Hitoshi Yusa

Distinct Responses to Mechanical Grinding and Hydrostatic Pressure in Luminescent Chromism of Tetrathiazolylthiophene

Luminescent mechanochromism has been intensively studied in the past few years. However, the difference in the anisotropic grinding and the isotropic compression is not clearly distinguished in many cases, in spite of the importance of this discrimination for the application of such mechanochromic materials. We now report the distinct luminescent responses of a new organic fluorophore, tetrathiazolylthiophene, to these stresses. The multichromism is achieved over the entire visible region using the single fluorophore. The different mechanisms of a blue shift by grinding crystals and of a red shift under hydrostatic pressure are fully investigated, which includes a high-pressure single-crystal X-ray diffraction analysis. The anisotropic and isotropic modes of mechanical loading suppress and enhance the excimer formation, respectively, in the 3D hydrogen-bond network.

Thermodynamic properties of α-quartz, coesite, and stishovite and equilibrium phase relations at high pressures and high temperatures

Isobaric heat capacities of α -quartz, coesite, and stishovite were measured by differential scanning calorimetry at 183–703 K. The heat capacity data of coesite represent a significant revision of the previous data. The heat capacities and entropies were also calculated using Kieffers model. By high-temperature solution calorimetry, transition enthalpy for the β-quartz-coesite at 979 K was measured to be 1.27±0.39 kJ/mol. The enthalpies for the α-quartz-coesite and coesite-stishovite transitions at 298 K were measured to be 3.40±0.56 and 33.62±1.01 kJ/mol, respectively, by differential drop-solution calorimetry. The enthalpy of the coesite-stishovite transition obtained in this study is about 10–15 kJ/mol smaller than those in the previous studies. Phase relations in SiO2 at high pressures and high temperatures were calculated using these new thermodynamic data. The calculated boundary for the α-quartz-coesite transition is consistent with those determined experimentally. For the coesite-stishovite transition, the calculated boundary having a slope of 2.5±0.3 MPa/K disagrees with that by Yagi and Akimoto but is generally consistent with that by Zhang et al.s new in situ X ray diffraction study.

Pressure-Induced Spin-State Transition in BiCoO3

The structural and electronic properties of BiCoO(3) under high pressure have been investigated. Synchrotron X-ray and neutron powder diffraction studies show that the structure changes from a polar PbTiO(3) type to a centrosymmetric GdFeO(3) type above 3 GPa with a large volume decrease of 13% at room temperature revealing a spin-state change. The first-order transition is accompanied by a drop of electrical resistivity. Structural results show that Co(3+) is present in the low spin state at high pressures, but X-ray emission spectra suggest that the intermediate spin state is present. The pressure-temperature phase diagram of BiCoO(3) has been constructed enabling the transition temperature at ambient pressure to be estimated as 800-900 K.

Isothermal compressibility of hydrous ringwoodite and its relation to the mantle discontinuities

High pressure X-ray diffraction experiments of hydrous ringwoodite, containing 2.8 ± 0.2 wt% H2O, have been carried out by using X-rays from a synchrotron radiation source with a diamond anvil cell under hydrostatic pressure up to 6 GPa. The isothermal bulk modulus (K0) was determined to be 148 ± 1 GPa with the pressure derivative (K′0) fixed to 5 using the Birch-Murnaghan equation of state. This value is almost 80% of that of anhydrous ringwoodite. The relations of the bulk modulus and zero pressure volumes (V0) with H2O content are estimated within the solid solution range. Combining the present results with recent seismological data, the nature of the 520 km and 660 km seismic discontinuities is discussed.

Calorimetric study of MgSiO3 garnet and pyroxene: Heat capacities, transition enthalpies, and equilibrium phase relations in MgSiO3 at high pressures and temperatures

Enthalpy of the MgSiO3 pyroxene-tetragonal garnet transition was measured by high-temperature solution calorimetry, giving ΔH°983 = 30.80 ± 3.11 kJ/mol at 983 K. Heat capacities of MgSiO3 pyroxene and tetragonal garnet were also measured by differential scanning calorimetry from temperatures of 150 to 700 K. Using these calorimetric data and published thermodynamic data, equilibrium phase boundaries of high-pressure transitions in MgSiO3 were calculated at pressures up to 26 GPa and at temperatures up to 2600 K. In calculating the stability field of MgSiO3 tetragonal garnet, the effect of partial disorder of Mg and Si cations in the octahedral sites of garnet on the phase boundaries was examined. The calculated stability field of tetragonal garnet was generally consistent with the high-pressure experimental data. The calculated boundaries for the pyroxene-garnet and garnet-perovskite transitions have negative and positive slopes, respectively.

Structure and stability of high pressure synthesized Mg–TM hydrides (TM = Ti, Zr, Hf, V, Nb and Ta) as possible new hydrogen rich hydrides for hydrogen storage

A series of hydrogen rich Mg6–7TMH14–16 (TM = Ti, Zr, Hf, V, Nb and Ta) hydrides have been synthesized at 600 °C in a high pressure anvil cell above 4 GPa. All have structures based on a fluorite type metal atom subcell lattice with a ≈ 4.8 A. The TM atom arrangements are, however, more ordered and can best be described by a superstructure where the 4.8 A FCC unit cell axis is doubled. The full metal atom structure corresponds to the Ca7Ge type structure. This superstructure was also observed from electron diffraction patterns. The hydrogen atoms were found from powder X-ray diffraction using synchrotron radiation to be located in the two possible tetrahedral sites. One coordinates three Mg atoms and one TM atom and another coordinates four Mg atoms. These types of new hydrogen rich hydrides based on immiscible metals were initially considered as metastable but have been observed to be reversible if not fully dehydrogenated. In this work, DFT calculations suggest a mechanism whereby this can be explained: with H more strongly bonded to the TM, it is in principle possible to stepwise dehydrogenate the hydride. The remaining hydrogen in the tetrahedral site coordinating the TM would then act to prevent the metals from separating, thus making the system partially reversible.

Synthesis of rhenium nitride crystals with MoS2 structure

Rhenium nitride (ReN2) crystals were synthesized from a metathesis reaction between ReCl5 and Li3N under high pressure. The reaction was well controlled by the addition of a large amount of NaCl as reaction inhibitor to prevent a violent exothermic reaction. The largest rhenium nitride crystals obtained had a millimeter-order size with a platelet shape. X-ray diffraction analysis revealed that rhenium nitride has MoS2 structure similar to hexagonal rhenium diboride (ReB2) which has recently been investigated as an ultra-hard material. The structure was different from any structures previously predicted for ReN2 by theoretical calculations.

Peculiar High-Pressure Behavior of BiMnO3

High-pressure structural properties of perovskite-type BiMnO(3) have been investigated by synchrotron X-ray powder diffraction at room temperature. A new monoclinic phase having P2(1)/c symmetry was found between about 1.5 and 5.5 GPa. Above 8 GPa, the orthorhombic GdFeO(3)-type phase (space group Pnma) is stable. The crystal structure of BiMnO(3) at 8.6 GPa and room temperature was investigated (a = 5.5132(3) A, b = 7.5752(3) A, c = 5.4535(3) A). The orthorhombic phase of BiMnO(3) has an orbital order similar to LaMnO(3) but with a different arrangement of orbitals in the ac plane. High-pressure room-temperature behavior of BiMnO(3) differs from high-temperature behavior at ambient pressure in comparison with BiCrO(3) and BiScO(3). These findings may open new directions in investigation of BiMnO(3).

High-pressure high-temperature transitions in MgCr2O4 and crystal structures of new Mg2Cr2O5 and post-spinel MgCr2O4 phases with implications for ultrahigh-pressure chromitites in ophiolites

Abstract We determined phase relations in MgCr2O4 at 12-28 GPa and 1000-1600 °C using a multi-anvil apparatus. At 12-15 GPa, spinel-type MgCr2O4 (magnesiochromite) first decomposes into a mixture of new Mg2Cr2O5 phase + corundum-type Cr2O3 at 1100-1600 °C, but it dissociates first into MgO periclase + corundum-type Cr2O3 at l000 °C. At about 17-19 GPa, the mixture of Mg2Cr2O5 phase + corundum-type Cr2O3 transforms to a single MgCr2O4 phase. Structure refinements using synchrotron X-ray powder diffraction data indicated that the high-pressure MgCr2O4 phase has a CaTi2O4-type structure (Cmcm), and that the basic structure of the Mg2Cr2O5 phase is the same as that of recently found modified ludwigite-type Mg2Al2O5 and Fe2Cr2O5 (Pbam). The phase relations in this study may suggest that natural chromitites in the Luobusa ophiolite regarded as the deep-mantle origin were derived from the mantle shallower than the depths corresponding to pressure of 12-15 GPa because of absence of the assemblage of (Mg,Fe)2Cr2O5 + Cr2O3 in the chromitites.

Perovskite, LiNbO3, Corundum, and Hexagonal Polymorphs of (In1–xMx)MO3

LiNbO(3) (LN), corundum (cor), and hexagonal (hex) phases of (In(1-x)M(x))MO(3) (x = 0.143; M = Fe(0.5)Mn(0.5)) were prepared. Their crystal structures were investigated with synchrotron X-ray powder diffraction, and their properties were studied by differential thermal analysis, magnetic measurements, and Mössbauer spectroscopy. The LN-phase was prepared at high pressure of 6 GPa and 1770 K; it crystallizes in space group R3c with a = 5.25054(7) Å, c = 13.96084(17) Å, and has a long-range antiferromagnetic ordering near T(N) = 270 K. The cor- and hex-phases were obtained at ambient pressure by heating the LN-phase in air up to 870 and 1220 K, respectively. The cor-phase crystallizes in space group R-3c with a = 5.25047(10) Å, c = 14.0750(2) Å, and the hex-phase in space group P6(3)/mmc with a = 3.34340(18) Å, c = 11.8734(5) Å. T(N) of the cor-phase is about 200 K, and T(N) of the hex-phase is about 140 K. During irreversible transformations of LN-(In(1-x)M(x))MO(3) with the (partial) cation ordering, the In(3+), Mn(3+), and Fe(3+) cations become completely disordered in one crystallographic site of the corundum structure, and then they are (partially) ordered again in the hex-phase. LN-(In(1-x)M(x))MO(3) exhibits a reversible transformation to a perovskite GdFeO(3)-type structure (space group Pnma; a = 5.2946(3) Å, b = 7.5339(4) Å, c = 5.0739(2) Å at 10.3 GPa) at room temperature and pressure of about 5 GPa.