TY - JOUR A1 - Stoyanov, Hristiyan A1 - Kollosche, Matthias A1 - McCarthy, Denis N. A1 - Kofod, Guggi T1 - Molecular composites with enhanced energy density for electroactive polymers N2 - Actuators based on soft dielectric elastomers deform due to electric field induced Maxwell's stress, interacting with the mechanical properties of the material. The relatively high operating voltages of such actuators can be reduced by increasing the permittivity of the active material, while maintaining the mechanical properties and high electrical breakdown strength. Approaches relying on the use of highly polarizable molecules or conjugated polymers have so far provided the best results, however it has been difficult to maintain high breakdown strengths. In this work, a new approach for increasing the electrostatic energy density of a soft polymer based on molecular composites is presented, relying on chemically grafting soft gel-state pi-conjugated conducting macromolecules (polyaniline (PANI)) to a flexible elastomer backbone SEBS-g-MA (poly-styrene-co-ethylene-co-butylene-co-styrene-g-maleic anhydride). The approach was found to result in composites of increased permittivity (470% over the elastomer matrix) with hardly any reduction in breakdown strength (from 140 to 120 V mu m(-1)), resulting in a large increase in stored electrostatic energy. This led to an improvement in the measured electromechanical response as well as in the maximum actuation strain. A transition was observed when amounts of PANI exceeded 2 vol%, which was ascribed to the exhaustion of the MA- functionality of the SEBS-g-MA. The transition led to drastic increases in permittivity and conductivity, and a sharp drop in electrical breakdown strength. Although the transition caused further improvement of the electromechanical response, the reduction in electrical breakdown strength caused a limitation of the maximum achievable actuation strain. Y1 - 2010 UR - http://www.rsc.org/Publishing/Journals/jm/index.asp U6 - https://doi.org/10.1039/C0jm00519c SN - 0959-9428 ER - TY - JOUR A1 - Stoyanov, Hristiyan A1 - Kollosche, Matthias A1 - Risse, Sebastian A1 - Wache, Remi A1 - Kofod, Guggi T1 - Soft conductive elastomer materials for stretchable electronics and voltage controlled artificial muscles JF - Advanced materials N2 - Block copolymer elastomer conductors (BEC) are mixtures of block copolymers grafted with conducting polymers, which are found to support very large strains, while retaining a high level of conductivity. These novel materials may find use in stretchable electronics. The use of BEC is demonstrated in a capacitive strain sensor and in an artificial muscle of the dielectric elastomer actuator type, supporting more than 100% actuation strain and capacity strain sensitivity up to 300%. KW - soft electrical connections KW - stretchable electronics KW - elastic conductor KW - compliant electrodes Y1 - 2013 U6 - https://doi.org/10.1002/adma.201202728 SN - 0935-9648 VL - 25 IS - 4 SP - 578 EP - 583 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Stoyanov, Hristiyan A1 - Mc Carthy, Denis N. A1 - Kollosche, Matthias A1 - Kofod, Guggi T1 - Dielectric properties and electric breakdown strength of a subpercolative composite of carbon black in thermoplastic copolymer N2 - We investigate the dielectric properties and electric breakdown strength of subpercolative composites of conductive carbon black particles in a rubber insulating matrix. A significant increase in the permittivity in the vicinity of the insulator to conductor transition was observed, with relatively low increases in dielectric loss; however, a rapid decrease in electric breakdown strength was inevitable. A steplike feature was ascribed to agglomeration effects. The low ultimate values of the electric field strength of such composites appear to prohibit practical use. Y1 - 2009 UR - http://apl.aip.org/ U6 - https://doi.org/10.1063/1.3154553 SN - 0003-6951 ER - TY - JOUR A1 - Zhu, Jian A1 - Stoyanov, Hristiyan A1 - Kofod, Guggi A1 - Suo, Zhigang T1 - Large deformation and electromechanical instability of a dielectric elastomer tube actuator N2 - This paper theoretically analyzes a dielectric elastomer tube actuator (DETA). Subject to a voltage difference between the inner and outer surfaces, the actuator reduces in thickness and expands in length, so that the same voltage will induce an even higher electric field. This positive feedback may cause the actuator to thin down drastically, resulting in electrical breakdown. We obtain an analytical solution of the actuator undergoing finite deformation when the elastomer obeys the neo-Hookean model. The critical strain of actuation is calculated in terms of various parameters of design. We also discuss the effect of the strain-stiffening on electromechanical behavior of DETAs by using the model of freely joined links. (C) 2010 American Institute of Physics. [doi:10.1063/1.3490186] Y1 - 2010 UR - http://jap.aip.org/ U6 - https://doi.org/10.1063/1.3490186 SN - 0021-8979 ER - TY - JOUR A1 - McCarthy, Denis N. A1 - Stoyanov, Hristiyan A1 - Rychkov, Dmitry A1 - Ragusch, Huelya A1 - Melzer, Michael A1 - Kofod, Guggi T1 - Increased permittivity nanocomposite dielectrics by controlled interfacial interactions JF - Composites science and technology N2 - 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. KW - Ceramics KW - Nanocomposites KW - Actuator KW - Interface KW - Electrical properties Y1 - 2012 U6 - https://doi.org/10.1016/j.compscitech.2012.01.026 SN - 0266-3538 VL - 72 IS - 6 SP - 731 EP - 736 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Kofod, Guggi A1 - Risse, Sebastian A1 - Stoyanov, Hristiyan A1 - McCarthy, Denis N. A1 - Sokolov, Sergey A1 - Krähnert, Ralph T1 - Broad-spectrum enhancement of polymer composite dielectric constant at ultra low volume fractions of silica-supported copper nanoparticles JF - ACS nano N2 - A new strategy for the synthesis of high permittivity polymer composites is demonstrated based on well-defined spatial distribution of ultralow amounts of conductive nanoparticles. The spatial distribution Was realized by immobilizing Cu nanoparticles within the pore system of Alia microspheres, preventing direct contact between individual Cu particles. Both Cu-loaded and unloaded silica microspheres were-then used as fillers in polymer composites prepared with thermoplastic SEBS rubber is the matrix. With a metallic Cu content of about 0.26 vol % In the compoilte, a relative increase of 94% In real permittivity was obtained. No Cu-induced relaxations were observed in the dielectric spectrum within the studied frequency range of 0.1 Hz to 1 MHz. When related to the amount of conductive nanoparticles, the obtained composites achieve the highest broad spectrum enhancement of permittivity ever reported for a polymer based composite. KW - nanocomposite KW - broad-spectrum permittivity enhancement KW - metal nanoparticles KW - uniform spatial arrangement Y1 - 2011 U6 - https://doi.org/10.1021/nn103097q SN - 1936-0851 VL - 5 IS - 3 SP - 1623 EP - 1629 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Stoyanov, Hristiyan A1 - Kollosche, Matthias A1 - Risse, Sebastian A1 - McCarthy, Denis N. A1 - Kofod, Guggi T1 - Elastic block copolymer nanocomposites with controlled interfacial interactions for artificial muscles with direct voltage control JF - Soft matter N2 - Soft, physically crosslinking, block copolymer elastomers were filled with surface-treated nanoparticles, in order to evaluate the possibility for improvement of their properties when used as soft dielectric actuators. The nanoparticles led to improvements in dielectric properties, however they also reinforced the elastomer matrix. Comparing dielectric spectra of composites with untreated and surface-treated particles showed a measurable influence of the surface on the dielectric loss behaviour for high filler amounts, strongly indicating an improved host-guest interaction for the surface-treated particles. Breakdown strength was measured using a test bench and was found to be in good agreement with the results from the actuation measurements. Actuation responses predicted by a model for prestrained actuators agreed well with measurements up to a filler amount of 20%(vol). Strong improvements in actuation behaviour were observed, with an optimum near 15%(vol) nanoparticles, corresponding to a reduction in electrical field of 27% for identical actuation strains. The use of physically crosslinking elastomer ensured the mechanical properties of the matrix elastomer were unchanged by nanoparticles effecting the crosslinking reaction, contrary to similar experiments performed with chemically crosslinking elastomers. This allows for a firm conclusion about the positive effects of surface-treated nanoparticles on actuation behavior. Y1 - 2011 U6 - https://doi.org/10.1039/c0sm00715c SN - 1744-683X SN - 1744-6848 VL - 7 IS - 1 SP - 194 EP - 202 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kollosche, Matthias A1 - Stoyanov, Hristiyan A1 - Laflamme, Simon A1 - Kofod, Guggi T1 - Strongly enhanced sensitivity in elastic capacitive strain sensors JF - Journal of materials chemistry N2 - Strain sensors based on dielectric elastomer capacitors function by the direct coupling of mechanical deformations with the capacitance. The coupling can be improved by enhancing the relative permittivity of the dielectric elastomer. Here, this is carried out through the grafting of conducting polymer (poly-aniline) to the elastomer backbone, leading to molecular composites. An enhancement in capacitance response of 46 times is observed. This could help to extend the possible range of miniaturization towards even smaller device features. Y1 - 2011 U6 - https://doi.org/10.1039/c0jm03786a SN - 0959-9428 VL - 21 IS - 23 SP - 8292 EP - 8294 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kofod, Guggi A1 - Stoyanov, Hristiyan A1 - Gerhard, Reimund T1 - Multilayer coaxial fiber dielectric elastomers for actuation and sensing JF - Applied physics : A, Materials science & processing N2 - A simple dip-coating technique was employed to manufacture coaxial actuators with multiple layers of alternating dielectric and conducting layers. A thin rubber string was coated with an electrode-insulator-electrode structure, giving rise to a thin, fiber-like actuator with coaxial geometry. The process was repeated to achieve a compact multilayer actuator with up to three coaxial dielectric layers. Mechanical and electromechanical characterization of the actuators is presented, showing actuation strains up to 8% and proper voltage-thickness scaling behavior. Also presented is a capacitance vs. extension plot, demonstrating that these structures can be used for compact and accurate capacitive strain sensing. Y1 - 2011 U6 - https://doi.org/10.1007/s00339-010-6066-5 SN - 0947-8396 SN - 1432-0630 VL - 102 IS - 3 SP - 577 EP - 581 PB - Springer CY - New York ER - TY - THES A1 - Stoyanov, Hristiyan T1 - Soft nanocomposites with enhanced electromechanical response for dielectric elastomer actuators T1 - Elastomer-Nanokomposite mit erhöhter elektro-mechanischer Sensitivität für dielektrische Elastomer Aktoren N2 - Electromechanical transducers based on elastomer capacitors are presently considered for many soft actuation applications, due to their large reversible deformation in response to electric field induced electrostatic pressure. The high operating voltage of such devices is currently a large drawback, hindering their use in applications such as biomedical devices and biomimetic robots, however, they could be improved with a careful design of their material properties. The main targets for improving their properties are increasing the relative permittivity of the active material, while maintaining high electric breakdown strength and low stiffness, which would lead to enhanced electrostatic storage ability and hence, reduced operating voltage. Improvement of the functional properties is possible through the use of nanocomposites. These exploit the high surface-to-volume ratio of the nanoscale filler, resulting in large effects on macroscale properties. This thesis explores several strategies for nanomaterials design. The resulting nanocomposites are fully characterized with respect to their electrical and mechanical properties, by use of dielectric spectroscopy, tensile mechanical analysis, and electric breakdown tests. First, nanocomposites consisting of high permittivity rutile TiO2 nanoparticles dispersed in thermoplastic block copolymer SEBS (poly-styrene-coethylene-co-butylene-co-styrene) are shown to exhibit permittivity increases of up to 3.7 times, leading to 5.6 times improvement in electrostatic energy density, but with a trade-off in mechanical properties (an 8-fold increase in stiffness). The variation in both electrical and mechanical properties still allows for electromechanical improvement, such that a 27 % reduction of the electric field is found compared to the pure elastomer. Second, it is shown that the use of nanofiller conductive particles (carbon black (CB)) can lead to a strong increase of relative permittivity through percolation, however, with detrimental side effects. These are due to localized enhancement of the electric field within the composite, which leads to sharp reductions in electric field strength. Hence, the increase in permittivity does not make up for the reduction in breakdown strength in relation to stored electrical energy, which may prohibit their practical use. Third, a completely new approach for increasing the relative permittivity and electrostatic energy density of a polymer based on 'molecular composites' is presented, relying on chemically grafting soft π-conjugated macromolecules to a flexible elastomer backbone. Polarization caused by charge displacement along the conjugated backbone is found to induce a large and controlled permittivity enhancement (470 % over the elastomer matrix), while chemical bonding, encapsulates the PANI chains manifesting in hardly any reduction in electric breakdown strength, and hence resulting in a large increase in stored electrostatic energy. This is shown to lead to an improvement in the sensitivity of the measured electromechanical response (83 % reduction of the driving electric field) as well as in the maximum actuation strain (250 %). These results represent a large step forward in the understanding of the strategies which can be employed to obtain high permittivity polymer materials with practical use for electro-elastomer actuation. N2 - Die Palette von elektro-mechanischen Aktuatoren, basierend auf dem Prinzip weicher dehnbarer Kondensatoren, scheint besonders für Anwendungen in der Medizin und für biomimetische Applikationen unbegrenzt. Diese Wandler zeichnen sich sowohl durch hohe Reversibilität bei großer mechanischer Deformation als auch durch ihre Flexibilität aus, wobei die mechanischen Deformationen durch elektrische Felder induziert werden. Die Notwendigkeit von hoher elektrischer Spannung zur Erzeugung dieser mechanischen Deformationen verzögert jedoch die technisch einfache und breite Markteinführung dieser Technologie. Diesem Problem kann durch eine gezielte Materialmodifikation begegnet werden. Eine Modifikation hat das Ziel, die relative Permittivität zu erhöhen, wobei die Flexibilität und die hohe elektrische Durchbruchsfeldstärke beibehalten werden sollten. Durch eine Materialmodifikation kann die Energiedichte des Materials bedeutend erhöht und somit die notwendige Betriebsspannung des Aktuators herabgesetzt werden. Eine Verbesserung der funktionalen Materialeigenschaften kann durch die Verwendung von Nanokompositen erzielt werden, welche die fundamentalen Eigenschaften der Nanopartikel, d.h. ein gutes Verhältnis von Oberfläche zu Volumen nutzen, um eine gezielte makroskopische Materialmodifikation zu bewirken. Diese Arbeit behandelt die Anwendung innovativer Strategien für die Erzeugung von Nanomaterialien mit hoher Permittivität. Die so erzeugten Materialien und deren relevante Aktuatorkenngrößen werden durch elektrische und mechanische Experimente vollständig erfasst. Mittels der klassischen Mischansätze zur Erzeugung von Kompositmaterialen mit hoher Permittivität konnte durch nichtleitendes Titaniumdioxid TiO2 (Rutile) in einem Thermoplastischen-Block-Co-Polymer SEBS (poly-styrene-co-ethylene-cobutylene-co-styrene) die Permittivität bereits um 370 % erhöht und die elektrische Energiedichte um 570 % gesteigert werden. Diese Veränderungen führten jedoch zu einem signifikanten Anstieg der Steifigkeit des Materials. Aufgrund der positiven Rückkopplung von elektrischen und mechanischen Eigenschaften des Kompositmaterials ermöglicht bereits dieser einfache Ansatz eine Verbesserung der Aktuation, bei einer 27 %-igen Reduktion der Aktuatorbetriebsspannung. Eine direkte Verwendung von leitfähigen Nanopartikeln kann ebenso zu einem Anstieg der relativen Permittivität beitragen, wobei jedoch die Leitfähigkeit dieser Nanopartikel bedeutende Wechselwirkungen verursacht, welche somit die Energiedichte des Materials negativ beeinflusst und die praktische Verwendung dieses Kompositsystems ausschließt. Als ein völlig neuer Ansatz zur Steigerung der relativen Permittivität und Energiedichte und abweichend vom klassischen Mischverfahren, wird die Herstellung eines "Molekularen Komposits", basierend auf einem chemischen Propfverfahren, präsentiert. In diesem Ansatz wird ein π-konjugiertes leitfähiges Polymer (PANI) an die Hauptkette des Elastomers der Polymermatrix gebunden. Die daraus resultierende Ladungsverteilung entlang der Elastomerhauptkette bewirkt eine 470 %-ige Steigerung der Permittivität des "Molekularen Komposits" im Vergleich zur Permittivität des unbehandelten Elastomermaterials. Aufgrund der Verkapselung der chemischen Bindungen der PANI-Kette entstehen kaum negative Rückwirkungen auf die elektrischen und mechanischen Eigenschaften des so erzeugten Komposits. Diese Materialeigenschaften resultieren in einem signifikanten Anstieg der Energiedichte des Materials. Das mittels dieses Verfahrens erzeugte Komposit zeigt sowohl eine Steigerung der Sensitivität der elektromechanischen Antwort (Reduktion des elektrischen Felds um 83 %) als auch eine bedeutende Steigerung der maximalen Aktuation (250 %). Die Ergebnisse und Ideen dieser Arbeit stellen einen wesentlichen Sprung im Verständnis zur Permittivitätssteigerung in Polymermaterialien dar und werden deshalb in der Erforschung und Entwicklung von Elastomeraktuatoren Beachtung finden. KW - dielektrische Elastomere KW - Nanokomposite KW - hohe Permittivität KW - elektrostatische Energiedichte KW - elektromechanische Reaktion KW - dielectric elastomers KW - nanocomposites KW - high permittivity KW - electrostatic energy density KW - electromechanical response Y1 - 2011 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-51194 ER -