FE simulation of hydrogen diffusion in duplex stainless steel

ABAQUS FE simulations of hydrogen diffusion in duplex stainless steel have been performed. Three models with different ferrite–austenite configurations have been applied and the hydrogen diffusion and the hydrogen coefficient have been evaluated as a function of austenite phase size and shape and the calculated diffusion coefficients compared to literature. Hydrogen concentration due to stress and plastic strain close to an embedded flaw has also been evaluated. An important observation is that the simulations show that when the austenite phases are saturated with hydrogen there is no large difference in the overall diffusion rate between the small and large phased models, i.e. no influence of tortuosity is observed. The work clearly demonstrates that both microstructure and flaws will influence the hydrogen diffusion and the hydrogen concentration and hence, must be taken into account when evaluating the susceptibility of hydrogen stress cracking in duplex stainless steels.     

Hydrogen absorption of different welded duplex steels

In this study, hydrogen absorption and storage was investigated for various high-alloyed ferritic–austenitic duplex stainless steels. On account of the specific transformation and solidification behaviour, respectively, of duplex stainless steels as compared to single-phase ferritic and austenitic steels, special conditions have to be considered concerning hydrogen absorption which may ultimately lead to microstructure-dependent hydrogen-assisted weld metal cracking. Hydrogen absorption during welding may occur via the shielding gas, moisture from the surroundings or via the welding filler material. As a contribution to the interpretation and prediction of hydrogen-induced cracking in welded duplex stainless steels, the actual hydrogen absorption via the arc as well as the weld metal hydrogen diffusion was investigated in a duplex stainless steel DSS (1.4462) and in a lean-duplex stainless steel LDS (1.4162). Isothermal heat treatment using carrier gas hot extraction enabled quantification of the amounts of hydrogen trapped in the respective microstructures. The total hydrogen concentrations were found to be nearly identical. Trapped hydrogen was however observed to be dependent on the material and on the microstructure condition. The influence of hydrogen on the mechanical properties of the weld metal was characterized with the help of tensile tests. In addition, hydrogen embrittlement was detected in scanning electron microscopic analyses.     

Hydrogen embrittlement of super duplex stainless steel in acid solution

Super duplex stainless steel (SDSS) is a good choice of material when resistance to harsh environments is needed. Despite the material’s excellent corrosion resistance and high strength, a number of in-service failures have been recorded. The root cause of these failures was environmentally induced cracking initiated at manufacturing and in-service metallurgical defects. In this study the hydrogen embrittlement of pre-strained super duplex stainless steel specimens was investigated after 48 h cathodic charging in 0.1 M H₂SO₄. The metallurgical changes that resulted from four levels of cold work (4, 8, 12, and 16% plastic strain) were considered and their effect on the embrittlement of the SDSS alloy was investigated. After hydrogen charging, the specimens were pulled immediately to failure and the mechanical properties evaluated. The obtaining fracture morphology was investigated using low and high magnification microscopy. Experimental results indicated that charging the super duplex stainless steel alloy with hydrogen caused varying degrees of embrittlement depending on cold work level. Increasing cold work resulted in a reduction of the elongation to failure. Microscopic investigation confirmed the significant effect of cold work on the hydrogen embrittlement susceptibility of the super duplex stainless steel alloy investigated.     

Hydrogen embrittlement of super duplex stainless steel – Towards understanding the effects of microstructure and strain

The effects of austenite spacing, hydrogen charging, and applied tensile strain on the local Volta potential evolution and micro-deformation behaviour of grade 2507 (UNS S32750) super duplex stainless steel were studied. A novel in-situ methodological approach using Digital Image Correlation (DIC) and Scanning Kelvin Probe Force Microscopy (SKPFM) was employed. The microstructure with small austenite spacing showed load partitioning of tensile micro-strains to the austenite during elastic loading, with the ferrite then taking up most tensile strain at large plastic deformation. The opposite trend was seen when the microstructure was pre-charged with hydrogen, with more intense strain localisation formed due to local hydrogen hardening. The hydrogen-charged microstructure with large austenite spacing showed a contrasting micro-mechanical response, resulting in heterogeneous strain localisation with high strain intensities in both phases in the elastic regime. The austenite was hydrogen-hardened, whereas the ferrite became more strain-hardened. SKPFM measured Volta potentials revealed the development of local cathodic sites in the ferrite associated with hydrogen damage (blister), with anodic sites related to trapped hydrogen and/or micro voids in the microstructure with small austenite spacing. Discrete cathodic sites with large Volta potential variations across the ferrite were seen in the coarse-grained microstructure, indicating enhanced susceptibility to micro-galvanic activity. Microstructures with large austenite spacing were more susceptible to hydrogen embrittlement, related to the development of tensile strains in the ferrite.     

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.     

Novel approach to image hydrogen distribution and related phase transformation in duplex stainless steels at the sub-micron scale

The effect of electrochemical charging of hydrogen on the structure of a lean duplex stainless steel LDX 2101^® (EN 1.4162, UNS S32101) was examined by both Time-of-Flight secondary ion mass spectrometry and electron back-scatter diffraction. The goal is to correlate hydrogen concentration and induced structural changes. Chemical and structural characterizations were done for the same region at the sample's surface with sub-micron spatial resolution. Regions of interest were varying in size between 50 × 50 μm and 100 × 100 μm. The results show a phase transformation of austenite to mainly a defect-rich BCC and scarcely a HCP phase. The phase transformation occurred in deuterium rich regions in the austenite.     

Role of microstructure on electrochemical hydrogen permeation properties in advanced high strength steels

The hydrogen permeation process in steels is closely associated with the microstructure of steels that greatly affect hydrogen trapping and hydrogen diffusion behaviors. In this study, the electrochemical hydrogen permeation experiment using a modified Devanathan-Stachurski (D-S) cells was employed to evaluate the hydrogen permeation properties in advanced high strength steels with four types of microstructures (from single phase, dual phase to complex phase). Results showed that both phase interfaces and retained austenite (RA) could act as the trapping sites for hydrogen and consequently reduced the hydrogen diffusion coefficient in steels. Furthermore, it was suggested that the role of RA on hydrogen trapping behaviors depended on its morphology. Finally, the lattice diffusion coefficient (D_L) in each steel was determined and the correlations between the microstructure in steels and hydrogen evolution reaction (HER) kinetics were also investigated.     

Influence of macro segregation on hydrogen environment embrittlement of SUS 316L stainless steel

The objective of this work is to identify microstructural variables that lead to the large scatter of the relative resistance of 316 grade stainless steels to hydrogen environment embrittlement. In slow displacement rate tensile testing, two almost identical (by nominal chemical composition) heats of SUS 316L austenitic stainless steel showed significantly different susceptibilities to HEE cracking. Upon straining, drawn bar showed a string-like duplex microstructure consisting of α′-martensite and γ-austenite, whereas rolled plate exhibited a highly regular layered α′-γ structure caused by measured gradients in local Ni content (9.5–13 wt%). Both martensite and austenite are intrinsically susceptible to HEE. However, due to Ni macro segregation and microstructural heterogeneity, fast H-diffusion in martensite layers supported a 10 times faster H-enhanced crack growth rate and thus reduced tensile reduction in area. Nickel segregation is thus a primary cause of the high degree of variability in H₂ cracking resistance for different product forms of 316 stainless steel.     

Nanomechanical characterization of the hydrogen effect on pulsed plasma nitrided super duplex stainless steel

Pulsed plasma nitriding (PPN) is used to nitride super duplex stainless steel (SDSS). Different analytical techniques are used to characterize the nitride layer on both ferrite and austenite phases existing in the SDSS. In-situ electrochemical nanoindentation is used to examine the effect of electrochemically charged hydrogen on the mechanical properties of both the SDSS substrate metal and the nitride layer. By applying this method, we were able to trace the changes in the mechanical properties due to the absorption of atomic hydrogen. The results clearly show that the hydrogen charging of the nitriding layer can soften the layer and reduce the hardness within both the compound and diffusion layers. The effect is completely reversible, and removal of the hydrogen causes the hardness to recover to its original value. The findings show that nitriding is a promising way to control the hydrogen embrittlement of SDSS.     

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.     

Effect of specific microstructures on hydrogen embrittlement susceptibility of a modified AISI 4130 steel

The focus of this study is to analyze hydrogen embrittlement susceptibility of a modified AISI 4130 steel by means of incremental step loading tests. Three different microstructures with a hardness of 40 HRC were analyzed: martensite with large and small prior austenite grains and dual-phase (martensite/ferrite). According to the results, the dual-phase microstructure presented the lowest hydrogen embrittlement susceptibility and martensite with large prior austenite grains, the highest. This behavior was attributed to the lower fraction of high-angle boundaries presented by the martensite with large prior austenite grains, which led to a higher diffusible hydrogen content. Moreover, the ferrite local deformation in the dual-phase microstructure enhanced its hydrogen embrittlement resistance by lowering the stress concentration. A synergic effect of decohesion and localized plasticity was identified on the hydrogen induced fracture of the tested microstructures leading to an intergranular + quasi-cleavage fracture in the martensite and quasi-cleavage in the dual-phase microstructure.     

Hydrogen trapping sites and hydrogen-induced cracking in high strength quenching & partitioning (Q&P) treated steel

The effect of hydrogen on the tensile properties and fracture characteristics was investigated in the quenching & partitioning (Q&P) treated high strength steel with a considerable amount of retained austenite. Slow strain-rate tensile (SSRT) tests and fractographic analysis on cathodically charged specimens were performed to evaluate the hydrogen embrittlement (HE) susceptibility. Total elongation was dramatically deteriorated from 19.5% to 2.5% by introducing 1.5 ppmw hydrogen. Meanwhile, hydrogen caused a transition from ductile microvoid coalescence to a mixed morphology of dimples, “quasi-cleavage” regions and intergranular facets. Moreover, hydrogen trapping sites were directly observed by means of three-dimensional atom probe tomography (3DAPT). Results have shown that hydrogen in austenite (33.9 ppmw) is 3 times more soluble than that in martensite (10.7 ppmw). By using DENT specimen, hydrogen-induced cracking (HIC) cracks were found to initiate at martensite/austenite interfaces and then propagate through retained austenite and martensite. No crack was observed to be initiating from ferrite phase.     

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.     

Numerical interpretation of thermal desorption spectra of hydrogen from high-carbon ferrite-austenite dual-phase steel

The peak in the thermal desorption spectra of hydrogen from a high-carbon ferrite-austenite dual-phase steel shifts to the high-temperature side as the amount of charged hydrogen increases. However, the hydrogen-trapping state and the peak formation process are unclear. We interpreted the spectra by reproducing them using the previously reported model. Introducing a diffusion barrier from the ferrite phase to the austenite phase and excluding hydrogen entering the austenite phase shows that the peak is attributed to the carbide trap site when the amount of charged hydrogen is comparatively small and hydrogen trapped by the interface trap site increasingly influences the peak as the amount of charged hydrogen increases. We also found that the thickness dependence of the peak for the interface trap site could be attributed to a different reason than the conventional diffusion-determining process.     

Texture dependence of hydrogen diffusion in nanocrystalline nickel by atomistic simulations

Atomistic simulations were performed to highlight the importance of the texture on the diffusion of hydrogen atoms in nanocrystalline nickel. Significant anisotropic diffusion is observed in longitudinal and through thickness directions. Our results show that the diffusion coefficient of hydrogen atoms through thickness in [001] textured nickel is larger than those values obtained for [011] and [111]. The diffusivity along longitudinal and transverse directions in [111] textured samples is found to be higher than that along thickness direction. Additionally, it is determined that the presence of hydrogen atoms changes the vacancy formation of the substrate and the vacancy defects are responsible for the anisotropy of hydrogen diffusion. These findings improve our understanding of hydrogen diffusivity at the atomistic level for hydrogen storage in the materials.     

Insight into hydrogen effect on a duplex medium-Mn steel revealed by in-situ nanoindentation test

Medium-Mn steel is the newly developed steel acting as a promising candidate of the 3rd-generation advanced high strength steels. In the present study, the effect of hydrogen on the mechanical behavior and martensite transformation process in a duplex medium-Mn steel is investigated by in-situ nanoindentation test. The mechanical response of individual phase: ferrite, and retained austenite by introducing hydrogen is studied. With the presence of hydrogen, the reduction of activation energy for dislocation nucleation was verified by using a stress-biased, statistical thermal activation model. The stacking fault energy (SFE) was reduced, which was revealed by electron channeling contrast (ECC) technique. Magnetic force microscopy (MFM) revealed a suppression of retained austenite to α′-martensite transformation with the presence of hydrogen, which is related to hydrogen induced SFE reduction and enhanced slip planarity.     

Improvement of hydrogen embrittlement resistance by intense pulsed ion beams for a martensitic steel

Intense pulsed ion beams (IPIB) have been applied on the surface of a lath martensitic steel with aim to improve its hydrogen embrittlement resistance and reveal the key cmaterial factors leading to failure. Hydrogen charging slow strain rate tensile tests show that IPIB can increase the ultimate fracture strength. The main fracture mode changes from intergranular fracture (untreated) to quasi-cleavage fracture (treated). Atomic probe tomography reveals that C atoms segregate at prior austenite grain boundaries for the untreated steel. After IPIB treatment, the C content at the PAGBs is reduced and high-carbon martensite forms in the treated layer, which improves the HE resistance. This study suggests that C segregation at grain boundaries is one of the main factors to cause the high HE susceptibility for the investigated lath martensitic steel and C segregation should be avoided when developing high strength steels with high HE resistance.     

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.     

A coupled elastoplastic-transient hydrogen diffusion analysis to simulate the onset of necking in tension by using the finite element method

Hydrogen-enhanced localized plasticity (HELP) is an acceptable mechanism for hydrogen embrittlement which is based on the experimental observations and the theoretical computations. The underlying principle in the HELP theory is that the presence of hydrogen causes the localization of the slip bands which results in the decrease of the fracture strength. In a sample under plane-strain tensile stress, plastic instability can lead to either the concentration of plastic flow in a narrow neck or bifurcation from homogeneous deformation into a mode of an exclusively localized narrow band of intense shear. Recently, it has been demonstrated that the presence of hydrogen can indeed induce shear banding bifurcation at macroscopic strains. By using a steady-state equilibrium equation for hydrogen diffusion analysis, the effect of hydrogen on the bifurcation of a homogeneous deformation in a plane-strain tension specimen into a necking or a shear localization mode of deformation has already been studied. In the present research, using a transient hydrogen diffusion analysis and introducing a new constitutive equation accompanied by considering the reduction in the local flow stress upon hydrogen dissolution into the lattice, the effect of hydrogen on shear localization is investigated. In addition, progress has been made in that, the changes in the distribution of the total and trapping hydrogen concentrations through the loading time and particularly during the development of the necking event have been determined.     

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.