Cation partitioning versus temperature in (Mg_0.70Fe_0.23)Al_1.97O₄ synthetic spinel by in situ neutron powder diffraction

Abstract 

Neutron powder diffraction experiments in the temperature range 300–1770 K were performed at BENSC, Berlin, Germany, on synthetic (Mg_0.70Fe_0.23) Al_1.97O₄. The cation partitioning over the crystallographic tetrahedral and octahedral sites was determined as a function of temperature through joint Rietveld refinements and advanced minimization techniques. The thermal expansion coefficients of the lattice parameter and inter-atomic bond lengths were also obtained from the full-profile structure refinements. The behaviour of the polyhedral bond-lengths, especially the T−O distances, and of the cell constant upon heating, clearly indicate that the interdiffusion of tetrahedral and octahedral Mg/Al cations starts at about 950 K. This result is straightforwardly supported by the direct analysis of the neutron site scattering factors: Fe always retains tetrahedral coordination at all temperatures, and the cation rearrangement is entirely due to Mg and Al diffusion.