Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho foram preparados nanocompósitos de elastômeros termoplásticos à base de PP/EPDM/argila organofílica. Foram utilizados como agentes interfaciais polipropileno e terpolímero de etileno-propileno-dieno ambos modificados com grupos anidrido maleico, PP-MA e EPDM-MA, respectivamente. Dois tipos de argila organofílica, que se diferenciam pela estrutura química do surfactante e conseqüentemente pela estabilidade térmica, foram empregados como carga inorgânica. Os nanocompósitos foram preparados pela técnica de intercalação por fusão em câmara interna de mistura e a incorporação da argila foi feita pela adição de masterbatches previamente preparados. Foram investigadas as propriedades de tração, reométricas e ainda a morfologia (cristalinidade e estrutura obtida) dos nanocompósitos a fim de estabelecer a influência do tipo e quantidade de argila organofílica e agente interfacial. Os resultados mostraram que a adição de agente interfacial melhorou a dispersão da argila organofílica na matriz de PP/EPDM, particularmente o PP-MA. Foram obtidos nanocompósitos com estruturas mistas intercaladas e esfoliadas, que resultaram em maiores valores de módulo de elasticidade e manutenção dos valores de deformação. As propriedades reométricas confirmaram o maior grau de dispersão da argila organofílica em nanocompósitos contendo PP-MA. Teores crescentes de argila reduziram a cristalinidade dos nanocompósitos, os quais quando reprocessados, mantiveram as características inerentes ao TPE de origem. Por fim, a estrutura do surfactante presente / In this work it was prepared nanocomposites based in PP/EPDM thermoplastic elastomer and organoclay. Maleinized polypropylene and ethylene-propylene-diene rubber, PP-MA and EPDM-MA, respectively, were employed as interfacial agents. Also two kinds of organoclays, differing about surfactant chemical structure and as consequence thermal stability, were investigated as inorganic filler. Nanocomposites were prepared by melt intercalation in an internal chamber mix and organoclay was incorporated by masterbatches addition, which ones were previously made. It was investigated the influence of amount and kind of organoclay and interfacial agent on tensile properties, rheology and morphology (crystallinity and structure type) of nanocomposites obtained. The results showed that interfacial agents addition promoted a better dispersion degree of organoclay platelets in PP/EPDM matrix, mainly PP-MA. Nanocomposites with both intercalated and exfoliated structures were obtained. These exhibited higher Young modulus and kept their elongation values. The better dispersion degree of clay platelets in nanocomposites containing PP-MA was confirmed by rheology measurements. Increasing amounts of organoclay lowered the crystallinity degree of nanocomposites but the reprocessability was maintained similar to that of pure TPE. Finally, the chemical structure of surfactants did not change the intercalation/exfoliation process due to the similarity of organoclay basal spacing and moderated TPE processing temperature.

Orientador: Fauze Ahmad Aouada / Resumo: Os hidrogéis são polímeros hidrorretentores reticulados, que são capazes de reter e absorver grande quantidade de água. A combinação de polissacarídeos e nanoargila na matriz polimérica otimiza o desenvolvimento de materiais biodegradáveis e nanoestruturados que podem ser utilizados na agricultura. Nesta dissertação foram preparados e caracterizados hidrogéis nanoestruturados biodegradáveis, afim de aplicá-lo como um acelerador no crescimento de mudas de hortaliça. Os hidrogéis foram preparados fixando as concentrações de acrilamida (AAm) em 6% m/v e carboximetilcelulose (CMC) em 1% m/v, e incorporando diferentes concentrações de nanoargila cloisita-Na+. Diferentes quantidades de hidrogéis foram incorporadas ao substrato e investigado a sua eficiência no cultivo de alface. Foram analisadas as propriedades hidrofílicas e cinéticas em água destilada e em soluções salinas. Os hidrogéis demonstraram excelentes resultados de intumescimento. A incorporação de nanoargila na matriz do polímero aumentou a velocidade de absorção de água (indicada pelo aumento da constante cinética k) quando intumescido em água destilada. A formação das redes poliméricas foi confirmada pela análise de espectroscopia no infravermelho com transformada de Fourier (FTIR). A difração do raios-x (DRX) e a espectroscopia de energia dispersiva de Raios-X (EDX) permitiu avaliar a conformação das plaquetas de nanoargila e os elementos químicos presente nos nanocompósitos, respectivamente. A microscopia eletrônica... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Hydrogels are water-retainer crosslinked polymers which are able to retain and absorb large quantities of water. The combination of polysaccharides and nanoclay in the polymeric matrix enhanced the development of nanostructured and biodegradable materials and it can be used in agriculture. In this work, nanostructured biodegradable hydrogels was prepared in order to improve germination and seedling quality of lettuce cultivation. The hydrogels were prepared by fixing the concentrations of acrylamide (AAm) in 6% w/v carboxymethylcellulose (CMC) in 1% w/v, containing different nanoclay Cloisite-Na+ concentrations. Different amounts of hydrogel were incorporated to the substrate and investigated their efficiency in lettuce cultivation. Hydrophilic and kinetic properties were investigated in distilled water and in saline solutions. The hydrogels showed excellent swelling degree results. Also, the incorporation of nanoclay in the polymer matrix increased the water absorption speed (indicated by an increase in kinetic constant k) when swollen in distilled water. The formation of polymer networks was confirmed by Fourier transform infrared spectroscopy (FTIR) analysis. The x-ray diffraction (XRD) and energy dispersive spectroscopy X-ray (EDX) corfimed the conformation of the nanoclay platelets and chemical elements present in the nanocomposite, respectively. The scanning electron microscopy (SEM) showed porous structures morphology with well-defined shapes, but with heterogeneity in... (Complete abstract click electronic access below) / Mestre

L'objectif de ce travail est une approche pluridisciplinaire dans le but de comprendre l'impact des phénomènes microscopiques, l'interaction charge-matrice avec ou sans agent de couplage et la dispersion des charges sur les propriétés macroscopiques. La caractérisation de l'impact de la stratégie de mélange avec ou sans un agent de couplage, la cinétique, l'état final et les différents scénarii de dispersion possibles sont ainsi étudiés. L'incorporation de microperles de silice dans une matrice SBR est réalisée dans un mélangeur interne. Finalement, la silice est dispersée à l'échelle nanométrique (10-100 nm). Les nanocomposites obtenus sont alors caractérisés par des techniques complémentaires (spectroscopie mécanique, MET, mesure du taux d'élastomère lié à la charge) dans le but de caractériser quantitativement les interactions charge-matrice et charge-charge. L'outil rhéologique est un outil très sensible pour caractériser l'évolution de la dispersion de charges dans une matrice élastomère. En particulier, le module de conservation G' montre un plateau significatif pour les faibles fréquences de déformation. Ce plateau est très sensible à l'état de dispersion ainsi qu'à la nature des interactions entre les charges. En couplant les mesures rhéologiques, l'analyse d'image faite sur des photos MET et la mesure du taux d'élastomère lié, il est possible d'établir un scénario de dispersion de la silice dans l'élastomère en fonction des conditions de mélange et de mettre en évidence les paramètres élémentaires de la dispersion impliqués. En complément, la modélisation de certains modules montre toute sa pertinence dans la caractérisation de la rupture des agglomérats ou de l'évolution des interactions charge-charge au cours du mélangeage. Enfin, la dimension fractale des réseaux de charges obtenus est déterminée à partir de nos descripteurs de la dispersion.

Les composants passifs hyperfréquences deviennent de plus en plus commercialisés et employés dans les systèmes de télécommunications. La croissance technologique et l'augmentation de la demande des nouvelles applications requièrent de meilleures performances et de moindres coûts. Dans les applications sans fil et notamment dans les modules " émission/réception ", les circulateurs sont utilisés pour l'émission et la réception des signaux simultanément à l'aide d'une seule antenne. Les couches magnétiques traditionnellement déposées et intégrées exigent une cristallisation à haute température ainsi que l'application d'un champ magnétique externe pour garder l'orientation des moments magnétiques. Cette orientation est cependant obtenue par des aimants lourds et volumineux. Devant ces limitations technologiques ainsi que la demande de miniaturisation, l'emploi de l'hexaferrite de baryum sous sa forme particulaire devrait permettre le développement de circulateurs auto-polarisés et miniaturisés à matériaux magnétiques composites. Les travaux présentés dans ce manuscrit ont pour objectif d'étudier et de réaliser un circulateur hyperfréquence à nano particules magnétiques orientées dans la bande 40-60 GHz. L'état de l'art expose les différentes topologies de circulateurs dont la topologie coplanaire est choisie pour notre application. L'étude analytique est basée sur les travaux de Bosma permettant de modéliser le circulateur triplaque. Les principales dimensions géométriques obtenues sont ensuite transposées vers la structure coplanaire en 3D à l'aide de l'outil de simulation HFSS. Devant les limitations de cet outil, différentes structures ont été étudiées et simulées numériquement pour présenter au mieux le matériau composite. Plusieurs séries de prototypes sont ensuite fabriquées à partir des structures optimisées en simulation numérique. Le matériau magnétique composite déposé a des épaisseurs de 40 et 100 μm. Les caractérisations hyperfréquences montrent la performance des dispositifs réalisés. Des pistes de recherche sont proposées pour l'amélioration des performances de nos prototypes.

Le travail de thèse présenté dans ce manuscrit s'inscrit dans une dynamique d'intégration de matériaux non conventionnels en systèmes microfluidiques. Il vise à démontrer le potentiel du cPDMS, un matériau nanocomposite formé d'une matrice de polydiméthylsiloxane rendu conducteur par l'ajout de nanoparticules de carbone. Compatible avec les procédés technologiques habituels, le cPDMS peut être structuré dans une large gamme d'épaisseurs et de géométries mais présente surtout l'avantage de pouvoir être collé irréversiblement sur verre, PDMS et silicium. Son intégration est parfaitement étanche, rapide à mettre en oeuvre, et très économique. La première partie du manuscrit est consacrée à la caractérisation de ce matériau. Ses propriétés électriques et de surface, pouvant être critiques pour une utilisation en microfluidique, ont été particulièrement étudiées. Les champs électriques offrant de nombreuses possibilités pour réaliser des fonctions clés en microfluidique (détection, séparation, manipulation de fluides ou de particules), nous avons choisi d'évaluer l'intérêt d'électrodes de cPDMS dans deux types d'applications. Les aspects de détection ont d'abord été mis en évidence à l'aide de mesures électrochimiques. Cette méthode a permis à la fois de caractériser la surface du cPDMS tout en validant son utilisation potentielle pour des applications d'analyses électrochimiques. Dans la dernière partie du manuscrit, le matériau a été testé pour la manipulation de particules à travers l'observation de différents phénomènes électrocinétiques. Ceux-ci ont conduit à la mise au point de dispositifs microfluidiques (intégrant des lectrodes de cPDMS) dédiés à la lyse et à l'électrofusion de cellules.

Clay minerals have historically played a consequential role in human health. While the beginnings were rooted in geophagy, a primitive act of consuming earth, the health-related uses of clay minerals have evolved and diversified over time. As excipients in pharmaceutical formulations, clay minerals can attribute novel properties onto intercalated compounds. Intercalating oxybenzone, a UV filter, within the interlamellar space of montmorillonite is desirable in order to minimize direct contact with skin. Intercalating resveratrol, a compound known for attributing beneficial effects onto human health, may be advantageous since this compound is susceptible to cis-trans isomerisation. The strategy of using alkylammonium–modified clay was undertaken and proved successful for the intercalation of oxybenzone. The field of biopolymer/layered silicate nanocomposites is heavily researched for use in a multitude of applications. Novel montmorillonite nanocomposites were prepared with neutral guar gum and cationic guar gum, using an environmentally friendly process and are fully characterized.

Clay minerals have historically played a consequential role in human health. While the beginnings were rooted in geophagy, a primitive act of consuming earth, the health-related uses of clay minerals have evolved and diversified over time. As excipients in pharmaceutical formulations, clay minerals can attribute novel properties onto intercalated compounds. Intercalating oxybenzone, a UV filter, within the interlamellar space of montmorillonite is desirable in order to minimize direct contact with skin. Intercalating resveratrol, a compound known for attributing beneficial effects onto human health, may be advantageous since this compound is susceptible to cis-trans isomerisation. The strategy of using alkylammonium–modified clay was undertaken and proved successful for the intercalation of oxybenzone. The field of biopolymer/layered silicate nanocomposites is heavily researched for use in a multitude of applications. Novel montmorillonite nanocomposites were prepared with neutral guar gum and cationic guar gum, using an environmentally friendly process and are fully characterized.

The present work provides a micromechanics approach based on the generalized self-consistent composite cylinders method as a non-Eshelby approach towards for assessing the impact of carbon nanotubes on the multi-functional nature of nanocom-posites in which they are a constituent. Emphasis is placed on the effective elastic properties as well as electrical and thermal conductivities of nanocomposites con-sisting of randomly oriented single walled carbon nanotubes in epoxy. The effective elastic properties of aligned, as well as clustered and well-dispersed nanotubes in epoxy are discussed in the context of nanotube bundles using both the generalized self-consistent composite cylinders method as well as using computational microme-chanics techniques. In addition, interphase regions are introduced into the composite cylinders assemblages to account for the varying degrees of load transfer between nanotubes and the epoxy as a result of functionalization or lack thereof. Model pre-dictions for randomly oriented nanotubes both with and without interphase regions are compared to measured data from the literature with emphasis placed on assessing the bounds of the effective nanocomposite properties based on the uncertainty in the model input parameters. The generalized self-consistent composite cylinders model is also applied to model the electrical and thermal conductivity of carbon nanotube-epoxy nanocomposites. Recent experimental observations of the electrical conductivity of carbon nanotube polymer composites have identified extremely low percolation limits as well as a per-ceived double percolation behavior. Explanations for the extremely low percolation limit for the electrical conductivity of these nanocomposites have included both the creation of conductive networks of nanotubes within the matrix and quantum effects such as electron hopping or tunneling. Measurements of the thermal conductivity have also shown a strong dependence on nanoscale effects. However, in contrast, these nanoscale effects strongly limit the ability of the nanotubes to increase the thermal conductivity of the nanocomposite due to the formation of an interfacial thermal resistance layer between the nanotubes and the surrounding polymer. As such, emphasis is placed here on the incorporation of nanoscale effects, such as elec-tron hopping and interfacial thermal resistance, into the generalized self-consistent composite cylinder micromechanics model.

In this study, the effects of organoclay loading, compatibilizer loading and polyethylene type on the morphology, rheology, thermal properties and mechanical properties of polyethylene/compatibilizer/organoclay nanocomposites were investigated. As compatibilizer, terpolymer of ethylene-methacrylate-glycidyl methacrylate (Lotader&reg / AX8900), as organoclay Cloisite&reg / 15A were used. All samples were prepared by a co-rotating twin screw extruder, followed by injection molding. Considering ternary nanocomposites, highest impact strength results were obtained with 10% compatibilizer plus 2% organoclay / highest yield stress, elastic modulus, flexural strength, flexural modulus were obtained with 5% compatibilizer plus 4-6% organoclay. DSC data indicated that addition of organoclay and compatibilizer did not change the melting point remarkably / on the other hand it affected the crystallinity. The organoclay used had no nucleation effect on polyethylene, and the compatibilizer decreased the crystallinity of the matrix. X-ray diffraction showed that in all ternary nanocomposites and in binary nanocomposite of high density polyethylene with organoclay, layer separation associated with intercalation of the clay structure occurred,. The highest increase of interlayer gallery spacing was obtained with 10% compatibilizer plus 2% organoclay, which were 25%, 28% and 27% for HDPE, LLDPE and LDPE matrices respectively.

The aim of this study is to demonstrate the possibility of production of nanocables as an alternative to the other one dimensional metal/polymer composite structures like nanowires and nanorods. There is no certain definition of nanocables / however they could be considered as assemblies of nanowires. Nanocable structure can be defined as a core-shell structure formed by a polymeric shell and a metal core that runs continuously within this shell. To produce nanocables, two main steps were carried out. Firstly, monodispersed silver metal nanoparticles to be aligned within the cable core were produced. Investigations on reduction reactions in the presence of strong and weak reducing agents and different capping agents revealed the importance of the kinetics of reduction in the production of monodispersed nanoparticles. Use of capping agents to give a positive reduction potential, resulted in the slow reduction rates that was critical for fine tuning of the final particle sizes between 1-10 nm. Hydrazine hydrate and oleylamine/ oleic acid systems were used as strong and weak reducing agents, respectively. By using weak reducing agent, monodisperse spherical silver nanoparticles with the diameter of 2.7 nm were produced. It was shown that particles with controlled diameter and size distribution can be obtained by tuning the system parameters. Secondly, particles produced as such were electrospun within the core of the polymer nanofibers and long continuous nanocables were produced. Polyvinyl pyrrolidone and polycaprolactone were used in shell part of nanocables. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), photon correlation spectroscopy (PCS), X-ray diffraction (XRD) and surface plasmon resonance spectroscopy (SPR) analyses were carried out in order to understand the mechanism by which the nanoparticles were reduced and for further characterization of the product.