Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} spinels: The case for a solid solution
In prior first-principles theoretical work we predicted a complete solid solution in the Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} system, with a negligibly small mixing enthalpy. In this work we tested this prediction on bulk, large-grained specimens across the Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} join, combining oxide melt solution calorimetry, differential scanning calorimetry, precise lattice parameter measurements, anomalous X-ray and neutron diffraction, and in situ electrical measurements. The calorimetric results confirm the presence of a solid solution at high temperatures, but with a large enthalpy of mixing that exceeds the predicted value. Because Co{sub 3}O{sub 4} and Co{sub 2}ZnO{sub 4} have essentially identical lattice parameters, this energetic destabilization must arise from factors other than the strain energy resulting from size mismatch. Changes in Co{sup 3+} spin states vs. temperature and zinc content are proposed to account for the positive excess enthalpy, and may also provide additional entropy to stabilize the solid solution at high temperature. - Graphical abstract: The first-principles theoretical prediction of a complete solid solution in Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} spinels has been confirmed experimentally by calorimetric, structural, and electrical measurements. The large mixing enthalpy observed exceeds the predicted value and cannot be accounted for by strain or cation distribution contributions alone, since such effects are small in this system; instead, changes in the spin state of Co{sup 3+} are proposed to account for the mixing thermodynamics. Highlights: Black-Right-Pointing-Pointer Experiments confirm theory prediction of a solid solution in Co{sub 3}O{sub 4}-Co{sub 2}ZnO{sub 4} spinels. Black-Right-Pointing-Pointer Thermodynamics of mixing studied by calorimetric, electrical, structural methods. Black-Right-Pointing-Pointer Cation distributions found to be mostly normal for various compositions. Black-Right-Pointing-Pointer Mixing enthalpy is larger than prediction and inconsistent with strain effects. Black-Right-Pointing-Pointer Changes in Co{sup 3+} spin state proposed as source of large mixing enthalpy/entropy.