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With the introduction of a hydrogen-based energy and national economy, safety-relevant components for hydrogen technologies are becoming increasingly important. Characteristic of hydrogen technologies are, for example, harsh environmental conditions such as cryogenic or high-pressure storage, corrosion issues in fuel cells and electrolyzers, turbines, and many more. Additive manufacturing of components is becoming increasingly important and irreplaceable for the production of complex technical systems. Using the case studies of burners for gas turbines and electrodes and membranes for polymer (PEMFC) and solid oxide (SOFC) fuel cells, this article shows the potential of additive manufacturing of components. At the same time, however, the challenge of considering divergent mechanical properties depending on the direction of assembly in a "hydrogen-compatible" manner is also highlighted. Finally, the challenges posed by additive manufacturing and hydrogen for materials testing are highlighted under scenarios that are as realistic as possible.
Offshore wind turbines are an important goal in national energy strategies worldwide. Foundation structures are manufactured from submerged arc welded (SAW) plates with thicknesses up to 200 mm. In that connection, high-strength steels like the S420G2+M are more and more applied offering the possibility for increased stability and load-bearing capacity of the foundations. These offshore steel grades can show a susceptibility for delayed hydrogen assisted cold cracking of the weld joints. For that purpose, a minimum waiting time (MWT) of up to 48 h (dependent on applied standards) is recommended before non-destructive testing is allowed and conducted. But this concept is based on older steel grades that have been used for three or more decades. Nowadays, the metallurgical improvements (clean steels, proper rolling, and heat treatment) of base materials and well as welding consumables must be anticipated. Hence, the MWT concept should be critically discussed as it is assumed to be very conservative. For that reason, the focus of this study was to investigate the diffusion behavior in S420G2+M steel and its multi-layer SAW joint. Electrochemical permeation experiments were carried at room temperature. Boundary conditions were anticipated in terms of using different sample thicknesses. From the experimental data, hydrogen diffusion coefficients and absorbed diffusible hydrogen concentrations had been calculated. It was shown that hydrogen diffusion in the base material is increased compared to the weld metal. In addition, the sample thickness had a significant on the calculated diffusion coefficients. The minimum and maximum diffusion coefficients had been used for numerical modelling of the hydrogen diffusion in the welding joint. It became clear that a MWT must be always regarded together with a critical initial diffusible hydrogen concentration for the evaluation of a possible delayed cracking as diffusion times were mostly > 48 h due to the thick plates.
High-entropy alloys (HEAs) are innovative high-performance materials that have attracted more and more research attention. HEAs are characterized by a solid solution of typically five equiatomic metallic elements. In addition, medium-entropy alloys (MEA, with three elements) are of interest and become more and more important. Depending on the alloy concept, HEAs and MEAs show exceptional mechanical properties, especially high-strength and ductility combinations at both cryogenic and elevated temperatures combined with excellent corrosion resistance. Future structural HEA/MEA components can be exposed to potential applications with hydrogen containing environments like high-temperature water in pressurized nuclear reactors or aerospace structures. Other potential applications could be in materials for vessel walls in the field of cryogenic and high-pressure hydrogen storage. So far, the susceptibility of HEAs/MEAs to hydrogen assisted cracking (if any) and the hydrogen diffusion is not investigated in detail yet and can limit or extend possible applications of HEA/MEA as structural materials. In our work, we focused on the hydrogen absorption, diffusion, and distribution in a HEA (CoCrFeMnNi the original Cantor-alloy) and a MEA (CoCrNi). Cathodic hydrogen charging was carried out for the hydrogen ingress, and thermal desorption analysis (TDA) revealed complex hydrogen trapping in both alloy types up to 300 °C. The absorbed total hydrogen concentrations were > 100 ppm for the HEA and > 40 ppm for MEA. In addition, the assessment of the peak deconvolution is not trivial and must consider both experimental and microstructure influences.
Joining processes for components in hydrogen technologies: Current need and future importance
(2022)
This presentation gives an overview on the importance of joining processes for component fabrication in hydrogen technologies. For that reason, the current need and future research and developement activites are highlighted for the three technological fields: hydrogen storage, transport and use (in terms of the emerging field of additive manufacturing). Finally, some remarks are given for necessary changes in the standardization.
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.
This study gives an overview on the important field of joining processes for component fabrication in hydrogen technologies. For that reason, the current need and future research and developement activites are highlighted for the different technological field of hydrogen generation, storage, transport and use. In addition, the emerging field of additive manufacturing is included. Finally, some remarks are given for necessary changes in the standardization and its challenges.
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.
Metals that are exposed to high pressure hydrogen gas may undergo detrimental failure by embrittlement. Understanding the mechanisms and driving forces of hydrogen absorption on the surface of metals is crucial for avoiding hydrogen embrittlement. In this study, the effect of stress-enhanced gaseous hydrogen uptake in bulk metals is investigated in detail. For that purpose, a generalized form of Sievert's law is derived from thermodynamic potentials considering the effect of microstructural trapping sites and multiaxial stresses. This new equation is parametrized and verified using experimental data for carbon steels, which were charged under gaseous hydrogen atmosphere at pressures up to 1000 bar. The role of microstructural trapping sites on the parameter identification is critically discussed.
The steel grade 20MnMoNi5-5 (according to German DIN standard or 16MND5 according to French AFNOR standard) is widely applied in (weld) fabrication of reactor pressure vessel components. Thus, a wide range of welding technologies (like submerged arc welding (SAW) or tungsten inert gas (TIG)) is used resulting in different heat affected zone (HAZ) microstructures. During weld fabrication, the weld joints may take up hydrogen. Especially, the HAZ shows an increased susceptibility for a degradation of the mechanical properties in presence of hydrogen. In addition, the hydrogen-assisted degradation of mechanical properties is influenced by three main local factors: hydrogen concentration, microstructure, and load condition. Hence, the base material (BM) and two different simulated non-tempered as-quenched HAZ microstructures were examined using hydrogen-free and hydrogen-charged tensile specimens. The results indicate that the effect of hydrogen on the degradation is significantly increased in case of the HAZ compared to the BM. In addition, hydrogen has remarkable effect in terms of reduction of ductility. It was ascertained that the degradation of the mechanical properties increases in the order of BM, bainitic HAZ, and the martensitic HAZ. Scanning electron microscope (SEM) investigation showed a distinct change of the fracture topography depended on the microstructure with increasing hydrogen concentration in case of the as-quenched HAZ microstructures.
Carrier gas hot extraction (CGHE) technique was used for measurement of hydrogen in press-hardened (and as delivered) condition of 22MnB5 steel primarily coated with a thin layer of Al–Si. The CGHE technique was applied using different temperature programs: isothermal heating, temperature step, and linear heating in solid state. The effusing hydrogen was measured using thermal conductivity device (TCD) and high resolution mass spectroscopy (MS). Single isothermal heating at 400 and 900 °C allowed determining absolute value of effusing hydrogen. The linear heating, also known as thermal desorption analysis (TDA), revealed temperature dependent hydrogen effusion peaks. The deconvolution of the TDA spectra by peak fitting allowed the calculation of hydrogen desorption energies for each peak. The results showed good agreement between hydrogen concentrations measured with MS and TCD. In addition, the as-received ferrite-perlite microstructure showed only hydrogen effusion above 400 °C. The subsequent press hardening process leads to hydrogen uptake in the microstructure. In general, the press-hardened 22MnB5 revealed a hydrogen concentration of 0.4 to 0.5 ppm. The biggest concentration was released at isothermal holding at 400 °C indicating reversibly trapped hydrogen. TDA results with different heating rates confirmed mostly diffusible and reversible trapped hydrogen due to calculated activation energies in the range from 4 to 20 kJ mol-1; it was ascertained that nearly 90 % of the hydrogen left the specimens below 400 °C. Melt extraction (ME) was performed to measure the total hydrogen amount (including the diffusible and trapped hydrogen) and showed that above 900 °C up to 1 ppm hydrogen is trapped.
Low-alloyed CrMoV steels, such as T24, are widely used for welded components in fossil power stations due to their excellent creep-strength. Spectacular failure cases in the recent years exhibited severe cracking in T24 welds. The results showed that hydrogen-assisted cracking (HAC) occurring up to 200 degree Celsius cannot be excluded. Hence, a basic understanding is necessary on how hydrogen affects the material properties of welded microstructures. In this regard, each weld microstructure (HAZ and weld metal) has influence on the HAC susceptibility and respective hydrogen diffusion. Thus, the present contribution summarizes different results obtained from experiments with grades T24 (CrMoV alloy) and T22 (CrMo) and thermally simulated HAZ. Tensile tests were conducted with hydrogen charged specimens and compared to hydrogen-assisted stress corrosion cracking results obtained from slow strain rate tests (SSRT) up to 200 degree Celsius. Electrochemical permeation and degassing experiments were performed to identify a particular weld microstructure influence on hydrogen diffusion and trapping (especially in the HAZ). The results showed that T24 base material has improved resistance to hydrogen-assisted degradation/cracking. In contrast, the as-welded HAZ had remarkably increased susceptibility (tesnile tests at hydrogen concentration of 1 to 2 ppm). SSRT experiments confirmed this at elevated temperatures for both the T24 and the T22. Hence, the evaluation of a particular degradation of the mechanical properties should be performed independently for each weld microstructure. In addition, the HAZ showed decreased diffusion coefficients (at room temperature) of approximately one magnitude compared to the base materials. Trapped hydrogen was determined in the T24 at temperatures up to 120 degree Celsius compared to 75 degree Celsius in the T22. This has to be considered in case of changing operational temperatures, e.g. in the case of start-up and shutdown processes of boiler components.
Laboratory experiments on press hardened steels in different delivered states exposed to hydrogen
(2015)
The legal and economical demands in the automotive industry lead to increasing efforts reducing the CO2 emissions. A way to achieve that goal is to reduce the total weight of the car and therefore the fuel consumption. With the application of high strength steels in car body manufacturing it is possible to decrease the sheet thickness of the used materials and therefore the weight of the automobile. Components made of high strength steels can be produced by cold forming as well as by hot forming. In high strength steel the hydrogen content plays a crucial role for the component behavior. It is known that the hydrogen diffusivity and solubility are based on several factors, for example increasing dislocation density by cold working processes, vacancies, chemical composition and grain boundaries. The understanding and the control of the interaction between hydrogen and the high strength press hardened steels is an important factor for the application of the materials. The scope of this work is the determination of hydrogen diffusion and permeability kinetics in press hardened steel samples. An electrochemical hydrogen permeation method was applied on boron-manganese steel grades with different rolling reduction in initial ferrite/pearlite matrix as well as for the as-quenched martensite microstructure. The diffusible hydrogen contents of the specimens were measured using the carrier gas hot extraction technique (CGHE).
Low-alloyed heat-resistant steels have a fundamental contribution to the currently applied steel grades in pressurized and temperature loaded components like membrane walls(water walls)or pressure vessels. Here, the main advantages of the low-alloy concept can be used in terms of superior high temperature mechanical properties, workability and decreased amounts of expensive alloy elements. The main challenge for the future is to further increase the power plant thermal efficiency independent of the type of power plant concept, i.e. fossil-fired or nuclear power plant, where the material selection can directly affect reduction of CO2 emissions.
In power plant design, welding is the most applied manufacturing technique in component construction. The necessary weld heat input causes metallurgical changes and phase transitions in the heat affected zone (HAZ) of the base materials and in the deposited weld metal. The weld joint can absorb hydrogen during welding or in later service - This absorption can cause degradation of mechanical properties of the materials, and in certain loading conditions, hydrogen-assisted cold cracks can occur. This cracking phenomenon can appear time delayed due to the temperature dependency of the hydrogen diffusion and
the presence of a “critical” hydrogen concentration. Additionally, each specific weld microstructure shows a certain hydrogen diffusion and solubility that contribute to susceptibility of the cracking phenomenon. Therefore hydrogen cannot be neglected as possible failure effect, which was identified recently in the case of T24 creep-resistant tubeto-tube weld joints. It is necessary to identify and assess the hydrogen effect in weld joints of low-alloyed steel grades for to improve further early detection of possible failures.
For each specific weld joint microstructure, it is necessary to separate the interdependencies between mechanical load and the hydrogen concentration. The
diffusivity and solubility must be considered to identify hydrogen quantities in the material at any given time. In this case, the effects of mechanical loading were dealt with independently. For the characterization of the mechanical properties, hydrogen charged tensile specimens were investigated for the base materials and thermally simulated HAZ
microstructures. The hydrogen diffusion was characterized with the permeation technique at room temperature and at elevated temperature ranges up to 400°C - It was investigated by interpreting the hydrogen effusion behavior with carrier gas hot extraction technique (CGHE). For realistic determination of the hydrogen diffusion coefficients, an improved
method was developed encompassing accelerated specimen heating and hydrogen determination via mass spectrometer (MS). Simultaneously, the corresponding temperature
dependent trapped and total hydrogen concentrations were determined.
The determined experimental results showed increased susceptibility to the hydrogen affected
degradation of the HAZ compared to the base material, which is independent of the investigated alloy composition. In particular, the martensitic coarse grain HAZ is the most susceptible microstructure to hydrogen-affected degradation. The results of the tensile
tests allowed the definition of consistent microstructure specific failure criteria (envelope curves) versus quantified hydrogen concentrations for the reactor pressure vessel 16MND5 steel (20MnMoNi-5-5) and the creep-resistant T24 steel (7CrMoVTiB10-10). The procedure of quantifying hydrogen concentrations in HAZ microstructures is novel and supports a new method of analysis for hydrogen degradation effects. Further investigations with the T22
steel (10CrMo9-10), as compared to the creep-resistant T24 steel (7CrMoVTiB10-10),
confirmed the beneficial effect of Vanadium as an alloying element to improve the resistance to degradation. In general, Mn-Mo-Ni base material grades show a higher resistance compared to Cr-Mo steels that do not include Vanadium alloying.
The investigations showed the decreased diffusion coefficient of the HAZ microstructure compared to the base material microstructure. This is caused by the stronger trapping effects that are present which simultaneously increase the hydrogen solubility as well. In
general, trapping effects above 100°C are negligible. It is noted that after testing the T24 grade, these trapping effects were observed above 100°C and must be considered. At elevated temperatures, the calculated hydrogen diffusion coefficients are sometimes greater than those in literature. This is primarily due to the unique applied specimen heating procedure resulting in a varied hydrogen effusion from the specimen.
The significance of the obtained results can be characterized in three perspectives. First, the direct comparison of the degradation was possible in terms of microstructure-specific hydrogen effects on the mechanical properties. Second, consistent failure criteria were established to quantify degradation vs. the hydrogen concentration. Third, the determination of more accurate hydrogen diffusion coefficients is now available.
From a scientific point of view, important contributions were made to further interpret the hydrogen effects on the macroscopic mechanical properties, with respect to the alloy composition and the microstructure. From a procedural standpoint, the mentioned deviation in the elevated temperature diffusion coefficients can be caused by the calculation method. This can be an explanation for the reported data scatter in the references.
In terms of an economic view, the presented experimental results contribute to a safe and reliable weld workability of the steel grades. Thus, the identified temperature levels of hydrogen trapping can be applied in the definition of minimum preheat, interpass or postheat temperatures. In addition, recommendations for suitable dehydrogenation heat treatment (DHT) procedures, with accurate temperature values and holding times, can be derived from these results. In the future, the application of the mechanical and diffusion data is intended to support numerical analysis methods to provide an improved prediction of hydrogen effects on material degradation in weld microstructures.
Modeling of Hydrogen-Assisted Cracking (HAC) in Duplex Stainless Steels (DSS):
- Hydrogen causes significant degradation in DSS and consequently HAC
- Mechanisms of HAC have not been fully understood in two-phase microstructures
- Mesoscale numerical modeling for HAC in DSS was created, coupled to the macroscale, enabling simulation of HAC in both phases independent from predefined crack paths
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 can be helpful to calculate appropriate hydrogen removal heat treatment procedures.
In the field of modelling hydrogen assisted cracking (HAC) phenomenon, hydrogen diffusivity is an important input parameter for numerical simulation. In terms of hydrogen diffusion coefficients, they have great impact on realistic assessment of the evolution of possible crack critical hydrogen concentrations. In addition, the chemical compositions of steels can have a strong effect on hydrogen diffusion. Unfortunately, literature provides a wide range of available hydrogen diffusion coefficients even for similar microstructures and equal temperatures. The scattering of the data can lead to significant deviations in the results of simulating the evolving hydrogen concentrations due to hydrogen uptake (by fabrication or service). Thus, the application of such data to crack-models or for component life tie predictions can be realized up to the present only by considering envelope curves of such value, corresponding to a work or bench case scenario, respectively. For improved reliability of numerical simulaitons, it is necessary to minimize the mentioned deviation of these data. Hence, this work focuses on the validation of hydrogen diffusion coefficients obtained from permeation experiments at room temperature. Two baintic steels with different alloying concepts were investigated, the creep-resistant 7CrMoVTiB10-10 and the reactor pressure vessel grade 20MnMoNi4-5. A numerical model is presented for simulation of the corresponding hydrogen diffusion during permeation experiments using the finite element software ANSYS. Three different diffusion coefficients (obtained from different common calculation methods) are considered and compared to numerical results. The vases of thes calculation methods are permeation transients which are a direct measure for hydrogen. The results of the simulated hydrogen diffusion coefficients show that only one procedure for calculation of diffusion coefficitnes is suitable in comparision to the experimental values. Thus, it is suggested to use this method for analysis of experimental results in case of hydrogen diffusion during permeation experiments. Furthermore, this work supplies validated values for the hydrogen diffusion coefficients of both steel grades.
In order to satisfy the growing requirements towards lightweight design and resource efficiency in modern steel constructions, e.g., mobile cranes and bridges, high-strength steels with typical yield strength ≥ 690 MPa are coming into use to an increasing extent. However, these steels require special treatment in welding. The susceptibility for degradation of the mechanical properties
in the presence of hydrogen increases significantly with increasing yield strength. In case of missing knowledge about how and the amount of hydrogen that is uptaken during welding, hydrogen-assisted cracking (HAC) can be a negative consequence.
Moreover, modern weld technology like the modified spray arc process enables welding of narrower weld seams. In this context,
a reduced number of weld beads, volume, and total heat input are technical and economical benefits. This work presents the influence of welding parameters on the diffusible hydrogen content in both (1) single-pass and (2) multi-layer welds. Different
hydrogen concentrations were detected by varied contact tube distance, wire feed speed, arc length, and varied arc type (transitional
arc and modified spray arc). The results show that all welding parameters have significant influence on the diffusible hydrogen concentration in the single-pass welds. By increasing the number of weld beads in case of multi-layer welding, the
hydrogen concentration has been reduced. Whereby, differences in hydrogen concentrations between both arc types are present.
Hydrogen determination in weld seams is standardized in ISO 3690. In accordance to this standard, a defined time for hydrogen collection has to be anticipated for different extraction temperatures. In other words, the temperature is the most important value that has to be monitored in addition to the aimed hydrogen determination.
The specimen geometry has influence on the real sample temperature during CGHE vs. the adjusted furnace temperature. This presentation gives a short summary on possible influences on the "correct" hydrogen determination temperature during carrier gas hot extraction (CGHE) using infrared radiation driven furnace. The main findings are: (1) specimen surface is important in terms of polished or oxidized condition, (2) specimen geometry is important for fast heating, (3) PID-values of control software are a considerable influence to accelerate the heating process depite thick specimens and (4) independent sample temperature determination before CGHE is strongly recommended.
Carrier gas hot extraction (CGHE) is a commonly applied technique for determination of hydrogen in welded joints using a thermal conductivity device (TCD) for quantitative measurement. The CGHE is based on the accelerated hydrogen effusion due to thermal activation at elevated temperatures. The ISO 3690 standard suggests different specimen geometries as well as necessary minimum extraction time vs. temperature. They have the biggest influence on precise hydrogen determination. The present study summarizes the results and experience of numerous test runs with different specimen temperatures, geometries and factors that additionally influence hydrogen determination. They are namely: specimen surface (polished/as-welded), limited TCD sensitivity vs. specimen volume, temperature measurement vs. effects of PID-furnace controller as well as errors due to insufficient data assessment. Summarized, the temperature is the driving force of the CGHE. Two different methods are suggested to increase the heating rate up the reach the desired extraction temperature without changing the experimental equipment. Suggestions are made to improve the reliability of hydrogen determination depended on the hydrogen signal stability during extraction accompanied by evaluation of the recorded data. Generally, independent temperature measurement with calibration specimens is useful for further data analysis, especially if this data is used for calculation of trapping kinetics by thermal desorption analysis (TDA).
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.
High-entropy alloys (HEAs) are characterized by a solid solution of minimum five and medium-entropy alloys (MEAs) of minimum three principal alloying elements in equiatomic proportions. They show exceptional application properties, such as high-strength and ductility or corrosion resistance. Future HEA/MEA-components could be exposed to hydrogen containing environments like vessels for cryogenic or high-pressure storage where the hydrogen absorption and diffusion in these materials is of interest. In our study, we investigated the HEA Co20Cr20Fe20Mn20Ni20 and the MEA Co33.3Cr33.3Ni33.3. For hydrogen ingress, cathodic charging was applied and diffusion kinetic was measured by high-resolution thermal desorption spectros-copy using different heating rates up to 0.250 K/s. Peak deconvolution resulted in high-temperature desorption peaks and hydrogen trapping above 280 °C. A total hydrogen concentration > 40 ppm was identified for the MEA and > 100 ppm for HEA. This indicates two important effects: (1) delayed hydrogen diffusion and (2) considerable amount of trapped hydrogen that must be anticipated for hydrogen assisted cracking phenomenon. Local electrochemical Volta potential maps had been measured for the hydrogen free condition by means of high-resolution Scanning Kelvin Probe Force Microscopy (SKPFM).
Welded components of P91 9% Cr steel demand for careful welding fabrication with necessary post weld heat treatment (PWHT). Before the PWHT, a hydrogen removal heat treatment is necessary for avoidance of hydrogen assisted cracking (HAC). In this context, the microstructure and temperature-dependent hydrogen diffusion is important, and reliable diffusion coefficients of P91 weld metal are rare. For that reason, the diffusion behavior of P91 multi-layer weld metal was investigated for as-welded (AW) and PWHT condition by electrochemical permeation experiments at room temperature and carrier gas hot extraction (CGHE) from 100 to 400 °C. Hydrogen diffusion coefficients were calculated, and the corresponding hydrogen
concentration was measured. It was ascertained that both heat treatment conditions show significant differences. At room
temperature the AW condition showed significant hydrogen trapping expressed by to seven times lower diffusion coefficients. A preferred diffusion direction was found in perpendicular direction expressed by high permeability. The CGHE experiments
revealed lower diffusion coefficients for the AW condition up to 400 °C. In this context, a hydrogen concentration of approximately 21 ml/100 g was still trapped at 100 °C. For that reason, a certain HAC susceptibility of as-welded P91 weld metal cannot
be excluded, and hydrogen removal should be done before PWHT.
9 %-Cr steel P91 is 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 weld metal are rare. Hence, the diffusion behavior of P91 multi-layer weld metal was investigated in two different microstructure conditions: AW and further PWHT (760 °C for 4 h). Two different experimental techniques were used to cover a wide range of hydrogen diffusion temperatures: the electrochemical permeation technique (PT) at room temperature and the carrier gas hot extraction (CGHE) for a temperature range from 100 to 400 °C. From both techniques typical hydrogen diffusion coefficients were calculated and the corresponding hydrogen concentration was measured. It was ascertained that both heat treatment conditions show significant differences in hydrogen diffusivity. The biggest deviations were identified for room temperature. In this case, the AW condition shows significant hydrogen trapping and up to seven times lower diffusion coefficients. Additionally, PT investigations showed a preferred diffusion direction of hydrogen in the weld metal expressed by the diffusion coefficients and the permeability for both heat treatment conditions. The CGHE generally revealed lower diffusion coefficients for the AW microstructure up to 200 °C. In addition, the AW condition showed hydrogen concentrations up to 50 ml/100 g (considering electrochemical charging). Nonetheless, this hydrogen was not permanently (reversibly) trapped. Nonetheless, this temperature is approximately 100 °C below recommended dehydrogenation heat treatment (DHT). This has two main consequences: (I) in case of welding is interrupted or no DHT is conducted, a HAC susceptibility of hardened martensitic P91 weld metal cannot be excluded and (II) DHT can be conducted at temperatures around 200 °C below the recommended temperatures.
Hydrogen was once called “the versatile embrittler” [1], which summarizes very well the effect on reduction of ductility and/or toughness in technical alloys like steel. In that connection, welding is one of the most important component fabrication technologies. During welding, hydrogen can be transferred to the weld pool from manifold sources (like contaminations, residuals at the surface, etc.). As hydrogen embrittles a material, the safety of welded components with hydrogen is always a critical issue. Weld heat input causes additional changes in the microstructure like grain growth or partial dissolution of precipitates and many more. All these things influence the mechanical properties and also represent hydrogen traps. These traps decrease the hydrogen diffusion compared to the ideal lattice. The result can be so-called delayed hydrogen assisted cracking (HAC) of the weld joint due to the significantly decreased diffusivity by trapped hydrogen. This is often an underestimated risk as those cracks can appear in the weld joint even after some days!
It is essential to know about hydrogen ingress during welding and the microstructure specific hydrogen diffusion. Both are depended on weld parameter influence and the chemical composition of the base material and weld metal. For that purpose, gas analytic methods like solid-state carrier gas hot extraction (CGHE) are useful tools to: (1) identify detrimental hydrogen concentrations from weld joints, (2) binding energies from hydrogen traps by thermal desorption analysis or (3) high-temperature diffusion coefficients. Those values are extremely important for welding practice in terms of recommendations on realistic hydrogen removal heat treatment (HRHT) after welding. Considering the increasing use of “digital” experiments, the data is also needed for reliable numerical simulations of HAC process or HRHT-effectiveness.
The present contribution gives an overview on the influence of hydrogen on weld joints, the necessity, methods and standards for hydrogen determination (CGHE) with the aim of fabrication of safe welded and crack-free components.
[1] R. A. Oriani (1987), Corrosion 43(7):390-397. doi: 10.5006/1.3583875
Offshore wind turbines (OWT) are a major goal of the energy strategy of Germany encompassing the increase of the installed wind power. OWT components are manufactured from welded steel plates with thicknesses up to 200 mm. The underlying standards and technical recommendations for construction of OWTs encompass specifications of so-called minimum waiting time (MWT) before non-destructive testing of the weld joints is allowed. Reason is the increased risk of time-delayed hydrogen assisted cold cracking as hydrogen diffusion is very slow due to the very thick plates. The strict consideration of those long MWT up to 48 h during the construction of OWTs leads to significant financial burden (like disproportionately high costs for installer ships as well as storage problems (onshore)). In this study, weld joints made of S355 ML were examined in comparison with the offshore steel grade S460 G2+M. The aim was to optimize, i.e., reduce, the MWT before NDT considering varied heat input, hydrogen concentration and using self-restraint weld tests. This would significantly reduce the manufacturing time and costs of OWT construction. To quantify the necessary delay time until hydrogen-assisted cold cracks appear, acoustic emission analysis was applied directly after welding for at least 48 h.
Trapping in T24 steel weld joints – Effects on activation energy for hydrogen diffusion during TDA
(2017)
Failure cases in the past decade exhibited severe cracking in T24 welds and showed that generally hydrogen-assisted cracking (HAC) occurring up to 200°C cannot be excluded. A basic understanding is necessary on how hydrogen diffusion is influenced by the weld process. In this regard, both weld microstructures HAZ and weld metal have particular influence on hydrogen diffusion compared to the base material. In general, hydrogen diffusion at a certain temperature is described by diffusion coefficients representing an effective value of combined lattice diffusion and effects of reversible hydrogen traps. Those traps are typically precipitates, interstitials, grain boundaries and so on. A common approach to describe the trap character and its effect on diffusion is the determination of so-called activation energy. This can be done by respective thermal desorption analysis (TDA) with linear heating. In the present study, different T24 as-welded microstructures (BM, HAZ, WM) were investigated. For that purpose, electrochemically hydrogen charged specimens were analyzed by TDA with linear heating using a mass spectrometer for detection of ultra-low hydrogen amounts. The results showed that typically the as-welded HAZ had higher energy traps than the tempered base material. Nonetheless two important effects were ascertained: (1) it is strictly necessary to monitor the sample temperature due to its great impact on the hydrogen desorption peak temperature and (2) the real heating rate in the specimen vs. the applied heating rate has to be considered. Both influence the calculated activation energy, i.e. the assigned hydrogen trap character (moderate or strong trap), which changed up to a factor of two in terms of the calculated activation energy. This effect can be much more important compared to the microstructure effect itself. Hence, suitable experimental boundary conditions should be mandatory for the determination of hydrogen trap kinetics.
In order to satisfy the growing requirements towards lightweight design and resource efficiency in modern steel constructions, e.g. mobile cranes and bridges, high-strength steels with typical yield strength ≥ 690 MPa are coming into use to an increasing extent. However, these steels require special treatment in welding. The susceptibility for degradation of the mechanical properties in presence of hydrogen increases significantly with increasing yield strength. In case of missing knowledge about how and which amount of hydrogen is uptaken during welding, hydrogen assisted cracking (HAC) can be a negative consequence. Moreover, modern weld technology like the modified spray arc process enables welding of narrower weld seams. In this context, a reduced number of weld beads, volume and total heat input are technical and economic benefits. This work presents the influence of welding parameters on the diffusible hydrogen content in both singlepass and multi-layer welds. Different hydrogen concentrations were detected by varied contact tube distance, wire feed speed, arc length as well as varied arc type (transitional arc and modified spray arc). The results show, that all welding parameters have significant influence on the diffusible hydrogen concentration in the single-pass welds. By increasing the number of weld beads in case of multi-layer welding, the hydrogen concentration have been substantially reduced. Whereby, differences in hydrogen concentrations between both arc types are present.
Carrier gas hot extraction (CGHE) is a commonly applied technique for determination of hydrogen in weld joints using a thermal conductivity detector (TCD) for hydrogen measurement. The CGHE is based on the accelerated hydrogen effusion due to thermal activation at elevated temperatures. The ISO 3690 standard suggests different specimen geometries as well as necessary minimum extraction time vs. temperature. They have the biggest influence on precise hydrogen determination. The present study summarizes the results and experience of numerous test runs with different specimen temperatures, geometries (ISO 3690 type B and small cylindrical samples), and factors that additionally influence hydrogen determination. They are namely specimen surface (polished/as-welded), limited TCD sensitivity vs. specimen volume, temperature measurement vs. effects of PI-furnace controller, as well as errors due to insufficient data assessment. Summarized, the temperature is the driving force of the CGHE. Two different methods are suggested to increase the heating rate up to the desired extraction temperature without changing the experimental equipment. Suggestions are made to improve the reliability of hydrogen determination depended on the hydrogen signal stability during extraction accompanied by Evaluation of the recorded data. Generally, independent temperature measurement with dummy specimens is useful for further data analysis, especially if this data is used for calculation of trapping kinetics by thermal desorption analysis (TDA).
High-strength low-alloyed (HSLA) steels with yield strength ≥ 690 MPa are gaining popularity in civil engineering and construction of heavy vehicles. With increasing yield strength, the susceptibility for degradation of the mechanical properties in the presence of diffusible hydrogen, i.e., hydrogen-assisted cracking (HAC), generally increases. HAC is a result of the critical interaction between local microstructure, mechanical load, and hydrogen concentration. In existing standards for welding of HSLA-steels, recommendations including working temperatures and dehydrogenation heat treatment (DHT) are given to Limit the amount of introduced hydrogen during welding. These recommendations are based on investigations into conventional arc welding processes. In the past decade, modern weld technologies were developed to enable welding of narrower weld seams with V-grooves of 30°, e.g., the modified spray arc process. In that connection, a reduced number of weld runs and weld volume are important technical and, economic benefits. In the present study, the hydrogen distribution in S960QL multi-layer welds with thickness of 20 mm was analyzed. The influence of different weld seam opening angles, heat input, working temperature and DHT were investigated. The results show that weldments with narrow grooves contained an increased amount of diffusible hydrogen. Hydrogen concentration has been reduced by decreasing both the heat input and working temperature. Hydrogen-free weldments were only achieved via subsequent DHT after welding. Furthermore, hydrogen distribution was experimentally determined across the weld seam thickness in HSLA gas metal arc welded multi-layer welds for the first time.
The study provides an overview of the aspects of joining and its importance in manufacturing of components for the more and more important field of hydrogen as key factor for the energy transition to a decarburized future. To this end, the fundamentals of the technology fields of hydrogen production, storage, transport, and application are presented and the state of the art of manufacturing of components for hydrogen technologies by joining is summarized. Based on representative examples from practice, research and development, the importance of joining technology in hydrogen technologies is clearly highlighted and perspectives for the future are derived. From a macroeconomic perspective, the focal points, or trends of joining technologies here include: the erection of new infrastructure for hydrogen storage and transport, and the safe conversion of existing natural gas infrastructure and its challenges for welded materials. In addition, we show the problems that are anticipated with in-service repair welding of hydrogen pipelines. In hydrogen applications, the efficient mass production of fuel cells and electrolysers is becoming increasingly important. For that reason, the importance of additive manufacturing is highlighted. Finally, the challenges for technical regulations and standardization by using hydrogen are shown.
Multi-principal element alloys (MPEAs) are innovative materials that have attracted extensive research attention within the last decade. MPEAs are characterized by a solid solution of equiatomic metallic elements. Depending on the number of elements, they are also referred as high entropy alloys (HEAs with n ≥ 4 elements like CoCrFeMnNi) and medium-entropy alloys (MEA with n = 3 elements CoCrNi). Depending on the alloy concept, MPEAs show exceptional properties in terms of mechanical performance or corrosion resistance at extreme environments. In that connection, hydrogen and its challenges for the most metallic materials gets more and more important. MPEAs are candidate materials for the substitution of conventional materials like austenitic stainless steels e.g., at very high-pressure up to 1000 bar. Those pressures are typically reached in valves or compressors for refueling of tanks with operational pressure of 700 bar. So far, the susceptibility of HEA/MEAs to hydrogen assisted cracking (if any) and the especially the underlying hydrogen uptake and diffusion was not within the scientific scope and not investigated in detail yet. For that reason, we focused on the hydrogen absorption the characterization of the hydrogen diffusion and trapping at elevated temperatures in a CoCrFeMnNi-HEA (each element with 20 at.-%) and CoCrNi-MEA, each element with 33.3 at.-%). As reference grade, the commercially available austenitic stainless steel AISI 316L was investigated. High-pressure hydrogen charging was conducted at different pressures in autoclave environment with maximum value of 1,000 bar. Thermal desorption analysis (TDA) via carrier gas hot extraction with coupled mass spectrometry was used with a max. heating rate of 0.5 K/s up to 650 °C. The measured desorption spectra of the different samples were deconvoluted into a defined number of individual peaks. The individually calculated peak temperatures allowed the definition of activation energies for predominant trap sites in the respective materials as well as the percentage share of the totally absorbed hydrogen concentration. The results present for the first time the complex interaction of both MPEAs and high-pressure hydrogen charging. A deconvolution of four peaks was selected and a main desorption peak was identified the dominant hydrogen trap containing the biggest share of the absorbed hydrogen concentration. The chemical composition an austenitic phase of both MPEAs is responsible for delayed hydrogen diffusion and strong, but mostly reversible, trapping. The comparison with the 316L samples showed significantly higher activation energies in the MPEAs, whereas hydrogen was also trapped at very high extraction temperatures. The absorbed maximum hydrogen concentration at 1,000 bar was 130 ppm for the CoCrFeMnNi-HEA, 50 ppm for the CoCrNi-MEA and 80 ppm for the 316L. It is interesting that the CoCrFeMnNi-HEA has obviously a way higher trapping capability compared to the conventional austenitic 316L, which could be a major advantage in terms of resistance to hydrogen assisted cracking.
Effect of Tensile Loading and Temperature on the Hydrogen Solubility of Steels at High Gas Pressure
(2023)
The hydrogen solubility in ferritic and martensitic steels is affected by hydrostatic stress, pressure, and temperature. In general, compressive stresses decrease but tensile stresses increase the hydrogen solubility. This important aspect must be considered when qualifying materials for high‐pressure hydrogen applications (e.g., for pipelines or tanks) by using autoclave systems. In this work, a pressure equivalent for compensating the effect of compressive stresses on the hydrogen solubility inside of closed autoclaves is proposed to achieve solubilities that are equivalent to those in pipelines and tanks subjected to tensile stresses. Moreover, it is shown that the temperature effect becomes critical at low temperatures (e.g., under cryogenic conditions for storing liquid hydrogen). Trapping of hydrogen in the microstructure can increase the hydrogen solubility with decreasing temperature, having a solubility minimum at about room temperature. To demonstrate this effect, the generalized law of the hydrogen solubility is parameterized for different steels using measured contents of gaseous hydrogen. The constant parameter sets are verified and critically discussed with respect to the high‐pressure hydrogen experiments.
This study gives an overview on the important field of joining processes for component fabrication in hydrogen technologies. The current main issues and future perspectives are highlighted for the different technological field of hydrogen generation, storage, transport and use. In addition, the emerging field of additive manufacturing is included. Some remarks are given for standardization and regulations.
In the course of tomorrow's hydrogen-based energy transition, the construction of the corresponding infrastructure will play a central role. In that context, large diameter long-distance transmission pipelines for hydrogen will be the backbone in the European Union with service pressures from 70 to 90 bar (e.g., de-pending on national regulations). It is a major goal to repurposing the existing natural gas (NG) infrastructure despite the necessity of new pipelines. From that point of view repair welding or further welding of branch pipe etc. can be necessary during in-service, i.e., permanent flow of pressurized hydrogen. The reason is that a shut-down of large diameter pipelines is not easy or sometimes merely impossible. At the moment, it is entirely open if current repair welding procedures for NG pipe-lines can be transferred to pure hydrogen pipelines. For that reason, a collaborative project between BAM, DVGW (German Association for Gas and Water Professions) and a large number of gas grid operators, pipeline manufacturers and construction companies was initiated in 2023 to answer questions on: (1) How many hydrogen is additionally absorbed during the preheating and maintaining at interpass temperature under remaining operational pressures? (2) Is the hydrogen concentration sufficient to reach a critical condition? (3)Which material and weld microstructure are the most susceptible? (4) Is there a difference in the repair welding behavior of NG pipelines with materials in “used” condition? (5) Which welding parameters and joint dimensions must be ensured for safe repair welding? The final aim of this project is the publication of a recommended practice for repair welding of in-service hydrogen pipelines. For that reason, the present study gives an overview on: (A) current practice in repair welding of in-service pipelines and (b) plans for hydrogen pipelines and first results of international research projects.
This contribution briefly summarizes the standardization activities in accordance with the "Nationale Roadmap Wasserstofftechnologien" and presents selected results on the activities in Germany with scope on hydrogen transport in pipelines. The talk was given during a panel discussion to set-up a steering committee for standardization for hydrogen pipelines and welding , coordinated by the International Institute of Welding.
As energy carrier of the future, green hydrogen can make a decisive contribution to a sustainable energy supply. Particularly important is the decarbonization of heavy industry. Therefore, a reliable supply of hydrogen must be guaranteed. A hydrogen pipeline grid can achieve this purpose. In Europe concrete plans for a hydrogen pipeline grid already exist, as the so called “European Hydrogen backbone”. As building a completely new pipeline grid is economically not justifiable, a dual-way strategy of repurposing natural gas (NG) pipelines and newly built pipelines is intended. Long distance pipeline grids require regular maintenance and repairs. For natural gas (NG) pipelines in-service welding is state of the art. Concepts such as hot-tapping (drilling into pressurized pipelines) and “stoppling” (sealing off pipeline sections after installing bypasses or pressure relieves) allow the repair of damaged pipeline sections or the installation of new branches without shutting the pipeline down, which in most cases isn’t possible from an economic standpoint. The EIGA 121/14 guideline already pointed out in 2014 that “a hydrogen hot-tap shall not be considered a routine procedure”. This shows that the determination of the transferability of these repair concepts to hydrogen pipelines is of utmost importance. Due to the degrading effects of hydrogen on mechanical proper-ties, commonly referred to as “hydrogen embrittlement” it is necessary to understand and investigate the occurring effects. In the special case of repair welding on in-service hydrogen pipelines an increased hydro-gen uptake due to a large heat input and microstructural changes in the material needs to be considered. Therefore, material degradation must be investigated to determine whether modifications of repair procedures are necessary to ensure a reliable and safe hydrogen transportation via pipelines. For this reason, this paper gives an overview on existing weld repair concepts and its risks and limitations in terms of hydrogen absorption and possible embrittlement effects when transferred to hydrogen pipelines. The complexity lies in a large variety of materials (low alloyed steels), pipeline diameters and corresponding welded joints. The material compatibility of materials in used (repurposed NG-pipelines) and new condition must be investigated. Particularly for repurposed/used pipelines the effect of a pre-matured/corroded inner surface and sometimes insufficient documentation of the material “history” needs to be considered. An overview on ongoing and completed R&D-projects with respect to repair concepts for hydrogen pipelines and hydrogen effects on pipeline materials is given. The focus hereby lies on possible methods of material testing and modeling. Its current difficulties, limits and possible solution will be discussed.
Joining and welding technologies are of high importance for the manufacturing of components and parts used in sustainable energy generation, conversion, and transport. In that connection, offshore and on-shore installed wind turbines are of high interest for the generation of electrical energy as well as photo-voltaic systems (solar cells). The electricity can be either directly transported or conversed via power-to-gas e.g., to hydrogen. In that scope, electrolyzer up to MW-range are of interest as well as the conver-sion back to electricity via fuel cells. In addition, hydrogen is a key element of the decarburization of in-dustries as well as the mobility sector encompassing sea, air and land transportation driven by hydrogen or its derivates. Well-known examples cover the direct reduction of iron ore to replace the conventional blast furnace process up to gas turbines or fuel cells for home-end use. All mentioned technologies re-quire reliable components, which are to a high extend dependent on joining and especially welding pro-cessing of materials. Especially, the (petro-) chemical industry has many years of experience with both materials used in hydrogen applications. The challenge is e.g., the transition to mass production of sys-tem components of electrolyzers/fuel cells and for distribution grids. At this point, the scalability of cur-rently applied joining processes often limits the economic efficiency, whereas especially laser welding or additive manufacturing will be of high interest. In that connection, it is very important to provide answers by joint research of universities, institutes, and industrial companies. Very often, solutions are already available and “just” have to be investigated and adapted for the new application, like repair welding of NG pipelines. For that reason, we want to set up a series of comprehensive papers with the aforementioned title. The idea is to get an in-depth but manageable overview of the importance of joining technologies in sustaina-ble energy generation, conversion, and transport encompassing current processes, limitations, and fur-ther perspectives. In that connection, the additive manufacturing is gaining more and more attention. If applicable, current challenges in the adaption or creation of new standards/regulations shall be addressed.
Offshore wind turbines continuously increase in size and weight and demand adequate offshore foundations concepts like monopiles, tripods, or jackets. These components are typically constructed using submerged arc welding (SAW) with high-strength thick steel plates like the S420ML. During welding, the occurrence of delayed hydrogen-assisted cracking (HAC) must be anticipated. HAC is a critical combination of the local hydrogen concentration within a susceptible microstructure under certain mechanical load, i.e., the occurring (welding) residual stresses. The welding sequence of the thick-walled plates complicates the residual stress distribution due to the necessary repeated thermal cycling, i.e., welding seam/layer deposition to fill the joint. For that purpose, SAW with two-wire-technique was used to weld a specially designed and prototype-like mock-up of a real component with a thickness of 50 mm, filled with over 20 passes and a seam length of 1000 mm. Additional welded stiffeners simulated the effect of a high restraint, to achieve critical HAC conditions. The necessity of a minimum waiting time (MWT) before the NDT can be conducted (to exclude HAC) was critically verified by the application of ultrasonic testing of the welded joint at different time-steps of the NDT of up to 48 h after the completion welding. The residual stresses were determined by a robot XRD goniometer. Tensile residual stresses up to the yield limit are found both in the weld metal and in the heat-affected zone. Numerical modeling allowed the qualitative estimation of the hydrogen diffusion in the weld. No noticeable HAC occurrence was identified and confirms the high cracking resistance of the investigated material. Finally, the applicability of the MWT concept should be critically discussed.
The hydrogen economy requires large-scale storage and transportation options like long-distance transmission pipelines. The applied materials (typically steels) must be carefully tested under different conditions (pressure, temperature, impact of impurities, etc.) for their suitability and service with hydrogen. In combination with mechanical load, as occurs in every gas network, hydrogen can induce degradation of the mechanical properties and promote finally resulting in embrittlement, i.e., the formation of cracks. The conventional testing procedures consist of autoclaves in which samples are strained under pressurized hydrogen. The test apparatus requires large amounts of hydrogen and thus a high level of safety and costs. In very specific cases, these tests might be replaced by simplified electrochemical charging. However, these test alternatives raise several questions regarding the equivalency of both testing scenarios. In the early 1980’s the idea of a so-called hollow tensile sample raised and was reinitiated 2021 in ISO TC 164 by T. Ogata (NIMS, Japan) and further developed (e.g. by Fraunhofer IWM, Germany). The idea was: the sample itself represents the autoclave instead of charging a sample from outside. For that reason, a hole is drilled through the sample and the inner surface is pressurized by hydrogen gas during the mechanical testing. Indeed, this represents the main advantage as no expensive pressure-resistant autoclave equipment for large H-volumes is necessary, which significantly reduces the safety-related issues and thus the high costs. In the following, we show recent activities at BAM Berlin on adaption of the hollow-specimen technique for slow strain rate testing (SSRT). The current research activities are focussed on macroscopic influences like the sample geometry, minimum necessary dimensions, and microscopic influences e.g., on the surface by the processing method (drill hole quality and geometric precision) as well as the gas pressure effect (mechanical deformation of surface in different media).
The presentation gives an overview of BAM's activities on processing influences and application properties of MPEAs in the form of joined and machined high and medium entropy alloys (CoCrFeMnNi and CoCrNi). In the case of welding, the focus is on defect-free welded joints with sufficient mechanical properties. In the case of machining, the focus is on the possible influence on the surface quality of the materials through adequate milling parameters. In addition, the hydrogen absorption and diffusion properties as well as the electrochemical corrosion behavior are fundamentally examined.