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.     

Persistent polarization in poly(vinylidene fluoride). I. Surface charges and piezoelectricity of poly(vinylidene fluoride) thermoelectrets

Persistent polarization in poly(vinylidene fluoride) (PVDF) thermoelectrets prepared under high electric field strengths has been studied by measurements of surface charge and piezoelectricity. An anomalous heterocharge appears after the normal homocharge disappears. A model is proposed to explain the surface charge phenomena; the anomalous heterocharge is expressed as a sum of a hidden homocharge and a hidden heterocharge. It is concluded that the anomalous heterocharge as well as the apparent homocharge are not responsible for the piezoelectricity of PVDF electrets. The piezoelectricity is shown to depend on the structure of the original PVDF films or the amount of β-form crystals. However, the piezoelectricity is not attributed to stress dependence of the spontaneous polarization in the β-form crystal of PVDF, but to the hidden polarization which bring about the anomalous heterocharge. The hidden polarizations are attributed to trapped charges.     

Piezoelectricity,pyroelectricity, and the electrostriction constant of poly(vinylidene fluoride)

A new device for measuring the electrostriction constant of polymer films is described. Observed values for various polymers except poly(vinylidene fluoride) and poly(methyl methacrylate) agree well with those calculated from the Clausius-Mosotti equation. Elongational piezoelectricity, the pyroelectric current, and the electrostriction constant are measured for undrawn and roll-drawn poly(vinylidene fluoride) films. The piezoelectricity and pyroelectric current are attributed to space charges antisymmetrically distributed along thickness direction of the film for two reasons: (1) the polarity coincides between these two phenomena for all specimens, and (2) the piezoelectricity and the electrostriction constant have the same anisotropy for drawn films. Similarity of signs between piezoelectricity and pyroelectric current is observed also in poly(vinyl chloride) films. The electrical behavior of poly(vinylidene fluoride) is interpreted in terms of the ferroelectric nature of the β-form crystal.     

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.     

Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. III. Gel properties and irreversible modifications of poly(vinylidene fluoride) membranes under swelling in liquid electrolytes

Microporous poly(vinylidene fluoride) (PVdF) separators for lithium-ion batteries, used in liquid organic electrolytes, have been characterized with respect to the swelling phenomena on dense PVdF membranes (obtained through hot pressing). In the first and second parts of this study, we have described the swelling equilibria and swelling kinetics of dense PVdF. Here the thermal properties of PVdF gels and their irreversible modifications induced by swelling are characterized. Particular attention is paid to crystallinity modifications, polymer plasticization, and membrane degradation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2308–2317, 2004     

Dielectric relaxations in poly(vinylidene fluoride)

Molecular motions in poly(vinylidene fluoride) were studied by the dielectric technique. Three distinct absorption peaks (α_c, α_a, and β) were observed in the frequency range from 0.1 cps to 300 kcps and in the temperature range from ?66 to 100°C. The molecular mechanisms for these absorptions and their temperature dependence are discussed, and results are compared with x-ray diffraction and the NMR measurements. It is concluded that the α_c absorption located at 97°C (1 kcps) is related to molecular motion in the crystalline region. The α_a absorption located at ?27°C (1 kcps) can be interpreted as due to the micro-Brownian motion of the amorphous main chains. The β absorption located at ?47°C (1 kcps) is attributed to local oscillation of the frozen main chains.     

Quantitative confirmation of the crystal-amorphous interphase in semicrystalline poly(vinylidene fluoride) and poly (vinylidene fluoride)/poly (ethyl methacrylate) blends

Dielectric and thermal characterizations were performed for poly (vinylidene fluoride) (PVDF)/poly (ethyl methacrylate) (PEMA) blends of different composition. The characteristics of PVDF β relaxation were shown to be little affected in the semicrystalline blends with PEMA. The relaxation strength, however, depends strongly on the PEMA content and a linear relation was found between the intensity of the β relaxation and the weight fraction of the PVDF crystal-amorphous interphase. Phase structures of the PVDF/PEMA blends are also proposed. © 1994 John Wiley & Sons, Inc.     

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.     

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.     

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.     

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.     

Aging of piezoelectricity in poly(vinylidene fluoride)

This report describes isothermal aging of piezoelectricity in poly(vinylidene fluoride) (PVDF) based on long-term heat treatments between 40 and 160°C. The results demonstrate that no piezoelectric decay occurs below about 60°C, that between 60 and 160°C the aging behavior follows logarithmic kinetics, and that aging is linearly dependent on temperature. Both uniaxial and biaxial PVDF show similar trends, but piezoelectric decay is more rapid for uniaxial film. Decay of permanent poling-induced polarization is identified as the likeliest cause of piezoelectric aging, and piezoelectric decay is found to be associated with long-range annealing effects which also produce macroscopic shrinkage of the PVDF film.     

Effects of annealing on the polarization switching of phase I poly(vinylidene fluoride)

To obtain information about microscopic processes involved in the polarization switching in uniaxially oriented poly (vinylidene fluoride) film, a least-squares estimation of nonlinear parameters was developed to yield parameters of an equation which describes the nucleation and domain growth process. Time domain measurements of polarization reversal revealed that switching times decreased as the annealing temperature T_a increased (67.0, 52.4, and 41.3 μs at –20°C under a 200 MV/m pulse field for the as-stretched samples, the samples being annealed at 120 and 160°C, respectively). The analysis showed that the value of the domain growth speed increased as T_a increased. This is consistent with x-ray diffraction data which indicated that the annealing process brought about better chain packing and increased crystallite perfection. The analysis also showed that the nucleation probability significantly increased as T_a increased. This result was interpreted in terms of a morphological transformation, which was indicated by the decrease in elastic modulus with increasing T_a with no corresponding loss of orientation. It is suggested that the annealing process brought about an increase in the number of nucleation sites as a result of a transformation from a fibrous structure to a crystal-amorphous series structure which has increased boundary zone area.     

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.