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beta-phase poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) copolymer films were prepared by uniaxially stretching solution-cast or melt-quenched samples. Different preparation routes lead to different amounts of the crystalline alpha and beta phases in the films, as detected by means of Fourier-transform infrared spectroscopy and X-ray diffractometry. The beta phase is significantly enhanced in melt-quenched and stretched films in comparison to solution-cast and stretched films. This is particularly true for copolymer samples with higher HFP content. The beta- phase enhancement is also observed in ferroelectric-hysteresis experiments where a rather high polarization of 58 mC/ m(2) was found on melt-quenched and stretched samples after poling at electric fields of 140 MV/m. After poling at 160 MV/m, one of these samples exhibited a piezoelectric d(33) coefficient as high as 21 pC/N. An electric-field-induced partial transition from the alpha to the beta phase was also observed on the melt-quenched and stretched samples. This effect leads to a further increase in the applications-relevant dipole polarization. Uniaxially stretched ferroelectric- polymer films are highly anisotropic. Dielectric resonance spectroscopy reveals a strong increase of the transverse piezoelectric d(32) coefficient and a strong decrease of the transverse elastic modulus c(32) upon heating from 20 to 50 degrees C.
Ferroelectrets are thin films of polymer foams, exhibiting piezoelectric properties after electrical charging. Ferroelectret foams usually consist of a cellular polymer structure filled with air. Polymer-air composites are elastically soft due to their high air content as well as due to the size and shape of the polymer walls. Their elastically soft composite structure is one essential key for the working principle of ferroelectrets, besides the permanent trapping of electric charges inside the polymer voids. The elastic properties allow large deformations of the electrically charged voids. However, the composite structure can also possibly limit the stability and consequently the range of applications because of, e. g., penetration of gas and liquids accompanied by discharge phenomena or because of a mechanical pre-load which may be required during the application. Here, we discuss various stability aspects related to the piezoelectric properties of polypropylene ferroelectrets. Near and below room temperature, the piezoelectric effect and the stability of the trapped charges are practically independent from humidity during long-time storage in a humid atmosphere or water, or from operating conditions, such as continuous mechanical excitation. Thermal treatment of cellular polypropylene above -10 degrees C leads to a softening of the voided structure which is apparent from the decreasing values of the elastic modulus. This decrease results in an increase of the piezoelectric activity. Heating above 60 degrees C, however, leads to a decrease in piezoelectricity
Zerstörungsfreie Tomographie von Raumladungs- und Polarisationsverteilungen mittles Wärmepulsen
(2007)
Non-destructive, three-dimensional imaging of space-charge and polarization distributions in electret materials has been implemented by means of laser-induced thermal pulses. In pyroelectric films of poled poly(vinylidene fluoride), images of up to 45 x 45 pixels with a depth resolution of less than 0.5 mu m and a lateral resolution of 40 mu m were recorded, the latter being limited by fast thermal diffusion in the absorbing metallic front electrode. Initial applications include the analysis of polarization distributions in corona-poled piezoelectric sensor cables and the detection of patterned space-charge distributions in polytetrafluoroethylene films.
Polyvinylidene fluoride was dissolved together with solid sodium hydroxide as catalyst in a dimethylsulfoxide/ acetone mixture and moderately dehydrofluorinated. The dehydrofluorination leads to a partial degradation of the fluorohydrocarbons, and in particular to main-chain scission and to formation of carbon double or triple bonds. This enhances the absorption at UV-vis frequencies. The degradation process also generates a large amount of excess charges in the polymer, which influence the electrical polarization behavior of the dehydrofluorinated polymer. Uniaxial stretching of moderately dehydrofluorinated polyvinylidene fluoride leads to films in a polar phase. Dipole polarization in the degraded and stretched films is demonstrated by means of switching experiments
In this paper, a measuring technique is presented for the detection of radial oscillations of tube walls excited by changes in internal air pressure. On organ pipes, the oscillations were investigated by means of piezoelectric polymer films slightly tensioned around the pipe bodies. Employing sensors with patterned electrodes, the well-known elliptical oscillation of the cross section as well as an additional monopole breathing of the organ-pipe body were detected. For the monopole breathing, a close relationship between the pressure distribution of the air-column resonances inside the pipe and the circumference variations along the pipe was observed
Elastic properties and electromechanical coupling factor of inflated polypropylene ferroelectrets
(2006)
Charging properties and time-temperature stability of innovative polymeric cellular ferroelectrets
(2007)
After appropriate mechanical and electrical treatments, some cellular polymers become able to retain space charge for a long time, i.e. they acquire electret behavior. The electrical treatment consists of charging under high levels of DC electric field. The mechanical treatment, based on the application of stretching forces to cellular polymer slabs that were before expanded under pressurized gas, affects the cavity size and shape, and therefore also the effectiveness of the charging process itself. An investigation of charging mechanisms, as well as of mechanical treatment, is therefore fundamental for optimizing the ferro- and piezo-electret properties. The aim of this paper is to discuss the effect of the physical dimension of the cavities on the charging behavior of cellular ferroelectrets and to focus on the time-temperature stability for two families of polymeric cellular ferroelectrets based on polypropylene (PP) and on a cyclo-olefin copolymer (COC). Emphasis will be given to the stretching process and in particular to the expansion rate applied during the manufacturing process (which affects the radial dimension and the height of the cavities, respectively). Space-charge and partial-discharge measurements as a function of time and temperature are the main tools to infer the influence of the cavity size on charging and stability characteristics.
We present calculations on the deformation of two- and three-layer electret systems. The electrical field is coupled with the stress-strain equations by means of the Maxwell stress tensor. In the simulations, two-phase systems are considered, and intrinsic relative dielectric permittivity and Young's modulus of the phases are altered. The numerically calculated electro-mechanical activity is compared to an analytical expression. Simulations are performed on two- and three-layer systems. Various parameters in the model are systematically varied and their influence on the resulting piezoelectricity is estimated. In three-layer systems with bipolar charge, the piezoelectric coefficients exhibit a strong dependence on the elastic moduli of the phases. However, with mono-polar charge, there is no significant piezoelectric effect. A two-dimensional simulation illustrated that higher piezoelectric coefficients can be obtained for non-uniform surface charges and low Poisson's ratio of phases. Irregular structures considered exhibit low piezoelectric activity compared to two-layer structures. (C) 2004 Elsevier B.V. All rights reserved
Cellular polypropylene (PP) films were treated with sulfur hexafluoride (SF6) gas in order to study the SF6 penetration behaviour and optimize the electric charging conditions. There were differences in the penetration of SF6 for different cellular PP materials, depending on the microscopic properties, which manifest themselves in the voided structure as well as in the mechanical stiffnesses of the cellular films. The penetration of SF6 after long-term pressure treatment is confirmed in strongly inflated cellular PP films with a low mechanical stiffness of about 1 MPa. No SF6 penetration occurs for slightly inflated cellular PP films with smaller void sizes and higher mechanical stiffnesses of around 5.8 MPa. The observed thickness variations, the higher charging fields during corona charging because of SF6 penetration and the SF6 environment, as well as the resulting electromechanical properties are discussed
High-resolution, large-area three-dimensional mapping of polarization profiles in electret polymers was carried out by means of a fast thermal pulse technique with a focused laser beam. A lateral resolution of 38 mu m and a near- surface depth resolution of less than 0.5 mu m was achieved. At larger depths, fast thermal diffusion in the metal electrode rather than the laser spot size becomes the limiting factor for the lateral resolution. (c) 2005 American Institute of Physics
Piezoelectric cellular polypropylene films, so-called ferroelectrets, are assembled in a stack with two active transducer layers. The stack is characterized with respect to its linear and quadratic response in a frequency range from 1 kHz to 80 kHz. A relatively smooth frequency response in the sound-pressure level is found for the individual layers as well as for both layers driven in phase. The piezoelectric response of the two-layer stack is twice the response of an individual layer over a rather broad frequency range. Furthermore, the influence of the preparation conditions on the resonance frequency and the effect of the quadratic distortion on the radiated sound are investigated both for the individual transducer films in the stack and for the stack system as a whole
In this paper, a recently developed numerical method to analyze dielectric-spectroscopy data is applied to alpha-phase polyvinylidene fluoride (PVDF). The numerical procedure is non-parametric and does not contain any of the extensively used empirical formulas mentioned in the literature. The method basically recovers the unknown distribution of relaxation times of the generalized dielectric function representation by simultaneous application of the Monte Carlo integration method and of the constrained least-squares optimization. The relaxation map constructed after the numerical analysis is compared to a-phase PVDF data presented in the literature and results of the parametric analysis with a well- known empirical formula. (c) 2005 Elsevier B.V. All rights reserved
The conductivity of alpha-polyvinylidene fluoride is obtained from dielectric measurements performed in the frequency domain at several temperatures. At temperatures above the glass-transition, the conductivity can be interpreted as an ionic conductivity, which confirms earlier results reported in the literature. Our investigation shows that the observed ionic conductivity is closely related to the amorphous phase of the polymer. (C) 2005 American Institute of Physics