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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.
New ferroelectrets were developed on the basis of foams from cyclo-olefin polymers and copolymers. The results obtained on the cyclo-olefin polymer foam demonstrate a significant improvement of the service temperature for ferroelectret transducer materials. Suitable compounding and preparation led to cyclo-olefin ferroelectrets with an electromechanical activity of around 15 pC/N, which is thermally stable at least up to 110 degrees C. The properties in sensor and actuator applications are strongly dependent on the processing parameters related to film-making, sensor and actuator preparation, gas content and electric charging. The processing window for the film stretching was very narrow compared to the earlier developed polypropylene ferroelectrets. The film porosity, softness and thus the electromechanical activity are adjusted by gas-diffusion expansion. The activity of the electromechanically operating sensors and actuators was increased by stacking several layers of cellular cyclo-olefin film. For applications such as flat loudspeakers, the foamed films are tuned by tensioning them on a support frame. Correct tensioning was essential also for reducing the distortion levels.
Electrically charged cellular polymer films can exhibit very high piezoelectric activity and are therefore more and more often employed in advanced electromechanical and electro-acoustical transducers. In this paper, we report an optimized sequence of steps for preparing such ferroelectrets from commercial nonvoided ploy(ethylene terephthalate) (PETP) films by means of foaming with CO2 biaxial mechanical stretching, controlled void inflation, and bipolar electric charging. The nonvoid PETP films foamed with supercritical CO2 at a suitably high pressure and subsequently annealed for stabilization. The cellular foam structure was further optimized by means of well controlled biaxial stretching in a commercial stretcher and sometimes subsequent inflamation in a pressure chamber. Bipolar electric charging of the internal voids was achieved through the application of high electric fields in an SF0 atmosphere. The new optimized PETP ferroelectric exhibit quite large piezoelectric coefficients up to almost 500 pCN(-1), for which unusually low elastic stiffness of only around 0.3 MPa are essential. The PETP foam ferroelectrics posses unclamped thickenss-extension resonance frequences between approximately 120 and 250 kHz, and are thus highly suitable for several established as well as novel ultrasonic-transductant applications.
When exposed to sufficiently high electric fields, polymer-foam electret materials with closed cells exhibit ferroelectric-like behavior and may therefore be called ferroelectrets. In cellular ferroelectrets, the influence of the cell size and shape distributions on the application-relevant properties is not yet understood. Therefore, controlled inflation experiments were carried out on cellular polypropylene films, and the resulting elastical and electromechanical parameters were determined. The elastic modulus in the thickness direction shows a minimum with a corresponding maximum in the electromechanical transducer coefficient. The resonance frequency shifts as a function of the elastic modulus and the relative density of the inflated cellular films. Therefore, the transducer properties of cellular ferroelectrets can be optimized by means of controlled inflation. (C) 2004 American Institute of Physics
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.
Temporal evolution of the re-breakdown voltage in small gaps from nanoseconds to milliseconds
(2013)
A detailed understanding of electric breakdown in dielectrics is of scientific and technological interest. In gaseous dielectrics, a so-called re-breakdown is sometimes observed after extinction of the previous discharge. Although time-dependent re-breakdown voltage is essentially known, its behavior immediately after the previous discharge is not precisely understood. We present an electronic circuit for accurate measurements of the time-dependent re-breakdown voltage in small gaps from tens of nanoseconds to several milliseconds after the previous spark. Results from such experiments are compared with earlier findings, and relevant physical mechanisms such as heating of the gas, decay of the plasma, and ionization of excited atoms and molecules are discussed. It is confirmed that the thermal model is not valid at times below several microseconds.
In recent communications from these laboratories, we observed that amine-rich thin organic layers are very efficient surfaces for the adhesion of mammalian cells. We prepare such deposits by plasma polymerization at low pressure, atmospheric pressure, or by vacuum-ultraviolet photo-polymerization. More recently, we have also investigated a commercially available material, Parylene diX AM. In this article we first briefly introduce literature relating to electrostatic interactions between cells, proteins, and charged surfaces. We then present certain selected cell-response results that pertain to applications in orthopedic and cardiovascular medicine: we discuss the influence of surface properties on the observed behaviors of two particular cell lines, human U937 monocytes, and Chinese hamster ovary cells. Particular emphasis is placed on possible electrostatic attractive forces due to positively charged R-NH3+ groups and negatively charged proteins and cells, respectively. Experiments carried out with electrets, polymers with high positive or negative surface potentials are added for comparison.
A template-based lamination technique for the manufacture of ferroelectrets from uniform electret films was recently reported. In the present work, this technique is used to prepare similar ferroelectret structures from low-density polyethylene (LDPE) films and from fluoro-ethylene-propylene (FEP) copolymer films. A comparative analysis of the pressure-, temperature-, and frequency-dependent piezoelectric properties has been performed on the two ferroelectret systems. It is observed that the FEP ferroelectrets exhibit better piezoelectric responses and are thermally more stable. The difference between the piezoelectric d(33) coefficients of the two ferroelectret systems is partially explained here by their different elastic moduli. The anti-resonance peaks of both structures have been investigated by means of dielectric resonance spectroscopy and electroacoustic sound-pressure measurements. A difference of more than 10 kHz is observed between the anti-resonance frequencies of the two ferroelectret systems.
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.
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.
Piezoelectrets are novel transducer materials which can be widely applied in sensors and actuators. Here, three techniques for determining piezoelectric d(33) coefficients of piezoelectrets are reviewed and compared. Two types of piezoelectrets, polyethylene-naphthalate (PEN) polymer-foam piezoelectrets and fluorinated ethylene-propylene (FEP) copolymer-layer piezoelectrets, have been prepared and measured by means of dynamic, resonance, and acoustical methods. The dynamic measurements show that the d(33) coefficient of PEN-foam samples clearly decreases with increasing stress, but 80% of the initial d(33) can be retained after 1800 cycles of a continuous dynamic measurement in a mechanical fatigue test. The resonance measurements demonstrate that both PEN-foam and FEP-layer samples exhibit clear electro-mechanical resonances. PEN-foam samples show elastic moduli in the range from 1 to 12 MPa and d(33) values up to 500 pC N-1, while FEP-layer samples show homogeneous elastic moduli of about 0.3 MPa and d(33) values of about 280 pC N-1. The acoustical measurements reveal that both PEN-foam and FEP-layer samples exhibit stable frequency responses in the range from 5.7 to 20 kHz. In addition, d(33) coefficients obtained with different experimental methods are in good agreement with each other, which confirms the reliability of all three techniques.
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.
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.
The influence of the temperature in the gas-filled cavities on the charging process of ferroelectret film systems has been studied in hysteresis measurements. The threshold voltage and the effective polarization of the ferroelectrets were determined as functions of the charging temperature TP. With increasing TP, the threshold voltage for triggering dielectric barrier discharges in ferroelectrets decreases. Thus, increasing the temperature facilitates the charging of ferroelectrets. However, a lower threshold voltage reduces the attainable remanent polarization because back discharges occur at lower charge levels, as soon as the charging voltage is turned off. The results are discussed in view of Paschen's law for electrical breakdown, taking into account the respective gas temperature and a simplified model for ferroelectrets. Our results indicate that the thermal poling scheme widely used for conventional ferroelectrics is also useful for electrically charging ferroelectrets.
Ferroelectrets (sometimes also called piezoelectrets) are relatively new members of the family of piezo-, pyro-, and ferroelectric materials.1–5 As their name indicates, ferroelectrets are space-charge electrets that show ferroic behavior. They are non-uniform electret materials or materials systems with electrically charged internal cavities. As space-charge electrets, ferroelectrets usually do not contain any molecular dipoles. However, the cavities inside the material can be turned into macroscopic dipoles through a series of micro-plasma discharges at high electric fields, so-called dielectric barrier discharges (DBDs).6–8 The gas inside the cavities is ionized when the internal electric field exceeds the threshold for electrical breakdown, generating charges of both polarities.9 The positive and negative charges travel in opposite directions, and are eventually trapped at the internal top and bottom surfaces of the cavities, respectively. After charging, the cavities may be regarded as macroscopic dipoles that can be switched by reversing the applied voltage.
An electric-polarization-vs.-electric-field (P(E)) hysteresis is considered as an essential criterion for ferroelectricity. P(E)-hysteresis curves are usually characterized by the spontaneous polarization, the coercive field, and the remanent polarization. Recently, we have demonstrated P(E)-hysteresis loops on two different types of ferroelectrets, namely, cellular polypropylene ferroelectrets and tubular-channel fluoroethylene-polypropylene copolymer ferroelectrets.10,11 The P(E)-hysteresis loops not only prove the ferroic behavior of ferroelectrets, but also allow us to determine such parameters as the coercive field and the remanent polarization.
It is widely accepted that Paschen breakdown is the underlying mechanism for the inception of DBDs in ferroelectrets.12–14 On this basis, the charging behavior and the resulting piezoelectricity of ferroelectrets in different gases at various pressures have been studied.15–17 Paschen's law describes the conditions for electrical breakdown in a gas at a constant temperature (usually room temperature), and it needs to be modified for gas breakdown at other temperatures. The temperature stability of the piezoelectricity in ferroelectrets after charging at elevated temperatures was investigated by several researchers.18–21 Recently, a preliminary report about the effects of the charging temperature on the hysteresis loops in ferroelectrets has been presented.22
In this letter, the influence of the gas temperature on the charging of ferroelectret systems is investigated in more detail by means of quasi-ferroelectric hysteresis-loop measurements. Teflon™ fluoroethylenepropylene (FEP) copolymer samples with tubular channels were prepared via thermal lamination as described previously.23 To this end, two FEP films with a thickness of 50 μm each were laminated at 300 ° C
around a 100 μm thick polytetrafluoroethylene (PTFE) template (total area 35 mm × 45 mm) that contains parallel rectangular openings (area 1.5 mm × 40 mm each). After lamination, the template was removed, which results in an FEP film system with open tubular channels. The samples were metallized on both surfaces with aluminum electrodes of 20 mm diameter.
P(E)-hysteresis loops were obtained with a modified Sawyer–Tower (ST) circuit.10,11 A high-voltage (HV) capacitor C1 (3 nF) and a large standard capacitor Cm (1 μF) were connected in series with the sample. A bipolar sinusoidal voltage with a frequency of 10 mHz was applied from an HV power supply (FUG HCB 7-6500) controlled by an arbitrary-waveform generator (HP 33120a). The voltage Vout
on Cm is measured by means of an electrometer (HP 3458a), and the charge flowing through the circuit is determined as Q(t)=CmVout(t)
. The experiments were carried out at isothermal conditions in a Novocontrol® Quatro cryosystem.
With the modified ST circuit, Q–V loops have been measured on a tubular-channel FEP ferroelectret system at different temperatures. The sample capacitance of about 34.5 pF is determined by a linear fit of the initial part of the Q–V curve recorded at 20 °C
, where the voltage has been raised up from zero on a fresh sample. The hysteresis loops are obtained from the Q–V curves by subtracting the contribution that results from charging of the sample capacitance.10 Figure 1 shows the hysteresis loops of the sample at −100, 0, and +100 ° C, respectively. According to previous theoretical and experimental studies,24,25 the length of each of the horizontal sides of the parallelogram-like hysteresis loops is given by 2Vth where Vth is the threshold voltage. As the charging temperature decreases, the hysteresis loop becomes wider and less high, i.e., the threshold voltage increases, while the polarization at maximum voltage decreases.
A recently reported novel class of elastomers was tested with respect to its dielectric properties. The new elastomer material is based on a commercially available poly(dimethylsiloxane) composition, which has been modified by embedding glycerol droplets into its matrix. The approach has two major advantages that make the material useful in a dielectric actuator. First, the glycerol droplets efficiently enhance the dielectric constant, which can reach astonishingly high values in the composite. Second, the liquid filler also acts as a softener that effectively decreases the elastic modulus of the composite. In combination with very low cost and easy preparation, the two property enhancements lead to an extremely attractive dielectric elastomer material. Experimental permittivity data are compared to various theoretical models that predict relative permittivity changes as a function of filler loading, and the applicability of the models is discussed. (c) 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44153.
Polymer-dispersed liquid crystals (PDLCs) of ferroelectric poly(vinylidene fluoride-trifluoroethylene) and nematic 4-cyano-4ʹ-n-hexylbiphenyl (6CB) or 4-cyano-4ʹ-n-pentylbiphenyl (5CB) were prepared to study the effect of the remanent polarisation of the polymer on the liquid crystal alignment. We measured the macroscopic alignment of the liquid crystal molecules in the thickness direction by means of Infrared Transition-Moment Orientational Analysis. Electrical poling at 100 V/µm caused an increased order parameter up to 0.15. After subsequent annealing above the nematic-to-isotropic phase-transition temperature, the order parameter was reduced to 0.02. Nevertheless, the order parameter was still higher than for non-poled film indicating a slight orientation in thickness direction. Both values are lower than those expected from model calculations. In agreement with dielectric measurements, we attribute this result to the shielding effect of mobile charge carriers within the liquid crystal inclusions.
Fast, three-dimensional polarization mapping in piezoelectric sensor cables was performed by means of the novel thermal-pulse tomography (TPT) technique with a lateral resolution of 200 mum. The active piezoelectric cable material (a copolymer of polyvinylidene fluoride with trifluoroethylene) was electrically poled with a point-to-cable corona discharge. A focused laser was employed to heat the opaque outer electrode, and the short-circuit current generated by the thermal pulse was used to obtain 3D polarization maps via the scale transformation method. The article describes the TPT technique as a fast non-destructive option for studying cylindrical geometries.
Nowadays, structural health monitoring of critical infrastructures is considered as of primal importance especially for managing transport infrastructure however most current SHM methodologies are based on point-sensors that show various limitations relating to their spatial positioning capabilities, cost of development and measurement range. This publication describes the progress in the SENSKIN EC co-funded research project that is developing a dielectric-elastomer sensor, formed from a large highly extensible capacitance sensing membrane and is supported by an advanced micro-electronic circuitry, for monitoring transport infrastructure bridges. The sensor under development provides spatial measurements of strain in excess of 10%, while the sensing system is being designed to be easy to install, require low power in operation concepts, require simple signal processing, and have the ability to self-monitor and report. An appropriate wireless sensor network is also being designed and developed supported by local gateways for the required data collection and exploitation. SENSKIN also develops a Decision-Support-System (DSS) for proactive condition-based structural interventions under normal operating conditions and reactive emergency intervention following an extreme event. The latter is supported by a life-cycle-costing (LCC) and life-cycle-assessment (LCA) module responsible for the total internal and external costs for the identified bridge rehabilitation, analysis of options, yielding figures for the assessment of the economic implications of the bridge rehabilitation work and the environmental impacts of the bridge rehabilitation options and of the associated secondary effects respectively. The overall monitoring system will be evaluated and benchmarked on actual bridges of Egnatia Highway (Greece) and Bosporus Bridge (Turkey).
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.