Yohei Kojima

CaCu3Pt4O12: The First Perovskite with the B Site Fully Occupied by Pt4+

A novel A-site ordered perovskite CaCu(3)Pt(4)O(12) was synthesized under high pressure and high temperature of 12 GPa and 1250 degrees C. CaCu(3)Pt(4)O(12) is the first perovskite in which the B site is fully occupied by Pt(4+). The crystal structure refinement based on the synchrotron powder X-ray diffraction data shows that CaCu(3)Pt(4)O(12) crystallizes in the space group Im3 (cubic) with a lattice constant of a = 7.48946(10) A. The magnetic susceptibility data show the antiferromagnetic transition at T(N) = 40 K, which is attributed to the magnetic ordering of Cu(2+) spins with S = 1/2.

High-pressure rotational deformation apparatus to 135 GPa

A large-strain, torsional deformation apparatus has been developed based on diamond anvil cells at high pressures, up to 135 GPa with a help of hard nano-polycrystalline diamond anvils. These pressure conditions correspond to the base of the Earths mantle. An X-ray laminography technique is introduced for high-pressure in situ 3D observations of the strain markers. The technique developed in this study introduces the possibility of the in situ rheological measurements of the deep Earth materials under ultrahigh-pressure conditions.

High-pressure and high-temperature synthesis of rhenium carbide using rhenium and nanoscale amorphous two-dimensional carbon nitride

Abstract Both Re2C and Re2N are ultra incompressible and have a bulk modulus of about 400 GPa. These materials are synthesized under high pressure and high temperature. The synthesis pressures are about 10 GPa or below for Re2C and 20–30 GPa for Re2N. If the synthesis pressure of Re2N was about 10 GPa or below, a large volume high-pressure cell like a multi-anvil apparatus can be used to synthesize Re2N. To realize this, a proper solid nitrogen source is needed instead of liquid or gas nitrogen. We used a precursor of a mixture of rhenium and home-made nanoscale amorphous two-dimensional carbon nitride as a solid nitrogen source. Consequently, the synthesis reaction produced Re2C but not Re2N. We characterized the synthesized Re2C by various techniques including high-pressure x-ray diffraction (XRD). The bulk modulus B0 of the synthesized Re2C under hydrostatic conditions was estimated to be 385.7 ± 18.0 GPa. This value is a little smaller than the previous data. When the pressure medium became non-hydrostatic, the peculiar compression behaviour occurred; the rate of broadening of XRD lines increased and the compression became negligible in the range of a few GPa. The reason for this peculiar behaviour is not known.

Transition mechanism of sH to filled-ice Ih structure of methane hydrate under fixed pressure condition

The phase transition mechanism of methane hydrate from sH to filled-ice Ih structure was examined using a combination of time-resolved X-ray diffractometry (XRD) and Raman spectroscopy in conjunction with charge-coupled device (CCD) camera observation under fixed pressure conditions. Prior to time-resolved Raman experiments, the typical C-H vibration modes and their pressure dependence of three methane hydrate structures, fluid methane and solid methane were measured using Raman spectroscopy to distinguish the phase transitions of methane hydrates from decomposition to solid methane and ice VI or VII. Experimental results by XRD, Raman spectroscopy and CCD camera observation revealed that the structural transition of sH to filled-ice Ih occurs through a collapse of the sH framework followed by the release of fluid methane that is then gradually incorporated into the filled-ice Ih to reconstruct its structure. These observations suggest that the phase transition of sH to filled-ice Ih takes place by a typical reconstructive mechanism.

Reexamination of Solvothermal Synthesis of Layered Carbon Nitride

“Graphitic carbon nitride” synthesized by the solvothermal reaction between cyanuric chloride (C3N3Cl3) and sodium amide (NaNH2), which was one of the most common methods reported so far, was carefully examined by several analytical techniques for its chemical and structural characteristics. The chemical quantification by the electron microprobe and combustion methods showed that the product synthesized has a significant amount of hydrogen with a composition C3N5H3. Moreover, we found by FT-IR and IR-Raman measurements that the product consists mainly of stacked s-triazine units on the basis of the structural framework of cyanuric chloride, suggesting that s-triazine-based carbon nitride is more stable than heptazine-based one under a mild temperature condition (~200°C). The present study clearly demonstrates that hydrogen-free, pure graphitic C3N4 cannot be produced by the present solvothermal reaction proposed by the earlier study.

Anvil design for slip-free high pressure deformation experiments in a rotational diamond anvil cell

ABSTRACT A rotational diamond anvil cell is the most suitable deformation apparatus with which to investigate the rheological properties of deep-Earth materials at pressures similar to those found in the lower mantle and core. However, slip between the sample and piston is still a problem, since the slip prevents the attainment of a constant strain rate and interferes with the uniform deformation of a sample. In this paper, we report that using a diamond anvil with deep grooves results in a marked improvement in the coupling between the sample and the diamond anvils.

Neutron powder diffraction and high-pressure synchrotron x-ray diffraction study of tantalum nitrides*

Tantalum nitride (TaN) compact with a Vickers hardness of 26 GPa is prepared by a high-pressure and hightemperature (HPHT) method. The crystal structure and atom occupations of WC-type TaN have been investigated by neutron powder diffraction, and the compressibility of WC-type TaN has been investigated by using in-situ high-pressure synchrotron x-ray diffraction. The third-order Birch–Murnaghan equation of state fitted to the x-ray diffraction pressure–volume (P – V) sets of data, collected up to 41 GPa, yields ambient pressure isothermal bulk moduli of B 0 = 369(2) GPa with pressure derivatives of for the WC-type TaN. The bulk modulus of WC-type TaN is not in good agreement with the previous result (B 0 = 351 GPa), which is close to the recent theoretical calculation result (B 0 = 378 GPa). An analysis of the experiment results shows that crystal structure of WC-type TaN can be viewed as alternate stacking of Ta and N layers along the c direction, and the covalent Ta–N bonds between Ta and N layers along the c axis in the crystal structure play an important role in the incompressibility and hardness of WC-type TaN.