Yes / Biomaterials capable of precisely controlling the delivery of agrochemicals/biologics/drugs/fragrances have significant markets in the agriscience/healthcare industries. Here, we report the development of degradable electroactive polymers and their application for the controlled delivery of a clinically relevant drug (the anti-inflammatory dexamethasone phosphate, DMP). Electroactive copolymers composed of blocks of polycaprolactone (PCL) and naturally occurring electroactive pyrrole oligomers (e.g., bilirubin, biliverdin, and hemin) were prepared and solution-processed to produce films (optionally doped with DMP). A combination of in silico/in vitro/in vivo studies demonstrated the cytocompatibility of the polymers. The release of DMP in response to the application of an electrical stimulus was observed to be enhanced by ca. 10-30% relative to the passive release from nonstimulated samples in vitro. Such stimuli-responsive biomaterials have the potential for integration devices capable of delivering a variety of molecules for technical/medical applications. / This research was funded by a variety of sources, and the authors acknowledge the UK Engineering and Physical Sciences Research Council (EPSRC) National Productivity Investment Fund (NPIF) for a PhD Studentship for M.D.A. (Grant references: EP/R512564/1, 2065445), in support of the EPSRC First Grant for J.G.H. (Grant reference: EP/ R003823/1); the UK Royal Society for support of J.G.H. (Grant reference: RG160449); and the UK Royal Society and CONICET (Argentina) for supporting M.D.A., S.M., M.F.D., and J.G.H. (Grant Reference: A103355).

The main objectives of this thesis are 1) to evaluate the effect of cross-linking polar cyano phenyl (CN) groups on poly (dimethyl siloxane) (PDMS) and 2) to characterize the electromechanical properties of the resulting CN-PDMS blend as an electroactive actuator. Materials responding to an external stimulus are referred to as electroactive materials. There are several phenomena, which govern the mechanism in these materials, such as piezoelectricity, Maxwell's effect, ferroelectricity, electrostriction to name a few. These electroactive materials can be employed in several applications such as biomedical devices, robots, MEMs, aerospace vehicles, where the application is governed by the specific mechanism. However in order for the materials to be used effectively, they need to be thoroughly characterized to understand their behavior under factors like electric field, temperature, frequency and time.The present work focuses on developing an electroactive actuator, which has tailorable properties, allowing a wide operational temperature window from -100°C to 200°C and stability in harsh conditions. The characterization of the CN-PDMS polymer blend is done in two folds. First the physical properties of the polymer system are characterized by performing tests such as Dielectric Spectroscopy, Differential Scanning Calorimetery and Thermally Stimulated Current measurement. These techniques offer complete understanding of the structure-property relationship and effects of the functional groups on the dielectric and relaxation behavior of the polymer. The Dielectric Spectroscopy and the Thermally Stimulated Current analysis are used to elucidate the primary and the secondary relaxations, such as molecular mobility, interfacial polarization and dipolar relaxation. Dielectric Spectroscopy reveals that the molecular weight of PDMS does not affect the dielectric permittivity of the polymer blend. Also, Dielectric Spectroscopy clarifies the role of the CN polar group in the polarization of the CN-PDMS blend, inducing electromechanical strain in the polymer blend through electrostriction.The Differential Scanning Calorimetery is used to quantify the thermal behavior of the CN-PDMS polymer blend by quantifying properties such as melting temperature (Tm) and re-crystallization temperature of the PDMS polymer cross-linked with CN functional group. Results reveal that the thermal characteristics of the blend are not affected when PDMS is cross-linked with the functional CN moieties, meaning CN-PDMS maintains the advantages of PDMS in terms of stability towards harsh conditions, wide operating temperature and resistance to ultraviolet radiations.Following the physical characterization, electromechanical characterization of the CN-PDMS polymer blend is done to assess the electromechanical strain induced in the blend in response to electric field. The electromechanical strain is studied in two configurations; the electromechanical strain induced along the length of the polymer blend and induced through the thickness of the blend. These strain measurements are performed by applying both direct current as well as alternating current electric fields, and the induced electromechanical strain is studied as a function of amplitude and frequency of the electric field as well as the time of application of the electric field. The mechanism behind the development of the electromechanical strain and the nature of the strain under electric field is elucidated. The performance of the electroactive polymer is compared with several other polymeric actuators such as PVDF and PVDF-TrFE, polyurethane based actuators and ionomers. Comparison gives favorable results in terms of strains. In addition, CN-PDMS polymer system has the advantage of allowing control of processing of the blend, which is not present in all the other commercial electroactive polymers. The maximum electromechanical strain yielded along the length of the CN-PDMS polymer blend is 1.74 % when an electric field of 0.2MV/m is applied along the length of the polymer. Through the thickness, the maximum induced strain is 0.12 % for an electric field of 0.8 MV/m. Based on the nature of the strain yielded it is observed that the strain induced in the CN-PDMS blend is consistently proportional to the square of the electric field (E2). Moreover, the strain is driven by the concentration of the dipolar moieties (CN) present in the polymer blend.All the above-mentioned techniques used for thermal and electromechanical characterization of the CN-PDMS polymer blend illustrate the electrostrictive nature of the polymer under the study.

Electroactive polymers (EAP) are an emerging branch of smart materials that possess the capability to change shape in the presence of an electric field. Opportunities for the advancement of knowledge were identified in the branch of EAP consisting of inherently electrically conductive polymers. This dissertation explores methods by which the unique properties of composite materials having conductive polymers as a constituent may be exploited. Chapter 3 describes the blending of polyaniline with conventional thermoplastics. Processing these polyblends into foams yielded a porous conductive material. The effect of blend composition and processing parameters on the resulting porous morphology and electrical conductivity was investigated. These findings represent the first systematic study of porous conductive polymer blends. In Chapter 4, multilayer electroactive polymer actuators consisting of polypyrrole films electropolymerized on a passive polymer membrane core were harnessed as actuators. The membrane is vital in the transport of ionic species and largely dictates the stiffness of the layered configuration. The impact of the mechanical properties of the membrane on the actuation response of polypyrrole-based trilayer bending actuators was investigated. Candidate materials with distinct morphologies were identified and their mechanical properties were evaluated. These results indicated that polyvinylidene difluoride membranes were superior to the other candidates. An electrochemical synthesis procedure was proposed, and the design of a novel polymerization vessel was reported. These facilities were utilized to prepare actuators under a variety of synthesis conditions to investigate the impact of conductive polymer morphology on the electromechanical response. Characterization techniques were implemented to quantitatively assess physical and electrochemical properties of the layered composite. Chapter 5 proposes a new unified multiphysics model that captures the electroactive actuation response inherent to conductive polymer trilayer actuators. The main contribution of this investigation was the proposal and development of a new hybrid model that unifies concepts from charge transport and electrochemomechanical models. The output of the proposed model was compared with published data and shown to be accurate to within 10%. Finally, Chapter 6 demonstrated the application of these materials for use as precision mirror positioners in adaptive optical systems.

Electroactive polymers (EAP) are an emerging branch of smart materials that possess the capability to change shape in the presence of an electric field. Opportunities for the advancement of knowledge were identified in the branch of EAP consisting of inherently electrically conductive polymers. This dissertation explores methods by which the unique properties of composite materials having conductive polymers as a constituent may be exploited. Chapter 3 describes the blending of polyaniline with conventional thermoplastics. Processing these polyblends into foams yielded a porous conductive material. The effect of blend composition and processing parameters on the resulting porous morphology and electrical conductivity was investigated. These findings represent the first systematic study of porous conductive polymer blends. In Chapter 4, multilayer electroactive polymer actuators consisting of polypyrrole films electropolymerized on a passive polymer membrane core were harnessed as actuators. The membrane is vital in the transport of ionic species and largely dictates the stiffness of the layered configuration. The impact of the mechanical properties of the membrane on the actuation response of polypyrrole-based trilayer bending actuators was investigated. Candidate materials with distinct morphologies were identified and their mechanical properties were evaluated. These results indicated that polyvinylidene difluoride membranes were superior to the other candidates. An electrochemical synthesis procedure was proposed, and the design of a novel polymerization vessel was reported. These facilities were utilized to prepare actuators under a variety of synthesis conditions to investigate the impact of conductive polymer morphology on the electromechanical response. Characterization techniques were implemented to quantitatively assess physical and electrochemical properties of the layered composite. Chapter 5 proposes a new unified multiphysics model that captures the electroactive actuation response inherent to conductive polymer trilayer actuators. The main contribution of this investigation was the proposal and development of a new hybrid model that unifies concepts from charge transport and electrochemomechanical models. The output of the proposed model was compared with published data and shown to be accurate to within 10%. Finally, Chapter 6 demonstrated the application of these materials for use as precision mirror positioners in adaptive optical systems.

Metal ion contamination in surface and ground water is a major threat as it has a direct implication on the health of terrestrial and aquatic flora and fauna. Lead (Pb2+), mercury (Hg2+), cadmium (Cd2+), nickel (Ni2+), copper (Cu2+) and cobalt (Co2+) are few of these metal ions which are classified under the high risk category. Of these, lead and mercury are of greater concern, as even nanomolar concentrations can be lethal, as they can be bio-accumulated and result in physiological as well as neurological disorders. In Asian countries like India and China, heavy metal pollution is more prevalent, as a consequence of poor governmental policies or ineffective or inadequate measures to combat this problem. In recent times, the monitoring and assessment of water pollution is a critical area of study, as it has a direct implication for its prevention and control. The major techniques used for metal ion detection are atomic absorption spectroscopy (AAS), X-ray fluorescence, ion chromatography, neutron activation, etc. Alternatively, the electrochemical, optical and electrical methods provide a platform for the fabrication of portable devices, which can facilitate the on-site analysis of samples in a rapid and cost-effective manner. This has led to a new field of research called chemical sensors or chemo sensory devices. The main aim of this study is to develop various chemosensory materials and test their response towards metal ion sensing. In this study, electroactive polymers have been synthesized for various sensor applications. The focus has been to design synthesize and test various functionalized electroactive polymers (FEAP) for the development of electrochemical, optical and chemoresistive sensors. Electroactive polymers like polyaniline, polypyrrole, polypyrrole grafted to exfoliated graphite oxide and dipyrromethene conjugated with p-(phenylene vinylene) have been synthesized and evaluated after functionalizing with metal coordinating ligands. These metal coordinating ligands were selected, in order to enhance their metal uptake capacity. Various metal ligands like imidazole, tertiary amine group, iminodiacetic acid, and dipyrromethene incorporated either in the polymer backbone or as a part of the backbone have been chosen for the metal binding. These functionalized electroactive polymers (FEAP) served as active material for metal ion sensing. The present investigation is subdivided into three sections. The first part includes design and chemical synthesis of the functionalized polymers by a series of organic reactions. The synthesis has been followed up by characterization using spectroscopic methods including NMR, FTIR, GCMS and Mass spectrometry. In the second part of the investigation, the synthesized polymer has been characterized for the changes in electronic, electric and optical properties after interaction with the selected metal ions. For this, the FEAP is allowed to interact with various metal ions and the changes in the relevant properties have been measured. This includes the study of changes in the conductivity, electronic properties like absorption or emission of the polymer, changes in the redox properties, etc. The third phase of investigation deals with the fabrication of the devices using the active FEAP. The sensor devices comprised of either films, or electrode modified with FEAP or solution of the FEAP, in combination with an appropriate technique has been used for the sensing. The major objectives are enumerated below 1. Functionalzation of polyaniline with imidazole functional group to get imidazole functionalized polyaniline (IMPANI) and study of the electronic, electrical and optical properties of the same. 2. Preparation of films of IMPANI and study of the change in conductivity of the film upon interaction with various metal ions, namely Cu2+, Co2+ and Ni2+ in their chloride form. 3. Synthesis of amine functionalized aniline monomer and chemical graft polymerization onto exfoliated graphite oxide as a substrate to synthesise the amine funtionalised polyaniline grafted to exfoliated graphite oxide (EGAMPANI). Modification of the carbon paste electrode (CPE) with EGAMPANI and study of the electrode characteristic. 4. Study of the electrode properties of EGAMPANI modified carbon paste electrode. 5. Evaluation of the EGAMPANI modified carbon paste electrode as a multi-elemental voltammetric sensor for Pb2+, Hg2+ and Cd2+ in aqueous system. 6. Functionalization of polypyrrole with iminodiacetic acid and characterization of the polymer to synthesis iminodiacetic acid functionalized polypyrrole (IDA-PPy). 7. Modification of the CPE with IDA-PPy by drop casting method and evaluation of the Pb2+ sensing properties. 8. Study of the effect of other metal ions say Hg2+, Co2+, Ni2+, Zn2+, Cu2+ and Cd2+ on the anodic stripping current of Pb2+ using EGAMPANI modified CPE. 9. Synthesis of dipyrromethene-p-(phenylene vinylene) conjugated polymer for heavy metal ion sensing. 10. Study of the changes in the optical absorption and emission properties of the polymer in THF and evaluation of the change in these optical properties upon interaction with the metal ions as analyte. The salient findings of the research work are highlighted as follows, In the first synthesis, aniline has been functionalized with imidazole group and this monomer has been chemical oxidatively polymerized to obtain imidazole functionalized polyaniline (IMPANI). The synthesized polymer possesses a nano-spherical structure, as confirmed from the morphological characterisation using scanning electron microscopy. The IMPANI has been interacted with a representative metal ion, copper (II) chloride, and the copper complexed polymer (Cu-IMPANI) has been subjected to various studies. The coordination of copper with IMPANI results in an increase of molecular weight of the polymer as a result of aggregation, as observed from dynamic light scattering measurements. Apart from this, a significant finding is the decrease of the pH of the system after copper ion coordination attesting to the generation of a secondary hydrochloride ion during the coordination of the copper to the imidazole side chain. This is further confirmed by an increase in conductivity of the Cu-IMPANI compared to IMPANI, measured using the four-probe technique. The increase of conductivity due to copper coordination is one order of magnitude higher. The films which have been prepared from IMPANI and Cu-IMPANI exhibit different morphology. The Cu-IMPANI film prepared by prior co-ordination of Cu ion with IMPANI powder shows a flaky structure, which is not preferable for the conductivity measurements, as a consequence of discontinuity in the medium. To overcome this problem, IMPANI films were initially prepared and then interacted with copper ions for a desired duration, before measurement of the conductivity. This latter procedure enabled the preparation of smooth films for the development of chemoresistive sensors. In continuation of the initial study highlighted above, IMPANI films of thickness 0.02 ± 0.001 mm have been prepared using IMPANI and PANI in DMPU in the ratio of 7:3 by mass. After exposure of the films with respective metal chlorides, such as Ni2+, Co2+ and Cu2+, a change in conductivity is observed in the concentration range of 10-2 to 1 M of metal chlorides. The sensor response may be arranged in the sequence: Ni2+ > Cu2+ > Co2+ at 1M concentration. On the contrary, films prepared from PANI-EB under identical conditions do not exhibit any appreciable change in conductivity. The optimum exposure time is determined to be 10 min for a maximum change in conductivity, after exposure to the chosen metal ions. In the second system taken up for investigation, a tertiary amine containing polyaniline (AMPANI) has been grafted to exfoliated graphite oxide. The amine containing polyaniline grafted to exfoliated graphite oxide (EGAMPANI) has been characterised for structural, morphological and elemental composition. The grafting percentage has been determined to be 7 % by weight of AMPANI on the EGO surface. The synthesized EGAMPANI (5 weight %) has been used to modify carbon paste electrode (CPE) for electrochemical sensor studies. Based on the differential pulse anodic stripping voltammetric studies, the electrochemical response may be arranged in the following sequence: Pb 2+>Cd 2+>Hg 2+ The minimum detection levels obtained are 5×10-6, 5×10-7, and 1.0×10-7 M for Hg2+, Cd2+ and Pb2+ ions respectively. In the next study, an iminodiacetic acid functionalized polypyrrole (IDA-PPy) has been synthesized and characterised for its elemental and structural properties. This has been further used to modify the CPE by drop casting method and used for the specific detection of Pb2+ in acetate buffer. Various parameters governing the electrode performance such as concentration of depositing solution, pH of depositing solution, deposition potential, deposition time, and scan rate, have been optimized to achieve maximum performance and found to be 20 μl, 4.5, -1.3 V, 11 min, 8 mV s-1 respectively for the chosen parameters. Additionally, the influence of other heavy metal ions on the lead response has been studied and it is observed that Co, Cu and Cd ions are found to be interfering. Further, the response of Cd, Co, Cu, Hg, Ni and Zn on IDA-PPy functionalized electrode has been evaluated. The selectivity of IDA-PPy modified electrode for Pb2+ is observed in the concentration range of 1 × 10-7 M and below. The IDA-PPy modified CPE shows a linear correlation for Pb2+ concentration in the range from 1×10-6 to 5×10-9 M and with a lowest limit of detection (LLOD) of 9.6×10-9 M concentration. The efficacy of the electrode for lead sensing has also been evaluated with an industrial effluent sample obtained from a lead battery manufacturing unit. The fourth synthesis pertained to the development of an optical sensor for Fe2+, and Co2+ ions. For this, dipyrromethene as a metal coordinating ligand in conjugation with p-phenylenevinylene has been synthesized and tested for its structural as well as optical properties. It is observed that the polymer shows three absorptions, namely at 294 nm, 357 nm and a major absorption observed as a broad band ranging from 484 to 670 nm. The emission spectrum of the polymer excited at 357 nm shows a characteristic blue emission with a maximum intensity centered at 425 nm. The emission quenching in the presence of various metal ions have been tested and are found to be quenched in presence of Fe2+ and Co2+ ions. All the other metal ions tested namely, Cr3+, Cu2+, and Zn2+ are not found to exhibit any change in the emission spectra below the concentration of 1 × 10-4 M. The linear correlation of the emission intensity with the concentration of the Co2+ and Fe2+ ions has been determined using Stern-Volmer plot. For Co2+ the Stern-Volmer regime is observed from 1×10-4 to 9×10-4 M concentration and the quenching constant Ksv is determined to be 8.67 ×103 M-1. For Fe2+, the linearity is found to be in the regime of 1×10-5 to 9×10-5 M and the quenching constant Ksv is determined to be 7.90 × 103 M-1. In conclusion, different electroactive polymers functionalized with metal coordinating ligands have been synthesized, characterised and evaluated for metal sensing applications. Techniques like electrochemical, optical and conductivity have been used to characterise the response of these FEAP towards metal sensing. It is can be concluded that the electrochemical sensors are more reliable for sensing especially at very low concentrations of metal ions such as Pb, Cd and other techniques like optical and conductimetric are good for detecting metal ions namely Fe, Co, Ni, Cu. The selectivity towards the metal ions is a function of the metal chelating ligand and the extent of sensitivity is dependent upon the technique employed.

This thesis presents a preliminary design of a fully articulated five-fingered anthropomorphic human hand prosthesis with particular emphasis on the controller and actuator design. The proposed controller is a modified artificial neural network PID-based controller with application to the nonlinear and highly coupled dynamics of the hand prosthesis. The new solid state actuator has been designed based on electroactive polymers, which are a type of material that exhibit electromechanical behavior and a liquid metal alloy acts as the electrode. The solid state actuators reduce the overall mechanical complexity, risk failure and required maintenance of the prosthesis. / Graduate

<p>Soft actuators and sensors are currently used in many industrial applications due to their capability to produce an accurate response. Researchers have studied dielectric electroactive polymers (DEAPs) because these types of structures can be utilized as actuators and as sensors being able to convert electrical energy into mechanical and vice versa. However, production of this kind of structures is complex and in general involve several steps that are time consuming. Customization of these types of structures will be ideal to enhance the performance of the devices based on the specific application. 3D printing technologies have emerged as innovative manufacturing processes that could improve fabrication speed, accuracy, and consistency with low cost. This additive manufacturing technique allows for the possibility of increased device complexity with high versatility. </p> <p>This research studied the potential of 3D printing technologies to produce DEAPs, soft actuators, and flexible sensors. The study presents novel designs of these composite flexible structures, utilizing the most flexible conductive and nonconductive materials available for fused deposition modeling, achieving versatility and high performance in the produced devices. <a>Produced DEAP actuators showed an actuation and electric resistivity higher than other electroactive structures like shape memory alloys and ferroelectric polymers.</a> In addition, this research describes the electromechanical characterization of a flexible thermoplastic polyurethane, (TPU), produced by additive manufacturing, including measurement of the dielectric constant, percentage radial elongation, tensile proprieties, pre-strain effects on actuation, surface topography, and measured actuation under high voltage. DEAP actuators were produced with two different printing paths, concentric circles and lines, showed an area expansion of 4.73% and 5.71% respectively. These structures showed high resistance to electric fields having a voltage breakdown of 4.67 kV and 5.73 kV respectively. <a>Those results are similar to the resistant of the most used dielectric material “VHB 4910”. </a></p> <p>The produced soft pneumatic actuators were successfully 3D printed in one continuous process without support material. The structures were totally sealed without the use of any sealing material or post process. Computational simulations were made to predict the response of the designed structures under different conditions. These results were compared with experimental results finding that the theoretical model is able to predict the response of the printed actuators with an error of less than 7%. This error is satisfactorily small for modeling 3D printed structures and can be further minimized by characterization of the elastomeric material. Besides that, two different grippers were designed based on the opening and closing movements of single bellows actuators. The functionality of both designs was simulated and tested, finding that both designs are capable lifting a heavier rigid structure. </p> <p>Finally, this study presents a computational simulation of a 3D printed flexible sensor, capable of producing an output signal based on the deformation caused by external forces. Two different sensors were designed and tested, working based on a capacitance and resistance change produced by structural deformation. Computational analysis indicate the capacitance sensor should undergo change of capacitance from 3 to 8.5 pF when is exposed to 30 kPa; and the resistance sensor should experience an increase from 101.8 to 103 kΩ when is exposed to 30 kPa. </p>

Cette thèse s’intéresse au rapport entre la forme et la géométrie d’un objet. Elle s’articule autour de 3 chapitres. Dans le premier, nous utilisons des "polymères électro-actifs", des systèmes capables de se déformer dans le plan lorsqu’ils sont soumis à un champ électrique,pour mimer une sorte de croissance biologique. Nous avons regardé comment une croissance inhomogène pouvait déclencher une instabilité de flambage dans une plaque électro-active.Nous avons ensuite cherché à contrôler de manière locale la croissance, dans l’espoir d’obtenir des objets capables de changer de forme sur commande. Dans le deuxième chapitre, nous nous avons étudié un problème inverse : au lieu de chercher à donner une nouvelle forme naturelle à l’objet, nous le forçons à adopter une forme qui ne lui est pas naturelle. Nous avons aplati des coques élastiques hémisphériques. La transformation d’une sphère en plan n’étant pas isométrique, cette opération crée des contraintes dans l’objet. Il se produit alors une instabilité mécanique que nous avons étudiée. Enfin, nous nous sommes penchés sur le problème des "lentilles de contact" en nous demandant si l’on pouvait coller l’une sur l’autre deux portions de sphères ayant des courbures différentes. Ici encore, la différence de courbure de Gauss entre les deux surfaces conduit à des motifs d’instabilités dans la coque élastique / From a general point of view, my thesis deals with the links between the geometry and the shape of an object. It is composed of three main chapters. In the first one, we use "electro-active polymers", systems that undergo planar expansion when submitted to an electric field, to mimic a kind of biological growth. We looked at how an inhomogeneous growth can trigger buckling instability in this electro-active plate. We then tried to control locally this growth, hoping to create objects that can change shape on command. In the second chapter, we studied the opposite problem: instead of giving it a new natural shape, we force the object in adopting a non natural shape. We squashed hemispherical elastic caps. Changing a sphere into a plane is not an isometrical transformation, this operation thus creates strains in the object. We studied the mecanical instability hence produced. Finally we focused on the "contact lens" problem by wondering if it is possible to stick two spherical caps having different curvature. Here again, the mismatch of Gaussian curvature leads to patterns of instability in the elastic shell

Ein Dielektrischer Elastomer Aktuator (DEA) ist ein dehnbarer Kondensator, der aus einem Elastomerfilm besteht, der sich zwischen zwei flexiblen Elektroden befindet. Bei Anlegen einer elektrischen Spannung, ziehen sich die Elektroden aufgrund elektrostatischer Wechselwirkungen an, wodurch das Elastomer in z-Richtung zusammengepresst wird und sich dementsprechend in der x-,y-Ebene ausdehnt. Hierdurch werden Aktuationsbewegungen erreicht, welche sehr präzise über die Spannung gesteuert werden können. Zusätzlich sind DEAs kostengünstig, leicht und aktuieren geräuschlos. DEAs können beispielsweise für Produkte im medizinischen Bereich oder für optischer Komponenten genutzt werden. Ebenso kann aus diesen Bauteilen Strom erzeugt werden. Das größte Hindernis für eine weite Implementierung dieser Materialien liegt in den erforderlichen hohen Spannungen zum Erzeugen der Aktuationsbewegung, welche sich tendenziell im Kilovolt-Bereich befinden. Dies macht die Elektronik teuer und die Bauteile unsicher für Anwender. Um geringere Betriebsspannungen für die DEAs zu erreichen, sind signifikante Materialverbesserungen - insbesondere des verwendeten Elastomers - erforderlich. Um dies zu erreichen, können die dielektrischen Eigenschaften (Permittivität) der Elastomere gesteigert und/oder deren Steifigkeit (Young-Modul) gesenkt werden. In der vorliegenden Arbeit konnte die Aktuationsleistung von Silikonfilmen durch die Addition organischer Dipole erheblich verbessert werden. Hierfür wurde ein Verfahren etabliert, um funktionalisierte Dipole kovalent an das Polymernetzwerk zu binden. Dieser als "One-Step-Verfahren" bezeichnete Ansatz ist einfach durchzuführen und es werden homogene Filme erhalten. Die Dipoladdition wurde anhand verschiedener Silikone erprobt, die sich hinsichtlich ihrer mechanischen Eigenschaften unterschieden. Bei maximalem Dipolgehalt verdoppelte sich die Permittivität aller untersuchten Silikone und die Filme wurden deutlich weicher. Hierbei war festzustellen, dass die Netzwerkstruktur der verwendeten Silikone einen erheblichen Einfluss auf die erreichte Aktuationsdehnung hat. Abhängig vom Netzwerk erfolgte eine enorme Steigerung der Aktuationsleistung im Bereich von 100 % bis zu 4000 %. Dadurch können die Betriebsspannungen in DEAs deutlich abgesenkt werden, so dass sie tendenziell bei Spannungen unterhalb von einem Kilovolt betrieben werden können. / Dielectric elastomer actuators (DEAs) are compliant capacitors consisting of an elastomer film between two flexible electrodes. When a voltage is applied the electrostatic attraction of the electrodes leads to a contraction of the polymer in the z-direction and to a corresponding expansion in the x,y-plane. DEAs show high actuation strains, which are very accurate and adjustable by the applied voltage. In addition these devices are low-cost, low-weight and the actuation is noise-free. DEAs can be used for medical applications, optical components or for energy harvesting. The main obstacle for a broad implementation of this technology is the high driving voltage, which tends to be several thousand volts. For this reason the devices are unsafe for users and the needed electronic components are expensive. A significant improvement of the materials - especially of the used elastomer - is necessary to lower the actuation voltages. This can be achieved by improving the dielectric properties (permittivity) of the elastomer and/or by lowering it's stiffness (Young's modulus). In this work the actuation performance of silicone lms was improved significantly by the addition of organic dipoles. A simple procedure was developed, in which functionalized dipoles were bound to the polymer matrix, leading to homogenous and transparent films. This so-called "one-step-film-formation" was tested on various silicones with different mechanical properties. For the highest dipole content the permittivity of all tested silicones was doubled and the modified films showed a substantially lower stiffness. It was proven that the structure of the macromolecular network has a clear impact on the achievable actuation properties. For the highest dipole contents the actuation performance increased remarkably by 100 % up to 4000 % in respect to the investigated network. The addition of organic dipoles to the elastomer enables a signicant reduction of the needed driving voltage for DEAs below one kilovolt.

Récupérer l'énergie mécanique ambiante est une alternative prometteuse afin d'assurer l'autonomie énergétique d'appareils nomades. Le développement des générateurs électrostatiques souples reste toutefois à ce jour anecdotique du fait des hautes tensions de polarisation employées, de la nécessité de grandes déformations mécaniques mais aussi de l'utilisation de matériaux peu conventionnels et mal caractérisés. Le but de cette thèse est d'apporter des avancées scientifiques et des solutions aux verrous technologiques précités. Tout d'abord, une caractérisation rigoureuse des propriétés électriques et mécaniques de deux matériaux communément utilisés pour ces applications (acrylate VHB 4910 et silicone Polypower) nous a donné accès aux propriétés physiques dans un fonctionnement réel de ces polymères : influence de la précontrainte, de la nature des électrodes... Ces données ont permis d'élaborer des lois analytiques fiables que nous avons ensuite insérées dans un modèle thermodynamique permettant de définir avec précision les puissances et densités d'énergie récupérables pour ces générateurs. Des pistes d'amélioration des matériaux utilisés dans les applications générateurs peuvent être dégagées de notre modèle. Le second verrou à lever concerne la source haute tension de polarisation nécessaire à ces générateurs électrostatiques. Pour cela, nous avons proposé une solution innovante couplant l'élastomère diélectrique à un électret. Différentes configurations de générateurs hybrides dans des géométries 2D et 3D ont été évaluées. Enfin, nous avons réalisé un prototype qui a délivré une puissance de l'ordre de 35µW sachant qu'une optimisation de ce prototype est réalisable et que des puissances récupérées de plusieurs centaines de µW sont tout à fait réalistes. / Scavenging mechanical ambient energy is a promising solution to ensure the autonomy of wearable transducers. Nevertheless, the development of soft electrostatic generator (DEG) is up to now slow down due to the use of high bias voltage, high strain and innovative mischaracterized materials. The aim of this Ph-D thesis is to propose innovative solutions to these technological barriers. Firstly, a complete characterization of the electrical and mechanical properties of two commonly used dielectric polymer (acrylate VHB 4910 and silicone Polypower) has revealed the true physical properties of these polymers and especially the influence of the pre-stress and the nature of the electrode used. Thanks to these data, reliable analytic laws have been proposed and inserted into our thermodynamic model in order to predict the output power and scavenged energy density for the DEG. Moreover, our model allow us to propose improvements for the materials used in these applications. The second challenge is to propose an alternative to the high bias voltage needed for these soft generators. We have proposed an innovative solution combining an electret and a dielectric elastomer. Various configurations of hybrid generators in 2D or 3D geometry have been modelled and evaluated. Finally, a prototype has been designed allowing scavenging 35µW. With an appropriate optimization of our prototype, hundreds of µW can be scavenged.