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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The study of grain size effects in ferroelectric ceramics has attracted great research interest over the last 50 years. Although different theoretical models have been proposed to account for the variation in structure and properties with grain size, the underlying mechanisms are still under debate, creating a significant level of uncertainty in the field. Here, we report the results of a study on the influence of grain size on the structural and physical properties of Ba(Ti0.96Sn0.04)O3, which represents a model perovskite system, where the effects of point defects, stoichiometry imbalance and phase transitions are minimized by Sn substitution. It was found that different microscopic mechanisms are responsible for the various grain size dependences observed. In fine-grained ceramics, high permittivity is due to high domain wall density and polar nanoregions; high d33 in coarse-grained ceramics results from a high degree of domain alignment during poling; large electric field-induced strain in intermediate-grained ceramics is an outcome of a favourable interplay between constraints from grain boundaries and reversible reorientation of non-180º domains and polar nanoregions. These paradigms can be regarded as general guidelines for the optimization of specific properties through grain size control. I.

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The electromechanical response of pure lead zirconate titanate (PZT) and Mn-doped PZT thin ferroelectric films under nanoindentation forces of up to 500 mN was investigated. The stress-induced current transients were measured as a function of the externally applied load on films of different thicknesses using a spherical WC–Co cermet indenter of 500 μm nominal radius. It was found that the quasi-static current generated through the direct piezoelectric effect is superimposed with a contribution from irreversible domain processes during the loading/unloading cycle. The film thickness dependency of the electrical transients and an asymmetry of the current-force curves are attributed to the in-plane clamping stress in the films produced by a dissimilar substrate. Analysis of corresponding charge-force hysteresis loops revealed a significant role for the residual stress state on the polarization switching in thin films. By the application of an indentation force, a portion of Barkhausen jumps was empirically estimated to increase as a consequence of reduction of the clamping effect on domains. The Rayleigh hysteretic charge-force curves showed recovery of the charge released during the load-unload stress cycle. For the thicker 700 nm films, the total charge released during loading was fully recovered with weak hysteresis. In contrast, strong in-plane clamping stresses in the 70 nm thick films are suggested to be reponsible for incomplete recovery upon unloading. A considerable domain-wall contribution to the electromechanical response was demonstrated by an enhanced polarization state, which was shown by an increase of the effective piezoelectric coefficient deff of about 35% of its initial value for the thin films at a maximum force of 500 mN.

The need for more energy-efficient and environmentally-friendly alternatives in the refrigeration industry to meet global emission targets has driven efforts towards materials with a potential for solid state cooling. Adiabatic depolarisation cooling, based on the electrocaloric effect (ECE), is a significant contender for efficient new solid state refrigeration techniques. Some of the highest ECE performances reported are found in compounds close to the morphotropic phase boundary (MPB). This relationship between performance and the MPB makes the ability to tune the position of the MPB an important challenge in electrocaloric research. Here, we report direct ECE measurements performed on MPB tuned NBT-06BT bulk ceramics with a combination of A-site substitutions. We successfully shift the MPB of these lead-free ceramics closer to room temperature, as required for solid state refrigeration, without loss of the criticality of the system and the associated ECE enhancement.