Influence of surface martensite layer on hydrogen embrittlement of Fe-Mn-C-Mo steels in wet H2S environment

This study investigated the effect of thermally induced surface martensite layer on hydrogen embrittlement of Fe-16Mn-0.4C-2Mo (wt.%) (16Mn) and Fe-25Mn-0.4C-2Mo (wt.%) (25Mn) steels through slow strain rate stress corrosion cracking testing and proof ring testing in wet H₂S environment. The 16Mn steel had a surface layer of less than 150 μm in depth containing ε-martensite, α′-martensite and austenitic twins. The martensite layer is found to reduce the hydrogen embrittlement resistance of the steel. In comparison, the 25Mn steel developed a full α′-martensite surface layer, which exhibited practically nil effect on the hydrogen embrittlement resistance of the steel. The ε-martensite provides much larger interface areas with the mechanical twins of the austenite in the 16Mn steel than the α′-martensite/austenite interfaces in the 25Mn steel. These interfaces are hydrogen trapping sites and are prone to initiate surface cracks, as observed in the scanning electron microscope. The formation of the cracks is attributed to hydrogen concentration at the ε-martensite and austenitic twin interfaces, which accelerates material fracture.     

The influence of intergranular and interphase boundaries and δ-ferrite volume fraction on hydrogen embrittlement of high-nitrogen steel

We study the effect of grain size of austenitic and ferritic phases and volume fraction of δ-ferrite, which were obtained in different solution-treatment regimes (at 1050, 1100, 1150 and 1200 °C), on hydrogen embrittlement of high-nitrogen steel (HNS). The amount of dissolved hydrogen is similar for the specimens with different densities of interphase (γ-austenite/δ-ferrite) and intergranular (γ-austenite/γ-austenite, δ-ferrite/δ-ferrite) boundaries. Despite, the susceptibility of the specimens to hydrogen embrittlement, depth of the hydrogen-assisted surface layers, hydrogen transport during tensile tests and mechanisms of the hydrogen-induced brittle fracture all depend on grain size and ferrite content. The highest hydrogen embrittlement index I_H = 32%, the widest hydrogen-affected layer and a pronounced solid-solution hardening by hydrogen atoms is typical of the specimens with the lowest fraction of the boundaries. Even though fast hydrogen transport via coarse ferritic grains provides longer diffusion paths during H-changing, the width of the H-affected surface layer in the dual-phase structure of the HNS specimens is mainly determined by the hydrogen diffusivity in austenite. In tension, hydrogen transport with dislocations increases with the decrease in density of boundaries due to the longer dislocation free path, but stress-assisted diffusion transport does not depend on grain size and ferrite fraction. The contribution from intergranular fracture increases with an increase in the density of intergranular and interphase boundaries.     

Characteristics of hydrogen-related fatigue fracture in 2Mn-0.1C martensitic steel

This study investigated the hydrogen-related fatigue fracture in 2Mn-0.1C steel having a lath martensite microstructure. The presence of hydrogen significantly reduced the fatigue life. The transgranular surface was a main component in each stress range of the uncharged specimen, while the intergranular surface was frequently observed in the hydrogen-charged specimen. The crystallographic orientation analysis by electron backscattering diffraction revealed that the cracks mainly propagated along {011} planes regardless of the presence of hydrogen. Compared with the uncharged specimen, however, plastic deformation was localized near the fatigue crack in the hydrogen-charged specimen. According to the reconstructed fracture process by fracture surface topography analysis, the hydrogen-related fatigue fracture was discontinuous and composed of isolated nucleation of intergranular cracks and quasi-cleavage crack propagation initiated at the pre-existing intergranular cracks.     

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.     

Pre-oxidized and nitrided stainless steel alloy foil for proton exchange membrane fuel cell bipolar plates: Part 1. Corrosion, interfacial contact resistance, and surface structure

Thermal (gas) nitridation of stainless steel alloys can yield low interfacial contact resistance (ICR), electrically conductive and corrosion-resistant nitride containing surface layers (Cr₂N, CrN, TiN, V₂N, VN, etc.) of interest for fuel cells, batteries, and sensors. This paper presents results of scale-up studies to determine the feasibility of extending the nitridation approach to thin 0.1 mm stainless steel alloy foils for proton exchange membrane fuel cell (PEMFC) bipolar plates. Developmental Fe-20Cr-4V alloy and type 2205 stainless steel foils were treated by pre-oxidation and nitridation to form low-ICR, corrosion-resistant surfaces. As-treated Fe-20Cr-4V foil exhibited target (low) ICR values, whereas 2205 foil suffered from run-to-run variation in ICR values, ranging up to 2× the target value. Pre-oxidized and nitrided surface structure examination revealed surface-through-layer-thickness V-nitride particles for the treated Fe-20Cr-4V, but near continuous chromia for treated 2205 stainless steel, which was linked to the variation in ICR values. Promising corrosion resistance was observed under simulated aggressive PEMFC anode- and cathode-side bipolar plate conditions for both materials, although ICR values were observed to increase. The implications of these findings for stamped bipolar plate foils are discussed.     

Pre-oxidized and nitrided stainless steel alloy foil for proton exchange membrane fuel cell bipolar plates. Part 2: Single-cell fuel cell evaluation of stamped plates

Thermal (gas) nitridation of stainless steel alloys can yield low interfacial contact resistance (ICR), electrically conductive and corrosion-resistant nitride containing surface layers (Cr₂N, CrN, TiN, V₂N, VN, etc.) of interest for fuel cells, batteries, and sensors. This paper presents results of proton exchange membrane (PEM) single-cell fuel cell studies of stamped and pre-oxidized/nitrided developmental Fe-20Cr-4V weight percent (wt.%) and commercial type 2205 stainless steel alloy foils. The single-cell fuel cell behavior of the stamped and pre-oxidized/nitrided material was compared to as-stamped (no surface treatment) 904L, 2205, and Fe-20Cr-4V stainless steel alloy foils and machined graphite of similar flow field design. The best fuel cell behavior among the alloys was exhibited by the pre-oxidized/nitrided Fe-20Cr-4V, which exhibited ∼5-20% better peak power output than untreated Fe-20Cr-4V, 2205, and 904L metal stampings. Durability was assessed for pre-oxidized/nitrided Fe-20Cr-4V, 904L metal, and graphite plates by 1000+ h of cyclic single-cell fuel cell testing. All three materials showed good durability with no significant degradation in cell power output. Post-test analysis indicated no metal ion contamination of the membrane electrode assemblies (MEAs) occurred with the pre-oxidized and nitrided Fe-20Cr-4V or graphite plates, and only a minor amount of contamination with the 904L plates.     

Crystallographic feature of hydrogen-related fracture in 2Mn-0.1C ferritic steel

The present paper investigated crystallographic feature of hydrogen-related fracture in a 2Mn-0.1C steel having a simple ferritic microstructure. We found that the mechanical properties (in particular post-uniform elongation) were degraded by concurrent hydrogen-charging. Most of the fracture surfaces (over 90%) of the concurrently hydrogen-charged specimens showed quasi-cleavage morphologies with serrated markings, but no intergranular fracture surface was observed. Through a detailed crystallographic orientation analysis using EBSD, we have clarified that micro-cracks formed at ferrite grain boundaries and the micro-cracks propagated inside grains along crystallographic {011} planes of ferrite, leading to the quasi-cleavage fracture. Hydrogen micro-print technique revealed that hydrogen accumulated along ferrite grain boundaries under tensile-loading. On the basis of the obtained results, we propose that the fracture on {011} planes is an intrinsic characteristic of hydrogen-related quasi-cleavage fracture in steels having BCC phases.     

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.     

Strain rate and hydrogen effects on crack growth from a notch in a Fe-high-Mn steel containing 1.1 wt% solute carbon

Effects of strain rate and hydrogen on crack propagation from a notch were investigated using a Fe-33Mn-1.1C steel by tension tests conducted at a cross head displacement speeds of 10⁻² and 10⁻⁴ mm/s. Decreasing cross head displacement speed reduced the elongation by promoting intergranular crack initiation at the notch tip, whereas the crack propagation path was unaffected by the strain rate. Intergranular cracking in the studied steel was mainly caused by plasticity-driven mechanism of dynamic strain aging (DSA) and plasticity-driven damage along grain boundaries. With the introduction of hydrogen, decrease in yield strength due to cracking at the notch tip before yielding as well as reduction in elongation were observed. Coexistence of several hydrogen embrittlement mechanisms, such as hydrogen enhanced decohesion (HEDE) and hydrogen enhanced localized plasticity (HELP) were observed at and further away from the notch tip resulting in hydrogen assisted intergranular fracture and cracking which was the key reason behind the ductility reduction.     

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.     

Hydrogen environment embrittlement of an ODS RAF steel – Role of irreversible hydrogen trap sites

The microstructure and the effects of 10 MPa hydrogen atmosphere on the tensile properties of a oxide dispersion strengthened (ODS) reduced activation ferritic (RAF) steel were investigated. The microstructure consists of a fine grained ferritic matrix with Me₃O₄ (Me = Cr, Fe or Mn), VN and Cr₂₃C₆ grain boundary precipitates as well as dispersed yttrium oxide nano precipitates in the ferritic matrix. The yield and ultimate tensile strength were unaffected by the H₂ atmosphere whereas elongation at fracture and reduction in area were markedly reduced. In H₂ atmosphere, the fracture morphology was found to be a mixture of intergranular H-assisted fracture and a smaller amount of transgranular hydrogen enhanced localized plasticity (HELP) fracture. The sensitivity of the ODS RAF steel to hydrogen embrittlement is attributed to the large number grain boundary precipitates which enhance the tendency for intergranular fracture.     

Influence of precipitated phases on properties during prolonged aging in TP347H steel at 700 °C

The aging of austenitic stainless steel TP347H (18% Cr-12% Ni-1% Nb) was performed at 700 °C for 500, 800, 1500, 2500 and 3650 h. Microstructure, precipitates and mechanical properties were examined on aged materials to analyze the impact of microstructure on mechanical properties. These tests showed that the main precipitate of the TP347 specimen was Nb(C,N) while M₂₃C₆ carbides precipitated at the aging time of 500 h, with the coarsening of M₂₃C₆ and MX phases during prolonged aging. The fine and dispersive Nb(C,N) particle precipitation up to 1500 h aging is a benefit for hardness and creep resistance. After aging for 3650 h, σ phase precipitated. Meanwhile, coarsening of Cr₂₃C₆ and Nb(C,N) led to creep cavity and brittle intergranular fracture. No clear change in tensile properties at room temperature during aging were observed. A distinct decline in creep properties was caused by an average diameter increase and precipitation of σ phase and bulky Cr₂₃C₆.     

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.     

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).     

Hydrogen-assisted failure in a bimodal twinning-induced plasticity steel: Delamination events and damage evolution

The effect of the bimodal grain size distribution on the hydrogen susceptibility of a high-Mn fully austenitic twinning-induced plasticity (TWIP) steel was investigated by tensile testing under ongoing electrochemical hydrogen charging. Observation of the surface microstructure of the hydrogen-charged specimen yielded a correlation between the microstructure, crack initiation sites, and crack propagation path. The observed embrittlement arose from crack initiation/propagation along the grain and twin boundaries and delamination governed crack growth. In the present bimodal TWIP steel, the fine grained regions mostly showed intergranular cracking along the grain boundaries between the fine and coarse grains. By contrast, the coarse grained region exhibited transgranular cracking along the twin boundaries. The delamination cracking phenomena is rationalized by the evident nucleation, growth, and coalescence of microvoids in the tensile direction. The results reveal that the bimodal grain size distribution of TWIP steel plays a major role in hydrogen-assisted cracking and the evolution of delamination-related damage.     

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.     

Effect of high temperature aging on microstructure and mechanical properties of HR3C heat resistant steel

Abstract

Microstructure and mechanical properties of the HR3C austenite heat resistant steel were investigated after artificial aging at 650°C for time up to 3000 h. The results show that as the aging time increased, the room temperature tensile and impact fracture mechanisms of the HR3C steel change from trans- to intergranular fracture. M₂₃C₆ type carbides and MX type carbonitrides continuously precipitate during aging, leading to the change of the mechanical properties and fracture mode of the steel. Moreover, the dissolution of the coherent twins and the transformation from the incoherent twins to the thermodynamically stable austenite subgrains have great effects on the mechanical properties of the aged steel, too. When increasing the aging time to ≧2000 h, the microstructure and mechanical properties of the steel are nearly constant, indicating a good thermal stability of the HR3C steel at elevated temperature.     

Creep fracture behavior of dissimilar weld joints between T92 martensitic and HR3C austenitic steels

The creep fracture of T92/HR3C dissimilar weld joints is investigated. HR3C austenitic steel is welded with T92 martensitic steel to obtain a T92/HR3C weld joint. After welding, creep tests are carried out at 625 °C in the stress range 110–180 MPa. The results indicate that the creep fracture mechanism is dependent on stress. When stresses ≥140 MPa, the fracture location is at the T92 base material and the connection of adjacent dimples results in transcrystalline fracture. For stresses <140 MPa, the fracture location is at the T92 coarse-grained heat affected zone and growth of M₂₃C₆ particles as well as Laves phase (Fe₂(W, Mo)) precipitation on the grain boundaries leads to intergranular fracture.     

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.     

An experimental and modelling study of brittle cleavage crack propagation in transformable ferritic steel

Abstract

Flaws that can be present within pressure vessels, pipework and other engineering structures are assessed using the principles of engineering fracture mechanics. It is necessary to support such an approach with an understanding of the underlying fracture mechanisms. Moreover, many of these components are fabricated using transformable steels. In the present paper, the authors describe the fracture of an A508 type steel, heat treated to produce a tempered bainitic microstructure, and subsequently impact tested at ?196°C. In particular, focused ion beam microscopy has been used to produce high resolution fractography, combined with information relating to the underlying microstructure and crystallography. The results of cleavage crack propagation across prior austenite grain, lath packet and lath boundaries are described and then correlated with predictions from a three-dimensional geometric model of brittle cleavage fracture in polycrystalline steel. This model includes a consideration of a lath substructure developed within the grains and is based upon a Kurdjumov–Sachs orientation relationship with the parent austenite grain.