Hydride Phase Transformation Research Articles

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.

Exploring solute-defect interactions in nanosized palladium hydrides across multiple time scales

We employ two different atomistic methods to investigate solute-defect interactions in nanosized palladium–hydrogen (Pd–H) systems across multiple time scales. The first method, referred to as Diffusive Molecular Dynamics (DMD), focuses on capturing hydride phase transformation and the evolution of solute-induced lattice defects over a diffusive time scale. The second method, Molecular Dynamics (MD), provides more detailed insights into atomic movements and lattice relaxation over the time scale of thermal vibrations. These two methods are connected with MD simulations initialized using statistical measures of microscopic variables obtained from DMD at different H/Pd ratios. Our study demonstrates that DMD effectively captures the propagation of an atomistically sharp hydride phase boundary as well as the dynamics of solute-induced misfit dislocations and stacking faults. While the H-concentrated phase leads to a reduction in the vibrational energy, the presence of stacking faults locally increases the vibrational energy of both Pd and H atoms. Furthermore, the MD simulation results align with DMD in terms of equilibrium potential energy, the preservation of hydride phase boundary, and the spatial distribution of stacking faults. We thoroughly characterize the lattice crystalline structures in four key regions of the particle. We observe a preference for H atoms to occupy tetrahedral interstitial sites near stacking faults due to the lower stacking fault energies provided by these sites within the H-concentrated phase.

Revealing the role of hydrogen content on the mechanical behavior and cracking mechanisms of Zircaloy-4 under strain

The mechanical property of zirconium-alloy reactor cladding materials inevitably degrades because of hydrogen absorption and hydride precipitation. In this study, mechanical behavior and delayed hydrogen cracking (DHC) mechanisms of Zircaloy-4 alloys with a broad range of hydrogen contents were investigated. Scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM), and a universal testing machine were jointly employed for this purpose. Results showed that the mechanical property of the hydrogenated specimen not only depended on the size and orientation of hydride, but also was affected by the continuity degree of the load-bearing matrix. The relevant microstructural observation indicated that the lower continuity degree of the load-bearing matrix, the less ductility of Zircaloy-4. More importantly, hydride phase transformation from δ-ZrH 1.5 to γ-ZrH occurred around the crack tip and reduced the local strain, while twinning just appeared at the crack bridging sites in the higher hydrogen-content specimens for changing the crystal orientation and mitigating the local stress concentration. Both those effects are expected to be potential mechanisms of the reappearing yield phenomenon because they are closely linked to dislocation movement. Additionally, based on the combination effect of crack blunting of γ-ZrH and the strain accommodation of twinning, the trend of crack propagation is delayed locally as expected. • The hydride phase transformation and twinning phenomenon around cracks were analyzed using EBSD. • The continuity of the load-bearing matrix profoundly influenced the mechanical properties of hydrided zircaloy-4. • The appearance and disappearance of yield-suppression phenomenon in hydrided zircaloy-4 were investigated. • Both γ-ZrH and twins are beneficial to delay the localized crack propagation.

Structure of a seeded palladium nanoparticle and its dynamics during the hydride phase transformation

Palladium absorbs large volumetric quantities of hydrogen at room temperature and ambient pressure, making the palladium hydride system a promising candidate for hydrogen storage. Here, we use Bragg coherent diffraction imaging to map the strain associated with defects in three dimensions before and during the hydride phase transformation of an individual octahedral palladium nanoparticle, synthesized using a seed-mediated approach. The displacement distribution imaging unveils the location of the seed nanoparticle in the final nanocrystal. By comparing our experimental results with a finite-element model, we verify that the seed nanoparticle causes a characteristic displacement distribution of the larger nanocrystal. During the hydrogen exposure, the hydride phase is predominantly formed on one tip of the octahedra, where there is a high number of lower coordinated Pd atoms. Our experimental and theoretical results provide an unambiguous method for future structure optimization of seed-mediated nanoparticle growth and in the design of palladium-based hydrogen storage systems.

Delayed-hydride cracking (DHC) of cladding materials: An analysis for storage and disposal of spent nuclear fuel

This paper assesses potential delayed-hydride cracking (DHC) of cladding materials in long-term storage and disposal of spent nuclear fuel (SNF). The potential stress development of cladding is evaluated based on time-dependent UO2 matrix swelling by alpha-decay irradiation effects, especially. Quantitative assessment of thermal swelling is used as a mathematical representation for the irradiation-induced swelling. The stress developed could be sufficient to cause DHC in very long-term storage and disposal of high burnup SNF. Hydride nucleation process is presented to explain time-dependent DHC process. Hydrogen super-saturation theories are also evaluated further. The hydrogen super-saturation comes from (i) crystalline hydride phase transformation, (ii) temperature decrease with time, and (iii) spatial thermal gradient. The nucleation, growth and fracture of hydride from hydrogen super-saturation at below 180 °C are considered to decrease the threshold stress intensity factor for DHC. Various relevant models for nucleation, growth and fracture of hydride, laboratory test data and reactor operation experience are discussed to check for self-consistency and DHC consequence.

Atomistic modeling and analysis of hydride phase transformation in palladium nanoparticles

Palladium-hydrogen (Pd-H) is a prototypical system for studying solute-induced phase transformation in various energy conversion and storage applications. While the behaviors of bulk Pd-H have been studied extensively, the detailed atomic picture of hydride phase transformation within individual Pd nanoparticles is still unclear. In this work, we employ a novel atomistic computational model, referred to as Diffusive Molecular Dynamics (DMD), to characterize the H absorption dynamics in Pd nanoparticles of spherical, octahedral and cubic shapes. The DMD model couples a non-equilibrium thermodynamic model with a discrete diffusion law, which allows it to reach diffusive time scales with atomic resolution. The model is capable of capturing the propagation of an atomistically sharp hydride phase boundary. A remarkable feature of the phase boundary structure that is predicted by the calculations is the emergence of misfit dislocations distributed over the interface. These dislocations relieve the elastic residual stresses induced by the change of volume that accompanies the phase transformation. Shape effects are also investigated in this work. More specifically, in both spherical and octahedral nanoparticles, we observe stacking faults during the H absorption process while the phase boundary in the cubic nanoparticle remains coherent. The spatial distribution of the stacking faults in the spherical sample is investigated in detail using an elastic core-shell model. We also identify the mechanisms that enable the movement of the stacking faults as they track the propagation of the phase boundary. Finally, we find that the rate of H absorption is reduced by the formation and movement of the stacking faults.

Phase analysis of hydride blister in zirconium alloy

This paper mainly concerns phase analysis of hydride blister and phase transformation at elevated temperature with Zircaloy-4 cladding. With electron diffraction patterns from the blister sample, single δ phase hydride is selected, especially, to investigate the phase transformation of δ-hydride with TEM. Under the rapid cooling condition, single δ-hydride transforms to heterogeneous ultrafine lamellar-like structure with the δ and γ-hydride phases. However, the phase transformation from δ-hydride to γ-hydride has not been reported around δ-phase domain in the Zr-H phase diagram, and thus, we suggest that the γ-hydride is able to be generated in the δ phase domain as well as in the α+δ phase domain. It is also proven that the γ phase tends to transform to the stable δ phase with sufficient holding time at the elevated temperature during in-situ TEM experiment.

The self-healing of defects induced by the hydriding phase transformation in palladium nanoparticles

Nanosizing can dramatically alter material properties by enhancing surface thermodynamic contributions, shortening diffusion lengths, and increasing the number of catalytically active sites per unit volume. These mechanisms have been used to explain the improved properties of catalysts, battery materials, plasmonic materials, etc. Here we show that Pd nanoparticles also have the ability to self-heal defects in their crystal structures. Using Bragg coherent diffractive imaging, we image dislocations nucleated deep in a Pd nanoparticle during the forward hydriding phase transformation that heal during the reverse transformation, despite the region surrounding the dislocations remaining in the hydrogen-poor phase. We show that defective Pd nanoparticles exhibit sloped isotherms, indicating that defects act as additional barriers to the phase transformation. Our results resolve the formation and healing of structural defects during phase transformations at the single nanoparticle level and offer an additional perspective as to how and why nanoparticles differ from their bulk counterparts.

Imaging the Hydrogen Absorption Dynamics of Individual Grains in Polycrystalline Palladium Thin Films in 3D.

Defects such as dislocations and grain boundaries often control the properties of polycrystalline materials. In nanocrystalline materials, investigating this structure-function relationship while preserving the sample remains challenging because of the short length scales and buried interfaces involved. Here we use Bragg coherent diffractive imaging to investigate the role of structural inhomogeneity on the hydriding phase transformation dynamics of individual Pd grains in polycrystalline films in three-dimensional detail. In contrast to previous reports on single- and polycrystalline nanoparticles, we observe no evidence of a hydrogen-rich surface layer and consequently no size dependence in the hydriding phase transformation pressure over a 125-325 nm size range. We do observe interesting grain boundary dynamics, including reversible rotations of grain lattices while the material remains in the hydrogen-poor phase. The mobility of the grain boundaries, combined with the lack of a hydrogen-rich surface layer, suggests that the grain boundaries are acting as fast diffusion sites for the hydrogen atoms. Such hydrogen-enhanced plasticity in the hydrogen-poor phase provides insight into the switch from the size-dependent behavior of single-crystal nanoparticles to the lower transformation pressures of polycrystalline materials and may play a role in hydrogen embrittlement.

Three-dimensional imaging of dislocation dynamics during the hydriding phase transformation

Crystallographic imperfections significantly alter material properties and their response to external stimuli, including solute-induced phase transformations. Despite recent progress in imaging defects using electron and X-ray techniques, insitu three-dimensional imaging of defect dynamics remains challenging. Here, we use Bragg coherent diffractive imaging to image defects during the hydriding phase transformation of palladium nanocrystals. During constant-pressure experiments we observe that the phase transformation begins after dislocation nucleation close to the phase boundary in particles larger than 300 nm. The three-dimensional phase morphology suggests that the hydrogen-rich phase is more similar to a spherical cap on the hydrogen-poor phase than to the core-shell model commonly assumed. We substantiate this using three-dimensional phase field modelling, demonstrating how phase morphology affects the critical size for dislocation nucleation. Our results reveal how particle size and phase morphology affects transformations in the PdH system.

Phase equilibria of Ce–Mg–Ni ternary system at 673 K and hydrogen storage properties of selected alloy

The isothermal section of Ce–Mg–Ni ternary system at 673 K was constructed through thermodynamic calculation coupled with experimental verification. Under guidance of the phase diagram in Mg-rich corner, Ce2.92Mg91.84Ni5.24 was designed to investigate its hydrogen storage properties. Moreover, the mechanism of α-to-β (α: diluted phase and β: hydride) phase transformation in the Ce2.92Mg91.84Ni5.24–H2 system was elucidated by in situ synchrotron powder X-ray diffraction (SR-PXRD). The alloy showed a good activated ability and displayed two plateaus in the pressure–composition–temperature curves. The kinetic mechanisms of hydriding and dehydriding reactions were analyzed by Chou model. The rate-controlling steps were the diffusion for the initial stage in hydriding reaction and the surface penetration for dehydriding reaction. SR-PXRD patterns indicated that the activated Ce2.92Mg91.84Ni5.24 gradually transformed into CeH2.51, (Mg) (with solid solution of H atoms) and Mg2NiH0.3, finally transformed into CeH2.51, MgH2 and Mg2NiH4 during the first hydriding process.

Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles.

Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. Our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.

Ti(Ni,Cu) pseudobinary compounds as efficient negative electrodes for Ni–MH batteries

The effect of Ni by Cu substitution on the structural, solid–gas and electrochemical hydrogenation properties of TiNi has been investigated. Pseudo-binary TiNi1−xCux (x ≤ 0.5) compounds have been synthesized by induction melting. They crystallize in B2 structure above 350 K and either in B19′ (x < 0.1) or B19 (0.2 ≤ x ≤ 0.5) at room temperature (RT). For all compounds, Pressure-Composition Isotherms at 423 K exhibit a single slopping plateau pressure within the range 10−3–1 MPa of hydrogen pressure revealing a metal to hydride transformation. Both the hydrogenation capacity and the hydride stability decrease with Cu-content. The hydrided pseudobinary compounds crystallize in the tetragonal S.G. I4/mmm structure as for TiNi hydride. The electrochemical discharge capacity increases with Cu content from 150 mAh g−1 for TiNi up to 300 mAh g−1 for TiNi0.8Cu0.2 and then decreases again for larger Cu amounts. Electrochemical isotherms and in-situ neutron diffraction measurements at RT demonstrate that such a capacity increase results from a metal to hydride phase transformation in which the hydride phase is destabilized by Cu substitution. The TiNi0.8Cu0.2 compound exhibits interesting cycling stability for 30 cycles and good high-rate capability at D/2 rate. This compound has promising electrochemical properties as compared to commercial LaNi5-type alloys with the advantage of being rare-earth metal free.

Mechanism of the α-to-β phase transformation in the LaNi 5–H 2 system

High-energy synchrotron in situ X-ray powder diffraction has been used to elucidate the mechanism of the hydriding phase transformation in a LaNi 5 model hydrogen storage intermetallic in real time. The transformation proceeds at 10 °C via the transient growth of an interfacial phase, the γ phase, with lattice parameters intermediate between those of the α (dilute solid solution) and β (concentrated hydride) phases. The γ phase forms to partially accommodate the 24% change in unit cell volume between the α and β phases during hydriding and dehydriding. The α, γ and β phases coexist at the nanoscopic level.

Hydrogen related peaks in Cu–LaNi 4.7Al 0.3

In this work, the effect of Ni substitution by Cu in the LaNi 4.7Al 0.3 hydride-forming alloy was studied in order to apply it to the negative electrodes of Ni–MH batteries. SEM, EDS and X-ray diffraction techniques were used to analyze the microstructure, composition and crystalline structure of the samples. A maximum electrochemical discharge capacity of 130 mAh/g was obtained. Internal friction (IF) and shear modulus ( G) were measured by means of low frequency mechanical spectroscopy, between 100 and 450 K. In the electrochemical activated sample, two main IF peaks and typical relaxation steps in G showed up at 200 and 280 K. The first is ascribed to interactions between hydrides and H atoms in solid solution and dislocations, while the last one is attributed to the β ↔ α hydride phase transformation.

Delayed hydride cracking of spent fuel rods in dry storage

Failures of zirconium alloy cladding tubes during a long-term storage at room temperature were first reported by Simpson and Ells in 1974, which remains unresolved by the old delayed hydride cracking (DHC) models. Using our new DHC model, we examined failures of cladding tubes after their storage at room temperature. Stress-induced hydride phase transformation from γ to δ at a crack tip creates a difference in hydrogen concentration between the bulk region and the crack tip due to a higher hydrogen solubility of the γ-hydride, which is a driving force for DHC at low temperatures. Accounting for our new DHC model and the failures of zirconium alloy cladding tubes during long-term storage at room temperature, we suggest that the spent fuel rods to be stored either in an isothermal condition or in a slow cooling condition would fail by DHC during their dry storage upon cooling to below 180 °C. Further works are recommended to establish DHC failure criterion for the spent fuel rods that are being stored in dry storage.

Changes in the grain and fine structures of palladium as a result of hydrogen phase naklep

Changes in the grain and fine structures of palladium that occur after the occurrence of reverse β → α hydride phase transformation in the metal are studied. It is shown that hydrogen treatment does not change the microstructure of palladium but strongly affects its fine structure.

X-ray diffraction cell for studying solid–gas reactions under gas pressures to 100 bar

A pressure cell designed for high-energy X-ray diffraction in transmission mode is described. The cell is intended for use at temperatures up to 573 K with samples that are large enough to permit the real-time determination of the amount of absorbed gas by measuring the gas pressure. The design is driven by the need to ensure that the sample temperature is constant and uniform, despite the heat flow accompanying the reaction between the gas and the sample. The use of the cell is illustrated by its application to elucidating the hydriding phase transformation in the LaNi5–H2system.

Mechanical properties and fine structure of annealed and HPN-treated palladium

Strengthening of palladium using hydrogen-induced transformation hardening (“hydrogen phase naklep” (HPN)) in the course of the reverse β → α hydride phase transformation in palladium-hydrogen alloys has been studied. It has been shown that the degree of HPN is mainly determined by the difference of the specific volumes of the transforming phases. As the transformation temperature decreases and the difference of the specific volumes of the transforming phases increases, the degree of strengthening of palladium during HPN systematically increases and its plasticity decreases, which is accompanied by an increase in the dislocation density and magnitude of microdistortions and by a decrease in the dimensions of the mosaic blocks.

Pressure-Induced Phase Transformations in Li-based Complex Hydrides

AbstractAn overview of the pressure-induced transformations and order-disorder phenomena in LiAlH4 (up to 7 GPa) and LiNH2 (up to 25 GPa) are presented. The analysis of pressure-induced changes in Raman spectra suggest a phase transition at ∼3 GPa for LiAlH4 and ∼14 GPa for LiNH2. New results on the metastable recovery of the high pressure β-LiAlH4 phase are also presented. An examination of the lattice translational and librational modes reveals that the high pressure β-LiAlH4 phase is disordered while there is evidence of orientational ordering in the high pressure beta-LiNH2 phase.