Pronounced Surface Effects on the Curie Transition Temperature in Nanoconfined P(VDF-TrFE) Crystals

[Image: see text] Changes in the Curie transition temperature of nanoconfined poly(vinylidene fluoride–trifluoroethylene) P(VDF-TrFE) copolymers can have a severe impact on the electroactive behavior and the application range of these materials. Therefore, the origin of the change in the Curie transition temperature requires a profound understanding. In this work, block copolymer self-assembly into a spherical morphology proves to be a viable method to effectively confine P(VDF-TrFE) in three dimensions for studying the effect of nanoconfinement on the Curie transition. Using differential scanning calorimetry and wide-angle X-ray scattering, easily accessible experimental techniques, we follow the crystalline phase transitions, showing that confining P(VDF-TrFE) in a nonpolar polystyrene (PS) or poly(4-tert-butoxystyrene) (PtBOS) matrix results in an increase of the Curie transition upon cooling and heating. However, when a more polar matrix is used to nanoconfine P(VDF-TrFE), the Curie transition temperature is drastically reduced due to surface effects.