Engineered poly(vinylidene fluoride) based composites containing inorganic inclusions as materials for energy-related applications: process-structure-properties correlations

In recent years the continuous and rapid development of the electronic industry together with the need for more efficient electric energy harvesting have notably increased the demand for: (i) high dielectric constant and breakdown strength materials for high energy density capacitors and (ii) piezoelectric flexible materials, with the ability to bend into diverse shapes, for powering low-power portable devices and self-powered electronic systems. Polymer-based composites and nanocomposites with inclusions of a ceramic active phase are very attractive for these applications because they combine materials with different characteristics, allowing the possibility to tune and optimize the dielectric and piezoelectric properties in the ensuing composite systems. In particular, many parameters can affect the material performance: (i) the nature of the polymer matrix and active component; (ii) the phases connectivity; (iii) the filler concentration, shape and dimensions; (iv) the filler/matrix interactions; (v) the preparation technique and processing. All this variability expands the possible applications of polymer-composites for energy-related purposes but also increases the difficulty in realistically predicting their ultimate properties. The design of polymer composites thus requires a rational selection of components, good interface engineering and proper processing optimization. To achieve this, a thorough comprehension of the process-structure-properties correlations is very important. This is the principal aim of this thesis work, which focus on the preparation of poly(vinylidene fluoride) homopolymer (PVDF) or poly(vinylidene fluoride-co-hexafluoropropylene) copolymer (PVDF-HFP) based composites with 0-3 connectivity containing different perovskite fillers, namely, BaTiO3 (BT), Pb(Zr,Ti)O3 (PZT) and Na0.5Bi0.5TiO3 - BaTiO3 (BNBT). The filler particles were used as prepared or properly surface modified and several techniques were employed for the composites preparation (i.e., solvent casting, melt blending, hot-pressing, compression moulding). Initially, a study of the neat polymer matrices was performed, by using, for the first time in literature, the compression moulding technique to tune the polymorphism of PVDF. A principal component analysis was performed on the infrared spectra of the moulded films to validate the equation usually employed for determining the electroactive phase amount (FEA) then multiple linear regression was applied to better understand how the processing parameters affect the FEA value. A double-step procedure was proven fundamental in inducing the formation of PVDF β phase and improving the dielectric properties of the ensuing polymer films. After this preparatory investigation, the study of the process-structure-properties correlations was extended to PVDF-based composites, addressing three main issues: (i) the influence of processing on the ultimate properties of the prepared samples; (ii) the influence of particles dimensions and surface modification on the dielectric behaviour of the composite materials; (iii) the response of flexible piezoelectric composites. The preparation technique affects the microstructure at different levels, but it was found that not always a flawless particles dispersion necessary leads to the best final performance of the composite. Whereas, a proper moulding method, by affecting the polymorphism of the polymer matrix and the compactness of the film, can improve significantly the dielectric response. The presence of an inorganic shell around BT particles allows a modulation of the effective permittivity of the composites; if intrinsic factors (i.e., the permittivity of the components) prevail on extrinsic ones (i.e., interfacial polarization), the composites response can be predicted by FEM calculations. However, in these conditions, the reduction in the dielectric constant compensates for the increase of the breakdown strength promoted by the shell and, as a whole, the stored energy decreases. It is worth noting that the composites containing core-shell particles are characterized by low tunability, a condition which is important for application as dielectric capacitors. The functionalization of the ceramic particles with the tested coupling agents, despite decreasing to a certain extent the dielectric permittivity of the ensuing composites (due to the intrinsic low permittivity of the silane moieties), increases the maximum electric field, thus leading to an energy recovering capability comparable or slightly higher than that of the composite containing pristine BT particles. The dielectric response of the composites is affected by the particles dimensions even though the films containing pristine BT and those containing TiO2-coated particles exhibit a different trend of dielectric permittivity with filler size; this suggests a not negligible contribution of the interfaces, which varies with the method of particles synthesis. As concerns the piezoelectric composites, the piezoelectric coefficient (d33), in general, increases if the filler dimensions increase significantly. The higher response of the samples containing sintered and crushed PZT or BNBT particles (with respect to simply calcined powders) probably derived from the higher particles connectivity inside the agglomerates, which in turn leads to higher local stresses inside the material. As far as we know, the piezoelectric properties of composites made of fluorinated polymer matrices and BNBT filler had not been studied yet. The obtained d33 are in line with those of many flexible lead-free composites made with particles different from BNBT, suggesting the potentiality of these composites in the field of energy harvesting. As principal achievements, I obtained: (i) an alternative and smart method to tune the polymorphism of PVDF homopolymer and its copolymers, by exploiting a simple and easily-scalable processing technique; (ii) solvent-free fabrication of polymer-based composites with dielectric properties improved by the moulding process; (iii) a better comprehension about the role of the interfaces, useful to tune the final performance of the dielectric composites; (iv) flexible lead-free polymer-based composites with a good piezoelectric response for potential application as safe energy harvesting devices.