Nitride Metallurgy: Thermodynamics of Nitrides and Development of New Synthesis Methods

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As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M=Mg, Al, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of the cell at temperatures between 800 and 1100 K was measured. While the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03V were found. It was difficult to determine temperature dependence of the Emf. The Gibbs energy change for the reaction, 1/3 Li_3N(s)+1/3Mg_3N_2(s)=LiMgN (s), at 900 K was determined to be △G^o_r (LiMgN) = -13.2 (±2.9) kJ/mol. Using thermodynamic information on the binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be ΔG^o_f (LiMgN) = -121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of the stability region of the LiMgN phase. The diagram was found to be in good agreement with the isothermal phase diagram determined by the alloy equilibration method. Although the obtained data includes large uncertainties, the results provide a better understanding of the thermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.