Nanoconfinement-Induced β-Phase Formation Inside Poly(vinylidene fluoride)-Based Block Copolymers

The electroactive properties of poly(vinylidene fluoride) (PVDF) are a direct consequence of its crystalline phases. Although poorly understood, nanostructuring PVDF in confined geometries can drastically change its crystallization behavior. Therefore, we synthesized a variety of PVDF-based triblock copolymers to gain a better understanding of the melt crystallization and explore how crystallization is affected by the morphology and chemical nature of the amorphous block. Differential scanning calorimetry, small-/wide-angle X-ray scattering, and transmission electron microscopy gave us excellent insights into the morphology and the corresponding crystalline phases. We find that crystallization of PVDF inside spherical nanodomains occurs via a homogeneous nucleation mechanism leading to a large undercooling and the formation of the thermodynamically favorable ferroelectric beta-phase. On the contrary, when confined crystallization occurs inside a lamellar morphology, or in the case of breakout crystallization, a heterogeneous nucleation process leads to the formation of the nonferroelectric alpha-phase. Furthermore, favorable melt interactions between both blocks induce crystallization into the polar gamma-phase at moderate cooling rates.