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Saori Kawaguchi-Imada

Publications and source records attributed to Saori Kawaguchi-Imada.

3 recordsLinked to original sources

The tetragonal-cubic transition of davemaoite: Implications for lower mantle seismic anomalies

Davemaoite (CaSiO3 perovskite) is the third most abundant mineral in Earth's lower mantle and a dominant phase in subducted oceanic crust. Its crystal structure is distorted (tetragonal or orthorhombic) at ambient conditions but is considered to transform to cubic at high temperatures. Previous experiments reported low, nearly pressure-independent transition temperatures (approximately 600 K), demonstrating a long-standing discrepancy with theoretical predictions that mostly exceed 1000 K. Here, we determine the phase stability and thermal equation of state of CaSiO3 davemaoite and its titanium-bearing solid solution [Ca(Si0.75,Ti0.25)O3] under simultaneous high-pressure and high-temperature conditions using a laser-heated diamond anvil cell combined with synchrotron X-ray diffraction. We find that the tetragonal-to-cubic transition occurs at substantially higher temperatures than previously reported, with the titanium substitution further stabilizing the tetragonal phase and shifting the transition boundary to even higher temperatures. These findings indicate that CaSiO3 davemaoite in subducted oceanic crust likely undergoes its ferroelastic transition in the mid-lower mantle, whereas Ti-rich davemaoite may remain tetragonal throughout most of the lower mantle, transforming to cubic near the core-mantle boundary. Our results demonstrate that the compositionally dependent phase behaviour of davemaoite can account for the seismic anomalies observed in both the mid-lower mantle and the lowermost mantle.

physics.geo-ph↗

Unlock Anionic Behavior of Calcium Through Pressure Engineering

An isolated calcium (Ca) atom has empty d-orbitals under ambient conditions. However, s-d band hybridization has been observed in both elemental Ca and compounds by manipulating thermodynamic conditions. Here, we reveal that the Ca 3d-band can even capture electrons from halogen atoms under pressure, exhibiting anionic behaviors in iodides. We predict a CsCl-type monovalent CaI at above 50 GPa by employing first-principles structural searching and successfully identified the phase at 84 GPa using in situ X-ray diffraction. We further reveal that, due to the effect of orbital broadening, unusual charge transfer from the 5p orbitals of I to the 3d orbitals of Ca in CaI, gradually reverses the ionicity of Ca and becomes the anionic ICa at 485 GPa. Multivalent Ca stabilizes a set of metallic iodides with eight- to ten-fold iodine hyper-coordination. Our findings demonstrate that the valence states of Ca can vary from negative to +2, suggesting much greater complexity of Ca chemistry under ultrahigh pressures.

cond-mat.mtrl-sci↗

Pressure-induced volumetric negative thermal expansion in CoZr2 superconductor

We investigate the thermal expansion and superconducting properties of a CuAl2-type (tetragonal) superconductor CoZr2 under high pressures. We perform high-pressure synchrotron X-ray diffraction in a pressure range of 2.9 GPa < P < 10.4 GPa and discover that CoZr2 exhibits volumetric negative thermal expansion under high pressures. Although the uniaxial positive thermal expansion (PTE) along the a-axis is observed under ambient pressure, that is suppressed by pressure, while the large uniaxial negative thermal expansion (NTE) along the c-axis is maintained under the pressure regime. As a result of a combination of the suppressed uniaxial PTE along the a-axis and uniaxial NTE along the c-axis, volumetric negative thermal expansion is achieved under high pressure in CoZr2. The mechanisms of volumetric NTE would be based on the flexible crystal structure caused by the soft Co-Co bond as seen in the iso-structural compound FeZr2, which exhibits uniaxial NTE along the c-axis. We also perform high-pressure electrical resistance measurements of CoZr2 to confirm the presence of superconductivity under the examined pressure regime in the range of 0.03 GPa < P < 41.9 GPa. We confirm the presence of superconductivity under all pressures and observe dome-like shape pressure dependence of superconducting transition temperature. Because of the coexistence of two phenomena, which are volumetric NTE and superconductivity, in CoZr2 under high pressure, the coexistence would be achievable under ambient pressure by tuning chemical compositions after our present observation.

cond-mat.mtrl-sci↗