)
chemical compositions, 1285(T)
creep stress-time to rupture curve,
1290(F)
elongation, 1288(F)
experimental procedure, 12851286
FENIX-700 first trial forging, 1284(F)
gamma-prime particles, FE-SEM
micrographs, 1287(F)
grain size numbers, 1287(F)
reduction of area, 1288(F)
results and discussion, 12861290
specimen collection positions, 1285(F)
specimen microstructures, 1286(F)
tensile stress, 1288(F)
trial production, 1284
12Cr steel (MTR10A), 479(F)
12Cr steel (TMK-1), 471(F)
12Cr1MoVG/12Cr1MoVG tube, 542544,
542(T), 547
12Cr2MoWVTiB steel, membrane walls,
12201231(F,T)
25CR-20NI-NB-N, precipitation,
modelling and optimizing, 11631172
aged Tp310HCbN sample, 1165(F)
aging at 650C, 1168(F)
aging at 750C, 1169(F)
chemical composition, Tp310HCbN,
1164(T)
composition, phases, 1166(T)
discussion, 11701171
equilibrium calculation, 1166(F)
experimental, 1164
phase fraction, 1168(F), 1169(F)
precipitates, mean radius, 1168(F),
1170(T)
precipitates, phase fraction, 1170(T)
results, 11641170
Scheil calculation, 1166(F)
1457
A
advanced 9%Cr-Mo-Co-B steel, welded
joints, 948959
chemical compositions, 950(T)
creep rupture properties, 954(F)
cross weld tensile tests, 950(T)
1458
1459
1460
A-USC
boiler materials, 765776(F,T)
Fe/Ni dissimilar-weld turbine rotor,
13411351(F,T)
A-USC boilers
Ni-based alloy weldments, 903913
Ni-based alloys, hot corrosion
properties, 14221431(F,T)
tempered martensitic 9Cr-boron steel,
11271138(F)
A-USC power plants
creep crack growth behavior, 180
189(F)
high temperature strength, 242253(F,T)
austenitic stainless steels
characterization of, 10591070(F,T)
steam oxidation behavior, 782787(F)
austenitic steels
Fe-20Cr-30Ni-2Nb (at.%), 815820(F)
HR3C, 100(F), 101(F), 102(F)
steam oxidation behavior, 788789
Super304H, 100(F), 101(F), 102(F),
103(F)
TP347H, 100(F), 101(F)
B
Boiler Risk Management and Life
Prediction System, 11821189
background, 11821183
components, 1187(T)
life prediction method, 1187(T)
LPRM, 11841188
qualitative risk assessment module,
1186(F)
risk rating, list, 1186(F)
risk rating, low temperature header,
1186(F)
semi-qualitative risk assessment
module, 1186(F)
structure, 1184(F)
system architecture, 11831184
boiler tube materials
steam oxidation behavior, 777790(F,T)
supercritical oxidation resistance, 791
802(F,T)
boiler tubes (A 617 and C 283), 167170
chemical composition, Power Austenite
MoW, 168(T)
experience, 167
microstructure, samples, 169(F)
1461
1462
1463
1464
1465
D
defect tolerant design concepts, 12061219
Charpy FATT, 1214(F)
chemistry, 1215(T)
compositional parameter N, 1213(F)
constant displacement rate tests, 1211(F)
crack growth resistance, 1211(F)
crack propagation, 1216(F)
creep parameter comparison, Cr-Mo-V,
1209(F)
creep-fatigue crack growth, 1212(F)
critical crack size, 1216(F)
discussion, 1218
disk root, 1215(F)
inlet casing, 1217(F)
load displacement curve, 1210(F)
1466
F
FB2 trial rotor, 306313
aged specimens, microstructural
analysis, 312313
BN + MnO on FB2 tensile specimen,
310(F)
BN equilibrium diagram, 309(F)
BN plus MnO, Al and Ti on FB2 tensile
specimen, 310(F)
chemical composition, 308(T)
COST trial rotor dimensions, 308(F)
creep master curve tests, 311(F)
creep properties, 310311
elongation, broken specimens, 311(F)
flow chart, 306(F)
fully tempered martensitic
microstructure, 309(F)
manufacture at SdF, 306308
mean dimension, precipitates, 312(T)
microstructural characterisations, 309
310
microstructural evolution, 311312
microstructure, 312(F)
precipitation, 313(F)
product characterisations, 308309
reduction, broken specimens, 311(F)
required and obtained chemical
composition, 307(T)
US inspection results, 307(T)
US NDT control, 308(F)
Fe-20Cr-30Ni-2Nb (at.%), steam oxidation
of, 815820
experimental, 815816
oxide scale, surface morphology, 817(F)
1467
1468
G
G115 ferritic heat resistant steel, 174176
China, 700C A-USC-PP, 174176
creep rupture strength, pipe, 176(F)
high temperature strength, during aging,
175(F)
M23C6 and Laves phases during aging,
175(F)
martensitic lath width during aging,
175(F)
mechanical properties, 174(T)
oxide resistance, steel pipe, 176(F)
G115 ferritic heat resistant steel
after aging, 174(F)
gas and steam turbine forgings, 281292
Alloy 625 trial rotor, 291(F)
1469
1470
1471
H
HALF YIELD, 11391150
0.5Cr-0.5 Mo steel tubes, stress versus
time to rupture curves, 1143(F)
12Cr-1Mo-1W- 0.3V steels, stress
versus time to rupture curves, 1145(F)
1Cr-1Mo-0.25V turbine rotor steels,
stress versus time to rupture curves,
1145(F)
2.25Cr-1Mo steel plates, stress versus
time to rupture curves, 1143(F),
1144(F)
9Cr-1Mo steel tubes, stress versus time
to rupture curves, 1144(F)
Alloy 800H, stress versus time to
rupture curves, 1147(F)
ASME Grade 122 type, creep rupture
life, 1141(F)
ASME Grade 122 type, plastic strain,
1140(F)
creep strength, 1142(F)
experimental creep test, 1149(F)
inflection of stress-creep rupture life
curve, 11401142
Mod.9Cr-1Mo steel, predicted creep
rupture lives, 1142(F)
stress dependence, creep rupture life,
11431147
stress dependence of microstructural
change, 1142(F)
temperature dependence, 11471149,
1148(F)
TP304H steels, stress versus time to
rupture curves, 1146(F)
1472
1473
1474
1475
I
impression creep testing, Grade 91
components, 11731181
average results compared to mean
properties, 1179(T)
creep lives, 1178(F)
1476
1477
1478
J
Japan, A-USC technology development,
2440
1000MW class double reheat steam
turbine, 38(F)
700deg-C class A-USC, 26(F)
A-USC, concept of, 2629
boiler candidate materials, 32(F)
boiler component test, 3839
boiler component test facility, 39(F)
boiler component test, schedule, 39(F)
boiler technology development, 3134
case studies, 27(F)
casted materials, 38(F)
cooled turbine, 28(F)
development project, 30
existing plants and steam conditions,
27(F)
HR6W, creep rupture strength, 32(F)
HR6W weld, creep rupture strength,
33(F)
large diameter pipe, header mock-up,
33(F)
LTES700R, before forging, 36(F)
LTES700R, coefficient of thermal
expansion, 35(F)
LTES700R, creep rupture strength,
36(F)
LTES700R, welding test, 36(F)
master schedule, 30(F)
pipe trial bending, 34(F)
pipe welding test, 34(F)
pipes, materials test, 33(F)
power generation and fuel share trend,
25(F)
project structure, 31(F)
reheater header mock-up, 34(F)
SAVE12AD pipe trial bending, 34(F)
SAVE12AD pipe welding, 34(F)
selected materials, case A, 29(F)
steam conditions, trend of, 26(F)
steam turbine rotor materials, 35(F)
thermal efficiency, estimated, 29(F)
TOS1X creep rupture strength, 37(F)
TOS1X rotor material, 37(F)
turbine rotor test, 3839
1479
K
KEMCOP probes, 77(F)
consumable, 1009(T)
HR6W HST weld joint, creep rupture
strength, 1011(F)
HR6W pipe weldment, 1009(F)
HR6W weldment, hardness profiles,
1010(F)
HR6W weldment, macro/microstructure,
1010(F)
long term crept HR6W weldment,
1011(F)
mockup test, 10121014
narrow gap HST butt welding, 1013(F)
narrow gap HST weld joint, 10101012
narrow gap HST welding equipment,
1007(F)
narrow gap HST welding procedure, Ni
based pipes, 1012(F)
narrow gap HST welding procedure,
thick wall pipe, 10081010
narrow gap HST welding technology,
10071008
narrow gap HST weldment,
macrostructure, 1008(F)
narrow gap HST weldments,
macrostructure, 1012(F)
narrow gap welding, 1008(F)
Ni based alloy header component, 1012
1014
schematic comparison, narrow gap HST
weldment, 1008(F)
stub tube orbital welding, 1013(F)
stub-header socket welding, 1013(F)
superheater header mockup of HR6W,
1013(F)
superheater header pipe, 1013(F)
long-term creep strength, 13631371
applied stress, 1368(F)
chemical free energy, 1367(F)
creep, 1369(F)
creep time, 1366(F), 1367(F), 1369(F),
1370(F)
elastic strain energy, 1367(F), 1368(F)
interfacial energy, 1369(F)
mean diameter of precipitates, 1369(F)
parameter P, 1370(F)
precipitate, 1366(F)
rate constant, 1368(F)
results and discussion, 13651371
system free energy, 13641365, 1370(F)
time to rupture curve, predicted, 1371(F)
1480
LTES700R, 468481
700MW class double reheat steam
turbine, 469(F)
alloy design, 470471
analysis positions, 476(F)
ASTM grain size, 477(F)
Charpy impact value, 478(F)
chemical composition, 476(F)
coefficient of thermal expansion, 35(F)
creep rupture strength, 36(F)
creep rupture strength, 12Cr steel,
479(F)
creep rupture strength, LTES700R,
479(F)
before forging, 36(F)
low cycle fatigue test, 479(F)
macrostructure, 476(F)
manufacturing process flow, 472(F)
mean coefficients of thermal expansion,
471(F)
medium-sized trial production, 475(F)
microstructure, 470(F), 477(F)
prediction using forging simulation,
475(F)
proof strength, 471(F)
Rastegaeph compression test, 473(F,T)
recrystallization and grain growth,
473(F), 474(F)
rotating bending fatigue test, 479(F)
tensile properties, 478(F)
tensile strength, 471(F)
trial manufacturing, 471475
trial manufacturing, results, 475480
trial production shape, 472(F)
welding test, 36(F)
PWHT-condition, 660(F)
PWHT-condition, influence to
toughness, 661(F)
PWHT-temperature, influence of,
663(F)
Thermanit MTS 616, 663(F)
toughness, 661(F)
Masing behavior, 259(F)
MatCalc, 938(F), 939(F), 942(T)
materials technology, advances in, 491
503
10,500Kg Alloy 625 HP Casing, 493(F)
Alloy 740H impact specimen, 501(F)
broken impact specimens, 501(F)
broken tensile specimens, 501(F)
casting during solution treatment,
493(F)
casting material
processing/manufacturing complexity,
492(F)
cracking, Alloy 740, 499(F)
feeders, 496(F)
HP Casings heaviest section, 493(F)
induction feeder unit, 498(F)
maximum casting sizes, 493(T)
nozzle box castings, 494(F)
oxidation prevention, 495(F)
oxide defects, 495(F)
precipitation hardened alloys, 499501
room temperature chemical properties,
500(T)
shrinkage cavity, 495497
solidification stress cracks, 497(F)
solidification time, comparisons, 497(F)
step blocks, chemistries, 500(T)
theoretical freezing range, 496(T)
measured displacements across a test
specimen. See small punch test method
membrane walls, 12201231
12Cr2MoWVTiB, chemical
composition, 1221(T)
as-received 12Cr2MoWVTiB steel,
1227(F)
butt welded joints, 1225(F)
butt welded joints with PWHT,
macrostructure, 1229(F)
butt welded joints with PWHT,
microstructure, 1229(F)
butt welded joints without PWHT,
macrostructure, 1228(F)
M
MagmasoftTM, 83(F)
MARBN concept, 915917(F)
MARBN steel, 920(F)
martensitic steels P92, matching filler
metals for, 659664. See also P92 steels,
creep damage and cavitation
Ac1-temperature, 662(T)
heat control, during welding, 660(F)
mechanical properties, 663(T)
procedure qualification test, 662(T)
pure deposited weld metal, results,
660(T)
1481
N
National 700C Consortium, 35(F)
NEXTGENPOWER, 7485
averaged length reduction rates, 77(F)
base material, 79(F)
boiler, 7579
controlled atmosphere furnace setup,
76(F)
creep properties, 80(F)
feeders compared with feeder pipe
prediction, 83(F)
integration, 83-84
KEMCOP probes, 77(F)
MagmasoftTM, solidification simulation,
83(F)
mechanical test results, 81(F)
steam turbine, 7983
NEXTGENPOWER project, similar and
dissimilar welding, 459467
base materials, chemical composition,
461(T)
Charpy impact test, A263 + A263 weld
joint, 462(F)
Charpy impact test, A263 + COST F
weld joint, 465(F)
experimental, 460461
microstructure, A263 + COST F weld
joint, 466(F)
Nimonic 263 + COST F, 460(F)
1482
1483
1484
1485
O
Orr-Sherby-Dorn analysis, 733(F)
oxide scale exfoliation, in boilers, 821831
assumed operating conditions, TP347H,
823(T)
bend loop geometry, 824(F)
blockage geometry, 825(F)
calculated blockage fraction, 827(F)
deposit volume fraction and area
blockage fraction, 825(T)
exfoliation and blockage models, 825
826, 826(T)
fraction of exfoliated area, 822(F)
magnetite exfoliation, 827(F), 828(F)
operating conditions, 823825
outage schedules, 829(T)
predicted fraction of tube flow section,
828(F)
predicted oxide spinel layer, 827(F)
results and discussion, 826829
secondary superheater outlet loop,
823(F)
stored elastic energy function, 822(F)
temperature profile, 347H tube, 824(F)
TP347H superheater outlet loop hairpin
bend, 829(F)
tube dimensions, 823825
oxygen content, steam. See steam oxidation
behavior
1486
1487
Q
qualifying welding procedures, high
temperature components, 973981
4Cr1MoV Valve Body, 977(F)
all weld metal specification
requirements, 980(T)
as-welded strength properties, 980(T)
base metals, 973
carbon denuded zone, 978(F)
coefficient of expansion, 976(F)
cracking, 978(F)
discussion, 978981
dissimilar welds and repairs, 979(T)
filler metal selection table, 975(T)
P91 base metal, 978(F)
post weld heat treatment precautions,
975978
PWHT temperatures, 979(T)
stress relieved strength properties,
980(T)
weld metals, 974
weldments & HAZ considerations, 974
R
Rastegaeph compression test, 473(F,T)
RE element, influence on SA335P91 weld
metal, 982991
deposited metal, microstructure, 985(F)
discussion, 988990
elongation of deposited metal, 985(F)
experiment, 983
hardness test result, 986(T)
1488
S
SA335P91 weld metal, effect of trace RE
element, 982991(F,T)
Satoh Test, 516(F)
SAVE12AD pipe
trial bending, 34(F)
welding, 34(F)
SCC. See stress corrosion cracking (SCC)
Schaeffler diagram, 651(F), 656(F)
seam welded tubes, 13391340(F)
selected area diffraction patterns (SADPs),
374(F)
shot peening
measured oxide thickness, 809(F)
steamside oxidation exfoliation, 772
774(F,T)
single crystal nickel superalloy,
NiCoCrAlYHf. See NiCoCrAlYHf
coating, multiple refurbishment
processing
small punch test method, 12441255
calculated experimental strain, 1250(F)
calibration curves, 12501251, 1251(F)
creep analysis, 12521253
crosshead displacements, 1246(F)
experimental, 12451247
1489
1490
1491
T
T23, material behavior, 513524
allowable stress values, 515(F)
1492
1493
1494
1495
U
ultrasupercritical steam turbine rotors, 293
303
boundary mapping, 299(F)
chemical compositions, 295(T)
creep rupture strength, 295(F)
creep-ruptured specimens, SEM back
scatter images, 298(F)
ductility, 295(F)
EDX analysis, 301(F)
1496
V
VALID project, 1322(F)
Vickers hardness, 643(F), 746(F)
VL1steel, 590(F)
VM12-SHC, 655659
1497
1498
X
X13CrMoCoVNbNB9-2-1, trial rotor
forging, 321332
Charpy impact tests, 325(T)
chemical analysis, 325(T)
creep rate, 327(F)
creep rupture strength, 326(F)
experimental procedures, 323
forging process, 324(F)
heating cycle, 324(F)
ingot making process, 322(F)
manufacturing sequence, 323(F)
materials, 323324
optical micrographs, ESHT ingot,
328(F)
optical micrographs, ESR ingot, 328(F)
phase mapping, ESHT ingot, 330(F)
phase mapping, ESR ingot, 329(F)
residue, 331(F)
results and discussion, 325331
STEM image, ESHT ingot, 330(F)
STEM image, ESR ingot, 329(F)
TEM images, ESHT ingot, 328(F)
TEM images, ESR ingot, 328(F)
tensile tests, 325(T)
Y
Young's modulus, 245(F)
yttrium, influence on SA335P91 weld
metal, 982991(F,T)
Z
Z-phase, precipitation process, 11041115
alloys, composition, 1108(T)
1499
1500