Search

Copolymers based on vinylidene fluoride are potential materials for ferroelectric memory elements. The trend in studies showing that a decrease in the degree of crystallinity can lead to an unexpected increase in the electric breakdown field is noted. An analysis of the literature data reveals that in fluorine-containing ferroelectric polymers, when using a bipolar triangular field, the hysteresis loop has an unclosed shape, with each subsequent loop being accompanied by a decrease in the dielectric response. In this work, the effect of the structure of self-polarized films of copolymers of vinylidene fluoride with tetrafluoroethylene and hexafluoropropylene on breakdown processes was studied. The structure of the polymer films was monitored using infrared spectroscopy (IR) and X-ray diffraction. Kelvin probe force microscopy (KPFM) was applied to characterize the local electrical properties of the polymers. For the films of the first copolymer, which crystallize in the polar β-phase, asymmetry in the dielectric response was observed at fields greater than the coercive field. For the films of the copolymers of vinylidene fluoride with hexafluoropropylene, which crystallize predominantly in the nonpolar α-phase, polarization switching processes have also been observed, but at lower electric fields. The noted phenomena will help to identify the influence of the structure of ferroelectric polymers on their electrical properties. [ABSTRACT FROM AUTHOR]

Polymer films doped by different porphyrins, obtained by crystallization from the acetone solutions, differ in absorption and fluorescence spectra, which we attribute to the differences in the structuring and composition of the rotational isomers in the polymer chains. According to the infrared spectroscopy data, the crystallization of the films doped with tetraphenylporphyrin (TPP) proceeds in a mixture of α- and γ-phases with TGTG− and T3GT3G− conformations, respectively. Three bonds in the planar zigzag conformation ensures the contact of such segments with the active groups of the porphyrin macrocycle, significantly changing its electronic state. Structuring of the films in the presence of TPP leads to an increase in the low-voltage AC-conductivity and the registration of an intense Maxwell-Wagner polarization. An increased conductivity by an order of magnitude in TPP-doped films was also observed at high-voltage polarization. The introduction of TPP during the film formation promotes the displacement of the chemical attachment defects of "head-to-head" type in the monomeric units into the surface. This process is accompanied by a significant increase in the film surface roughness, which was registered by piezo-force microscopy. The latter method also revealed the appearance of hysteresis phenomena during the local piezoelectric coefficient d33 measurements. [ABSTRACT FROM AUTHOR]

General problems of structural changes which occur at storage of two‐phase crystalline polymers with a metastable structure at room conditions are considered on the example of a vinylidene fluoride ‐ hexafluoropropylene copolymer. The physical aging occurs in flexible‐chain crystalline polymers (polyethylene, fluoropolymers under consideration, etc.), where, due to low glass transition temperatures, the liquid‐like dynamics of amorphous phase chains is realized at room temperature through cooperative micro‐Brownian motions with short relaxation times. Taking into account that covalent‐bound sections of the chains of the amorphous phase can enter the crystallites, the noted mobility may initiate changes in the size of the latter. Such a possibility is proved by the example of the noted copolymer. At low‐temperature crystallization of a vinylidene fluoride ‐ hexafluoropropylene copolymer from a solution the formed α‐phase crystals have little perfection. The size of the crystals increases when the films are stored in room conditions. Because of the crystal polymorphism, at the same time a certain fraction of γ‐phase crystals which are present in initial films undergo a polymorphic transformation γ → α. These processes lead to an increase in crystallinity. Moreover, during such processes additional structuring is observed, which is reduced to the displacement of various kinds of intra‐chain defects into the amorphous phase (and especially into the surface). Since the copolymers under study are ferroelectrics, they were studied by piezo force microscopy. It was found that despite the crystallization predominantly in nonpolar α‐phase, piezo force microscopy revealed a domain structure, which formation mechanism is discussed. The structural changes at physical aging of the films affect the character of the noted domain structure. Thus, it is suggested that the mechanism of the described structural changes is realized through the developed cooperative mobility of the chains in the amorphous phase, which characterizes the processes of rotational diffusion. [ABSTRACT FROM AUTHOR]