Structural evolutions of VDF-based terpolymers with temperature and CTFE content. • Thermal correlation of SAXS-WAXS, DSC, DMA, dielectric spectroscopy and D−E loops data. • One or two crystal-crystal transitions are observed depending on CTFE content. • A model for continuous transition from orthorhombic RFE to hexagonal PE is proposed. • Enhancement of electroactive properties in the temperature range of the RFE-PE transition.
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