Hydrogen Charging Research Articles

Hydrogen resistance of reduced graphene oxide coatings prepared by electrophoretic deposition on duplex stainless steel

In this study, reduced graphene oxide (rGO) coatings were fabricated on duplex stainless steel (DSS) substrates using the electrophoretic deposition (EPD) method to evaluate their hydrogen resistance performance. The successful fabrication of rGO coatings was confirmed using Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). The structural characteristics were characterized using Raman spectroscopy and X-ray Diffraction (XRD). The results indicate that the EPD voltage is a crucial factor affecting the surface quality of and hydrogen resistance performance of rGO. Lower voltages resulted in lower degrees of rGO reduction and higher surface wrinkle density, while higher voltages caused bubble formation, significantly degrading the coating quality and hydrogen resistance performance. The optimal hydrogen resistance was achieved at an EPD voltage of 7.5V and a deposition time of 6 minutes. Electrochemical hydrogen charging tests and thermal desorption analysis (TDA) demonstrated that rGO coatings prepared under optimal conditions exhibited excellent hydrogen resistance efficiency, significantly reducing hydrogen atom penetration in hydrogen environments. The study further revealed that bubble formation significantly reduces the hydrogen resistance of rGO, which is attributed to increased interlayer spacing and the loss of the “labyrinth effect”.

Autothermal hydrogen release from liquid organic hydrogen carrier systems

A typical feature that the LOHC technology shares with other types of chemical hydrogen storage is that the release of hydrogen from the carrier requires an input of heat. In many use cases where waste heat from external sources is not available (e.g. in heavy-duty mobility), this is seen as a major drawback. In this paper, we show that autothermal LOHC dehydrogenation offers a very attractive way to overcome this drawback. In detail, we demonstrate autothermal hydrogen release from dicyclohexylmethane using diphenylmethane oxidation to benzophenone as source of heat. The full storage cycle involves benzophenone hydrodeoxygenation to dicyclohexylmethane, dicyclohexylmethane dehydrogenation to diphenylmethane, and diphenylmethane oxidation to benzophenone. We studied both the individual reaction steps using pure feedstocks and the integral cycle in which the intermediates and by-products of each reaction remain in the system for the subsequent reaction step. Although no efforts have yet been made to develop special catalyst materials for this purpose, the results with the applied commercial hydrodeoxygenation (Pd/C), dehydrogenation (Pt on alumina) and partial oxidation (VOx/TiO2) catalysts are already very promising. The storage cycle can be closed with high selectivity and with only minor total oxidation losses. The proposed concept of autothermal LOHC dehydrogenation offers the potential to increase the amount of useable hydrogen from a given amount of charged hydrogen carrier by up to 30%.

Corrosion Resistance and Fracture Toughness of Cryogenic-Treated X153CrMoV12 Tool Steel

Abstract Cryogenic treatment can be employed as an additional heat treatment step for martensitic steels, particularly high-carbon and high-alloy tool steels, to improve their mechanical properties and wear resistance. This enhancement results from a transformation of retained austenite and precipitation of finely distributed secondary carbides. The present study examines the impact of a shallow cryogenic treatment, performed between the quenching and tempering processes, on the corrosion resistance and fracture toughness of cold work tool steel X153CrMoV12. The influence of the shallow cryogenic treatment was evaluated using potentiodynamic polarization test, salt spray tests and three-point bending tests in various hydrogen charging conditions. In addition, the microstructure and phase transformation of the tool steel were investigated using high-resolution scanning electron microscopy, X-ray diffraction and dilatometer tests. The results suggest that the shallow cryogenic treatment followed by a single tempering cycle can slightly enhance the corrosion resistance of the steel. More importantly, the shallow cryogenic treatment positively affects fracture toughness and reduces hydrogen susceptibility. It is discussed how these improvements in the properties of the X153CrMoV12 steel are linked to the microstructural changes induced by the shallow cryogenic treatment.

Numerical investigation on thermal performance of three configurations of solar thermal collector integrated with metal hydride

This study investigates the optimal configuration of a Metal Hydride-based Solar Thermal Collector (MH-STC) by developing a transient 3D mathematical model to simulate three distinct configurations: C1, C2, and C3. These configurations differ in the placement of water pipes within the metal hydride bed C1 features pipes in the top region, C2 in the core zone, and C3 at the bottom. The performance of these configurations was rigorously compared based on hydrogen charge state, outlet water temperature, useful energy output, and thermal efficiency across varying water flow rates. Results reveal that configuration C1 achieves superior thermal performance during daytime operation, producing outlet temperatures up to 10 °C higher than the other configurations. Conversely, configuration C3 excels at nighttime heating, delivering water temperatures approximately 11.5 °C higher than C1. Furthermore, the analysis indicates that hydrogen desorption pressure significantly impacts outlet water temperature; for instance, increasing the pressure from 2.41 bar to 6 bar enhances the average outlet temperature of the C3 design by about 20 °C during the day and reduces it by approximately 15 °C at night. These findings highlight the critical need for optimizing solar collector designs to effectively meet the thermal demands of both daytime and nighttime applications.

Hydrogen-induced cracking behaviors of Ni–Cr–Mo-based superalloy fabricated by wire arc additive manufacturing under different solution temperature

The hydrogen embrittlement behavior of Ni–Cr–Mo-based superalloy fabricated by wire arc additive manufacturing (WAAM) with or without solution treatment was investigated by electrochemical hydrogen charging. The results show that the dissolution of the Laves phase promotes the precipitation of the δ phase in the matrix of WAAM superalloy after solution treatment at 980 °C. When the solution temperature goes up to 1080 °C, the large Laves phase disappears and only MC exists in the matrix. The interfaces between the Laves phase/δ phase and matrix generally could act as hydrogen traps, which would reduce the motion of hydrogen and lead to high hydrogen embrittlement resistance of the WAAM and ST-980 °C samples. However, hydrogen mainly accumulates on grain boundaries in the ST-1080 °C due to the disappearance of the Laves phase and δ phase. Hydrogen-induced intergranular brittle fracture occurs during the slow strain rate tensile test and the ST-1080 °C samples exhibit higher hydrogen embrittlement susceptibility than that of the WAAM and ST-980 °C samples.

Coupling effect of precipitates and hydrogen on pitting corrosion of stainless steel: Low potential region around precipitates

The coupling effect of hydrogen and NbCrN precipitate on pitting initiation and propagation of stainless steel were studied. After hydrogen charging, HMT results showed that more hydrogen was enriched on and around the precipitates. According to In-situ SKPFM and immersion results, the Volta potential of the precipitates is higher than that of the matrix before and after hydrogen charging. However, after hydrogen charging, a low Volta potential region appeared around the precipitates. The enrichment of hydrogen around the precipitates, the low potential around the precipitates, and consequent galvanic coupling effect lead to pits preferentially initiating and developing around the precipitates.

The adverse effect of grain refinement on hydrogen embrittlement in a high Mn austenitic steel

This study presents a novel observation wherein the reduction in grain size (GS) from 20 μm to 1 μm in austenitic steel adversely affects hydrogen embrittlement (HE). The findings indicate an increase in total absorbed hydrogen with grain refinement when subjected to cathodic hydrogen charging. The results demonstrate that even with grain refinement to 1 μm, the primary mode of hydrogen damage remains intergranular, with a significant increase in relative elongation loss (REL%). This phenomenon is attributed to the early nucleation of intergranular hydrogen-induced cracks (HICs) and the accelerated propagation rates of HICs, leading to local stress increments and rapid alloy failure. The accelerated development of HICs is ascribed to the impact of grain refinement on intensified normal stress exerted on grain boundary planes, as well as the suppression of ε-martensite and its positive effect on crack arresting. Besides the enhanced degradation rate of the hydrogen-affected area (HAA) due to grain refinement, the higher ratio of HAA to the entire cross-sectional area was identified as a crucial factor contributing to rapid failure and the inverse effect of grain refinement on HE resistance.

Hydrogen Embrittlement Behavior of API X70 Linepipe Steel under Ex Situ and In Situ Hydrogen Charging.

This study investigates the hydrogen embrittlement behavior of API X70 linepipe steel. The microstructure was primarily composed of a dislocation-rich bainitic microstructure and polygonal ferrite. Slow strain-rate tests (SSRTs) were performed under both ex situ and in situ electrochemical hydrogen charging conditions to examine the difference between hydrogen diffusion and trapping behaviors. The ex situ SSRTs showed almost the same tensile properties as air and a limited brittle fracture confined to near the surface. In contrast, the in situ SSRTs showed an abrupt failure after the maximum tensile load, leading to a brittle fracture across the entire fracture surface with stress-oriented hydrogen-induced cracking (SOHIC). The crack trace analysis results indicated that SOHIC propagation paths were influenced by localized hydrogen accumulation due to high-stress fields. As a result, the dominant hydrogen embrittlement mechanisms, such as hydrogen-enhanced localized plasticity (HELP) and hydrogen-enhanced decohesion (HEDE), changed. These findings provide critical insights into the microstructural factors affecting hydrogen embrittlement, which are essential for the design of hydrogen-resistant steels in hydrogen infrastructure applications.

Effects of hydrogen on the fretting wear behavior of laser cladded FeCoCrNiMo0.2 high entropy alloy coating

This study investigates laser-cladded high entropy alloy (HEA) coatings on high-speed train axles to enhance wear resistance under specific fretting conditions. Axles in humid and acidic environments absorb hydrogen, leading to accumulation in grain boundaries, which weakens their structure and causes damage under alternating stress. Despite this, the impact of hydrogen damage on the fretting wear behavior of HEA coatings has not been explored. To address this, we performed fretting wear tests on a laser-cladded FeCoCrNiMo0.2 coating and a GCr15 steel ball friction system, evaluating their performance before and after hydrogen exposure. The results of the study indicate that under a constant load of Fn = 10N and a displacement amplitude of D = 50 μm, the friction coefficient, maximum wear depth, wear volume, and wear rate increased when the system was in the hydrogen charging state compared to the non-hydrogen charging state. Specifically, the friction coefficient increased from 0.60 to 0.93, the maximum wear depth increased from 2.82 μm to 3.63 μm, the wear volume increased from 14.106 × 104μm3 to 22.098 × 104μm3, and the wear rate increased from 28.213 × 10−6 mm/Nm to 36.600 × 10−6 mm/Nm. Under the hydrogen charging state, the friction coefficient, maximum wear depth, wear volume, and wear rate all increased. This is due to hydrogen damage, including the formation of pitting pits and cracks on the surface of the coating, stress concentration, and brittle failure caused by hydrogen infiltration into the material. The presence of hydrogen makes the surface of the coating more prone to detachment, resulting in finer wear debris, deeper grooves, and increased oxidation. These factors accelerate the wear of the coating. This finding will contribute to the development and improvement of advanced surface modification techniques for materials in the hydrogen environment.

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.

Hydride and halide abstraction reactions behind the enhanced basicity of Be and Mg clusters with nitrogen bases.

In this study, we investigate the protonation effects on the structure, relative stability and basicity of complexes formed by the interaction of monomers and dimers of BeX2 and MgX2 (X = H, F) with NH3, CH2NH, HCN, and NC5H5 bases. Calculations were performed using the M06-2X/aug-cc-pVTZ formalism, along with QTAIM, ELF and NCI methods for electron density analysis and MBIE and LMO-EDA energy decomposition analyses for interaction enthalpies. The protonation of the MH2- and M2H4-Base complexes occurs at the negatively charged hydrogen atoms of the MH2 and M2H4 moieties through typical hydride abstraction reactions, while protonation at the N atom of the base is systematically less exothermic. The preference for the hydride transfer mechanism is directly associated with the significant exothermicity of H2 formation through the interaction between H- and H+, and the high hydride donor ability of these complexes. The basicity of both, MH2 and M2H4 compounds increases enormously upon association with the corresponding bases, with the increase exceeding 40 orders of magnitude in terms of ionization constants. Due to the smaller exothermicity of HF formation, the basicity of fluorides is lower than that of hydrides. In Be complexes, the protonation at the N atom of the base dominates over the fluoride abstraction mechanism. However, for the Mg complexes the fluoride abstraction mechanism is energetically the most favorable process, reflecting the greater facility of Mg complexes to lose F-.

Hydrogen susceptibility of Al 5083 under ultra-high strain rate ballistic loading

Abstract The effect of hydrogen on the ballistic performance of aluminum (Al) 5083H131 was examined both experimentally and numerically in this study. Ballistics tests were conducted at a 30° obliquity in accordance with the ballistic test standard MIL-DTL-46027 K. The strike velocities of projectiles were ranged from 240 m s−1 to 500 m s−1 level in the room temperature. Electrochemical hydrogen charging method was utilized to introduce hydrogen into material. Chemical composition of material was analyzed using energy dispersive X-ray (EDX) analysis. Instant camera pictures were captured using high-speed camera to compare H-uncharged and H-charged specimen ballistics tests. The volume loss in partially penetrated specimens were assessed using the 3D laser scanning method. Microstructural examinations were conducted utilizing scanning electron microscopy (SEM). It was observed that with the increased deformation rate, the dominance of the HEDE mechanism over HELP became evident. Furthermore, the experimental findings were corroborated through numerical methods employing finite element analysis (FEM) along with the Johnson–Cook plasticity model and failure criteria. Inverse optimization technique was employed to implement and fine-tune the Johnson–Cook parameters for H-charged conditions. Upon comparing the experimental and numerical outcomes, a high degree of consistency was observed, indicating the effective performance of the model.

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.

Hydrogen-induced delayed fracture behavior of notched 316L austenitic stainless steel: Role of grain refinement

Generally, grain refinement is considered to strengthen and mitigate the hydrogen embrittlement resistance of material. However, the effect of grain refinement on hydrogen-induced delayed fracture is rarely reported, especially concerning the extensive existence of geometric inhomogeneity such as notches. In this work, the effect of grain size on hydrogen-induced delayed cracking of notched 316L stainless steel under in-situ hydrogen charging is investigated. It is found that the brittle zone of delayed fracture of notched specimens is much larger than that in slow strain rate tensile of smooth specimens. This is due to the alternation of hydrogen diffusion and crack propagation during delayed fracture. After grain refinement, the time of delayed fracture increases significantly for the notched specimens, even the fracture does not happen, owing to the increase of austenitic stability. It is unusual that, regardless of grain size, α’ martensite is not detected at the crack tip, because the accumulated hydrogen at crack tip reduces plastic strains and suppresses martensite transformation.

Effect of degree of substitution of octenyl succinate on starch micelles for synthesis and stability of selenium nanoparticles: Towards selenium supplements

To develop a promising selenium supplement that overcomes the instability and poor water dispersibility of selenium nanoparticles (SeNPs), we synthesized a series of amphiphilic octenyl succinic anhydride starch (OSAS) through esterification. As the degree of substitution (DS) increased, the particle size of OSAS micelles and the critical micelle concentration (CMC) decreased. FTIR and XRD analysis confirmed the successful introduction of octenyl succinic anhydride groups onto starch. Subsequently, OSAS micelles were used as carriers to synthesize SeNPs via in situ chemical reduction, forming SeNPs-loaded self-assembled starch nano-micelles (OSAS-SeNPs). The OSAS-SeNPs exhibited spherical dispersion in water with an average diameter of 116.1 ± 2.3 nm, contributed to enhanced hydrophobic interactions. TEM images showed a core-shell structure with SeNPs as the core and OSAS as the shell. FTIR results indicated hydrogen bonding interactions between OSAS and SeNPs. Due to the negatively charged OSAS shell and hydrogen bonding (OH⋯Se), OSAS-SeNPs remained non-aggregated for one month at room temperature, demonstrating remarkable stability. This study suggests that using OSAS can address the synthesis and stability issues of SeNPs, making it a potential selenium supplement candidate for further evaluation as an anticancer agent.

Heat pipe for thermally coupled fuel cell and metal hydride as well as for cooling metal hydride hydrogen charging

ABSTRACT In this paper, a metal hydride (MH) canister and a PEM fuel cell are coupled using heat pipes to study the minimum number of heat pipes required, the operating range of the fuel cell, and the temperature change patterns of the MH. We account for temperature difference limitations between the fuel cell and the MH (∆T = 35–55 K) on the heat pipe dynamics, which has been neglected in previous similar studies. Since the hydrogen absorption rate of the MH canisters exhibits an initial increase followed by a decrease with increasing temperature, an analysis was conducted to select the appropriate heat pipe under different hydrogen filling pressures. This analysis ensured that the MH canisters remained at the optimal charging temperature (326 K) and achieved the maximum charging rate (6.64 slpm).

Investigating the Fatigue Response of Cathodically Charged Cold-Finished Mild Steel to Varied Hydrogen Concentrations

This study investigates the fatigue behavior of cold-finished mild steel subjected to electrochemical hydrogen charging under controlled conditions. Samples were subjected to hydrogen charging at constant time in a fixed electrolyte pH, after which the samples underwent fatigue testing under constant loading condition with fixed frequency. The primary objective was to assess the impact of varying hydrogen permeation levels on the number of cycles to failure. The experimental results revealed a complex relationship between hydrogen concentration and fatigue life. Initially, as hydrogen permeation increased, the number of cycles to failure substantially decreased, demonstrating the detrimental effect of diffused hydrogen on the fatigue resistance of samples. This decline in fatigue life was attributed to hydrogen embrittlement (HE) and hydrogen-enhanced decohesion (HEDE) phenomena, which collectively facilitate crack initiation and propagation. However, at high hydrogen concentrations, an unexpected increase in the number of cycles to failure was observed suggesting the existence of a threshold hydrogen concentration beyond which the fatigue mechanisms may be altered, potentially due to a saturation of hydrogen-related defects and mechanisms such as hydrogen-enhanced localized plasticity (HELP). The discovery from this research has significant implications for the material’s application in hydrogen-rich environments, such as those encountered in the energy and transportation industries.

Effect of heat input on the microstructure and hydrogen embrittlement susceptibility of the coarse-grain heat-affected zone of CrMo steels generated using a Gleeble 3500 welding simulator

The changes in microstructure and hydrogen embrittlement (HE) susceptibility of the simulated coarse-grain heat-affected zone (CGHAZ) of CrMo steels under three distinct heat input conditions were investigated. The cooling time from 800 °C to 500 °C, represented by t8/5, increased from 100 s to 200 and 400 s.. The sample with t8/5 = 100 s has a microstructure consisting of martensite and a small amount of lower bainite. When the t8/5 was increased to 200 s and 400 s, the HAZ consisted of 65.43 % martensite and 34.57 % lower bainite and 4.53 % martensite with 95.47 % bainite, respectively. The HE susceptibility was assessed by slow strain rate tensile (SSRT) testing of hydrogen-charged samples, and the HE susceptibility index (IHE) declined from 87.89 % to 61.37 % when t8/5 increased from 100 to 400 s. The high dislocation density and hydrogen concentration in the sample with t8/5 = 100 s led to intergranular fracture and incresaed HE susceptibility. The martensite lath and cementite/ferrite interface are the sites of crack initiation in the sample with t8/5 = 200 s. In the sample with a cooling time of 400 s, the martensite/ferrite interfaces are the main crack initiation sites under hydrogen charging.

Liquid Hydrogen Properties Affecting Fracture Toughness

In this study, fracture toughness with the base metal of 9% Ni steel, a cryogenic steel, was evaluated under conditions without hydrogen charging (WO-H) and with hydrogen charging (W-H). Hydrogen charging was performed using an electrochemical cathodic charging method in a electrolyte of 3% NaCl + 0.3% NH4SCN at 19℃ with a current density of 50 A/m². Fracture toughness was assessed at -80℃, -100℃, -130℃, and -160℃ using CTOD (Crack Tip Opening Displacement) tests. The results for WO-H indicated a decrease in fracture toughness values with decreasing temperature, while the results for W-H showed an increase in fracture toughness values as the temperature decreased. In addition, the fracture surfaces and fracture toughness of WO-H and W-H became increasingly similar as the temperature decreased, as observed through scanning electron microscopy (SEM). At -80℃, there was a significant difference in fracture toughness between the WO-H and W-H conditions. WO-H was influenced only by the low temperature, whereas W-H was affected by both low temperature and hydrogen, showing combined effects that led to a decrease in fracture toughness due to hydrogen embrittlement. However, at -160℃, the fracture toughness values for both WO-H and W-H conditions were nearly identical. This suggests that the temperature effect on fracture toughness reduction is greater than hydrogen embrittlement at very low temperatures.

Effects of Electrochemical Hydrogen Charging Parameters on the Mechanical Behaviors of High-Strength Steel.

Extended exposure to seawater results in the erosion of the structural high-strength steels utilized in marine equipment, primarily due to the infiltration of hydrogen. Consequently, this erosion leads to a decrease in the mechanical properties of the material. In this investigation, the mechanical responses of Q690 structural high-strength steel specimens were investigated by considering various hydrogen charging parameters, such as the current density, charging duration, and solution concentration values. The findings highlighted the significant impacts of electrochemical hydrogen charging parameters on the mechanical behaviors of Q690 steel samples. Specifically, a linear relationship was observed between the mechanical properties and the hydrogen charging current densities, while the associations with the charging duration and solution concentration were nonlinear. Additionally, the fracture morphology under various hydrogen charging parameters was analyzed and discussed. The results demonstrate that the mechanical properties of the material degrade with increasing hydrogen charging parameters, with tensile strength and yield stress decreasing by approximately 2-4%, and elongation after fracture reducing by about 20%. The findings also reveal that macroscopic fractures exhibit significant necking in uncharged conditions. As hydrogen charging parameters increase, macroscopic necking gradually diminishes, the number of microscopic dimples decreases, and the material ultimately transitions to a fully brittle fracture.