Effect of electrode material on contact high-voltage polarization in a vinylidene fluoride-hexafluoropropylene copolymer

High-voltage polarization processes occurring in alternating fields of various frequencies in extruded films of vinylidene fluoride-hexafluoropropylene copolymers are studied. Remanent polarization typical for ferroelectric polymers with a polar cell appears during crystallization in the nonpolar α phase. This effect is associated with the presence of a highly imperfect ferroelectric (or antiferroelectric) phase in the copolymer, where chains assume planar zigzag conformations. The magnitude of remanent polarization depends on the frequency of the applied bipolar sawtooth voltage. This observation may be explained by the fact that the resulting field is created not only by the external source but also by the space charge that is contributed by carriers injected from electrodes. With the use of deposited Au and Al, the role of electrode material in polarization and conduction processes is ascertained. In the case of Al, Al₂O₃ and new Al-C chemical bonds are formed on the polymer surface. Owing to formation of these additional dielectric layers at the copolymer/metal interface, electrodes may be blocked partially. The above new chemical bonds facilitate formation of deeper surface traps for carriers; as a result, the remanent surface potential appears in polarized samples even after storage in the short-circuit mode.     

Surface topography and crystal and domain structures of films of ferroelectric copolymer of vinylidene difluoride and trifluoroethylene

The crystallization of a copolymer from a solution at room temperature is found to lead to the formation of a metastable structure, characterized by the coexistence of ferroelectric and paraelectric phases. The fraction of the latter decreases after annealing above the Curie point. Atomic force microscopy (AFM) has revealed a difference in the surface topographies between the films contacting with air and the films contacting with a glass substrate. The microstructure of copolymer chains has been investigated by ¹⁹F NMR spectroscopy. The chain fragments with “defect” attached monomeric units are ejected to the surface. The character of the ferroelectric domains formed during crystallization and their size distribution are analyzed.

     

Separating overlapping bands in the IR spectra of polymers

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 51, No. 1, pp. 58–63, July, 1989.     

Heterogeneous chemical crosslinking and high-voltage polarization in a ferroelectric copolymer of vinylidene fluoride and tetrafluoroethylene

The low-temperature chemical crosslinking of a copolymer of vinylidene fluoride and tetrafluoroethylene was studied through various physicochemical methods. The reaction was conducted in solution in the presence of diethylenetriamine as a crosslinking agent. The penetration of the mixture molecules and the crosslinking agent only in the amorphous phase of the copolymer was provided via selection of the ratio between a good solvent (dimethylformamide) and a poor solvent (ethanol). Owing to this, the crosslinking reaction occurred in the amorphous phase and hardly involved the crystals. This outcome was confirmed by wide-angle X-ray diffraction data. The structural and chemical changes in the amorphous phase during crosslinking were recorded with the use of IR spectroscopy and differential scanning calorimetry. It is shown that crosslinking is accompanied by the formation of C=C bonds in the copolymer chains. The study of high-voltage polarization and conductivity during exposure to bipolar rectangular pulses suggested that crosslinking leads to an increase in the carrier concentration. It was found that the surface potentials in the films increase with an increase in the number of high-voltage pulses applied to the sample. This circumstance is attributed to the fact that the double bonds formed in the copolymer chains can effectively trap negatively charged carriers.     

Piezoelectricity in crystallizing ferroelectric polymers: Poly(vinylidene fluoride) and its copolymers (A review)

The piezoelectricity observed in poly(vinylidene fluoride) (PVDF) and its copolymers involves three components that are associated with the presence of at least two phases (crystalline and amorphous) in the polymer structure. The main contributions to the phenomenon observed are made by the size effect and electrostriction, which are related to each other. These contributions manifest themselves through the mechanism of strain-induced reversible transformations of a number of domains of the anisotropic amorphous phase into the crystalline state under the action of mechanical or electrical fields. With due regard for different packings of chains in the amorphous and crystalline phases, this mechanism accounts for the large Poisson ratios μ₃₁ obtained for textured films of flexible-chain crystallizing polymers. The dependence of the piezoelectric coefficient d ₃₂ on the static stress in textured films is governed by the change in the fraction of the crystalline phase due to strong anisotropy of the elastic constants in the film plane. It is shown that the shear deformations of polymers are characterized by a strong piezoelectric response. The specific features revealed in the piezoelectric effect under bending deformations are described for films with an inhomogeneous distribution of polarization over the cross section. The general regularities of the electrostriction in the polymers and inorganic relaxor ferroelectrics studied are considered.     

Influence of Dye Molecules on the Polarization of Ferroelectric Vinylidene Fluoride Copolymer

Crystallography Reports - Electrical, electromechanical, and structural–optical properties of films of vinylidene fluoride copolymer with tetrafluoroethylene TFE, doped with Rhodamine 6G dye,...     

Investigation of the mobility in poly(vinylidene fluoride) ferroelectric films with different structures

The molecular mobility in two isotropic poly(vinylidene fluoride) samples crystallized in the α phase from the melt with different crystallinities and lattice perfections has been investigated by broadband dielectric spectroscopy. It has been revealed that the local-mobility parameters are insensitive to structural features. The average relaxation times of micro-Brownian motion in the disordered phase are found to be identical in the samples under consideration, which can be associated with the localization of the mobility in the interphase layer at the crystal-amorphous phase interface. The motion in the crystal (α _c transition) has been described using the soliton mechanism of relaxation. It has been found that, as should be expected, the average relaxation time increases with an increase in the longitudinal crystal size; however, in this case, a strict quantitative correlation is absent. According to the small-angle X-ray scattering data, this is caused by different microstructures of interlamellar amorphous regions. It has been demonstrated that the samples with a higher degree of crystallinity are characterized by a larger difference in the electron densities of the crystalline and amorphous phases and a larger size of the amorphous layer. It has been assumed that an increase in the concentration of chemical defects in the interlamellar layers with a simultaneous increase in their length is responsible for the increased probability of attenuation of the solitary wave (conformational defect) in its passage between neighboring lamellar crystals.     

Polarization of block textured films of ferroelectric copolymers of vinylidene fluoride with tetrafluoroethylene in an external field

The polarization of oriented films of the ferroelectric copolymer of vinylidene fluoride and tetrafluoroethylene in a sinusoidal electric field is studied. In low fields, the copolymer behaves as a linear dielectric whose permittivity nonlinearly increases with the amplitude of the alternating field. This behavior is related to the preferential orientation of the dipole moment of the chain along the normal to the surface and to the monocrystal-structure formation. In higher fields, the hysteresis behaves formally coincidently with the behavior of an antiferroelectric. The important role of through stressed chains in the amorphous phase in the initiation of domains of a new direction in polar crystals is observed. Increased adsorption of water molecules on the surface of a polarized film is found and is attributed to the formation of the final density of the stable polarization charge on it.