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

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 β-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 α-phase. Furthermore, favorable melt interactions between both blocks induce crystallization into the polar γphase at moderate cooling rates.

Sign up for access to the world's latest research.

checkGet notified about relevant papers

checkSave papers to use in your research

checkJoin the discussion with peers

checkTrack your impact