Τα Νανοσύνθετα συστήματα πολυμερικής μήτρας – σιδηροηλεκτρικών ή πιεζοηλεκτρικών σωματιδίων (κεραμικά εγκλείσματα) αναμένεται να αποτελέσουν μια νέα γενιά υψηλού τεχνολογικού ενδιαφέροντος που θα επιδεικνύουν λειτουργικές ιδιότητες λόγω της ποικίλης πόλωσης των κεραμικών νανοσωματιδίων. Η διασπορά κεραμικών εγκλεισμάτων στο εσωτερικό πολυμερικής μήτρας προσδίδει στα σύνθετα συστήματα βελτιωμένη μηχανική και ηλεκτρική συμπεριφορά. Τέτοιου τύπου συστήματα υλικών, που έχουν υψηλή ηλεκτρική διαπερατότητα (high-Κ materials) χρησιμοποιούνται σε ηλεκτρονικές εφαρμογές, καθώς μειώνουν τα ρεύματα διαρροής και παράλληλα λειτουργούν ως ενσωματωμένοι νανο-πυκνωτές και αισθητήρες ακουστικών εκπομπών. Η ηλεκτρική απόκριση τους, εκφράζεται κυρίως μέσω της ηλεκτρικής διαπερατότητας και μπορεί να ρυθμιστεί, ελέγχοντας τον τύπο, το μέγεθος και την ποσότητα της κεραμικής ενίσχυσης. Η ενσωμάτωση σιδηροηλεκτρικών ή πιεζοηλεκτρικών κρυστάλλων, που επιδεικνύουν υψηλή πόλωση, σε μια πολυμερική μήτρα, όπως η εποξειδική ρητίνη – που εν γένει είναι ηλεκτρικός μονωτής- με χαμηλή ηλεκτρική διαπερατότητα και υψηλή διηλεκτρική αντοχή μπορεί να οδηγήσει στην ανάπτυξη ενός ευφυούς συστήματος. Σκοπός αυτής της εργασίας είναι η παρασκευή και ο χαρακτηρισμός σύνθετων πολυμερικών συστημάτων εποξειδικής ρητίνης – νανοσωματιδίων τιτανικού ψευδάργυρου (ZnTiO3) καθώς και σύνθετων υβριδικών συστημάτων εποξειδικής ρητίνης - νανοσωματιδίων τιτανικού ψευδάργυρου (ZnTiO3) και τιτανικού βαρίου (BaTiO3) ώστε να οδηγηθούμε σε ένα σύστημα υλικών με βέλτιστη συμπεριφορά. Στο θεωρητικό κομμάτι αυτής της εργασίας συζητούνται βασικές έννοιες και θεωρίες που αφορούν τα σύνθετα υλικά, τη θεωρία των διηλεκτρικών και ενεργών διηλεκτρικών, την ηλεκτρική συμπεριφορά σύνθετων υλικών με πολυμερική μήτρα καθώς και πειραματικές τεχνικές χαρακτηρισμού. Στο πειραματικό μέρος, νανοσύνθετα πολυμερικά συστήματα παρασκευάστηκαν από εποξειδική ρητίνη και νανοσωματίδια ZnTiO3 και BaTiO3. Η μέση διάμετρος σωματιδίων βάσει των προδιαγραφών του προμηθευτή ήταν λιγότερο από 100nm για το ZnTiO3 και στην περιοχή των 30 - 50nm για το BaTiO3. Στη συνέχεια τα νανοσύνθετα υποβλήθηκαν σε μορφολογικό, θερμικό και ηλεκτρικό χαρακτηρισμό. Η μορφολογία των δειγμάτων εξετάστηκε για τυχούσα παρουσία κενών (voids) και συσσωματωμάτων (clusters) μέσω του Ηλεκτρονικού Μικροσκοπίου Σάρωσης (SEM) και η θερμική τους απόκριση μέσω της Διαφορικής Θερμιδομετρίας Σάρωσης (DSC). Η διασπορά των κεραμικών εγκλεισμάτων θεωρήθηκε ικανοποιητική, παρόλο που συνυπάρχουν οι νανοδιασπορές με συσσωματώματα. Οι διηλεκτρικές ιδιότητες και τα σχετιζόμενα φαινόμενα διεργασιών χαλάρωσης μελετήθηκαν με χρήση της Διηλεκτρικής Φασματοσκοπίας Ευρέως Φάσματος (BDS) στο εύρος θερμοκρασιών -100 oC έως 160 oC και στο διάστημα συχνοτήτων 10-1 Hz έως 106 Hz. Η ανάλυση των πειραματικών αποτελεσμάτων διεξήχθη με τη χρήση των φορμαλισμών της ηλεκτρικής διαπερατότητας και του ηλεκτρικού μέτρου. Από τα πειραματικά αποτελέσματα προκύπτει πως παρατηρούνται διηλεκτρικές χαλαρώσεις που οφείλονται τόσο στην πολυμερική μήτρα, όσο και στην ενισχυτική φάση. Τα φάσματα των υβριδικών συστημάτων καταγράφουν τουλάχιστον τέσσερεις διακριτούς τρόπους χαλάρωσης. Αυτά αποδίδονται στη διεπιφανειακή πόλωση (Interfacial Polarization ή φαινόμενο MWS) μήτρας/εγκλεισμάτων, στην α- χαλάρωση λόγω υαλώδους μετάβασης του πολυμερούς και στην β- και γ- χαλάρωση εξαιτίας της κίνησης πλευρικών πολικών ομάδων και τοπικής κίνησης μικρών τμημάτων της πολυμερικής αλυσίδας. Η λειτουργικότητα των νανοσύνθετων σχετίζεται με την μεταβολή της πόλωσης, που σχετίζεται ευθέως με το πραγματικό μέρος της ηλεκτρικής διαπερατότητας, την εξάρτηση της ειδικής αγωγιμότητας από την θερμοκρασία και την περιεκτικότητα σε ενισχυτικό μέσο και την δυνατότητα αποθήκευσης ενέργειας. / Nanocomposite systems, which include ferroelectric or piezoelectric particles represent a novel class of materials which are expected to exhibit functional properties because of the varying polarization of the ceramic particles. Dispersing ceramic inclusions within a polymer matrix, results in enhanced mechanical and electrical behavior. Such material systems exhibiting enhanced electrical response are used in electronic applications, for the reduction of leakage currents, as integrated nano- capacitors and as acoustic emission sensors. The electrical response of these composites, namely dielectric permittivity and conductivity can be tailored, by controlling the type, the size and the amount of ceramic inclusions. The ceramic filler could be ferroelectric and/or piezoelectric crystal particles. Their high level of polarization can be combined with a polymer host, like an epoxy resin – which is, in general, electrical insulator – with low dielectric permittivity and high dielectric breakdown strength. This combination could lead in the development of a smart materials’ system. The aims of this work are the preparation and characterization of epoxy resin nanocomposites with embedded zinc titanate (ZnTiO3) and nanoparticles and in tandem hybrid system of epoxy resin– zinc titanate (ZnTiO3) and barium titanate (BaTiO3) nanoparticles. In the first part of this work basic aspects concerning composite materials, dielectric theory, electrical behaviour and characterization techniques of polymer matrix composites are presented. In the experimental part of this study, nanocomposites were prepared by employing commercially available materials such as epoxy resin, ceramic ZnTiO3 and BaTiO3 nanopowder. The mean particle diameter, as indicated by the supplier, was less than 100nm for ZnTiO3 and 30-50nm for BaTiO3 particles. Furthermore, morphology, thermal and electrical response of the produced specimens was examined. The morphology of the specimens was checked for voids and clusters, by means of Scanning Electron Microscopy and the thermal response via Differential Scanning Calorimetry (DSC). Ceramic particles distribution is considered as satisfactory, although clusters co-exist with nanodispersions in all the examined systems. The dielectric properties and the related relaxation phenomena were studied by means of Broadband Dielectric Spectroscopy (BDS) in the temperature range from -100 oC to 160 oC and frequency range from 10-1 Hz to 10-6 Hz. Experimental data analysis was conducted by means of dielectric permittivity and electric modulus formalisms. Based on the conducted analysis, the recorded relaxation phenomena include contributions from both the polymeric matrix and the reinforcing phase. In the spectra of hybrid nanocomposites at least four relaxation processes can be detected. They were attributed to Interfacial Polarization phenomenon (MWS effect), α-mode due to glass/rubber transition of the polymer and β- , γ- modes resulting from the motion of polar side groups and local motion of small segments of the polymer chain. The functionality of the nanocomposite systems is related to the variation of polarization, which is directly connected to the real part of dielectric permittivity, the dependence of conductivity on the temperature and the filler content, and the energy storage efficiency expressed by the density of energy.

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / In the context of the so-called smart materials, shape memory alloys (SMA) have been extensively investigated aiming at various applications in different types of engineering prob- lems as well as interdisciplinary problems. Specifically, SMAs have been used for the mitiga- tion of mechanical vibrations, owing to their characteristic pseudoelastic effect, which is re- sponsible for the occurrence of hysteresis. Another relevant feature of these materials is the coexistence of two crystallographic phases (martensite and austenite), which have dissimilar mechanical properties, whose relative fractions depend on temperature and stress. In the present dissertation, this latter feature is explored in association with a strategy of passive vibration control which is based on tunable dynamic vibration absorbers (TDVA). These de- vices, once connected to a vibrating structure, can have their inertia and/or stiffness and/or damping adjusted to match the excitation frequency. Specifically, such tuning is achieved by controlling the martensite/austenite fraction by applying convenient thermal loads. By means of numerical simulations, which include the integration of the equations of motion, it is put in evidence the possibility of tuning a TDVA applied to a single degree-of-freedom system, with- in a given frequency band using two configurations of the resilient element (SMA rod and helicoidal spring). The results enable to evaluate the levels of vibration mitigation achieved and confirm that the strategy investigated can provide improved performance in terms of vibration attenuation. / No contexto dos chamados materiais inteligentes, as ligas com memória de forma (Shape Memory Alloys SMA) vêm sendo intensivamente investigadas com vistas a aplicações em diversos tipos de sistemas de engenharia e em problemas interdisciplinares. Especificamente, as SMA têm sido utilizadas para a mitigação de vibrações mecânicas, graças ao chamado efeito pseudoelástico, responsável pela ocorrência de histerese. Outra característica relevante desses materiais é a coexistência de duas fases cristalográficas (martensita e austenita), com propriedades mecânicas distintas, cujas frações relativas dependem da temperatura e da tensão. No presente trabalho, esta última característica é explorada em associação com uma estratégia de controle passivo de vibrações, baseada nos chamados absorvedores dinâmicos de vibrações sintonizáveis (ADV), que são dispositivos conectados à estrutura vibratória, cuja rigidez e/ou inércia podem ser ajustados em conformidade com a frequência de excitação, de modo que a vibração da estrutura seja altenuada. Especificamente, explora-se a possibilidade de confecção de ADVs sintonizáveis cuja rigidez pode ser ajustada por meio de variações controladas da fração relativa martensita/austenita induzidas por alterações da temperatura. Por meio de simulações numéricas, evidencia-se a possibilidade de sintonizar um ADV aplicado a um sistema vibratório de um grau de liberdade, dentro de uma dada faixa de valores de frequência, utilizando duas configurações do elemento resiliente (barra e mola helicoidal de SMA), e quantificam-se as reduções de amplitudes obtidas. Os resultados das simulações confirmam o aumento da eficiência na atenuação de vibrações proporcionado pela estratégia empregada. / Mestre em Engenharia Mecânica

Les multicouches de polyélectrolytes, systèmes auto-assemblés par adsorptions successives de polycations et polyanions, peinent à trouver des applications concrètes en raison de leur fragilité mécanique et du temps nécessaire à leur assemblage. Pour améliorer leur tenue mécanique, nous avons développé une méthode d'assemblage couche-par-couche par liaisons covalentes de films polymères. Des films formés de polymères portant des groupements alcynes et azides ont ainsi été réticulés par une réaction click catalysée par les ions Cu+ obtenus par voie électrochimique. Pour améliorer le mode d'assemblage, l'auto-construction en une seule étape de films par approche morphogénique, a été développée. Cette approche, confinée à la surface et caractérisée par la présence en solution de l'ensemble des constituants, marque une rupture. Elle permet ainsi un contrôle spatial de l'assemblage des films et la combinaison de plusieurs modes d'interactions pendant leur assemblage. Des films dont la cohésion repose sur des interactions covalentes, hôtes-invités et supramoléculaires, ont ainsi été assemblés. L'introduction de nanoparticules métalliques dans les films (multicouches et auto-construits) a également été effectuée dans le but de développer des électrodes de grande surface spécifique. / Polyelectrolyte multilayer films, built by alternated adsorption of polycations and polyanions, face two main challenges: their construction process is tedious and their mechanical stability is poor. We developped a layer-by-layer strategy to improve the film stability by covalent reticulation of the polymers chains by click chemistry. Polymers bearing alkyne and azide functions were reticulated by triggering electrochemically the production of Cu+ catalyst ions. A one pot morphogen driven self-construction strategy was also developped to improve the buildup process of the films.In this case, all the constituants are simultaneously present in solution while the film grows up only at the electrode. Films based on covalent, host-guest and supramolecular interactions were obtained and the possibility of combining different interactions was also demonstrated. Nanoparticles were also included in layer-by-layer and self-constructed films in order to improve the electrode specific area.

Hold down release mechanisms (HDRMs) are used for tightly attaching segments of bodies together when it is desired to release them rapidly at some point. When transporting sensitive payloads on launch vehicles, the challenge arises of releasing the fastened segments of the spacecraft without risking damage to the costly equipment. Non-explosive HDRMs are favourable from a safety perspective as there is a lower risk of producing potentially destructive shock-waves throughout the structure.  One variant of a non-explosive HDRM uses a so called 'split spool initiator'. This initiator can only be used once in the actuator mechanism and to reuse the HDRM the initiator must be replaced. The purpose of this thesis is to design an improved split spool initiator which can be reusable while conserving the functionality aspects of the existing design. To achieve this, different ideas were considered and ultimately a solution using shape memory alloys (SMAs) was explored. A prototype was constructed to demonstrate the functionality of the design and simulations are done to determine the forces acting on different parts of the mechanism. / Hold down release-mekanismer (HDRM) används för att säkert kunna fästa samman delar av strukturer för att sedan kunna lossa dessa vid rätt tillfälle. När det transporteras känslig last på exempelvis rymdfarkoster uppkommer utmaningen att göra så på ett sätt som inte riskerar att skada den ofta dyra utrustningen. Det finns en mängd olika HDRM, dessa kan delas upp i två typer som är icke explosiva release-mekanismer och pyrotekniska release-mekanismer. Icke explosiva release-mekanismer har en fördel över pyrotekniska som är att de inte producerar potentiellt destruktiva chock-vågor som sprids genom strukturen. En typ av icke-explosiva release-mekanismer är den så kallade split spool-initieraren. Denna kan endast användas en gång när fästelementet är aktiverat och för att kunna använda fästelementet igen måste hela initieraren bytas ut. Syftet med denna studie har varit att att designa en förbättrad split spool-initierare som är återanvändbar, medan funktionaliteten hos den ursprungliga designen är bevarad. För att åstadkomma detta övervägdes olika idéer och slutligen valdes en lösning som använder minnesmetaller eller Shape memory alloys på engelska (SMA). En prototyp konstruerades för att demonstrera funktionaliteten hos designen. Simuleringar gjordes även för att bestämma krafter som agerade på split spool-strukturen och för att få en överblick över spänningsfördelningen genom initieraren.

Stoichiometric polyelectrolyte-surfactant complexes represent a type of comb-shaped polymers, in which every polymer chain unit has an electrostatically bound "side chain". These complexes are water-insoluble. In the solid state they assemble spontaneously into mesogenic structures. The [X,Y]-ionenes ([(CH2)XN+(CH3)2(CH2)YN+(CH3)2]nBr-2n) investigated formed stoichiometric complexes with alkyl sulfates. The ionene alkyl sulfate complexes display mesogenicity, i.e. optically isotropic dry complexes underwent lyotropic and thermotropic phase transitions to the optically anisotropic phase (and vice versa) under controlled relative humidity. The optically anisotropic phases exhibited hexagonal textures as revealed by polarizing microscopy. A new feature is the lyotropic transition brought about by the uptake of water through the gas phase. The complexes were all sensitive to both humidity and temperature. In principle, the effects can be applied to measure humidity.

The integration of shape memory alloys (SMAs) into textile-reinforced composites produces a class of smart materials whose shape can be actively influenced. In this paper, Ni-Ti SMA wires are inserted during the weaving of a glass fiber reinforcement textile. This ‘‘active’’ reinforcement is then combined with an elastomeric matrix to produce a highly flexible composite sheet, which maintains high rigidity in the longitudinal direction. By activating the SMAs, high deflection ratios of up to 35% (relative to the component’s length) are achieved. To adjust the composite’s deflection to defined values, a closed-loop control is set up to adjust the current flow through the SMA wires. A control algorithm is designed and evaluated for several test cases. The high deformability and the controllable behavior show the high potential of these materials for applications such as aerodynamic flow control, automation and architecture.

No description available.

Future robotic systems will be pervasive technologies operating autonomously in unknown spaces that are shared with humans. Such complex interactions make it compulsory for them to be lightweight, soft, and efficient in a way to guarantee safety, robustness and long-term operation. This set of qualities can be achieved using soft multipurpose systems that combine, integrate and commute between conventional electromechanical and fluidic drives, as well as harvest energy during inactive actuation phases for increased energy efficiency. Recent research work has shown that dielectric fluids with specific properties, can be combined with stretchable or flexible shell structures made of polymeric dielectric/electrode composite films, to implement a novel type of soft electrically-driven fluidic transducers with self-healing and self-sensing capabilities that take the name of Liquid-based Electro-Active Polymer transducers (LEAPs). These devices are similar to dielectric elastomer transducers in regards to their electrostatic working principle, but they can potentially produce larger displacements due to their lower mechanical stiffness. In this thesis a novel electrostatic transducer is presented; the transducer is made of thin polymer films and liquid dielectrics, combined with rigid stiffening elements to form a circular electrostatic bellow muscle (EBM) unit capable of out-of-plane contraction. These units are easy to manufacture and can be arranged in arrays and stacks that can be employed as contractile artificial muscles, pumps for fluid-driven soft robots, or as energy harvesters. As artificial muscles, EBMs of 20 - 40 millimeters in diameter can exert forces of up to 6 newtons, lift loads over a hundred times their own weight, and reach contractions of over 40 per cent with strain rates over 1200 per cents per second, with a bandwidth over 10 Hz. As pump drivers, EBMs produce flow rates of up 0.63 liters per minute and maximum pressure head of 6 kilopascals, whereas as generators, they reach a conversion efficiency close to 20 per cent. The compact shape, low cost, simple assembling procedure, high reliability and large contractions make the EBM a promising technology for high-performance robotic systems.

Thin active elements can be added to rigid surfaces for the tuning of mechanical contact properties. The deformation of the active structures leads to the forming of arches. Depending on the forming of the arch, the force–displacement curve for contact becomes more or less steep. This can be understood as changing the interaction property between soft and hard. Herein, this concept is presented with hydrogels inside the active elements. Analytical derivations and finite-element simulation results for actuation and contact, based on the stimulus expansion model, are shown. This modeling approach appropriately captures the stimulus-dependent swelling properties of the material and can be easily applied in commercial finite-element tools. Special considerations are taken for the encapsulation of the active materials. A thin encapsulation foil allows 1) the use of swelling agents, such as water, without contaminating the contact objects. Furthermore, 2) appropriate water reservoirs for the swelling process can be included. The simulation results show that a surface softness tuning can be realized. The presented active material and dimensions are exemplary; the concept can be applied to other active materials for tuning surface interactions.

Photoschalter sind Moleküle, die eine reversible lichtgesteuerte Umwandlung zwischen zwei Zuständen mit unterschiedlichen Eigenschaften durchlaufen. In den letzten zehn Jahren hat der Einbau dieser photochromen Moleküle in intelligente, auf Stimuli ansprechende Materialien zunehmende Aufmerksamkeit erregt, da sie die einzigartige Fähigkeit bieten, makroskopische Eigenschaften mit einem externen optischen Stimulus reversibel zu verstärken und zu verändern. Die begrenzte Leistung von Photoschaltern in festen Medien bleibt eine Herausforderung. In diesem Zusammenhang werden in dieser Arbeit zwei wichtige Aspekte näher untersucht. Erstens der Prozess der Entwicklung neuer Photoschalter mit maßgeschneiderten Eigenschaften und zweitens die Implementierung von Photoschaltern in feste Materialien und die damit verbundenen Herausforderungen. Im ersten Teil dieser Arbeit wurde Dynamisch-kovalente Chemie (DCC) verwendet, um die Entdeckung und Entwicklung einer neuartigen Klasse von Photoschaltern mit drei Zuständen zu beschleunigen. Die dynamische Natur der zentralen Doppelbindung von α-Cyanodiarylethenen wurde genutzt, um ein thermodynamisches Gleichgewicht mit anderen Arylacetonitrilen herzustellen. Die entwickelte Methode kombiniert eine schnelle Diversifizierung mit einer Rasterung auf spezifische Eigenschaften, die durch einen externen Stimulus aufgedeckt werden, und ermöglicht die effiziente Untersuchung der Beziehung zwischen Struktur und den zugehörigen Eigenschaften. Im zweiten Teil der Arbeit wird die Entwicklung und die Synthese eines Zweikomponenten-Kern-Schale-MOFs mit einem internen nicht-funktionalisierten Kompartiment, das von einer dünnen photoschaltbaren Außenschale bedeckt ist, vorgestellt. Diese Strategie ermöglicht ein effizientes Schalten des Chromophors und die resultierende dünne „intelligente“ Schale fungiert als modulare kinetische Barriere für die molekulare Gastdiffusion in das Material, die durch Licht gesteuert werden kann. / Photoswitches are molecules that undergo a reversible light-triggered conversion between two states with different properties. In the past decade, the incorporation of these photochromic molecules in smart stimuli-responsive materials has gained increased attention as it offers the unique ability to reversibly amplify and change macroscopic properties with an external optical stimulus. The limited performance of photoswitches in solid mediums remains a challenge. In this context two important aspects are studied in more detail in this thesis. First, the process of developing new photoswitches with tailored properties and second, the implementation of photoswitches in solid materials and the challenges associated with it. In the first part of this thesis dynamic covalent chemistry (DCC) was used to accelerate the discovery and development of a novel three-state photoswitch class. The dynamic nature of the central double bond of α-cyanodiarylethenes was exploited to establish a thermodynamic equilibrium with other arylacetonitriles. The developed DCC tool combines fast and efficient diversification with screening for specific photochemical properties revealed by an external stimulus, enabling the rapid study of the relationship between structure and the associated properties. The second part of this thesis summarizes the design and synthesis of a two-component core-shell MOF with an internal non-functionalized compartment covered by a thin photoswitchable outer shell. This strategy allows efficient switching of the chromophore and the resulting thin “smart” shell acts as a modular kinetic barrier for molecular guest diffusion into the material that can be controlled by light.