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Nucleation is a fundamental part in most syntheses of ceramic materials. Yet, few techniques enable control of this step, which would offer possibilities to attain full-scale kinetic selectivity of the syntheses to reach novel compounds with unique properties. Herein, we present a nucleation-controlled crystallization pathway to synthesize coatings of aluminum titanate (Al2TiO5)─renowned for its low-to-negative thermal expansion─at significantly reduced temperatures than conventional solid-state techniques. Based on a kinetic study using in situ X-ray diffraction, detailed mechanistic insights into the crystallization process and phase evolutions within the Al–Ti–O system are obtained. The lowest activation energies for crystallization are given when the Al–Ti ratio is close-to-stoichiometric or Ti-enriched. Along with these compositions’ similar kinetics at the earliest stages of the transformation, a joint nucleation behavior is discovered, revealing the elemental role of titanium in nucleating the main Al2TiO5 phase. Based on classical nucleation theory, we deduce the significant influence of the configurational entropy (Sconfig) when crystallization occurs in the nucleation-controlled domain. Finally, peculiar transition features are observed in the Al-enriched regime during annealing at intermediate temperatures, whose causes are ascribed to the presence of secondary nucleation events and possibilities of structural relaxations in the amorphous matrixes when crystallizing.

Solid-state hydrogen storage materials that are optimized for specific use cases could be a crucial facilitator of the hydrogen economy transition. Yet the discovery of novel hydriding materials has historically been a manual process driven by chemical intuition or experimental trial-and-error. Data-driven materials' discovery paradigms provide an alternative to traditional approaches, whereby machine/statistical learning (ML) models are used to efficiently screen materials for desired properties and significantly narrow the scope of expensive/time-consuming first-principles modeling and experimental validation. Here we specifically focus on a relatively new class of hydrogen storage materials, high entropy alloy (HEA) hydrides, whose vast combinatorial composition space and local structural disorder necessitates a data-driven approach that does not rely on exact crystal structures in order to make property predictions. Our ML model quickly screens hydride stability within a large HEA space and permits down selection for laboratory validation based not only on targeted thermodynamic properties, but also secondary criteria such as alloy phase stability and density. To experimentally verify our predictions, we performed targeted synthesis and characterization of several novel hydrides that demonstrate significant destabilization (70x increase in equilibrium pressure, 20 kJ/molH2 decrease in desorption enthalpy) relative to the benchmark HEA hydride, TiVZrNbHfHx. Ultimately, by providing a large composition space in which hydride thermodynamics can be continuously tuned over a wide range, this work will enable efficient materials selection for various applications, especially in areas such as metal hydride based hydrogen compressors, actuators, and heat pumps.

A number of high-entropy alloys (HEAs) in the TiVZrNbHf system have been synthesized by arc melting and systematically evaluated for their hydrogen sorption characteristics. A total of 21 alloys with varying elemental compositions were investigated, and 17 of them form body-centered-cubic (bcc) solid solutions in the as-cast state. A total of 15 alloys form either face-centered-cubic (fcc) or body-centered-tetragonal (bct) hydrides after exposure to gaseous hydrogen with hydrogen per metal ratios (H/M) as high as 2.0. Linear trends are observed between the volumetric expansion per metal atom [(V/Z)fcc/bct – (V/Z)bcc/hcp]/(V/Z)bcc/hcp with the valence electron concentration and average Pauling electronegativity (χp) of the alloys. However, no correlation was observed between the atomic size mismatch, δ, and any investigated hydrogen sorption property such as the maximum storage capacity or onset temperature for hydrogen release., The effect of the composition on hydrogen sorption has been studied on high-entropy alloys based on TiVZrNbHf. Most alloys crystallize in body-centered-cubic solid solutions and form fluorite-type metal hydrides. The desorption behavior of three selected metal deuterides was studied with in situ neutron diffraction coupled with gravimetric analysis. It was found that when Zr is added to TiVNb, deuterium first jumps from tetrahedral interstitial sites to octahedral sites before leaving the structure.

International audience; A novel high entropy alloy containing Mg and refractory elements has been prepared by mechanochemical synthetic method under inert atmosphere. The Mg0.10Ti0.30V0.25Zr0.10Nb0.25 alloy adopts a single-phase bcc lattice and can absorb hydrogen within 1 minute at room temperature forming a hydride phase with 1.7 H/M (2.7 wt.%) capacity. During the reaction with hydrogen the alloy undergoes a single-step and reversible phase transformation from bcc (alloy) to fcc lattice (hydride). The absorption/desorption cycling properties prove a small fading of the capacity for the first cycle followed by stabilization to 1.5 H/M (2.4 wt.%) for the next cycles. A simple comparison between this quinary HEA and the quaternary alloy containing only refractory elements Ti0.325V0.275Zr0.125Nb0.275 proves an important enhancement of the cycling properties by Mg addition. These insights seem to suggest that insertion of lightweighted metals such as, Mg, can guide future design of novel HEA with improved performances for hydrogen storage.

International audience; A new quinary multi-principal element alloy Ti0.30V0.25Zr0.10Nb0.25Ta0.10 was prepared by high temperature melting technique and the physicochemical as well as hydrogen sorption properties have been determined. The as-cast alloy crystallizes into a single-phase bcc lattice and can very quickly absorb hydrogen at room temperature forming a fcc hydride phase with capacity of 2 H/M (2.5 wt.%). The absorption/desorption of hydrogen is reversible and occurs within one step, as proven by in situ neutron diffraction for the desorption reaction. The capacity is slightly fading during the first 10 cycles and then stabilizes at around 2.2 wt.% for the next 10 cycles.

The remarkable mechanical properties of high-entropy alloys can be further improved by interstitial alloying. In this work we employ density functional theory calculations to study the solution energies of dilute carbon interstitial atoms in tetrahedral and octahedral sites in bcc HfNbTiVZr. Our results indicate that carbon interstitials in tetrahedral sites are unstable, and the preferred octahedral sites present a large spread in the energy of solution. The inclusion of carbon interstitials induces large structural relaxations with long-range effects. The effect of local chemical environment on the energy of solution is investigated by performing a local cluster expansion including studies of its correlation with the carbon atomic Voronoi volume. However, the spread in solution energetics cannot be explained with a local environment analysis only pointing towards a complex, long-range influence of interstitial carbon in this alloy. Funding Agencies|Swedish Research Council (VR)Swedish Research Council [2019-05403, 2018-04834]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University, Faculty Grant SFOMatLiU [2009 00971]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW2018.0194]; Swedish Foundation for Strategic Research through the Future Research Leaders 6 program [FFL 15-0290]; RFBRRussian Foundation for Basic Research (RFBR) [20-02-00178]; NordForsk Nordic Neutron Science Programme through the functional hydrides (FunHy) project [81942]

Many of the materials properties of high-entropy alloys (HEAs), like increased hardness, reduced thermal and electrical conductivity, and interesting hydrogen storage properties, are proposed to be related to local lattice distortions of the crystal structure due to the significant size differences between the elements of the alloy. However, direct evidence of this effect is very limited in the literature, and it therefore remains a hypothesis. This work presents a detailed assessment of the local lattice distortion in three body-centered cubic (bcc) HEAs TiVNb, TiVZrNb and TiVZrNbHf with varying atomic size differences using total scattering measurements and Reverse Monte Carlo structure modelling. The analysis indicates that the amount of local lattice distortion in the alloys increases with the elemental size difference in the alloy. The amount of lattice distortion is relieved when dideuterides with CaF2-type structures ( F m 3 ¯ m ) are formed from the bcc ( I m 3 ¯ m ) HEAs. Analyses of the local environments around the deuterium atoms reveal an interesting correlation between the valence-electron concentration (VEC) of the nearest-neighbour metals and the stability of tetrahedral interstices with respect to deuterium occupation. Moreover, there is a tendency towards Ti/Nb short-range order in TiVNbD5.7 where the mixing entropy is lowest. In TiVZrNbHfD10, about 6 % of the deuterium atoms are displaced from the tetrahedral interstices with smaller volumes to octahedral interstices.

Journal of solid state chemistry 277, 37 - 45 (2019). doi:10.1016/j.jssc.2019.05.033, Hydrides Eu3Si4H2+x were obtained by exposing the Zintl phase Eu3Si4 to a hydrogen atmosphere at a pressure of 30 bar and temperatures from 25 to 300 °C. Structural analysis using powder X-ray diffraction (PXRD) data suggested that hydrogenations in a temperature range 25–200 °C afford a uniform hydride phase with an orthorhombic structure (Immm, a ≈ 4.40 Å, b ≈ 3.97 Å, c ≈ 19.8 Å), whereas at 300 °C mixtures of two orthorhombic phases with c ≈ 19.86 and ≈ 19.58 Å were obtained. The assignment of a composition Eu3Si4H2+x is based on first principles DFT calculations, which indicated a distinct crystallographic site for H in the Eu3Si4 structure. In this position, H atoms are coordinated in a tetrahedral fashion by Eu atoms. The resulting hydride Eu3Si4H2 is stable by −0.46 eV/H atom with respect to Eu3Si4 and gaseous H2. Deviations between the lattice parameters of the DFT optimized Eu3Si4H2 structure and the ones extracted from PXRD patterns pointed to the presence of additional H in interstitials also involving Si atoms. Subsequent DFT modeling of compositions Eu3Si4H3 and Eu3Si4H4 showed considerably better agreement to the experimental unit cell volumes. It was then concluded that the hydrides of Eu3Si4 have a composition Eu3Si4H2+x (x, Published by Academic Press, Orlando, Fla.

High Entropy Alloys (HEA), where five or more elements are mixed together in near equiatomic ratios offer promising properties as hydrogen storage materials due to their ability to crystallize in simple cubic structures in the presence of large lattice strain originating from the different sizes of the atoms. In this work, the hydrogen absorption and desorption as well as the cycling properties of the TiZrNbHfTa HEA have been studied by in situ Synchrotron X-Ray diffraction, Pressure-Composition-Isotherm, Thermal Desorption Spectroscopy and Differential Scanning Calorimetry. The alloy crystallizes in a cubic bcc phase and undergoes a two-stage hydrogen absorption reaction to a fcc dihydride phase with an intermediate tetragonal monohydride, very similar to the V-H system. The hydrogen absorption/desorption in TiZrNbHfTa is completely reversible and the activation energy of desorption could be calculated. Furthermore, we have observed an interesting macrostructure following parallel planes after the formation of the dihydride phase, which is retained after desorption.

We have investigated the structure and hydrogen storage properties of a series of Ti, V, Zr, Nb and Ta based high-entropy alloys (HEAs) with varying degree of local lattice strain by means of synchrotron radiation powder X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and manometric measurements in a Sieverts apparatus. The obtained alloys have body-centred cubic (bcc) crystal structures and form face-centred cubic (fcc) metal hydrides with hydrogen-to-metal ratios close to 2. No correlation between the hydrogen storage capacity and the local lattice strain is observed in this work. Both bcc and fcc unit cells expand linearly with the zirconium-to-metal ratio [Zr]/[M], and increased concentration of Zr stabilizes the hydrides. When heated, the hydrides decompose into the original bcc alloys if [Zr]/[M]

While the overwhelming number of papers on multi-principal-element alloys (MPEAs) focus on the mechanical and microstructural properties, there has been growing interest in these alloys as solid-state hydrogen stores. We report here the synthesis optimization, the physicochemical and the hydrogen sorption properties of Ti0.325V0.275Zr0.125Nb0.275. This alloy was prepared by two methods, high temperature arc melting and ball milling under Ar, and crystallizes into a single-phase bcc structure. This MPEA shows a single transition from the initial bcc phase to a final bct dihydride and a maximum uptake of 1.7 H/M (2.5 wt%). Interestingly, the bct dihydride phase can be directly obtained by reactive ball milling under hydrogen pressure. The hydrogen desorption properties of the hydrides obtained by hydrogenation of the alloy prepared by arc melting or ball milling and by reactive ball milling have been compared. The best hydrogen sorption properties are shown by the material prepared by reactive ball milling. Despite a fading of the capacity for the first cycles, the reversible capacity of the latter material stabilizes around 2 wt%. To complement the experimental approach, a theoretical investigation combining a random distribution technique and first principle calculation was done to estimate the stability of the hydride.

A high-entropy alloy (HEA) of HfNbTiVZr was synthesized using an arc furnace followed by ball milling. The hydrogen absorption mechanism was studied by in situ X-ray diffraction at different temperatures and by in situ and ex situ neutron diffraction experiments. The body centered cubic (BCC) metal phase undergoes a phase transformation to a body centered tetragonal (BCT) hydride phase with hydrogen occupying both tetrahedral and octahedral interstitial sites in the structure. Hydrogen cycling of the alloy at 500 °C is stable. The large lattice strain in the HEA seems favorable for absorption in both octahedral and tetrahedral sites. HEAs therefore have potential as hydrogen storage materials because of favorable absorption in all interstitial sites within the structure.