arXiv subjects

Hiroyuki Kagi

Publications and source records attributed to Hiroyuki Kagi.

7 recordsLinked to original sources

arXiv2026

Hydrogen-induced volume expansion in hexagonal close-packed iron: Effects of pressure and temperature

Hydrogen is a promising candidate for the light element in terrestrial planetary cores. Its incorporation into iron causes significant volume expansion, leading to a substantial density deficit. Although extensive studies have been conducted on iron hydride (FeH$_{x}$) with the fcc structure, the thermoelastic properties on FeHx with hcp structure (hcp-FeH$_{x}$) remain unconstrained because of the experimental difficulties to control hydrogen content. Here, we synthesized hcp-FeH$_{x}$ with controlled hydrogen contents under high-pressure and high-temperature conditions. We carried out \textit{in situ} X-ray diffraction measurements on hcp-FeH$_{x}$ at 10--25~GPa and 300--900~K using a Kawai-type mutilanvil apparatus and constructed their equations of state. By combining our results with previously reported equations of state for hcp-Fe and experimental determinations of hydrogen content in hcp-FeH$_{x}$, we demonstrated that the discrepancies in the hydrogen-induced volume expansion coefficient can be clearly explained by its pressure and temperature dependence. Our results revealed that the hydrogen-induced volume expansion of hcp-Fe exhibits a strong temperature dependence at low pressures, but its temperature effect significantly weakens with increasing pressure. We also showed that the density reduction of Fe by hydrogenation depends on its crystal structure. These findings demonstrate that estimates of hydrogen content in iron at planetary interior conditions based on hydrogen-induced volume expansion need to be revised by properly accounting for its $PT$-dependence and crystal structure.

cond-mat.mtrl-sci↗

arXiv2025

New metastable ice phases via supercooled water

Water exhibits rich polymorphism, where more than 20 crystalline phases have been experimentally reported. Five of them are metastable and form at low temperatures by either heating amorphous ice or degassing clathrate hydrates. However, such metastable phases rarely crystallise directly from liquid water, making it challenging to study metastable phase relations at relatively high temperatures. Here, we report that high-pressure metastable phases of ice, including two unknown phases named ices XXI and XXII, crystallise directly from liquid water in a deeply supercooled region around the homogeneous nucleation temperature. The key is to use emulsified water to stabilise supercooled water in laboratory timescales. Ices XXI and XXII are obtained by isothermal compression of emulsified water at 295 K and 250 K, respectively. Our powder x-ray and neutron diffraction analyses combined with molecular dynamics (MD) simulations revealed the surprisingly complex structures of these new phases with Z = 152 (ice XXI) and 304 (ice XXII). Ice XXI is topologically identical to 'ice T2' previously predicted by MD simulations, and our experimental structural model can be used as a benchmark for its structures in simulations, which depend on the force fields. On cooling, ice XXI transforms into an orientationally ordered counterpart named ice XXIII. Our results revealed the "hidden" structural complexity of water underlying the phase diagram, as implied by previous computational works. Further efforts at unveiling such metastable phase relations will bridge the large gaps between computational and experimental phase diagrams of water.

cond-mat.mtrl-sci↗

arXiv2025

Pressure-induced thermal expansion anomalies in dhcp iron hydride associated with magnetoelastic coupling

Iron hydride with a double hexagonal close-packed structure (dhcp-FeH$_{x}$) undergoes a ferromagnetic-paramagnetic transition without changing its crystal structure. Despite its relevance to metal-hydrogen interactions and magnetically driven elasticity, the extensive investigation of this phase is almost limited to room temperature. Here, we performed XRD measurements at high pressure and high temperature, identifying the singularity in the temperature-volume relationship as the Curie temperature ($T_\text{C}$). Pressurization lowered the $T_\text{C}$ of dhcp-FeH$_{x}$, and pronounced volume anomalies, indicating that pressure enhanced magnetoelastic coupling. Density functional theory combined with dynamical mean-field theory (DFT+DMFT) reproduced the spontaneous magnetization and its negative pressure dependence of $T_\text{C}$, consistent with our experimental results. This establishes a methodology for determining magnetic transition temperatures and magnetoelastic coupling effects, and highlights dhcp-FeH$_{x}$ as a unique model system for providing new insights into itinerant-electron magnetism.

cond-mat.mtrl-sci↗

arXiv2022

Experimentally shock-induced melt veins in basalt: Improving the shock classification of eucrites

Basaltic rocks occur widely on the terrestrial planets and differentiated asteroids, including the asteroid 4 Vesta. We conducted a shock recovery experiment with decaying compressive pulses on a terrestrial basalt at Chiba Institute of Technology, Japan. The sample recorded a range of pressures, and shock physics modeling was conducted to add a pressure scale to the observed shock features. The shocked sample was examined by optical and electron microscopy, electron back-scattered diffractometry, and Raman spectroscopy. We found that localized melting occurs at a lower pressure (~10 GPa) than previously thought (>20 GPa). The shocked basalt near the epicenter represents shock degree C of a recently proposed classification scheme for basaltic eucrites and, as such, our results provide a pressure scale for the classification scheme. Finally, we estimated the total fraction of the basaltic eucrites classified as shock degree C to be ~15% by assuming the impact velocity distribution onto Vesta.

astro-ph.EP↗

arXiv2021

Pressure-induced transition from Jeff=1/2 to S=1/2 states in CuAl2O4

The spin-orbit entangled (SOE) Jeff-state has been a fertile ground to study novel quantum phenomena. Contrary to the conventional weakly correlated Jeff=1/2 state of 4d and 5d transition metal compounds, the ground state of CuAl2O4 hosts a Jeff=1/2 state with a strong correlation of Coulomb U. Here, we report that surprisingly Cu2+ ions of CuAl2O4 overcome the otherwise usually strong Jahn-Teller distortion and instead stabilize the SOE state, although the cuprate has relatively small spin-orbit coupling. From the x-ray absorption spectroscopy and high-pressure x-ray diffraction studies, we obtained definite evidence of the Jeff=1/2 state with a cubic lattice at ambient pressure. We also found the pressure-induced structural transition to a compressed tetragonal lattice consisting of the spin-only S=1/2 state for pressure higher than Pc=8 GPa. This phase transition from the Mott insulating Jeff=1/2 to the S=1/2 states is a unique phenomenon and has not been reported before. Our study offers a rare example of the SOE Jeff-state under strong electron correlation and its pressure-induced transition to the S=1/2 state.

cond-mat.str-el↗

arXiv2020

New diversity form of ice polymorphism: Discovery of second hydrogen ordered phase of ice VI

More than 20 crystalline and amorphous phases have been reported for ice so far. This extraordinary polymorphism of ice arises from the geometric flexibility of hydrogen bonds and hydrogen ordering, and makes ice a unique presence with its universality in the wide fields of material and earth and planetary science. A prominent unsolved question concerning the diversity is whether a hydrogen-disordered phase of ice transforms into only one hydrogen-ordered phase, as inferred from the current phase diagram of ice, although its possible hydrogen configurations have close energies. Recent experiments on a high-pressure hydrogen-disordered phase, ice VI, revealed an unknown hydrogen-ordered form ($β$-XV) besides the known ordered phase, ice XV, which would be a counterexample of the question. However, due to lack of experimental evidence, it has not been clarified whether $β$-XV is a distinct crystalline phase. Herein we report a second hydrogen-ordered phase for ice VI, ice XIX, unambiguously demonstrated by neutron diffraction measurements. The phase boundary between ice VI and ice XIX shows that ice VI contracts upon the hydrogen ordering, which thermodynamically stabilizes ice XIX in higher-pressure region than ice XV because of its smaller volume than ice XV. The pressure-driven phase competition between hydrogen-ordered phases, also theoretically suggested in other ice polymorphs, can induce hydrogen ordering of ice in different manners. Thus, this study demonstrates a hitherto undiscovered polymorphism of ice.

cond-mat.mtrl-sci↗

arXiv2019

Ice Ic without stacking disorder by evacuating hydrogen from hydrogen hydrate

Water freezes below 0 °C at ambient pressure, ordinarily to ice Ih with an ABAB... hexagonal stacking sequence. However, it is also known to produce "ice Ic" nominally with an ABCABC... cubic stacking sequence under certain conditions1, and its existence in Earth's atmosphere, or in comets is debated. "Ice Ic", or called as cubic ice, was first identified in 1943 by König, who used electron microscopy to study the condensation of ice from water vapor to a cold substrate. Subsequently, many different routes to "ice Ic" have been established, such as the dissociation of gas hydrates, warming amorphous ices or annealing high-pressure ices recovered at ambient pressure, freezing of $μ$- or nano-confined water. Despite the numerous studies on "ice Ic", its structure has not been fully verified, because the diffraction patterns of "ice Ic" show signatures of stacking-disorder, and ideal ice Ic without stacking-disorder had not been formed until very recently. Here we demonstrate a route to obtain ice Ic without stacking-disorder by degassing hydrogen from the high-pressure form of hydrogen hydrate, C$_2$, which has a host framework that is isostructural with ice Ic. Surprisingly, the stacking-disorder free ice Ic is formed from C$_2$ via an intermediate amorphous or nano-crystalline form under decompression, unlike the direct transformations that occur in the cases of recently discovered ice XVI from neon hydrate, or ice XVII from hydrogen hydrate. The obtained ice Ic shows remarkable thermal stability until the phase transition to ice Ih at 250 K; this thermal stability originates from the lack of dislocations, which promote changes in the stacking sequence. This discovery of ideal ice Ic will promote understanding of the role of stacking-disorder on the physical properties of ice as a counter end-member of ice Ih.

cond-mat.mtrl-sci↗