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IX-C-1066-16

A Study on the Development of Welding Consumables

Applied to P91 Steel for Thermal Power Plants
Yasutaka BANNO*, Hideaki TAKAUCHI*, Shigenobu NANBA**, Hidenori NAKO**
* Technical Center, Welding Business, Kobe Steel, Ltd. Kanagawa, Japan
** Materials Research Laboratory, Kobe Steel Ltd., Hyogo, Japan
e-mail: banno.yasutaka@kobelco.com, phone : +81-466-20-3287, fax : +81-466-20-3289

Abstract
It is performed to investigate microstructure, Ac1 temperature and creep rupture time of P91 deposited metals.
Reductions of Mn and Ni contents promoted the formation of retained -ferrite. In contrast, it was revealed that
addition of 0.4-0.8 % Co was effective to suppress the -ferrite formation. Moreover, as the Mn+Ni content
decreased, the Ac1 and Ae1 temperatures rose. And an addition of 0.4-0.8 % Co had no effect on them. Furthermore,
the reduction of the Ni content lengthened the creep rupture time.

1. Introduction
P91 steel has already been used in a number of fossil-fuel thermal power boilers due to its excellent properties of
oxidation resistance, linear expansion coefficient and high temperature strength. The international standards
relating to welding consumables for P91 steel, such as ASME (American Society of Mechanical Engineering) and
AWS (American Welding Society) have been changed over the last decade. Key changes are the requirements for
restriction of Mn+Ni content and PWHT (Post Weld Heat Treatment) temperature, which is closely related to Mn
and Ni contents. P91 steel welded joints are subject to PWHT under suitable conditions to form tempered
martensite microstructures with a large number of fine carbo-nitride precipitates in order to secure mechanical
properties such as creep rupture strength. However, the mechanical properties of these weld metals could be
unstable if the PWHT temperature exceeds their Ac1 transformation temperature, because fresh martensite
microstructure could form1). Therefore, the upper limits of the Mn+Ni content and PWHT temperature have been
revised continuously in ASME and AWS. For instance, the upper limit of PWHT temperature is specified as 775
o

C in case of filler metal having a Mn+Ni content of 1.0-1.2 %, and 800 oC in case of less than or equal to 1.0 %

respectively in the ASME B&PV Code Section I:2015.

Nevertheless, although the welding consumables, satisfying the requirement of Mn+Ni<1.0 % or 1.2 % are
demanded, the influence of Mn+Ni contents on the properties of P91 deposited metals still remain to be clarified.
In the present study, therefore, the authors have evaluated the effects of Mn and Ni contents on the properties of
P91 deposited metals.

2. Experimental procedures

2.1. Specimens
Shielded Metal Arc Welding (SMAW) deposited metals were prepared with current of 150 A DCEP (Direct
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Current Electrode Positive) polarity, voltage of 24 V and an average welding speed of 10 cm/min. The linear heat
input was calculated at 22 kJ/cm. 6 trial covered electrodes with different levels of Mn, Ni, Cr and Co contents
were used. The chemical compositions of deposited metals are shown in Table 1. The welding groove
configuration and pass-sequences are shown in Fig. 1. All specimens except for Ac1 temperature measurement and
some TEM observation were carried out PWHT at 760 oC for 4 hours.

Code
(a)
(b)
(c)
(d)
(e)
(f)

C
0.10
0.10
0.10
0.09
0.09
0.09

Si
0.3
0.3
0.3
0.3
0.3
0.2

Table 1 Chemical compositions of deposited metals

Mn
Ni
Cr
Mo
V
0.9
0.5
9.0
1.0
0.24
0.9
0.3
9.0
1.1
0.24
0.5
0.3
9.0
1.1
0.26
0.7
0.4
8.5
1.0
0.26
0.7
0.4
8.5
1.0
0.26
0.7
0.4
8.4
1.0
0.26

(mass%)
Co
<0.02
<0.02
<0.02
<0.02
0.4
0.8

Nb
0.04
0.04
0.04
0.03
0.03
0.03

N
0.03
0.03
0.02
0.03
0.03
0.03

Mn+Ni
1.4
1.2
0.8
1.1
1.1
1.1

2.2. Ac1 transformation temperature measurement

Ac1 temperature is defined as a temperature at which the / reverse transformation starts during heating. In this
study, the measurements of Ac1 temperatures were carried out using cylindrical specimens 12 mm in height and 8
mm in diameter taken longitudinally from the center of deposited metals. Ac1 temperature was measured by
detecting dimensional change in the diameters of the specimen using a high-accuracy LED apparatus during a
induction-heating process in a vacuum of 10-3 MPa. The heating rate was set to 5 C/second up to 600 C, then
changed to a lower rate of 5 C/min in a range between 600-1050 C, where reverse transformation is expected to
occur. The validity of this method was sufficiently verified by a preliminary study1).

2.3. Creep rupture test

Creep rupture specimens have 6 mm diameter and 30 mm gauge length and they were taken from the middle of
deposited metals longitudinally. Creep rupture tests were conducted at 650 C and applied 100 MPa.

2.4. Microstructure evaluation

The microstructure was observed by optical microscopy in order to know the influence of chemical composition
on remaining -ferrite. In addition, for some deposited metals, the configurations of the precipitates and lath
microstructures in before and after creep rupture testing were observed using a Transmission Electron Microscope
(TEM, JEOL JEM-2010F operated at 200 kV).
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3. Results and discussion

3.1. Optical microstructure

Optical microstructures of the deposited metals after PWHT are shown in Fig. 2. Martensitic microstructure was
observed over the entire surface of the code (a) deposited metal. However, retained polygonal -ferrite grains were
formed in codes (b) and (C) which have lower Ni content than code (a). In particular, when the Ni content was
reduced below 1.0 % as in code (c), obvious amounts of -ferrite were observed. On the other hand, by reducing
the Cr content from 9.0 % to 8.5 %, smaller amount of -ferrite was observed in code (d) compared to code (b). In
this study, -ferrite could be observed only in the as-casted zone of the last bead which was not re-heated by
following passes.

According to previous researches, carried out on P91 and 12Cr steels, long term creep rupture properties are
degraded by the presence of -ferrite2, 3). In addition, the EPRI (Electric Power Research Institute) notes that all Gr.
91 products should exhibit a fully tempered martensite microstructure, which is free of -ferrite4). In our study, the
influence of Co on -ferrite was evaluated as well. Generally, Co is not added as an alloying element for either
P91 steel or welding consumables. However, in high Cr ferritic heat resistant steel, it may be added to suppress the
formation of -ferrite5). In the AWS A5.5/5.5M: 2014 Specification for Low-alloy Steel Electrodes for Shielded
Metal Arc Welding, the addition of Co in the B91 classification is not restricted but required to be reported if Co is
added intentionally or Co content is larger than 0.20 %. In this study, -ferrite was not observed both in codes (e)
and (f) deposited metals containing 0.4 % and 0.8 % of Co respectively, albeit high Mn+Ni content 1.2 %. It was
confirmed that Co addition is effective to inhibit formation of -ferrite in the P91 deposited metals.

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3.2. Ac1 transformation temperature
Fig. 3 shows the relationship between the contents of Mn+Ni and Ac1 (measured) and Ae1 (calculated by
Thermo-Calc. Ver. S / Data base: TCFE_7) temperatures of deposited metals with various Co content. As is well
known, with the increase of the Mn+Ni content, the Ac1 and Ae1 temperatures became lower in the deposited
metals as well. The Ac1 temperatures estimated in this study were 790-800 C with Mn+Ni=1.2 %, and
810-820 C with Mn+Ni=1.0 %. These results support the validity of the maximum PWHT temperatures specified
in ASME Sec. I

In this study, the influences of Co on Ac1 and Ae1 temperatures were evaluated as well. Zhang et al. demonstrated
that additions of Ni, Mn and Co reduced the Ac1 temperature of P92 deposited metals, though Co had only a 40 %
effect compared to the other 2 elements6). On the other hand, in Fig. 3, it can be seen that the Ac1 temperatures of
the deposited metals containing 0.4 % and 0.8 % Co were plotted in varying ranges of other experimental results.
Furthermore, the Ae1 temperatures of the deposited metals containing 0.4 % and 0.8 % Co did not differ from
those of the deposited metals containing less than 0.02 % Co. It is concluded that the Co addition of up to 0.8 %
did not have a significant effect on Ac1 and Ae1 temperatures in the P91 deposited metals. Fig. 4 shows the binary
phase diagrams of the Fe-Mn, Fe-Ni and Fe-Co systems7). Focusing on the -region in each diagram, Mn, Ni and
Co are effective to raise the Ae3 temperature. Meanwhile, only Mn and Ni lower the Ac1 temperature and Co has
no effect on it. This peculiar feature of Co can support our experimental results, which Co is effective to suppress
the -ferrite without lowering the Ac1 temperature.

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3.3. Creep rupture property and microstructural change during creep testing

3.3.1. Influences of Mn, Ni and Co on creep rupture time

Fig. 5 shows the results of creep rupture tests as a function of Mn, Ni and Co contents. Since all the specimens for
these tests were taken longitudinally from the center of deposited metal, their microstructures were martensitic
without any -ferrite. Hence, the influence of -ferrite on the creep rupture time was not involved here. It could be
seen clearly that rupture time became longer with a decrease in Ni content. There was no clear correlation between
rupture time and either Mn or Co contents.

3.3.2. Carbide precipitation

Fig. 6 shows the replica TEM images of the deposited metals before creep testing. Code (b) and (c) deposited
metals contain lower Ni and lower both Mn and Ni respectively compared to code (a). Submicron-size carbides
were observed in all deposited metals. Fig. 7 shows a replica TEM image of code (c) deposited metal at higher
magnification. Fine carbides of nano-scale were observed (indicated by thick arrow) in addition to the
submicron-size carbides, which are observed in Fig. 6. The EDS (Energy Dispersive x-ray Spectroscopy) spectra
taken from points (a) P1 and (b) P2 (thin arrows) are shown in Fig. 8. In both points, there were strong peaks of Cr.
Thus, these submicronsize carbides were considered to be M23C6. According to equilibrium calculation by
Thermo-Calc software, the stable carbides are M23C6 (where M=Cr, Fe) and MC (where M=V, Nb) in the code (c).
The fine carbides of nano-scale, therefore, were presumed to be MC. The number and size of M23C6 particles were
almost the same in all deposited metals shown in Fig. 6, albeit the variations of Mn and Ni contents.
The carbides in the deposited metals after creep testing are shown in Fig. 9, where 1 and 2 indicate the
difference of magnification. Comparing Fig. 9 with Fig. 6, the coarsening of M23C6 took place and the number of
M23C6 was decreased. On the other hand, the coarsening of MC was not observed. There was only slight a
difference in size and number of M23C6 particles among codes (a), (b) and (c). The number of MC particle in
codes (b) and (c) deposited metals containing lower amounts of Ni clearly increased compared to code (a). There
was no influence of the Mn content on the number of MC particles.

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3.3.3. Lath microstructure and dislocation
Fig. 10 shows the bright field TEM images of deposited metals before creep testing. Here, elongated lath
microstructures are observed. In the deposited metals (b) and (c) with lower Ni content, the width of martensite
lath is smaller than in code (a). On the other hand, comparing code (b) with (c), the difference of lath width was
negligible small. This result implies the influence of Mn content on lath width was not large.
Fig. 11 shows the bright field TEM images of deposited metals (a), (b) and (c) after creep testing.
Equiaxed-subgrain was observed instead of lath microstructures, which had existed before creep testing. The
increase of the subgrain size associated with the progress of creep deformation has been detected as reported in
previous study5). In comparison with code (a), codes (b) and (c) had smaller subgrain. There was no clear
correlation between Mn content and subgrain size.
The boundary of these recovered lath microstructures were composed of rearranged dislocations as shown in Fig.
12-(1). Some of dislocation edges were in contact with M23C6 and lath boundaries, or trapped by MC (Fig. 12-(2)).
These facts could suggest that M23C6, MC and lath boundaries acted as obstacles to dislocation motion in creep
testing.

3.3.4. The influence of Ni

Creep rupture time became longer with a decrease of Ni content, as shown in Fig.5. A remarkable smaller lath
microstructure of low Ni deposited metal after creep testing was considered to be a direct reason for the longer
rupture time8). On the creep test condition of high temperature and applied stress, lath recovery involves the
reduction in dislocation density and the rearrangement of dislocations8). Thus, it is presumed that the inhibition of
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dislocation motion down was caused by the reduction of the Ni content. In this section, therefore, we would like to
consider the mechanism of slower dislocation motion through the reduction of the Ni content.
First of all, one of the main obstacles in dislocation mobility is the pinning effect by carbide particles. As
mentioned above, the size and number of M23C6 did not differ among each deposited metal. Conversely, it should
be noted that a great number of fine MC particles were observed in low-Ni deposited metal after creep testing.
The recovery and lath growth was considered to be delayed because MC particles acted as obstacles to dislocation
motion. Therefore, the question is why MC particles become more stable with a decrease of Ni content. The
following three mechanisms can be stated in general:

A) Delay of the MC / Z-phase transition.

B) The inhibition of Ostwald ripening in MC.
C) A decrease of dislocation mobility.

A) In P91 steel, it is recognized that the precipitation of the Z-phase occurs as a consumption of MC particles in
creep testing, resulting in the degradation of pinning effect of MC for dislocation motion5). The decrease in creep
rupture strength of Grade 91 steel by Ni addition has been reported by Kimura et al.3).In his study, it is considered
that this was due to the nucleation and growth of the Z-phase, which was promoted by Ni addition. However, the
formation of Z-phase was observed in long-term creep rupture tests with test time of over a thousand hours. In this
study, which dealt with short-term creep rupture tests, the formation of Z-phase was not observed.

B) Since MC contains Nb and V, the Ostwald ripening of MC particle was considered to be controlled by the
diffusion of Nb, which has the lowest diffusion coefficient at the testing temperature of 650C9). It is known that
the reduction of Ni content decreases diffusion coefficient of high Cr ferritic steel5). It is probable that decrease of
Ni content lowered diffusion coefficient of Nb, resulting in the inhibition of the Ostwald ripening of MC. In this
case, reduction of Ni content should be also effective to inhibit the Ostwald ripening of M23C6. However, there
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was little difference in size or number of M23C6 among the deposited metals containing various amount of Ni.
Hence, it is considered that change in diffusion coefficient of alloy elements by Ni reduction is not large enough to
affect the inhibition of the Ostwald ripening of MC.

C) The study for the mechanism of toughness improvement by Ni addition was carried out by Maeno et al., who
concluded that the improvement of toughness was caused by the increase of dislocation mobility together with Ni
at low temperature below -40 C10). Also, it is probable that the decrease of Ni content lowered the dislocation
mobility and delayed the recovery of lath microstructures. The reason that the number of MC particles after creep
testing increased by lowering of Ni content can be considered as follows:

As shown in Fig. 12, a dislocation is pinned by several MC particles during creep testing. Therefore, it is
presumed that the dislocation acted as a diffusion path of alloy elements among MC particles, resulting in the
acceleration of the Ostwald ripening. In addition, it is supposed that a decrease of dislocation mobility in a low-Ni
deposited metal causes a reduction of number of dislocations pinned by MC particles. Based on this assumption, it
is believed that the Ostwald ripening of MC particles by pipe diffusion through dislocations was suppressed in the
deposited metals with lower Ni content, which causes larger number density of MC particles after creep testing. If
this hypothesis would be true, the inhibition of the recovery of lath microstructures was considered to be
accomplished synergistically by the decrease of dislocations mobility due to the large number density of MC
particles.

4. Conclusion
In the P91 deposited metal,
1) A reductions of Mn and Ni contents promoted the formation of retained -ferrite. The addition of 0.4 and 0.8 %
Co was effective to suppress -ferrite formation.
2) As the Mn+Ni content decreased, the Ac1 and Ae1 temperatures rose. An addition of 0.4 or 0.8 % Co had little
effect on the Ac1 and Ae1 temperatures.
3) The reduction of the Ni content lengthened the creep rupture time by stabilizing the MC particles and inhibiting
the recovery of lath microstructures.

References
1) L. Chen et al.: Effect of PWHT temperature and mechanical properties of High-Cr ferritic heat-resistant steel
weld metal, Weld in the world, 56 (2012).
2) F. Abe: Structural Alloys for Power Plants, Development of creep-resistant steels and alloys, Woodhead
Publishing (2014), 277.
3) K. Kimura et al.: Influence of Chemical Composition and Heat Treatment on Long-term Creep Strength of
Grade 91 Steel, Procedia Engineering, 55 (2013), 2.
4) Electric Power Research Institute: Guidelines and Specifications for High-Reliability Fossil Power Plants 2nd
Edition 3002006390 Final report, (2015).
5) K. Maruyama et al.: Strengthening Mechanisms of Creep Resistant Tempered Martensitic Steel, ISIJ
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International, 41-6 (2001), 641.
6) Z. Zhang et al.: Properties of T/P92 Steel Weld Metals for Ultra Super Critical Power Plant, OMMI, 6-1 (2009).
7) S. Nagasaki et al.: Binary Phase Diagram, AGNE Gijutsu Center (2001).
8) K. Sawada et al.: Residual Creep Life Assessment by Change of Martensitic Lath Structure in Modified
9Cr-1Mo Steels, Tetsu-to-Hagan, 84-8 (1998), 580.
9) The Japan Institute of Metals and Materials: Metal Data Book, Maruzen Publishing, (2004).
10) K. Maeno et al.: Changein Dislocation Mobility with Ni content in Ferritic Steels and Its Effect on
Brittle-to-Ductile Transition, Tetsu-to-Hagan, 98-12 (2012), 667.

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