@phdthesis{Mellinger2004,
  author    = {Mellinger, Axel},
  title     = {Charge storage in electret polymers: mechanisms, characterization and applications},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-5689},
  school      = {Universit{\"a}t Potsdam},
  year      = {2004},
  abstract  = {Electrets are materials capable of storing oriented dipoles or an electric surplus charge for long periods of time. The term "electret" was coined by Oliver Heaviside in analogy to the well-known word "magnet". Initially regarded as a mere scientific curiosity, electrets became increasingly imporant for applications during the second half of the 20th century. The most famous example is the electret condenser microphone, developed in 1962 by Sessler and West. Today, these devices are produced in annual quantities of more than 1 billion, and have become indispensable in modern communications technology. Even though space-charge electrets are widely used in transducer applications, relatively little was known about the microscopic mechanisms of charge storage. It was generally accepted that the surplus charges are stored in some form of physical or chemical traps. However, trap depths of less than 2 eV, obtained via thermally stimulated discharge experiments, conflicted with the observed lifetimes (extrapolations of experimental data yielded more than 100000 years). Using a combination of photostimulated discharge spectroscopy and simultaneous depth-profiling of the space-charge density, the present work shows for the first time that at least part of the space charge in, e.g., polytetrafluoroethylene, polypropylene and polyethylene terephthalate is stored in traps with depths of up to 6 eV, indicating major local structural changes. Based on this information, more efficient charge-storing materials could be developed in the future. The new experimental results could only be obtained after several techniques for characterizing the electrical, electromechanical and electrical properties of electrets had been enhanced with in situ capability. For instance, real-time information on space-charge depth-profiles were obtained by subjecting a polymer film to short laser-induced heat pulses. The high data acquisition speed of this technique also allowed the three-dimensional mapping of polarization and space-charge distributions. A highly active field of research is the development of piezoelectric sensor films from electret polymer foams. These materials store charges on the inner surfaces of the voids after having been subjected to a corona discharge, and exhibit piezoelectric properties far superior to those of traditional ferroelectric polymers. By means of dielectric resonance spectroscopy, polypropylene foams (presently the most widely used ferroelectret) were studied with respect to their thermal and UV stability. Their limited thermal stability renders them unsuitable for applications above 50 °C. Using a solvent-based foaming technique, we found an alternative material based on amorphous Teflon® AF, which exhibits a stable piezoelectric coefficient of 600 pC/N at temperatures up to 120 °C.},
  subject      = {Elektret},
  language  = {en}
}
@phdthesis{Fang2010,
  author    = {Fang, Peng},
  title     = {Preparation and investigation of polymer-foam films and polymer-layer systems for ferroelectrets},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-48412},
  school      = {Universit{\"a}t Potsdam},
  year      = {2010},
  abstract  = {Piezoelectric materials are very useful for applications in sensors and actuators. In addition to traditional ferroelectric ceramics and ferroelectric polymers, ferroelectrets have recently become a new group of piezoelectrics. Ferroelectrets are functional polymer systems for electromechanical transduction, with elastically heterogeneous cellular structures and internal quasi-permanent dipole moments. The piezoelectricity of ferroelectrets stems from linear changes of the dipole moments in response to external mechanical or electrical stress. Over the past two decades, polypropylene (PP) foams have been investigated with the aim of ferroelectret applications, and some products are already on the market. PP-foam ferroelectrets may exhibit piezoelectric d33 coefficients of 600 pC/N and more. Their operating temperature can, however, not be much higher than 60 °C. Recently developed polyethylene-terephthalate (PET) and cyclo-olefin copolymer (COC) foam ferroelectrets show slightly better d33 thermal stabilities, but usually at the price of smaller d33 values. Therefore, the main aim of this work is the development of new thermally stable ferroelectrets with appreciable piezoelectricity. Physical foaming is a promising technique for generating polymer foams from solid films without any pollution or impurity. Supercritical carbon dioxide (CO2) or nitrogen (N2) are usually employed as foaming agents due to their good solubility in several polymers. Polyethylene propylene (PEN) is a polyester with slightly better properties than PET. A "voiding + inflation + stretching" process has been specifically developed to prepare PEN foams. Solid PEN films are saturated with supercritical CO2 at high pressure and then thermally voided at high temperatures. Controlled inflation (Gas-Diffusion Expansion or GDE) is applied in order to adjust the void dimensions. Additional biaxial stretching decreases the void heights, since it is known lens-shaped voids lead to lower elastic moduli and therefore also to stronger piezoelectricity. Both, contact and corona charging are suitable for the electric charging of PEN foams. The light emission from the dielectric-barrier discharges (DBDs) can be clearly observed. Corona charging in a gas of high dielectric strength such as sulfur hexafluoride (SF6) results in higher gas-breakdown strength in the voids and therefore increases the piezoelectricity. PEN foams can exhibit piezoelectric d33 coefficients as high as 500 pC/N. Dielectric-resonance spectra show elastic moduli c33 of 1 - 12 MPa, anti-resonance frequencies of 0.2 - 0.8 MHz, and electromechanical coupling factors of 0.016 - 0.069. As expected, it is found that PEN foams show better thermal stability than PP and PET. Samples charged at room temperature can be utilized up to 80 - 100 °C. Annealing after charging or charging at elevated temperatures may improve thermal stabilities. Samples charged at suitable elevated temperatures show working temperatures as high as 110 - 120 °C. Acoustic measurements at frequencies of 2 Hz - 20 kHz show that PEN foams can be well applied in this frequency range. Fluorinated ethylene-propylene (FEP) copolymers are fluoropolymers with very good physical, chemical and electrical properties. The charge-storage ability of solid FEP films can be significantly improved by adding boron nitride (BN) filler particles. FEP foams are prepared by means of a one-step procedure consisting of CO2 saturation and subsequent in-situ high-temperature voiding. Piezoelectric d33 coefficients up to 40 pC/N are measured on such FEP foams. Mechanical fatigue tests show that the as-prepared PEN and FEP foams are mechanically stable for long periods of time. Although polymer-foam ferroelectrets have a high application potential, their piezoelectric properties strongly depend on the cellular morphology, i.e. on size, shape, and distribution of the voids. On the other hand, controlled preparation of optimized cellular structures is still a technical challenge. Consequently, new ferroelectrets based on polymer-layer system (sandwiches) have been prepared from FEP. By sandwiching an FEP mesh between two solid FEP films and fusing the polymer system with a laser beam, a well-designed uniform macroscopic cellular structure can be formed. Dielectric resonance spectroscopy reveals piezoelectric d33 coefficients as high as 350 pC/N, elastic moduli of about 0.3 MPa, anti-resonance frequencies of about 30 kHz, and electromechanical coupling factors of about 0.05. Samples charged at elevated temperatures show better thermal stabilities than those charged at room temperature, and the higher the charging temperature, the better is the stability. After proper charging at 140 °C, the working temperatures can be as high as 110 - 120 °C. Acoustic measurements at frequencies of 200 Hz - 20 kHz indicate that the FEP layer systems are suitable for applications at least in this range.},
  language  = {en}
}
@article{FangHollaenderWirgesetal.2012,
  author    = {Fang, Peng and Hollaender, Lars and Wirges, Werner and Gerhard, Reimund},
  title     = {Piezoelectric d(33) coefficients in foamed and layered polymer piezoelectrets from dynamic mechano-electrical experiments, electro-mechanical resonance spectroscopy and acoustic-transducer measurements},
  series = {Measurement science and technology},
  volume    = {23},
  journal   = {Measurement science and technology},
  number    = {3},
  publisher = {IOP Publ. Ltd.},
  address   = {Bristol},
  issn      = {0957-0233},
  doi       = {10.1088/0957-0233/23/3/035604},
  pages     = {9},
  year      = {2012},
  abstract  = {Piezoelectrets are novel transducer materials which can be widely applied in sensors and actuators. Here, three techniques for determining piezoelectric d(33) coefficients of piezoelectrets are reviewed and compared. Two types of piezoelectrets, polyethylene-naphthalate (PEN) polymer-foam piezoelectrets and fluorinated ethylene-propylene (FEP) copolymer-layer piezoelectrets, have been prepared and measured by means of dynamic, resonance, and acoustical methods. The dynamic measurements show that the d(33) coefficient of PEN-foam samples clearly decreases with increasing stress, but 80\% of the initial d(33) can be retained after 1800 cycles of a continuous dynamic measurement in a mechanical fatigue test. The resonance measurements demonstrate that both PEN-foam and FEP-layer samples exhibit clear electro-mechanical resonances. PEN-foam samples show elastic moduli in the range from 1 to 12 MPa and d(33) values up to 500 pC N-1, while FEP-layer samples show homogeneous elastic moduli of about 0.3 MPa and d(33) values of about 280 pC N-1. The acoustical measurements reveal that both PEN-foam and FEP-layer samples exhibit stable frequency responses in the range from 5.7 to 20 kHz. In addition, d(33) coefficients obtained with different experimental methods are in good agreement with each other, which confirms the reliability of all three techniques.},
  language  = {en}
}
@article{ZhangZhangYouetal.2014,
  author    = {Zhang, Xiaoqing and Zhang, Xinwu and You, Qiong and Sessler, Gerhard M.},
  title     = {Low- cost, large- area, stretchable piezoelectric films based on irradiation- crosslinked poly ( propylene)},
  series = {Macromolecular materials and engineering},
  volume    = {299},
  journal   = {Macromolecular materials and engineering},
  number    = {3},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1438-7492},
  doi       = {10.1002/mame.201300161},
  pages     = {290 -- 295},
  year      = {2014},
  abstract  = {Low cost, large area, lightweight, stretchable piezoelectric films, based on space-charge electret with a foam structure (i.e., ferroelectrets or piezoelectrets), have been fabricated by using commercially available irradiation cross-linked poly(propylene) (IXPP) foam sheets. Piezoelectric d(33) coefficients are as high as 100pCN(-1). The piezoelectric performance in such IXPP films is well preserved for repeated strains of less than 10\%. Piezoelectric d(33) coefficients are frequency independent in the range from 2 to 100Hz. Such new class materials may be applied in sensory skins, smart clothing, bio-inspired systems, microenergy harvesters, and so on.},
  language  = {en}
}
@article{WangDanielsConnellyetal.2021,
  author    = {Wang, Ningzhen and Daniels, Robert and Connelly, Liam and Sotzing, Michael and Wu, Chao and Gerhard, Reimund and Sotzing, Gregory A. and Cao, Yang},
  title     = {All-organic flexible ferroelectret nanogenerator with fabric-based electrodes for self-powered body area networks},
  series = {Small : nano micro},
  volume    = {17},
  journal   = {Small : nano micro},
  number    = {33},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1613-6810},
  doi       = {10.1002/smll.202103161},
  pages     = {11},
  year      = {2021},
  abstract  = {Due to their electrically polarized air-filled internal pores, optimized ferroelectrets exhibit a remarkable piezoelectric response, making them suitable for energy harvesting. Expanded polytetrafluoroethylene (ePTFE) ferroelectret films are laminated with two fluorinated-ethylene-propylene (FEP) copolymer films and internally polarized by corona discharge. Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)-coated spandex fabric is employed for the electrodes to assemble an all-organic ferroelectret nanogenerator (FENG). The outer electret-plus-electrode double layers form active device layers with deformable electric dipoles that strongly contribute to the overall piezoelectric response in the proposed concept of wearable nanogenerators. Thus, the FENG with spandex electrodes generates a short-circuit current which is twice as high as that with aluminum electrodes. The stacking sequence spandex/FEP/ePTFE/FEP/ePTFE/FEP/spandex with an average pore size of 3 mu m in the ePTFE films yields the best overall performance, which is also demonstrated by the displacement-versus-electric-field loop results. The all-organic FENGs are stable up to 90 degrees C and still perform well 9 months after being polarized. An optimized FENG makes three light emitting diodes (LEDs) blink twice with the energy generated during a single footstep. The new all-organic FENG can thus continuously power wearable electronic devices and is easily integrated, for example, with clothing, other textiles, or shoe insoles.},
  language  = {en}
}