Cation Short-Range Ordering of MgAl₂O₄ and NiAl₂O₄ Spinel Oxides at High Temperatures via In Situ Neutron Total...

Complex oxides that adopt the isometric spinel structure (AB₂O₄) are important for numerous technological applications and are relevant for certain geological processes, which involve exposure to extreme environments such as high pressures and temperatures. Recent studies have shown that the changes to the spinel structure caused by these environments are complex and depend on the material length scale under consideration. In this study, we have expanded this approach to the behavior of spinels under high temperatures. In situ neutron total scattering experiments, coupled with pair distribution function analysis, performed on two spinel compositions with various levels of pre-existing disorder (MgAl₂O₄ and NiAl₂O₄) revealed that both compositions trend to a state of maximum disorder where the A and B cations are randomly distributed among the two available sites. Temperature-induced cation inversion, conventionally understood as an exchange of cations on the A and B sites, is locally expressed as an atomic rearrangement to a tetragonal symmetry, a correlation that is retained up to the maximum temperature studied (1000 °C). A complex thermal expansion behavior is revealed wherein the oxide materials expand heterogeneously at the level of coordination polyhedra with an apparent dependence on bond strength.