Hydrogen Trapping Sites Research Articles

Hydrogen diffusion mechanisms in the 4130X steel: An integrated study with electrochemical experiments and molecular dynamics simulations

In this work, hydrogen diffusion behavior and mechanisms in the 4130X steel influenced by temperature, locally high concentration, and grain boundary were studied by leveraging both electrochemical hydrogen permeation experiments and molecular dynamics simulations. It was revealed that the hydrogen diffusion coefficient of the 4130X steel was increased with increasing temperature and decreasing locally high hydrogen concentration. The grain boundaries with misorientation below 15° characterized by an electron backscatter diffraction map were identified as hydrogen trapping sites, thus rendering a lower mean square displacement of hydrogen atoms and localized hydrogen diffusion trajectories. Furthermore, at a high hydrogen concentration of 4 at. %, these grain boundaries were saturated by hydrogen atoms, and platelet-like hydrogen clusters were formed within the lattice, which further inhibited the diffusive motion of hydrogen atoms. These findings would deepen our understanding of hydrogen embrittlement mechanisms by establishing the connections between macroscopic permeation behavior and atomic-scale hydrogen diffusion in structural materials.

Trapping and diffusion in high-pressure hydrogen charged CoCrFeMnNi high entropy alloy compared to austenitic steel 316L

High entropy alloys (HEAs) have attracted considerable research attention as potential substitute materials for austenitic steels in high-pressure hydrogen environments. The corresponding hydrogen absorption, diffusion and trapping has received less scientific attention. Therefore, the CoCrFeMnNi-HEA was investigated and compared to an austenitic steel AISI 316L. Both were subjected to high-pressure hydrogen charging at 200 bar and 1000 bar. Thermal Desorption Analysis (TDA) was used to clarify the specific desorption behavior and hydrogen trapping. For this purpose, the underlying TDA spectra were analyzed in terms of a reasonable peak deconvolution into a defined number of peaks and the activation energies for the respective and predominant hydrogen trapping sites were then calculated. Both materials show comparable hydrogen diffusivity. However, there were significant differences in the absorbed hydrogen concentrations at both charging pressures. The calculated activation energies suggest strong hydrogen trapping in the CoCrFeMnNi-HEA.

Effect of tempering temperature on mechanical properties and hydrogen embrittlement resistance of a dual-precipitation-hardened martensitic steel

ABSTRACT The effects of dual-precipitation on the mechanical properties and hydrogen embrittlement (HE) resistance of a Ti-Mo-alloyed martensitic steel were investigated using a quenching and tempering (QT) procedure. The precipitate-free QT200 sample exhibited high tensile strength and brittle fracture after hydrogen charging. In contrast, the QT300 sample demonstrated a dual-precipitation constitution of (Ti, Mo)C and ϵ-carbide, achieving a high yield strength (∼1400 MPa) without sacrificing tensile ductility (∼10%). More importantly, it showed higher resistance to HE (elongation loss: ∼4.2%) compared to the low-strength QT400 sample. The unusual HE susceptibility of the QT300 samples can be attributed to a higher hydrogen trapping ability of ϵ-carbide compared to (Ti, Mo)C precipitates. This results in high densities of irreversible hydrogen trapping sites and a completely ductile fracture mode characterised by numerous dimples.

Nano hydride precipitation-induced disappearance of yield drop in zirconium alloy at elevated temperature

Hydrogen-induced variations in mechanical behavior of zirconium alloys impose detrimental influence on nuclear fuel cladding integrity. This work reports a disappearance of intrinsic yield drop in a recrystallized zirconium alloy following hydrogen-charging treatment. Microstructure characterizations reveal that the nano-hydrides precipitation, mediated by second phase particles Zr(Fe,Cr)2 acting as hydrogen trapping sites, leads to emission of substantial dislocations in α-matrix grains due to strong strain concentrations, as identified by high-angular resolution EBSD. These mobile dislocations preserved at elevated temperatures can maintain the applied plastic strain and impede rapid dislocation multiplication as well, a conclusion validated by comparative analysis of dislocation densities prior to and near yielding stage. These findings are expected to shed light on the underlying mechanisms governing the interaction between hydrogen and microstructural defects in Zr-based nuclear fuel cladding materials.

Multi-scale structural heterogeneity promoting hydrogen embrittlement in additively manufactured pure nickel

In this study, how physical differences in the microstructure of additively manufactured (AM) pure Ni affect its susceptibility to hydrogen embrittlement (HE) are investigated. The presence of high-density dislocation cells (DCs) and grain boundaries in AM Ni could absorb more hydrogen therein, with the DC boundaries serving as reversible hydrogen trapping sites. The DC boundaries overlapped with the grain boundaries might lead to an enhanced hydrogen diffusion therein for AM Ni. Consequently, an increased depth of hydrogen-affected region and accelerated failure process were observed in AM Ni during tensile testing due to intergranular cracking. Furthermore, the HE resistance can be slightly improved by a dislocation-cell elimination heat treatment for AM Ni-800, but it remains lower than that of traditionally manufactured Ni, primarily due to the residue of bi-modal grains with small grains along the molten pool boundaries. The underlying HE mechanism based on the structural heterogeneities at different scales for pure Ni is discussed.

Effect of hydrogen on the microstructural evolution and local mechanical properties of 430 ferritic stainless steel at high-temperature conditions

The present study investigated the impact of hydrogen on the microstructural evolution and mechanical properties of 430 ferritic stainless steel at high-temperature conditions. Hydrogen trap sites were analyzed at high temperatures using thermal desorption spectrometry through high-temperature hydrogen atmosphere charging and electrolytic hydrogen charging. The microstructural evolution was characterized using scanning electron microscopy and electron backscatter diffraction. The nanoindentation technique was employed to analyze the local mechanical properties of ferrite matrix, grain boundaries, and M23C6/matrix interfaces. Hydrogen trap sites in 430 ferritic stainless steel included ferrite crystal lattice, grain boundaries, intragranular dislocations, and M23C6/matrix interfaces where hydrogen could not intrude at room temperature. At high temperatures, hydrogen caused a decrease in grain size. Furthermore, at high temperatures, hydrogen altered the crystal orientation and texture of the ferrite matrix. There was an increase in the number of ferrite grains with (001) and (101) orientation increase and the formation of a new α-fiber texture. Hydrogen inhibited the triggering of the slip system in body centered cubic crystal lattice and induced an increase in dislocation density and internal stress. While hydrogen at high temperatures had a minimal impact on the matrix strength limit, it reduced the strength limit of the near grain boundaries and (Fe, Cr)23C6 precipitates. The influence of hydrogen on the microstructural evolution and mechanical properties of 430 ferritic stainless steel could be elucidated by the mechanisms of hydrogen enhanced decohesion, hydrogen-enhanced localized plasticity, and hydrogen enhanced specific crystal plane rotation suggested in the present study.

Resolving Hydrogen Trapping Sites in Steels at Ultra-High Resolution Using Cryogenic Atom Probe Tomography

Resolving Hydrogen Trapping Sites in Steels at Ultra-High Resolution Using Cryogenic Atom Probe Tomography

Influences of (Al, Ca, Si, Nb, Mn)-oxy-sulfide inclusions on corrosion degradation for newly designed 17–4 martensitic PH steel in simulated geothermal environments

Influences of (Al, Ca, Si, Nb, Mn)-oxy-sulfide inclusions on hydrogen trapping and stress corrosion cracking in a newly designed 17–4 martensitic PH steel were carried out under simulated geothermal environments based on experiments and calculations. The results indicate that CaS and MnS in inclusions are not only prone to preferential dissolution, but also more likely to become hydrogen trapping sites at the interface with matrix than other components. The number of pits rapidly increase before the sample fracture at 159.25 h, while cracks around external pits and internal gourd-like cavities are probably attributed to the uneven expansion of inclusion-triggered pits.

In situ investigation of hydrogen embrittlement induced by δ phase in selective laser-melted GH4169 superalloy

Direct evidence of hydrogen-assisted crack nucleation and propagation associated with the δ phase in the selective laser melted GH4169 superalloy was obtained. The analysis of hydrogen trapping sites using thermal desorption spectroscopy revealed that the δ phase exhibits strong hydrogen capture capability, with a hydrogen desorption activation energy of 35.45 ± 2.51 kJ/mol. In addition, spatially resolved hydrogen mapping conducted by scanning Kelvin probe force microscopy and hydrogen microprint technique provided further evidence for the δ phase as a deep hydrogen trapping site. The atomic-scale characterization sufficiently reveals the deformation mechanism of the δ phase induced by dislocation accumulation. Hydrogen-promoted dislocation slip localization facilitates the formation of microvoid defects in the δ phase, which is the main reason for the δ phase fracture, and induces intergranular and transgranular cracks.

Effect of Microstructural Constituents on Hydrogen Embrittlement Resistance of API X60, X70, and X80 Pipeline Steels

This study describes how microstructural constituents affected the hydrogen embrittlement resistance of high-strength pipeline steels. The American Petroleum Institute (API) X60, X70, and X80 pipeline steels demonstrated complicated microstructure comprising polygonal ferrite (PF), acicular ferrite, granular bainite (GB), bainitic ferrite (BF), and secondary phases, e.g., the martensite-austenite (MA) constituent, and the volume fraction of the microstructures was dependent on alloying elements and processing conditions. To evaluate the hydrogen embrittlement resistance, a slow strain rate test (SSRT) was performed after electrochemical hydrogen charging. The SSRT results indicated that the X80 steel with the highest volume fraction of the MA constituent demonstrated relatively high yield strength but exhibited the lowest hydrogen embrittlement resistance because the MA constituent acted as a reversible hydrogen trap site.

Capacity of hydrogen traps affects H-assisted crack initiation and propagation mechanisms in martensitic steels

Low-carbon martensitic steels are candidate materials for different hydrogen applications. Hydrogen embrittlement (HE) of the steels can be mitigated by designing trap site characteristics. In this study, the different capacities of hydrogen trapping, and reversibility of the trap sites are studied to reveal the extent of HE susceptibility of the steels and H-assisted crack initiation and propagation mechanisms. The trap sites in Ti-contained and Mo-contained martensitic steels were identified and discussed. The trap sites in Ti-contained martensitic steel include basic martensitic microstructure, the interface of the TiC/matrix interface and carbon vacancies inside the TiC carbides. The trap sites in Mo-contained martensitic steel including basic martensitic microstructure and interface of the Mo2C/matrix interface. Ti-contained steel indicates a mitigated HE susceptibility, controlled by carbon vacancies inside TiC acting as strong hydrogen trap sites, and a higher possibility of building up a critical hydrogen content at Mo2C carbide due to lower hydrogen capacity. These results prove that hydrogen trapping capacity at the designated hydrogen trap sites is a determinant factor for H-assisted crack initiation and propagation in martensitic steels. A critical local hydrogen amount should be built up at the trap site to assist the crack to develop. It was also revealed that crack initiation originated from Mo2C carbides accompanied by interfacial decohesion at the interface of martensitic matrix/Mo2C carbides and propagated in quasi-cleavage patterns along {011} planes.

Influence of sample extraction location on thermal desorption spectroscopy from a heat-resistant 13CrMo4-5 steel plate and correlation with microstructure features

Thermal desorption spectroscopy (TDS) is a highly sensitive and widely used method to directly measure the total hydrogen concentration and indirectly assess the hydrogen trapping sites and mechanisms from the spectra features in steels. Thus, there is a need to investigate the influence of sample location from a 5 mm plate of hot-rolled heat-resistant structural steel on TDS spectra. Via a new highly sensitive and specific correlation coefficient (microToH), the TDS results are correlated with low-angle grain boundaries volume fraction, grain size with different misorientation thresholds, microhardness, and geometrically necessary dislocations at different densities.The results indicate that sample location influences 133 % and 62 % in the hydrogen desorption of peak 1 (at 515 K), and total hydrogen concentration via the influence of peak 2 (at 634 K), respectively. Thus, sample location needs to be considered as one relevant aspect in a research plan based on TDS analysis. The influence on peak 3 (at 762 K) was found to be negligible as it is related to the first exothermic peak of the heating cycle, associated with carbide precipitation phenomena. The individual grain analysis performed with high-resolution adaptive DMM and GND maps emphasises the accumulation of the deformation in the ferritic domain at the vicinity of the pearlite structures.

Research on Hydrogen-Induced Induced Cracking Sensitivity of X80 Pipeline Steel under Different Heat Treatments.

X80 pipeline steel has played a vital role in oil and gas transportation in recent years. However, hydrogen-related issues frequently lead to pipeline failures during service, resulting in significant losses of properties and lives. Three heat treatment processes (furnace cooling (FC), air cooling (AC), and water cooling (WC)) were carried out to investigate the effect of different microstructures on hydrogen-induced cracking (HIC) susceptibility of X80 pipeline steel. The WC sample demonstrated the highest hydrogen embrittlement index, registering at 21.9%, while the AC and FC samples exhibited progressively lower values of 15.45% and 10.98%, respectively. Under equivalent hydrogen charging durations, crack dimensions with a maximum length exceeding 30 μm in the WC sample generally exceed those in the FC sample and AC sample. The variation is attributed to the difference in microstructures of the samples, predominantly lath bainite (LB) in water-cooled samples, granular bainite (GB) in air-cooled samples, and ferrite/pearlite (F/P) in FC samples. The research results demonstrate that the sensitivity of lath bainite (LB) to HIC is significantly higher than that of pearlite, ferrite, and granular bainite (GB). The presence of a large amount of martensite/austenite (M/A) constituents within bainite results in a multitude of hydrogen trap sites. HIC cracks in bainite generally propagate along the profiles of M/A constituents, showing both intergranular and transgranular cracking modes.

Synergistic influence of dislocations and helium cluster on hydrogen atom in tungsten

Dislocations are common line defects in the preparation and irradiation processes of tungsten (W), and they can serve as trapping sites for hydrogen (H) and helium (He) atoms. Existing studies have indicated that dislocations preferentially capture He atoms to form dislocation-He cluster structures. The focus of this study was on the effects of this new structure on the trapped and diffusion behavior of H atoms using molecular dynamics (MD) method. The study considered the number of He atoms from 1 to 150, and they were classified as small He cluster and large He cluster. By calculating the binding energy, the study revealed that the capture strength is positively correlated with the He clusters’ size. However, it is negatively correlated with the distance from the dislocation core and the captured H atoms’ number. This study output the stable configurations to analyze the growth patterns of He cluster in dislocations, and it was observed that the interstitial atoms caused by trap mutation preferentially aggregate into dislocation loops due to the dislocation core structure. Moreover, the study investigated the diffusion behavior of H atoms around the dislocation-He cluster structure at 600 K within 1 ns. The hydrogen atoms tend to migrate towards the He cluster and distribute around it uniformly. The distribution range narrows with the helium cluster's size, and the distribution pattern depends on the dislocations’ type. This demonstrated the formation of dislocation-He cluster structure, promoting the increased H retention.

The effect of low hydrogen content on hydrogen embrittlement of additively manufactured 17–4 stainless steel

This work aims to evaluate the impact of small amounts of hydrogen on the hydrogen-assisted cracking (HAC) of 17-4 martensitic stainless steel (SS) prepared by additive manufacturing (AM). To elucidate the effect of processing on the hydrogen–material interactions, the obtained results were compared with a conventionally manufactured (CM) counterpart. It was found that the hydrogen uptake of AM 17-4 SS is higher compared to CM; however, its resistance to HAC is improved. These differences are attributed to the presence of stronger hydrogen trapping sites, retained austenite and the absence of Nb-rich precipitates in the AM 17-4 SS. The effect of processing on the microstructure and the susceptibility to hydrogen-induced damage and hydrogen embrittlement is discussed in detail.

Effect of Microstructural Constituents on Hydrogen Embrittlement Resistance of API X60, X70, and X80 Pipeline Steels

This study describes how microstructural constituents affected the hydrogen embrittlement resistance of high-strength pipeline steels. The American Petroleum Institute (API) X60, X70, and X80 pipeline steels demonstrated complicated microstructure comprising polygonal ferrite (PF), acicular ferrite, granular bainite (GB), bainitic ferrite (BF), and secondary phases, e.g., the martensite-austenite (MA) constituent, and the volume fraction of the microstructures was dependent on alloying elements and processing conditions. To evaluate the hydrogen embrittlement resistance, a slow strain rate test (SSRT) was performed after electrochemical hydrogen charging. The SSRT results indicated that the X80 steel with the highest volume fraction of the MA constituent demonstrated relatively high yield strength but exhibited the lowest hydrogen embrittlement resistance because the MA constituent acted as a reversible hydrogen trap site.

Effect of Metal Carbides on Hydrogen Embrittlement: A Density Functional Theory Study

This study uses plane wave density functional theory (DFT) to investigate the effect of certain metal carbides (Niobium carbide, Vanadium carbide, Titanium carbide, and Manganese sulfide) on hydrogen embrittlement in pipeline steels. Our results predict that the interaction of hydrogen molecules with these metal carbides occurs in the long range with binding energy varying in the energy window [0.043 eV to 0.70 eV].In addition, our study shows the desorption of H2 molecules from these metal carbides in the chemisorptions. Since atomic state hydrogen interacts with NbC, VC, TiC, and MnS to cause embrittlement, we classified the strength of the hydrogen trapping as TiC + H > VC + H > NbC + H> MnS + H. In addition, our study reveals that the carbon site is a more favorable hydrogen-trapping site than the metal one.

Effect of δ–ferrite and strain-induced martensite on hydrogen embrittlement of STS 308 L and STS 316 L all-weld metals

The susceptibility of multipass flux-cored arc welds of STSs 308 L and 316 L to hydrogen embrittlement (HE) was investigated at various temperatures. Cracks predominantly initiated and propagated along the δ-ferrite in the interdendritic region at 25 °C. δ-ferrite served as preferred hydrogen trap sites, and the δ/γ boundary became the stress concentration site. At −100 °C, STSs 308 L and 316 L exhibited high susceptibility to HE owing to strain-induced martensite formation, providing additional hydrogen trap sites and dislocation accumulation. Despite strain-induced martensite actively transformed at −196 °C, the HE disappeared owing to the sluggish diffusion of hydrogen to stress-concentrated areas.

Combining muon spin relaxation and DFT simulations of hydrogen trapping in Al6Mn

Hydrogen at the mass ppm level causes hydrogen embrittlement in metallic materials, but experimentally elucidating the hydrogen trapping sites is extremely difficult. We exploit the fact that positive muons can act as light isotopes of hydrogen to study the trapping state of hydrogen in matter. Zero-field muon spin relaxation experiments and density functional theory (DFT) calculations of the hydrogen trapping energy are carried out for Al6Mn. The DFT calculations reveal four possible trapping sites for hydrogen in Al6Mn, at which the hydrogen trapping energies are 0.168 (site 1), 0.312 (site 2), 0.364 (site 3), and 0.495 (site 4) in units of eV/atom. The variations in the deduced dipole field width (Δ) with temperature indicate noticeable changes at 94, 193, and 236 K. Considering the site densities, the observed Δ change temperatures are interpreted as muon trapping at sites 1, 3, and 4.

Annealing of hydrogen trap sites in displacement-damaged EUROFER

For future fusion power plants, the reduced activation ferritic/martensitic (RAFM) steel EUROFER is considered to be the primary choice as a structural material for plasma facing components (PFC) of the first wall, such as the blanket modules. Its exposure to high energy fusion neutrons will lead to creation of radiation-induced defects, which could act as trapping sites for hydrogen isotopes (HI) and consequently, strongly affect HI diffusion and retention. For predictive simulations of HI retention, the concentration of these trap sites needs to be known as a function of the temperature. In this work, EUROFER samples are irradiated by 20 MeV W-ions at 290 K to create displacement damage. Subsequently, they are exposed to deuterium (D) plasma at 370 K to decorate the created defects. Partial thermal desorption spectroscopy (TDS) is conducted in 50 K steps up to 620 K. D depth profiles are determined by nuclear reaction analysis (NRA) after each partial-TDS step. Following this analysis, the defects are again decorated with D and the D depth profiles are measured again by NRA to monitor the evolution of the concentration of trap sites. Most of the D is lost already at 470 K due to thermal de-trapping. Full recovery of the displacement damage is reached at 620 K.