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- Cellular polypropylene (PP) (1)
- Ferroelectrets (1)
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- dielectric barrier discharge (DBD) (1)
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Cellular polypropylene (PP) ferroelectrets combine a large piezoelectricity with mechanical flexibility and elastic compliance. Their charging process represents a series of dielectric barrier discharges (DBDs) that generate a cold plasma with numerous active species and thus modify the inner polymer surfaces of the foam cells. Both the threshold for the onset of DBDs and the piezoelectricity of ferroelectrets are sensitive to repeated DBDs in the voids. It is found that the threshold voltage is approximately halved and the charging efficiency is clearly improved after only 10(3) DBD cycles. However, plasma modification of the inner surfaces from repeated DBDs deteriorates the chargeability of the voids, leading to a significant reduction of the piezoelectricity in ferroelectrets. After a significant waiting period, the chargeability of previously fatigued voids shows a partial recovery. The plasma modification is, however, detrimental to the stability of the deposited charges and thus also of the macroscopic dipoles and of the piezoelectricity. Fatigue from only 10(3) DBD cycles already results in significantly less stable piezoelectricity in cellular PP ferroelectrets. The fatigue rate as a function of the number of voltage cycles follows a stretched exponential. Fatigue from repeated DBDs can be avoided if most of the gas molecules inside the voids are removed via a suitable evacuation process.
Polymer foams are in industrial use for several decades. More recently, non-polar polymer foams were found to be piezoelectric (so-called piezoelectrets) after internal electrical charging of the cavities. So far, few studies have been carried out on the electrical-insulation properties of polymer foams. Here, we compare the piezoelectric and the DC-voltage electrical-insulation properties of cellular polypropylene (PP) foams. Their cavity microstructure can be adjusted via inflation in high-pressure nitrogen gas in combination with a subsequent thermal treatment. While inflation is effective for improving the piezoelectricity, it is detrimental for the electrical-insulation properties. The original cellular PP foam shows a breakdown strength of approximately 230 MV/m, within the same range as that of solid PP. The breakdown strength decreases with increasing degree of inflation, and the dependence on the foam thickness follows an inverse power law with an exponent of 1.2. Nevertheless, up to a thickness of 140 mu m (3.5 times the original thickness), the breakdown strength of cellular-foam PP films is at least 7 times that of an air gap with the same thickness. In addition, the influence of high temperatures and high humidities on the piezoelectricity and the breakdown strength of cellular PP was studied. It was found that the piezoelectric d(33) coefficient decays rapidly already at 70 degrees C, while the breakdown strength slightly increases during storage at 70 or 90 degrees C. Under a relative humidity of 95%, the breakdown strength increases with storage time, while the piezoelectric d(33) coefficient slightly decreases.
Dielectric elastomers (DE) are soft polymer materials exhibiting large deformations under electrostatic stress. When a prestretched elastomer is stuck to a flat plastic frame, a complex structure that can be used as an actuator (DEA) is formed due to self-organization and energy minimization. Here, such a DEA was equipped with a ferroelectret film. Ferroelectrets are internally charged polymer foams or void-containing polymer-film systems combining large piezoelectricity with mechanical flexibility and elastic compliance. In their dielectric spectra, ferroelectrets show piezoelectric resonances that can be used to analyze their electromechanical properties. The antiresonance frequencies ( ) of ferroelectret films not only are directly related to their geometric parameters, but also are sensitive to the boundary conditions during measurement. In this paper, a fluoroethylenepropylene (FEP) ferroelectret film with tubular void channels was glued to a plastic frame prior to the formation of self-organized minimum-energy DEA structure. The dielectric resonance spectrum (DRS) of the ferroelectret film was measured in-situ during the actuation of the DEA under applied voltage. It is found that the antiresonance frequency is a monotropic function of the bending angle of the actuator. Therefore, the actuation of DEAs can be used to modulate the of ferroelectrets, while the can also be taken for in-situ diagnosis and for precise control of the actuation of the DEA. Combination of DEAs and ferroelectrets brings a number of possibilities for application.
Direct hysteresis measurements on ferroelectret films by means of a modified Sawyer-Tower circuit
(2013)
Ferro- and piezo-electrets are non-polar polymer foams or film systems with internally charged cavities. Since their invention more than two decades ago, ferroelectrets have become a welcome addition to the range of piezo-, pyro-, and ferro-electric materials available for device applications. A polarization-versus-electric-field hysteresis is an essential feature of a ferroelectric material and may also be used for determining some of its main properties. Here, a modified Sawyer-Tower circuit and a combination of unipolar and bipolar voltage waveforms are employed to record hysteresis curves on cellular-foam polypropylene ferroelectret films and on tubular-channel fluoroethylenepropylene copolymer ferroelectret film systems. Internal dielectric barrier discharges (DBDs) are required for depositing the internal charges in ferroelectrets. The true amount of charge transferred during the internal DBDs is obtained from voltage measurements on a standard capacitor connected in series with the sample, but with a much larger capacitance than the sample. Another standard capacitor with a much smaller capacitance-which is, however, still considerably larger than the sample capacitance-is also connected in series as a high-voltage divider protecting the electrometer against destructive breakdown. It is shown how the DBDs inside the polymer cavities lead to phenomenological hysteresis curves that cannot be distinguished from the hysteresis loops found on other ferroic materials. The physical mechanisms behind the hysteresis behavior are described and discussed.
Fluoropolymer piezoelectrets with tubular channels resonance behavior controlled by channel geometry
(2012)
Ferro- or piezoelectrets are dielectric materials with two elastically very different macroscopic phases and electrically charged interfaces between them. One of the newer piezoelectret variants is a system of two fluoroethylenepropylene (FEP) films that are first laminated around a polytetrafluoroethylene (PTFE) template. Then, by removing the PTFE template, a two-layer FEP structure with open tubular channels is obtained. After electrical charging, the channels form easily deformable macroscopic electric dipoles whose changes under mechanical or electrical stress lead to significant direct or inverse piezoelectricity, respectively. Here, different PTFE templates are employed to generate channel geometries that vary in height or width. It is shown that the control of the channel geometry allows a direct adjustment of the resonance frequencies in the tubular-channel piezoelectrets. By combining several different channel widths in a single ferroelectret, it is possible to obtain multiple resonance peaks that may lead to a rather flat frequency-response region of the transducer material. A phenomenological relation between the resonance frequency and the geometrical parameters of a tubular channel is also presented. This relation may help to design piezoelectrets with a specific frequency response.
Polarization and Hysteresis in Tubular-Channel Fluoroethylenepropylene-Copolymer Ferroelectrets
(2014)
Polarization-vs.-applied-voltage hysteresis curves are recorded on tubular-channel fluoroethylene-propylene (FEP) copolymer ferroelectrets by means of a modified Sawyer-Tower circuit. Dielectric barrier discharges (DBDs) inside the cavities are triggered when the applied voltage is sufficiently high. During the DBDs, the cavities become man-made macroscopic dipoles which build up an effective polarization in the ferroelectret. Therefore, a phenomenological hysteresis curve is observed. From the hysteresis loop, the remanent polarization and the coercive field can be determined. Furthermore, the polarization can be related to the respective piezoelectric coefficient of the ferroelectret. The proposed method is easy to implement and is useful for characterization, further development and optimization of ferro- or piezoelectrets.
Laminated polymer-film systems with well-defined void structures were prepared from fluoroethylenepropylene (FEP) and polytetrafluoroethylene (PTFE) layers. First the PTFE films were patterned and then fusion-bonded with the FEP films. The laminates were subjected to either corona or contact charging in order to obtain the desired piezoelectricity. The build-up of the "macro-dipoles" in the laminated films was studied by recording the electric hysteresis loops. The resulting electro-mechanical properties were investigated by means of dielectric resonance spectroscopy (DRS) and direct measurements of the stress-strain relationship. Moreover, the thermal stability of the piezoelectric d (33) coefficient was investigated at elevated temperatures and via thermally stimulated discharge (TSD) current measurements in short circuit. For 150 mu m thick laminated films, consisting of one 25 mu m thick PTFE layer, two 12.5 mu m thick FEP layers, and a void of 100 mu m height, the critical voltage necessary for the build-up of the "macro-dipoles" in the inner voids was approximately 1400 V, which agrees with the value calculated from the Paschen Law. A quasi-static piezoelectric d (33) coefficient up to 300 pC/N was observed after corona charging. The mechanical properties of the film systems are highly anisotropic. At room temperature, the Young's moduli of the laminated film system are around 0.37 MPa in the thickness direction and 274 MPa in the lateral direction, respectively. Using these values, the theoretical shape anisotropy ratio of the void was calculated, which agrees well with experimental observation. Compared with films that do not exhibit structural regularity, the laminates showed improved thermal stability of the d (33) coefficients. The thermal stability of d (33) can be further improved by pre-aging. E.g., the reduction of the d (33) value in the sample pre-aged at 150A degrees C for 5 h was less than 5% after annealing for 30 h at a temperature of 90A degrees C.
Cellular polyethylene-naphthalate (PEN) ferroelectrets are useful as soft and flexible electromechanical transducer materials. Improved cellular PEN foams are prepared by means of a "voiding + inflation + stretching" process and investigated with respect to their structure and their applications-relevant properties. It is found that most of the cellular voids have heights below 8 mu m. The polymer walls do not allow sufficient gas exchange between the voids and the ambient atmosphere, when the cellular films are exposed to atmospheric pressures between a millibar and a few bars. As expected for ferroelectrets, a threshold voltage for charging is observed: A reasonable piezoelectric coefficient d(33) is only found when the charging voltage is higher than 4 kV. Furthermore, d(33) increases with charging voltage and reaches saturation at approximately 8 kV. Annealing after charging or charging at elevated temperatures may enhance the thermal stability of the PEN ferroelectrets. The d(33) of properly annealed samples is stable up to the respective annealing temperatures, but the annealing process reduces the piezoelectric activity of charged ferroelectret films to some extent. Samples charged at suitable elevated temperatures show much better thermal stability than those charged at room temperature, but the charging temperature should be limited to values below the material's glass-transition temperature T-g. Furthermore, the relevant elastic modulus c(33) of PEN ferroelectrets may decrease upon thermal treatment.