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.

     

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.     

Separating overlapping bands in the IR spectra of polymers

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

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.     

The role of new functional groups in the surface layer of LDPE during its high-voltage contact polarization

New functional groups containing Al-C bonds and Al₂O₃ molecules are formed in the surface layer of the polymer during depositing of aluminum on polyethylene films. This effect is absent when Au is deposited on the films. For capacitors with Al and Au electrodes, processes of high-voltage contact polarization and conductivity are studied at various configurations of the external electric field. If Al-C organometallic bonds and Al₂O₃ or, for example, Al-O-C bonds are formed in the surface layer during application of high electric fields, a number of dielectric “anomalies” are observed. They manifest themselves as the fact that an increase in the amount of cycles of a bipolar saw-tooth voltage is accompanied by a marked increase in the residual surface charge density. At such a configuration of the external field, a decrease in its frequency (for region, where dE/dt > 0) leads to a marked reduction in high-voltage dielectric permittivity to negative values. This phenomenon is explained by the fact that, along with the external field, an internal field appears owing to formation of the space charge near metal/polymer boundaries.     

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,...     

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.