Polymer-based nanocomposites containing inorganic ferroelectric inclusions, typically ABO₃ perovskites, have emerged as innovative dielectric materials for energy storage and electric insulation, potentially coupling the high breakdown strength (BDS) and easy processing of polymers with the enhancement of dielectric constant provided by the ferroelectric phase. In this paper, experimental data and three-dimensional finite element method (3D FEM) simulations were combined to shed some light on the effect of microstructures on the dielectric properties of poly(vinylidene fluoride) (PVDF)-BaTiO₃ composites. The existence of particle aggregates or touching particles has a strong effect on the effective dielectric constant and determines an increase of the local field in the neck region of the ferroelectric phase with a detrimental effect on the BDS. The distribution of the field and the effective permittivity are very sensitive to the specific microstructure considered. The degradation of the BDS can be overcome by coating the ferroelectric particles with a thin shell of an insulating oxide with a low dielectric constant, such as SiO₂ (ε_r = 4). The local field is highly concentrated on the shell, while the field in the ferroelectric phase is reduced almost to zero and that on the matrix is close to the applied one. The electric field in the matrix becomes less homogeneous with increasing the dielectric constant of the shell material, as happens with TiO₂ (ε_r = 30). These results provide a solid background to explain the enhanced dielectric properties and the superior BDS of composites containing core-shell inclusions.

The hydrothermal/solvothermal method is one of the most versatile synthetic routes for producing a large number of compounds. The thermodynamic aspects, the control of morphology and the crystallisation mechanisms are reviewed and discussed in this highlight, with special emphasis on the synthesis of SrTiO ₃ , as a model system.

It is well known that disordered relaxor ferroelectrics exhibit local polar correlations. The origin of localized fields that disrupt long‐range polar order for different substitution types, however, is unclear. Currently, it is known that substituents of the same valence as Ti⁴⁺ at the B‐site of barium titanate lattice produce random disruption of TiOTi chains that induces relaxor behavior. On the other hand, investigating lattice disruption and relaxor behavior resulting from substituents of different valence at the B‐site is more complex due to the simultaneous occurrence of charge imbalances and displacements of the substituent cation. The existence of an effective charge mediated mechanism for relaxor behavior appearing at low (<10%) substituent contents in heterovalent modified barium titanate ceramics is presented in this work. These results will add credits to the current understanding of relaxor behavior in chemically modified ferroelectric materials and also acknowledge the critical role of defects (such as cation vacancies) in lattice disruption, paving the way for chemistry‐based materials design in the field of dielectric and energy storage applications.