Structure and ferroelectric phase transition of vinylidene fluoride-trifluoroethylene copolymers: 2. VDF 55% copolymer

Abstract

Molecular and crystal structure changes in ferroelectric phase transition of vinylidene fluoride-trifluoroethylene (VDF-TrFE) copolymer with a VDF content of 55 mol% have been investigated by X-ray diffraction and infra-red and Raman spectroscopy. As the temperature rises from room temperature to the Curie point of ∼60°C, the polar low-temperature phase consisting of all- trans chains experiences a first-order transition to the phase of tilted long trans segments connected by some skew bonds. At higher temperature this new phase transforms continuously and steeply to the non-polar high-temperature phase, where the molecular structure consists of a random combination of TG, TḠ, T 3 G and T 3 G ̄ rotational sequences. In the cooling process the high-temperature phase transforms to the cooled phase, which is essentially equivalent to the phase appearing intermediately in the heating process from the low-temperature to the high-temperature phase. The cooled phase gives a tilting X-ray fibre diagram and is found by X-ray analysis to contain an appreciable amount of so-called 60° domain structure. These are well interpreted by a conformational model of tilting trans structure containing skew linkages. The tensile stress along the fibre axis causes the transformation from the cooled phase to the low-temperature phase, where the probability of 60° domain structure and the degree of chain tilting are remarkably reduced.