High-pressure synthesis is a powerful method for the preparation of novel materials with high elastic moduli and hardness. Additionally, such materials may exhibit interesting thermal, optoelectronic, semiconductuing, magnetic or superconducting properties. Here, we report on the high-pressure synthesis of zirconium and hafnium nitrides with the stoichiometry M3N4, where M = Zr, Hf. Synthesis experiments were performed in a laser-heated diamond anvil cell at pressures up to 18 GPa and temperatures up to 3,000 K. We observed formation of cubic Zr3N4 and Hf3N4 (c-M3N4) with a Th3P4-structure, where M-cations are eightfold coordinated by N anions. The c-M3N4 phases are the first binary nitrides with such a high coordination number. Both compounds exhibit high bulk moduli around 250 GPa, which indicates high hardness. Moreover, the new nitrides, c-Zr3N4 and c-Hf3N4, may be the first members of a larger group of transition metal and/or lanthanide nitrides with interesting ferromagnetic or superconducting behaviour.
The melting curves of two compositions of (Mg,Fe) SiO3-perovskite, the likely dominant mineral phase in the lower mantle, have been measured in a C02 laser-heated diamond cell with direct temperature measurements and in situ detection of melting. At 625 kilobars, the melting temperature is 5000 +/- 200 kelvin, independent of composition. Extrapolation to the core-mantle boundary pressure of 1.35 megabar with three different melting relations yields melting temperatures between 7000 and 8500 kelvin. Thus, the temperature at the base of the lower mantle, accepted to lie between 2550 and 2750 kelvin, is only at about one-third of the melting temperature. The large difference between mantle temperature and corresponding melting temperature has several important implications; particularly the temperature sensitivity of the viscosity is reduced thus allowing large lateral temperature variations inferred from seismic tomographic velocity anomalies and systematics found in measured velocity-density functions. Extensive melting of the lower mantle can be ruled out throughout the history of the Earth.
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