@article{AssagraAltafimdoCarmoetal.2020, author = {Assagra, Yuri A.O. and Altafim, Ruy Alberto Pisani and do Carmo, Joao P. and Altafim, Ruy A.C. and Rychkov, Dmitry and Wirges, Werner and Gerhard, Reimund}, title = {A new route to piezo-polymer transducers: 3D printing of polypropylene ferroelectrets}, series = {IEEE transactions on dielectrics and electrical insulation}, volume = {27}, journal = {IEEE transactions on dielectrics and electrical insulation}, number = {5}, publisher = {Inst. of Electr. and Electronics Engineers}, address = {Piscataway}, issn = {1070-9878}, doi = {10.1109/TDEI.2020.008461}, pages = {1668 -- 1674}, year = {2020}, abstract = {Here, a promising approach for producing piezo-polymer transducers in a one-step process is presented. Using 3D-printing technology and polypropylene (PP) filaments, we are able to print a two-layered film structure with regular cavities of precisely controlled size and shape. It is found that the 3D-printed samples exhibit piezoelectric coefficients up to 200 pC/N, similar to those of other PP ferroelectrets, and their temporal and thermal behavior is in good agreement with those known of PP ferroelectrets. The piezoelectric response strongly decreases for applied pressures above 20 kPa, as the pressure in the air-filled cavities strongly influences the overall elastic modulus of ferroelectrets.}, language = {en} } @article{WangRychkovNguyenetal.2020, author = {Wang, Jingwen and Rychkov, Dmitry and Nguyen, Quyet Doan and Gerhard, Reimund}, title = {Unexpected bipolar space-charge polarization across transcrystalline interfaces in polypropylene electret films}, series = {Journal of applied physics}, volume = {128}, journal = {Journal of applied physics}, number = {13}, publisher = {American Institute of Physics, AIP}, address = {Melville, NY}, issn = {0021-8979}, doi = {10.1063/5.0022071}, pages = {7}, year = {2020}, abstract = {A double-layer transcrystalline polypropylene (PP) film with a flat central interface layer between its two transcrystalline layers is obtained by recrystallization from the melt between two polytetrafluoroethylene (PTFE) surfaces on both sides of the PP film. Its electret properties are studied and compared with those of a single-layer transcrystalline PP film re-crystallized in contact with only one PTFE surface. Within experimental uncertainty, the two types of transcrystalline films exhibit the same thermal properties and crystallinities. After thermal poling, however, two hetero-charge layers of opposite polarity are found on the internal interfaces of the double-layer transcrystalline films and may together be considered as micrometer-sized dipoles. The unexpected phenomenon does not occur in single-layer transcrystalline samples without a central interface layer, suggesting that the interfaces between the transcrystalline layers and the micrometer-thick central interface layer may be the origin of deeper traps rather than the crystalline structures in the transcrystallites or the spherulites. The origin of the interfacial charges was also studied by means of an injection-blocking charging method, which revealed that intrinsic charge carriers introduced during recrystallization are most likely responsible for the interfacial charges. It is fascinating that a material as familiar as PP can exhibit such intriguing properties with a special bipolar space-charge polarization across the central interface layer after quasi-epitaxial surface moulding into a double-layer transcrystalline form. In addition to applications in electret (micro-)devices for electro-mechanical transduction, the highly ordered structures may also be employed as a new paradigm for studying charge storage and transport in polymer electrets and in dielectrics for DC electrical insulation.}, language = {en} } @article{WangRychkovGerhard2021, author = {Wang, Jingwen and Rychkov, Dmitry and Gerhard, Reimund}, title = {Space-charge electret properties of polypropylene films with transcrystalline or spherulitic structures}, series = {Journal of applied physics : AIP's archival journal for significant new results in applied physics / publ. by the American Institute of Physics}, volume = {129}, journal = {Journal of applied physics : AIP's archival journal for significant new results in applied physics / publ. by the American Institute of Physics}, number = {6}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/5.0039867}, pages = {7}, year = {2021}, abstract = {Spherulite-related space-charge electret properties of polypropylene (PP) have been widely discussed in the past decades. In the present paper, a less-common crystalline structure in PP-transcrystalline PP-is studied regarding its electret behavior in comparison with the typical spherulitic morphology. Polarized light microscopy and differential scanning calorimetry were employed to characterize the crystallite types and crystallinities of transcrystalline and spherulitic PP. Their electret functionality is investigated by means of thermally stimulated discharge experiments, where the cross-over phenomenon is observed on transcrystalline PP films, whereas surface-potential saturation and undercharging on the surface occur on the spherulitic samples. Besides, an asymmetrical behavior of positive and negative surface-charge stabilities is found on PP with spherulites, the negatively charged spherulitic surfaces show a better charge stability. It is shown that PP electrets are very sensitive to changes in the microscopic crystalline structures and their interfaces as well as in the molecular conformations controlled through adjustments of the respective processing steps. In addition, surface and bulk nanocomposites of PP or low-density polyethylene with inorganic particles are included in the comparison. In view of recent developments in the areas of PP-based electret-fiber filters and cellular-foam ferroelectrets, the observed changes in the charge-storage properties may have particular relevance, as the required film, fiber, or foam processing might significantly modify crystalline morphologies and nano-scale interfaces in PP electrets. Limitations in the charge-storage capabilities of interface structures may also be of interest in the context of high-voltage electrical-insulation materials where reduced space-charge accumulation and slightly increased charge transport can be advantageous.}, language = {en} } @article{WangRychkovNguyenetal.2020, author = {Wang, Jingwen and Rychkov, Dmitry and Nguyen, Quyet Doan and Gerhard, Reimund}, title = {The influence of orthophosphoric-acid surface modification on charge-storage enhancement in polypropylene electrets}, series = {Journal of applied physics}, volume = {128}, journal = {Journal of applied physics}, number = {3}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/5.0013805}, pages = {6}, year = {2020}, abstract = {Bipolar electrets from polypropylene (PP) are essential, e.g., in electret air filters and in cellular-foam ferroelectrets. Therefore, the mechanism of surface-charge stability enhancement on PP electrets via orthophosphoric-acid surface treatment is investigated in detail. It is shown that the significant charge-stability enhancement can be mainly attributed to deeper surface traps originating from deposited chemicals and topographic features on the modified surfaces. Thermally stimulated discharge of chemically treated and non-treated PP films with different surface-charge densities is used to test the limits of the newly formed deep traps in terms of the capacity for hosting surface charges. When the initial surface-charge density is very high, more charges are forced into shallower original traps on the surface or in the bulk of the treated PP samples, reducing the effect of the deeper surface traps brought by the surface modification. The well-known crossover phenomenon (of the surface-charge decay curves) has been observed between modified PP electrets charged to +/- 2kV and to +/- 3kV. Acoustically probed charge distributions in the thickness direction of PP electrets at different stages of thermal discharging indicate that the deep surface trapping sites may have preference for negative charges, resulting in the observed asymmetric charge stability of the modified PP films.}, language = {en} } @article{RychkovGerhardKuznetsovetal.2018, author = {Rychkov, Dmitry and Gerhard, Reimund and Kuznetsov, Alexey and Rychkov, Andrey}, title = {Influence of charge density on the trap energy spectrum in fluoroethylenepropylene copolymer films with chemically modified surfaces}, series = {IEEE transactions on dielectrics and electrical insulation}, volume = {25}, journal = {IEEE transactions on dielectrics and electrical insulation}, number = {3}, publisher = {Inst. of Electr. and Electronics Engineers}, address = {Piscataway}, issn = {1070-9878}, doi = {10.1109/TDEI.2018.007437}, pages = {840 -- 844}, year = {2018}, abstract = {Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) films were treated with titanium-tetrachloride vapor by means of molecular-layer deposition. The treatment leads to considerable improvements of the electret-charge stability on positively charged films. A slight improvement is also observed for negatively charged films. In line with our previous findings, we attribute the improvement in electret properties to the formation of deeper traps on the chemically modified polymer surfaces. Here, we investigate the influence of the charge density on electret stability of FEP films with modified surfaces. Trap-energy spectra obtained from thermally-stimulated-discharge measurements indicate that the charge stability on modified FEP films depends on how the surface traps are populated and on the availability of additional deeper traps.}, language = {en} } @article{RychkovAltafim2018, author = {Rychkov, Dmitry and Altafim, Ruy Alberto Pisani}, title = {Template-based fluoroethylenepropylene ferroelectrets with enhanced thermal stability of piezoelectricity}, series = {Journal of applied physics}, volume = {124}, journal = {Journal of applied physics}, number = {17}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/1.5041374}, pages = {5}, year = {2018}, abstract = {In ferroelectrets, the piezoelectricity stems from the charges of both polarities trapped on the inner surfaces of the cavities in the material, so that its thermal stability is defined by the stability of the respective charges. In the present work, a template-based lamination technique has been employed to fabricate tubular-channel ferroelectrets from fluoroethylenepropylene (FEP) films. It has been shown that the piezoelectricity in FEP ferroelectrets decays at relatively low temperatures due to the inherently lower thermal stability of the positive charge. In order to improve charge trapping, we have treated both FEP films and inner surfaces of the ferroelectret cavities with titanium-tetrachloride vapor, using the atomic-layer-deposition technique. Using surface-potential-decay measurements on FEP films, we have found that the charge-decay curves shift by more than 100 degrees C to the higher temperatures as a result of the surface treatment. Direct measurements of piezoelectric d(33) coefficients as a function of temperature have shown that the piezoelectric stability is likewise improved with the d(33)-decay curves shifted by 60 degrees C to the right. The improvement of electret/ferroelectret properties can be attributed to the formation of the deeper traps on the chemically modified FEP surface. SEM micrographs and EDS analysis reveal island-like structures with titanium- and oxygen-containing species that can be responsible for the deeper trapping of the electret charges. Published by AIP Publishing.}, language = {en} } @article{WangRychkovGerhard2017, author = {Wang, Jingwen and Rychkov, Dmitry and Gerhard, Reimund}, title = {Chemical modification with orthophosphoric acid enhances surface-charge stability on polypropylene electrets}, series = {Applied physics letters}, volume = {110}, journal = {Applied physics letters}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.4983348}, pages = {5}, year = {2017}, abstract = {The low surface-charge stability of polypropylene (PP) frequently limits its application as an electret material. In this paper, we demonstrate how the treatment of PP-film surfaces with orthophosphoric acid (H3PO4) enhances their charge stability. To discriminate between the effects of chemical modification and thermal treatment, as-received and annealed PP films are used as reference samples. The electret properties of treated and non-treated PP films are characterized with thermally stimulated discharge (TSD) and isothermal surface-potential decay (ISPD) experiments, from which considerable improvement in thermal and temporal charge stability is observed for samples modified with H3PO4. The half-value temperature (T-1/2) observed on TSD curves of chemically treated PP increases to 131 and 145 degrees C for positive and negative charges, respectively. The enhancement might be attributed to the phosphoric compounds detected on the H3PO4-modified surfaces via attenuated-total-reflection infrared spectroscopy. Deeper surface traps formed at the "foreign" phosphorus-containing structures are able to capture the charges over longer time periods and at higher temperatures, thus leading to significant improvements in the temporal and thermal surface-charge stabilities of PP electrets. Published by AIP Publishing.}, language = {en} } @article{RychkovKuznetsovRychkov2011, author = {Rychkov, Dmitry and Kuznetsov, Alexey and Rychkov, Andrey}, title = {Electret properties of polyethylene and polytetrafluoroethylene films with chemically modified surface}, 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.2011.5704487}, pages = {8 -- 14}, year = {2011}, abstract = {This paper investigates the effect of chemical surface modification of polytetrafluoroethylene (PTFE) and low density polyethylene (LDPE) films on their electret properties. PTFE films were subjected to wet treatment with three different chemicals: orthophosphoric acid, tetrabutyl titanate and tetraethoxysilane. The technique based on the principles of molecular layer deposition (MLD) method was used to modify the surface of LDPE films with phosphorus trichloride vapors. The surfaces of the films were then corona charged, and the electret charge stability was studied by means of isothermal and thermally stimulated surface potential decay. Both PTFE and LDPE films, after the surface treatment, displayed a considerable enhancement in the charge stability compared to the virgin samples. It is important to note that the enhancement of the charge stability was achieved in the positively charged PTFE films, a result important to practical applications. We attribute this effect of charge stabilization to the formation of new energetically deep traps on the modified surface. Decrease in molecular mobility, due to attachment of new chemical structures to the surface macromolecules, may also contribute to the overall growth of the charge stability.}, language = {en} } @article{RychkovGerhard2011, author = {Rychkov, Dmitry and Gerhard, Reimund}, title = {Stabilization of positive charge on polytetrafluoroethylene electret films treated with titanium-tetrachloride vapor}, series = {Applied physics letters}, volume = {98}, journal = {Applied physics letters}, number = {12}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.3565166}, pages = {3}, year = {2011}, abstract = {The surface of polytetrafluoroethylene films was treated with titanium-tetrachloride vapor. The treatment was carried out in a flow reactor by means of molecular-layer deposition, a method from the arsenal of chemical nanotechnology. X-ray photoelectron spectroscopy reveals that such a treatment results in considerable changes in the chemical composition at and near the surface of the fluoropolymer film. Both, defluorination and oxidation of the surface were observed. At the same time, samples treated with titanium tetrachloride show a significant enhancement in the thermal stability of the positive homocharge. The thermally stimulated surface-potential-decay curves were observed to shift to higher temperatures by more than 100 degrees C.}, language = {en} } @article{McCarthyStoyanovRychkovetal.2012, author = {McCarthy, Denis N. and Stoyanov, Hristiyan and Rychkov, Dmitry and Ragusch, Huelya and Melzer, Michael and Kofod, Guggi}, title = {Increased permittivity nanocomposite dielectrics by controlled interfacial interactions}, series = {Composites science and technology}, volume = {72}, journal = {Composites science and technology}, number = {6}, publisher = {Elsevier}, address = {Oxford}, issn = {0266-3538}, doi = {10.1016/j.compscitech.2012.01.026}, pages = {731 -- 736}, year = {2012}, abstract = {The use of nanoparticles in polymer composite dielectrics has promised great improvements, but useful results have been elusive. Here, the importance of the interfacial interactions between the nanoparticles and the polymer matrix are investigated in TiO2 nanocomposites for dielectric materials using surface functionalisation. The interface is observed to dominate the nanocomposite properties and leads to a threefold increase in permittivity at volume fractions as low as 10\%. Surface functionalisation of the filler nanoparticles with silanes allows control of this interface, avoiding significant degradation of the other important material properties, particularly electrical breakdown strength, and resulting in a material that is demonstrated successfully as an active material in a dielectric elastomer actuator application with increased work output compared to the pure polymer. Although further permittivity increases are observed when the interface regions have formed a percolation network, the other material properties deteriorate. The observation of percolation behaviour allows the interface thickness to be estimated.}, language = {en} }