Overview of hydrogen embrittlement in high-Mn steels

Hydrogen and fuels derived from it will serve as the energy carriers of the future. The associated rapidly growing demand for hydrogen energy-related infrastructure materials has stimulated multiple engineering and scientific studies on the hydrogen embrittlement resistance of various groups of high performance alloys. Among these, high-Mn steels have received special attention owing to their excellent strength – ductility – cost relationship. However, hydrogen-induced delayed fracture has been reported to occur in deep-drawn cup specimens of some of these alloys. Driven by this challenge we present here an overview of the hydrogen embrittlement research carried out on high-Mn steels. The hydrogen embrittlement susceptibility of high-Mn steels is particularly sensitive to their chemical composition since the various alloying elements simultaneously affect the material's stacking fault energy, phase stability, hydrogen uptake behavior, surface oxide scales and interstitial diffusivity, all of which affect the hydrogen embrittlement susceptibility. Here, we discuss the contribution of each of these factors to the hydrogen embrittlement susceptibility of these steels and discuss pathways how certain embrittlement mechanisms can be hampered or even inhibited. Examples of positive effects of hydrogen on the tensile ductility are also introduced.     

A thermodynamic approach for the development of austenitic steels with a high resistance to hydrogen gas embrittlement

The CALPHAD method was employed to assess the austenite stability of model alloys based on the Cr–Mn–Ni–Cu system. Stability was evaluated as the difference in Gibbs free energy between the austenite and ferrite phases. This energy difference represents the chemical driving force for the martensitic transformation and is employed as a design criterion. Six novel alloys featuring a lower driving force compared to the reference material AISI 316L were produced in laboratory. The susceptibility of all alloys to hydrogen gas embrittlement was evaluated by slow strain-rate tensile testing in air and hydrogen gas at 40 MPa and −50 °C. The mechanical properties and ductility response of four of the six alloys exhibited an equivalent performance in air and hydrogen. Thermodynamic calculations were in agreement with the amount of α′-martensite formed during testing. Furthermore, a 4.5 wt.% reduction in the nickel content in comparison to 316L promises a cost benefit for the novel materials.     

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.     

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.     

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.     

Phase transformations and microstructure evolutions during depressurization of hydrogenated Fe–Mn–Si–Cr alloy

Hydride formation and associated phase transformations have been extensively studied in pure Fe. However, the understanding of hydrogenation in Fe-based alloy systems is still lacking. Such an investigation is particularly important in the case of austenitic (face-centered cubic) steels given that hydrogen has been reported to alter the austenite phase stability. In the current work, we investigate the phase transformations associated with depressurization of non-hydrogenated and hydrogenated Fe–Mn–Si–Cr alloy (FMS) (Fe-28.84Mn-7.04Cr-6.14Si, in mass %) using in-situ x-ray diffraction technique. Additionally, we study the change in microstructure using electron backscatter diffraction (EBSD) and electron channeling contrast imagining (ECCI).     

Characterisation of as cast model Mn–Si–Cr–Ni steels for reactor pressure vessel applications

Abstract

Initial results are reported from a study aimed to investigate the role and influence of the elements Cr, Ni, Mn and Si on the radiation stability of reactor pressure vessel steels. Twelve as cast model ferritic steels with basic composition typical of those used in Russian WWER-1000 and Western PWR reactor pressure vessel materials were subjected to Charpy impact, magnetic Barkhausen noise (MBN), Vickers hardness tests and SEM examination. Higher Cr content in model steels was found generally to give increased RMS values independent of Mn and Si contents. The ductile–brittle transition temperatures (DBTT) and hardness values of the model steels were found to be independent of composition. Two steels, with low concentration of Ni and high concentration of Cr or vice versa , showed high transition temperatures (?16 and ?42°C respectively). An additional heat treatment to improve the properties is being considered for these compositions. The correlation between DBTT and MBN results has potential for rapid determination of the effect of composition and irradiation on the steel properties. The next stage of the assessment will investigate the effect of irradiation of the model steels to accumulated neutron fluences of ～10¹⁹ cm^?2.     

Effect of chromium,manganese and yttrium on microstructure and hydrogen storage properties of TiFe-based alloy

In this paper, we report the microstructure and hydrogen storage properties of TiFe-based alloys containing chromium (Cr), manganese (Mn) and yttrium (Y). Four alloy samples with chemical composition of TiFe_0.9Cr_0.1, TiFe_0.9Cr_0.1Y_0.05, TiFe_0.9Mn_0.1 and TiFe_0.9Mn_0.1Y_0.05 were prepared by arc melting, and the effects of alloying elements Cr, Mn and Y on microstructure and hydrogenation kinetics and thermodynamics were investigated in detail. It was found that all the four alloys have the main phase of TiFe intermetallic compound. A small amount of secondary phase can be also detected in the alloy samples. Cr substituted alloys have larger lattice parameters than that of Mn substituted alloys. Y in the alloys is mainly existed in the form of α-Y phase, and it transform into YH₃ during hydrogenation process. Very sloped equilibrium plateau regions are observed in Cr substituted alloys, while the Mn substituted alloys have flat equilibrium plateaus. Y addition has almost no influence on pressure–composition–isotherm (p–c–T) curves of Cr substituted alloy, but slightly decrease the equilibrium plateaus of Mn substituted alloys. Hydrogen absorption and desorption kinetics strongly depend on the equilibrium plateau pressures. As a result, the Cr substituted alloys with lower equilibrium plateau pressure have faster hydrogen absorption and slower desorption kinetics compared with Mn substituted alloys. The Cr substituted alloys have poor powdering resistance compared with Mn substituted alloys during hydrogenation cycles, which can be ascribed to the higher hardness of alloy matrix caused by Cr substitution.     

Hydrogen embrittlement behavior of high strength low carbon medium manganese steel under different heat treatments

Hydrogen embrittlement (HE) behavior was investigated in a low carbon medium Mn steel with three different volume fraction of retained austenite (RA), which was obtained after different heat treatments. The hydrogen permeation test showed a higher permeability for directly water quenched specimen compared to quench-tempered specimens. Melt extraction test showed hydrogen concentration increased with hydrogen charging current density in the order of directly quenched specimen, QLA, quenched with low-temperature annealed specimens and QHA quenched with high-temperature annealed specimens. Slow strain-rate tensile test was employed to examine the HE behavior, the HE indices decreased with the increase of RA irrespective of increased hydrogen concentration. HE susceptibility can be suppressed by raising intercritical annealing temperature because Mn enrichment increases the stability of RA.     

Influence of hydrogen content on the tensile properties and fracture of austenitic stainless steel welds

This study evaluates the effects of internal hydrogen on the tensile properties and fracture behaviours of a tungsten inert gas (TIG) weld and an autogenous electron beam (EB) weld of a 304L steel tube. Tensile specimens were thermally charged with hydrogen gas to achieve three different levels of hydrogen in these materials. Metallographic examination revealed that the TIG weld contained skeletal and lathy ferrite, whilst the EB weld displayed a fine dispersion of skeletal and vermicular ferrite. Average volume fractions of ferrite in these welds were 8% and 1%, respectively. The tensile data showed that hydrogen increased the yield and tensile strength, and caused a significant loss in ductility, particularly for the TIG weld. Fractographic analysis revealed that hydrogen induced a change in the fracture mode of the welds and promoted cracking at or near ferrite–austenite interfaces. The TIG weld was found to exhibit a higher susceptibility to hydrogen embrittlement than that of the EB and base metal.     

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.     

Effects of hydrogen pressure and prior austenite grain size on the hydrogen embrittlement characteristics of a press-hardened martensitic steel

The effects of hydrogen gas pressure and prior austenite grain size (PAGS) on the susceptibility of a 22MnB5 press-hardened martensitic steel (PHS) to hydrogen embrittlement were studied. The hydrogen test apparatus at NIST-Boulder was modified for tensile testing of plate-type and sheet-type specimens in gaseous hydrogen. This modification made it possible to evaluate the slow strain rate tensile (SSRT) properties of the PHS with three different PAGS at various hydrogen pressures (0.21 MPa–5.5 MPa). SSRT testing in gaseous hydrogen resulted in significant reductions of both the tensile strength and ductility, as compared to those measured in air. In addition, the presence of gaseous hydrogen resulted in a transition in fracture morphology from the near-45° slant fracture to a more brittle fracture along a plane perpendicular to the tensile axis. The hydrogen-affected fracture zones were connected to the sheet specimen free surfaces, signifying the effect of external hydrogen. The fracture surfaces of the hydrogen-embrittled specimens contained relatively flat, “cleavage-like” facets, the size of which depended on the PAGS or packet size. The PHS having the largest PAGS represented generally larger secondary cracks and straighter crack paths in addition to a greater area fraction of the “cleavage-like” facets, likely indicative of a lower frequency of crack deflections. Compared to the largest PAGS condition, the two PHS with smaller PAGS were more resistant to the hydrogen-induced fracture especially at relatively low hydrogen gas pressures (<0.52 MPa). In contrast, with an increase in hydrogen pressure, all PHS specimens exhibited significant decreases in tensile strength and ductility. The positive effect of refining martensitic microstructure, at the low hydrogen pressures, is likely associated with improved toughness of the smaller grain-sized specimens.     

Intercritical annealing temperature dependence of hydrogen embrittlement behavior of cold-rolled Al-containing medium-Mn steel

The present investigation attempts to evaluate the influence of intercritical annealing temperature (T_IA) on the hydrogen embrittlement (HE) of a cold-rolled Al-containing medium-Mn steel (Fe-0.2C-4.88Mn-3.11Al-0.62Si) by using electrochemical hydrogen-charging, slow strain rate tensile test and scanning electron microscope. The results show that an excellent combination of strength and ductility (the product of ultimate tensile strength and total elongation) up to ∼53 GPa·% was obtained for the specimen intercritically annealed at an intermediate temperature of 730 °C, whereas the HE index increases significantly with an increase in T_IA up to 850 °C. Being different from the typical dimple ductile fracture for the uncharged specimen, the hydrogen-charged specimen exhibits a mixed brittle interface decohesion and ductile intragranular fracture mode in the crack initiation region and the brittle fracture fraction increases with increasing T_IA. Both the stability and amount of austenite play a critical role in governing the HE behavior of TRIP-assisted medium-Mn steel. Thus, it is suggested that suitable T_IA should be explored to guarantee the safety service of automotive parts made of this type of steel in addition to acquiring excellent mechanical properties.     

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.     

合金元素对20CrMnTi凝固组织影响的数值模拟

利用CA（元胞自动机）和FE（有限元）耦合模型，模拟齿轮钢中Si、 Mn、 Cr、 Ti 4种元素对连铸坯凝固组织的影响。模拟所得温度场和凝固组织跟实际数据基本吻合。在国标规定的成分范围内， Si含量增加可降低钢种液相线温度，增加形核动力，从而增加晶粒数目，细化晶粒； Ti含量可增加钢中异相形核数，从而增加晶粒数目，细化晶粒； Si， Ti含量增加还可降低枝晶尖端生长速度，从而减小柱状晶区域，扩大等轴晶区域； Mn， Cr含量变化对于钢种的液相线温度以及枝晶尖端生长速度影响不大，因此对于晶粒数目，等轴晶面积影响较小。     

Study on fracture strain of Cr–Mo steel in high pressure hydrogen

Cr–Mo steel is often used as the material of the hydrogen storage vessel, but its ductility can be deteriorated by high pressure hydrogen, which makes it possible that the local area of strain concentration on the hydrogen storage vessel made of Cr–Mo steel may fail due to excessive plastic deformation. The limit criterion of local strain established according to the study of the fracture strain is the basis for local failure assessment of the vessel. However, the correlation between the fracture strain and the stress state of Cr–Mo steel in high pressure hydrogen is still unclear, so the limit criterion of local strain for hydrogen storage vessel made of Cr–Mo steel has not been established. In this paper, the slow strain rate tensile test (SSRT) of notched specimens with different notch sizes was carried out in air, 45 MPa hydrogen and 100 MPa hydrogen, respectively. Based on the test results, the whole process from tensile to fracture of the specimens was simulated by finite element method. The distribution of stress triaxiality and plastic strain during the tensile process was analyzed, and the correlations between the stress triaxiality and the fracture strain in different environments were obtained. Finally, the limit criterion of local strain for local failure assessment of 4130X hydrogen storage vessel was established.     

Weld metal microstructure analysis of 9–12% Cr steels

High-strength 9–12% Cr steels have been developed to meet the demand by power generation companies to increase efficiency by operating at higher temperatures. The 9–12% Cr steels used for high-temperature components in power plants are generally required to possess good mechanical properties, corrosion resistance, creep strength and fabricability. Although such steels normally have a fully martensitic microstructure, they are also susceptible to the formation of delta ferrite, mainly during the welding process. Delta ferrite has several detrimental effects on properties such as creep, ductility and toughness. Thus, it is important to avoid its formation.This paper analyses the microstructure in the weld metal of high-strength 9–12% Cr steels for several samples with variations of key alloying elements. The results indicate that the most effective way to avoid delta ferrite in the weld metal to obtain a fully martensitic microstructure is to reduce the ferrite former elements as low as possible. The partial substitution of Mo for W favours austenite stability and would be expected to improve the mechanical properties at high temperature.     

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.     

Hydrogen embrittlement of Cr-Mn-N-austenitic stainless steels

Cr-Mn-N austenitic steels show a unique combination of properties, i.e. high strength, high ductility, non magnetic and good corrosion resistance at costs being much lower compared to Cr-Ni austenitic steels. Hydrogen environment embrittlement (HEE) was investigated by slow displacement tensile testing in hydrogen atmosphere at 10 MPa and −50 °C. The fracture appearance of stable Cr-Mn-N austenitic steels with lower Mn contents (12Mn-0.7N) was transgranular whereas higher Mn contents (18Mn-0.7N) resulted in twin boundary fracture. This change in fracture morphology was related to a modest change in macroscopic ductility. Such fracture behaviour is similar to what is known from metastable Cr-Ni austenitic steels, therefore, Mn and/or N cannot be used to replace Ni in stable austenitic high HEE resistant steels.