Influence of Ferroelectric Filler Size and Clustering on the Electrical Properties of (Ag-BaTiO3)-PVDF Sub-Percolative Hybrid Composites.

The paper presents a study concerning the role of ferroelectric filler size and clustering in the dielectric properties of 20%BaTiO3-80%PVDF and of 20% (2%Ag-98%BaTiO3)-PVDF hybrid nanocomposites. By finite element calculations, it was shown that using fillers with ε > 103 does not provide a permittivity rise in the composites and the effective dielectric constant tends to saturate to specific values determined by the filler size and agglomeration degree. Irrespective of the ferroelectric filler sizes, the addition of metallic ultrafine nanoparticles (Ag) results in permittivity intensification and the effect is even stronger if the metallic nanoparticles are connected to a higher degree with the ferroelectric particles' surfaces. When using coarse ferroelectric fillers, the probability of clustering is higher, thus favoring the permittivity increase by field concentration in small regions close to the interfaces separating dissimilar materials. The modeling results were validated by an experimental dielectric analysis performed in a series of PVDF-based thick films with the same amount of BaTiO3 fillers or with Ag-BaTiO3 hybrid fillers. Similar trends as predicted by simulations were found experimentally but with slightly higher permittivity values which were assigned to the modifications of the polymer phase composition due to the presence of nanofillers and the local sample inhomogeneity (the presence of clustering, in particular for coarse BaTiO3 grains), which create regions with enhanced local fields.

Optimization of Processing Steps for Superior Functional Properties of (Ba, Ca)(Zr, Ti)O3 Ceramics.

Lead-free piezoelectric ceramics with nominal composition at morphotropic phase boundary Ba0.85Ca0.15Ti0.9Zr0.1O3 (BCTZ) prepared by different processing routes and sintered either by conventional solid-state reaction or by spark plasma sintering (SPS) techniques were comparatively investigated to observe the role of structural modifications and of microstructures on the dielectric, ferroelectric, piezoelectric and electrocaloric responses. The ceramics presented relative densities from 75% to 97% and showed variations in their phase composition as a result of variable mixing and different synthesis and sintering parameters providing local compositional heterogeneity. As result, all of the ceramics showed diffuse phase transition and ferroelectric switching responses, with parameters affected mostly by density (Pr between 3.6 to 10.1 µC/cm2). High values for the electrocaloric response in the Curie range were found for the ceramics with predominantly orthorhombic character. Field-induced structural modifications were probed by tunability anomalies and by XRD experiments in remanence conditions. Piezoelectric effects with notably high figure of merit values were assigned to the better densification and poling efficiency of BCTZ ceramics.

Role of Density and Grain Size on the Electrocaloric Effect in Ba0.90Ca0.10TiO3 Ceramics.

Pure perovskite Ba0.90Ca0.10TiO3 ceramics, with a relative density of between 79 and 98% and grain sizes larger than 1 µm, were prepared by solid-state reaction. The dielectric and electrocaloric properties were investigated and discussed considering the density and grain size of the samples. Room temperature impedance measurements show good dielectric properties for all ceramics with relative permittivity between 800 and 1100 and losses of <5%. Polarization vs. E loops indicates regular variation with increasing sintering temperature (grain size and density), an increase in loop area, and remanent and saturation polarization (from Psat = 7.2 µC/cm2 to Psat = 16 µC/cm2). The largest electrocaloric effect was 1.67 K for ceramic with GS = 3 µm at 363 K and electrocaloric responsivity (ζ) was 0.56 K mm/kV. These values are larger than in the case of other similar materials; thus, Ba0.90Ca0.10TiO3 ceramics with a density larger than 90% and grain sizes of a few µms are suitable materials for electrocaloric devices.

Scale-Dependent Dielectric Properties in BaZr0.05Ti0.95O3 Ceramics.

In the present work, BaZr0.05Ti0.95O3 ceramics with grain sizes between 0.45 and 135 µm were prepared by solid-state reaction and classical sintering. The effect of grain size on dielectric properties was systematically explored, and it was found that dielectric permittivity reaches a maximum value for grain sizes between 1.5 and 10 µm and then rapidly drops for larger grain sizes. A numerical finite element method was employed to eliminate the effect of porosity on the effective values of permittivity. The results indicate that it is possible to have a critical size in slightly doped barium titanate ceramics with enhanced functional properties for a grain size between 1.5 and 10 µm.

Effect of Porosity on Functional Properties of Lead-Free Piezoelectric BaZr0.15Ti0.85O3 Porous Ceramics.

The present paper reports the dependence of dielectric, ferroelectric and piezoelectric properties on the porosity level in BaZr0.15Ti0.85O3 ceramics with porosity from 5% to 21%. Microporosity with 0-3 connectivity has been produced using PMMA microspheres as a sacrificial template. The functional properties (dielectric, ferroelectric and piezoelectric effect) are mostly affected by the "dilution effect": permittivity decreases by 40% when porosity increases by 21%, and Pmax decreases from 13 to 5 µC/cm2 while the Prem is in the range of (2-8) µC/cm2. However, the reduction of the zero-field permittivity and hysteretic behaviour of ε(E) while the tunability level is still high makes from porous ceramics interesting materials for tunability application.