A self-consistent polycrystal model for the spontaneous polarization of ferroelectric ceramics

Motivated by the observation that the spontaneous polarization process of a ferroelectric polycrystal under the influence of a superimposed stress and/or electric field involves heterogeneous evolution of the ferroelectric phase among its constituent grains, a self-consistent electromechanical model is developed to determine the effective behaviour of the polycrystalline ceramic from such a heterogeneous electromechanical state. We start out from consideration of a micromechanics-based thermodynamic process to establish the kinetic equation of the crystallite and use it to evaluate the evolution of its ferroelectric domain. Then together with the Curie-Weiss law for the dielectric constants of the tetragonal phase, a dual-phase mixture theory is adopted to determine the change of its electromechanical moduli as temperature cools down below its Curie point. The overall property of the polycrystal is subsequently calculated by the self-consistent model through orientational average over its constituent grains. This two-level micromechanics model is applied to examine the shift of Curie temperature and evolution of the effective electromechanical moduli of a BaTiO₃ ceramic under cooling. The calculated results show that its Curie temperature decreases with increasing hydrostatic pressure, but increases with a superimposed axial compression or a biased electric field. The predicted temperature shift and change of the dielectric constants are found to be consistent with experimental observations.