A Novel Multiple Shape Memory Effect in PVDF‐Based Ferroelectric Copolymers and Terpolymers

Abstract Shape memory polymers (SMPs) have been extensively investigated because of their wide range of biomedical and robot applications. In most of SMPs, only one temporary shape can be formed and recovered through the mechanism of melting or glass transition. Herein, a multiple shape memory effect (mSME), i.e., formation of at least two temporary shapes, can be realized in polyvinylidene fluoride (PVDF)‐based ferroelectric polymers by exploiting their expanded ferroelectric–paraelectric (F‐P) phase transition temperature range. Although P(VDF‐TrFE) (TrFE: trifluoroethylene) (55/45) copolymer is thought to be a normal ferroelectric, its ferroelectric phase transforms into a paraelectric phase through an intermediate relaxor ferroelectric‐like state and mSME is observed in this extended phase transition temperature range. By incorporating CTFE (chlorotrifluoroethylene) into P(VDF‐TrFE), P(VDF‐TrFE‐CTFE) becomes a relaxor ferroelectric with a further extended phase transition temperature range. The terpolymer exhibits improved mSME and at least three temporary shapes can be formed and recovered. A comparison of SME and structures of several PVDF‐based copolymer and terpolymers suggests that the amount of polar phase is a critical factor affecting the SME. This study not only demonstrates mSME in ferroelectric polymers, which expands their application potential, but also provides an in‐depth understanding of the shape memory mechanism of the polymers.