On the microstructures of equilibrated and quenched spinel-containing nickel titanates

Electron microscopy has been used to study the microstructures of equilibrated and quenched NiO-TiO2 mixtures containing 5, 10, 15, 20 and 25 wt% TiO2. All the specimens contained rocksalt- and spinel-structured phases on a nanometre scale. The microstructure suggests that a non-stoichiometric spinel decomposed during quenching. The 25 wt% TiO2 specimen exhibited a lamellar microstructure composed of NiTiO3 and spinel-NiO. These phases had the usual orientation relationships, i.e., (111)cubic∥(0001)hex and 〈11̄0〉cubic∥〈11̄00〉hex. Faceted NiO solid-solution regions with coherent cube-on-cube interfaces with the spinel were found in the four specimens of lower TiO2 contents. When large (15 and 20 wt% TiO2), these regions were faceted cuboidal particles. With lower TiO2 contents, these regions were no longer equiaxed and could be interconnected. The specimens were chemically homogeneous on a length scale of about 1 μm. Morphological evidence is presented to explain which part of the microstructure most probably already existed in this form during equilibration. In particular, the large-scale NiTiO3 and the spinel lamella in the 25 wt% TiO2 material form during long-term equilibration.