@article{QiuWirgesGerhard2016, author = {Qiu, Xunlin and Wirges, Werner and Gerhard, Reimund}, title = {Thermal poling of ferroelectrets: How does the gas temperature influence dielectric barrier discharges in cavities?}, series = {Applied physics letters}, volume = {108}, journal = {Applied physics letters}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.4954263}, pages = {1687 -- 1697}, year = {2016}, abstract = {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 \&\#956;m each were laminated at 300 ° C around a 100 \&\#956;m 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 \&\#956;F) 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 \&\#8722;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.}, language = {en} } @article{BassoQiuWirgesetal.2013, author = {Basso, Heitor Cury and Qiu, Xunlin and Wirges, Werner and Gerhard, Reimund}, title = {Temporal evolution of the re-breakdown voltage in small gaps from nanoseconds to milliseconds}, series = {Applied physics letters}, volume = {102}, journal = {Applied physics letters}, number = {1}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.4773518}, pages = {5}, year = {2013}, abstract = {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.}, language = {en} } @article{AltafimQiuWirgesetal.2009, author = {Altafim, Ruy Alberto Pisani and Qiu, Xunlin and Wirges, Werner and Gerhard, Reimund and Altafim, Ruy Alberto Pisani and Basso, Heitor Cury and Jenninger, Werner and Wagner, Joachim}, title = {Template-based fluoroethylenepropylene piezoelectrets with tubular channels for transducer applications}, issn = {0021-8979}, doi = {10.1063/1.3159039}, year = {2009}, abstract = {We describe the concept, the fabrication, and the most relevant properties of a piezoelectric-polymer system: Two fluoroethylenepropylene (FEP) films with good electret properties are laminated around a specifically designed and prepared polytetrafluoroethylene (PTFE) template at 300 degrees C. After removing the PTFE template, a two-layer FEP film with open tubular channels is obtained. For electric charging, the two-layer FEP system is subjected to a high electric field. The resulting dielectric barrier discharges inside the tubular channels yield a ferroelectret with high piezoelectricity. d(33) coefficients of up to 160 pC/N have already been achieved on the ferroelectret films. After charging at suitable elevated temperatures, the piezoelectricity is stable at temperatures of at least 130 degrees C. Advantages of the transducer films include ease of fabrication at laboratory or industrial scales, a wide range of possible geometrical and processing parameters, straightforward control of the uniformity of the polymer system, flexibility, and versatility of the soft ferroelectrets, and a large potential for device applications e.g., in the areas of biomedicine, communications, production engineering, sensor systems, environmental monitoring, etc.}, language = {en} } @article{QiuMellingerWirgesetal.2007, author = {Qiu, Xunlin and Mellinger, Axel and Wirges, Werner and Gerhard, Reimund}, title = {Spectroscopic study of dielectric barrier discharges in cellular polypropylene ferroelectrets}, doi = {10.1063/1.2786597}, year = {2007}, abstract = {The transient light emission from the dielectric barrier discharges (DBDs) in cellular polypropylene ferroelectrets subjected to high electric poling fields was spectroscopically measured. The spectrum shows strong emission from the second positive system of molecular nitrogen, N-2(C (3)Pi(u))-> N-2(B (3)Pi(g)), and the first negative system of N-2(+), N-2(+)(B (2)Sigma(+)(u))-> N-2(+)(X (2)Sigma(+)(g)), consistent with a DBD in air. When a dc voltage is applied stepwise to the ferroelectret film, light emission starts above a threshold, coinciding with the threshold voltage in obtaining piezoelectricity. From selected vibronic band strength ratios, the electric field in the discharge was determined and found to agree with Townsend breakdown.}, language = {en} } @article{SborikasQiuWirgesetal.2014, author = {Sborikas, Martynas and Qiu, Xunlin and Wirges, Werner and Gerhard, Reimund and Jenninger, Werner and Lovera, Deliani}, title = {Screen printing for producing ferroelectret systems with polymer-electret films and well-defined cavities}, series = {Applied physics : A, Materials science \& processing}, volume = {114}, journal = {Applied physics : A, Materials science \& processing}, number = {2}, publisher = {Springer}, address = {New York}, issn = {0947-8396}, doi = {10.1007/s00339-013-7998-3}, pages = {515 -- 520}, year = {2014}, abstract = {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.}, language = {en} } @article{FangQiuWirgesetal.2010, author = {Fang, Peng and Qiu, Xunlin and Wirges, Werner and Gerhard, Reimund and Zirkel, Larissa}, title = {Polyethylene-naphthalate (PEN) ferroelectrets : cellular structure, piezoelectricity and thermal stability}, issn = {1070-9878}, doi = {10.1109/TDEI.2010.5539678}, year = {2010}, abstract = {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.}, language = {en} } @article{SunZhangXiaetal.2011, author = {Sun, Zhuanlan and Zhang, Xiaoqing and Xia, Zhongfu and Qiu, Xunlin and Wirges, Werner and Gerhard, Reimund and Zeng, Changchun and Zhang, Chuck and Wang, Ben}, title = {Polarization and piezoelectricity in polymer films with artificial void structure}, series = {Applied physics : A, Materials science \& processing}, volume = {105}, journal = {Applied physics : A, Materials science \& processing}, number = {1}, publisher = {Springer}, address = {New York}, issn = {0947-8396}, doi = {10.1007/s00339-011-6481-2}, pages = {197 -- 205}, year = {2011}, abstract = {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.}, language = {en} } @article{QiuWirgesGerhard2014, author = {Qiu, Xunlin and Wirges, Werner and Gerhard, Reimund}, title = {Polarization and Hysteresis in Tubular-Channel Fluoroethylenepropylene-Copolymer Ferroelectrets}, series = {Ferroelectrics}, volume = {472}, journal = {Ferroelectrics}, number = {1}, publisher = {Routledge, Taylor \& Francis Group}, address = {Abingdon}, issn = {0015-0193}, doi = {10.1080/00150193.2014.964603}, pages = {100 -- 109}, year = {2014}, abstract = {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.}, language = {en} } @article{AltafimAltafimQiuetal.2012, author = {Altafim, Ruy Alberto Pisani and Altafim, Ruy Alberto Pisani and Qiu, Xunlin and Raabe, Sebastian and Wirges, Werner and Basso, Heitor Cury and Gerhard, Reimund}, title = {Fluoropolymer piezoelectrets with tubular channels resonance behavior controlled by channel geometry}, series = {Applied physics : A, Materials science \& processing}, volume = {107}, journal = {Applied physics : A, Materials science \& processing}, number = {4}, publisher = {Springer}, address = {New York}, issn = {0947-8396}, doi = {10.1007/s00339-012-6848-z}, pages = {965 -- 970}, year = {2012}, abstract = {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.}, language = {en} } @article{QiuHollaenderWirgesetal.2013, author = {Qiu, Xunlin and Holl{\"a}nder, Lars and Wirges, Werner and Gerhard, Reimund and Basso, Heitor Cury}, title = {Direct hysteresis measurements on ferroelectret films by means of a modified Sawyer-Tower circuit}, series = {Journal of applied physics}, volume = {113}, journal = {Journal of applied physics}, number = {22}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/1.4809556}, pages = {8}, year = {2013}, abstract = {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.}, language = {en} }