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Creep-resistant steels such as the 13CrMoV9-10, used in the construction of thick-walled pressure vessels, are most commonly submerged arc welded (SAW). These steels can develop stress relief cracks (SRC) if the mandatory post weld heat treatment (PWHT) is performed improperly. Current PWHT parameters, such as heating rate and holding time at a specific holding temperature, are based on both empirical experience and conventional free shrinking welding experiments to characterize the SRC-susceptibility of the weld. These cannot adequately depict the higher residual stresses caused by the structurally induced stiffness of the surrounding construction. This study discusses the development of a repeatable, precise, and time-efficient methodology to study the effects of different stress levels and heating rates on the SRC susceptibility of the coarse grain heat-affected zone (CGHAZ). For that purpose, samples were thermically treated to simulate a coarse grain heat-affected zone (CGHAZ) and subsequently exposed to representative levels of stress during the heating phase of a PWHT. The recorded stress and heating rate–dependent strains were mathematically analyzed via curve tracing/calculus to identify interdependent effects. This procedure facilitates the measurement of material characteristics such as carbide growth on grain boundaries at the µm-scale via an integrated value over the entire sample volume. The first and second derivatives show a slight, precipitate-dependent, increase in hardness of the sample, depending on the heating rate and applied stress. This new methodology generates an improved assessment of the SRC susceptibility of SAW microstructures of creep-resistant CrMoV steels.
This presentation summarizes the latest research results of the influence of the post weld heat treatment (PWHT) rate and
the global mechanical stress conditions on the stress relief cracking (SRC) susceptibility of low-alloyed and creep-resistant CrMoV steel submerged arc weld joints. It was found that a certain effect of very low heating rates could be confirmed. In addition, the interlinking of SRC susceptibility increasing effects during the PWHT and the ex-post indentification in metallographic cross-section via microstructure characterization is very complex.
Martensitic 9 %-Cr steels like P91 and P92 can show an increased susceptibility to delayed hydrogen assisted cracking. The focus of this study was the microstructure and heat treatment effect on the mechanical properties of P92 base material and P91 multi-layer weld metal in both as-welded and post weld heat treated (PWHT) condition.
Tensile tests with hydrogen free reference samples and electrochemically hydrogen charged samples were carried out, the mechanical properties were assessed and supported by dedicated fractographic analysis. In addition, hydrogen and microstructure dependent fracture criteria were calculated. All investigated microstructures showed a hydrogen influenced degradation of the mechanical properties compared to the hydrogen free reference samples. In that connection, the as welded martensitic P91 weld metal had the highest degree of degradation in presence of hydrogen. The P91 PWHT weld metal and the P92 base material had comparable properties. From that point of view, a significantly increased risk for hydrogen assisted cold cracking during welding fabrication of P91 weld joints must be considered before any heat treatment is conducted.
Martensitic 9% Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. Limited data on room temperature diffusion coefficients reported in literature vary widely by several orders of magnitude (mostly attributed to variation in microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. From the results obtained, diffusion coefficients were calculated using to different methods, time-lag, and inflection point. Results show that, despite microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
Martensitic 9 %-Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. The small number of available diffusion coefficients varies already at room temperature by several orders of magnitude (mostly regarded as result of present microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. The diffusion coefficients are calculated by two methods (time-lag and inflection point method) were performed. The results show that, despite of microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
For higher operational temperatures and pressures required in petrochemical plants, the modified 13CrMoV9-10 steel was developed providing high resistance against creep and compressed hydrogen. Extreme care during the welding procedure is necessary for this steel, attributed to low toughness, high strength in as-welded state, and increased susceptibility to stress relief cracking (SRC) during post-weld heat treatment (PWHT). Previous research of SRC in creep-resistant steels discussed mainly thermal and metallurgical factors. Few previous findings addressed the influences of welding procedure on crack formation during PWHT considering real-life manufacturing conditions. These investigations focus on effects of welding heat control on stresses during welding and subsequent PWHT operations close to realistic restraint and heat dissipation conditions using a special 3D testing facility, which was presented in parts I and II of this contribution. Part III addresses investigations on residual stress evolution affecting crack formation and discusses the transferability of results from large-scale testing to laboratory-scale. Experiments with test set-ups at different scales under diverse rigidity conditions and an assessment of the residual stresses of the weld-specimens using X-ray (surface near) and neutron diffraction analysis (bulk) were performed. This study aims to provide a way of investigating the SRC behaviour considering component-specific residual stresses via small-scale testing concepts instead of expensive weld mock-ups.
Martensitic 9 %-Cr steels like P91 and P92 show susceptibility to delayed hydrogen assisted cracking depending on their microstructure. In that connection, effective hydrogen diffusion coefficients are used to assess the possible time-delay. The small number of available diffusion coefficients varies already at room temperature by several orders of magnitude (mostly regarded as result of present microstructure). Especially P91 weld metal diffusion coefficients are rare so far. For that reason, electrochemical permeation experiments had been conducted using P92 base metal and P91 weld metal (in as-welded and heat-treated condition) with different thicknesses. The diffusion coefficients are calculated by two methods (time-lag and inflection point method) were performed. The results show that, despite of microstructural effects, the sample thickness must be considered as it influences the calculated diffusion coefficients. Finally, the comparison of calculated and measured hydrogen concentrations (determined by carrier gas hot extraction) enables the identification of realistic diffusion coefficients.
Efficiency and flexibility are currently a major concern in the design of modern power plants and chemical processing facilities. The high requirements for economic profitability and in particular climate change neutrality are driving this development. Consequently, plant equipment and chemical reactor components are designed for higher operating pressure and temperature. Creep-resistant CrMo steels had been used as constructional materials for decades but came to operational limitations, for example the resistance against so-called high-temperature hydrogen attack in petrochemical reactors. For that purpose, 20 years ago V-modified CrMo steels had been developed for use in the petrochemical industry due to their very good creep-strength and hydrogen pressure resistance at elevated temperatures enabling long service life of the respective components. For example, the 13CrMoV9-10 steel is applicable for process temperatures of up to 482 °C and hydrogen pressures of up to 34.5 MPa.
Due to the large dimensions and wall thickness of the reactors (wall thickness up to 475 mm) and the special alloy concept, reliable weld manufacturing of the components is extremely challenging. First, low toughness and high strength of the weld joint in the as-welded condition are critical regarding weld cracking. High welding residual stresses are the result of the highly restrained shrinkage of the component welds. For this purpose, the entire component must be subjected to Post-Weld Heat Treatment (PWHT) after completion of the welding operation. The aim is to increase the toughness of the weld joints as well as to reduce the welding induced residual stresses. Before and during PWHT, extreme caution is required to prevent cracking. Unfortunately, V-modified CrMo steels possess an increased susceptibility to cracking during stress relaxation the so-called stress relief cracking (SRC).
Available literature studies have largely focused on thermal and metallurgical factors. However, little attention has been paid on the influence of the welding procedure on crack formation during PWHT considering actual manufacturing conditions. For that reason, we investigated in our previous studies (part I and II), the influence of heat control on the mechanical properties by simulating actual manufacturing conditions prevailing during the construction of petrochemical reactors using a special 3D- acting testing facility. The focus of part I was put on the influence of the welding heat control on mechanical stresses and the effect on cracking during PWHT. Part II was mainly dedicated to the metallurgical causes of SRC during PWHT and the interaction with the occurring mechanical stresses. It could be shown that not only high welding-induced stresses due to increased weld heat input cause higher susceptibility for SRC formation. It was further intensified by an altered precipitation behaviour in presence of mechanical stresses that are caused by the component related restraint. The present part III shows how residual stresses, which are present in such welded components and significantly influence the crack formation, can be transferred to the laboratory scale. As a result, the effect on the residual stresses on the SRC behaviour can be evaluated on simplified small-scale specimens instead of expensive mock-ups. For this purpose, experiments with test set-ups at different scales and under different rigidity conditions were designed and carried out.
Welding of 13CrMoV9-10 vanadium steel requires care due to an increased susceptibility to stress relief cracking during post weld heat treatment. Previous research into the crack formation in creep-resistant steels has focused on thermal and metallurgical factors; however, little knowledge has been gathered regarding the crack formation during post weld heat treatment considering real-life restraint conditions. This work is subdivided in two parts. Part I showed that an increasing heat input during submerged arc welding under restraint led to an increasing stress level in the joint prior to the post weld heat treatment. The magnitude of stress relief cracking observed in the heat-affected zone after the post weld heat treatment is affected by the heat input. In Part II of this work, the cracks and the associated microstructure which occurred under restraint were studied. The application of a Special acoustic emission analysis indicated that the cracks formed in a temperature range between 300 and 500 °C during the post weld heat treatment. The toughness in the heat-affected zone of the restrained welds was affected by the welding heat input.
Microstructural analyses of all specimens revealed accelerated aging due to precipitation of carbides during post weld heat treatment under restraint.
The avoidance of failures during the fabrication or operation of petrochemical reactors made of creep-resistant, low-alloy steels as 13CrMoV9-10 requires still research despite over 60 years of international investigations in the field of stress relief cracking. The quality of modern base materials and filler metals leads to the fact that previously known crack causes, such as impurities of S or P, recede into the background. Rather, the causes are increasingly to be found in the fabrication process. Investigations on the influence of heat control on the stresses in welded components and thus on the stress relief cracking sensitivity under realistic manufacturing conditions are not yet available. This work is subdivided in two parts. Part 1 of this study focused on the effect of heat control during submerged arc welding on the stresses. For this purpose, a testing facility was applied, which allows to observe the forces and moments accumulating during welding or heat treatment in a component-like specimen under shrinkage restraint. The stress acting in the specimen increases with higher preheat/interpass temperatures and higher heat input. During the heat treatment, the stresses are relieved. Nevertheless, cracks are formed already during heating. The total crack length correlates with the heat input.
Over the past years economic and environmental considerations have led to a markedly increased demand for efficiency and flexibility in petrochemical plants. The operational temperatures and pressures required today can only be achieved by using new creep-resistant grades of steel. The modified 13CrMoV9-10 vanadium steel shows a good resistance against creep and compressed hydrogen and has been in use for the construction of petrochemical reactors since the mid-1990s. Nevertheless, processing of this type of steel requires extreme care during the welding procedure. This is due to its low toughness and high strength in the welded state when not post weld heat treated combined with increased susceptibility to cracking during stress relaxation. Previous research into crack formation in creep-resistant steels has largely focused on thermal and metallurgical factors; however, little knowledge has been gathered regarding the influence of the welding procedure on crack formation during post weld heat treatment considering real-life manufacturing conditions. The influence of heat control on the mechanical properties has been investigated by simulating the welding and subsequent post weld heat treatment operations during the construction of petrochemical reactors using a special 3-D testing facility on the laboratory scale.
This work is subdivided in two parts. In part I of this study the stresses resulting from preheating, welding, dehydrogenation heat treatment and the final post weld heat treatment were analyzed during experiments under varied heat control. In all experiments stress relief cracks formed during post weld heat treatment could be observed. The total crack lengths correlated with the welding induced stresses.
Part II of this work is dedicated to the characterization of the cracks and the microstructure. The application of a special acoustic emission analysis indicated that the cracks formed in a temperature range between 300 °C and 500 °C during the post weld heat treatment. In comparison to small scale specimens welded without additional shrinkage restraint, the toughness of the restrained welds was significantly decreased. SEM and TEM analyses of all samples revealed accelerated aging due to early precipitation of special carbides during post weld heat treatment under component relevant restraint.
When assessing the performance of welded components residual stresses are vital. The possibilities of transferring the real boundary conditions of welding, which influence the residual stress, into the laboratory are highlighted in this contribution. The potentials of a test system specially developed for this purpose are demonstrated. The component design induces global process-, geometry- and material-dependent stresses, which can be simulated and quantified in the system. In addition, the resulting local residual stress distribution can be exactly determined with high spatial resolution with the aid of X-ray diffraction. Examples are presented of how the conditions to be found during production are simulated in the laboratory.
Over the past years economic and environmental considerations have led to a markedly increased demand for efficiency and flexibility in petrochemical plants. The operational temperatures and pressures required today can only be achieved by using new creep-resistant grades of steel. The modified 13CrMoV9-10 vanadium steel shows a good resistance against creep and compressed hydrogen and has been in use for the construction of petrochemical reactors since the mid-1990s. Nevertheless, processing of this type of steel requires extreme care during the welding procedure. This is due to its low toughness and high strength in the welded state when not post weld heat treated combined with increased susceptibility to cracking during stress relaxation. Previous research into crack formation in creep-resistant steels has largely focused on thermal and metallurgical factors; however, little knowledge has been gathered regarding the influence of the welding procedure on crack formation during post weld heat treatment considering real-life manufacturing conditions. The influence of heat control on the mechanical properties has been investigated by simulating the welding and subsequent post weld heat treatment operations during the construction of petrochemical reactors using a special 3-D testing facility on the laboratory scale.
This work is subdivided in two parts. In part I of this study the stresses resulting from preheating, welding, dehydrogenation heat treatment and the final post weld heat treatment were analyzed during experiments under varied heat control. In all experiments stress relief cracks formed during post weld heat treatment could be observed. The total crack lengths correlated with the welding induced stresses.
Part II of this work is dedicated to the characterization of the cracks and the microstructure. The application of a special acoustic emission analysis indicated that the cracks formed in a temperature range between 300 °C and 500 °C during the post weld heat treatment. In comparison to small scale specimens welded without additional shrinkage restraint, the toughness of the restrained welds was significantly decreased. SEM and TEM analyses of all samples revealed accelerated aging due to early precipitation of special carbides during post weld heat treatment under component relevant restraint.
9 %-Cr steels like P91 and P92 are widely used in power plants due to the excellent creep-resistance. Components of this steel are typically welded and demand for careful welding fabrication, whereas a so-called post weld heat treatment (PWHT), must be conducted to increase the toughness and decrease the hardness of the martensitic as-welded (AW) microstructure. Before the PWHT, a hydrogen removal (or dehydrogenation) heat treatment is necessary as hardened AW martensitic microstructure is generally prone to delayed hydrogen assisted cracking (HAC). The microstructure and temperature dependent hydrogen diffusion is an important issue as it determines how long a potential crack-critical hydrogen concentration could remain in the microstructure. In this context, reliable hydrogen diffusion coefficients of P91 and P92 weld metal are rare.
Over the past years economic and environmental considerations have led to a markedly increased demand for efficiency and flexibility in petrochemical plants. The operational temperatures and pressures required today can only be achieved by using new creep-resistant grades of steel. The modified 13CrMoV9-10 vanadium steel shows a good resistance against creep and compressed hydrogen and has been in use for the construction of petrochemical reactors since the mid-1990s. Nevertheless, processing of this type of steel requires extreme care during the welding procedure. This is due to its low toughness and high strength in the welded state when not post weld heat treated combined with increased susceptibility to cracking during stress relaxation. Previous research into crack formation in creep-resistant steels has largely focused on thermal and metallurgical factors; however, little knowledge has been gathered regarding the influence of the welding procedure on crack formation during post weld heat treatment considering real-life manufacturing conditions.
In this work, the influence of heat control on the mechanical properties has been investigated by simulating the real-life manufacturing conditions prevailing during the construction of petrochemical reactors using a special 3-D testing facility. The stresses resulting from preheating, welding, dehydrogenation heat treatment and the final post weld heat treatment were measured during experiments under varied heat control. In all experiments stress relief cracks formed during post weld heat treatment could be observed. The total crack lengths correlated with the stresses due to welding. The application of a special acoustic emission analysis indicated that the cracks formed during post weld heat treatment in a temperature range between 300 °C and 500 °C. In comparison to small scale samples welded without additional shrinkage restraint, the toughness of the restrained welds was significantly decreased. SEM and TEM analyses of all samples revealed accelerated aging due to early precipitation of special carbides during post weld heat treatment under component relevant restraint.
Submerged arc welded (SAW) components of creep-resistant low-alloyed Cr-Mo-V steels are used for thick-walled heavy petrochemical reactors (wall-thickness up to 475 mm) as well as employed in construction of modern high-efficient fossil fired power plants. These large components are accompanied by significant restraints during welding fabrication, especially at positions of different thicknesses like welding of nozzles. As a result, residual stresses occur, playing a domi-nant role concerning so-called stress relief cracking (SRC) typically during post weld heat treat-ment (PWHT). Besides specific metallurgical factors (like secondary hardening due to re-precipitation), high tensile residual stresses are a considerable influence factor on SRC. For the assessment of SRC susceptibility of certain materials mostly mechanical tests are applied which are isolated from the welding process. Conclusions regarding the influence of mechanical factors are rare so far. The present research follows an approach to reproduce loads, which occur during welding of real thick-walled components scaled to laboratory conditions by using tests designed on different measures. A large-scale slit specimen giving a high restraint in 3 dimensions by high stiffness was compared to a medium-scale multi-pass welding U-profile specimen showing a high degree of restraint in longitudinal direction and a small-scale TIG-re-melted specimen. The small-scale specimens were additionally subjected to mechanical bending to induce loads that are found during fabrication on the real-scale in heavy components. Results show for all three cases compa-rable high tensile residual stresses up to yield strength with high gradients in the weld metal and the heat affected zone. Those high tensile stresses can be significant for cracking during further PWHT.
Hydrogen absorption and diffusion in T24 steel weld joints and effect on mechanical properties
(2018)
The present contribution summarizes results obtained from experiments with low-alloyed boiler steel grades T24 (CrMoV alloy), T22 (CrMo) and thermally simulated T24 HAZ microstructure and pure weld metal. The hydrogen absorption and diffusion behavior was investigated by permeation experiments and thermal desorption analysis (TDA). The results showed significant weld microstructure influence on diffusion by hydrogen trapping. Trapped hydrogen was determined in the T24 BM at temperatures up to 120 °C compared to 75 °C in the T22. In addition, the T24 HAZ showed decreased diffusion coefficients (at room temperature) of approximately one magnitude compared to the BM. For the mechanical properties, tensile tests were conducted with electrochemically hydrogen charged specimens and compared to results obtained from slow strain rate tests (SSRT) in high-temperature water up to 200 °C. The as-welded HAZ had remarkably increased susceptibility compared to the BM already at low hydrogen concentration of 1-2 ppm. The SSRT were conducted for free corrosion and acidic environment and confirmed this behavior at elevated temperatures for both HAZ microstructures of T24 and T22. Summarized, each weld microstructure has specific diffusion coefficients and shows different susceptibility to degradation of the mechanical properties, i.e. delayed hydrogen assisted cracking or stress corrosion cracking.
Hydrogen absorption and diffusion in T24 steel weld joints and effect on mechanical properties
(2018)
The present contribution summarizes results obtained from experiments with low-alloyed boiler steel grades T24 (CrMoV alloy), T22 (CrMo) and thermally simulated T24 HAZ microstructure and pure weld metal. The hydrogen absorption and diffusion behavior was investigated by permeation experiments and thermal desorption analysis (TDA). The results showed significant weld microstructure influence on diffusion by hydrogen trapping. Trapped hydrogen was determined in the T24 BM at temperatures up to 120 °C compared to 75 °C in the T22. In addition, the T24 HAZ showed decreased diffusion coefficients (at room temperature) of approximately one magnitude compared to the BM. For the mechanical properties, tensile tests were conducted with electrochemically hydrogen charged specimens and compared to results obtained from slow strain rate tests (SSRT) in high-temperature water up to 200 °C. The as-welded HAZ had remarkably increased susceptibility compared to the BM already at low hydrogen concentration of 1-2 ppm. The SSRT were conducted for free corrosion and acidic environment and confirmed this behavior at elevated temperatures for both HAZ microstructures of T24 and T22. Summarized, each weld microstructure has specific diffusion coefficients and shows different susceptibility to degradation of the mechanical properties, i.e. delayed hydrogen assisted cracking or stress corrosion cracking.
Hydrogen-assisted cracking is a critical combination of local microstructure, mechanical load and hydrogen concentration. Welded microstructures of low-alloyed creep-resistant Cr-Mo-V steels show different hydrogen trapping kinetics. This influences the adsorbed hydrogen concentration as well as the diffusion by moderate or strong trapping. A common approach to describe hydrogen traps is by their activation energy that is necessary to release hydrogen from the trap. In the present study, Cr-Mo-V steel T24 (7CrMoVTiB10-10) base material and TIG weld metal were investigated. Electrochemically hydrogen charged specimens
were analyzed by thermal desorption analysis (TDA) with different linear heating rates. The results show two different effects. At first, the microstructure effect on trapping is evident in terms of higher hydrogen concentrations in the weld metal and increased activation energy for hydrogen release. Secondly, it is necessary to monitor the real specimen temperature. A comparison between the adjusted heating rate and the real specimen temperature shows that the calculated activation energy varies by factor two. Thus, the trap character in case of the base material changes to irreversible at decreased temperature. Hence, the effect of the experimental procedure must be considered as well if evaluating TDA results. Finally, realistic temperature assessment is mandatory for calculation of activation energy via TDA.
Literature provides a wide range of hydrogen diffusion coefficients for low alloyed steels used in power plants. In fact, experimental boundary conditions and calculation methods have influence on the determination of these coefficients. The diffusion and trapping behavior in creep-resistant steel 7CrMoVTiB10-10 has been studied. Based on experimental carrier gas hot extraction (CGHE) data, a numerical model has been developed to describe the hydrogen transport and respective hydrogen distribution at elevated temperatures. The numerical results suggest that common calculation methods for diffusion coefficients are limited for experimental data analysis. The sample preparation time before CGHE experiment influences the determined diffusion coefficients with the consequence that non-homogeneous hydrogen concentration profiles have to be considered in the simulations.
Hydrogen-assisted cracking (HAC) represents a significant failure risk for (high strength) creep resistant low-alloyed steel components in fossil-fired power plant applications at temperatures of up to and above 200 °C. This particularly applies to respective start-up and shut-down processes associated with alternating service-conditions in terms of load flexible power plants. For quantitative determination of localized crack critical hydrogen concentrations, the temperature dependent hydrogen diffusion coefficients have to be determined as exactly as possible.
However, available literature provides a wide range of hydrogen diffusion coefficients for low alloyed steels with similar microstructures. Additionally, the available diffusion data seem not to be very reliable and their scatter increases with decreasing temperature. One reason is that the experimental boundary conditions can have a major impact on the determination of respective effective diffusion coefficients. Hence, the scope of this study is to evaluate the influence of the experimental boundary conditions on the derived diffusion coefficients. In addition, different methods for calculating diffusion coefficients are discussed. To elucidate such influences and to draw a line to practical application, the diffusion and trapping behavior in the creep resistant steel 7CrMoVTiB10 10 has been studied.
For such purpose, hydrogen charged specimens were isothermally degassed at different temperatures using carrier gas hot extraction (CGHE). Based on experimental data, a numerical model has been developed by which the hydrogen transport behavior and the respective hydrogen distribution during CGHE can be assessed.
It is demonstrated that the specimen heating rate has a large influence on the calculated diffusion coefficients under assumption of isothermal degassing which elsewhere has been underestimated in the assessment of diffusion data in creep-resistant steels. The numerical results suggest that calculation methods for diffusion coefficients are limited if compared to experimental results. It also turned out that the sample preparation time before CGHE can enormously influence determined diffusion coefficients. Consequently, non-homogeneous hydrogen concentration profiles have to be anticipated in the simulations to arrive at characteristic effusion curves consistent to respective CGHE experiments. In turn, validated diffusion coefficients are now available for the low-alloyed Cr-Mo-V steel which might be helpful to calculate appropriate hydrogen removal heat treatment procedures, for instance.