Temperature dependence of the cation distribution in CuAl2O4 spinel

The temperature dependence of the cation distribution in CuAl₂O₄ spinel has been determined from 600 to 1100°C on quenched specimens by powder X-ray diffraction, and from room temperature to 1000°C by in-situ high-temperature powder neutron diffraction. The results, in agreement with earlier work, show that CuAl₂O₄ is a largely normal spinel, which is already highly disordered at 600°C, the lowest temperature at which the cation distribution is inferred to be in equilibrium, with an inversion parameter, x, at this temperature of 0.35 ± 0.005 from the neutron diffraction experiments. Increasing temperature to 1000°C only causes a modest increase in x, to 0.40 ± 0.005. This somewhat unusual behaviour may be ascribed to local distortions from the Jahn-Teller effect in both octahedrally and tetrahedrally coordinated Cu²⁺. Thermodynamically, the ordering may be described either with a large entropy of disordering, or alternatively, with a large and positive quadratic term in the enthalpy of disordering. The Jahn-Teller effect produces no long-range distortion of the structure, which has cubic symmetry (space group Fd3̄m) under all investigated conditions.