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In this paper, two non-destructive thermal methods are used in order to determine, with a high degree of accuracy, three-dimensional polarization distributions in thin films (12 mu m) of poly(vinylidenefluoride- trifluoroethylene) (PVDF-TrFE). The techniques are the frequency-domain Focused Laser Intensity Modulation Method (FLIMM) and time-domain Thermal-Pulse Tomography (TPT). Samples were first metalized with grid-shaped electrode and poled. 3D polarization mapping yielded profiles which reproduce the electrode-grid shape. The polarization is not uniform across the sample thickness. Significant polarization values are found only at depths beyond 0.5 mu m from the sample surface. Both methods provide similar results, TPT method being faster, whereas the FLIMM technique has a better lateral resolution.
The prehistory of electrets is not known yet, but it is quite likely that the electrostatic charging behavior of amber (Greek: τò ηλεκτρoν, i.e., “electron”) already was familiar to people in ancient cultures (China, Egypt, Greece, etc.), before the Greek philosopher and scientist Thales of Miletus (6th century BCE)-or rather his disciples and followers-reported it in writing (cf. Figure 1). More than two millennia later, William Gilbert (1544–1603), the physician of Queen Elizabeth I, coined the term “electric” in his book De Magnete, Magneticisque Corporibus, et de Magno Magnete Tellure (1600) for dielectric materials that attract like amber and that included sulfur and glass [1]. The second half of the 18th century saw the invention of the electrophorus or electrophore [2], a capacitive electret device, in 1762 by Johan Carl Wilcke (1732–1796).
Here, a promising approach for producing piezo-polymer transducers in a one-step process is presented. Using 3D-printing technology and polypropylene (PP) filaments, we are able to print a two-layered film structure with regular cavities of precisely controlled size and shape. It is found that the 3D-printed samples exhibit piezoelectric coefficients up to 200 pC/N, similar to those of other PP ferroelectrets, and their temporal and thermal behavior is in good agreement with those known of PP ferroelectrets. The piezoelectric response strongly decreases for applied pressures above 20 kPa, as the pressure in the air-filled cavities strongly influences the overall elastic modulus of ferroelectrets.
Due to their electrically polarized air-filled internal pores, optimized ferroelectrets exhibit a remarkable piezoelectric response, making them suitable for energy harvesting. Expanded polytetrafluoroethylene (ePTFE) ferroelectret films are laminated with two fluorinated-ethylene-propylene (FEP) copolymer films and internally polarized by corona discharge. Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)-coated spandex fabric is employed for the electrodes to assemble an all-organic ferroelectret nanogenerator (FENG). The outer electret-plus-electrode double layers form active device layers with deformable electric dipoles that strongly contribute to the overall piezoelectric response in the proposed concept of wearable nanogenerators. Thus, the FENG with spandex electrodes generates a short-circuit current which is twice as high as that with aluminum electrodes. The stacking sequence spandex/FEP/ePTFE/FEP/ePTFE/FEP/spandex with an average pore size of 3 mu m in the ePTFE films yields the best overall performance, which is also demonstrated by the displacement-versus-electric-field loop results. The all-organic FENGs are stable up to 90 degrees C and still perform well 9 months after being polarized. An optimized FENG makes three light emitting diodes (LEDs) blink twice with the energy generated during a single footstep. The new all-organic FENG can thus continuously power wearable electronic devices and is easily integrated, for example, with clothing, other textiles, or shoe insoles.
The standard charging process for polymer ferroelectrets, e. g., from polypropylene foams or layered film systems involves the application of high DC fields either to metal electrodes or via a corona discharge. In this often-used process, the DC field triggers the internal breakdown and limits the final charge densities inside the ferroelectret cavities and, thus, the final polarization. Here, an AC + DC charging procedure is proposed and demonstrated in which a high-voltage high-frequency (HV-HF) wave train is applied together with a DC poling voltage. Thus, the internal dielectric-barrier discharges in the ferroelectret cavities are induced by the HV-HF wave train, while the final charge and polarization level is controlled separately through the applied DC voltage. In the new process, the frequency and the amplitude of the HV-HF wave train must be kept within critical boundaries that are closely related to the characteristics of the respective ferroelectrets. The charging method has been tested and investigated on a fluoropolymer-film system with a single well-defined cylindrical cavity. It is found that the internal electrical polarization of the cavity can be easily controlled and increases linearly with the applied DC voltage up to the breakdown voltage of the cavity. In the standard charging method, however, the DC voltage would have to be chosen above the respective breakdown voltage. With the new method, control of the HV-HF wave-train duration prevents a plasma-induced deterioration of the polymer surfaces inside the cavities. It is observed that the frequency of the HV-HF wave train during ferroelectret charging and the temperature applied during poling of ferroelectrics serve an analogous purpose. The analogy and the similarities between the proposed ferroelectret charging method and the poling of ferroelectric materials or dipole electrets at elevated temperatures with subsequent cooling under field are discussed.
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.
The addition of nano-Al2O3 has been shown to enhance the breakdown voltage of epoxy resin, but its flashover results appeared with disputation. This work concentrates on the surface charge variation and dc flashover performance of epoxy resin with nano-Al2O3 doping. The dispersion of nano-Al2O3 in epoxy is characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The dc flashover voltages of samples under either positive or negative polarity are measured with a finger-electrode system, and the surface charge variations before and after flashovers were identified from the surface potential mapping. The results evidence that nano-Al2O3 would lead to a 16.9% voltage drop for the negative flashovers and a 6.8% drop for positive cases. It is found that one-time flashover clears most of the accumulated surface charges, regardless of positive or negative. As a result, the ground electrode is neighbored by an equipotential zone enclosed with low-density heterocharges. The equipotential zone tends to be broadened after 20 flashovers. The nano-Al2O3 is noticed as beneficial to downsize the equipotential zone due to its capability on charge migration, which is reasonable to maintain flashover voltage at a high level after multiple flashovers. Hence, nano-Al2O3 plays a significant role in improving epoxy with high resistance to multiple flashovers.
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 with electrically charged cellular voids, the so-called ferroelectrets, are soft piezoelectric transducer materials. Several polymers such as polyethylene terephthalate or cyclo-olefin copolymers are under investigation with respect to their suitability as ferroelectrets. Here, the authors report an additional ferroelectret polymer, cellular polyethylene-naphthalate (PEN), which was prepared from commercial uniform polymer films by means of foaming in supercritical carbon dioxide, inflation, biaxial stretching, electrical charging, and metallization. Piezoelectric d(33) coefficients of up to 140 pC/N demonstrate the suitability of such cellular PEN films for transducer applications. Their piezoelectricity is partially stable at elevated temperatures as high as 100 degrees C.
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.
Characterization and calibration of piezoelectric polymers in situ measurements of body vibrations
(2011)
Piezoelectric polymers are known for their flexibility in applications, mainly due to their bending ability, robustness, and variable sensor geometry. It is an optimal material for minimal-invasive investigations in vibrational systems, e.g., for wood, where acoustical impedance matches particularly well. Many applications may be imagined, e. g., monitoring of buildings, vehicles, machinery, alarm systems, such that our investigations may have a large impact on technology. Longitudinal piezoelectricity converts mechanical vibrations normal to the polymer-film plane into an electrical signal, and the respective piezoelectric coefficient needs to be carefully determined in dependence on the relevant material parameters. In order to evaluate efficiency and durability for piezopolymers, we use polyvinylidene fluoride and measure the piezoelectric coefficient with respect to static pressure, amplitude of the dynamically applied force, and long-term stability. A known problem is the slow relaxation of the material towards equilibrium, if the external pressure changes; here, we demonstrate how to counter this problem with careful calibration. Since our focus is on acoustical measurements, we determine accurately the frequency response curve - for acoustics probably the most important characteristic. Eventually, we show that our piezopolymer transducers can be used as a calibrated acoustical sensors for body vibration measurements on a wooden musical instrument, where it is important to perform minimal-invasive measurements. A comparison with the simultaneously recorded airborne sound yields important insight of the mechanism of sound radiation in comparison with the sound propagating in the material. This is especially important for transient signals, where not only the long-living eigenmodes contribute to the sound radiation. Our analyses support that piezopolymer sensors can be employed as a general tool for the determination of the internal dynamics of vibrating systems.