Structure and Properties of (Ba,Ca) TiO3 Ceramics Prepared Using (Ba,Ca)TiO3 Ceramics I, Crystallographic and Microstructural Studies

Ba_1–xCa_xTiO₃ powders have been prepared using a novel route involving solid-state reaction in a mixture of Ba_1–xCa_xCO₃ and TiO₂. The Ba_1–xCa_xCO₃ precursors used in this method were prepared by a chemical coprecipitation route to ensure a uniform supply of Ba and Ca ions during thermochemical reaction with TiO₂. The compositional homogeneity of Ba_1–xCa_xTiO₃ powder prepared by such a semiwet route is compared with those prepared by the conventional dry route, involving thermochemical reaction in a mixture of BaCO₃, CaCO₃, and TiO₂, using principles of X-ray line broadening. It is shown that the powders obtained by the semiwet route possess better compositional homogeneity, over a length scale of 1800 Å corresponding to the coherently scattering domain size, than those prepared by the conventional dry route. Microstructural studies have revealed grain sizes of the order of 1 μm and several micrometers, respectively, for ceramics prepared by the semiwet and conventional dry routes. The solid solubility limit of Ca in Ba_1–xCa_xTiO₃ ceramics fired at 1300°C is 16 mol% for samples prepared by the semiwet route while conventionally processed ceramics had a Ca solid Solubility limit of 12 mol% at the same temperature.