High Hydrogen Embrittlement Research Articles

Hydrogen-induced cracking behaviors of Ni–Cr–Mo-based superalloy fabricated by wire arc additive manufacturing under different solution temperature

The hydrogen embrittlement behavior of Ni–Cr–Mo-based superalloy fabricated by wire arc additive manufacturing (WAAM) with or without solution treatment was investigated by electrochemical hydrogen charging. The results show that the dissolution of the Laves phase promotes the precipitation of the δ phase in the matrix of WAAM superalloy after solution treatment at 980 °C. When the solution temperature goes up to 1080 °C, the large Laves phase disappears and only MC exists in the matrix. The interfaces between the Laves phase/δ phase and matrix generally could act as hydrogen traps, which would reduce the motion of hydrogen and lead to high hydrogen embrittlement resistance of the WAAM and ST-980 °C samples. However, hydrogen mainly accumulates on grain boundaries in the ST-1080 °C due to the disappearance of the Laves phase and δ phase. Hydrogen-induced intergranular brittle fracture occurs during the slow strain rate tensile test and the ST-1080 °C samples exhibit higher hydrogen embrittlement susceptibility than that of the WAAM and ST-980 °C samples.

Influence of dislocation cells on hydrogen embrittlement in wrought and additively manufactured Inconel 718

Hydrogen embrittlement (HE) is a major issue for the mechanical integrity of high-strength alloys exposed to hydrogen-rich environments, with diffusion and trapping of hydrogen being critical phenomena. Here, the role of microstructure on hydrogen diffusion, trapping and embrittlement in additively manufactured (AM) and wrought Inconel 718 is compared, revealing the key role played by dislocation cells. Trapping behaviour in hydrogen-saturated alloys is analysed by thermal desorption spectroscopy and numerical simulations. A high density of hydrogen traps in cell walls, attributed to dense dislocations and Laves phases, are responsible for the local accumulation of hydrogen, causing significant loss in strength, and triggering cracking along dislocation cell walls. The influential role of dislocation cells alters fracture behaviour from intergranular in the wrought alloy to intragranular for the AM alloy, due to the large proportion of dislocation cells in AM alloys. In addition, the cellular network of dislocations accelerates hydrogen diffusion, enabling faster and deeper penetration of hydrogen in the AM alloy. These results indicate that the higher HE susceptibility of nickel superalloys is intrinsically associated with the interaction of hydrogen with dislocation walls.

Microstructural evolution and hydrogen embrittlement in simulated reheated coarse-grained heat-affected zone of a high-strength naval steel

The influence of simulated reheated coarse-grained heat-affected zones (CGHAZ) on the microstructural evolution and hydrogen embrittlement in high-strength naval steel was investigated by scanning electron microscopy, microhardness testing, electron backscatter diffraction, slow strain rate tensile test and fracture morphology analysis. Twinned martensites were observed in both the intercritical and super-critically reheated CGHAZ, with a widely spaced region in the former. Intercritical reheated coarse-grained HAZ (ICCGHAZ) was the weakest zone of reheated CGHAZ when the peak temperature was 660 °C, exhibiting the intergranular cracking feature. Twinned martensite and coarsening grain size were therefore concluded to be the main reasons for high hydrogen embrittlement susceptibility in the reheated CGHAZ.

Effect of I-phase formation on hydrogen embrittlement behaviour of as-cast Mg-8 wt%Li based alloys

By performing microstructural characterization, tensile testing and failure analysis, the effects of electrochemical H-charging on microstructure and mechanical behaviour of two as-cast Mg-8Li (in wt%) based alloys were investigated and compared. Due to the in-situ formation of I-phase, the failure elongation ratio for Mg-8Li-6Zn-1Y alloy was 31.2 % and its hydrogen embrittlement (HE) susceptibility was about 1/4 that of Mg-8Li alloy after H-charging for 24 h. Moreover, the preferential location of H-induced pores transferred from two matrix phases to I-phase/matrix eutectic pockets due to the preferential H absorption of I-phase, resulting in the higher HE resistance of Mg-8Li-6Zn-1Y alloy.

Hydrogen-enhanced microbanding in an austenitic FeMnAlC low-density steel: Effect on hydrogen embrittlement resistance

We have investigated the influence of 101 mass ppm hydrogen content on the room temperature deformation structure and mechanical behavior of an austenitic Fe30Mn6.5Al0.3C (wt.%) low-density steel by several electron microscopy techniques, such as electron channeling contrast imaging (ECCI), electron backscatter diffraction (EBSD), and scanning transmission electron microscopy (STEM). The steel exhibits a high hydrogen embrittlement resistance associated with a moderated increase in strength (yield stress increase of 10%) and ductility (increase in the elongation to fracture of ∼ 8%). Analysis of the deformation structure reveals that hydrogen influences the deformation behavior by promoting deformation mechanisms associated with inhomogeneous plasticity (hydrogen-enhanced deformation banding (HEDB)) and strain localization (hydrogen-enhanced microbanding (HEMB)). These deformation mechanisms are ascribed to hydrogen-induced effects on dislocation plasticity, resulting in macroscopic kink bands, sub-micron localized strain gradients, and localized shear at cell blocks. We find that HEMB plays a relevant role in the deformation behavior of sub-micron localized strain gradients by promoting plastic relaxation and the enhanced storage of geometrically necessary dislocations within them. These effects mitigate the activation of damage mechanisms and enhance the strain-hardening capacity, contributing to the high HE resistance of the steel, comparable to that of high HE-resistant fcc alloys and steels.

Change in Hydrogen Trapping Characteristics and Influence on Hydrogen Embrittlement Sensitivity in a Medium-Carbon, High-Strength Steel: The Effects of Heat Treatments.

Medium-carbon, high-strength steels are widely used in the field of hydrogen energy because of their good mechanical properties, and they can be readily tailored by heat treatment processes such as the normalizing-tempering (N&T) and quenching-tempering (Q&T) methods. The hydrogen embrittlement (HE) susceptibility of a medium-carbon, high-strength steel was investigated utilizing microstructural characterization with scanning electron microscopy (SEM), the electron backscatter diffraction (EBSD) technique, and transmission electron microscopy (TEM). A study was also conducted on the steel's hydrogen transport behavior as affected by the N&T and Q&T treatments. The steel contained more hydrogen traps, such as dislocations, grain boundaries, lath boundaries, and carbide interfaces, after the Q&T process, which was associated with a lower HE sensitivity when comparing the two treatments. In comparison, the N&T process produced larger-size and lesser-density carbides distributed along the grain boundaries, and this resulted in a relatively higher HE susceptibility, as revealed by the slow-strain-rate tensile (SSRT) tests of the hydrogen-charged steels and by the fractographic study of the fracture surface.

Hydrogen embrittlement of FeCrAl alloys: The significant role of Laves phase and AlN particles

The addition of Nb to FeCrAl alloy enhanced its mechanical properties owing to the precipitated-phase strengthening effect. However, the additive amount and its effect on hydrogen embrittlement (HE) susceptibility have to be evaluated before implementation, as the hydrogen produced by fission and corrosion in the reactor may affect its mechanical properties. Therefore, hydrogen pre-charged tensile bar specimens were tested, and the HE mechanism was investigated. The results demonstrate that though FeCrAl alloys show low HE susceptibility, the Nb-doped FeCrAl alloys still exhibit a slightly higher HE susceptibility than Nb-free FeCrAl alloys. Their reduced ductility was mainly caused by decohesion and cracking of Fe2(Nb, Mo) precipitates and quasi-cleavage cracking induced by AlN inclusions. The underlying HE mechanisms for the Nb-doped FeCrAl alloys are hydrogen-enhanced localized plasticity (HELP) and HELP-mediated hydrogen-enhanced decohesion (HEDE).

Improved resistance to hydrogen embrittlement in the nugget zone of friction stir welded medium Mn steel via post-welding annealing

In this work, medium-Mn steel was friction stir welded and then intercritically annealed. Hydrogen diffusion and hydrogen embrittlement (HE) behavior in the nugget zone (NZ) were investigated. The as-welded NZ exhibited the highest HE index (HEI) of 79.2%, and hydrogen‑induced cracks propagated along the grain boundary, probably depending on grain boundary decohesion caused by H segregation. However, this condition was improved by post-welding annealing since fine lath reversed austenite, acting as a strong hydrogen trap, was introduced into the ferritic matrix, inhibiting the segregation of H to grain boundaries. Ultimately, the lowest HEI of 10.7% was obtained in the as-annealed NZ.

Effects of microstructure and morphological distribution on hydrogen-embrittlement sensitivity of Ti–6Al–4V alloy welded joint

The effects of the organizational characteristics and morphological distribution of Ti–6Al–4V alloy welded joint on their resistance to hydrogen embrittlement were investigated. The β-phase continuity of the base material (BM) was poor, and the large volume of the striped α-phase hindered hydrogen diffusion. Consequently, the BM has low hydrogen embrittlement sensitivity. The basket-like phase distribution of the weld material (WM) had better β-phase continuity and higher phase boundary density compared with the BM, providing a more convenient channel for hydrogen diffusion and more hydrogen absorption sites. Therefore, the WM had a high hydrogen embrittlement sensitivity.

Effect of heat treatment on the hydrogen embrittlement susceptibility of selective laser melted 18Ni-300 maraging steel

The effects of heat treatment on the hydrogen embrittlement (HE) susceptibility of selective laser melted 18Ni-300 maraging steel were investigated. The results demonstrate that the as-built steel has a microstructure consisting of an Fe–Ni martensite matrix and a cellular structure. Substantial microstructural changes are observed following various heat treatment processes (solution, direct aging, and solution-aging), resulting in varying degrees of increased HE susceptibility. Specifically, after solution treatment, the complete elimination of cellular structure and the growth of grains concurrently increased hydrogen diffusion coefficient of the steel. However, its lower proportion of ∑3 boundaries and higher proportion of ∑11 boundaries played an advantageous role that lead to a marginal increase in the HE susceptibility. In contrast, direct aging and solution-aging treatments enhance the HE susceptibility significantly, which is primarily related to the decomposition of the cellular structure and reversible hydrogen trapping and precipitation strengthening effects of the newly formed Ni3(Ti, Mo) precipitates. Compared with the solution-aging treatment, the direct aging treatment results in the formation of a localized austenite aggregation zone near the molten pool boundaries, which promotes the initiation of hydrogen-assisted cracking and leads to a higher HE susceptibility.

Effect of inclusions on the hydrogen embrittlement of martensitic medium-Mn steel

In this study, we investigated the hydrogen embrittlement (HE) of martensitic medium-Mn steels with varying levels of S and Ti contents using thermal desorption analysis, silver decoration, slow strain rate tensile testing, and fractography. The S or S–Ti added specimens demonstrated higher HE resistance compared to the S-free specimens. This is because the S or S–Ti added specimens had a large volume fraction of fine MnS or Ti(C,N)–MnS complex inclusions with a size less than ∼1 μm, which provide strong irreversible H trap sites. However, coarse elongated inclusions were found to be detrimental to HE resistance. Therefore, we concluded that to improve the HE resistance of martensitic medium-Mn steel, it is important to distribute a large volume fraction of fine MnS or Ti(C,N)–MnS complex inclusions without coarse elongated ones.

Hydrogen-induced failure in a partially-recrystallized Al-Zn-Mg-Cu alloy with different aging conditions: Influence of deformation behavior dominated by microstructures

Hydrogen-induced failure in a partially-recrystallized Al-Zn-Mg-Cu alloy with different aging conditions was studied by in-situ electrochemical hydrogen charging method, and the hydrogen-induced cracking mechanism was elucidated by investigating the microstructure-dominated deformation behavior. It was found that in naturally-aged and peak-aged samples, cracks initiate at sample surfaces, and deformation dominated by shearing facilitates hydrogen diffusion, resulting in a high hydrogen embrittlement susceptibility. However, in the over-aged sample, deformation dominated by bypassing cannot transport hydrogen efficiently, which exerts no effect on crack initiation at the sample center. In addition, the same cracking pattern exists on all samples in silicone oil and in-situ hydrogen charging environments. The grain boundary of recrystallized grains is prone to strain localization, leading to intergranular cracking. In unrecrystallized grains, transgranular cracks propagate along intersections of slip lines and subgrain boundaries. This study improves the understanding of hydrogen embrittlement in new generation Al-Zn-Mg-Cu alloy by linking the existing hydrogen embrittlement mechanism to the deformation behavior dominated by microstructures.

Effect of microstructure on the hydrogen embrittlement, diffusion, and uptake of dual-phase low alloy steels with varying ferrite-martensite ratios

This study investigates the microstructure-dependent hydrogen transport properties and hydrogen embrittlement (HE) resistance of dual-phase (DP) ferritic-martensitic low alloy steels (LASs) for hydrogen-related applications. Ferritic-pearlitic and fully martensitic microstructures were also included as control conditions. Our results demonstrate that tempering DP-LAS reduces hardness and enhances carbide precipitation, leading to increased hydrogen diffusion coefficients and reduced hydrogen trapping. This effect is believed to be primarily associated with dislocation annihilation. Additionally, higher martensite content decreases the hydrogen diffusion coefficient in both as-quenched and tempered conditions. In slow strain rate tests, DP-LASs samples with approximately 50% tempered martensite exhibited the highest HE resistance. These findings offer new insights into the microstructure design of DP-LASs for hydrogen applications, particularly in the tempered condition.

Effect of additive manufacturing and subsequent heat and/or surface treatment on the hydrogen embrittlement sensitivity of 316L austenitic stainless steel

Austenitic stainless steels (ASS) offer attractive characteristics for use in hydrogen service, such as low hydrogen diffusivity and high solubility. The role of the production process is, however, still unclear. Especially the effect of additive manufacturing (AM) on the hydrogen interaction is not extensively researched yet. The present work compares the hydrogen embrittlement sensitivity of conventional (cold rolled and annealed) and additive manufactured 316L ASS and evaluates the possible advantage of performing a heat treatment and/or reducing the surface roughness post printing. AM increases the hydrogen solubility but the hydrogen diffusivity was only slightly reduced. The heat treatment reduced the hydrogen solubility of the AM materials and significantly increased the hydrogen diffusivity. Despite these observations, the conventional 316L ASS shows a higher hydrogen embrittlement (HE) sensitivity compared to AM316L. This is linked to the increased hydrogen-assisted cracking sensitivity of conventional 316L ASS. The heat treated microstructure behaves similarly as the as-built material in terms of HE sensitivity, while a major improvement is observed when the surface oxide layer formed during the heat treatment is maintained since this reduces hydrogen absorption. Surface polishing intensifies the HE sensitivity which is linked to a higher surface hydrogen concentration leading to more crack initiation.

Effects of the microstructure and reversed austenite on the hydrogen embrittlement susceptibility of Ni-Cr-Mo-V/Nb high-strength steel

The effects of the microstructure and reversed austenite (RA) on the hydrogen embrittlement (HE) behavior were investigated in NiCrMoV/Nb high-strength steel prepared using three different heat treatments. The quenching and tempering (QT) steel showed a noble HE resistance for the lowest hydrogen diffusion and maximum apparent hydrogen concentration compared to quenching (Q) steel and quenching, lamellarizing, and tempering (QLT) steel. Thermal desorption spectroscopy (TDS) analysis confirmed that RA had an activation energy of 32.5 kJ/mol which indicates a stable trapping site. The QLT steel containing more RA exhibited a higher HE susceptibility, suggesting that RA degrades the HE resistance.

The high strength and hydrogen embrittlement resistance of selective laser melted 304 austenitic stainless steel

3D printing technology can be used to produce a variety of complex parts for hydrogen service. In this study, 304 austenitic stainless steel (ASS) sample was manufactured by selective laser melting (SLM), one of the 3D printing technologies, then its high strength and hydrogen embrittlement resistance were discovered in comparison to traditional solution-treated 304 ASS. The unique high-density dislocation cellular structure of SLM sample remarkably restrained the nucleation of α'-martensite and slowed down the diffusion of hydrogen. Moreover, the possibility of hydrogen induced intergranular fracture was significantly reduced because of the alleviated hydrogen segregation at the grain boundary.

Effect of manganese content on the hydrogen embrittlement of twinning-induced plasticity (TWIP) steels under hydrogen charging and hydrogen environment

The hydrogen embrittlement behavior of two stabilized austenitic twinning-induced plasticity (TWIP) steels under high-pressure thermal hydrogen charging and hydrogen environment were investigated by slow strain rate tensile and fatigue crack growth tests. The results show that the two TWIP steels with Mn content (16% and 25%) do not produce strain-induced martensite after deformation, but both show a certain susceptibility to hydrogen embrittlement after hydrogen charging, in which the TWIP steel with higher Mn content shows weaker hydrogen embrittlement. This is mainly due to the high hydrogen embrittlement susceptibility of deformation twins. In the H2 environment, compared with slow strain rate tensile tests, fatigue crack growth tests is more likely to reflect the hydrogen embrittlement susceptibility of the TWIP steel, and the hydrogen environment is more likely to promote the crack growth of the TWIP steel with lower Mn content. This is related to the inter-granular cracking of TWIP steel with low Mn content under H2 environment. The increase of Mn content reduces the hydrogen diffusion coefficient and hydrogen solubility of TWIP steel, which is also one of the reasons for the weak hydrogen embrittlement of TWIP steel with high Mn content in hydrogen charging and hydrogen environment.

Effects of an inhomogeneous electron density distribution on the hydrogen distribution in TiZrTaNbAl multi-principal element alloys

A body-centered cubic equiatomic TiZrTaNbAl multi-principal element alloy (MPEA) with elemental fluctuations was investigated to further understand the relationship between the microstructure and hydrogen distribution. In this study, a composition dependence of the hydrogen distribution was observed in the TiZrTaNbAl MPEA. An inhomogeneous electron density distribution of the MPEA was revealed by advanced differential phase-contrast scanning electron microscopy (DPC-STEM) for the first time. The results showed that the electron density has a significant effect on the hydrogen distribution in TiZrTaNbAl MPEAs. This work provides new insight into the design of materials with high hydrogen storage capacity and high hydrogen embrittlement resistance.

Stiffness-based method to identify the threshold load of low hardness steels using the Incremental step loading test

Hydrogen embrittlement (HE) is one of the main problems related to the use of metallic materials in sour or wet environments. The Incremental Step-Loading (ISL) test used to evaluate the susceptibility to HE of steels has gained more visibility over recent years, thus allowing for the determination of the threshold load (Pth) in H+ enriched environments. However, the ISL standard, ASTM F1624, limits the test to steels with a minimum hardness of 33 HRC. Even for those steels with 33 HRC, the results present some misinterpretations. In addition to this fact, one needs to consider that there are several applications where steels with hardness below 33 HRC are used, as for instance, in fasteners and tool joints under cathodic protection used in the oil and gas industry, for which hardness varies from 26 to 32 HRC. In light of the aforementioned, the standard limitation represents a major disadvantage related to the application of the ISL test. Grounded upon the said, the aim of the present study is to propose a methodology based on the specimen stiffness to be used in the ISL test results, allowing the Pth determination of steels with hardness lower than 33HRC. Conventional and extended ISL tests were performed in two steels (4137-M and 4130-M) with a 32HRC hardness values. Applying the stiffness-based method on the the conventional ISL test results, a threshold load (Pth) of 71.5 %PFFS and 66.0 %PFFS were found for the 4137-M and 4130-M steels, respectively. To validate these results, extended ISL tests were performed on both steels and the results showed a Pth of 73.7 %PFFS for the 4137-M steel and 66.0 %PFFS for the 4130-M steel. The results from the conventional ISL test, using the stiffness-based method proposed in this study, provided values similar or with differences lower than 5 %PFFS, when compared alongside the extended ISL tests. Moreover, ISL tests were performed on the same steels with 40 HRC hardness, and the AISI4137-M presented a Pth of 21.6 %PFFS and for 4130-M the Pth was 22.0 %PFFS. The main conclusion obtained from these tests was that, when large amount of plastic deformation is not present on ISL test, the load drop visual detection is sufficient to determine the Pth. As expected, it was observed that both steels with 40 HRC presented higher HE susceptibility than the 32 HRC ones. This behavior was due to higher stress concentration at the notch root presented by the higher hardness condition. The stiffness-based method proved to be robust and capable of separate yielding from hydrogen induced cracking of low hardness steels and could also be used to identify the Pth values of steels with hardness lower than that specified by the ASTM F1624 standard, and which are tested using the ISL test.

The d band center as an indicator for the hydrogen solution and diffusion behaviors in transition metals

Understanding the hydrogen solution and diffusion behaviors are crucial to design the hydrogen embrittlement resistant structural materials in industry applications. Whether there exists an indicator for prediction of the hydrogen solution and diffusion behaviors is an important but unclarified question. In this study, the hydrogen solution and diffusion behaviors in transition metals and alloys were investigated by density functional theory (DFT) and nudged elastic band (NEB) method calculations. The calculation results reveal that the d band center is directly correlated with hydrogen solution ability in structural materials. The strain and alloying effects on the variations of hydrogen solution energy and d band center have also been considered and the well variation consistency between them is established. With respect to the hydrogen diffusion in transition metals, the transition state has a lower d band center than the initial state. Especially, the hydrogen diffusion energy barrier is proportional to the d band center difference between the initial state and transition state in alloying Fe. Thus the d band center can be regarded as an indicator for hydrogen solution and diffusion in structural materials, which can enlighten us to design the structural materials with high hydrogen embrittlement resistance.