Dmytro Dzivenko

Possible Superhardness of CrB4

Chromium tetraboride [orthorhombic, space group Pnnm (No. 58), a = 474.65(9) pm, b = 548.0(1) pm, c = 286.81(5) pm, and R value (all data) = 0.041], formerly described in space group Immm, was found not to be superhard, despite several theory-based prognoses. CrB(4) shows an almost temperature-independent paramagnetism, consistent with low-spin Cr(I) in a metallic compound. Conductivity measurements confirm the metallic character.

High Pressure Synthesis of Marcasite-Type Rhodium Pernitride

Marcasite-type rhodium nitride was successfully synthesized in a direct chemical reaction between a rhodium metal and molecular nitrogen at 43.2 GPa using a laser-heated diamond-anvil cell. This material shows a low zero-pressure bulk modulus of K0 = 235(13) GPa, which is much lower than those of other platinum group nitrides. This finding is due to the weaker bonding interaction between metal atoms and quasi-molecular dinitrogen units in the marcasite-type structure, as proposed by theoretical studies.

Elastic moduli and hardness of c-Zr2.86(N0.88O0.12)4 having Th3P4-type structure

The equation of state of the recently discovered oxygen-bearing cubic zirconium (IV) nitride, c-Zr2.86(N0.88O0.12)4, was measured at room temperature in a diamond anvil cell using x-ray powder diffraction combined with synchrotron radiation. From these studies the bulk modulus B0=219(13)GPa and its first pressure derivative B0′=4.4(1.0) [or B0=223(5)GPa, for B0′ fixed at 4] were obtained. Applying nanoindentation techniques the reduced modulus Er≈220GPa and hardness H≈18GPa were measured for porous c-Zr2.86(N0.88O0.12)4. The shear modulus of c-Zr2.86(N0.88O0.12)4 was estimated to be at least G0=96(13)GPa using the experimental data of B0 and Er, exclusively.

Pressure-Induced Decomposition of Indium Hydroxide

A static pressure-induced decomposition of indium hydroxide into metallic indium that takes place at ambient temperature is reported. The lattice parameter of c-In(OH)(3) decreased upon compression from 7.977(2) to approximately 7.45 A at 34 GPa, corresponding to a decrease in specific volume of approximately 18%. Fitting the second-order Birch-Murnaghan equation of state to the obtained compression data gave a bulk modulus of 99 +/- 3 GPa for c-In(OH)(3). The c-In(OH)(3) crystals with a size of approximately 100 nm are comminuted upon compression, as indicated by the grain-size reduction reflected in broadening of the diffraction reflections and the appearance of smaller (approximately 5 nm) incoherently oriented domains in TEM. The rapid decompression of compressed c-In(OH)(3) leads to partial decomposition of indium hydroxide into metallic indium, mainly as a result of localized stress gradients caused by relaxation of the highly disordered indium sublattice in indium hydroxide. This partial decomposition of indium hydroxide into metallic indium is irreversible, as confirmed by angle-dispersive X-ray diffraction, transmission electron microscopy imaging, Raman scattering, and FTIR spectroscopy. Recovered c-In(OH)(3) samples become completely black and nontransparent and show typical features of metals, i.e., a falling absorption in the 100-250 cm(-1) region accompanied by a featureless spectrum in the 250-2500 cm(-1) region in the Raman spectrum and Drude-like absorption of free electrons in the region of 4000-8000 cm(-1) in the FTIR spectrum. These features were not observed in the initial c-In(OH)(3), which is a typical white wide-band-gap semiconductor.

High-pressure high-temperature synthesis of novel binary and ternary nitride phases of group 4 and 14 elements

Our recent experiments on high-pressure high-temperature synthesis of novel ternary nitrides of group 4 and 14 elements are presented. Dense carbon nitride imide, C2N2(NH), was synthesized for the first time in a laser heated diamond anvil cell (LH-DAC) at pressures above 27 GPa and temperatures around 2000 K. Based on results of the electron diffraction-, EELS-and SIMS-measurements combined with theoretical calculations the structure of this new C-N-H phase was suggested to be of the defect-wurtzite type. Farther, macroscopic amounts of a new oxynitride of zirconium having cubic Th3P4-type structure, c-Zr2.86(N0.88O0.12)4, were synthesized at high pressures and temperatures using a multi-anvil apparatus. Earlier this structure was observed for binary nitrides of zirconium(IV) and hafnium(IV) synthesized in microscopic amounts in a LH-DAC. The lattice parameter of c-Zr2.86(N0.88O0.12)4 was found to be a0 = 6.7549(1) A which is slightly larger than that of c-Zr3N4. Isotropic bulk and shear moduli of c-Zr2.86(N0.88O0.12)4 of B0 = 219 GPa and G0 = 96 GPa, respectively, were determined from the compression and nanoindentation measurements. The Vickers microhardness, HV(1), of the porous (about 30 vol. %) sample of c-Zr2.86(N0.88O0.12)4 was measured to be 12 GPa, similar to that of single crystal δ-ZrN.