Permeability,solubility and diffusivity of hydrogen isotopes in stainless steels at high gas pressures

In this report, we provide a framework for describing the permeability, solubility and diffusivity of hydrogen and its isotopes in austenitic stainless steels at temperatures and high gas pressures of engineering interest for hydrogen storage and distribution infrastructure. We demonstrate the importance of using the real gas behavior for modeling permeation and dissolution of hydrogen under these conditions. A simple one-parameter equation of state (the Abel–Noble equation of state) is shown to capture the real gas behavior of hydrogen and its isotopes for pressures less than 200 MPa and temperatures between 223 and 423 K. We use the literature on hydrogen transport in austenitic stainless steels to provide general guidance on and clarification of test procedures, and to provide recommendations for appropriate permeability, diffusivity and solubility relationships for austenitic stainless steels. Hydrogen precharging and concentration measurements for a variety of austenitic stainless steels are described and used to generate more accurate solubility and diffusivity relationships.     

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

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

The role of induced α′-martensite on the hydrogen-assisted fatigue crack growth of austenitic stainless steels

The effects of rolling on the hydrogen-assisted fatigue crack growth characteristics of AISI 301, 304L and 310S stainless steels (SSs) were investigated. In hydrogen, cold rolled specimens with a 20% thickness reduction were found to increase the fatigue crack growth rates (FCGRs) in the 301 and 304L SSs, and to a much lesser extent in the 310S SS. However, enhanced slip was observed for the 310S specimen in hydrogen. Hydrogen-accelerated FCGRs of the 301 and 304L SSs were related with the crack growth through the strain-induced martensite formed in the plastic zone ahead of the crack tip.     

Hydrogen embrittlement and hydrogen diffusion behavior in interstitial nitrogen-alloyed austenitic steel

The susceptibility to hydrogen embrittlement and diffusion behavior of hydrogen were evaluated in interstitial nitrogen-alloyed austenitic steel QN1803 and 304 and 316 L stainless steels. The amount of transformed martensite and the activation energy of hydrogen diffusion were revealed via electron backscattering diffraction and thermal desorption spectroscopy. The austenite stability of QN1803 during the deformation process was higher than that of 304 and 316 L. However, the hydrogen content of QN1803 was high because of the small grain size and low activation energy of hydrogen diffusion. For the stable QN1803 and 316 L austenitic steels, martensite had no evident harmful effect because of its discrete distribution. A planar dislocation slip was observed in QN1803 during deformation. Hydrogen charging enhanced dislocation mobility, leading to severe strain localization. Thus, the severe strain in QN1803 promoted microcracking.     

Effect of strain-induced martensite on hydrogen embrittlement of austenitic stainless steels investigated by combined tension and hydrogen release methods

The hydrogen transport behavior together with hydrogen embrittlement (HE) in hydrogen-charged type 304 and 316 stainless steels during deformation was investigated by combined tension and outgassing experiments. The specimens were thermally hydrogen-charged in 30 MPa hydrogen at 473 K for 48 h. HE of hydrogen-charged type 304 steel decreases with increasing prestrain and almost no HE is observed in hydrogen-charged type 316 steel. Prior strain-induced α′ martensite formed by the prestrain at 208 K has little relation with HE, while dynamic α′ martensite formed during deformation after the prestrain shows obvious HE. The differences in hydrogen diffusivity and solubility between α′ martensite and austenite (γ) induce hydrogen diffusion from dynamic α′ martensite and then its accumulation at the boundary between the α′-rich and γ-rich zones, resulting in crack initiation at the boundary between the α′-rich and γ-rich zones.     

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

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

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

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

Hydrogen diffusivity and tensile-ductility loss of solution-treated austenitic stainless steels with external and internal hydrogen

The effects of external and internal hydrogen on the slow-strain-rate tensile (SSRT) properties at room temperature were studied for ten types of solution-treated austenitic stainless steels containing a small amount of additive elements. The hydrogen diffusivity and solubility of the steels were measured with high-pressure hydrogen gas. The remarkable tensile-ductility loss observed in the SSRT tests was attributed to hydrogen-induced successive crack growth (HISCG) and was successfully quantified according to the nickel-equivalent content (Ni_eq), which represents the stability of the austenitic phase. The relative reduction in area (RRA) of the steels with a larger Ni_eq was influenced by the hydrogen distribution, whereas that of the steels with a smaller Ni_eq was not. This unique trend was interpreted with regard to the hydrogen distribution and fracture morphology (HISCG or microvoid coalescence).     

Analyses of hydrogen distribution around fatigue crack on type 304 stainless steel using secondary ion mass spectrometry

Secondary Ion Mass Spectrometry (SIMS) analyses were carried out on type 304 austenitic stainless steel. On annealed specimen exposed to hydrogen (10 MPa, 358  K), Element Depth Profiles SIMS mode was able to describe quantitatively the hydrogen profile content computed by the Fick’s law. Based on SIMS analyses on the wake of a fatigue crack (propagation in hydrogen gas at 0.6 MPa and RT), it was possible to compute an apparent diffusivity and solubility in the crack tip region. The apparent solubility and diffusivity in the deformed regions were two times and five orders of magnitude higher than the ones on annealed material, respectively. High hydrogen content was found around the crack tip, where the plastic deformation was well developed (pronounced slip activity). The high apparent diffusivity is presumed to result from enhanced hydrogen transport induced by cyclic plastic activity at the crack tip.     

Effect of hydrogen and strain rate on nanoindentation creep of austenitic stainless steel

The effect of hydrogen and strain rate on nanoindentation creep of austenitic stainless steel was investigated by nanoindentation loading and creep tests. The loading segment mainly reflects dislocation nucleation, but creep mainly indicates dislocation movement. The strain rate significantly influences dislocation nucleation, resulting in increased creep displacement with strain rate. The interaction between hydrogen and dislocation is responsible for the increased creep displacement in 310S steel. Hydrogen greatly enhances the displacement burst after small strain rate due to increased dislocation nucleation rate. Hydrogen slightly enhances creep of 304 steel as hydrogen diffuses through strain-induced α′ martensite to accumulate under the indenter before creep and enhances dislocation movement.     

Fatigue crack initiation and propagation in austenitic stainless steels for light water reactors

The determination of fatigue life of components containing defects usually takes into account crack propagation only. In a real situation, a number of cycles are often required to reach fatigue crack initiation and predictive evaluation of fatigue crack initiation phases of real defects in austenitic stainless steel welded joints are presented. Fatigue crack growth rates in wrought and cast austenitic stainless steels and associated welds are also presented. Effects of various mechanical parameters (R ratio and variable amplitude loading) of a PWR environment and of metallurgical factors (δ ferrite content and ageing in cast austenitic stainless steels) are discussed.     

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.     

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 dependence of hydrogen embrittlement on hydrogen transport in selective laser melted 304L stainless steel

The mechanical property and hydrogen transport characteristics of selective laser melting (SLM) 304L stainless steel were investigated by tensile tests and thermal desorption spectroscopy (TDS). The heat treatment affected the hydrogen embrittlement (HE) susceptibility and the treatment at 950 °C showed the larger HE effects. Cellular structures and melt-pool boundaries were dissolved at 850 and 950 °C, respectively. TDS results indicate that the hydrogen diffusivity of the as-received SLM 304L was lower than that of wrought 304L and the hydrogen diffusion activation energy increased with the recrystallisation degree, which was related to the dislocation density. Dislocations, rather than strain-induced martensite, were the main cause of HE owing to the high austenite stability of the samples. The pre-existing dislocations in the SLM 304L sample heat-treated at 950 °C for 4 h affected the hydrogen transport behaviour during sample stretching and led to severe HE.     

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.     

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.     

Effect of plastic deformation at room temperature on hydrogen diffusion of S30408

Understanding the influence of plastic deformation on diffusion is critical for hydrogen embrittlement (HE) study. In this work, thermal desorption spectroscope (TDS), slow strain rate test (SSRT), feritscope, transmission electron microscope (TEM) and TDS model were used to study the relation between plastic deformation and hydrogen diffusion, aiming at unambiguously elucidating the effect of plastic deformation on hydrogen diffusion of austenitic stainless steel, S30408. An effective method was developed to deduce apparent hydrogen diffusion coefficient of austenitic stainless steel in this paper. Results indicate apparent hydrogen diffusion coefficient decreases firstly and then increases with increasing plastic deformation at room temperature. Hydrogen diffusion effected by plastic deformation is a complicated process which is suggested to be divided into two processes controlled by dislocation and strain-induced martensite, respectively, and the transition point is about 20% strain demonstrated by experiments in this case.     

Effect of residual hydrogen content on the tensile properties and crack propagation behavior of a type 316 stainless steel

The tensile properties and crack propagation rate in a type 316 austenitic stainless steel prepared by vacuum induction melting method with different residual hydrogen contents (1.1–11.5 × 10⁻⁶) were systematically investigated in this research work. The room temperature tensile properties were measured under both regular tensile (12 mm/min) and slow tensile (0.01 mm/min) conditions, and the fracture properties of the tensile fractures with both rates were analyzed. It shows that the hydrogen induced plasticity loss of stainless steel strongly depends on the tensile rate. Under regular tensile condition, there is no plastic loss even when the hydrogen content is up to 11.5 × 10⁻⁶ while in the slow tensile condition, the plastic loss can be clearly identified rising with the increasing H contents. The fatigue crack propagation rate was tested at room temperature, and the crack growth rate formula (Paris) of the 316 stainless steels with varied H contents were obtained. The fatigue crack propagation rate test shows that the crack growth rate of the 316 stainless steel with 8.0–11.5 × 10⁻⁶ hydrogen is significantly higher than that of benchmark steel.     

Material performance of age-hardened beryllium–copper alloy,CDA-C17200, in a high-pressure,gaseous hydrogen environment

In order to develop safer and more energy-efficient, hydrogen pre-cooling systems for use in hydrogen refueling stations, it is necessary to identify a high-strength metallic material with greater thermal conductivity and lower susceptibility to hydrogen embrittlement, as compared with ordinary, stable austenitic stainless steels. To accomplish this task, the hydrogen compatibility of a precipitation-hardened, high-strength, copper-based alloy was investigated by slow-strain-rate tensile (SSRT), fatigue-life, fatigue-crack-growth (FCG) and fracture toughness tests in 115-MPa hydrogen gas at room temperature. The hydrogen solubility and diffusivity of the alloy were also determined. The hydrogen solubility of the alloy was two or three orders of magnitude lower than that of austenitic stainless steels. The alloy also demonstrated absolutely no hydrogen-induced degradation of its strength properties, a factor which could contribute to the reduction of costs related to the construction and maintenance of hydrogen refueling stations, owing to the downsizing and improved cooling performance of the pre-cooling systems.     

Highly sensitive secondary ion mass spectrometric analysis of time variation of hydrogen spatial distribution in austenitic stainless steel at room temperature in vacuum

Hydrogen contained in austenitic stainless steel is classified as diffusible or nondiffusible. The hydrogen distribution in austenitic stainless steel changes with time owing to hydrogen diffusion at room temperature, and such changes in hydrogen distribution cause the mechanical properties of the steel to change as well. It is therefore important to analyze the time variation of the hydrogen distribution in austenitic stainless steel at room temperature to elucidate the effects of hydrogen on the steel's mechanical properties. In this study, we used secondary ion mass spectrometry (SIMS), a highly sensitive detection method, to analyze the time variation of the distribution of hydrogen charged into 316L austenitic stainless steel. SIMS depth profiles of hydrogen that were acquired at the three measurement times were analyzed, and the results were compared among the measurement times. ¹H⁻ intensities and distribution of the intensities changed with time due to diffusion of hydrogen in the hydrogen-charged 316L steel sample at room temperature. Moreover, the time variation of the hydrogen concentration distribution of the hydrogen-charged 316L sample was calculated using a one-dimensional model based on Fick's second law. The time variations of the measured hydrogen intensities and of the calculated values are compared.