Refine
Year of publication
Document Type
- Article (24)
- Habilitation Thesis (1)
- Other (1)
- Postprint (1)
Language
- English (27)
Is part of the Bibliography
- yes (27)
Keywords
- dielectric barrier discharge (DBD) (2)
- piezoelectret (2)
- Cellular polypropylene (PP) (1)
- Ferroelectret (1)
- Ferroelectrets (1)
- Ferroelektrete (1)
- Forcemyography (1)
- Piezo-, Pyro-und Ferroelektrizität (1)
- charge storage (1)
- dielectric (1)
Institute
Three poly(tetrafluoroethylene-hexafluoropropylene-vinylidenefluoride) (TFE-HFP-VDF or THV) terpolymers (Dyneon (R)) with different monomer ratios are investigated to demonstrate the concept of "modified" PTFE for space-charge electrets. HFP and VDF monomers distort the highly ordered PTFE molecules, which effectively enhances processability and adversely affects space-charge storage. Particularly, VDF component renders the material polar and probably also more conductive, partially undermining the space-charge-storage capabilities of PTFE. Nevertheless, the terpolymer THV815 with a TFE/HFP/VDF wt% ratio of 76.1/10.9/13 combines easy processability and relatively good space-charge stability. Our results shed light on novel concepts for space-charge electret materials with enhanced processing properties and reasonable charge-storage capabilities.
Here, piezoelectric transducers consisting of a P(VDF-TrFE) layer with either silver or PEDOT:PSS screen-printed electrodes are studied. The influence of electrodes on the dielectric and electroacoustic properties are studied in dielectric-spectroscopy and ferroelectric-hysteresis measurements. Only when both the bottom and the top electrodes are made of silver, the typical dielectric relaxation of the P(VDF-TrFE) layer is clearly observed. When one or two of the electrodes are of PEDOT:PSS, a Debye-like relaxation is present. Compared with silver electrodes, PEDOT:PSS electrodes allow for moderate self-healing. Consequently, samples with bottom and top PEDOT:PSS electrodes can be poled to saturation, while samples with silver electrodes can hardly be poled to saturation due to destructive electric breakdown. Acoustic transducer measurements show that silver electrodes facilitate higher and broader frequency operation, while PEDOT:PSS electrodes bring slightly lower total harmonic distortion. Overall, the acoustic performance shows no significant deviations between differently electroded samples so that silver electrodes do not offer any advantages for the transducers studied here due to their much higher tendency for destructive electric breakdown.
During muscle contractions, radial-force distributions are generated on muscle surfaces due to muscle-volume changes, from which the corresponding body motions can be recorded by means of so-called force myography (FMG). Piezo- or ferroelectrets are flexible piezoelectric materials with attractive materials and sensing properties. In addition to several other applications, they are suitable for detecting force variations by means of wearable devices. In this paper, we prepared piezoelectrets from cellular polypropylene films by optimizing the fabrication procedures, and developed an FMG-recording system based on piezoelectret sensors. Different hand and wrist movements were successfully detected on able-bodied subjects with the FMG system. The FMG patterns were evaluated and identified by means of linear discriminant analysis and artificial neural network algorithms, and average motion-classification accuracies of 96.1% and 94.8%, respectively, were obtained. This paper demonstrates the feasibility of using piezoelectret-film sensors for FMG and may thus lead to alternative methods for detecting body motion and to related applications, e.g., in biomedical engineering or structural-health monitoring.
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.
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.
Ferroelectrets are non-polar polymer foams or polymer systems with internally charged cavities. They are charged through a series of dielectric barrier discharges (DBDs) that are caused by the electrical breakdown of the gas inside the cavities. Thus, the breakdown strength of the gas strongly influences the charging process of ferroelectrets. A gas with a lower breakdown strength has a lower threshold voltage, thus decreasing the onset voltage for DBD charging. However, a lower threshold voltage also leads to a lower value for the remanent polarization, as back discharges that are caused by the electric field of the internally deposited charges can take place already at lower charge levels. On this basis, a charging strategy is proposed where the DBDs start in a gas with a lower breakdown strength (in the present example, helium) and are completed at a higher breakdown strength (e.g., nitrogen or atmospheric air). Thus, the exchange of the gas in the cavities during charging can significantly enhance the charging efficiency, i.e., yield much higher piezoelectric coefficients in ferroelectrets at significantly lower charging voltages. Published by AIP Publishing.
Ferroelectrets are internally charged polymer foams or cavity-containing polymer-_lm systems that combine large piezoelectricity with mechanical flexibility and elastic compliance. The term “ferroelectret” was coined based on the fact that it is a space-charge electret that also shows ferroic behavior. In this thesis, comprehensive work on ferroelectrets, and in particular on their preparation, their charging, their piezoelectricity and their applications is reported.
For industrial applications, ferroelectrets with well-controlled distributions or even uniform values of cavity size and cavity shape and with good thermal stability of the piezoelectricity are very desirable. Several types of such ferroelectrets are developed using techniques such as straightforward thermal lamination, sandwiching sticky templates with electret films, and screen printing. In particular, uoroethylenepropylene (FEP) _lm systems with tubular-channel openings, prepared by means of the thermal lamination technique, show piezoelectric d33 coefficients of up to 160 pC/N after charging through dielectric barrier discharges (DBDs) . For samples charged at suitable elevated temperatures, the piezoelectricity is stable at temperatures of at least 130°C. These preparation methods are easy to implement at laboratory or industrial scales, and are quite flexible in terms of material selection and cavity geometry design. Due to the uniform and well-controlled cavity structures, samples are also very suitable for fundamental studies on ferroelectrets.
Charging of ferroelectrets is achieved via a series of dielectric barrier discharges (DBDs) inside the cavities. In the present work, the DBD charging process is comprehensively studied by means of optical, electrical and electro-acoustic methods. The spectrum of the transient light from the DBDs in cellular polypropylene (PP) ferroelectrets directly confirms the ionization of molecular nitrogen, and allows the determination of the electric field in the discharge. Detection of the light emission reveals not only DBDs under high applied voltage but also back discharges when the applied voltage is reduced to sufficiently low values. Back discharges are triggered by the internally deposited charges, as the breakdown inside the cavities is controlled by the sum of the applied electric field and the electric field of the deposited charges. The remanent effective polarization is determined by the breakdown strength of the gas-filled cavities. These findings form the basis of more efficient charging techniques for ferroelectrets such as charging with high-pressure air, thermal poling and charging assisted by gas exchange. With the proposed charging strategies, the charging efficiency of ferroelectrets can be enhanced significantly.
After charging, the cavities can be considered as man-made macroscopic dipoles whose direction can be reversed by switching the polarity of the applied voltage. Polarization-versus-electric-field (P(E)) hysteresis loops in ferroelectrets are observed by means of an electro-acoustic method combined with dielectric resonance spectroscopy. P(E) hysteresis loops in ferrroelectrets are also obtained by more direct measurements using a modified Sawyer-Tower circuit. Hysteresis loops prove the ferroic behavior of ferroelectrets. However, repeated switching of the macroscopic dipoles involves complex physico-chemical processes. The DBD charging process generates a cold plasma with numerous active species and thus modifies the inner polymer surfaces of the cavities. Such treatments strongly affect the chargeability of the cavities. At least for cellular PP ferroelectrets, repeated DBDs in atmospheric conditions lead to considerable fatigue of the effective polarization and of the resulting piezoelectricity.
The macroscopic dipoles in ferroelectrets are highly compressible, and hence the piezoelectricity is essentially the primary effect. It is found that the piezoelectric d33 coefficient is proportional to the polarization and the elastic compliance of the sample, providing hints for developing materials with higher piezoelectric sensitivity in the future. Due to their outstanding electromechanical properties, there has been constant interest in the application of ferroelectrets. The antiresonance frequencies (fp) of ferroelectrets are sensitive to the boundary conditions during measurement. A tubular-channel FEP ferroelectret is conformably attached to a self-organized minimum-energy dielectric elastomer actuator (DEA). It turns out that the antiresonance frequency (fp) of the ferroelectret film changes noticeably with the bending angle of the DEA. Therefore, the actuation of DEAs can be used to modulate the fp value of ferroelectrets, but fp can also be exploited for in-situ diagnosis and for precise control of the actuation of the DEA. Combination of DEAs and ferroelectrets opens up various new possibilities for application.
We report a process for preparing polymer ferroelectrets by means of screen printing-a technology that is widely used for the two-dimensional patterning of printed layers. In order to produce polymer-film systems with cavities that are suitable for bipolar electric charging, a screen-printing paste is deposited through a screen with a pre-designed pattern onto the surface of a polymer electret film. Another such polymer film is placed on top of the printed pattern, and well-defined cavities are formed in-between. During heating and curing, the polymer films are tightly bonded to the patterned paste layer so that a stable three-layer system is obtained. In the present work, polycarbonate (PC) films have been employed as electret layers. Screen printing, curing and charging led to PC ferroelectret systems with a piezoelectric d (33) coefficient of about 28 pC/N that is stable up to 100 C-a similar to. Due to the rather soft patterned layer, d (33) strongly decreases already for static pressures of tens of kPa. The results demonstrate the suitability of screen printing for the preparation of ferroelectret systems.
Fast actuation speed, large-shape deformation and robust responsiveness are critical to synthetic soft actuators. A simultaneous optimization of all these aspects without trade-offs remains unresolved. Here we describe porous polymer actuators that bend in response to acetone vapour (24 kPa, 20 degrees C) at a speed of an order of magnitude faster than the state-of-the-art, coupled with a large-scale locomotion. They are meanwhile multi-responsive towards a variety of organic vapours in both the dry and wet states, thus distinctive from the traditional gel actuation systems that become inactive when dried. The actuator is easy-to-make and survives even after hydrothermal processing (200 degrees C, 24 h) and pressing-pressure (100 MPa) treatments. In addition, the beneficial responsiveness is transferable, being able to turn 'inert' objects into actuators through surface coating. This advanced actuator arises from the unique combination of porous morphology, gradient structure and the interaction between solvent molecules and actuator materials.
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.