Hydride Phase Research Articles

Atom probe tomography of deuterium-charged optimised ZIRLO

AbstractThis study investigates the morphology and composition of hydrides in Optimized ZIRLO following electrochemical deuterium charging. Both ZrO and ZrDx phases were formed upon charging. The interfaces between these phases are investigated by using atom probe tomography aided by cryogenic sample transfer. The Ga and Sn have formed a “net”-like structure at the original atom probe specimen surface, which is assumed to be associated with the boundaries between individual hydride laths/needles, as it thought to have formed as these species were excluded from the hydrides. Calculation of the D/Zr ratio throughout the sample allows for identification of the ZrDx phases, revealing the specimen consists of a complex arrangement of different hydride phases. In some areas there is small excess of D in the hydride, i.e. ZrD2+y. This result is interpreted as deuterium which was “frozen” as it was passing through the hydride during electrochemical charging. The observed microstructural changes and interfacial phenomena contribute valuable insights that may prove useful for improving the performance and safety of Zr alloys.

Direct observation of nanometer size hydride precipitations in superconducting niobium.

Superconducting niobium serves as a key enabling material for superconducting radio frequency (SRF) technology as well as quantum computing devices. Niobium has a high propensity for the uptake of hydrogen. At room temperature, hydrogen commonly occupies tetragonal sites in the Nb lattice as the metal (M)-gas (H) phase. When the temperature is decreased, however, a solid solution of Nb-H begins to precipitate. In this study, we show the first identified topographical features associated with nanometer-size hydride phase (Nb1-xHx) precipitates on the surface of the metallic superconducting niobium using cryogenic-atomic force microscopy (AFM). Further, high energy grazing incidence X-ray diffraction reveals information regarding the structure and stoichiometry of these precipitates. Finally, through time-of-flight secondary ion mass spectroscopy (ToF-SIMS), we locate atomic hydrogen sources near the top surface. This systematic study clarifies nanometer scale hydrides precipitated on the surface of the SRF Nb cavity that exhibit performance degradation at a high accelerating field regime.

Synthesis of Laves phase hydrides YFe2H6 and YFe2H7 at high pressure: reaching a limit of interstitial hydrogen uptake

The C15 Laves phase compound YFe2 has been extensively studied for its significant hydrogen absorption in its tetrahedral interstitial sites. It can stably hold up to five hydrogen atoms per formula unit under ambient conditions. However, the maximum hydrogen capacity in such Laves phase materials remains an open question. The use of high pressure is a tool that facilitates the formation of polyhydrides with high hydrogen-to-metal ratios. By subjecting YFe2H4.2 to hydrogen pressures up to 50 GPa in a diamond anvil cell without any heating, two new interstitial compounds, YFe2H6 and YFe2H7, were synthesized. Synchrotron X-ray diffraction and ab initio calculations reveal that these new compounds have ordered hydrogen atoms occupying two types of tetrahedral interstitial sites, A2B2 and B4, and a new triangular interstitial site AB2, in an orthorhombic structure distorted from the C15 Laves phase. The magnetic properties of YFe2Hx hydrides have to be taken into account to reproduce experimental volumes, identify stable compounds on the convex hull of the YFe2-H system, and explain deviations from Vegard’s law regarding volume expansion with hydrogen concentration. These compounds cannot be retrieved at ambient pressure upon pressure release.

Multiscale modeling of metal-hydride interphases—quantification of decoupled chemo-mechanical energies

The quantification of interphase properties between metals and their corresponding hydrides is crucial for modeling the thermodynamics and kinetics of the hydrogenation processes in solid-state hydrogen storage materials. In particular, interphase boundary energies assume a pivotal role in determining the kinetics of nucleation, growth, and coarsening of hydrides, alongside accompanying morphological evolution during hydrogenation. The total interphase energy arises from both chemical bonding and mechanical strains in these solid-state systems. Since these contributions are usually coupled, it is challenging to distinguish via conventional computational approaches. Here, a comprehensive atomistic modeling methodology is developed to decouple chemical and mechanical energy contributions using first-principles calculations, of which feasibility is demonstrated by quantifying chemical and elastic strain energies of key interfaces within the FeTi metal-hydride system. Derived materials parameters are then employed for mesoscopic micromechanical analysis, predicting crystallographic orientations in line with experimental observations. The multiscale approach outlined verifies the importance of the chemo-mechanical interplay in the morphological evolution of growing hydride phases, and can be generalized to investigate other systems. In addition, it can streamline the design of atomistic models for the quantitative evaluation of interphase properties between dissimilar phases and allow for efficient predictions of their preferred phase boundary orientations.

High-temperature structure, elasticity, and thermal expansion of ε-ZrH1.8

Zirconium hydride is a promising candidate material for nuclear microreactor applications as a solid-state moderator component, owing to its favorable neutronics properties and good thermal stability over other metal hydrides. In the present work, the crystal structure, thermal expansion, and elastic properties of the hydrogen-rich ε phase hydride were measured at elevated temperatures in the range 300–900 K. Samples were prepared by direct hydriding Zircaloy-4 metal – a nuclear-grade zirconium alloy. Room-temperature lattice parameters agree well with those reported from literature for unalloyed zirconium hydride and fall within an observed quadratic H-content dependence. The coefficients of thermal expansion, determined from lattice expansion and dilatometry, agree well within our work but were about 30 % lower than those reported by others for unalloyed hydrides. Density functional theory-based molecular dynamics simulations were used to compare with thermal expansion and elasticity measurements. Results showed lattice parameter temperature dependence and slope of thermal expansion align with those from measurements. Based on diffraction scans at select temperatures, ε phase remained stable in air up to at least 770 K. Likewise, dilatometry showed smooth thermal expansion up to the thermal decomposition temperature around 950 K. The precise decomposition temperature was not determined via diffraction due to sparse scanning. The complete elastic property measurements were gathered for ε-phase Ziracloy-4 hydride for the first time. Young's modulus was lower compared to the metal and δ hydride phases. High-temperature elasticity measurements were limited to <350 K due to acoustic dissipation effects.

Hydrogen implantation in lanthanum thin films for ambient pressure hydride formation

Near room temperature superconductivity of metal superhydrides has been shown both theoretically and experimentally at high pressures (>100 GPa). Taking advantage of room temperature superconductivity for engineering applications requires decreasing the pressure of formation while retaining the superconducting hydride phase. We implanted lanthanum thin films with various doses of hydrogen ions at ambient pressure in order to form a lanthanum hydride phase. We found evidence for granular superconductivity below 5 K consistent with the phase coexistence of lanthanum hydride and lanthanum. As the H+ dose increased, TC decreased from 4.6 K to 3.2 K with broader superconducting transitions. Transmission electron microscopy showed increased substrate damage with increased ion dose and confirmed the granular structure of the films. Although a superhydride phase requires a higher H+ dose than what was attained in this work, we have demonstrated that ion implantation at ambient pressure is a feasible technique for superconducting lanthanum hydride formation.

Study of the mechanisms of change in hydride phases in zirconium beryllide during its linear heating

Abstract Beryllides have a number of unique properties that make them promising for use in various fields of industry and energy. Since some of the beryllides have the potential to dissolve large amounts of hydrogen (in some cases forming hydride phases), there is some interest in evaluating their possible applications in hydrogen technologies. This paper presents the results of studies of changes in the phase composition of the zirconium beryllide deuteride compound during its linear heating. The studies were carried out using a complex method including thermal gravimetrical analysis (TGA), differential scanning calorimetry (DSC) and mass spectrometry. Based on the results of the experiments, a number of parameters were obtained characterizing the transitions of deuteride from the phase of the Orthorhombic I mma crystal structure of deuteride ZrBe2D into the Orthorhombic C mcm crystal structure of deuteride ZrBe2D0.67, as well as the decomposition parameters of Orthorhombic C mcm crystal structure of ZrBe2D0.67. The energies of endothermic reactions of the corresponding transitions and decompositions of deuteride phases were estimated, and the activation energy of the interaction of water vapor with the surface of zirconium beryllide samples was also estimated.

Uncovering the electrochemical stability and corrosion reaction pathway of Mg (0001) surface: Insight from first-principles calculation

An understanding of the anomalously enhanced hydrogen evolution reaction (HER) of magnesium (Mg) under anodic polarisation in aqueous corrosion is paramount for a predictive theory of its corrosion and metal electrocatalysis. Previous theoretical and experimental studies have proposed that sub-surface hydride phases play a role in this behaviour but the underlying atomic mechanisms remain unclear. By constructing theoretical surface Pourbaix diagrams, based on density functional theory (DFT) calculations, we have identified the atomic structure of a sub-surface hydride phase on the Mg (0001) surface that remains electrochemically stable under significant anodic overpotentials across a wide pH range. Specifically, this stability persists up to 0.38 VSHE under mildly alkaline conditions (e.g., pH = 8), thus providing thermodynamic support for the proposed hydride-enhanced HER under anodic conditions. Reaction barrier analysis establishes that the proposed sub-surface hydride phase could promote anodic HER via a Heyrovsky pathway, based on hydrogen outward diffusion, with an energy barrier of 1.54 eV as the rate-limiting step, showing an anodic characteristic and significantly favouring external anodic polarisation. Furthermore, we have established that the surface adsorption condition, contingent on both the pH and potential, significantly influences the mechanism and kinetics of the initial corrosion of Mg.

Mechanical behavior of zirconium hydride phases: insights from molecular dynamics based simulations

Mechanical behavior of zirconium hydride phases: insights from molecular dynamics based simulations

Using pulse current to tailor hydride networks while improving the strength and plasticity of pure titanium

Interstitial hydrogen atoms in titanium usually deteriorate the mechanical properties of titanium by brittle hydride phase or hydrogen-enhanced localized plasticity. In this study, hydride was used as the second phase to improve the tensile strength and elongation of TA1 pure titanium. The continuous coarse hydride network is precipitated in TA1 pure titanium after the hydrogen-charged. Then pulse current treatment is used to decompose the original coarse hydride network and reduce the size and number of hydride strips. Finally, a small uniform hydride network is formed in TA1 pure titanium. The results of tensile experiments indicate that the tensile strength of hydrogen-charged TA1 pure titanium treated by pulse current increases from the 286.4 MPa to 316.1 MPa and the elongation increases from the 47.6 % to 56.8 %. The improvement of mechanical properties demonstrate that the small and uniform hydrides can significantly improve the mechanical properties of TA1 pure titanium. In hydrogen-charged TA1 pure titanium treated by pulse current, the increment of strength is mainly caused by hard phase hydrides, and the increase in plasticity is attributed to the role of twins in coordinating deformation during plastic deformation. This study manifests that in addition to being used as a temporary alloying element to optimize the microstructure of titanium, hydrogen can also be directly act as a second phase in titanium to improve the mechanical properties.

Investigation on the hydrogen storage properties, electronic, elastic, and thermodynamic of Zintl Phase Hydrides XGaSiH (X = sr, ca, ba)

This study presents a comprehensive investigation of the electronic, mechanical, and thermodynamic properties of Zintl phase hydrides XGaSiH (X = Sr, Ca, Ba) using Density Functional Theory (DFT) and the FP-LAPW method within the WIEN2k package. Our analysis covers the structural stability, electronic properties, and hydrogen interaction mechanisms in these compounds. The hydrides exhibit narrow band gaps, with values ranging from 0.1 to 0.5 eV using GGA and LDA functionals, and 0.6–1.0 eV with mBJ-GGA and mBJ-LDA. The hydrogen storage capacities are determined to be 0.34 wt %, 0.47 wt %, and 0.40 wt % for SrGaSiH, CaGaSiH, and BaGaSiH, respectively, highlighting their potential for energy storage applications. Thermodynamic properties, evaluated through the quasi-harmonic Debye model, provide insights into the Grüneisen parameter, heat capacity, and thermal expansion coefficient over a range of pressures (0–50 GPa) and temperatures (up to 1000 K). Elastic constants reveal that these compounds are mechanically stable, with a notable anisotropy in the {100} plane and varying degrees of compressibility among the different hydrides. Our study further highlights the slightly ordered hexagonal Ga and Si layers, which contribute to the enhanced hydrogen storage capabilities of these materials. The compounds demonstrate high structural stability, facilitating effective hydrogen retention and release at practical temperatures, making them promising candidates for hydrogen storage applications. Additionally, the analysis of electronic band structures and density of states suggests significant conductivity potential, with band gaps ranging from 0.1 to 1.0 eV, depending on the computational method used. The unique combination of structural, electronic, thermodynamic, and mechanical properties in XGaSiH compounds positions them as valuable materials for renewable energy applications. These findings lay the groundwork for future research focused on optimizing these materials through structural modifications or doping to enhance performance metrics such as hydrogen storage capacity and electrical conductivity.

Effect of Mn substitution on crystal structure and cyclic property of Y–Ni alloy with superlattice structure

This study investigated the crystal structure, P–C isotherm, and cyclic properties of YNi3. We discovered that hydrogen-induced amorphization (HIA) was appeared in three cycles of P–C isotherm at 303 K, but it was not observed at 273 K. An analysis of the three cycles at 303 K revealed a 55 % decrease in hydrogen capacity as compared to the first cycle. To enhance the hydrogenation properties, Mn was substituted for Ni. X-ray Rietveld refinements on YNi2·7Mn0·3H3.8 reveal that the hydride phase retains the PuNi3-type structure of the original alloy. The values of a, c, the unit cell, the MgZn2-type cell, and the CaCu5-type cell expanded 5.6 %, 9.3 %, 21.9 %, 25.0 %, and 18.8 % from the original alloy. The results indicated that YNi2·7Mn0.3 retained 91 % of its initial hydrogen capacity after three cycles at 303 K. After 120 cycles in the cyclic test, YNi3 and YNi2·7Mn0.3 retained 42 % and 90 % of their initial capacity, respectively. The XRD profile of YNi3 after 120 absorption-desorption cycles revealed significant peak broadening. Similarly, peak broadening was also observed in the XRD profile of YNi2·8Mn0.2 after 120 cycles. In comparison, the XRD profile of YNi2·7Mn0.3 after 120 cycles remained relatively unchanged from its initial state. It was observed that YNi2·7Mn0.3 experienced less lattice strain during hydrogenation than YNi2·8Mn0.2.

Neural network potential for Zr-H

The introduction of Hydrogen (H) into Zirconium (Zr) influences many mechanical properties, especially due to low H solubility and easy formation of Zirconium hydride phases. Understanding the various effects of H requires studies with atomistic resolution but at scales that incorporate defects such as cracks, interfaces, and dislocations. Such studies thus demand accurate interatomic potentials. Here, a neural network potential (NNP) for the Zr-H system is developed within the Behler-Parrinello framework. The Zr-H NNP retains the accuracy of a recent NNP for hcp Zr and exhibits excellent agreement with first-principles density functional theory (DFT) for (i) H interstitials and their diffusion in hcp Zr, (ii) formation energies, elastic constants, and surface energies of relevant Zr hydrides, and (iii) energetics of a common Zr/Zr-H interface. The Zr-H NNP shows physical behavior for many different crack orientations in the most-stable ε-hydride, and structures and reasonable relative energetics for the 〈a〉 screw dislocation in pure Zr. This Zr-H NNP should thus be very powerful for future study of many phenomena driving H degradation in Zr that require atomistic detail at scales far above those accessible by first-principles.

Hydrogen Absorption and Self-Corrosion of Mg Anode: Influence of Aqueous Electrolyte Species

This review examines the impact of various aqueous electrolytes on hydrogen absorption and self-corrosion in magnesium (Mg) anodes. The discussion integrates both historical and recent studies to explore the mechanisms behind self-corrosion and anomalous hydrogen evolution (HE) under conditions of the Negative Difference Effect (NDE) and Positive Difference Effect (PDE). The focus is on the formation and oxidation of magnesium hydride in regions of active dissolution under NDE conditions. In the case of PDE, anodic dissolution occurs through the passive MgO-Mg(OH)₂ film, which shields the metal from aqueous electrolytes, thereby reducing hydrogen absorption and abnormal HE. The NDE conditions showed delayed reduction activity at the surface, attributed to a hydride phase within the corrosion product layer. Hydride ions were quantified through their anodic oxidation in an alkaline electrolyte, measured by the electric charge passed. The review also considers the role of de-passivating halide ions, electrolyte acidity buffering, and the addition of ligands that form stable complexes with Mg2⁺ ions, on the rates of hydride formation, self-corrosion, and anodic dissolution of Mg. The study evaluates species that either inhibit or promote hydrogen absorption and self-corrosion.

Effect of rotation speed on hydrogen storage properties of Ti45Zr38Ni17 alloy ribbons produced by melt spinning

Abstract Ti/Zr-based icosahedral (i) quasicrystals are believed to have a Bergman-type cluster with a large number of tetrahedral interstitials, making them attractive as potential hydrogen storage materials. In this study, Ti45Zr38Ni17 alloy ribbons were prepared by melt spinning at different rotation speeds, and the effect of the rotation speed on the microstructures and hydrogen storage capacities was investigated. The i-phase with a small amount of Ti2Ni phase and/or some minor crystal phase was identified after melt spinning, but the amount of amorphous phase increased and the Ti2Ni and the other crystal phases decreased with increasing rotation speed. After gaseous hydrogen loading at 573 K and a pressure of 3 MPa, a hydride phase was observed in the samples with more amorphous phase, suggesting that the amorphous phase turned into the hydride phase. The maximum gaseous hydrogen capacity (H/M), 1.31, was obtained for the sample with more i-phase. After electrochemical hydrogen loading, a slightly higher maximum discharge capacity was observed in a less-quality quasicrystal sample at the first loading, that decreased drastically after the second cycle, but gradually increased with increasing cycling up to 20 cycles. The maximum hydrogen discharge capacity obtained in sample with more i-phase, reached about 10 mAh/g, while the less-amount one 4 mAh/g, suggesting the i-phase has higher hydrogen capacity than the crystal and the amorphous phases.

Hydrogen penetration into the NiTi superelastic alloy investigated in-situ by synchrotron diffraction experiments

Microstructural changes induced by a hydrogen permeation into the NiTi superelastic alloy were investigated in-situ using the X-ray synchrotron diffraction. A new design of an electrochemical cell enabled to uncover time and position dependent processes under a flat alloy surface exposed to the cathodic hydrogen. The diffraction data supported by thermo-elastic FEM calculations helped to quantify an evolution of compressive stresses in the B2 austenitic phase hosting hydrogen atoms. The compressive stress state initiates a formation of martensitic phases starting from the exposed surface layer and advancing into the alloy volume with increasing time of hydrogen charging. We have performed the ab-initio DFT study in order to rationalize volumetric changes associated with variations in the B2 austenite and B19′ martensite lattice parameters. The numerical results also contributed to the identification of a new hydride phase with orthorhombic crystal structure and lattice parameters a = 0.8505 nm, b = 0.7366 nm and c = 0.4722 nm.

Unexpected Ag-H bond in the predictive silver hydride phase under high pressure

Silver, typically acknowledged for its inertness toward hydrogen under standard conditions, exhibits a noteworthy shift in reactivity under elevated pressures. Employing first-principles variable-composition evolutionary search calculations, our investigation unveils the presence of thermodynamically stable Ag-H compounds. A novel stoichiometry, Ag2H, characterized by P3¯m1 symmetry, emerges as the thermodynamically stable phase at 100 GPa. Notably, the trigonal-Ag2H phase at 100 GPa demonstrates both mechanical and dynamic stability, as ascertained through the computation of elastic constants and phonon dispersions, respectively. Examination of the electronic band structure and density of states manifests the metallic nature of the resulting Ag2H compound. A comprehensive analysis involving crystal orbital bond index, Bader charge, and charge density plots substantiates the ionic character of Ag2H, attributable to effective charge transfer from silver atoms to hydrogen. Furthermore, application of the Allen-Dynes modified McMillan equation indicates the absence of superconducting behavior in Ag-H systems at the elevated pressure of 100 GPa.

Electrosynthesis of Unusual Nonfcc Palladium Hydride Nanoparticles.

Intercalation of hydrogen into the palladium atomic layers during the growth of Pd nanoparticles can lead to the synthesis of unique palladium hydride phases. Here, we discover an unusual nonfcc palladium hydride nanoparticle, a structure that is not face-centered cubic (fcc), formed through coreduction of water molecules and Pd ions in solution. Crystal structure determination based on atomic electron tomography points to potential triclinic unit cells, indicating the presence of more than one nonfcc phase, with some of those being a stack of loosened and distorted close-packed layer of atoms. The probability of finding the nonfcc phase in single-crystalline particles varies depending on the number and distribution of contact area with other particles. Roughly half of the isolated and one side-coalesced single-crystal particles exhibit a nonfcc structure, while fcc dominates multiple side-coalesced single crystals as well as polycrystal particles. These observations suggest a coalescence-induced phase transition from a nonfcc to a stable fcc structure, due to the metastable nature of the nonfcc phases. While hydrogen is proven to be a key component for the synthesis of the nonfcc structure, there was limited formation of the unusual phase in a H2 gas bubbling system. Thus, electrochemical pathways can be promising for the in situ creation and study of unique metastable nanomaterials.

In-situ EBSD analysis of hydride phase transformation and its effect on micromechanical behavior in Zircaloy-4 under uniaxial tensile loading

In this work, hydrogen charged Zircaloy-4 has been investigated under an in-situ electron backscatter diffraction during tensile loading. Aim were, first, to distinguish the hydride phase type and its spatial distribution, second to determine hydride phase transformation (HPT) and orientation relationship (OR) subjected to uniaxial tensile condition, and third to correlate the hydrides evolution and their effect on the micromechanical behavior, such as slip mode activation and lattice rotation, of Zircaloy-4. Apart from the applied stress, the analysis reveals that hydride reorientation is strongly related to temperature and loading mode. We noted that deformation induced δ-ZrH1.5 transformed to γ-ZrH and ε-ZrH2, and the former follows the confirmed OR {0001}α//{111}δ/γ with <11 2‾ 0>α//<110>δ/γ, while the latter's OR changed to {10 1‾ 0}α//{121}ε with <11 2‾ 0>α//<100>ε after HPT. The coexistence of δ-ZrH1.5 and γ-ZrH or ε-ZrH2 is observed, and the main corresponding OR is {111}δ//{111}γ with <121>δ//<121>γ, and {100}δ//{110}ε with <110>δ//<100>ε, respectively. The characterized microstructure and the measured lattice rotation results indicate that HPT delayed cracking in hydride and promoted deformation in parent grains. As the strain increases, the maintenance of hydride-matrix (H-M) coherent interfaces restricts further lattice rotation. HPT accelerates the hydride decomposition ascribed to the intensification of hydrogen diffusion under stress, and the hydride and the H-M interfaces act as priority sites for initiating microcracks. The sequence of HPT depends on the possibility of activated slip mode among grains. These findings contribute to developing the understanding of the HPT and hydrogen embrittlement.

Effect of double substitution on hydrogen absorption-desorption properties of Ti2CrV alloy

Doubly substituted Ti2CrV alloy with composition Ti1.5Sc0.3CrVNi0.2 was prepared by arc melting method followed by annealing. The annealed alloy exists in body centred cubic (BCC) structure and shows fast kinetics for hydrogen absorption and desorption at room temperature. BCC phase of the alloy undergoes phase transformation to face centred cubic (FCC) hydride phase with H atoms occupying tetrahedral sites in the lattice, reaching an overall H/M ratio >2.2 (storage capacity ∼ 4 wt%). Storage capacity decreases by 40% in the 2nd cycle and then stabilizes at a value of ∼2.5 wt% for the subsequent 10 cycles. A drastic reduction in hydride desorption temperature upon double substitution (Sc and Ni substitution in Ti2CrV alloy) has been confirmed by DSC studies. Furthermore, the change in isotope effect in doubly substituted Ti2CrV alloy is discussed in light of thermal stabilities of the hydrides and deuterides.