Grain Size-Dependent Properties of Dense Nanocrystalline Barium Titanate Ceramics

The grain size influence on the dielectric relaxation and nonlinear dielectric properties of BaTiO 3 ceramics with grain size in the range of (92÷936) nm densified by Spark Plasma Sintering (SPS) from ultrafine powders were investigated. The progressive reduction of the Curie temperature and of the effective permittivity results from a combination of intrinsic size effects and low-permittivity grain boundary layer. A model of dielectric cylindrical cavities was employed in order to calculate intrinsic effective permittivity values in GHz range. An interesting feature is the presence of a thermally activated Debye-like relaxation in the ferroelectric state of ceramics with grain size above 300 nm, with activation energies of 0.45-0.49 eV, which seems to be related to the domain walls forced motion under the applied field. By diminishing grain size, a progressive reduction of the ferroelectric nonlinear character was obtained, reaching a macroscopic non-switching character and a linear permittivity versus field dependence for the finest ceramics (grain size of 90-100 nm) until very high values of the applied field. The observed behavior supports the idea of frozen polarization induced by pinning centers as due to a large number of grain boundaries and charged defects in the fine structures.