Characteristics of the ferroelectricity in polyvinylidene fluoride (PVDF) and copolymers based on vinylidene fluoride (VDF) with different previous thermomechanical histories are analysed. Switching of polarisation and the fluctuation mechanism of formation of new nuclei upon the appearance of conformation defects such as kink bonds are considered. The role of the space charge, which stabilises the new polarisation position, is noted. It is shown that the Curie transition can be either a first-or second-order phase transition depending on the copolymer composition. The influence of the morphology of PVDF on some ferroelectric characteristics is found. In particular, the morphology of thick lamellar crystals is favourable for enhanced spontaneous polarisation. It is shown that a ferroelectric structure approaching the texture of an ideal single crystal can be created in Langmuir ± Blodgett films. As the number of unimolecular layers decreases, the concentration of conformational defects in these films increases and the crystallographic order in the lattice is violated. This intensifies the low-temperature Curie transition. The bibliography includes 247 references.
The molecular mobility in copolymers of vinylidene fluoride-hexafluoropropylene VDF/HFP of 93/7 and 86/14 ratios has been investigated by means of broadband dielectric relaxation spectroscopy (10 À1 -10 7 Hz), differential scanning calorimetry DSC (À100 to 1508C), and of wide angle X-ray diffraction WAXS. Four relaxation processes and one ferroelectric-paraelectric phase transition have been detected. The process of the local mobility b-(at temperatures below glass transition point) is not affected by chemical composition of the copolymer and the formed structure. Parameters of segmental mobility in the region of glass transition (a a -relaxation) depend on the ratio of comonomer with lower kinetic flexibility. a c -relaxation is clearly observed only in VDF/HFP 93/7 copolymer, which is characterized by a higher crystallinity and a higher perfection of crystals of a-(a p -) phase. Diffuse order-disorder relaxor type ferroelectric transition connected with the destruction of the domains in low-perfect ferroelectric phase in the amorphous regions has been detected for both copolymers. An intensive relaxation process (a-process) was observed for both copolymers in high-temperature region. DSC data shows that it falls on the broad temperature region of aphase crystals melting. It is considered to be connected with the space charge relaxation.
Polymer films based on poly(vinylidene fluoride) and its copolymers, which exhibit piezo-and pyro-electric properties after appropriate treatment, are described. The principal advantages of materials of this class include high values of the piezomoduli, which permit their practical use. Another valuable property, which is difficult to achieve in inorganic materials, is the wide range of frequencies over which the given active element can operate. The possibility of achieving large areas and fairly simple methods of preparation of thin films also leads to the assignment of the above polymers to the category of promising materials for the creation of new classes of recording devices. The trends in the development of new instruments based on these materials, where use is made of the phenomenon of photopyroelectric activity, are demonstrated. The advantages of using these materials for medical techniques are noted. The flexibility of the film and its acoustic impedance, which is close to that of a biological tissue, as well as the properties noted above place it beyond competition with other materials. Furthermore, the ferroelectric nature of the above polymers makes them promising for use in nonlinear optics. The bibliography includes 89 references.
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