Finite element analysis of hydrogen diffusion/plasticity coupled behaviors of low-alloy ferritic steel at large strain

Hydrogen embrittlement is commonly considered as a typical failure mechanism for low-alloy ferritic steel under high pressure hydrogen environment. Currently, the hydrogen enhanced localized plasticity theory has been largely recognized for studying the hydrogen embrittlement mechanism by introducing the localized plastic flow and the hydrogen induced strain concept. However, the hydrogen induced strain and the plastic strain are often solved respectively in this theory, which may weaken the effect of hydrogen on the plastic deformation. The purpose of this paper is to propose a modified theoretical model from the microstructural level by emphasizing the coupling mechanism between the hydrogen diffusion and the plastic deformation at large strain, where the hydrogen induced strain is superimposed on the equivalent plastic strain instead of on the strain components. Fully implicit backward Euler algorithm by finite element analysis (FEA) under the corotational configuration is used to implement the proposed model, where the hydrogen induced strain is involved in the stress return process within each iteration, indicating a more direct interaction between them than existing works. FEA by using finite element software ABAQUS-UMAT subroutine is performed for the smooth tensile specimen and the notch specimen respectively under slow tensile strain rate loading and different hydrogen pressure. Developed direct coupling model is expected to further gain insight into the hydrogen embrittlement effect on the plastic deformation, especially at the trapping sites.     

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.     

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.     

A first principles study on H-atom interaction with bcc metals

Solute hydrogen trapping has long been proposed as one of the mechanisms for hydrogen embrittlement in steel. It has been reported that the maximum hydrogen trapping energy of metallic solutes ranged from ?0.7 eV to ?0.9 eV. In this work, the mechanism of metal-H interaction in Cr-Mo steels was investigated with first principles calculations by modelling the binary alloy Fe-X (X = C, Si, Mn, Cr, Mo) system with reference to the chemical composition of Cr-Mo steels. The formation of hydrogen bonds in the case of H atoms located at different sites in Fe-X crystals was analyzed. Results indicated that various atomic doping had different roles in hydrogen effect in the steel, with C, Si and Mo doping making the solid solution of hydrogen in Fe crystals easier, while Mn and Cr doping was rather more difficult. In Fe-Mn and Fe-Cr crystals, the repulsion between Fe lattices was insignificant when H atoms were located in tetrahedral sites, which considerably reduced the binding energy in the crystal. When H atoms were dissolved into the crystal, the interatomic bonding interactions in Fe-X crystals were weakened, resulting in higher charge density fluctuations. The current work extends the understanding of H-atom diffusion and migration in steel from the microscopic scale to the atomic and electronic scales, which underpins the physics for tailoring chemical elements of bcc metals towards higher resistance to hydrogen embrittlement.     

Effects of hydrogen on the fracture toughness of CrMo and CrMoV steels quenched and tempered at different temperatures

Tempering temperatures ranging between 500 and 720 °C were applied in order to analyse the relationship between steel microstructure and the deleterious effect of hydrogen on the fracture toughness of different CrMo and CrMoV steels. The influence of hydrogen on the fracture behaviour of the steel was investigated by means of fracture toughness tests using CT specimens thermally pre-charged with hydrogen gas.First, the specimens were pre-charged with gaseous hydrogen in a pressurized reactor at 19.5 MPa and 450 °C for 21h and elasto-plastic fracture toughness tests were performed under different displacement rates. The amount of hydrogen accumulated in the steel was subsequently determined in order to justify the fracture toughness results obtained with the different steel grades. Finally, scanning electron microscopy was employed to study both the resulting steel microstructures and the fracture micromechanisms that took place during the fracture tests.According to the results, hydrogen solubility was seen to decrease with increasing tempering temperature, due to the fact that hydrogen microstructural trapping is lower in relaxed martensitic microstructures, the strong effect of the presence of vanadium carbides also being noted in this same respect. Hydrogen embrittlement was also found to be much greater in the grades tempered at the lowest temperatures (with higher yield strength). Moreover, a change in the fracture micromechanism, from ductile (microvoid coalescence, MVC), in the absence of hydrogen, to intermediate (plasticity-related hydrogen induced cracking, PRHIC) and brittle (intergranular fracture, IG), was appreciated with the increase in the embrittlement indexes.     

Improved hydrogen embrittlement resistance after quenching–tempering treatment for a Cr-Mo-V high strength steel

The effect of quenching-tempering (QT) treatment on the hydrogen embrittlement (HE) resistance of a reactor pressure vessel steel was studied. Decomposition of M₃C/VC carbides and precipitation of M₇C₃ carbides were confirmed by transmission electron microscopy and atom probe tomography observations. Tensile tests showed that HE sensitivity decreased to a negligible level after QT treatment. The improvement of HE resistance was mainly attributed to the decreased number of M₃C carbides which act as the reversible trapping sites for hydrogen. This was supported by the decreased concentration of reversible hydrogen as measured by thermal desorption spectroscopy. The amount of irreversible hydrogen (probably trapped at VC carbides) also decreased, which is however not considered responsible for the HE improvement.     

Development of methods for evaluating hydrogen compatibility and suitability

The embrittlement of metals exposed to hydrogen environments is well documented. With the deployment of hydrogen fuel cell vehicles in the consumer sector, there is a need to improve the engineering basis for the selection of materials of construction for equipment that stores and distributes high-pressure gaseous hydrogen. This brief overview summarizes publicly available guidance for evaluating materials compatibility with high-pressure gaseous hydrogen. Additionally, a new standard for measuring engineering data in gaseous hydrogen and evaluating materials suitability for service in gaseous hydrogen is introduced: the CHMC1 standard provides a general framework for qualifying materials for hydrogen service. The CHCM1 standard is unique in its broad scope and performance-based strategy for quantitatively assessing materials in their service environment and for the intended structural requirements.     

Hydrogenation method based on electrodeposited layers controlling the hydrogen desorption rate

An innovative hydrogenation method to investigate the hydrogen embrittlement of metals and alloys is hereby presented. The benefits of electroplating samples with copper and nickel prior to gaseous hydrogenation at mid-range temperatures are quantified. It is showed that these electrodeposited layers allow to control the hydrogen desorption rate occurring after hydrogenation, during the cooling of the hydrogenated specimen. The present study demonstrates the capability of the method to control the introduced total hydrogen concentration within a margin of 0.2 wt.ppm. The applicability of the described method to further investigations into hydrogen concentrations effects on hydrogen embrittlement of ferritic alloys by the means of mechanical tests is evaluated.     

Critical verification of the Kissinger theory to evaluate thermal desorption spectra

Multiple types of hydrogen trapping sites in advanced high-strength steels (AHSS) are often experimentally characterized by means of thermal desorption spectroscopy (TDS). The evaluation is regularly based on the peak deconvolution procedure combined with Kissinger's theory, which provides distinctive desorption energies of hydrogen trapping sites at microstructural defects. However, the desorption energies published in literature are often non-conclusive and from time to time contradictive in nature. Therefore, it is of utmost importance to verify the evaluation procedures according to Kissinger's theory for multiple types of hydrogen trapping sites. For that purpose, theoretical TDS spectra were simulated using a bulk diffusion model according to Oriani's theory. Binding energies and trap densities were chosen for providing TDS spectra with clearly separated as well as overlapping TDS peaks. Finally, the desorption energies according to Kissinger's theory were compared with the theoretical trapping energies used in the models. Based on this theoretical work, it is strongly recommended to apply the Kissinger theory only for the evaluation of single or well separated TDS peaks. If peaks overlap, complementary microstructural variation and characterization are a perquisite to correctly evaluate the TDS spectra.     

Modeling fatigue life and hydrogen embrittlement of bcc steel with unified mechanics theory

The fatigue life estimation of metals operating in hydrogen-rich environments such as hydrogen pipelines, hydrogen-burning internal combustion engines, etc. is important. Studies in the past 40 years have shown that the diffusion of hydrogen into steel and other metals causes various chemical reactions, hydrogen-material interactions, and microstructural changes. That leads to hydrogen embrittlement (HE) and other types of hydrogen damage mechanisms including hydrogen environmentally assisted cracking (HEAC). Hydrogen embrittlement mechanisms, such as hydrogen-enhanced localized plasticity (HELP) and hydrogen-enhanced decohesion (HEDE) can have synergetic effects in steel depending on the hydrogen concentration level. At concentrations above and below the critical hydrogen concentration, HEDE and HELP dominate the embrittlement process, respectively. Different HE mechanisms result in distinctly different fracture modes, both ductile and fully brittle. The ultrasonic vibration fatigue life of bcc steel with a ferrite-pearlite microstructure pre-charged with hydrogen at different concentrations is studied. Modeling is based on the unified mechanics theory (UMT), which does not need any empirical dissipation/degradation potential function or an empirical void evolution function. However, the UMT does require analytical derivation of the thermodynamic fundamental equation of the material, which is used to calculate the thermodynamic state index (TSI) of the material. The UMT is ab-initio unification of the second law of thermodynamics and the universal laws of motion of Newton [1]. Dissipation/degradation evolution is governed by Boltzmann's second law of thermodynamics entropy formulation. The original contribution of this paper is the derivation of the thermodynamic fundamental equation of pre-hydrogen embrittled bcc steel subjected to ultrasonic very high cycle fatigue and the numerical simulations of fatigue life estimation using the proposed novel model. The synergetic interaction of hydrogen embrittlement mechanisms in steel and other metallic materials, i.e., HELP and HEDE at different hydrogen concentrations (HELP + HEDE model) is also studied, reviewed, and applied. The synergetic effects between ultrasonic vibration fatigue life and synergistically active hydrogen embrittlement mechanisms in low carbon bcc steel (S355J2+N, equivalent to ASTM A656), according to the HELP + HEDE model for HE, is modeled for the first time using UMT and also thoroughly discussed.     

Effects of stress concentration on the mechanical properties of X70 in high-pressure hydrogen-containing gas mixtures

This study aims to investigate the mechanical properties of X70 pipeline steel under the synergistic influence of hydrogen and stress concentration. Slow strain rate tensile tests and low-cycle fatigue tests were performed on the specimens with different stress concentration factors (Kt) in 10 MPa nitrogen/hydrogen mixtures. Results show that the degradation degree of the ductility and fatigue life of X70 steel induced by hydrogen increases with the increase of Kt, and as the hydrogen partial pressure in mixtures increases, the influence of Kt on hydrogen-induced degradation increases as well. In addition, finite element analysis was performed via a modified hydrogen diffusion/plasticity coupled model to study the effect of Kt on hydrogen distribution in the specimens, which can influence the mechanical properties of X70. The maximum hydrogen concentration consistently appears at the notch tip of the specimen and increases with the increase of Kt, which is proposed to be one of the reasons for the severe hydrogen embrittlement of the specimens with large Kt. As the axial tensile force on the specimen increases, the maximum hydrogen concentration at the notch tip begins to be dominated by hydrogen in the normal interstitial lattice sites and, subsequently, in the trapping sites.     

Hydrogen embrittlement characteristics of hot-stamped 22MnB5 steel

Hydrogen embrittlement (HE) characteristics of 22MnB5 steel (U-bent specimen) manufactured using hot-stamping process at various temperatures were experimentally and numerically investigated. Steel resistance to HE was examined through delayed failure tests under static and cyclic loading during hydrogen charging. First, the low cyclic loading caused severe HE, in which a clear difference in the extent of HE was obtained depending on the hot-stamped sample, which directly affected the microstructural characteristics and stress–strain distribution. The hot-stamped samples with large martensite phase showed low resistance to HE compared with those with small martensite phase because of the high concentration of hydrogen trapped in the phase boundaries. Moreover, the dual phase (ferrite and martensite) of the hot-stamped samples reduced their resistance to HE, which is caused by the hydrogen trapped in the laminar-shaped pearlite phase. The resistance to HE was improved by low-temperature heating at 200 °C for 1 h because of the generation of ε-carbides as trap sites as they render the hydrogen non-diffusible. Furthermore, the internal strain in the U-bent sample could accelerate HE because of the high concentration of hydrogen. These results were verified by experimental and numerical analyses. Thus, the hydrogen trapping mechanism was proposed as a valid mechanism for HE in 22MnB5.     

Effect of precipitate coherency on the corrosion-induced hydrogen trapping in 2024 aluminum alloy

Hydrogen trapping is one of the factors leading to hydrogen embrittlement in heat-treatable high-strength aluminum alloys. The effect of coherency of precipitates on the corrosion-induced hydrogen trapping in aluminum alloy 2024 was investigated by performing artificial aging treatments before corrosion exposure. Two aging temperatures were employed, 170 and 210 °C, for aging times spanning the underaged, peak-aged and overaged conditions. Hydrogen uptake was induced by exfoliation corrosion. Hydrogen evolution from trapping sites was followed by thermal desorption spectroscopy. High resolution transmission electron microscopy combined with geometric phase analysis was performed to analyze the coherency of the precipitates. The results indicated that the coherency state between precipitates and the matrix plays an important role in hydrogen trapping. Hydrogen evolving at 300 °C (T2 state) corresponds to hydrogen trapped by the stress fields of coherent GPB zones and S΄΄ (Al₁₀Cu₃Mg₃) phases, which form at aging temperatures, below the corresponding solvus temperature.     

Effect of tensile stress on the hydrogen adsorption of X70 pipeline steel

The effect of stress on the cathodic hydrogen evolution behavior of X70 pipeline steel was investigated by electrochemical tests, tensile tests, and microstructural characterization. The results indicated that the tensile stress enhanced the activity of hydrogen adsorption sites on the metal surface, which was considered as the dominating factor a?ecting generation, adsorption, and permeation of hydrogen atoms. The subsurface hydrogen atom concentrations quantified by Cyclic voltammetry (CV) tests and the data calculated by hydrogen permeation experiments showed a good correspondence. The results indicated that the tensile stress enhanced the adsorption of hydrogen atoms on the surface and an inhibitory effect on the Tafel and Heyrovsky reaction, thereby leading to the increase of the subsurface hydrogen atom concentration, enhance the hydrogen embrittlement susceptibility of the X70 steel material as demonstrated by plasticity loss in the tensile tests.     

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.     

Investigation of hydrogen embrittlement properties of Ni-based alloy 718 fabricated via laser powder bed fusion

The hydrogen embrittlement behavior of heat-treated Alloy 718 fabricated by laser powder bed fusion was fundamentally investigated under electrochemical hydrogen charging. The H transitioned the fracture mode from ductile dimpled to transgranular fracture with a flat fracture surface. Crystallographic analysis showed that H promoted the dislocation slip band, and the resulting concentrated strain and H along the slip planes caused cracking regardless of the distribution of additive manufacturing (AM) microstructural features such as sub-grain boundaries. In addition, thermal desorption spectroscopy and H-permeation tests indicated that the AM microstructural features after heat treatment only slightly influenced the H trapping and diffusion.     

Modelling of hydrogen diffusion in a steel containing micro-porosity. Application to the permeation experiment

Two numerical models based on non-equilibrium and local equilibrium approaches respectively were developed to simulate hydrogen transport in porous metals, taking account of gaseous hydrogen trapping inside the micro-porosities. They were applied to the case of hydrogen permeation in a cast steel at room temperature. Numerical simulations revealed that the two models are equivalent under certain conditions. A parametric analysis was performed to explore the effect of external hydrogen fugacity, hydrogen solubility and porosity fraction on the hydrogen diffusion behavior. A comparison between experimental permeation data and the numerical results showed reasonable agreement considering no input parameter was adjusted.     

Hydrogen embrittlement resistance of GRCop-84

GRCop-84 contains approximately 5.5 wt% Nb. Nb can react with hydrogen and embrittle easily. Previous work had indicated the thermodynamic possibility that Cr₂Nb could react with hydrogen and form niobium hydrides in the presence of high pressure hydrogen. In this study, samples were charged with hydrogen and tested in both high pressure gaseous H₂ and He environments to determine if measurable differences existed which indicate that hydrogen embrittlement occurs in GRCop-84. Tensile, notched tensile, stress rupture and low cycle fatigue properties were surveyed. High pressure H₂ environment stress rupture testing resulted in a lower reduction in area than a high pressure He environment, and the LCF lives at high strain ranges fall below the lower 95% confidence interval for the baseline data, but in general no significant differences were noted either between H₂ and He environment tests or between H charged materials and the baseline, uncharged extruded GRCop-84 data sets. There was also no discernable evidence of the formation of hydrides or changes in fracture morphology indicating hydrogen embrittlement occurred.     

Effect of hydrogen on the ideal shear strength in metals and its implications on plasticity: A first-principles study

Hydrogen embrittlement limits the service life of various metallic components by causing a transition from a ductile to a brittle failure of inherently ductile alloys. In this work, using first-principles calculations, the effect of interstitial hydrogen on the ideal shear strength across various metals (Al, Ni, Fe, Nb, Ti, and Zr) and its implications on plasticity are discussed. The presence of hydrogen led to a volumetric expansion, which in turn had a key role in the observed shear strength response of cubic metals. However, in the case of HCP metals, the chemical contributions also have a significant part in the observed shear strength response. The interstitial hydrogen atom interacts strongly with valence d orbital metals (Ni, Fe, Nb, Ti, and Zr). Based on the Peierls-Nabarro framework, the presence of interstitial hydrogen reduces the Peierls stress across all the metals examined here. Finally, these findings provide insights to comprehensively understand hydrogen embrittlement.     

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.