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.     

Effect of the structure of a ferroelectric vinylidene fluoride-tetrafluoroethylene copolymer on the characteristics of a local piezoelectric response

The surface topography and characteristics of a local piezoelectric-response signal in isotropic films of a ferroelectric vinylidene fluoride-tetrafluoroethylene copolymer with a composition of 94: 6 are studied via scanning probe microscopy. The X-ray diffraction and IR spectroscopy data indicate that crystallization occurs in a mixture of β and γ polymorphic modifications. The exposure of the original film to a dc field bipolar leads to the formation of polarized regions exhibiting low stability. Recrystallization is followed by structural transformations accompanied by conformational transitions. As a result, there is a decrease in the concentration of chain segments in the T₃GT₃G^? conformation and, conversely, an increase in the concentration of isomers in the planar zigzag conformation. In addition, the characteristics of the local piezoelectric response after polarization become more stable, while the signal undergoes phase reversal. A second-harmonic piezoelectric response signal induced by the electrostriction effect is detected for the studied ferroelectric polymer samples. It is found that the original film has two types of regions that contribute to the measured signal. A change in the pattern of the second-harmonic piezoelectric-response signal in the recrystallized film is attributed to a change in the contribution of the electrostriction effect to the macroscopic piezoelectric response.     

Structure and appearance of residual polarization in thin films of polyvinylidene fluoride prepared via the Langmuir-Blodgett method

The relationship between electrophysical properties of super thin Langmuir-Blodgett films of polyvinylidene fluoride and their structural parameters via electron-diffraction and IR-spectroscopy methods was studied. According to analysis of the data, α and γ modifications were formed in addition to the β form. The occurrence of the α and γ species, which were responsible for the conformations TGTG ⁻ and T ₃ GT ₃ G ⁻, was detected both from the absorbance bands and from the respective reflections in the electron-diffraction patterns. In addition, the electron-diffraction data showed the formation of stratified textures. The polarization-switching curves acquired at 36°C revealed a low degree of spontaneous polarization within a wide energy distribution of domains, which were characterized by an average coercive field of 400 MV/m that reflected the change of polymorphous transformations in an electric field. Moreover, at 49°C, the spontaneous-polarization-switching curves indicated a process with a low coercive field. The observations probably are related to the higher mobility in the crystals of the α phase that might have eased the spontaneous polarization switching.     

Multiferroic properties and structural features of <Emphasis Type="Italic">M</Emphasis>-type Al-substituted barium hexaferrites

Precise studies of the crystal and magnetic structures of M-type substituted barium hexaferrites BaFe_12–x Al _x O₁₉ (0.1 ≤ x ≤ 1.2) have been performed by powder neutron diffraction in the temperature range 300–730 K. The electric polarization and the magnetization, and also the magnetoelectric effect of the compositions under study have been studied in electric (to 110 kV/m) and magnetic (to 14 T) fields at room temperature. The spontaneous polarization and significant correlation between the dielectric and magnetic subsystems have been observed at room temperature. The magnetoelectric effect value is, on average, about 5%, and it increases slightly with the aluminum cation concentration. The precise structural studies made it possible to reveal the cause and the mechanism of formation of the spontaneous polarization in M-type substituted barium hexaferrites BaFe_12–x Al _x O₁₉ (x ≤ 1.2) with a collinear ferromagnetic structure.     

Molecular mobility and structuring in textured films of the ferroelectric copolymer of vinylidene fluoride with tetrafluoroethylene

The processes of molecular mobility in vinylidene fluoride–tetrafluoroethylene ferroelectric copolymer–based films textured via uniaxial drawing are studied. It is found that the cooperative mobility in the amorphous regions of the copolymer is described by the Vogel–Fulcher equation, whose parameters are sensitive to the drawing conditions. It is shown that a decrease in the drawing temperature causes a reduction in the effective activation energy of the above-mentioned motion. In accordance with the X-ray diffraction data, this circumstance may be explained by an increase in the packing density of chains in interlamellar spaces. This effect is partially provided by deformation-induced processes of formation of small and defective crystals of the paraelectric or antiferroelectric phase in spaces between neighboring lamellar crystals at the primary stage of crystallization. The relationship between the value of the orientational polarization in oriented films and the topology of structure formation in microfibrils is discussed. It is observed that enlargement of the interlamellar space (filled with a liquidlike amorphous phase) between neighboring crystals in microfibrils promotes an increase in the orientational polarization of chains in the amorphous phase.