PVF2 crystalline phases

Poly(vinylidene fluoride), PVDF or PVF2, is usually manufactured from radical initiated batch polymerization process in aqueous emulsion or suspension of CH2=CF2 monomer. PVDF is a thermoplastic that exhibits interesting properties, such as piezoelectric, pyroelectrical, and ferroelectric behaviors. PVDF has even superior dielectric permittivity arising from the strong polymerization originating from C—F bonds, and the spontaneous orientation of dipoles in the crystalline phases makes it a polar polymer with good compatibility with polar chemicals. 

Yamada et al. [9,10] demonstrated that the copolymers were ferroelectric over a wide range of molar composition and that, at room temperature, they could be poled with an electric field much more readily than the PVF2 homopolymer. The main points highlighting the ferroelectric character of these materials can be summarized as follows (a) At a certain temperature, that depends on the copolymer composition, they present a solid-solid crystal phase transition. The crystalline lattice spacings change steeply near the transition point, (b) The relationship between the electric susceptibility e and temperature fits well the Curie-Weiss equation, (c) The remanent polarization of the poled samples reduces to zero at the transition temperature (Curie temperature, Tc). (d) The volume fraction of ferroelectric crystals is directly proportional to the remanent polarization, (e) The critical behavior for the dielectric relaxation is observed at Tc. 

Some polymorphic modifications can be converted from one to another by a change in temperature. Phase transitions can be also induced by an external stress field. Phase transitions under tensile stress can be observed in natural rubber when it orients and crystallizes under tension and reverts to its original amorphous state by relaxation (Mandelkem, 1964). Stress-induced transitions are also observed in some crystalline polymers, e.g. PBT (Jakeways etal., 1975 Yokouchi etal., 1976) and its block copolymers with polyftetramethylene oxide) (PTMO) (Tashiro et al, 1986), PEO (Takahashi et al., 1973 Tashiro Tadokoro, 1978), polyoxacyclobutane (Takahashi et al., 1980), PA6 (Miyasaka Ishikawa, 1968), PVF2 (Lando et al, 1966 Hasegawa et al, 1972), polypivalolactone (Prud homme Marchessault, 1974), keratin (Astbury Woods, 1933 Hearle et al, 1971), and others. These stress-induced phase transitions are either reversible, i.e. the crystal structure reverts to the original structure on relaxation, or irreversible, i.e. the newly formed structure does not revert after relaxation. Examples of the former include PBT, PEO and keratin. 

The symmetry requirements necessary for ferroelectricity in low-molecular mass compounds, which were discussed in Section 1.1.3, are valid for polymer mesophases too. If a tilted chiral smectic phase is stable after a polymerization process it must be ferroelectric. Following this idea, the first polymer liquid crystalline ferroelectric has been synthesized by Shibayev et al. [160]. Its spontaneous polarization did not differ very much from the precursor monomer [161]. After polyvinylidene fiuoride (PVF2)... 

The various crystalline structures of PVF2 obtained by chemical and radiation-initiated polymerization are described by Gal perin et al. [536,537]. PVF2 samples of different molar masses could be prepared (0.3 to 10 x 10 g/mol, determined from viscosimetry in DMF). Radiation polymerization in the gaseous phase resulted in polymers with the highest molar masses. It was also shown that the conformation of PVF2 chains was independent of the method of initiation but was influenced by the polarity of the medium in which polymerization took place. Radiation polymerization in polar solvents promoted formation of the p phase, while nonpolar solvents (or gaseous polymerization) yielded the a phase [521,537]. 

---