Microwave frequency dielectric properties of poly(vinylidene fluoride) films

The frequency dependence of dielectric constant ?′, dielectric loss ?″, and dielectric anisotropy were determined for poly(vinylidene fluoride) (PVDF) in microwave frequencies from 4 to 13 GHz. The ?′ and ?″ for PVDF films decreased with increasing frequency. Both ?′ and ?″ were larger in the transverse direction than in the machine direction or draw direction, but the values at 12 GHz were smaller than those observed at 4.0 GHz. The angular dependence of ?″ at microwave frequency reflects the orientational distribution of molecules in the amorphous region. The orientation function was determined to be about 0.04 and 0.01 for uniaxially and biaxially stretched PVDF, respectively. © 1995 John Wiley & Sons, Inc.     

Low-frequency dielectric behavior of hydrated poly(L-proline)II

The dielectric behavior of poly(L -proline) II has been studied by the dc transient method and a contactless pendulum technique. The comparison of measurements performed with and without contacting electrodes shows that the static and low-frequency dielectric behavior are due to bulk phenomena. Both mechanisms are strongly dependent upon the water content of the sample. At low hydration, the static conduction may be attributed to an electronic process. The observed low-frequency relaxation can be characterized by a relaxation time which increases with the water content. This behavior can be explained by an increase in stiffness of the poly(L -proline) chain: two adjacent carbonyl groups of the chain may be hydrogen bonded by two water molecules.     

Effects of a static electric field upon dielectric properties of poly(vinylidene fluoride) and poly(vinyl fluoride)

Dielectric measurements on poly(vinylidene fluoride) at higher temperatures result in anomalously large values of ε′ and ε″ at lower frequencies. When a static field is applied, a drastic decrease of ε′ and ε″ occurs. The effects of a static field can be summarized as follows: (1) the field effect upon ε′and ε″ is more significant at lower frequencies; (2) with increasing field strength, the rate of decrease of ε′and ε″ with time becomes greater and the ultimate values are smaller; (3) when the field is removed, ε′and ε″ recover but the ultimate recovery is incomplete; (4) the field effect depends strongly on temperature. Such behavior seems to be attributable to the displacement of ionic impurities and to their electrolysis. These results provided a method to remove the contribution of ionic impurities to ε′and ε″ and to measure the relaxation process due only to dipoles of a polymer. The application of this method revealed the dielectric high temperature absorption which had been masked by the ionic conduction in poly(vinyl fluoride).     

The morphology of poly(vinylidene fluoride) crystallized from blends of poly(vinylidene fluoride) and poly(ethyl acrylate)

A combined optical and electron microscopical study has been carried out of the crystallization habits of poly(vinylidene fluoride) (PVF₂) when it is crystallized from blends with noncrystallizable poly(ethyl acrylate) (PEA). The PVF₂/PEA weight ratios were 0.5/99.5,5/95, and 15/85. Isothermal crystallization upon cooling the blends from the single-phase liquid region was carried out in the range 135–155°C, in which the polymer crystallizes in the α-orthorhombic unit cell form. The 0.5/99.5 blend yielded multilayered and planar lamellar crystals. The lamellae formed at low undercoolings were lozenge shaped and bounded laterally by {110} faces. This habit is prototypical of the dendritic lateral habits exhibited by the crystals grown from the same blend at high undercoolings as well as by the constituent lamellae in the incipient spherulitic aggregates and banded spherulites that formed from the 5/95 and the 15/85 blends, respectively. In contrast with the planar crystals grown from the 0.5/99.5 blend, the formation of the aggregates grown from the 5/95 blend is governed by a conformationally complex motif of dendritic lamellar growth and proliferation. The development of these aggregates is characterized by the twisting of the orientation of lamellae about their preferential b-axis direction of growth, coupled with a fan-like splaying or spreading of lamellae about that axis. The radial growth in the banded spherulites formed from the 15/85 blend is governed by a radially periodic repetition of a similar lamellar twisting/fan-like spreading growth motif whose recurrence corresponds to the extinction band spacing. This motif differs in its fan-like splaying component from banding due to just a helicoidal twisting of lamellae about the radial direction. © 1993 John Wiley & Sons, Inc.     

Anisotropy of dielectric relaxation in crystal form II of poly(vinylidene fluoride)

The anisotropy of the crystalline relaxation (α relaxation) in oriented poly(vinylidene fluoride) in crystal form II has been studied. The dielectric increment Δε is analyzed on the basis of the two-site model. A linear relation between Δε/χξ and cos²θ is obtained, where χ is the degree of crystallinity, ξ is the ratio of the internal field to the applied field, and θ is the angle between the applied electric field and the molecular axis. The dipole moment changes direction only along the molecular axis in the relaxation in crystal form II; the molecular motion cannot be explained by chain rotation around the molecular axis. Possible models for the α relaxation are proposed: change in conformation with internal rotation can occur in the crystalline chains, and defects in the crystalline regions play an important role in the α relaxation.     

Interfacial behavior between atmospheric-plasma-fluorinated carbon fibers and poly(vinylidene fluoride)

Atmospheric-plasma fluorination was used to introduce fluorine functionalities onto the surface of carbon fibers without affecting their bulk properties. The interfacial adhesion between atmospheric-plasma-fluorinated carbon fibers and poly(vinylidene fluoride) (PVDF) was studied by means of direct wetting measurements and single fiber pullout tests. Measured contact angles of PVDF melt droplets on modified carbon fibers show that short exposure times of carbon fibers to atmospheric-plasma fluorination (corresponding to a degree of surface fluorination of F/C = 0.01 (1.1%)) leads to improved wettability of the fibers by PVDF melts. The apparent interfacial shear strength as a measure of practical adhesion, determined by the single-fiber pullout test, increases by 65% under optimal treatment conditions. The improved practical adhesion is not due to the formation of transcrystalline regions around the fibers or a change of the bulk matrix crystallinity or to an increased surface roughness; it seems to be due to the compatibilization of the interface caused of the atmospheric-plasma fluorination of the carbon fibers.     

Persistent polarization in poly(vinylidene fluoride). II. Piezoelectricity of poly(vinylidene fluoride) thermoelectrets

The piezoelectricity of PVDF thermoelect rets formed with vacuum-coated aluminum electrodes has been investigated in detail. The piezoelectricity depends on the β-form crystal structure of PVDF homopolymer and copolymers. However, the piezoelectricity is not attributed to the stress dependence of the spontaneous polarization of β-form crystals, but rather to the persistent polarization arising from trapped charges. The trapping mechanism is discussed.     

Solubility parameters of poly(vinylidene fluoride)

The solubility behavior of poly(vinylidene fluoride) (PVDF) in about 50 liquids was investigated. The results were input to a computer program to obtain a three-dimensional representation of the polymer solubility region in the Hansen space; the values of dispersion, hydrogen bonding, and polar components of the total solubility parameter δ_t,P were evaluated. The latter was also estimated from limiting viscosity number data in the eight solvents found. Both experimental methods gave δ_t,P values in very good agreement. Comparisons among our findings, the literature, and calculated results are discussed.     

Thermal expansion of poly(vinylidene fluoride)

The thermal expansion behavior of oriented poly(vinylidene fluoride) films has been studied over the temperature range ?75 to +20°C. Representative high draw, low draw, and voided samples have been examined. For all samples at low temperatures the transverse thermal expansion coefficients, both in the plane of the sheet and perpendicular to it, are similar and have positive values of about 10^?4 K^?1. In the draw direction the thermal expansion coefficients are much smaller in magnitude and can be either positive or negative, the room temperature values varying in the range +4 × 10^?6 K^?1 for low draw samples to ?14 × 10^?6 K^?;1 for high draw samples. As the temperature is raised the coefficients also increase but, above the glass transition temperature, the value in the draw direction, α₁, shows a rapid fall in value. It is shown that this effect can be related quantitatively to the presence of an internal shrinkage stress. Differences between samples can then be primarily related to differences in the magnitude of this internal stress and to differences in the temperature dependence of the modulus of the sample.     

Transcrystallization kinetics of poly(vinylidene fluoride)

We report the transcrystallinity of poly(vinylidene fluoride) on several different types of substrate materials. The supermolecular structure and its development were characterized with polarization microscopy, whereas differential scanning calorimetry was used for monitoring the isothermal and nonisothermal crystallization kinetics. Although only approximately applicable, an Avrami–Ozawa analysis of the latter yielded reliable exponents, which characterized the transcrystalline nucleation conditions, the related dimensionality of growth, and the resulting texture. The results complemented and agreed quantitatively with those of light microscopy. Several polymers, including poly(ethylene terephthalate), polytetrafluoroethylene, and polyimide, induced distinct transcrystallinity, but only a spherulitic supermolecular structure developed on glass and metallic substrates. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2130–2139, 2001     

Infrared spectrum of poly(vinylidene fluoride)

Two crystalline forms (α and β) of poly(vinylidene fluoride) were studied by infrared spectroscopy. The spectral differences permitted the study of the transformation and the ratio of the two forms. The ordinary \documentclass{article}\pagestyle{empty}\begin{document}$ \vec G,\vec F $\end{document} matrix method was used to calculate the fundamental mode with a Urey-Bradley type potential field, and a preferred set of the force constants was obtained.     

Vibrational analysis of poly(vinylidene fluoride)

A vibrational analysis has been carried out for the two crystalline forms of poly(vinylidene fluoride) (PVF₂). The Raman spectrum of the planar form of PVF₂ is also reported. The band assignments are made on the basis of the spectral properties including the infrared dichroism and Raman intensities. A force field is derived based on a force constant refinement procedure utilizing the frequency data for both crystal forms.     

Carbon nanotubes induced poly(vinylidene fluoride) crystallization from a miscible poly(vinylidene fluoride)/poly(methyl methacrylate) blend

Different contents of carbon nanotubes (CNTs) were introduced into a miscible poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend. The interfacial affinity between CNTs and components of the blend was evaluated by calculating the interfacial tension. The dispersion and microstructure of CNTs in the nanocomposites were investigated through scanning electron microscope and rheological measurement. The effect of CNTs on the crystallization of PVDF was comparatively investigated through nonisothermal and isothermal crystallization processes. The results showed that CNTs exhibited stronger interfacial affinity to PMMA. Homogeneous dispersion of CNTs in the nanocomposites was achieved. Largely enhanced crystallization temperature and increased crystallinity of PVDF were obtained by adding CNTs during the nonisothermal crystallization process. The results obtained from the isothermal crystallization process proved that CNTs induced the concentration fluctuation in the sample, which resulted in the formation of spherulites with different types, i.e., the banded spherulites and compact spherulites. Furthermore, both the crystallization temperature and the content of CNTs exhibited great influence on the crystalline morphology of PVDF.     

Crystallization behavior,tensile behavior and hydrophilicity of poly(vinylidene fluoride)/poly(vinyl pyrrolidone) blends

Binary polymer blends of hydrophobic poly(vinylidene fluoride) (PVDF) and hydrophilic poly(vinylpyrrolidone) (PVP) were prepared by melt blending. The crystallization behavior, mechanical properties and hydrophilicity of the binary blends were investigated using Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffractometry (WAXD), differential scanning calorimeter (DSC) scanning, non-isothermal crystallization kinetics, successive self-nucleation and annealing (SSA) fractionation, tensile tests and contact angle tests. The analysis of FTIR, WAXD, DSC scanning, non-isothermal crystallization kinetics and SSA fractionation showed that the addition of PVP greatly influenced the crystallization behavior of the sample. As the PVP content increased, the crystallization temperature, crystallization rate, degree of crystallinity, and the amount of thick lamellaes decreased gradually. Meanwhile, PVP favored the formation of β-phase of PVDF. The results of tensile test revealed that the addition of PVP increased the elongation at break of the sample, and lowered the yield stress. Besides, the result of contact angle test indicated that the hydrophilicity of PVDF was remarkably improved in the presence PVP. The relationship between crystallization behavior and the tensile behavior, hydrophilicity were discussed.     

Brillouin scattering of oriented films of poly(vinylidene fluoride) and poly(vinylidene fluoride) -poly( methyl methacrylate) blends

Temperature dependent Brillouin scattering studies of PVF₂ films stretched to various stretch ratios have been carried out. Elastic constants for unstretched and stretched films have been obtained as functions of temperature. The elastic constant C₃₃ of the stretched films has a greater temperature dependence than that of unstretched films. To elucidate the effect of the surrounding amorphous matrix on the Brillouin spectrum of semicrystalline PVF₂ film, we carried out Brillouin scattering studies of films made from blends of PVF₂ and PMMA.     

Alternating-current ionic conduction and dielectric relaxation of poly(vinylidene fluoride) at high temperatures

Dielectric properties of poly(vinylidene fluoride) have been studied in the frequency range 20 Hz to 1 MHz and between 100 and 220°C, during heating and cooling. The dielectric constant and loss change abruptly at the temperature T_m corresponding to the melting point. At lower frequencies, two types of ionic conductin are observed. One appears below T_m and is attributed to interfacial polarization. The other occurs above T_m and is related to electrode polarization. These results suggest that a crystalline polymer is a heterogeneous medium for ionic transport, while the melt is a homogeneous medium. From these results, the nature of ac ionic conduction in crystalline polymers is discussed. At high frequency, the α relaxation is observed below T_m. It is due to the molecular motion in the crystalline region and disappears at T_m.