Grain size effects on the physical properties of polycrystalline ferroelectrics have been extensively studied for decades; however there are still major controversies regarding the dependence of the piezoelectric and ferroelectric properties on the grain size. Dense BaTiO3 ceramics with different grain sizes were fabricated by either conventional sintering or spark plasma sintering using micro- and nano-sized powders. The results show that the grain size effect on the dielectric permittivity is nearly independent of the sintering method and starting powder used. A peak in the permittivity is observed in all the ceramics with a grain size near 1 μm and can be attributed to a maximum domain wall density and mobility. The piezoelectric coefficient d33 and remnant polarization Pr show diverse grain size effects depending on the particle size of the starting powder and sintering temperature. This suggests that besides domain wall density, other factors such as back fields and point defects, which influence the domain wall mobility, could be responsible for the different grain size dependence observed in the dielectric and piezoelectric/ferroelectric properties. In cases where point defects are not the dominant contributor, the piezoelectric constant d33 and the remnant polarization Pr increase with increasing grain size.

Lithium-substituted 0.95[0.94(Bi 0.5 Na (0.5−x) Li x )TiO 3 −0.06BaTiO 3 ]− 0.05CaTiO 3 materials include the polar rhombohedral R3c and the weakly polar tetragonal P4bm phases. On increasing lithium content, the (R3c/P4bm) phase ratio decreased, while the rhombohedral and tetragonal lattice distortions remained the same. The temperature corresponding to the shoulder in the dielectric permittivity shows no clear shift with respect to lithium substitution because of the rhombohedral distortion remaining constant. Electrical poling produced an increase of the rhombohedral phase fraction together with a rise of the rhombohedral and tetragonal distortion. This confirmed the occurrence of a phase transition from the weakly polar to the polar phase during electrical poling. Four peaks found in the current−electric field (I−E) loops are related to reversible electric field induced transitions. By studying the temperature dependence of the current peaks in the I−E loops, it was found that the minimum temperature where these electric field induced transitions take place decreases with increasing lithium substitution.

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