Atomistic calculations of the thermodynamic properties of mixing for tetravalent metal dioxide solid solutions: (Zr, Th, Ce)O2

The thermodynamic mixing properties for isometric ThxCe1-xO2, CexZr1-xO2, and ThxZr1-xO2 were determined using quantum-mechanical calculations and subsequent Monte-Carlo simulations. Although the ThxCe1-xO2 binary indicates exsolution below 600 K, the energy gain due to exsolution is small (E-exsoln=1.5 kJ/(mol cations) at 200 K). The energy gain for exsolution is significant for the binaries containing Zr; at 1000 K, E-exsoln=6 kJ/mol cations) for the CexZr1-xO2 binary, and E-exsoln=17 kJ/(mol cations) for the ThxZr1-xO2 binary. The binaries containing Zr have limited miscibility and cation ordering (at 200 K for x=0.5). At 1673 K, only 4.0 and 0.25 mol% ZrO2 can be incorporated into CeO2 and ThO2, respectively. Solid-solution calculations for the tetragonal ThxZr1-xO2 binary show decreased mixing enthalpy due to the increased end-member stability of tetragonal ZrO2. Inclusion of the monoclinic ZrO2 is predicted to further reduce the mixing enthalpy for binaries containing Zr. (C) 2012 Elsevier Inc. All rights reserved.