Safety and Reliability of Welded Components in Energy and Processing Industry

Toughness problems in steel welded joints during fabrication and service for thick components
Ph. BOURGES, C. CHAUVY, S. PILLOT
ARCELORMITTAL INDUSTEEL, Le Creusot, France E-mail: Philippe.bourges@arcelormittal.com

Abstract
Pressure Equipments are subjected to many requirements dealing with safety. Most of these requirements are dealing with the risk of brittle fracture. The assessment of this risk requires considering jointly material selection, fabrication, and service conditions. The Energy sector is probably using the largest components in the field of Pressure Equipment. So the requirements for are particularly important for both fabrication and service conditions. As an example, the case of high temperature reactors used under hydrogen pressure will be considered. Chromium-Molybdenum-Vanadium steels are more and more used for refining and petrochemical plants. The fabrication involves various kinds of heat treatments that must be monitored to insure a safe behaviour during and after fabrication. In service conditions, impact behaviour of ChromiumMolybdenum materials can be strongly affected by the level of hydrogen introduced particularly in the case of materials affected by temper embrittlement. Welded zones are more sensitive than the base material. The general behaviour shows a great advantage of Cr-Mo-V grades on Cr-Mo ones.

But both steels and weld metals have been improved and today the problem is slightly different. The objective of this document is to focus on various aspects of toughness as observed now considering the today materials and the requirements associated to fabrication and service. High Temperature steel grades (CrMo and CrMoV) will be considered as examples.

Optimization of ISR & PWHT for CrMoV steel

During pressure vessel fabrication, many troubles can occur. Among them, cold cracking is probably the most significant. Some hydrogen can be introduced in welds through the weld deposit. Besides, residual stresses are generated by the local heat treatment due to welding, involving local expansion. Heavy pressure vessels are particularly sensitive to these problems due to the additional restraint associated to high thickness. As a consequence solutions are needed to avoid this problem and generally this implies to heat treat the components to reduce hydrogen content and/or residual stresses. Two main types of heat treatments are used in course of fabrication to solve the previous problems: Dehydrogenation Heat treatment (DHT) is done at low temperature (typically below 400C) to insure the diffusion of hydrogen outside the sensitive areas. Intermediate Stress Relieving (ISR) heat treatments are done at mid temperatures (typically between 600C and 680C) to insure a partial removal of the residual stresses in the welds. The temperature level is defined as sufficiently low to insure less softening than that of PWHT. At the end of fabrication the Post Weld Heat Treatment (PWHT) is carried out to reduce effectively the residual stresses and also to define properly the service properties on the structure (tensile and impact properties).

Introduction
International standard ISO 16528-1 describes some essential requirements that must be considered as to define a construction code [1]. Among these requirements the risk of brittle fracture is one of the most important to consider. This has involved requirements in terms of toughness and generally in terms of minimum CVN Test values. The problem of toughness in welded zones is considered for times as a stringent one. Historically this is due mainly to the fear of hard martensitic HAZ. This was in accordance with the grades considered in the first IIW Carbon Equivalent developed in the 40s of the 20th century i.e. carbon steels [2].

- 197 -

Safety and Reliability of Welded Components in Energy and Processing Industry

The metallurgical effect of these heat treatments can be summarized through the Larson-Miller Parameter (LMP): LMP = T (20 + log t) (1)

Figure 1: CVN Transition Temperature Tk54J in weld metal (13CrMoV9.10) The Transition Temperature is only below 0C for Heat Treatments higher than 19200 (650C-8h). For lower ISR temperature or for DHT, the transition temperature is close to 100C. This implies that the weld metal is not fully ductile at the Preheating or Minimum Interpass Temperature (usually 200C) during the fabrication Heat affected Zone Figure 2 shows the evolution of CVN Transition Temperature (TK54J) in HAZ as a function of the LMP parameter for two cases: Simulated coarse grain HAZ, Actual SAW multipass HAZ.
50 CVN TT 54J (C) 0 -50 -100 -150 -200 17,5 18 18,5 19 19,5 20 20,5 21 21,5 TK54 ZAT TK54 Sim . ZAT

where T is the absolute temperature (in K) and t the soaking time at this temperature (in hours). Formula (1) can be integrated to consider numerous heat treatments [3]. Position of the problem The most typical grades for thick pressure vessels (hydrocrackers, hydrodesulfurisers) are 2,25Cr1Mo grades: the usual ASTM A387 grade 22 (EN 10028-2 grade 10CrMo9-10) and the improved one with 0,25V under the standard ASTM A542 grade D (EN10028-2 grade 13CrMoV9.10). Some years ago, some workers have shown the strong interest to perform DHT in substitution to ISR in the case of standard 10CrMo9-10 [4]. This procedure has been used satisfactory for many years, but during fabrication of reactors in 13CrMoV9.10, some problems have appeared dealing with cracks initiated in the welded zones, propagating in the base material [5]. In this case the ISR conditions that were used for 10CrMo9-10 have proved to be inefficient for 13CrMoV9.10. Therefore it is necessary to define once more the behaviour of 13CrMoV9.10 grade to assess safe conditions for fabrication. Behaviour of 13CrMoV9.10 during and after welding In actual cases the observed cracks have initiated in Weld Metal and then propagated through the Heat Affected Zone and the Base Material. Weld Metal Figure 1 gives the results of toughness for the various heat treatments. The 620C-2h (LMP 18000) decreases the results obtained after DHT (350C-2h) due to the effect of Vanadium carbides precipitation.
150 C V N T T 5 4 J ( C ) 100 50 0 -50 -100 -150 17000 18000 19000 20000 21000 22000 SAW SMAW SAW DHT

LMP=T/1000*(20+log(t))

Figure 2: CVN Transition Temperature TK54J of simulated and actual HAZ (13CrMoV9.10) It is clear that the behaviour of the actual HAZ shows the effect of multipass welding. The Larson-Miller Parameter due to the tempering effect of the welding sequence can be roughly estimated to 19300. Heat treatments lower than this value, have no effect on Transition Temperature. This means that the tempering effect of welding can be estimated to this slightly high value of the LM Parameter. This is in accordance with some assumptions done for numerical simulation of Weld Metal properties [6].

LMP = T[20+logt] (K-h)

- 198 -

Safety and Reliability of Welded Components in Energy and Processing Industry

Nevertheless, CVN properties remain slightly high. The Transition Temperature is practically always below -100C, but not in the case of the CGHAZ for Low Temperature Heat Treatments (typically lower than 18700 i.e. 650C-2h). Base material Figure 3 illustrates the evolution of CVN values and NDT (Pellini test) in base material with tempering. The most interesting point concerns NDT that goes below 0C only for tempering higher than 19500 despite very high values of CVN. It can be noticed that these results are in accordance with the usual correlations between CVN and NDT [7].

partially brittle at the usual preheating temperature of 200C. This could be particularly dangerous in the case of highly restrained conditions such as nozzle to head welds. Heat treatments carried out at 650C improve the impact properties of the weld metal. In most cases an ISR at 650C minimum would be done to insure that the toughness is sufficiently high at the usual minimum preheating temperature (200C). In any case, some care must be taken if the structure goes down to room temperature. ISR heat treatment temperature higher than 650C, clearly, would reduce the residual stress but in any case ISR must be below 690C, to be sufficiently lower than the usual 705C of the PWHT. Concerning Base Material it appears necessary to insure sufficient Crack-Arrest properties through a Tempering at a minimum temperature of 690C. But in any case, Post Weld Heat Treatment (PWHT) is necessary to determine the service behaviour. The usual minimum temperature of 705C for 8/10 h is a good compromise.

50 Temperature (C) 0 -50 -100 -150 -200 17,5 18 18,5 19 19,5 20 20,5 21 21,5 TK54J NDT

Service behaviour of CrMo (V) grades

LMP = T/1000*(20+log(t))

Figure 3: CVN Transition Temperature TK54J and NDT of base material (13CrMoV9.10) The delivery condition of the base material must insure a sufficiently low NDT to permit to arrest a crack initiated in the welded zones. This means that 690C (LMP 19500) could be convenient for the delivery condition. Discussion 13CrMoV9.10 behaves significantly differently than 10CrMo9-10 due to V addition and to the highest mechanical properties required for both base material and weld metal. Dehydrogenation Heat Treatment (DHT) insures a significant diffusion of hydrogen outside the sensitive areas as assessed before [8]. But toughness remains too low. Dehydrogenation Heat Treatment (DHT) must be limited to low restrained welds. In other cases Intermediate Stress Relieving (ISR) is necessary. ISR at 620C involves an embrittlement of the weld metal even if compared to the DHT. This is probably due to the precipitation of Vanadium carbides at this temperature. This behaviour (TK54J=115C) implies that the weld metal is

The previous results have shown that it is possible to insure safe behaviour in the as-delivered (PWHT) on 13CrMoV9.10. But this grade and 10CrMo9-10 are mainly used in severe conditions due to Temperature and Hydrogen atmosphere. Thermal aging The affect of thermal aging is considered by codes through requirements introducing the sensitivity to TemperEmbrittlement. The most common test to assess the steel behaviour is the Step-Cooling as described in ASTM procedures [9]. Hydrogen service Besides, the problem of Hydrogen is not considered but with Fracture Mechanics approaches involving K1SCC determinations that are not easily available. This is why people are generally designing reactors, using Impact Test values that are more commonly available. One of the main problems for end-users (and designers) is to validate the Minimum Pressurizing Temperature (MPT) of the component. This means to determinate the temperature where it is possible to pressurize without any risk of brittle fracture despite the fact that the material could be embrittled by aging at service temperature and filled with hydrogen dissolved in the microstructure.

- 199 -

Safety and Reliability of Welded Components in Energy and Processing Industry

F% = 100 x [Z%rf - Z%charged]/Z%rf

Usually people are only considering Thermal Aging effect on Impact Test. It has been considered for years that Hydrogen has no effect on Impact test results, but only on tensile properties and slow strain rate toughness tests. Tensile properties Tensile specimens are charged with hydrogen in an autoclave at relatively low temperature (maximum temperature is 450C) and various hydrogen pressures in order to saturate them with hydrogen. After charging, specimens are removed rapidly from the autoclave and put in liquid nitrogen to avoid degassing. Tensile tests are performed at room temperature. Charged specimens are compared to reference specimen to evaluate the effect of H2 content on the ductility properties (namely the reduction of area). In a general point of view, literature survey shows that the effect of hydrogen can be summarized by the following rules with an increasing H2 content: YS increases slightly UTS is stable Ductility parameters (Reduction of Area (RoA%) and Elongation (El.%)) strongly decrease. The ductility loss is generally characterized by F% computed by formula (1):

materials.
100 90 80 70 60 50 40 30 20 10 0 0 2 4 6 H2 content in material (ppm) 8 10
2,25Cr1Mo 700 C - 20H 2,25Cr1Mo 650 C - 20H 2,25Cr1MoV 690 C - 25H 2,25Cr1MoV 680 C - 9H 3Cr1MoV 9Cr1MoV

Figure 5 : Evolution of ductility loss as a function of H2 content As the sensibility of the material is directly linked to the slope of the curve, the comparison shows clearly that V added material is less sensitive to H2 embrittlement. A longer or warmer tempering is not beneficial to improve the material. One reason could be that tempering decreases dislocation density. As dislocations are preferred locations for H2 trapping, trapping sites are reduced. As hydrogen is concentrated on fewer sites, it induces a stronger embrittlement. Another reason could be the distribution of carbides. Coarser carbides can also reduce H2 trapping and can then also reduce the ductility of material. Impact test properties Some tests have shown that the assessment on a lack of Hydrogen effect on impact properties could be invalid [10]. To examine the situation it is necessary to determine CVN transition curves plotted for different zones of a welded joint in PWHT condition and after PWHT followed by Stepcooling to estimate the potential effect of service aging. Various microstructures have been tested: Bainitic base material SAW weld metal in the case of 10CrMo9-10. Simulated coarse grain martensitic HAZ. Materials have been characterized after hydrogen charging in accordance with service conditions: autoclave 50 bar Hydrogen 450C for 24 Hrs autoclave 150 bar Hydrogen 450C for 24 Hrs NACE conditions (following MR0175 standard). These conditions conduct to various hydrogen contents in the samples. Figure 6 gives the evolution of TK54J as a function of H2 content for 10CrMo9-10. Figure 7 presents the behaviour for 13CrMoV9.10.

F% =

RoAref RoAhyd RoAref

* 100

(1)

where: RoAref = Red. of Area of reference steel (without H2) RoAhyd = Red. of Area of charged steel (with H2). Figure 4 shows an example of a superposition of tensile curves obtained for various H2 charging conditions.

Figure 4 : Evolution of tensile curve submitted to various hydrogen charging Embrittlement is directly linked to F%. One common way to check the sensibility of materials regarding hydrogen is to plot this parameter as a function of H2 content in the specimen. This plot is given in figure 5 for classical CrMoV

- 200 -

Safety and Reliability of Welded Components in Energy and Processing Industry

-20 -40 CVN TT54J (C) -60 -80 -100 -120 -140 -160 0 0,5 1 1,5 C H2 (ppm) 2 2,5 3 BM PWHT BM PWHT+SC HAZ PWHT HAZ PWHT+SC WM PWHT WM PWHT+SC

first case aging improves the effect of Hydrogen. For 10CrMo9-10 base metal, the transition shift is comparable with the results in [12]: 10C/ppm in PWHT condition and about 20C/ppm in aged condition (after PWHT and SC). Weld metal has a similar behaviour than base metal. Simulated coarse grain martensitic HAZ corresponds to the HAZ of the last run of an actual joint for which no weld-tempering occurs. The sensitivity is very high (20C/ppm after PWHT and 30C/ppm after PWHT + SC). It is clearly the most sensitive zone in a welded joint and thus most risky zone facing hydrogen. Fortunately, it is counterbalanced by the fact that the value of FATT and TK54J is very low (about -140C after PWHT and -95C after SC). 13CrMoV9.10 is in every case much less susceptible to hydrogen embrittlement than 10CrMo9-10 despite higher Hydrogen contents. Base Material and HAZ can absorb a greater quantity of hydrogen due to trapping insured by Vanadium carbides. The levels of CVN values, associated with a lower sensitivity to hydrogen embrittlement allow getting a better resistance to hydrogen. Discussion Refining and Petrochemical industries must define safe conditions during service. Critical conditions occur after shutdown. The assessment of Minimum Pressurizing Temperature (MPT) needs to consider the conditions during shut-down: Low temperature in the vessel for maintenance (material is more brittle). Possible presence of existing defects in the material. Degradation of material properties due to temper embrittlement. Degradation of material properties due to H2 embrittlement. The risk is the result of the combination of these parameters (low temperature + defects & embrittlement + pressure) when the vessel is restarting. MPT must be calculated considering the phenomena affecting toughness. It means that both aging and hydrogen embrittlement must be considered as proposed on Figure 9.

Figure 6: Evolution of TK54J as a function of H2 content for 10CrMo9-10 and PWHT 690C-8h

-80

C V N T T 5 4 J (C )

-100 -120 -140 -160

BM PWHT BM PWHT+SC HAZ PWHT HAZ PWHT+SC

3 C H2 (ppm)

Figure 7: Evolution of TK54J as a function of H2 content for 13CrMoV9.10 and PWHT 705C-8h It appears clearly that in all cases, the introduction of Hydrogen has a strong effect on the transition temperature with various sensitivities depending from the location and the aging condition. The slope of the obtained evolutions is given by figure 8 for each studied zone.

40 35 30 25 20 15 10 5 0 Base Metal Martensitic HAZ Weld Metal

S lop e (K /pp m )

Gr. 22 PWHT Gr. 22 PWHT+SC Gr 22V PWHT Gr. 22V PWHT+SC

Figure 8: TK54J temperature shift per ppm of H2 in the different zones of a weld joint It appears from this last figure that standard 10CrMo9-10 is more sensitive to H2 embrittlement than 13CrMoV9.10. In the

- 201 -

Safety and Reliability of Welded Components in Energy and Processing Industry

Some examples have been presented on CrMo(V) steels.

Reference Mastercurve Temper Embrittlement Mastercurve KJC 1ppm T.E .+ H2 Mastercurve 2ppm 3ppm

100MPa.m1/2 TSC H2/ppm

In the case of fabrication conditions for 13CrMoV9.10 steel grade, some care must be taken on the various Heat Treatments that can occur. Dehydrogenation Heat Treatment (DHT) must be limited to low restrained welds. In other cases Intermediate Stress Relieving (ISR) is necessary, and must be done at a minimum temperature of 650C and with sufficient soaking times. Post Weld Heat Treatment (PWHT) is necessary to determine the service behaviour. The usual minimum temperature of 705C for 8/10 h is a good compromise. The behaviour of CrMo steel grades during Hydrogen Service has shown a strong advantage to 13CrMoV9.10 in front of 10CrMo9-10. The CVN Test values of the V grade are practically insensitive to Hydrogen content. In the case of the standard grade the Transition Temperature at 54 J can be increased by 10 to 30C/ppm of Hydrogen introduced. These behaviours must be considered in the assessment of the service conditions particularly in welded areas where the effect can be important.

T = To

T To ( C)

Figure 9 : Example of MPT approach using fracture mechanics In accordance with the Service Rules, MPT can be determined by two different ways: Fracture mechanics approach:

It is usual in this case to consider Hydrogen effect as it has been always admitted that slow strain rate conditions enhance hydrogen embrittlement. But this approach is not the most common due to a lack of data.

TK IC + x TK IC SC + C H 2 TK IC H 2 < MPT (3)

Description in CVN impact properties (for example using master curve approach by Wallin):

References
ISO Standard 16528-1, Boilers and pressure vessels Part 1 : Performance requirements [2] J.Dearden, H.ONeill, A guide to the selection and welding of low alloy structural steels, Trans. Inst. Weld., 3, pp 203-214 (1940) [3] C.Chauvy, G.Masson, Ph.Bourges, L.Coudreuse, P.Toussaint, S.Pillot, D.Cardamone, Effects of PWHT requirements on Service properties, International Conference Weld India 2008, Chennai 2008 January 8th10th [4] E.Takahashi, K.Iwai, Omission of Intermediate Post Weld Heat treatment (PWHT) by Utilizing Low-Temperature PWHT for Welds in Pressure Vessels, ASTM STP 755, p.418 [5] L.P.Antalffy, G.T.West, The new generation vanadium modified reactor steels, EFC WP 15 meeting minutes, Paris La Dfense, 15 November 2002 [6] Ph.Bourges, L.Jubin, P.Bocquet, Prediction of Mechanical Properties of Weld Metal based on some Metallurgical Assumptions in Mathematical Modelling of Weld Phenomena, The Institute of Material, 1993, edited by H.Cerjak and K.E.Easterling [7] G.Sanz, La rupture des aciers 1 : La rupture fragile, Collection IRSID-OTUA, Septembre 1974 [8] S.Pillot, P.Balladon, Ph.Bourges, A.Bertoni, M.Clerg, C.Boucher, Optimisation des traitements thermiques intermdiaires et du dtensionnement des aciers CrMoV , ESOPE 2004, Paris September 2004 [9] ASTM A 387/A 387M 05a S63 [10] T.Sakai and all: Effect of hydrogen on MPT and de-hydrogenation during shut down in hydroprocessing reactors , PVP Vol. 344, High Pressure Technology, ASME 1997 [1]

This is the most common approach (as CVN impact values are easy to obtain). But Hydrogen effect was not considered and must be. Therefore a new term would be introduced taking in account the effect of Hydrogen on CVN, following equation (4bis) in place of the usual equation (4).

FATT + x FATT FATT + x FATT

SC

SC

< MPT (4)

H2

+ C H 2 FATT

< MPT (4bis)

This assessment would be done for all the various zones of the vessel and particularly the welded areas that could be more sensitive than the base metal.

Conclusion
Welds are considered for a long time as sensitive areas regarding brittle fracture. The risk appears during fabrication (or directly linked to fabrication) or during service in severe conditions.

- 202 -