Hydrogen embrittlement and associated surface crack growth in fine-grained equiatomic CoCrFeMnNi high-entropy alloys with different annealing temperatures evaluated by tensile testing under in situ hydrogen charging

The effect of the annealing temperature after cold rolling on hydrogen embrittlement resistance was investigated with a face-centered cubic (FCC) equiatomic CoCrFeMnNi high-entropy alloy using tensile testing under electrochemical hydrogen charging. Decreasing annealing temperature from 800 °C to 750 °C decreased grain sizes from 3.2 to 2.1 μm, and resulted in the σ phase formation. Interestingly, the specimen annealed at 800 °C, which had coarser grains, showed a lower hydrogen embrittlement susceptibility than the specimen annealed at 750 °C, although hydrogen-assisted intergranular fracture was observed in both annealing conditions. Because the interface between the FCC matrix and σ was more susceptible to hydrogen than the grain boundary, the presence of the matrix/σ interface significantly assisted hydrogen-induced mechanical degradation. In terms of intergranular cracking, crack growth occurred via small crack initiation near a larger crack tip and subsequent crack coalescence, which has been observed in various steels and FCC alloys that contained hydrogen.     

Hydrogen embrittlement behavior in interstitial Mn–N austenitic stainless steel

The susceptibility to hydrogen embrittlement behavior was investigated in an interstitial Mn–N austenitic steel HR183 and stainless steel 316L. Hydrogen was introduced by cathodic hydrogen charging at 363 K. HR183 has stronger austenite stability than 316L despite its lower nickel content, the addition of manganese and nitrogen inhibited martensitic transformation during the slow strain rate tensile deformation. Due to the diffusion of hydrogen being delayed by the interstitial solution of nitrogen atoms and the uniform dislocation slips, hydrogen permeates more slowly in HR183 than 316L, contributing to an 84.79 μm thinner brittle fracture layer in HR183 steel. Hydrogen charging caused elongation losses in both 316L and HR183 steels associated with the hydrogen-enhanced localized plasticity (HELP) and hydrogen-enhanced decohesion (HEDE) mechanism. However, the hydrogen embrittlement susceptibility of HR183 is 3.4 times lower than that of 316L according to the difference in elongation loss between the two steel after hydrogen charging. Deformation twins trapped a lot amount of hydrogen leading to brittle intergranular fracture in 316L. The multiple directions of slip in HR183 steel suppressed the strain localization inside grains and delayed the adverse effects conducted by HELP and HEDE mechanism, eventually inhibiting server hydrogen embrittlement in the HR183 steel. This study is assisting in the development of low-cost stainless steel with excellent hydrogen embrittlement resistance that can be used in harsh hydrogen-containing environments.     

On the role of nitrogen on hydrogen environment embrittlement of high-interstitial austenitic CrMnC(N) steels

This work investigates the susceptibility of high-interstitial CrMn austenitic stainless steel CN0.96 to hydrogen environment embrittlement. In this context, an N-free model alloy of CN0.96 steel was designed, produced, and characterized. Both steels were subjected to tensile tests in air and in a high-pressure hydrogen gas atmosphere.Both steels undergo severe hydrogen embrittlement. The CN0.96 steel shows trans- and intergranular failure in hydrogen, whereas the N-free model alloy shows exclusively intergranular failure. The different failure modes could be related to different deformation modes that are induced by the presence or absence of N, respectively. In the CN0.96 steel, N promotes planar dislocation slip. Due to the absence of N in the model alloy, localized slip is less pronounced and mechanical twinning is a more preferred deformation mechanism. The embrittlement of the model alloy could therefore be related to mechanisms that are known from hydrogen embrittlement of twinning-induced plasticity steels.     

Influence of machining parameters on surface roughness and susceptibility to hydrogen embrittlement of austenitic stainless steels

In the present work, an investigation on the susceptibility to hydrogen embrittlement of AISI 304 and 310 austenitic stainless steels was performed. The hydrogen embrittlement process leads to degradation of mechanical properties and can be accelerated by the presence of surface defects combined with elevated surface hardness. Tensile test specimens of the selected materials were machined by turning with different cutting parameters in order to create variations in surface finish conditions. The samples thus prepared were submitted to tensile tests before and after hydrogen permeation by cathodic charging. Regarding the AISI 304 steel, it was possible to notice that the presence of strain-induced martensite on the material surface led to severe hydrogen embrittlement. In the case of the AISI 310 steel, due to its higher nickel amount, no martensite formation could be detected, and this steel was found to be less susceptible to embrittlement in the tested conditions.     

Overview of hydrogen embrittlement in high-Mn steels

Hydrogen and fuels derived from it will serve as the energy carriers of the future. The associated rapidly growing demand for hydrogen energy-related infrastructure materials has stimulated multiple engineering and scientific studies on the hydrogen embrittlement resistance of various groups of high performance alloys. Among these, high-Mn steels have received special attention owing to their excellent strength – ductility – cost relationship. However, hydrogen-induced delayed fracture has been reported to occur in deep-drawn cup specimens of some of these alloys. Driven by this challenge we present here an overview of the hydrogen embrittlement research carried out on high-Mn steels. The hydrogen embrittlement susceptibility of high-Mn steels is particularly sensitive to their chemical composition since the various alloying elements simultaneously affect the material's stacking fault energy, phase stability, hydrogen uptake behavior, surface oxide scales and interstitial diffusivity, all of which affect the hydrogen embrittlement susceptibility. Here, we discuss the contribution of each of these factors to the hydrogen embrittlement susceptibility of these steels and discuss pathways how certain embrittlement mechanisms can be hampered or even inhibited. Examples of positive effects of hydrogen on the tensile ductility are also introduced.     

The dependence of fatigue crack growth on hydrogen in warm-rolled 316 austenitic stainless steel

The fatigue crack growth rate of warm-rolled AISI 316 austenitic stainless steel was investigated by controlling rolling strain and temperature in argon and hydrogen gas atmospheres. The fatigue crack growth rates of warm-rolled 316 specimens tested in hydrogen decreased with increasing rolling temperature, especially 400 °C. By controlling the deformation temperature and strain, the influences of microstructure (including dislocation structure, deformation twins and α′ martensite) and its evolution on hydrogen-induced degradation of mechanical properties were separately discussed. Deformation twins deceased and dislocations became more uniform with the increase in rolling temperature, inhibiting the formation of dynamic α′ martensite during the crack propagation. In the cold-rolled 316 specimens, deformation twins accelerated hydrogen-induced crack growth due to the α′ martensitic transformation at the crack tip. In the warm-rolled specimens, the formation of α′ martensite around the crack tip was completely inhibited, which greatly reduced the fatigue crack growth rate in hydrogen atmosphere.     

Influence of surface martensite layer on hydrogen embrittlement of Fe-Mn-C-Mo steels in wet H2S environment

This study investigated the effect of thermally induced surface martensite layer on hydrogen embrittlement of Fe-16Mn-0.4C-2Mo (wt.%) (16Mn) and Fe-25Mn-0.4C-2Mo (wt.%) (25Mn) steels through slow strain rate stress corrosion cracking testing and proof ring testing in wet H₂S environment. The 16Mn steel had a surface layer of less than 150 μm in depth containing ε-martensite, α′-martensite and austenitic twins. The martensite layer is found to reduce the hydrogen embrittlement resistance of the steel. In comparison, the 25Mn steel developed a full α′-martensite surface layer, which exhibited practically nil effect on the hydrogen embrittlement resistance of the steel. The ε-martensite provides much larger interface areas with the mechanical twins of the austenite in the 16Mn steel than the α′-martensite/austenite interfaces in the 25Mn steel. These interfaces are hydrogen trapping sites and are prone to initiate surface cracks, as observed in the scanning electron microscope. The formation of the cracks is attributed to hydrogen concentration at the ε-martensite and austenitic twin interfaces, which accelerates material fracture.     

Metallurgical and mechanical properties of hydrogen charged carbide-free bainitic weld metals

Hydrogen embrittlement is a major concern during the welding of high-strength steels. The susceptibility of the welds to hydrogen embrittlement increases with increase in weld strength. The ever-increasing demand to increase the strength of steels necessitates the development of novel welding procedures and fillers to produce welds of high strength and with resistance to hydrogen embrittlement. In this current work, the susceptibility of carbide-free bainitic weld metals to hydrogen embrittlement is studied with varying volume fractions of constituent phases. Using three different weld metal compositions, six different weld metal microstructures of carbide-free bainite were generated. The hydrogen saturation behaviour of the various weld metals was studied by cathodic electrolytic charging and subsequent diffusible hydrogen measurements by the hot extraction method. Tensile tests were conducted on various weld metals with and without hydrogen charging to evaluate their susceptibility to hydrogen embrittlement. The results show that the carbide-free bainite weld metals are highly resistant to hydrogen embrittlement despite their very high strength.     

Influence of copper as an alloying element on hydrogen environment embrittlement of austenitic stainless steel

A Cu alloyed (18Cr–10Ni–3Cu) and a Cu free (18Cr–12.7Ni) austenitic stainless steel were tensile tested in gaseous hydrogen atmosphere at 20 °C and −50 °C. Depending on the test temperature, the Cu alloyed steel was extremely embrittled whereas the Cu free steel was only slightly embrittled. Austenite stability and inherent deformation mode are two main criteria for the resistance of austenitic stainless steels against hydrogen environment embrittlement. Based on the well known austenite stability criteria, the austenite stability of both steels should be very similar. Interrupted tensile tests show that martensite formation upon plastic deformation was much more severe in the Cu alloyed steel proving that the influence of Cu on austenite stability is overestimated in the empirical stability equations. When tested in high pressure H₂, replacing Ni by Cu resulted in a fundamental change in fracture mode atmosphere, i.e. Ni cannot be replaced by Cu to reduce the costs of SS without compromising the resistance to hydrogen environment embrittlement.     

Effect of pre-strain on hydrogen embrittlement of metastable austenitic stainless steel under different hydrogen conditions

The effects of internal hydrogen and environmental hydrogen on the hydrogen embrittlement of 304 austenitic stainless steels (ASSs) with varying degrees of pre-strain were investigated by a tensile test under cathodic hydrogen-charged, gaseous hydrogen and hydrogen-charged and gaseous hydrogen combined conditions. The internal hydrogen embrittlement of the 304 ASSs increased with increasing pre-strain, while the hydrogen embrittlement caused by the environment hydrogen increased and then decreased with increasing pre-strain. The hydrogen embrittlement mechanisms caused by the internal hydrogen or environmental hydrogen were different. The cracks caused by internal hydrogen or environmental hydrogen are mainly initiated in grain interior or at grain boundary, respectively. Under the coupling condition of internal hydrogen and environmental hydrogen, the hydrogen embrittlement of 304 ASSs was the strongest and increased with increasing pre-strain. Environmental hydrogen was dominant for low levels of pre-deformed specimens. Internal hydrogen was dominant for high levels of pre-deformed specimen.     

Development of a stable high-aluminum austenitic stainless steel for hydrogen applications

A novel high-aluminum austenitic stainless steel has been produced in the laboratory with the aim of developing a lean-alloyed material with a high resistance to hydrogen environment embrittlement. The susceptibility to hydrogen environment embrittlement was evaluated by means of tensile tests at a slow strain rate in pure hydrogen gas at a pressure of 40 MPa and a temperature of −50 °C. Under these conditions, the yield strength, tensile strength and elongation to rupture are not affected by hydrogen in comparison to companion tests carried out in air. Moreover, a very high ductility in hydrogen is evidenced by a reduction of area of 70% in the high-pressure and low-temperature hydrogen environment. The lean degree of alloying is reflected in the molybdenum-free character of the material and a nickel content of 8.0 wt.%. With regard to the alloy concept, a combination of high-carbon, high-manganese, and high-aluminum contents confer an extremely high stability against the formation of strain-induced martensite. This aspect was investigated by means of in-situ magnetic measurements and ex-situ X-ray diffraction. The overall performance of the novel alloy was compared with two reference materials, 304L and 316L austenitic stainless steels, both industrially produced. Its capability of maintaining a fully austenitic structure during tensile testing has been identified as a key aspect to avoid hydrogen environment embrittlement.     

Impact of chemical inhomogeneities on local material properties and hydrogen environment embrittlement in AISI 304L steels

This study investigated the influence of segregations on hydrogen environment embrittlement (HEE) of AISI 304L type austenitic stainless steels. The microstructure of tensile specimens, that were fabricated from commercially available AISI 304L steels and tested by means of small strain-rate tensile tests in air as well as hydrogen gas at room temperature, was investigated by means of combined EDS and EBSD measurements. It was shown that two different austenitic stainless steels having the same nominal alloy composition can exhibit different susceptibilities to HEE due to segregation effects resulting from different production routes (continuous casting/electroslag remelting). Local segregation-related variations of the austenite stability were evaluated by thermodynamic and empirical calculations. The alloying element Ni exhibits pronounced segregation bands parallel to the rolling direction of the material, which strongly influences the local austenite stability. The latter was revealed by generating and evaluating two-dimensional distribution maps for the austenite stability. The formation of deformation-induced martensite was shown to be restricted to segregation bands with a low Ni content. Furthermore, it was shown that the formation of hydrogen induced surface cracks is strongly coupled with the existence of surface regions of low Ni content and accordingly low austenite stability. In addition, the growth behavior of hydrogen-induced cracks was linked to the segregation-related local austenite stability.     

Hydrogen embrittlement of the coarse grain heat affected zone of a quenched and tempered 42CrMo4 steel

The coarse grain heat affected zone (CG-HAZ) of welds produced in a quenched and tempered 42CrMo4 steel was simulated by means of a laboratory heat treatment consisting in austenitizing at 1200 °C for 20 min, oil quenching and finally applying a post weld heat treatment at 700 °C for 2 h (similar to the tempering treatment previously applied to the base steel). A tempered martensite microstructure with a prior austenite grain size of 150 μm and a hardness of 230 HV, similar to the aforementioned CG-HAZ weld region, was produced. The effect of the prior austenite grain size on the hydrogen embrittlement (HE) behaviour of the steel was studied comparing this coarse-grained microstructure with that of the fine-grained base steel, with a prior austenite grain size of 20 μm.The specimens used in this study were charged with hydrogen gas in a reactor at 19.5 MPa and 450 °C for 21 h. Cylindrical specimens were used to determine hydrogen uptake and hydrogen desorption behaviour. Smooth and notched tensile specimens tested under different displacement rates were also used to evaluate HE.Embrittlement indexes, EI, were generally quite low in the case of hydrogen pre-charged tensile tests performed on smooth tensile specimens. However, very significant embrittlement indexes were obtained with notched tensile specimens. It was observed that these indexes always increase as the applied displacement rate decreases. Moreover, hydrogen embrittlement indexes also increase with increasing prior austenite grain size. In fact, the embrittlement index related to the reduction in area, EI_(RA), reached values of over 20% and 50% for the fine and coarse grain size steels, respectively, when tested under the lowest displacement rates (0.002 mm/min).A comprehensive fractographic analysis was performed and the main operative failure micromechanisms due to the presence of internal hydrogen were determined at different test displacement rates. While microvoids coalescence (MVC) was found to be the typical ductile failure micromechanism in the absence of hydrogen in the two steels, brittle decohesion mechanisms (carbide-matrix interface decohesion, CMD, and martensitic lath interface decohesion, MLD) were observed under internal hydrogen. Intergranular fracture (IG) was also found to be operative in the case of the coarse-grained steel tested under the lowest displacement rate, in which hydrogen accumulation in the process zone ahead of the notch tip is maximal.     

Notched-tensile properties under high-pressure gaseous hydrogen: Comparison of pipeline steel X70 and austenitic stainless type 304L, 316L steels

The effect of high-pressure gaseous H₂ on the fracture behavior of pipeline steel X70 and austenitic stainless steel type 304L and 316L was investigated by means of notched-tensile tests at 10 MPa H₂ gas and various test speed. The notch tensile strength of pipeline X70 steel and austenitic stainless steels were degraded by gaseous H₂, and the deterioration was accompanied by noticeable changes in fracture morphology. The loss of notch tensile strength of type 316L and X70 steels was comparable, but type 304L was more susceptible to hydrogen embrittlement than the others. In the X70 steel, hydrogen embrittlement increased as test speed decreased until the test speed reached 1.2 × 10^?3 mm/s, but the effect of test speed was not significant in 304L and 316L steels.     

Effects of grain size and dislocation density on the susceptibility to high-pressure hydrogen environment embrittlement of high-strength low-alloy steels

The tensile properties of several high-strength low-alloy steels in a 45 MPa hydrogen atmosphere at ambient temperature were examined with respect to the effects of grain size and dislocation density on hydrogen environment embrittlement. Grain size was measured using an optical microscope and dislocation density was determined by X-ray diffractometry. Both grain refinement and a reduction in dislocation density are effective in reducing the susceptibility to embrittlement. The steel that has high dislocation density or large grain size inclines to show a smooth intergranular fracture surface. Given only the grain size and dislocation density, a simple approximation of the embrittlement property of high-strength steel could be obtained. This method could be useful in selecting candidate materials in advance of the mechanical tests in high-pressure hydrogen gas.     

The influence of the processing route on the fragmentation of (Nb,Ti)C stringers and its role on mechanical properties and hydrogen embrittlement of nickel based alloy 718

The nickel-base superalloy 718 is a precipitation hardened alloy widely used in the nuclear fuel assembly of pressurized water reactors (PWR). However, the alloy can experience failure due to hydrogen embrittlement (HE). The processing route can influence the microstructure of the material and, therefore, the HE degree. In particular, the size and distribution of the (Nb,Ti)C particles can be affected by the processing. In this regard, the objective of this work was to analyze the influence of cold and hot deformation processing routes on the development of the microstructure, and the consequences on mechanical properties and hydrogen embrittlement. Tensile samples were hydrogenated through gaseous charging and compared to non-hydrogenated samples. Characterization was performed via scanning and transmission electron microscopies, as well as electron backscattered diffraction. The processing was effective to promote significant variations in average grain size and length fraction of special Σ3ⁿ boundaries, as well as reduction of average (Nb,Ti)C particle size, being these changes more intense for the cold-rolled route. For the mechanical properties, on one side, the cold-rolled route presented the highest increase in ductility for non-hydrogenated samples, while, on the other side, had the highest degree of embrittlement under hydrogen. This dual behavior was attributed to the interaction of hydrogen with the (Nb,Ti)C particles and stringers and its ensuing influence on the fracture processes.     

Combined effects of prior plastic deformation and sensitization on hydrogen embrittlement of 304 austenitic stainless steel

Austenite stainless steels (ASSs) may suffer from both cold deformation and sensitization prior to hydrogen exposure. There is scant data in literature on the combined effect of prior deformation and sensitization on the hydrogen embrittlement (HE) of ASSs. The present study investigated the combined effects of tensile plastic prestrain (PS) and 650 °C sensitization (ST) on the HE of 304 steel by hydrogen pre-charging and tensile testing. The results are explained by terms of pre-existing α′ martensite content. PS higher than 10% can enhance HE significantly by inducing severe α′ transformation prior to hydrogen exposure. Prior ST also enhances HE, but submitting the prestrained and α′-containing 304 steel to short-time ST can diminish the enhancement of HE by prestraining, as ST can cause the reversion of α′ to austenite, reducing pre-existing α′ content. It is inadvisable to make 304 steel be sensitized/welded firstly and deformed subsequently, even if the ST time is short such as what happens during welding, because this treating sequence can induce more α′ than prestraining alone, enhancing HE more significantly. Apparent hydrogen diffusivity can be related quantitatively to pre-existing α′ content, proving directly that α′ platelets can act as diffusion “highways” in ASSs. It is indicated that pre-existing α′ can enhance subsequently the HE of ASSs is because it can lead to a large amount of hydrogen entering the ASSs during hydrogen exposure by acting as diffusion “highways”. HE is enhanced by increasing hydrogen amount rather than by pre-existing α′ itself.     

Comparative study of embrittlement of quenched and tempered steels in hydrogen environments

The study of steels which guarantee safety and reliability throughout their service life in hydrogen-rich environments has increased considerably in recent years. Their mechanical behavior in terms of hydrogen embrittlement is of utmost importance. This work aims to assess the effects of hydrogen on the tensile properties of quenched and tempered 42CrMo4 steels. Tensile tests were performed on smooth and notched specimens under different conditions: pre-charged in high pressure hydrogen gas, electrochemically pre-charged, and in-situ hydrogen charged in an acid aqueous medium. The influence of the charging methodology on the corresponding embrittlement indexes was assessed. The role of other test variables, such as the applied current density, the electrolyte composition, and the displacement rate was also studied. An important reduction of the strength was detected when notched specimens were subjected to in-situ charging. When the same tests were performed on smooth tensile specimens, the deformation results were reduced. This behavior is related to significant changes in the operative failure micromechanisms, from ductile (microvoids coalescence) in absence of hydrogen or under low hydrogen contents, to brittle (decohesion of martensite lath interfaces) under the most stringent conditions.     

Effect of nano Nb and V carbides on the hydrogen interaction in tempered martensitic steels

The effect of precipitate type and distribution to mitigate the hydrogen embrittlement of high strength martensitic steels containing different levels of C, Nb, and V was studied. Even low additions of Nb and V contributed to an increase of the material resistance. The steel with a more homogeneous distribution of carbides, higher Nb, and lower V showed increased hydrogen solubility and presented a lower level of loss of ductility in tensile tests with hydrogen pre-charging. The presence of segregation of precipitates was responsible for a rise in the amount of diffusible hydrogen, thus increasing the hydrogen embrittlement susceptibility.     

Improving the hydrogen absorption properties of commercial Mg–Zn–Zr alloy

Commercial alloy ZK60 (Mg-6 wt%Zn-0.8 wt% Zr) was used as a hydrogen-storage material to study the effect of cold rolling, ball milling, and plus graphite additives on hydrogen-storage characteristics, hydrogen absorption–desorption behavior, and the related microstructural change of the alloy. Experimental results showed that cold-rolled alloy could not be activated easily. Even after ball milling for 20 h and hydrogen absorption–desorption cycling for 10 times, no saturated hydrogen absorption was observed for cold-rolled alloy. In contrast, alloys with 5 wt% graphite additives could be easily activated after the first hydrogen absorption–desorption cycle, and a saturated hydrogen absorption of 6.9 wt% was obtained after absorption–desorption cycling for five times. A hydrogen absorption of 5.52 wt%, equivalent to 80% of the saturated absorption amount, was measured in 5 min, showing a hydrogen absorption rate of 1.104 wt%/min. The sample reached saturation in 30 min.