Influence of Steric Hindrance on Ferro‐ and Piezoelectric Performance of Poly(vinylidene fluoride)‐Based Ferroelectric Polymers

Abstract Poly(vinylidene fluoride) (PVDF) and copolymers possess excellent ferro‐ and piezoelectric properties, and highly expected to be utilized as sensors in the areas covering the smart wearer, hydrophone, speaker, and medical ultrasonic devices. Besides PVDF in β crystalline phase, the copolymers with trifluoroethylene (TrFE) and tetrafluoroethylene (TFE) are widely investigated both in academia and industry. To illustrate how the steric hindrance between VDF and TrFE/TFE affects the condensed‐state structure and electric properties of the polymers, the electric properties and their dependences on molecular configuration and crystal structures of PVDF, P(VDF‐TrFE), and P(VDF‐TFE) are comparatively investigated. The introduction of same molar contents (20 mol%) of TrFE and TFE monomers into PVDF chain leads to the similar conformation transformation from α (γ ) phase to β phase and similar crystallinity in resultant P(VDF‐TFE) and P(VDF‐TrFE) thanks to the depressed energy of trans conformation and the increased energy barrier between anti‐gauche and trans conformation. That leads to the more preferred β‐phase and ferroelectric domains generated in P(VDF‐TrFE) and P(VDF‐TFE). Both the size of ferroelectric phase, the polarity of the polymer chain, the organization and orientation of the grains along the field are responsible for the excellent piezoelectric field resulted by the varied composition as well.