In contrast to the comprehensive understanding of novel ferroelectric [i.e., relaxor ferroelectric (RFE) and antiferroelectric] behavior in ceramics, RFE and double-hysteresis-loop (DHL) behavior in crystalline ferroelectric polymers have only been studied in the past fifteen years. A number of applications such as electrostriction, electric energy storage, and electrocaloric cooling have been realized by utilizing these novel ferroelectric properties. Nonetheless, fundamental understanding behind these novel ferroelectric behaviors is still missing for polymers. In this feature article, we intend to unravel the basic physics via systematic studies of poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)]-based terpolymers, electron-beam (e-beam) irradiated P(VDF-TrFE) copolymers, and PVDF graft copolymers. It is found that both the crystal internal structure and the crystal–amorphous interaction are important for achieving the RFE and DHL behaviors. For the crystal internal structure effect, dipole switching with reduced friction and nanodomain formation by pinning the polymer chains are essential, and they can be achieved through crystal repeating-unit isomorphism (i.e., defect modification). Physical pinning [e.g., in P(VDF-TrFE)-based terpolymers] induces a reversible, electric field-induced RFE↔FE phase transition and thus the DHL behavior, whereas chemical pinning [e.g., in e-beam irradiated P(VDF-TrFE)] results in the RFE behavior. Finally, the crystal–amorphous interaction (or the nanoconfinement effect) results in a competition between the polarization and depolarization local fields. When the depolarization field becomes stronger than the polarization field, a DHL behavior is observed. Obviously, the physics for ferroelectric polymers is different from that for ceramics/liquid crystals and can be largely attributed to the long-chain nature of semicrystalline polymers. This understanding will help us to design new ferroelectric polymers with improved properties and/or better applications

Piezoelectric polymers hold great potential for various electromechanical applications, but only show low performance, with |d₃₃ | < 30 pC/N. We prepare a highly piezoelectric polymer (d₃₃ = −62 pC/N) based on a biaxially oriented poly(vinylidene fluoride) (BOPVDF, crystallinity = 0.52). After unidirectional poling, macroscopically aligned samples with pure β crystals are achieved, which show a high spontaneous polarization (P_s) of 140 mC/m². Given the theoretical limit of P_s,β = 188 mC/m² for the neat β crystal, the high P_s cannot be explained by the crystalline-amorphous two-phase model (i.e., P_s,β = 270 mC/m²). Instead, we deduce that a significant amount (at least 0.25) of an oriented amorphous fraction (OAF) must be present between these two phases. Experimental data suggest that the mobile OAF resulted in the negative and high d₃₃ for the poled BOPVDF. The plausibility of this conclusion is supported by molecular dynamics simulations.

A novel mechanism for counterion-mediated attraction between like-charged spherical macroions is proposed, which originates from a depletion zone of counterions between nearly touching macroions that is induced by Coulomb interactions. Using computer simulations of the primitive model, we show that this depletion effect dominates over the electrostatic contribution in the case of strong Coulomb coupling when all the counterions form a quasi-two-dimensional layer on the spherical macroionic surface. Its range is given by the typical spacing of counterions on the macroion surface.

A recently developed mesoscopic solvent model with multiparticle-collision dynamics is applied to three-dimensional solvent flows in a channel with and without a spherical obstacle. The advantage of a gravitationally driven flow of the solvent over the flow induced by a pressure gradient in the calculation of the solvent viscosity is demonstrated. Three different algorithms for stochastic collision steps are investigated and compared. In particular, we have examined an alternative algorithm with relative velocities drawn from a Maxwell-Boltzmann distribution at each collision step. This algorithm increases the numerical efficiency of the mesoscopic model for solvent flows with low and intermediate Reynolds numbers. Our simulation results for the recirculation length of stationary vortices behind a spherical obstacle are in good agreement with the previous experimental measurements.