Relationship between hydrogen embrittlement and Md30 temperature: Prediction of low-nickel austenitic stainless steel's resistance

Hydrogen embrittlement (HE) of several low-nickel austenitic stainless steels (AISI 300 series) was studied with special attention to the impact of strain induced α′-martensite. The susceptibility of the steels to HE is judged with respect to the relative reduction of area (RRA): The HE susceptibility is lower for larger RRA-values. Strain-induced martensite formation was evaluated within in the framework of the Olson-Cohen model, revealing a linear relationship between RRA and the probability β of martensite nucleus formation in the steels. In order to widen the scope of data evaluation to literature data, the consideration of a parameter alternative to β is required. It is demonstrated that among other parameters the M_d30 temperature (Nohara), which assesses the stability against martensitic transformation, can serve as an indicator to predict HE of AISI 300 series steels. Regarding the M_d30 temperature (Nohara), a trend-line with respect to the RRA-values is found. Thereby, the RRA-values of low-nickel austenitic stainless steels group into three distinct regimes; (1) for M_d30 > −80 °C, where RRA-values decrease with increasing M_d30 temperature, (2) at M_d30 ≈ −80 °C, where RRA-values show a large variation (‘threshold band’), and (3) for M_d30 < −80 °C, showing constant RRA-values of nearly 100%. Some RRA data points that deviate from the trend line can be explained by the special microstructure of the investigated samples.     

Effect of ultrafine grain refinement on hydrogen embrittlement of metastable austenitic stainless steel

Micro-tensile tests were performed on high-pressure-torsion-processed specimens of type 304 steel with grain sizes in the range of 0.1–0.5 μm to clarify the effect of ultrafine grain refinement on the hydrogen embrittlement (HE) of metastable austenitic steel. The ultrafine-grained (UFG) specimens with average grain sizes < ～0.4 μm exhibited a limited uniform elongation followed by a steady-stress regime in the stress–strain curves, which was attributed to a martensitic transformation. A high yield stress and a moderate elongation to failure were attained for the UFG specimens with an average grain size of ～0.5 μm in the uncharged state. Hall–Petch relationships well hold between the yield stress and the average grain size for each uncharged and hydrogen-charged specimen. Hydrogen charging increased the friction stress by 40% but did not change the Hall–Petch coefficient. Hydrogen-induced ductility loss was mitigated by ultrafine grain refinement. Ductility loss due to hydrogen charging manifested in the local deformation after a martensitic transformation. This indicates that hydrogen does not significantly affect the martensitic transformation, but shortens the subsequent local deformation process.     

Effect of pre-strain on hydrogen embrittlement of metastable austenitic stainless steel under different hydrogen conditions

The effects of internal hydrogen and environmental hydrogen on the hydrogen embrittlement of 304 austenitic stainless steels (ASSs) with varying degrees of pre-strain were investigated by a tensile test under cathodic hydrogen-charged, gaseous hydrogen and hydrogen-charged and gaseous hydrogen combined conditions. The internal hydrogen embrittlement of the 304 ASSs increased with increasing pre-strain, while the hydrogen embrittlement caused by the environment hydrogen increased and then decreased with increasing pre-strain. The hydrogen embrittlement mechanisms caused by the internal hydrogen or environmental hydrogen were different. The cracks caused by internal hydrogen or environmental hydrogen are mainly initiated in grain interior or at grain boundary, respectively. Under the coupling condition of internal hydrogen and environmental hydrogen, the hydrogen embrittlement of 304 ASSs was the strongest and increased with increasing pre-strain. Environmental hydrogen was dominant for low levels of pre-deformed specimens. Internal hydrogen was dominant for high levels of pre-deformed specimen.     

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.     

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.     

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.     

On the physical differences between tensile testing of type 304 and 316 austenitic stainless steels with internal hydrogen and in external hydrogen

Seventeen metastable austenitic stainless steels (type 304 and 316 alloys) were tested in tension both with internal hydrogen and in external hydrogen. Hydrogen-assisted fracture in both environments is a competition between hydrogen-affected ductile overload and hydrogen-assisted crack propagation. In general, hydrogen localizes the fracture process, which results in crack propagation of particularly susceptible materials at an apparent engineering stress that is less than the tensile strength of the material. Hydrogen-assisted crack propagation in this class of alloys becomes more prevalent at lower nickel content and lower temperature. In addition, for the tests in this study, external hydrogen reduces tensile ductility more than internal hydrogen. External hydrogen promotes crack initiation and propagation at the surface, while with internal hydrogen surface cracking is largely absent, thus preempting hydrogen-assisted crack propagation from the surface. This is not a general result, however, because the reduction of ductility with internal and external hydrogen depends on the specifics of the testing conditions that are compared (e.g., hydrogen gas pressure); in addition, internal hydrogen can promote the formation of internal cracks, which can propagate similar to surface cracks.     

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.     

Hydrogen compatibility of austenitic stainless steel tubing and orbital tube welds

Refueling infrastructure for use in gaseous hydrogen powered vehicles requires extensive manifolding for delivering the hydrogen from the stationary fuel storage at the refueling station to the vehicle as well as from the mobile storage on the vehicle to the fuel cell or combustion engine. Manifolds for gas handling often use welded construction (as opposed to compression fittings) to minimize gas leaks. Therefore, it is important to understand the effects of hydrogen on tubing and tubing welds. This paper provides a brief overview of on-going studies on the effects of hydrogen precharging on the tensile properties of austenitic stainless tubing and orbital tube welds.     

Anisotropy of cold-worked Type-304 austenitic stainless steel: Focus on the hydrogen diffusivity

Anisotropic nature of effective hydrogen diffusivity was investigated on a cold-worked (CW) Type-304 stainless steel. The material was characterized by using disk-shaped specimens sampled from two directions of steel plates with various rolling ratio. The thickness direction of the disks was parallel to the rolling direction for SL specimens and perpendicular for LT ones. Electromagnetic induction (EMI) and electron backscatter diffraction (EBSD) clarified the content and distribution of strain-induced martensite (SIM). The effective diffusivities and solubilities were jointly determined by desorption method and thermal desorption analysis (TDA) in H-charged specimens with high-pressure gas. The increase of SIM with CW ratio and the differences of SIM distribution observed between LT and SL specimens could justify the anisotropic effective diffusivities. Finite element method (FEM) was used to simulate permeation tests based on multiple EBSD maps. Simulations supported the experimental findings: at the CW ratio of 60%, the CW process increased the diffusivity by twenty and the diffusivity was five time greater in the SL specimen than the LT one. The inhomogeneous SIM distribution justified the modifications of diffusion properties by CW in both specimens.     

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.     

Gaseous hydrogen embrittlement of a Ni-free austenitic stainless steel containing 1 mass% nitrogen: Effects of nitrogen-enhanced dislocation planarity

We investigated the effect of hydrogen on degradation of tensile properties in a Fe–25Cr–1N austenitic stainless steel. Hydrogen was introduced by exposure to a hydrogen gas atmosphere at 100 MPa and 270 °C. Hydrogen charging caused significant ductility loss associated with nitrogen-enhanced dislocation planarity. Specifically, even without hydrogen, the nitrogen-enhanced planar dislocation glide induced micro-stress concentration, which assisted the occurrence of hydrogen-induced intergranular and quasi-cleavage fractures. The hydrogen-assisted intergranular cracking occurred along boundaries of grains where primary slip was predominantly activated. On the other hand, the hydrogen-assisted quasi-cleavage fracture took place when multiple slip systems were activated. The hydrogen-related cracks emerged, but their growth was arrested via crack blunting associated with a significant plastic deformation. Instead, new cracks formed near the crack tips. Therefore, hydrogen-assisted crack propagation occurred through repetition of crack blunting, initiation, and coalescence.     

Hydrogen environment embrittlement of orbital welded austenitic stainless steels at −50 °C

Different stainless steels were TIG orbital welded resulting in δ-ferrite contents up to 5% in the weld seam. Tensile specimens tested in He atmosphere did fracture at the fusion line/heat affected zone (FL/HAZ), which is the typical failure mode for welded structures. In contrast, all specimens (except the one made of 1.4301) tested in H₂ did not fracture in the FL/HAZ but in the base material. These results clearly show that for the tests performed here δ-ferrite contents up to 5% did not enhance susceptibility to HEE compared to the base material.     

Hydrogen environment embrittlement of stable austenitic steels

Seven stable austenitic steels (stable with respect to γ → α′ transformation at room temperature) of different alloy compositions (18Cr–12.5Ni, 18Cr–35Ni, 18Cr–8Ni–6Mn–0.25N, 0.6C–23Mn, 1.3C–12Mn, 1C–31Mn–9Al, 18Cr–19Mn–0.8N) were tensile tested in high-pressure hydrogen atmosphere to assess the role of austenite stability on hydrogen environment embrittlement (HEE). The influence of hydrogen on tensile ductility was small in steels that are believed to have a high initial portion of dislocation cross slip (18Cr–12.5Ni, 18Cr–35Ni, 18Cr–8Ni–6Mn–0.25N), while the effects of hydrogen were significantly greater in steels with other primary deformation modes (planar slip in 18Cr–19Mn–0.8N and 1C–31Mn–9Al or mechanical twinning in 0.6C–23Mn and 1.3C–12Mn) despite comparable austenite stability at the given test conditions. It appears that initial deformation mode is one important parameter controlling susceptibility to HEE and that martensitic transformation is not a sufficient explanation for HEE of austenitic steels.     

Acoustic emission study of deformation behaviour of sensitised 304 stainless steel

Abstract

A systematic study has been undertaken to correlate the changes in acoustic emissions during tensile deformation of sensitised AISI type 304 stainless steel. Samples of a typical 304 stainless steel were sensitised at 700°C for 4, 14 and 24 h after being austenised at 1050°C for 30 min. AE signals were recorded during tensile test by using two sensors with 125 kHz resonant frequency. The results showed significant change in generation of AE during tensile deformation of sensitised AISI 304 stainless steel in compare to solution annealed material. This type of behaviour could be attributed to the microstructural changes in the sensitised specimens especially formation of continuous Cr₂₃C₆ carbides on grain boundaries which lead to increase in shearing by dislocations.     

Dependence of hydrogen embrittlement on hydrogen in the surface layer in type 304 stainless steel

Hydrogen embrittlement (HE) together with the hydrogen transport behavior in hydrogen-charged type 304 stainless steel was investigated by combined tension and outgassing experiments. The hydrogen release rate and HE of hydrogen-charged 304 specimens increase with the hydrogen pressure for hydrogen-charging (or hydrogen content) and almost no HE is observed below the hydrogen content of 8.5 mass ppm. Baking at 433 K for 48 h can eliminate HE of the hydrogen-charged 304 specimen, while removing the surface layer will restore HE, which indicates that hydrogen in the surface layer plays the primary role in HE. Scanning electron microscopy (SEM) and scanning tunnel microscopy (STM) observations show that particles attributed to the strain-induced α′ martensite formation break away from the matrix and the small holes form during deformation on the specimen surface. With increasing strain, the connection among small holes along {111} slip planes of austenite will cause crack initiation on the surface, and then the hydrogen induced crack propagates from the surface to interior.     

Effects of hydrogen on tensile properties and fracture surface morphologies of Type 316L stainless steel

The effects of hydrogen on the tensile properties and fracture surface morphologies of Type 316L stainless steel were investigated using virgin and prestrained specimens. Hydrogen gas exposure at 10 MPa and 250 °C for 192 h resulted in its uniform distribution in the specimens. Such internal hydrogen degraded the tensile ductility of the specimens. Cup–cone fracture occurred in the non-, Ar-, and H-exposed specimens. The fracture surfaces were covered with large and small dimples. The H-exposed specimens exhibited larger small-dimple areas than the non- and Ar-exposed ones. The diameter of the large dimples decreased with increasing small-dimple area. Three-dimensional analysis of the dimples showed that the small-dimple regions were void sheets produced by local shear strain. Hydrogen accelerated nucleation of voids and formation of the void sheets by enhancing localization of shear deformation, thereby reducing the average size of the dimples.     

Effect of grain size on hydrogen embrittlement in stable austenitic high-Mn TWIP and high-N stainless steels

Two stable austenitic steels, 20Cr-11Ni-5Mn-0.3N (wt%) stainless steel (STS) and 18Mn-1.5Al-0.6C (wt%) twinning-induced plasticity steel (TWIP), were investigated to understand the effect of grain size on hydrogen embrittlement (HE). Grain refinement promoted HE in the STS but suppressed HE in the TWIP. These opposite effects occurred because the steel composition affected deformation mechanism. Cr-N pair enhanced short-range ordering (SRO) in STS, which promoted planar slip and delayed mechanical twinning. In contrast, TWIP exhibited mechanical twinning which was more active in coarser grains. Final dislocation density after tensile deformation was increased by grain refinement in STS, but was decreased in TWIP. The damaging effects of hydrogen on strain energy at interfaces and on interfacial bonding strength were controlled by dislocation density; therefore, increase in dislocation density led to increase in susceptibility to HE.     

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.     

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.