Regulating Dielectric and Ferroelectric Properties of Poly(vinylidene fluoride-trifluoroethylene) with Inner CH=CH Bonds

Poly(vinylidene fluoride) (PVDF) based ferroelectric polymers have attracted considerable attention both academically and industrially due to their tunable ferroelectric properties. By pinning the conformation of the polymer chain and the ferroelectric phase physically or chemically, the ferroelectric behaviors of PVDF based polymers could be finely turned from normal ferroelectric into relaxor ferroelectric, anti-ferroelectric like, and even linear dielectric. Besides high energy electron irradiation and chemical copolymerization with the bulky monomers, in this work, an alternative strategy is presented to regulate the dielectric and ferroelectric performances of PVDF based ferroelectric polymer for the first time. CH=CH bonds with the desired content are inserted by a controlled dehydrofluorination reaction into a poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) copolymer (TrFE refers to trifluoroethylene) synthesized from the hydrogenation of P(VDF-CTFE) (CTFE refers to chlorothrifluoroethylene). The influence of the CH=CH bonds along with the fabrication conditions on the crystallization and ferroelectric relaxation of the resultant copolymers (referred to P(VDF-TrFE-DB)) was carefully characterized and discussed. The nonrotatable CH=CH bonds result in depressed dielectric and ferroelectric performances in the as-cast films by confining the orientation of ferroelectric grains in P(VDF-TrFE). The normal ferroelectric performance of P(VDF-TrFE) is turned into anti-ferroelectric like behavior in the resultant P(VDF-TrFE-DB). The cleavage of CH=CH bonds is responsible for the recovery of the ferroelectric behavior in the annealed samples. Uniaxial stretching favors the alignment of the polymer chain and ferroelectric domains, which may address the further regulated ferroelectric characters in the stretched samples.