Anomalous grain boundary conduction in BiScO3-BaTiO3 high temperature dielectrics

A combination of X-ray diffraction, analytical-electron microscopy, differential scanning calorimetry, impedance spectroscopy and electromotive force measurements (for oxide-ion transport number measurements, tion) are used to report on the influence of a small amount of a continuous Bi2O3-rich phase along the grain boundaries in sample composition x = 0.4 (BS0.4BT) of the high temperature dielectric solid solution series, x(BiScO3)-(1-x)(BaTiO3). Its presence produces a dramatic change in conductivity of ~ two orders of magnitude and a switch in tion over the range ~ 600 - 800 °C that is not observed for other ceramics with lower BiScO3 content. Below ~ 700 °C the grain boundaries in BS0.4BT act as electrically blocking layers and dominate the impedance of the ceramics. In contrast, at > 800 °C the grain boundaries become highly conductive due to a polymorphic phase transition to, and melting of δ-Bi2O3 which results in the current percolating along the grain boundaries and therefore avoiding the grains. The value of tion increases from ~ 0.13 at ~ 600 °C to near unity at ~ 800 °C for BS0.4BT, consistent with oxide ion conduction due to the presence of liquid Bi2O3 at grain boundary regions. This behaviour was reproduced by adding a small excess of 3 wt% Bi2O3 into x = 0.3 (BS0.3BT) samples to induce a Bi2O3-rich grain boundary phase, not otherwise present in this composition.