@article{LiChenQiuetal.2019, author = {Li, Changsheng and Chen, Gangjin and Qiu, Xunlin and Gao, Meng and Gerhard, Reimund}, title = {Modified polytetrafluoroethylene}, series = {Applied physics express : APEX}, volume = {13}, journal = {Applied physics express : APEX}, number = {1}, publisher = {IOP Publ. Ltd.}, address = {Bristol}, issn = {1882-0778}, doi = {10.7567/1882-0786/ab5b23}, pages = {5}, year = {2019}, abstract = {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.}, language = {en} } @article{QiuBenjaminRamanVenkatesanetal.2020, author = {Qiu, Xunlin and Benjamin, Aravindan Joseph and Raman Venkatesan, Thulasinath and Schmidt, Georg C. and Soler, Ricardo Alonso Quintana and Panicker, Pramul Muraleedhara and Gerhard, Reimund and H{\"u}bler, Arved Carl}, title = {Dielectric and electroacoustic assessment of screen-printed piezoelectric polymer layers as flexible transducers}, series = {IEEE transactions on dielectrics and electrical insulation}, volume = {27}, journal = {IEEE transactions on dielectrics and electrical insulation}, number = {5}, publisher = {Institute of Electrical and Electronics Engineers}, address = {New York, NY}, issn = {1070-9878}, doi = {10.1109/TDEI.2020.008864}, pages = {1683 -- 1690}, year = {2020}, abstract = {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.}, language = {en} } @article{FangMaLietal.2017, author = {Fang, Peng and Ma, Xingchen and Li, Xiangxin and Qiu, Xunlin and Gerhard, Reimund and Zhang, Xiaoqing and Li, Guanglin}, title = {Fabrication, Structure Characterization, and Performance Testing of Piezoelectret-Film Sensors for Recording Body Motion}, series = {IEEE Sensors Journal}, volume = {18}, journal = {IEEE Sensors Journal}, number = {1}, publisher = {Inst. of Electr. and Electronics Engineers}, address = {Piscataway}, issn = {1530-437X}, doi = {10.1109/JSEN.2017.2766663}, pages = {401 -- 412}, year = {2017}, abstract = {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.}, language = {en} } @article{QiuGrothWirgesetal.2018, author = {Qiu, Xunlin and Groth, Frederick and Wirges, Werner and Gerhard, Reimund}, title = {Cellular polypropylene foam films as DC voltage insulation and as piezoelectrets}, series = {IEEE transactions on dielectrics and electrical insulation}, volume = {25}, journal = {IEEE transactions on dielectrics and electrical insulation}, number = {3}, publisher = {Institut of Electr. and Electronics Engineers}, address = {Piscataway}, issn = {1070-9878}, doi = {10.1109/TDEI.2018.007192}, pages = {829 -- 834}, year = {2018}, abstract = {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.}, language = {en} } @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{Qiu2016, author = {Qiu, Xunlin}, title = {Significant enhancement of the charging efficiency in the cavities of ferroelectrets through gas exchange during charging}, series = {Applied physics letters}, volume = {109}, journal = {Applied physics letters}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.4971259}, pages = {2543 -- 2555}, year = {2016}, abstract = {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.}, language = {en} } @phdthesis{Qiu2017, author = {Qiu, Xunlin}, title = {Ferroelectrets: heterogenous polymer electrets with high electromechanical response}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-398425}, school = {Universit{\"a}t Potsdam}, pages = {viii, 172}, year = {2017}, abstract = {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.}, 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{ZhaoDunlopQiuetal.2014, author = {Zhao, Qiang and Dunlop, John William Chapman and Qiu, Xunlin and Huang, Feihe and Zhang, Zibin and Heyda, Jan and Dzubiella, Joachim and Antonietti, Markus and Yuan, Jiayin}, title = {An instant multi-responsive porous polymer actuator driven by solvent molecule sorption}, series = {Nature Communications}, volume = {5}, journal = {Nature Communications}, publisher = {Nature Publ. Group}, address = {London}, issn = {2041-1723}, doi = {10.1038/ncomms5293}, pages = {8}, year = {2014}, abstract = {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.}, 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{QiuGerhardMellinger2011, author = {Qiu, Xunlin and Gerhard, Reimund and Mellinger, Axel}, title = {Turning polymer foams or polymer-film systems into ferroelectrets dielectric barrier discharges in voids}, series = {IEEE transactions on dielectrics and electrical insulation}, volume = {18}, journal = {IEEE transactions on dielectrics and electrical insulation}, number = {1}, publisher = {Inst. of Electr. and Electronics Engineers}, address = {Piscataway}, issn = {1070-9878}, doi = {10.1109/TDEI.2011.5704490}, pages = {34 -- 42}, year = {2011}, abstract = {Polymer foams and void-containing polymer-film systems with internally charged voids combine large piezoelectricity with mechanical flexibility and elastic compliance. This new class of soft materials (often called ferro-or piezoelectrets) has attracted considerable attention from science and industry. It has been found that the voids can be internally charged by means of dielectric barrier discharges (DBDs) under high electric fields. The charged voids can be considered as man-made macroscopic dipoles. Depending on the ferroelectret structure and the pressure of the internal gas, the voids may be highly compressible. Consequently, very large dipole-moment changes can be induced by mechanical or electrical stresses, leading to large piezoelectricity. DBD charging of the voids is a critical process for rendering polymer foams piezoelectric. Thus a comprehensive exploration of DBD charging is essential for the understanding and the optimization of piezoelectricity in ferroelectrets. Recent studies show that DBDs in the voids are triggered when the internal electric field reaches a threshold value according to Townsend's model of Paschen breakdown. During the DBDs, charges of opposite polarity are generated and trapped at the top and bottom internal surfaces of the gas-filled voids, respectively. The deposited charges induce an electric field opposite to the externally applied one and thus extinguish the DBDs. Back discharges may eventually be triggered when the external voltage is reduced or turned off. In order to optimize the efficiency of DBD charging, the geometry (in particular the height) of the voids, the type of gas and its pressure inside the voids are essential factors to be considered and to be optimized. In addition, the influence of the plasma treatment on the internal void surfaces during the DBDs should be taken into consideration.}, language = {en} } @article{QiuWirgesGerhard2011, author = {Qiu, Xunlin and Wirges, Werner and Gerhard, Reimund}, title = {Beneficial and detrimental fatigue effects of dielectric barrier discharges on the piezoelectricity of polypropylene ferroelectrets}, series = {Journal of applied physics}, volume = {110}, journal = {Journal of applied physics}, number = {2}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/1.3610507}, pages = {8}, year = {2011}, abstract = {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.}, language = {en} } @misc{Qiu2011, author = {Qiu, Xunlin}, title = {Patterned piezo-, pyro-, and ferroelectricity of poled polymer electrets}, series = {Journal of applied physics}, volume = {110}, journal = {Journal of applied physics}, number = {5}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/1.3638069}, pages = {1}, year = {2011}, 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{WirgesRaabeQiu2012, author = {Wirges, Werner and Raabe, Sebastian and Qiu, Xunlin}, title = {Dielectric elastomer and ferroelectret films combined in a single device how do they reinforce each other?}, series = {Applied physics : A, Materials science \& processing}, volume = {107}, journal = {Applied physics : A, Materials science \& processing}, number = {3}, publisher = {Springer}, address = {New York}, issn = {0947-8396}, doi = {10.1007/s00339-012-6833-6}, pages = {583 -- 588}, year = {2012}, abstract = {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.}, 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{RychkovAltafimQiuetal.2012, author = {Rychkov, Dmitry and Altafim, Ruy Alberto Pisani and Qiu, Xunlin and Gerhard, Reimund}, title = {Treatment with orthophosphoric acid enhances the thermal stability of the piezoelectricity in low-density polyethylene ferroelectrets}, series = {Journal of applied physics}, volume = {111}, journal = {Journal of applied physics}, number = {12}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/1.4729866}, pages = {5}, year = {2012}, abstract = {Ferroelectrets have been fabricated from low-density polyethylene (LDPE) films by means of a template-based lamination. The temperature dependence of the piezoelectric d(33) coefficient has been investigated. It was found that low-density polyethylene ferroelectrets have rather low thermal stability with the piezoelectric coefficient decaying almost to zero already at 100 degrees C. This behavior is attributed to the poor electret properties of the polyethylene films used for the fabrication of the ferroelectrets. In order to improve the charge trapping and the thermal stability of electret charge and piezoelectricity, LDPE ferroelectrets were treated with orthophosphoric acid. The treatment resulted in considerable improvements of the charge stability in LDPE films and in ferroelectret systems made from them. For example, the charge and piezoelectric-coefficient decay curves shifted to higher temperatures by 60 K and 40 K, respectively. It is shown that the decay of the piezoelectric coefficient in LDPE ferroelectrets is governed by the relaxation of less stable positive charges. The treatment also leads to noticeable changes in the chemical composition of the LDPE surface. Infrared spectroscopy reveals absorption bands attributed to phosphorus-containing structures, while scanning electron microscopy shows new island-like structures, 50-200 nm in diameter, on the modified surface.}, language = {en} } @article{MenSiebenbuergerQiuetal.2013, author = {Men, Yongjun and Siebenb{\"u}rger, Miriam and Qiu, Xunlin and Antonietti, Markus and Yuan, Jiayin}, title = {Low fractions of ionic liquid or poly(ionic liquid) can activate polysaccharide biomass into shaped, flexible and fire-retardant porous carbons}, series = {Journal of materials chemistry : A, Materials for energy and sustainability}, volume = {1}, journal = {Journal of materials chemistry : A, Materials for energy and sustainability}, number = {38}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2050-7488}, doi = {10.1039/c3ta12302b}, pages = {11887 -- 11893}, year = {2013}, abstract = {Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 degrees C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as "activation agents" with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt\%). In addition, this "induced carbonization" and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.}, 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{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} } @article{MenSiebenbuergerQiuetal.2013, author = {Men, Yongiun and Siebenb{\"u}rger, Miriam and Qiu, Xunlin and Antonietti, Markus and Yuan, Jiayin}, title = {Low fractions of ionic liquid or poly(ionic liquid) can activate polysaccaride biomass into shaped, flexible and fire-retardant porous carbons}, doi = {10.1039/c3ta12302b}, year = {2013}, abstract = {Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 °C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as "activation agents" with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt\%). In addition, this "induced carbonization" and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.}, 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{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 = {Dielectric barrier discharges during the generation of ferroelectrets : optical spectroscopy for process monitoring}, isbn = {978-1-4244-1482-6}, year = {2007}, language = {en} } @article{QiuMellingerWegeneretal.2007, author = {Qiu, Xunlin and Mellinger, Axel and Wegener, Michael and Wirges, Werner and Gerhard, Reimund}, title = {Barrier discharges in cellular polypropylene ferroelectrets : how do they influence the electromechanical properties?}, year = {2007}, 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} } @misc{MenSiebenbuergerQiuetal.2013, author = {Men, Yongjun and Siebenb{\"u}rger, Miriam and Qiu, Xunlin and Antonietti, Markus and Yuan, Jiayin}, title = {Low fractions of ionic liquid or poly(ionic liquid) can activate polysaccharide biomass into shaped, flexible and fire-retardant porous carbons}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-95250}, pages = {11887 -- 11887}, year = {2013}, abstract = {Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 °C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as "activation agents" with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt\%). In addition, this "induced carbonization" and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.}, language = {en} }