Synthesis of Novel Superhard Phases in the B-C-N System

Novel ternary diamond-like phases of the B-C-N system were synthesized at pressures up to 30 GPa and temperatures up to 3500 K by static and dynamic compression of graphite-like BN-C solid solutions. Structure and properties of these new phases were studied using X-ray diffraction with synchrotron radiation, analytical transmission electron microscopy (ATEM), electron energy loss spectroscopy (EELS), microhardness measurements and nanoindentation.     

The 5v 3 bands of 18O enriched ozone: line positions of 16O16O18O, 16O18O16O, 16O18O18O and 18O16O18O

The four 5v ₃ bands of ¹⁸O enriched ozone have been observed and analysed for the first time. Two species (¹⁶O¹⁸O¹⁶O and ¹⁸O¹⁶O¹⁸O) belong to the C_2v symmetry group and two other (¹⁸O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O) to the C_s symmetry group. They have been recorded at a resolution of 0.008 cm^?1 with a pathlength of 32.16 m. Despite the very weak absorptions observed, almost 250 energy levels have been derived for each of the 4 species, with J ? 35 and K _a ? 13, and suitable sets of Hamiltonian parameters have been determined. For 3 species it has been necessary to account for the resonance between the (005) and (311) states to correctly reproduce the spectra observed. These resonances, anharmonic for C_2v, and hybrid (both anhar-monic and Coriolis) for C_s symmetry confirm the accidentally extremely strong coupling between the (005) and (311) states for ¹⁶O₃, due in that case to the very close distance between unperturbed energy levels. This work also confirms the excellent prediction of band centres of these four species derived from the recently determined isotopically invariant molecular potential function.     

Conference summary on the first international workshop on advanced superhard materials

Composite diamond anvils have been developed for high-pressure/high-temperature measurements of diamond anvil cells. The anvils are fabricated using single-crystal chemical vapor deposition (CVD) from previously used and/or slightly damaged anvils made of natural or synthetic diamond. These composite anvils can be fabricated to possess optical characteristics at least comparable to conventional diamond anvils, whereas the single-crystal CVD portion is more durable because of its enhanced toughness relative to natural diamond. The viability of such anvils is demonstrated in measurements on hydrogen at megabar pressures and high temperature.     

Synthesis and thermal stability of cubic ZnO in the salt nanocomposites

Cubic zinc oxide (rs-ZnO), metastable under normal conditions, was synthesized from the wurtzite modification (w-ZnO) at 7.7 GPa and ∼800 K in the form of nanoparticles isolated in the NaCl matrix. The phase transition rs-ZnO → w-ZnO in nanocrystalline zinc oxide under ambient pressure was experimentally studied for the first time by using differential scanning calorimetry and high-temperature X-ray diffraction analysis. It was shown that the transition occurs in the temperature range from 370 to 430 K and its enthalpy at 400 K is −10.2 ± 0.5 kJ mol⁻¹.     

Kinetics of the wurtzite-to-rock-salt phase transformation in ZnO at high pressure

Kinetics of the wurtzite-to-rock-salt transformation in ZnO has been studied in the 5-7 GPa pressure range at temperatures below the activation of diffusion processes. The detailed analysis of non-isothermal experimental data using the general evolution equation describing the kinetics of direct phase transformations in solids allowed us to study the kinetic particularities of both nucleation and growth of the rock-salt phase in parent wurtzite ZnO. The main rate-limiting processes are thermally activated nucleation (E(N) = 383 kJ mol(-1) at 6.9 GPa) and thermally nonactivated (most probably quasi-martensitic) growth (k(G) = 0.833 min(-1) at 6.9 GPa). The high impact of thermal deactivation of nucleation places has been evidenced in the case of slow heating, which indirectly indicates that the rs-ZnO nucleation places are mainly produced by pressure-induced stresses in the parent phase.     

Reduction of the laminar compound of graphite with FeCl3 by hydrogen at high pressure

Conclusions A method is proposed for the reduction of laminar graphite compounds at hydrogen pressure up to 70 kbar, which has a number of significant advantages relative to reported methods. This method may be used to obtain new acceptor LGC.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 450–452, February, 1986.The authors express their gratitude to P. B. Fabrichnyi for assistance in the Moessbauer spectral study of these compounds.     

Thermoanalytical study of the polymorphic transformations of wurtzitic boron nitride modification into graphite-like ones

The polymorphic transformations of wurtzitic modification of boron nitride into graphite-like ones have been studied using DSC, inverse drop-calorimetry and dilatometry over the temperature range of 500 to 1400 K. The transformation enthalpies at 1380 K were determined to be +14±2 kJ/mole and +17±3 kJ/mole for wBN→hBN and wBN→rBN transformations, respectively.

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Zusammenfassung Mittels DSC, inverser Dropkalorimetrie und Dilatometrie im Temperaturbereich von 500 bis 1400 K wurden die polymorphen Umwandlungen der Wurtzit-Modifikation von Bornitrid in die Graphit-Modifikation untersucht. Die Umwandlungsenthalpien bei 1380 K für die Umwandlungen wBN→hBN und wBN→rBN wurden mit +14±2 kJ/mol und mit +17±3 kJ/mol bestimmt.

     

Solid-state synthesis of boron subnitride, B6N: myth or reality?

Solid-state synthesis of boron subnitride, B₆N, as a result of chemical interaction between boron and boron nitride at 7.5 GPa and 1700 °C has been previously reported by Hubert et al. However, a critical analysis of the results has shown that the evidence for the formation of boron subnitride with B₆O-like structure is inconclusive. We have studied in situ the interaction between boron and BN at the same p–T conditions using X-ray diffraction with synchrotron radiation. At 7.4 GPa and 1700 °C the formation of a new phase has not been observed. At the same time, HP–HT treatment has resulted in strong and unpredictable preferred orientation of boron crystallites. This leads to the rise of some weak boron reflections that might be erroneously attributed to the appearance of a new phase. To cite this article: V.L. Solozhenko et al., C. R. Chimie 9 (2006).