Normal ferroelectric to ferroelectric relaxor conversion in fluorinated polymers and the relaxor dynamics

To elucidate the molecular origin of the polarization dynamics in the ferroelectric relaxor poly(vinylidene fluoride—trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer, a broadband dielectric study was carried out in the frequency range from 0.01 Hz to 10 MHz and temperatures from −150°C to 120°C for the terpolymer and a normal ferroelectric P(VDF-TrFE) copolymer. The relaxation processes were also studied using dynamic mechanical analysis. It was shown that in the terpolymer, which was completely converted to a ferroelectric relaxor, there is no sign of the relaxation process associated with the ferroelectric-paraelectric transition which occurs in the P(VDF-TrFE) copolymer. In the copolymer, three additional relaxation processes have been observed. It was found that the relaxation process β_a, which was commonly believed to be associated with the glass transition in the amorphous phase, in fact, contains significant contribution from chain segment motions such as domain boundary motions in the crystalline region. In the temperature range studied, the terpolymer exhibits the latter three relaxation processes with the one (termed β_r) near the temperature range of β_a significantly enhanced. This is consistent with the observation that in conversion from the normal ferroelectric to a ferroelectric relaxor, the macro-polar domains are replaced by nano-polar-clusters and the boundary motions as well as the reorientation of these nano-clusters generate the high dielectric response. The experimental data also reveal a broad relaxation time distribution related for the β_r process whose distribution width increases with reduced temperature, reflecting the molecular level heterogeneity in the crystalline phase due to the random introduction of the CFE monomer in the otherwise ordered macro-polar domains. The random interaction among the nano-clusters as well as the presence of the random fields produces ferroelectric relaxor behavior in the terpolymer.