Extended phase homogeneity and electrical properties of barium calcium titanate prepared by the wet chemical methods

Ca-substituted BaTiO3 with extended homogeneity range upto ∼50 mol% CaTiO3 have been prepared by three different chemical routes namely carbonate-oxalate (COBCT), gel-carbonate (GCBCT), and gel-to-crystallite conversion (GHBCT) followed by heat treatment above 1150 °C. X-ray powder diffraction (XRD) data show continuous decrease in the tetragonal unit cell parameters as well as c0/a0 ratio with CaTiO3 content, which are in accordance with the substitution of smaller sized Ca2+ ions at the barium sites. The microstructure as well as the dielectric properties are greatly influenced by the cationic ratio, α=(Ba+Ca)/Ti. The grain size decreases with CaTiO3 content for the stoichiometric samples (α=1), whereas ultrafine microstructure is observed in the case of off-stoichiometric samples (α>1) for the whole compositional range of CaTiO3 concentrations. Sharper εr–T characteristics at lower calcium content and broader εr–T with decreased εmax, in the higher calcium range are observed in the case of α=1. Whereas nanometer grained ceramics exhibiting diffuse εr–T characteristics are obtained in the case of α>1. The positive temperature coefficient of resistivity (PTCR) is realized for barium calcium titanate ceramics having 0.3 at.% Sb as the donor dopant for higher CaTiO3 (typically 30 mol%) containing samples (α=1), indicating that Ca2+ ions do not behave as acceptors if they were to substitute at the Ti4+ sites. Whereas the off-stoichiometric (α>1) ceramics retained high resistivity, indicative of the Ti-site occupancy for Ca2+ in fine grain ceramics.