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Thermodynamic study of some solid solutions in the CaOZrO2 system by emf method
Authors:VA Levitski  PB Narchuk  Ju Hekimov  JaI Gerassimov
Institution:Laboratory of Chemical Thermodynamics, Lomonosov University, Moscow, B-234, U.S.S.R.
Abstract:The thermodynamic properties of some solid solutions in the CaOZrO2 system have been investigated by using solid electrolyte galvanic cells of the type: O2, Pt|CaO, CaF2|CaF2 (tF = 1)| δCaO(1 ? δ)ZrO2, CaF2|Pt, O2. The influence of CaF2 added in electrodes on the thermodynamic equilibrium was investigated. It was shown that the heterogeneous field with cubic solid solution reaches the composition x = 0.17 mole of CaO. The results indicate that addition of ZrO2 to the saturated solid solution produces a significant decrease in the activity of CaO. Measured data were used to calculate thermodynamic parameters of reactions with saturated solid solutions Ca0.17 Zr0.83 O1.83, ZrO2, and CaZrO3. At temperatures below 820°C, saturated solid solutions have a tendency to decompose into CaZrO3 and ZrO2. A comparison of the thermodynamic results with available data on phase relationships in the CaOZrO2 system is presented. High thermodynamic stability of SrZrO3 and BaZrO3 is one of the reasons for the absence of cubic solid solutions in the system MeOZrO2 (MeSr, Ba).
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