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Over the past three decades, the steady decrease in fossil energy resources, combined with a sustained increase in the demand for clean energy, has led the scientific community to develop new ways to produce energy. As is well known, one of the main challenges to overcome with fossil fuel-based energy sources is the reduction or even elimination of pollutant gases in the atmosphere. Although some advances have helped to slow the emission of greenhouse gases into the atmosphere (e.g., electric cars and more fuel-efficient gas-burning automobiles), most experts agree that it is not enough. Proton Exchange Membrane (PEM) fuel cells have been widely recognized as a potentially viable alternative for portable and stationary power generation, as well as for transportation. However, the widespread commercialization Proton Exchange Membrane Fuel Cells (PEMFCs) involves a thorough understanding of complex scientific and technological issues. This study investigated the various structure-property relationships and materials durability parameters associated with PEMFC development. First, the correlation between perfluorinated ionomer membranes and processing/performance issues in fuel cell systems was investigated. As confirmed by small-angle X-ray scattering data, impedance analysis, and dynamic mechanical analysis, solution processing with mixed organic-inorganic counterions was found to be effective in producing highly arranged perfluorinated sulfonic acid ionomer (PFSI) membranes with more favorable organization of the ionic domain. Moreover, thermal annealing was shown to enhance the proton mobility, thereby facilitating reorganization of the polymer backbone and the hydrophilic region for improved crystallinity and proton transport properties. This research also confirmed an increase in water uptake in the solution-processed membranes under investigation, which correlated to an increase in proton conductivity. Thus, annealing and solution-processing techniques were shown to be viable ways for controlling morphology and modulating the properties/performance of PFSI membranes. Second, this study investigated the role of the morphology on water and proton transport in perfluorinated ionomers. When annealed at high temperatures, a significant decrease in water uptake and an increase in crystallinity were observed, both of which are detrimental to fuel cell performance. Additionally, controlling the drying process was found to be crucial for optimizing the properties and performance of these membranes, since drying at temperatures close or above the α-relaxation temperature causes a major reorganization within the ionic domains. Third, although many investigations have looked at key PEMFC components, (e.g., the membrane, the catalyst, and the bipolar plates), there have been few studies of more "minor" components—namely, the performance and durability of seals, sealants, and adhesives, which are also exposed to harsh environmental conditions. When seals degrade or fail, reactant gases leak or are mixed, it can degrade the membrane electrode assembly (MEA), leading to a performance decrease in fuel cell stack performance. This portion of the research used degradation studies of certain proprietary elastomeric materials used as seals to investigate their overall stability and performance in fuel cell environments with applied mechanical stresses. Additionally, characterization of the mechanical and viscoelastic properties of these materials was conducted in order to predict the durability based on accelerated aging simulations as well. Continuous stress relaxation (CSR) characterization was performed on molded seals over a wide range of aging conditions using a customized CSR fixture. The effects of temperature, stress, and environmental conditions are reported in terms of changes in momentary and stress relaxations, chain scission and secondary crosslink formation. Aging studies provided insights on how anti-degradants or additives affect the performance and properties of sealing materials, as well as how a variety of environmental considerations might be improved to extend the lifetime of these elastomers. / Ph. D.

The transition dynamics in silicon rubber based isotropic magnetorheological (MR) elastomers in terms of the normal force induced by an external homogeneous magnetic field is experimentally addressed. The primary goal was to evaluate dynamic performances of the MR elastic isotropic composite using a transparently presented measuring system with known characteristics in contrast to few previous studies on the topic. It was found that an increase in the magnetic field leads to an increase in the induced force and a decrease in the response time of the MR elastomer. At the same time, both the use of coarse particles as magnetic filler and a significant reduction in the stiffness of the polymer matrix reduce the response time of the MR elastomer under study. The analysis carried out takes into account the dynamics of the electromagnetic coil and the eddy currents induced in the magnet circuit. The shortest response times obtained for various MR elastomer samples are in the range of 27–72 ms for the maximal used magnetic field with an induction of 230 mT. These times correspond to the fastest previously reported ones for MR elastomers and MR elastomer based systems. In addition, the obtained results indicate the presence of different mechanisms responsible for the measured magnetodeformational effect observed in MR elastomers.

Servo valves are used in a broad variety of flow modulation applications. In the field of aerospace, servo valves are used in aero engines to meter fuel flow. The existing valves are labour intensive to manufacture and highly optimised such that to achieve improvements in performance requires a novel design. This research investigates smart material actuators and valve concepts. Specifically, a prototype pilot stage nozzle flapper valve is developed for the purpose of actuating a main stage spool. The typical nozzle flapper type servo valve uses a torque motor to actuate the flapper. In this research project, the torque motor has been substituted for two piezoelectric ring bender actuators. A novel mounting mechanism has been developed to secure the ring benders within the valve. Analytical and finite element models have been made to understand the displacement mechanism of a ring bender and the effects of the mount on the displacement and force from a ring bender, and the results were compared with experiment. The mounting stiffness at the inner and outer edges was found to decrease the displacement of the ring bender and it was found that the stiffness of the mount at the outer edge has a greater negative effect on displacement than the stiffness of the mount at the inner edge. The displacement of a ring bender was tested across the operational temperature range of an aero engine. It was found that the displacement of the ring bender is reduced at low temperatures and increases at high temperature. The variation of stiffness of the elastomeric mount was also tested with temperature and it was found that the displacement of a ring bender is significantly reduced when the mounting elastomer approaches its glass transition temperature. A prototype valve was built to test the pressures and flows that could be achieved at two control ports by using a ring bender as actuator. A single ring bender and two ring benders, mounted in tandem to provide redundancy, have been tested. An analytical model was developed and the predictions are compared with experimental results for pressures and flow. The full stroke of the valve was 300m when mounted and reduced to 150m when mounted in tandem with an inactive ring bender. The hysteresis of the valve is +/-10%. The pressures and flow at and between the control ports of the valve are consistent with the predictions.

This thesis proposes an algorithm that determine the geometry of 3D-printed, custom-designed spring element bands made of thermoplastic elastomer (TPE) for use in a wearable orthotic device to aid in the physical therapy of a human hand exhibiting spasticity after stroke. Each finger of the hand is modeled as a mechanical system consisting of a triple-rod pendulum with nonlinear stiffness at each joint and forces applied at the attachment point of each flexor muscle. The system is assumed quasi-static, which leads to a torque balance between the flexor tendons in the hand, joint stiffness and the design force applied to the fingertip by the 3D-printed spring element. To better understand material properties of the spring element’s material, several tests are performed on TPE specimens printed with different infill geometries, including tensile tests and cyclic loading tests. The data and stress-strain curves for each geometry type are presented, which yield a nonlinear relationship between stress and strain as well as apparent hysteresis. Polynomial curves are used to fit the data, which allows for the band geometry to be designed. A hypothetical hand is presented along with how input measurements might be taken for the algorithm. The inputs are entered into the algorithm, and the geometry of the bands for each finger are generated. Results are discussed, and future work is noted, providing a means for the design of a customized orthotic device.

Le contrôle de la microstructure des matériaux organiques est crucial pour des applications pratiques telles que la photonique, la biomédecine ou encore le domaine très dynamique de l'électronique organique. Les études récentes ont montré une possibilité de contrôler la structure des polymères à l'échelle nanométrique en utilisant l'auto-assemblage supramoléculaire sous confinement spatial. Bien que de nombreuses études ont déjà été effectuées dans ce domaine, plusieurs questions essentielles restent ouvertes. En particulier, il est important de comprendre comment les différents processus de formation structurale tels que la cristallisation, la formation d`une phase cristal liquide et la séparation de phases se déroulent sous confinement. Dans le présent travail, nous abordons l'effet du confinement à 1D et à 2D sur la formation de la structure pour une variété de systèmes, y compris les copolymères segmentés de poly(éther-ester-amide) (PEEA), les polymères cristaux liquides (CL) dont la chaîne principale appartient à la famille des poly(di-n-alkylsiloxane)s et des copolymères à bloc cristaux-liquides /semicristallins formés par complexation de poly(2-vinylpyridine-b-oxyde d'éthylène) (P2VP-PEO) avec un ligand cunéiforme, l'acide 4'-(3'',4'',5''-tris(octyloxy) benzamido) propanoïque. Pour être capable de traiter de façon adéquate la morphologie complexe de ces systèmes sous confinement, le travail a été effectué en utilisant une batterie de méthodes expérimentales. Les techniques principales opérationnelles dans l'espace direct et réciproque que nous avons employées sont décrites dans le chapitre 2. [...] / Controlling the micro-structure of organic materials is crucial for a variety of practical applications such as photonics, biomedicine or the rapidly growing field of organic electronics. Recent studies have shown a possibility of tailoring the polymer structure on the nanoscale using supramolecular self-assembly under spatial confinement. Despite extensive studies already performed in this field, many questions remain open. In particular, it will be important to understand how different structure formation processes such as crystallization, LC-phase formation, microphase separation, and others occur under confinement. In the present work, we address the effect of 1D- and 2D-confinement on the structure formation for a variety of systems including segmented poly(ether-ester-amide) (PEEA) copolymers, main-chain liquid-crystalline (LC) polymers belonging to the family of poly(di-n-alkylsiloxane)s and liquid-crystalline/semicrystalline block copolymers formed through complexation of poly (2-vinylpyridine-b-ethylene oxide) (P2VP-PEO) with a wedge-shaped ligand, 4'-(3'',4'',5''-tris(octyloxy) benzamido) propanoic acid. In order to reveal the morphological diversity of the studied systems under confinement, the work was carried out on bulk materials and on thin films employing a battery of experimental methods. The main experimental techniques operational in direct and reciprocal space applied in my work are described in chapter 2. [...]

De nombreux phénomènes à l’oeuvre dans le processus de déformation et d’endommagement des élastomères sont étudiés à partir de la réponse mécanique de ces matériaux. Cependant, la plupart de ces phénomènes dépendent de la température et ont des signatures calorimétriques qui pourraient permettre de mieux les comprendre. Dans le contexte industriel de la manufacture de pneumatiques, les élévations de température induites par le chargement peuvent fortement impacter les performances physiques des pneumatiques ainsi que la tenue en fatigue des constituants caoutchoutiques. L’objectif de cette thèse est donc de caractériser le comportement thermomécanique des élastomères chargés et non chargés sous divers types de chargement mécanique. Pour ce faire, des mesures de champs thermiques et cinématiques couplées ont été mises en oeuvre lors d’essais mécaniques à température ambiante. Dans un premier temps, des essais de traction uniaxiale sur éprouvettes indemnes ont permis de confirmer que l’hystérésis mécanique observée lors d’un cycle de traction sur un caoutchouc naturel non chargé est essentiellement due au phénomène de cristallisation et non à des phénomènes dissipatifs. Par ailleurs, la construction de bilans énergétiques sur un cycle mécanique a permis de distinguer la contribution des différents mécanismes dissipatifs (viscosité, effet Mullins) des couplages thermomécaniques (élasticité entropique, cristallisation). Dans un second temps, des essais de cisaillement pur ont été menés sur des éprouvettes préalablement entaillées. Les analyses thermomécaniques menées à l’échelle de la zone d’influence de la fissure ont montré que les phénomènes dissipatifs aux très grandes déformations ne s’expriment pas de la même manière qu’aux déformations plus faibles. En particulier, pour les mélanges considérés dans cette étude, les effets du couplage entropique et de la viscosité sont du même ordre à la décharge, si bien que le matériau n’absorbe pas de chaleur à la décharge. Ces résultats sont très prometteurs à la fois pour la compréhension des phénomènes physiques impliqués dans le processus de déformation et pour la modélisation du comportement thermomécanique des élastomères. / Usually, most of the physical phenomena involved in the deformation of elastomers are studied from purely mechanical approaches. However, almost all of such phenomena depend on temperature and have distinguishable calorimetric signatures, which can enable us to better understand them. Furthermore, in the tire industrial context, the temperature increase induced by loading and self-heating may strongly impact the physical performances of tires as well as the fatigue life of the rubber components. Consequently, the aim of this PHD thesis was to characterize the thermomechanical behavior of rubbers, filled and unfilled, subjected to different mechanical loadings. For this purpose, coupled thermal and kinetic full field measurements have been performed during mechanical tests at ambient temperature. First, homogeneous uniaxial tensile tests have enabled us to confirm that the hysteresis loop in terms of the stress-strain relationship is mainly induced by crystallization phenomenon in natural rubber, not to dissipative phenomena. In the same way, energetic balances over one mechanical cycle have enabled us to distinguish the contribution of different dissipative phenomena (viscosity, Mullins effect) and the thermomechanical couplings (entropic elasticity, crystallization). Second, the analysis of the pure shear tests with pre-cracked specimens has enabled us to analyze, for the first time, the calorimetric response of rubbers in the zone of crack influence. Results have shown that dissipative phenomena at large strains differ from those involved at smaller strains. More especially, for the materials considered in the present study, the effects of the entropic coupling and viscosity are of the same order of magnitude during unloading, so that the material does not absorb any heat during unloading. These results are promising and motivate further work in this field in order to better understand the physical phenomena involved in the deformation processes as well as to more relevantly model the thermomechanical behavior of elastomers.

Aufgrund der zunehmenden technischen Ansprüche der Gesellschaft sind sich aktiv bewegende Polymere in den Mittelpunkt aktueller Forschung gerückt. Diese spielen bei Anwen-dungen im Bereich von künstlichen Muskeln und Implantaten für die minimal invasive Chirurgie eine wichtige Rolle. Vor allem Formänderungs- und Formgedächtnispolymere stehen dabei im wissenschaftlichen Fokus. Während die kontaktlose Deformation einer permanenten Form in eine temporäre metastabile Form, charakteristisch für Formände-rungspolymere ist, kann bei Formgedächtnis-Materialien die temporäre Form, aufgrund der Ausbildung reversibler, temporärer Netzpunkte, fixiert werden. Ein Polymermaterial, das eine Kombination beider Funktionen aufweist würde zu einem Material führen welches kontaktlos in eine temporäre Form deformiert und in dieser fixiert werden kann. Zusätzlich würde aufgrund der kontaktlosen Deformation die Reversibilität dieser Funktion gewähr-leistet sein. Ein solches Material ist bislang noch nicht beschrieben worden. In dieser Arbeit wird untersucht, ob durch die Kopplung zweier separat schaltbarer, be-kannter Funktionen eine neue schaltbare Funktion erzielt werden kann. Daher wurden multi-stimuli sensitive Materialien entwickelt die eine Kopplung des Formänderungs- und des Formgedächtniseffektes aufweisen. Dazu wurden zwei Konzepte entwickelt, die sich hinsichtlich der Reihenfolge der verwendeten Stimuli unterscheiden. Im ersten Konzept wurden flüssigkristalline Elastomere basie-rend auf Azobenzenderivaten aufgebaut und hinsichtlich der Kombination des licht-induzierten Formänderungseffektes mit dem thermisch-induzierten Formgedächtniseffekt untersucht. Diese orientierten Netzwerke weisen oberhalb der Glasübergangstemperatur (Tg) eine kontaktlose Verformung (Biegung) durch Bestrahlung mit UV-Licht des geeigneten Wellenlängenbereichs auf, wodurch eine temporäre Form erhalten wurde. Hierbei spielt der Vernetzungsgrad eine entscheidende Rolle bezüglich der Ausprägung dieser Biegung. Eine fixierte, temporäre Form konnte durch gleichzeitiges Abkühlen des Materials unterhalb von Tg während der Bestrahlung mit UV-Licht erhalten werden. Nach erneutem Aufheizen über Tg konnte die Originalform wiederhergestellt werden. Dieser Vorgang konnte reversibel durchgeführt werden. Damit wurde gezeigt, dass eine neue schaltbare Funktion erzielt wurde, die auf der Kopplung des lichtinduzierten Formänderungs- mit dem thermisch-induzierten Formgedächtniseffekt basiert. Die Abstimmung der einzelnen Funktion wird in diesem Konzept über die Morphologie des Systems gewährleistet. Diese neue Funktion ermöglicht eine kontaktlose Deformation des Materials in eine temporäre Form, welche fixiert werden kann. Im zweiten Konzept wurde eine Kopplung des thermisch induzierten Formänderungs- mit dem licht-induzierten Formgedächtniseffekt angestrebt. Um dies zu realisieren wurden nematisch, flüssigkristalline Hauptkettenelastomere (NMC-LCE) entwickelt, die eine nied-rige Übergangstemperatur der nematischen in die isotrope Phase (TNI), als auch einen aus-geprägten thermisch induzierten Formänderungseffekt aufweisen. Zusätzlich wurde eine photosensitive Schicht aufgebaut, die Cinnamylidenessigsäuregruppen in der Seitenkette eines Polysiloxanrückgrates aufweist. Die Reversibilität der photoinduzierten [2+2]-Cycloaddition konnte für dieses photosensitive Polymer beobachtet werden, wodurch die-ses Polymersystem in der Lage ist reversible temporäre Netzpunkte, aufgrund der Bestrah-lung mit UV-Licht, auszubilden. Die kovalente Anbindung der photosensitiven Schicht an die Oberfläche des flüssigkristallinen Kerns wurde erfolgreich durchgeführt, wodurch ein Multi-Komponenten-System aufgebaut wurde. Die Kombination des thermisch-induzierten Formänderungs- mit dem licht-induzierten Formgedächtniseffektes wurde anhand dieses Systems untersucht. Während die Einzelkomponenten die erforderliche Funktion zeigten, ist hier noch Arbeit in der Abstimmung beider Strukturen zu leisten. Insbesondere die Variation der Schichtdicken beider Komponenten steht im Fokus zukünftiger Arbeiten. In dieser Arbeit wurde durch die Kopplung von zwei separat schaltbaren, bekannten Funktionen eine neue schaltbare Funktion erzielt. Dies setzt voraus, dass die Einzelkomponenten hinsichtlich einer Funktion schaltbar sind und in einem Material integriert werden können. Des Weiteren müssen die beiden Funktionen mit unterschiedlichen Stimuli geschaltet werden. Ein wichtiger Schritt bei der Kopplung der Funktionen, ist die Abstimmung der beiden Komponenten. Dies kann über die Variation der Morphologie oder der Struktur erzielt werden. Anhand der Vielzahl der vorhandenen stimuli-sensitiven Materialien sind verschiedene Kopplungsmöglichkeiten vorhanden. Demnach wird erwartet, dass auf diesem Gebiet weitere neue Funktionen erzielt werden können. / Actively moving polymers are high scientific significance due to their ability to move actively in response to an external stimulus. Most notably shape-change and shape-memory polymers are in the focus of current research. Shape-changing polymers exhibit a non-contact deformation from a permanent into a temporary shape, which is just stable as long the material is exposed to an external stimulus. In contrast shape-memory polymers are capable of a fixed temporary shape due to the formation of additional temporary netpoints, while the deformation is proceed by applying mechanical stress. A polymeric material, which combines both functions would result into a material that possesses the advantages of the shape-change, as well as the shape-memory effect. In this work, the coupling of two known functions is investigated which results into a new switchable function. Therefore, two different concepts were developed requiring different material structures. For the first concept monodomain, smectic liquid-crystalline elastomers (LCE) containing azobenzene moieties were prepared and the coupling of the light-induced shape-change with the thermally-induced shape-memory effect was investigated. These oriented LCE's exhibit a non-contact deformation into a temporary shape, above the glass transition temperature (Tg), due to the irradiation with UV-light. The temporary shape could be fixed by cooling the material below Tg, while the irradiation with light was kept constant. The permanent shape could be recovered by additional heating above Tg. This process could be repeated several times. Therefore, a new switchable function was developed, which based on the coupling of the light-induced shape-change with the thermally induced shape-memory effect. The second concept required a multi-component system and the coupling of the thermally-induced shape-memory withe the light-induced shape-change effect was investigated. The multi component system consists of a LCE-core and a photosensitive layer. Nematic, main-chain elastomers were prepared, which possess of low transition temperatures and high actuation performances. The photosensitive layer consists of cinnamylidene acetic moieties, that were attached to a siloxane backbone, while the photoreversibility of the light-induced [2+2]-cycloaddition was shown. Furthermore, the photosensitive layer was covalently attached to the surface of the LCE-core. While both components showed their functionality, the coupling of the thermally-induced shape-change with the light-induced shape-memory effect was not successful up to now. The Adjustment of both components on each other has to be improved. Mainly the variation of the layer thickness of both structural components should be in the focus of future work.