Atom doping in α-Fe2O3 thin films to prevent hydrogen permeation

Prevention of hydrogen (H) penetration into passive films and steels plays a vital role in lowering hydrogen damage. This work reports effects of atom (Al, Cr, or Ni) doping on hydrogen adsorption on the α-Fe₂O₃ (001) thin films and permeation into the films based on density functional theory. We found that the H₂ molecule prefers to dissociate on the surface of pure α-Fe₂O₃ thin film with adsorption energy of −1.18 eV. Doping Al or Cr atoms in the subsurface of α-Fe₂O₃ (001) films can reduce the adsorption energy by 0.03 eV (Al) or 0.09 eV (Cr) for H surface adsorption. In contrast, Ni doping substantially enhances the H adsorption energy by 1.08 eV. As H permeates into the subsurface of the film, H occupies the octahedral interstitial site and forms chemical bond with an O atom. Comparing with H subsurface absorption in the pure film, the absorption energy decreases by 0.01–0.22 eV for the Al- and Cr-doped films, whereas increases by 0.82–0.96 eV for the Ni-doped film. These results suggest that doping Al or Cr prevents H adsorption on the surface or permeation into the passive film, which effectively reduces the possibility of hydrogen embrittlement of the underlying steel.     

Role of solute atoms and vacancy in hydrogen embrittlement mechanism of aluminum: A first-principles study

Hydrogen trapping performances of Al with solute atoms X (X = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, or Zn) and X-vacancy defects are investigated using First-principles method. For X-doped Al supercells, most structures show strong alloying ability. Among the solute atoms studied, Cr is the most useful element to trap H due to its lowest H trapping energy. For vacancy@X-doped Al supercells, the strong interactions of X-vacancy are explored. All vacancy@X-doped Al supercells are more favorable to capture H than X-doped Al supercells. In addition, both elastic and chemical interactions should comparably contribute to H-X or H-X-vacancy interactions in Al. Solute atoms and vacancy may regulate electron distribution of Al to enhance the ability of capturing H. Overall, our insights present the quantitative role of solute atoms and vacancy in H trapping for Al, and guide the design of new alloys with high resistance to hydrogen embrittlement.     

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.     

Thermodynamics of spontaneous dissociation and dissociative adsorption of hydrogen molecules and hydrogen atom adsorption and absorption on steel under pipelining conditions

While hydrogen pipelines have attracted increased attention, safety of the pipelines has been a concern in terms of hydrogen embrittlement (HE) occurring upon hydrogen atom (H) generation and permeation in the steels. In this work, thermodynamic analyses regarding H generation and adsorption on pipeline steels by two potential mechanisms, i.e., spontaneous dissociation and dissociative adsorption, were conducted through theoretical calculations based on Gibbs free energy change of the H generation reactions. Moreover, H adsorption free energy and configurations were determined based on density functional theory (DFT) calculations. Effects of H adsorption site, H coverage and hydrostatic stress on H adsorption and absorption were discussed. Spontaneous dissociation of hydrogen gas molecules to generate hydrogen atoms is thermodynamically impossible. Dissociative adsorption is thermodynamically feasible at wide temperature and pressure ranges. Particularly, an increased hydrogen gas partial pressure and elevated temperature favor the dissociative adsorption of hydrogen. Hydrogen atoms generated by dissociative adsorption mechanism can adsorb stably at On-Top (OT) and 2-fold (2F) Cross-Bridge sites of Fe (100), while hydrogen adsorption at 2F site is more stable due to a higher electron density and a stronger electronic hybridization between Fe and H. The influence of H atom coverage on dissociative adsorption occurs at low coverages only, i.e., 0.25–1.00 ML as determined in this work. External stresses make dissociative adsorption more difficult to occur compared with a fully relaxed steel. Both tetrahedral sites (TS) and octahedral sites (OS) can potentially host absorbed H atoms at subsurface of the steel. Absorbed H atoms will be predominantly trapped at TS due to a low energy path and exothermic feature. Diffusion of H atoms from steel surface to the subsurface is more difficult compared with the dissociative adsorption.     

Atomistic simulation study of the grain-size effect on hydrogen embrittlement of nanograined Fe

Although hydrogen-induced fracture at grain boundaries has been widely studied and several mechanisms have been proposed, few studies of nanograined materials have been conducted, especially for grain sizes below the critical size for the inverse Hall-Petch relation. In this research work, molecular dynamics (MD) simulations are performed to investigate the hydrogen segregation and hydrogen embrittlement mechanism in polycrystalline Fe models. When the same concentration of H atoms is added, the H segregation ratio in the model with the smallest grain size is the highest observed herein, showing the high hydrogen trapping ability of small-grain Fe, while the H concentration at the grain boundaries (GBs) is, on the contrary, the lowest. Uniaxial tensile test simulations demonstrate that as the grain size decreases, the models show an increased resistance to hydrogen embrittlement, and for small-grain models (d < 10 nm), the GB-related deformation modes dominate the plastic deformation, where the segregated H mainly influences the toughness by inhibiting GB-related processes.     

Effect of alloying elements on hydrogen environment embrittlement of AISI type 304 austenitic stainless steel

The chemical composition of an AISI type 304 austenitic stainless was systematically modified in order to evaluate the influence of the elements Mo, Ni, Si, S, Cr and Mn on the material’s susceptibility to hydrogen environment embrittlement (HEE). Mechanical properties were evaluated by tensile testing at room temperature in air at ambient pressure and in a 40 MPa hydrogen gas atmosphere. For every chemical composition, the corresponding austenite stability was evaluated by magnetic response measurements and thermodynamic calculations based on the Calphad method. Tensile test results show that yield and tensile strength are negligibly affected by the presence of hydrogen, whereas measurements of elongation to rupture and reduction of area indicate an increasing ductility loss with decreasing austenite stability. Concerning modifications of alloy composition, an increase in Si, Mn and Cr content showed a significant improvement of material’s ductility compared to other alloying elements.     

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.     

Origin of deformation twins and their influence on hydrogen embrittlement in cold-rolled austenitic stainless steel

The effect of cold rolling on hydrogen embrittlement in stable 18Cr–1Mn–11Ni-0.15 N austenitic stainless steels was investigated. Alloy plates were cold-rolled to 15% or 30% reduction, then pre-charged with hydrogen and subjected to tensile testing with slow strain rate. Hydrogen-induced degradation of tensile elongation became increasingly severe with the increase in the degree of cold rolling. During cold rolling, deformation twins with various orientations were actively generated, and twins with specific orientations were vulnerable to hydrogen-induced cracking. Cold rolling also increased the density of defects, and thereby facilitated penetration of hydrogen into the steels. The combination of cracks generated at the twin boundaries, and the promoted hydrogen diffusion caused severe hydrogen embrittlement in the cold-rolled steels.     

Numerical simulation of the hydrogen trapping effect on crack propagation in API 5CT P110 steel under cathodic overprotection

The possibility of the development of hydrogen embrittlement processes increases in cathodic protection systems when cathodic overprotection occurs, and large amounts of hydrogen are produced. Additionally, the hydrogen embrittlement susceptibility of steel depends on solubility, diffusivity, and hydrogen trapping. This paper presents a numerical simulation of the reversible and irreversible hydrogen trapping effects on crack propagation in API 5CT P110 steel using a model based on a synthesis of fracture mechanics and continuum damage mechanics, in which the trapping term of the diffusion equation was replaced by the trapping terms of other more complete model. The simulation was performed with using a C(T) specimen loaded in the tensile opening mode, in the linear elastic regime, in plane strain state, under the action of a static mechanical loading and the effect of hydrogen. The simulations showed that the material degradation ahead of the crack tip increases with increases in hydrogen concentration at the crack tip due to the hydrogen trapping effect. Furthermore, the process of onset and crack growth in material with irreversible traps is slower than that in material with reversible traps. These results are consistent with macroscopic observations of the trapping effect, providing a better understanding of the hydrogen embrittlement in structural steels.     

Hydrogen environment embrittlement of an ODS RAF steel – Role of irreversible hydrogen trap sites

The microstructure and the effects of 10 MPa hydrogen atmosphere on the tensile properties of a oxide dispersion strengthened (ODS) reduced activation ferritic (RAF) steel were investigated. The microstructure consists of a fine grained ferritic matrix with Me₃O₄ (Me = Cr, Fe or Mn), VN and Cr₂₃C₆ grain boundary precipitates as well as dispersed yttrium oxide nano precipitates in the ferritic matrix. The yield and ultimate tensile strength were unaffected by the H₂ atmosphere whereas elongation at fracture and reduction in area were markedly reduced. In H₂ atmosphere, the fracture morphology was found to be a mixture of intergranular H-assisted fracture and a smaller amount of transgranular hydrogen enhanced localized plasticity (HELP) fracture. The sensitivity of the ODS RAF steel to hydrogen embrittlement is attributed to the large number grain boundary precipitates which enhance the tendency for intergranular fracture.     

Hydrogen adsorption studies of TiFe surfaces via 3-d transition metal substitution

Hydrogen adsorption over TiFe surface and doped TiFe surface is investigated within density functional theory. Surface energy calculations confirm that TiFe (111) surface has the minimum value among three low index crystallographic surfaces, (100), (111) and (110). The (111) TiFe surface has two different terminations one with Fe and the other with Ti. Here both the (111) surfaces with different terminations are considered for doping with all the 3-d transition metal atoms from Sc to Zn. Furthermore, the molecular hydrogen adsorption over all the doped surfaces is investigated. V was found to be the most suitable element for doping in Fe terminated (111) surface. V doping in Fe terminated surface enhanced E_ads by 0.6 eV from ?3.30 eV (undoped) to ?3.90 eV after doping. Whereas in case of Ti terminated surface Co was found to be the best element for doping as it enhanced E_ads by ～0.5 eV from ?2.64 eV (undoped) to ?3.15 eV after doping. A significant decrease in d-band width from 1.95 eV to 1.22 eV in case of Co substitution in Ti terminated surface and from 2.42 eV to 1.33 eV in case of V substitution in Fe terminated surface enhances the hydrogen adsorption in TiFe (111) surface. Thus, even using a very small amount of dopant can influence the hydrogen adsorption properties of TiFe alloy.     

Influence of substitutional impurities on hydrogen diffusion in B2-TiFe alloy

The hydrogen diffusion pathways were studied in B2-TiFe alloy within density functional theory (DFT) using the plane-wave pseudo-potential method. Our results confirm that the hydrogen diffusion between octahedral interstices where it is surrounded by two Fe and four Ti atoms along [10-1] direction is most preferential in TiFe bulk. The estimated hydrogen diffusion barrier of 0.62 eV differs insignificantly from values of barriers in pure Ti. The influence of substitutional transition and simple metal impurities on the energy barriers is discussed. It was found that impurities such as V, Cr, Mn decrease the hydrogen diffusion barriers along both considered pathways whereas Pd impurity decreases considerably the barrier along [00-1] direction that leads to the change of the diffusion mechanism. In general, the competition of structural and electronic factors strongly influences the hydrogen diffusion barriers. The present results provide a deep understanding of H behavior in TiFe bulk.     

An Fe–Ni–Cr–H interatomic potential and predictions of hydrogen-affected stacking fault energies in austenitic stainless steels

While Fe–Ni–Cr austenitic stainless steels exhibit relatively good resistance to hydrogen embrittlement, they still suffer from significant degradation of ductility, fatigue and fracture properties in gaseous hydrogen environments. Experimental studies in the literature suggest that hydrogen reduces stacking fault energy in austenitic stainless steels. This phenomenon causes a large separation of partial dislocations and lower propensity for cross-slip. Whereas lower stacking fault energy does not correlate well with loss of ductility in the absence of hydrogen, lower stacking fault energy trends toward greater loss of ductility when hydrogen is present. Calculations of stacking fault energy are challenging for austenitic stainless steels. One main issue is that in alloys, stacking fault energy is not a single value but rather varies depending on local composition. Herein, we first report an Fe–Ni–Cr–H quaternary interatomic potential and then use this potential to perform time-averaged molecular dynamics simulations to calculate stacking fault energies for tens of thousands of realizations of local compositions for selected stainless steels alloys with and without internal hydrogen. From statistical analyses, our results suggest that hydrogen reduces stacking fault energy, which likely impacts deformation mechanisms of Fe–Ni–Cr austenitic stainless steels when exposed to hydrogen environments. We then perform validation MD simulation tests to show that hydrogen indeed statistically increases the stacking fault widths due to statistically reduced stacking fault energies.     

The effect of age-hardening mechanism on hydrogen embrittlement in high-nitrogen steels

The effect of age-hardening regime on peculiarities of hydrogen-assisted fracture and tensile properties in two high-nitrogen Fe-23Cr-17Mn-0.1C-0.6N and Fe-19Cr-22Mn-1.5V-0.3C-0.9N steels was studied. A large number of intergranular (austenite/austenite) and interphase boundaries (austenite/coarse particle) provides high fraction of trapping sites for hydrogen atoms in V-alloyed steel. This leads to a change in fracture regime from transgranular brittle mode in coarse-grained V-free steel to intergranular brittle fracture of hydrogen-assisted surface layers in fine-grained V-alloyed steel with coarse (V,Cr)(N,C) particles. The formation of cells (Cr₂(N,C) particles and austenite) along the grain boundaries due to discontinuous precipitate-hardening reaction facilitates predominantly interphase hydrogen-assisted fracture for both steels. The complex reaction of the particle-strengthening mechanisms including discontinuous precipitation with formation of austenite/Cr₂(N,C)-plates interfaces or homogeneous nucleation of coherent (V,Cr)(N,C) particles in austenite (age-hardening regime 700 °C, 10 h) promotes mainly transgranular cleavage-like fracture mode under hydrogen-charging. The structural scheme is proposed to describe a change in hydrogen-assisted fracture micromechanisms and tensile properties of the steels with different density and distribution of interphase and intergranular boundaries.     

Enhanced gaseous hydrogen solubility in ferritic and martensitic steels at low temperatures

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. Finally, the parametrized equation is applied to calculate the stress-enhanced hydrogen solubility of thin-walled pipelines and thick-walled pressure vessels during service.     

Towards understanding the strong trapping effects of noble gas elements on hydrogen in tungsten

We have investigated the effects of noble gas elements (helium, neon, argon and krypton) on the dissolution and accumulation behavior of hydrogen (H) in tungsten (W) using a first-principles method, as well as the behaviors of themselves. Noble gas atoms energetically prefer to occupy the tetrahedral interstitial site (TIS) in W, as the same of H. The TIS → TIS is their optimal diffusion path, and the diffusion energies increase with the increasing of atomic radius. All of them are energetically favorable clustering by self-trapping. It is found that the presence of the noble gas elements have significant effect on H behavior in W. Both interstitial noble gas atoms and their complex with vacancy can serve as strong trapping centers of H, which can be attributed to the redistribution of electron density and lattice distortion induced by noble gas. Most importantly, we have demonstrated that H trapping capability of noble gas clusters will increase with the increasing of the number of noble gas atoms in both interstitial and vacancy-complex cases. The H trapping energy surrounding the noble gas clusters with four atoms is comparable to that in noble gas-free vacancy. Further, the formation of noble gas clusters is much easier than that of vacancy due to the self-trapping interaction between noble gas atoms (>1 eV for interstitial case and >4 eV for vacancy-complex case), and thus the H trapping centers will rapidly increase after noble gas pre-irradiation/implantation. Consequently, the self-trapping character of noble gas induces their strong trapping effect on H.     

Effect of the loading mode and temperature on hydrogen embrittlement behavior of 15Cr for steam turbine last stage blade steel

The hydrogen embrittlement of 15Cr martensitic stainless steel, for steam turbine last stage blades, was systematically studied by using slow strain rate tensile (SSRT) test and constant loading tensile (CLT) test at room temperature and 80 °C to simulate the service conditions. It was shown that, despite the lower hydrogen concentration absorbed during SSRT, the hydrogen-induced fracture strength of 15Cr steel for SSRT was lower than the threshold fracture strength for CLT. This was due to the remarkable enhancement in local hydrogen concentration due to the transportation of hydrogen by mobile dislocation during SSRT. In addition, although the higher hydrogen concentration was absorbed during SSRT at 80 °C, the hydrogen embrittlement susceptibility of 15Cr steel for SSRT at 80 °C was lower than that at room temperature, because the degree of local hydrogen accumulation decreased at a higher temperature.     

The detrimental effect of hydrogen at dislocations on the hydrogen embrittlement susceptibility of Fe-C-X alloys: An experimental proof of the HELP mechanism

The hydrogen trapping ability of 15 Fe-C-X alloys is compared in this work. Five types of carbides, i.e. Ti, Cr, Mo, W and V based carbides, and their effect on the hydrogen embrittlement susceptibility is considered while three carbon contents are prepared for each carbide former. Two conditions are compared for each alloy to evaluate the hydrogen/material interaction: an as quenched and quenched and tempered condition in which carbides are introduced. Next to the material characterization, also the interaction of hydrogen with the materials is completely elaborated. At first, in-situ tensile tests are done to determine the hydrogen induced ductility loss. To interpret the obtained degrees of hydrogen embrittlement, hot/melt extraction is done to determine the hydrogen content, whereas thermal desorption spectroscopy is performed to assess the hydrogen trapping capacity of the tempered induced precipitates and the different other potentially hydrogen trapping microstructural features. These measurements are done after hydrogen pre-charging till saturation. The tempered induced TiC and V₄C₃ are capable of trapping a significant amount of hydrogen, while the Mo₂C and Cr₂₃C₆ particles only trap a limited amount of hydrogen. The W₂C precipitates, however, are not able to trap hydrogen. The size and coherency of the carbides are considered to be the main factor determining their trapping ability. The degree of hydrogen embrittlement is correlated with the hydrogen present in the alloys. Three amounts of hydrogen were determined by the strength by which they were trapped by combining the different hydrogen characterization techniques, i.e. total, diffusible and mobile hydrogen. It was confirmed that hydrogen trapped by dislocations plays a determinant role. This further confirms the importance of an enhanced dislocation mobility in the presence of hydrogen, as described in the HELP mechanism.     

The role of delta ferrite in hydrogen embrittlement fracture of 17-4 PH stainless steel

The role of δ-Fe in hydrogen embrittlement (HE) of 17-4 PH steel is studied in this work. Scanning Kelvin probe force microscopy result indicates that δ-Fe is a hydrogen trapping site. Accordingly, δ-Fe can reduce the hydrogen concentration of surrounding martensite and prior austenite grain boundaries (PAGBs) and imped the brittle fracture along lath boundaries and PAGBs, which can be beneficial to the HE resistance improvement. However, a cleavage fracture of δ-Fe can occur under the synergetic action of hydrogen-enhanced localized plasticity (HELP) and hydrogen enhancement of the strain-induced generation of vacancies (HESIV). These findings indicate a new path to improving HE resistance of high strength martensitic steels.     

Effects of doping with a third element (Pd,Ru, Ta) on the structure and hydrogen permeation properties of V–10Mo solid solutions

Alloying is an effective method for improving the resistance of V metals to hydrogen embrittlement. The effects of the doping with a third element (Pd, Ru, Ta) on the structure and hydrogen permeation properties of V–10Mo solid solutions have been investigated in this study. As-prepared V–5Mo-5TM (TM = Mo, Pd, Ru, Ta) alloy samples composed of V-based solid solution with a bcc structure are hydrogenated into their corresponding solid solutions (α-phase). Structural changes caused by TM-doping have notable effects on the hydrogen permeation properties (particularly the hydrogen solubility) of V–10Mo alloy, and the ability of the doping element in decreasing the hydrogen solubility of the V–10Mo alloy follows the sequence: Pd > Ru > Ta. Their doping causes a slight decrease in the hydrogen diffusion coefficient as well as an increase in the Vickers hardness of the resulting alloys. This work demonstrates that the mechanical property of V–10Mo alloy can be improved via suitable structure control caused by alloying it with an appropriate element. In addition, this approach might be suitable for improving properties of other relevant binary alloys.