Core–double-shell-structured nanocomposite films consisting of polyvinylidene fluoride-grafted-barium titanate (PVDF-g-BT) incorporated into a P(VDF-co-hexafluoropropylene (HFP)) copolymer matrix were produced via a solution mixing method for energy storage applications. The resulting films were thoroughly investigated via spectroscopic, thermal, and morphological analyses. Thermogravimetric data provided an enhancement of the thermal stability, while differential scanning calorimetry indicated an increase in the crystallinity of the films after the addition of PVDF-g-BT. Moreover, broadband dielectric spectroscopy revealed three dielectric processes, namely, glass–rubber relaxation (α_a), relaxation associated with the polymer crystalline phase (α_c), and slower relaxation in the nanocomposites resulting from the accumulation of charge on the interface between the PVDF-g-BT filler and the P(VDF-co-HFP) matrix. The dependence of the dielectric constant from the composition was analyzed, and we found that the highest permittivity enhancement was obtained by the highest concentration filler added to the largest concentration of P(VDF-co-HFP). Mechanical analysis revealed an improvement in Young’s modulus for all nanocomposites versus pristine P(VDF-co-HFP), confirming the uniformity of the distribution of the PVDF-g-BT nanocomposite with a strong interaction with the copolymer matrix, as also evidenced via scanning electron microscopy. The suggested system is promising for use in high-energy-density storage devices as supercapacitors.

The complex dynamics of a nearly alternating copolymer of vinylidene cyanide (1,1-dicyanoethylene, VCN) with 2,2,2-trifluoroethyl methacrylate (TFEMA), including two α-relaxations with diverging time scale in the glass transition temperature range, was thoroughly characterized by dielectric spectroscopy over wide temperature and frequency ranges and analyzed in the frame of the Ngai’s coupling model. The dielectric relaxation strength as well as the glass transition temperature, the temperature dependence of the α-relaxation time, and the corresponding distribution of relaxation times were all larger than those of a reference TFEMA homopolymer, as expected from the introduction of the stiffening VCN units all along the macromolecular chain. The effect of casting solvent and applied poling electric field on the copolymer dielectric strength suggests the onset of local orientational order involving the strong dipoles in the VCN units, a requirement for piezo- and pyroelectricity in amorphous polymers.

Copolymerization of 2-phenyl-1,1-dicyanoethylene (PDE) with 4-fluorostyrene and pentafluorostyrene in solution with radical initiation (ABCN) at 70°C yielded random copolymers with PDE alternating units. The composition of the copolymers was calculated from nitrogen analysis and the structure was analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r₁) and the tendency toward alternation of monomer units in the copolymer for these two monomers, is 4-fluorostyrene (1.96) > pentafluorostyrene (0.51). Higher glass transition temperature of the copolymers in comparison with that of homopolymers indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit.