Diffusion Of Hydrogen Atoms Research Articles

Modelling deuterated isotopologues of methanol towards the pre-stellar core L1544

Context. In the extremely cold and dark environments of pre-stellar cores, methanol is formed on the surface of interstellar dust grains and released into the gas phase via non-thermal desorption mechanisms. Gaseous methanol constitutes the starting point for the formation of many massive complex organic molecules and is therefore of utmost importance for the build-up of chemical complexity. Aims. We aim to improve upon a previous model for the prediction of column densities and deuterium fractions of non-deuterated and singly deuterated methanol. Thereby, we try to identify crucial chemical and physical parameters for which the study of deuteration could provide valuable additional constraints. Methods. We employed a gas-grain chemical code to devise a model that is in agreement with the observed column density and deuterium fraction profiles of the innermost region of the pre-stellar core L1544. For that purpose, we developed a new treatment of reactive desorption, deriving an individual reactive desorption efficiency for every product species in a chemical reaction that depends on the reaction enthalpy and type of the underlying surface. Furthermore, we explored several options to promote the diffusion of hydrogen and deuterium atoms over the surface of interstellar dust grains in order to increase methanol formation. Results. Our fiducial model employs diffusion via the quantum tunnelling of hydrogen and deuterium atoms, resulting in CH3OH and CH2DOH column densities that are approximately an order of magnitude lower than the observed values, which is an improvement over the results of the previous model by a factor of 10. The N(CH2DOH)/N(CH3OH) ratio is reproduced within a factor of 1.2 for the centre and 1.8 for the position of the methanol peak. Given the large uncertainties that chemical models typically have, we consider our predictions to be in agreement with the observations. In general, we conclude that a diffusion process with a high diffusion rate needs to be employed to obtain methanol column densities that are in accordance with the observed values. Also, we find that the introduction of abstraction reactions into the methanol formation scheme suppresses deuteration when used in combination with a high diffusion rate.

Composition optimization and hydrogen storage properties of Ti–V–Mn–Fe alloys

Ti–V-based hydrogen storage alloys have garnered interest owing to their salient advantages of reversible hydrogen absorption/desorption at room temperature and excellent kinetic properties. However, the complicated smelting technology of high-purity V metal renders expensive prices, hampering their large-scale production and application. Herein, to overcome this hurdle, abundant and inexpensive Mn and Fe are added to obtain Ti–V–Mn–Fe hydrogen storage alloys. The novel alloy compositions were obtained using a uniform design method. The hydrogen absorption/desorption behaviors of alloys prepared using arc melting technology were analyzed in detail. Systematic investigations show that the activation, kinetics, and thermodynamic properties of alloys are closely correlated with the Ti/(Mn + Fe) ratios. The designed alloy compositions have a multiphase structure with a body-centered cubic (BCC) main phase. The lattice parameters of the BCC phase increase with increasing Ti/(Mn + Fe) ratio, and the large lattice parameters of alloys are beneficial to facilitate the diffusion of hydrogen atoms, resulting in fast kinetics. A reasonable Ti/(Mn + Fe) ratio positively affects the hydrogen storage properties. Among them, the Ti40V40Mn2Fe18 alloy with Ti/(Mn + Fe) = 2 achieved a hydrogen absorption capacity of 3.472 wt% at 298 K and an effective reversible hydrogen storage capacity of 1.485 wt% above 0.1 MPa at 363 K. This study provides a novel insight for designing Ti–V-based alloy compositions via the uniform design method.

Diffusion of hydrogen in the Volterra elastic fields around dislocations in α-Ti: Coupling DFT calculations and elasticity method

Hydrogen around dislocation has a great influence on the mechanical properties of Titanium (Ti) alloys. In this study, the diffusion of hydrogen around dislocations in α-Ti alloys is investigated by coupling density functional theory (DFT) calculations and the elasticity method. Initially, the attempt frequency and hopping activation energy of hydrogen atom in the α-Ti lattice are calculated using the DFT method under various simple strain fields, including volume strain, biaxial strain, and shear strains, within a strain range of −2%–2 %. It is observed that both volume strain and biaxial strain have the most pronounced effects on the hopping activation energy of hydrogen atom, while the attempt frequency remains relatively unaffected across different strain conditions. Subsequently, the hopping activation energy in the elastic strain field has been parameterized using an elasticity method based on elastic dipole and diaelastic polarizability. Using the elasticity method, an analysis is conducted on the effective activation energy of hydrogen atoms and their hopping tendencies in the Volterra elastic strain fields around the perfect edge and screw dislocations. The elastic strain field around screw dislocation enhances the diffusion of hydrogen atoms and simultaneously promotes their migration toward the dislocation core. In the vicinity of edge dislocation, the tensile elastic strain field enhances the diffusion of hydrogen atoms and facilitates their migration toward the dislocation core. Conversely, the compressive strain field retards the diffusion of hydrogen atoms and promotes their migration away from the dislocation core or towards regions with tensile strain.

Hydrogen atom solution and diffusion behaviors at Σ3 and Σ5 grain boundaries of Fe, Ni, Cu and Al: A first-principles study

Understanding the interactions between hydrogen atom and grain boundaries is essential for designing grain boundary structures that can improve the hydrogen embrittlement resistance. In this study, the DFT calculations have been performed to investigate the characteristics of Σ3 and Σ5 grain boundaries of Fe, Ni, Cu and Al and the hydrogen atom solution and diffusion behaviors at these grain boundaries. The calculation results indicate that for the same metallic material, the Σ5 grain boundary has larger grain boundary energy and lower work of separation than that of Σ3 grain boundary. The hydrogen atom solution energies at Σ5 grain boundaries are lower than those at Σ3 grain boundaries. The COHP calculations illustrate that the existence of hydrogen atom will weaken the metallic bond strength at grain boundary no matter in Σ3 or Σ5 grain boundary. With respect to the hydrogen atom diffusion behaviors at the grain boundaries, the hydrogen atom is easier to diffuse at the Σ5 grain boundary compared to that of Σ3 grain boundary for the same metallic material. Thus, increasing the ratio of grain boundaries with lower value of Σ will beneficial to improve the hydrogen embrittlement resistance of metallic polycrystalline materials.

Distribution of hydrogen atoms at metallurgical microphases of X52 pipeline steel studied by scanning Kelvin probe force microscopy and finite element modelling

The work combined scanning Kelvin probe force microscopy measurements and finite element modelling to study the diffusion and distribution of hydrogen (H) atoms at metallurgical microphases contained in X52 pipeline steel. Results show that the pearlite contained in the steel is more stable than the ferrite during electropolishing, as indicated by the measured topographic profiles and Volta potentials. The hydrogen (H)-charging enhances the electrochemical activity of both pearlite and ferrite, as shown by increased Volta potential and thus the decreased work function. As the H-charging time increases, the Volta potentials of both phases further increase, implying that their activities increase with the H-charging time. The pearlite has a greater Volta potential and thus a lower work function than the ferrite. This is associated with more H atoms accumulating at the pearlite than at the ferrite. The H atom diffusion and accumulation are affected by H diffusivity at phase boundaries, H-trap binding energy and the number of traps in the steel.

Effect of C14 Laves/BCC on microstructure and hydrogen storage properties of (Ti32.5V27.5Zr7.5Nb32.5) 1-xFex (x = 0.03, 0.06, 0.09) high entropy hydrogen storage alloys

In order to explore the effect of C14 Laves/BCC on the hydrogen storage properties of high entropy hydrogen storage alloys, (Ti32.5V27.5Zr7.5Nb32.5) 1-xFex (x = 0.03, 0.06, 0.09) high entropy hydrogen storage alloys are prepared. The C14 Laves/BCC rises with the increase of Fe content. The C14 Laves phase provides a path for the diffusion of hydrogen atoms, so that defects with higher hydrogen binding energy capture more hydrogen atoms to ensure the increase of initial hydrogen absorption content in the activation process. The appropriate ratio of C14 Laves/BCC ensures that the main hydrogen absorbing phase BCC phase of high entropy hydrogen storage alloy plays a full role. The (Ti32.5V27.5Zr7.5Nb32.5) 0.94Fe0.06 high entropy hydrogen storage alloy possesses the best hydrogen absorption capacity of 3.19 wt% at 150 °C under 3 MPa hydrogen pressure. The gradual increase of Fe content makes the VEC value of C14 Laves phase rise, so that the hydrogen binding energy decreases. The factor reduces the thermal stability of metal hydrides. The reversible phase transition of BCC phase + metal C14 Laves phase → FCC phase + metal hydride C14 Laves phase → BCC phase + metal C14 Laves phase occurs in the whole cycle.

Stress corrosion cracking failure of X80 carbon steel U-bend caused by Desulfovibrio vulgaris biocorrosion

Sulfate reducing bacteria (SRB) are widely present in oil and gas industry, causing pitting corrosion on pipeline steel. Stress corrosion cracking (SCC) often occurs in the presence of mechanical stress before pitting perforation failure, leading to economic losses and even catastrophic accidents. In this study, stress distribution simulation using the finite element method (FEM), corrosion analysis techniques and electrochemical corrosion measurements were employed to investigate the SCC mechanism of X80 pipeline steel caused by Desulfovibrio vulgaris, which is a common SRB strain used in microbiologically influenced corrosion (MIC) studies. It was found that D. vulgaris MIC caused sharp microcracks on an X80 U-bend coupon after only 2 weeks of immersion at 37 °C in the deoxygenated ATCC 1249 culture medium inoculated with D. vulgaris. The X80 U-bend coupon's weight loss-based uniform corrosion rate for the 12 cm2 surface was 60% of that for the unstressed flat square coupon (2.3 mg cm−2 vs. 3.8 mg cm−2). This was likely because the square coupon had wide MIC pits, providing a larger effective surface area for more sessile cells (4.2×108 cells cm−2 on square coupon vs. 2.4×108 cells cm−2 on U-bend coupon) to attach and harvest more electrons. An SCC failure occurred on an X80 U-bend pre-cracked at the outer bottom after a 6-week immersion in the D. vulgaris broth. Apart from MIC damage, this could also be because D. vulgaris metabolism increased the availability hydrogen atoms on the steel surface, and promoted the diffusion of hydrogen atoms into the metal lattice, thus increasing the brittleness of the steel.

Hydrogen-enhanced fatigue crack growth of martensitic stainless steel: A predictive model and experimental validation

Atomic hydrogen (H) diffusion in metallic structures affects the mechanical properties of steel alloys. However, the effect of hydrogen embrittlement on the fatigue crack propagation rate (FCGR) is not fully understood, and serious uncertainties can affect the design and inspection schedules of hydraulic turbine runners based on the defect-tolerance approach. The FCGR in a complex microstructure such as tempered martensitic stainless steel is governed by the H content, stress distribution, and microstructure at the crack tip. The synergetic interactions between these parameters should be kinetically studied as the crack propagates. In this study, an original model was proposed to predict the influence of H on the fatigue crack propagation rate. The model was developed specifically for tempered martensitic stainless steels containing austenite. Subsequently, it was validated through experiments performed on 415 martensitic stainless steel containing 20% of reformed austenite (RA). The material’s FCGR was tested in its raw condition, also after charging with H. Compact tension (CT) specimens were tested at two constant stress intensity factor ranges (ΔK = 8 MPa.m0.5 and 15 MPa.m0.5) and three cyclic loading frequencies (f = 35 Hz, 3.5 Hz, and 0.35 Hz). The results show a very good agreement with the predictions of the model. Moreover, both the model and the experimental results reveal that there is a critical ΔK that is dependent on the loading frequency at which the impact of H on the FCGR is maximum. Moreover, as predicted by the model, a decrease in the loading frequency led to an increase in the susceptibility of the FCGR to H.

ZIF-67 derived Co nanoparticles on ZIF-Derived carbon for hydrogen spillover and storage

Hydrogen spillover involves the dissociation of H2 on transition metal nanoparticles and further atomic hydrogen surface migration on catalyst supports. Hence, the spillover phenomenon has been reported in applications of heterogeneous catalysis in hydrogenation and room-temperature hydrogen storage. However, a proper catalyst design is requisite to initiate hydrogen spillover, considering the transition metal particle dispersion, sorbent surface modification, porosity, etc. In this report, we pyrolyzed the zeolitic imidazolate framework ZIF-67 for residual Co metal nanoparticles and N-dopant on ZIF-derived carbon (ZDC) for hydrogen adsorption via spillover effect. Catalyst optimization by proper ZIF carbonization process regarding manipulated pyrolytic temperatures, atmospheres, and ramping rates, results in different properties in ZDCs. Well-distributed Co nanoparticles can be obtained on N-rich graphitic sorbent ZDCs with retained high specific surface area. The Co on ZDC exhibits improved room-temperature hydrogen capacity of 0.77 wt% than neat ZIF-67 of 0.09 wt% at 30 bar, 300 K. The adsorption sites were examined experimentally by nitrogen hydrogenation, and possible atomic hydrogen diffusion was evaluated theoretically showing energy barrier reduced by over 0.1 eV. It demonstrates that cobalt nanoparticles can successfully initiate hydrogen spillover on ZIF-derived carbon with nitrogen functionality, even without noble metals.

Numerical analysis of hydrogen atom diffusion and trapping at an unconstrained dent on pipelines

In this work, a three-dimensional finite element-based mechanics-diffusion coupling model is developed to determine the stress/strain distribution and hydrogen (H) atom concentration at an unconstrained dent on an X52 steel pipe which is to be used for transport of high-pressure hydrogen gas. Both von Mises stress and equivalent plastic strain concentrations and a high hydrostatic stress gradient exist at the dent. The distribution of H atom concentration coincides with that of the hydrostatic stress. The maximum H atom concentration in the steel lattice locates at the dent bottom, while the distribution of the H atom concentration at metallurgical traps is consistent with that of the equivalent plastic strain. A competitive effect exists between the hydrostatic stress and the plastic strain on the H atom distribution. At low initial H atom concentrations (e.g., 0.001 mol/m3), the equivalent plastic strain dominates the distribution of H atoms. At high initial H atom concentrations (e.g., 0.1 and 1 mol/m3), the hydrostatic stress is more important to determine the distribution of H atom concentration. As the dent depth increases, both the von Mises stress and plastic strain at the dent increases, while the total H atom concentration decreases due to decreased hydrostatic stress. When the internal pressure increases from 5 MPa to 15 MPa, there are slightly increases in von Mises stress, equivalent plastic strain and the total H atom concentration.

Study by finite element modeling of hydrogen atom diffusion and distribution at a dent on existing pipelines for hydrogen transport

Pipelines, especially existing natural gas pipelines, provide an efficient and economical means for hydrogen transport, accelerating realization of a full-scale hydrogen economy. However, the existing aged pipelines usually contain dents, which serve as effective traps to accumulate hydrogen atoms, potentially causing hydrogen embrittlement and pipeline failures. To date, there has been a strong interest in development techniques for assessment of hydrogen atom distribution at a dent on pipelines. In this work, a three-dimensional nonlinear finite element-based model was developed to investigate the hydrogen atom diffusion and distribution at a constrained dent on an X52 steel pipe. Parametric effects, including dent depth and internal pressure, were determined. The presence of a dent on pipelines drastically changes the local stress and strain distributions, facilitating diffusion and accumulation of hydrogen atoms at the dent. The minimum hydrogen atom concentration at the crystalline lattice sites, (i.e., 3.8 mol/m3) is located on the outer surface of the dent center, and the maximum hydrogen atom concentration (i.e., 12.1 mol/m3) is found on both sides of the dent with 103 mm from the dent center in the circumferential direction. The hydrogen atom concentration at trap sites at the dent is much lower than that at the lattice sites. The diffusion and accumulation of hydrogen atoms at the dent area is affected by two competitive mechanisms, i.e., hydrostatic stress and plastic strain, depending on the initial concentration of hydrogen atoms entering the interior of the pipe steel. At a low initial concentration such as 0.001 mol/m3, the equivalent plastic strain dominates the distribution of hydrogen atoms at the dent, and the hydrogen atom concentration at the lattice sites is much lower than the concentration at the trap sites. At high initial hydrogen atom concentrations such as 0.1 and 1 mol/m3, the hydrostatic stress is the dominant factor to determine the distribution of hydrogen atoms, which mainly accumulate at the lattice sites. With an increased depth of the dent, both the von Mises stress and plastic strain concentrations increase, and so is the hydrogen atom concentration. The increase of internal pressure from 5 MPa to 15 MPa only slightly elevates the von Mises stress, equivalent plastic strain and the hydrogen atom concentration.

Recent advances in magnesium hydride for solid-state hydrogen storage by mechanical treatment: A DFT study

In this paper, using density functional theory (DFT), we investigate the impact of mechanical treatment in terms of uniaxial and biaxial strains on both hydrogenation states of magnesium compounds i.e. H2-free magnesium (Mg) and preliminarily hydrogenated magnesium (MgH2). The thermodynamic properties calculation shows that applying uniaxial and biaxial strains on the H2-free magnesium does not significantly affect the formation enthalpy and decomposition temperature of the hydride phase. On the other hand, strain energy contributions on preliminarily hydrogenated magnesium are found able to decrease and improve the formation enthalpy and the decomposition temperature, making it feasible for the operational conditions of proton exchange membrane (PEM) fuel cells at 289 – 393 K. Also, the findings demonstrate that the kinetic properties in terms of hydrogen atom diffusion show a decrease in the activation energy barrier, which means an improvement in the kinetics properties faster than that of strain-free magnesium hydride. These results potentially provide better clues for the development of a magnesium-based metal hydride for hydrogen storage applications.

Theoretical insights into the methane catalytic decomposition on graphene nanoribbons edges.

Catalytic methane decomposition (CMD) is receiving much attention as a promising application for hydrogen production. Due to the high energy required for breaking the C-H bonds of methane, the choice of catalyst is crucial to the viability of this process. However, atomistic insights for the CMD mechanism on carbon-based materials are still limited. Here, we investigate the viability of CMD under reaction conditions on the zigzag (12-ZGNR) and armchair (AGRN) edges of graphene nanoribbons employing dispersion-corrected density functional theory (DFT). First, we investigated the desorption of H and H2 at 1200K on the passivated 12-ZGNR and 12-AGNR edges. The diffusion of hydrogen atom on the passivated edges is the rate determinant step for the most favourable H2 desorption pathway, with a activation free energy of 4.17eV and 3.45eV on 12-ZGNR and 12-AGNR, respectively. The most favourable H2 desorption occurs on the 12-AGNR edges with a free energy barrier of 1.56eV, reflecting the availability of bare carbon active sites on the catalytic application. The direct dissociative chemisorption of CH4 is the preferred pathway on the non-passivated 12-ZGNR edges, with an activation free energy of 0.56eV. We also present the reaction steps for the complete catalytic dehydrogenation of methane on 12-ZGNR and 12-AGNR edges, proposing a mechanism in which the solid carbon formed on the edges act as new active sites. The active sites on the 12-AGNR edges show more propensity to be regenerated due lower free energy barrier of 2.71eV for the H2 desorption from the newly grown active site. Comparison is made between the results obtained here and experimental and computational data available in the literature. We provide fundamental insights for the engineering of carbon-based catalysts for the CMD, showing that the bare carbon edges of graphene nanoribbons have performance comparable to commonly used metallic and bi-metallic catalysts for methane decomposition.

Electrochemical Hydrogen Storage Kinetics and Microstructure of the Rapidly Quenched Alloy Mg2Ni0.75Zn0.25

The Mg2Ni0.75Zn0.25 alloys are prepared from Mg2Ni as master alloy and pure Zinc ingot by remelting process in this work. The microstructures, electrochemical properties and desorption kinetics of the as-cast and melt-spun alloys are investigated. The phase compositions and microstructures of the alloys are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron backscattering diffraction (EBSD). The results show that the segregation atoms rich in Zn can inhibit the growth of Mg2Ni grains, especially the nanocrystalline grains formed in Mg2Ni0.75Zn0.25 alloy after melt-spinning process. The rapidly quenched Mg2Ni0.75Zn0.25 alloy exhibits the largest discharge performance (102.1 mAh g−1) and dehydrogenation activation energy (14.68 kJ mol−1). The improvement of the kinetic properties is related to the hydrogen diffusion rate (D) in the alloys and the charge transfer reaction on the surface. The rapidly quenched Mg2Ni0.75Zn0.25 alloy has the largest D, 6.187 × 10−11 cm2 s−1. The doping of Zn aggravates the corrosion of alloy electrodes, which destroys the oxide layer on the alloy surface, provides a channel for the diffusion of hydrogen atoms.

Quantum tunneling in the surface diffusion of single hydrogen atoms on Cu(001)

The adsorption and diffusion of hydrogen atoms on Cu(001) are studied using first-principles calculations. By taking into account the contribution of zero-point energy (ZPE), the originally identical barriers are shown to be different for H and D, which are respectively calculated to be ∼158 meV and ∼139 meV in height. Using the transfer matrix method (TMM), we are able to calculate the accurate probability of transmission across the barriers. The crucial role of quantum tunneling is clearly demonstrated at low-temperature region. By introducing a temperature-dependent attempting frequency prefactor, the rate constants and diffusion coefficients are calculated. The results are in agreement with the experimental measurements at temperatures from ∼50 K to 80 K.

Improvement of decomposition temperature and gravimetric density of [formula omitted] by transition metals and vacancies: A comparison study

An ab initio study is investigated to study the effects of transition metals and vacancies on the thermodynamic characteristics of magnesium hydride (MgH2) and compare the calculation results in terms of the decomposition temperature and the gravimetric density. The Green's function method is used to perform our calculations. In particular, the magnesium vacancies facilitate faster diffusion of hydrogen atoms within the MgH2 while the transition metals weaken the strong band between hydrogen and magnesium, which both improve the decomposition temperature. The creation of vacancies is more favorable than doping with transition metals in MgH2, with a concentration range of vacancies from 3.3 to 4.6% for practical use. In addition, the vacancies allow increasing the gravimetric density from 7.658 to 8.269 wt%, while using the transition metals reduces the density from 7.658 to 7.064 wt% for Mg1-xCrxH2 and 7.658 to 7.006 wt% for Mg1-xMnxH2.

Suppression of hydrogen embrittlement of gear steel 20CrMnTiH with pulsed electric current

When steel is smelted and used, hydrogen penetration will lead to hydrogen embrittlement, reduce the service life of materials, and even cause safety accidents. Various defects in steel can trap hydrogen atoms as hydrogen traps, resulting in high hydrogen content in materials. In this study, 20CrMnTiH gear steel billets with high hydrogen content were treated by electric pulse. It was found that the elongation and tensile strength of the samples treated by electric pulse were improved, which is attributed to the reduction of diffusible hydrogen content in the sample. Meanwhile, as an irreversible hydrogen trap, FeO's reduction makes it easier for hydrogen atoms to diffuse and escape under the electric field. Pulse current not only promotes the diffusion of hydrogen atoms, but also eliminates some hydrogen traps. The hydrogen control method under pulse current provides another alternative for solid state dehydrogenation and repair of hydrogen embrittlement fracture.

Measurements by SKPFM and Finite‐Element Modeling of Hydrogen Atom Diffusion and Distribution in Ferrite and Bainite Contained in X80 Steel

Herein, the diffusion and distribution of hydrogen (H) atoms in ferrite and bainite contained in an X80 pipeline steel is studied by both scanning Kelvin probe force microscopy and finite‐element modeling. The effect of metallurgical microphases on H‐atom accumulation in the steel is analyzed. The results show that H‐charging elevates the electrochemical dissolution activity of both ferrite and bainite contained in the steel, as indicated by the increased Volta potential and thus the decreased work function. The H atoms tend to accumulate at ferrite, making the local H‐atom concentration much greater than the concentration at bainite. The results imply that, compared with bainite, ferrite is the location to accumulate more H atoms initiating hydrogen‐induced cracks once the local H‐atom concentration reaches a threshold value.

A novel method towards improving the hydrogen storage properties of hypoeutectic Mg-Ni alloy via ultrasonic treatment

Ultrasonic treatment has great contributions on modifying the morphology, dimension and distribution of constituent phases during solidification, which serve as dominate factors influencing the hydrogen storage performance of Mg-based alloys. In this research, ultrasonic treatment is utilized as a novel method to enhance the de-/hydriding properties of Mg-2Ni (at.%) alloy. Due to ultrasonic treatment, the microstructure of as-cast alloy is significantly refined and homogenized. Ascribing to the increased eutectic boundaries and shortened distance inside α-Mg for hydrogen atoms diffusion, the hydrogen uptake capacities and isothermal de-/hydriding rates improve effectively, especially at lower temperature. The peak desorption temperature reduces from 392.99 °C to 345.56 °C, and the dehydriding activation energy decreases from 101.93 kJ mol−1 to 88.65 kJ mol−1. Weakened hysteresis of plateau pressures and slightly optimized thermodynamics are determined from the pressure-composition isotherms. Owing to the refined primary Mg, a larger amount of hydrogen with the higher hydriding proportion is absorbed in the first stage when hydrides nucleate in eutectic region and grow on primary Mg periphery subsequently before MgH2 colonies impinging, resulting in the enhancement of hydrogenation rates and capacities.

Hydrogen-surface interaction from first-principles calculations and its implication to hydrogen embrittlement mechanisms of titanium

Hydrogen embrittlement (HE) caused by the interaction between hydrogen and crack tip is the key factors for the stress corrosion crack (SCC) of titanium alloys utilized in marine environment. In the present work, the interactions between hydrogen and the fresh surface of crack tip in titanium, including the adsorption, desorption, diffusion of hydrogen atom near the surface, are investigated systematically by using a first-principles method. The surface energy of titanium with H adsorption is calculated. We show that H atoms are prone to adsorb on the surface of titanium and then accumulate beneath the surface whereas both desorption of H atoms to form H2 and diffusion of H atom into bulk cost energy. The surface energy decreases with increasing coverage of H, which reduces the fracture work of titanium. The H-induced reduction of the fracture work at the crack tip is expected to accelerate the crack propagation. The accumulation of H beneath the surface facilitates the formation of hydride ahead the crack tip which is critical for the hydride induced embrittlement. The H2 pressure mechanism is not supposed to be responsible for the HE of titanium because the desorption of H atoms from the surface to form H2 is energetically unfavorable.