Dans l'objectif d'améliorer la mise en forme des polymères semi-conducteurs tels que le poly (3,4-éthylènedioxythiophène) et la polyaniline, nous avons développé leur synthèse par polymérisation en dispersion de leurs monomères respectifs en utilisant le poly(oxyde d'éthylène), le poly (vinyl alcool), le poly [(N-vinylpyrrolidone)-co-(vinyl alcool)] et le poly [(N-vinylpyrrolidone)-b-(vinyl alcool)] comme stabilisants réactifs dans des milieux dispersants aqueux. Des nano-objets de nature et de structure bien définis ont été obtenus. Afin de moduler la conductivité et les propriétés opto-électroniques de ces nano-objets, leurs composites avec des métaux tels que l'or, l'argent et le cuivre ont été préparés en utilisant les sels métalliques correspondants comme co-oxydants au cours de la polymérisation en dispersion. La morphologie des nano-objets a notamment été évaluée par Microscopie Electronique en Transmission, Microscopie Electronique à Balayage, et Microscopie à Force Atomique. Le nature cœur-écorce de ces nano-objets, le niveau de dopage et la présence de métaux dans les nano-composites ont été examinés par spectrométrie de photoélectrons induits par rayons X. / With the objective to improve the processability of “stiff” semi-conducting polymers, well defined poly(3,4-ethylenedioxythiophene) and polyaniline core-shell nano-objects were synthesized by dispersion polymerization of their respective monomers using poly(ethylene oxide), poly(vinyl alcohol), poly[(N-vinylpyrrolidone)-co-(vinyl alcohol)] and poly[(N-vinylpyrrolidone)-b-(vinyl alcohol)]-based reactive stabilizers in aqueous dispersant media. In order to improve the conductivity and opto-electronic properties of these nano-objects, their composite with gold, silver and copper were prepared using the metal salts as co-oxidants during dispersion polymerization. The morphology of the nano-objects was observed by microscopy analyses such as Transmission Electron Microscopy, Scanning Electron Microscopy, and Atomic Force Microscopy. The core-shell nature of these nano-objects, doping level and the presence of metals in the nano-composites were examined by X-rays Photoelectron Spectroscopy.

In recent decades, the use of fossil fuels has increased exponentially with a corresponding sharp increase in the pollution of the environment. The need for clean and sustainable technologies for the generation of power with reduced or zero environment impact has become critical. A number of attempts have been made to address this problem; one of the most promising attempts is polygeneration. Polygeneration technology is highly efficient and produces lower emissions than conventional methods of power generation because of the simultaneous generation of useable heat and electrical power from a single source of fuel. The overall efficiency of such systems can be as high as 90%, compared to 30-35% for conventional single-product power plants. A number of different technologies are available for polygeneration, such as micro gas turbines, sterling engines, solar systems, and fuel cells. Of these, fuel cell systems offer the most promising technology for polygeneration because of their ability to produce electricity and heat at a high efficiency (about 80%) with either low or zero emissions. Various fuel-cell technologies can be used in polygeneration systems. Of these, solid oxide fuel cells (SOFCs) are the most suitable because they offer high system efficiency for the production of electricity and heat (about 90%) coupled with low or zero emissions. Compared to other types of fuel cells, SOFCs have fuel flexibility (direct operation on hydrocarbon fuels, such as biogas, bio-ethanol, bio-methanol, etc.) and produce high-quality heat energy. The development of polygeneration systems using SOFCs has generally followed one of two approaches. The first approach involves the design of a SOFC system that operates at a temperature of 850 oC and uses natural gas as a fuel. The second approach uses low-temperature (generally 400-600 oC) SOFC (LTSOFC) systems with biomass, e.g., syngas or liquid fuels, such as bio-methanol and bio-ethanol. The latter systems have strong potential for use in polygeneration. High-temperature SOFCs have obvious disadvantages, and challenges remain for lowering the cost to meet commercial interest. The SOFC systems need lower operating temperatures to reduce their overall costs. This thesis focuses on the development of nanocomposites for advanced fuel-cell technology (NANOCOFC), i.e., the next generation SOFCs, which are low-temperature (400-600 oC), marketable, and affordable SOFCs. In addition, new concepts that pertain to fuel-cell science and technology—NANOCOFC (www.nanocofc.com)—are explored and developed. The content of this thesis is divided into five parts: In the first part of this thesis (Papers 1-5), the two-phase nanocomposite electrolytes, viz. ceria-salt and ceria-oxide, were prepared and studied using different electrochemical techniques. The microstructure and morphology of the composite electrolytes were characterised using XRD, SEM and TEM, and the thermal analysis was conducted using DSC. An ionic conductivity of 0.1 S/cm was obtained at 300 ºC, which is comparable to that of conventional YSZ operating at 1000 ºC. The maximum output power density was 1000 mW/cm2 at 550 oC. A co-doped ceria-carbonate was also developed to improve the ionic conductivity, morphology, and performance of the electrolyte. In the second part of this thesis (Papers 7-9), composite electrodes that contained less or no nickel (Ni) were developed for a low-temperature SOFC. All of the elements were highly homogenously distributed in the composite electrode, which resulted in high catalytic activity and good ASOFC performance. The substitution of Ni by Zn in these electrodes could reduce their cost by a factor of approximately 25. In the third part of this thesis (Papers 10), an advanced multi-fuelled solid-oxide fuel cell (ASOFC) with functional nanocomposites (electrolytes and electrodes) was developed. Several different types of fuel, such as gaseous (hydrogen and biogas) and liquid fuels (bio-ethanol and bio-methanol), were tested. Maximum power densities of 1000, 300, 600, and 550 mW/cm2 were achieved with hydrogen, bio-gas, bio-methanol, and bio-ethanol, respectively, in the ASOFC. Electrical and total efficiencies of 54% and 80%, respectively, were achieved when the single cell was used with hydrogen. The fourth part of this thesis (Papers 11) concerns the design of a 5 kW ASOFC system based on the demonstrated advanced SOFC technology. A polygeneration system based on a low-temperature planar SOFC was then designed and simulated. The efficiency of the overall system was approximately 80%. The fifth part of this thesis (Paper 12) describes a single-layer multi-fuelled electrolyte-free fuel cell that is a revolutionary innovation in renewable-energy sources. Conventional fuel cells generate electricity by ion transport through the electrolyte. However, this new device works without an electrolyte, and all of the processes occur at particle surfaces in the material. Based on a theoretical calculation, an additional 18% enhancement of the fuel cell’s efficiency will be achieved using this new technology compared to the conventional technologies. Our developed ASOFC systems with functional nanocomposites offer significant advantages in reducing the operational and capital costs for the production of power and heat by using different fuels based on the fuel-cell technology. ASOFC systems can be used for polygeneration with renewable fuels (i.e., biomass fuels) at high efficiency as a sustainable solution to energy generation in our society. The results have been achieved for this thesis work has demonstrated an advanced fuel cell technology. / <p>QC 20111213</p>

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / Molecular precursor derived ceramics (also known as polymer-derived ceramics or PDCs) are high temperature glasses that have been studied for applications involving operation at elevated temperatures. Prepared from controlled thermal degradation of liquid-phase organosilicon precursors, these ceramics offer remarkable engineering properties such as resistance to crystallization up to 1400 °C, semiconductor behavior at high temperatures and intense photoluminescence. These properties are a direct result of their covalent bonded amorphous network and free (-sp2) carbon along with mixed Si/B/C/N/O bonds, which otherwise can not be obtained through conventional ceramic processing techniques. This thesis demonstrates synthesis of a unique core/shell type nanowire structure involving either siliconboroncarbonitride (SiBCN) or siliconoxycarbide (SiOC) as the shell with carbon nanotube (CNT) acting as the core. This was made possible by liquid phase functionalization of CNT surfaces with respective polymeric precursor (e.g., home-made boron-modified polyureamethylvinylsilazane for SiBCN/CNT and commercially obtained polysiloxane for SiOC/CNT), followed by controlled pyrolysis in inert conditions. This unique architecture has several benefits such as high temperature oxidation resistance (provided by the ceramic shell), improved electrical conductivity and mechanical toughness (attributed to the CNT core) that allowed us to explore its use in energy conversion and storage devices. The first application involved use of SiBCN/CNT composite as a high temperature radiation absorbant material for laser thermal calorimeter. SiBCN/CNT spray coatings on copper substrate were exposed to high energy laser beams (continuous wave at 10.6 μm, 2.5 kW CO2 laser, 10 seconds) and resulting change in its microstructure was studied ex-situ. With the aid of multiple techniques we ascertained the thermal damage resistance to be 15 kW/cm2 with optical absorbance exceeding 97 %. This represents one order of magnitude improvement over bare CNTs (1.4 kW/cm2) coatings and two orders of magnitude over the conventional carbon paint (0.1 kW/cm2) currently in use. The second application involved use of SiBCN/CNT and SiOC/CNT composite coatings as energy storage (anode) material in a Li-ion rechargeable battery. Anode coatings (~1mg/cm2) prepared using SiBCN/CNT synthesized at 1100 °C exhibited high reversible (useable) capacity of 412 mAh/g even after 30 cycles. Further improvement in reversible capacity was obtained for SiOC/CNT coatings with 686 mAh/g at 40 cycles and approximately 99.6 % cyclic efficiency. Further, post cycling imaging of dissembled cells indicated good mechanical stability of these anodes and formation of a stable passivating layer necessary for long term cycling of the cell. This improved performance was collectively attributed to the amorphous ceramic shell that offered Li storage sites and the CNT core that provided the required mechanical strength against volume changes associated with repeated Li-cycling. This novel approach for synthesis of PDC nanocomposites and its application based testing offers a starting point to carry out further research with a variety of PDC chemistries at both fundamental and applied levels.

Ultra high molecular weight polyethylene (UHMWPE) is a polymer commonly used in various applications, particularly in hip joint replacements. Despite its good performance, it is susceptible to oxidation degradation, which can be mitigated with the addition of vitamin E, and to excessive wear against metal countersurfaces, which can potentially be improved with the addition of nanoparticles. In this work, sixteen newly developed UHMWPE nanocomposites with different nanofillers (multi-walled carbon nanotubes, graphene oxide and nanodiamonds), blended with and without vitamin E, and both irradiation crosslinked and non-crosslinked were studied. Thermomechanical characterisation (dynamic mechanical analysis and thermogravimetric analysis) and tribological pin-on-disc testing showed that both nanofillers and the addition of vitamin E ensured improved the performance of the nanocomposites compared to the virgin UHMWPE. Vitamin E improved the oxidative and thermal stability of UHMWPE, decreased the wear and increased the coefficient of friction. The nanoparticle reinforcements contributed to improved thermal stability to some degree and decreased the wear. Crosslinking was also shown to result in improved thermomechanical performance, although it appears that the addition of vitamin E inhibits the crosslinking process.

No presente trabalho foram realizadas a síntese e caracterizações estruturais, ópticas e espectroscópicas de materiais nanocompósitos na forma de guias de onda planares e pós de (100-x)SiO2-xNb2O5 dopados com íons lantanídeos pelo método sol-gel, para aplicação em Fotônica. Foi observada separação de fase controlada e cristalização, com distribuição e tamanho de partículas, bem como a fase cristalina de Nb2O5 formada, dependentes da composição (%Nb) e temperatura de tratamento térmico. Caracterizações estruturais revelaram a formação de duas fases cristalinas de Nb2O5, ortorrômbica (fase T) e monoclínica (fase M), com distribuição de tamanhos de nanopartículas da ordem de 7 a 30 nm. Essas duas fases cristalinas apresentaram-se na forma de nanocristais dispersos em uma matriz amorfa, formando sistemas nanocompósitos transparentes. A formação dessas diferentes fases cristalinas influenciou diretamente nas propriedades luminescentes dos materiais que apresentaram uma intensa emissão na região do Infravermelho próximo (com máximo de emissão em 1530 nm) sob excitação em 980 nm, com valores de largura de banda variando de 48 a 84 nm. A dependência dos espectros de emissão (largura inomogênea e componentes Stark), valores de largura de banda e tempos de vida do estado excitado 4I13/2 em relação às diferentes fases cristalinas de Nb2O5 formadas, permitiram a conclusão de que os íons Er3+ estão ocupando preferencialmente ambientes de baixa energia de fônon à base de Nb2O5. Estudos espectroscópicos dos nanocompósitos dopados com íons Eu3+ possibilitaram maiores evidências da ocupação dos íons lantanídeos em diferentes sítios de simetria no Nb2O5. A co-dopagem dos nanocompósitos com íons Er3+ e Yb3+ permitiu uma intensificação na emissão na região do Infravermelho próximo, correspondente à transição 4I13/24I15/2, decorrente da maior seção de choque dos íons Yb3+ em 980 nm e um processo eficiente de transferência de energia entre os íons Yb3+ e os íons Er3+ distribuídos nas matrizes estudadas. Essa transferência de energia eficiente intensificou também as emissões tanto na região do verde como do vermelho, decorrente de processos de conversão ascendente. Um estudo detalhado da dinâmica do processo de conversão ascendente foi realizado para os pós e guias de onda. No presente trabalho também foram obtidos guias de onda planares (100-x)SiO2-xNb2O5 dopados com íons Er3+ e co-dopados com íons Er3+ e Yb3+, com excelentes propriedades estruturais, morfológicas, ópticas e espectroscópicas para aplicação como amplificadores ópticos, tais como, superfícies livres de trinca, distribuição uniforme dos valores de índice de refração através da superfície e em função da profundidade, baixa rugosidade, alta porcentagem de confinamento da luz, uma excelente transparência das matrizes no visível e infravermelho próximo, bem como emissão em região usada para transmissão de sinal óptico em telecomunicações. Os guias de onda apresentaram intensas emissões tanto na região do Infravermelho próximo quanto no visível, decorrente de processos de conversão ascendente, apresentando ainda uma interessante variação das cores verde e vermelha, dependendo-se da potência de excitação utilizada e da proporção em mol (%) de Nb adicionada. Após a constatação dos excelentes resultados obtidos nos guias dopados com íons Er3+ e Yb3+, foram preparados nanocompósitos co-dopados com Tm3+ e Yb3+ na forma de pós e guias de onda planares, que apresentaram uma largura de banda de 120 nm na região do infravermelho próximo (com máximo de emissão em 1650 nm) e emissões na região do azul (475 nm) e no infravermelho (785 nm), decorrentes de processos de conversão ascendente. Por fim, foi realizada inscrição bem sucedida de canais nos guias de onda planares utilizando um laser de Ti:safira de femtosegundos. Em suma, os materiais nanocompósitos (100-x)SiO2-xNb2O5 apresentam um grande potencial de aplicação, especialmente em fotônica como amplificadores ópticos (EDWA) em telecomunicações, em circuitos fotônicos, lasers na região do visível (explorando conversão ascendente de energia), marcadores ópticos, dependendo fundamentalmente dos íons lantanídeos utilizados na dopagem. No caso especifico de amplificadores ópticos para telecomunicações, pôde-se concluir que as propriedades mais adequadas foram observadas nos materiais nanocompósitos (100-x)SiO2-xNb2O5 guias de onda planares contendo as proporções 80Si-20Nb e 70Si-30Nb tratados termicamente a 900oC co-dopados com íons Er3+/Yb3+ e Tm3+/Yb3+ / In the present work are reported the synthesis and structural, optical and spectroscopic characterizations of lanthanide doped (100-x)SiO2-xNb2O5 nanocomposites materials as planar waveguides and powders prepared by the sol gel method for photonic applications. The controlled phase separation and crystallization observed, as well as the particle size and distribution depended on the composition (%Nb) and the annealing temperature. The structural characterization revealed the formation of two Nb2O5 crystalline phases, orthorhombic (T-phase) and monoclinic (M-phase), with nanoparticle size distribution from 7 to 30 nm. The two crystalline phases were observed as nanocrystals dispersed in an amorphous matrix, constituting transparent nanocomposite systems. The formation of the different crystalline phases affected directly the materials luminescent properties which showed an intense near infrared emission (with maximum peak at 1530 nm) under 980 nm excitation, with bandwidth values from 48 to 84 nm. The dependence of emission spectra (inhomogeneous broadening and Stark components), the bandwidth values and the 4I13/2 excited state lifetimes dependence upon the different Nb2O5 crystalline phases formation, led to the Er3+ ions preferential occupation on low phonon energy, Nb2O5-rich environment. Spectroscopic studies with Eu3+-doped nanocomposites provided additional evidences of the lanthanide occupation of different symmetry sites on the Nb2O5-rich environment. The nanocomposites co-doping with Er3+ and Yb3+ ions allowed intensification on the near infrared emission, corresponding to the 4I13/24I15/2 transition, which resulted from the higher cross section of Yb3+ ions at 980 nm and an efficient energy transfer process between the Yb3+ ions and the Er3+ ions. This efficient energy transfer process also intensified the emissions both in green and red range, deriving from upconversion processes. A detailed study on the upconversion processes was made for nanocomposites and waveguides. In the present work, Er3+-doped and Er3+ and Yb3+ co-doped planar waveguides (100-x)SiO2-xNb2O5 with excellent optical, morphological and spectroscopic properties were also obtained, such as, crack free surfaces, a uniform refractive index profile across the surface and the thickness, low rugosity, high light confinement, low optical losses, and an excellent infrared and visible range matrix transparency, as well as emission used on optical telecommunication transmission. The waveguides showed emission both on near infrared and visible range, resulting from upconversion processes, showing an interesting color tuning phenomena in the green and red ranges, dependent on the excitation power and Nb content (mol%). After the excellent results verified with Er3+ and Yb3+, Tm3+ and Yb3+ co-doped nanocomposites and planar waveguides were prepared, which showed a bandwidth of 120 nm in the infrared range (with maximum peak at 1650 nm) and blue (475 nm) and near infrared (785 nm) emissions deriving from upconversion processes. Finally, channel writing using a femtosecond Ti:sapphire laser was successfully performed on the planar waveguides. Therefore, the (100-x)SiO2-xNb2O5 nanocomposite materials have shown great potential application, especially in photonic, such as, optical amplifiers (EDWA), photonic circuits, visible range lasers (exploring upconversion processes), and optical markers, depending on the lanthanide doping. In the specific case of optical amplifiers for telecommunication application, it could be concluded that the most adequate properties were observed on the ions Er3+/Yb3+ and Tm3+/Yb3+ co-doped (100-x)SiO2-xNb2O5 nanocomposites at 80Si-20Nb and 70Si-30Nb ratios, annealed at 900°C

Made available in DSpace on 2017-07-21T20:42:35Z (GMT). No. of bitstreams: 1 ALEXEYOSA.pdf: 5421732 bytes, checksum: d315c8a952abc240783ef27ca2d03d74 (MD5) Previous issue date: 2011-03-30 / The ceramic materials have great potential for structural applications because of their have excellent mechanical properties, eg, high hardness, high mechanical strength and resistance to aggressive media. However their low toughness and bending resistance, limiting their range of applications and open interest for researchers for better mechanical properties. Inclusions of nanometric particles in ceramic matrix, called nanocomposites, and the control of ceramic processing, by controlling grain size and densification, can be used for produce ceramic products with higher strength and toughness. One method to control the microstructure that has been studied is the two-step sintering, which has been successfully applied for the densification of nanometric and ultra fine ceramic powders without grain growth. In this work, the two-step sintering of nanocomposite of alumina with 5% volume nanoparticles zirconia was studied. Two proposals in two-step of sintering were studied, of which one consisted to heat the nanocomposite to a high temperature and then rapid cool down to a lower temperature sintering, and on the other proposal was made a step at a temperature below the initiation of densification, followed by heating to the maximum densification rate temperature. The sintering temperature for steps were chosen from constant-heating-rate and conventional sintering. The results showed that the two proposals were efficient to control the grain growth and densification in alumina-zirconia nanocomposites, and, with the sintering in twosteps, it was possible to reduce the grain size up to 70% of the grain size of nanocomposite sintered conventionally. / Os materiais cerâmicos apresentam grande potencial para aplicações estruturais, pois possuem excelentes propriedades mecânicas como, por exemplo, alta dureza, alta resistência mecânica à compressão e inércia química. Porém, a sua baixa tenacidade à fratura e baixa resistência à flexão, limitam sua gama de aplicações e gera interesse para estudos em busca de melhores propriedades mecânicas. A inclusão de partículas nanométricas numa matriz cerâmica, que são os chamados nanocompósitos, e o controle do processamento cerâmico, através do controle do tamanho de grão e densificação, podem auxiliar na obtenção de produtos cerâmicos de maior resistência mecânica e tenacidade. Um método de controle da microestrutura que vem sendo estudado é a sinterização em duasetapas, a qual vem sendo aplicada com sucesso para a densificação de pós cerâmicos nanométricos e ultra finos sem crescimento de grãos. Nesse trabalho, foi estudada a sinterização em duas-etapas de nanocompósitos de alumina com 5% em volume de partículas de zircônia nanométrica. Duas propostas de sinterização em duas etapas foram estudadas. Uma consistiu em aquecer o nanocompósito rapidamente a uma alta temperatura e em seguida resfria-lo ao patamar de sinterização; na outra proposta foi feito um patamar de queima numa temperatura abaixo do início do processo de densificação, seguido do aquecimento do nanocompósito até a temperatura de máxima taxa de densificação. As temperaturas para as etapas de sinterização foram escolhidas a partir da sinterização a taxa de aquecimento constante e da sinterização convencional. Os resultados mostraram que a duas propostas estudadas foram eficientes para controlar o crescimento de grãos e a densificação nos nanocompósitos alumina-zircônia, sendo que, com as sinterizações em duas-etapas, foi possível reduzir o tamanho de grão em até 70% do valor do tamanho de grão do nanocompósito sinterizado convencionalmente.

Made available in DSpace on 2017-07-21T20:42:41Z (GMT). No. of bitstreams: 1 Carlos Alberto Silva de LIma.pdf: 3634642 bytes, checksum: 8583be31697ada29693d8e5c36b484b5 (MD5) Previous issue date: 2014-01-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nowadays, polymeric nanocomposites are well established in terms of their importance. However, there is still a long way to be investigated, since its methods for obtaining, processing and characterization, as there are many variables to be changed to optimize the responses. There is need in understanding the behavior of such materials when subjected to degradative processes, such as nanoparticles influence responses, and maximize or minimize the occurrence of these effects. In this work the behavior of neat polypropylene, polypropylene with organically modified montmorillonite, with and without the presence of a coupling agent (polypropylene-graft-maleic anhydride) when subjected to reprocessing in a twin screw extruder. It was investigated the effect of molar mass of the polypropylene matrix. For this purpose, three types of polypropylenes (high, middle and low molar mass) were processed one, or up to five times. Compositions were prepared neat or with 5% by weight montmorillonite, with and without the presence of coupling agent in the ratio 3:1. The properties is going to be investigated by the techniques of X-ray diffraction, scanning electron microscopy, rheology, infrared spectroscopy by Fourier transform, thermogravimetry, differential scanning calorimetry, tests of Izod impact and colorimetry. First of all, it was proved the presence of iron in the nanoclay, which affects the color of the sample due to oxidation of the iron cation. It was found that the samples became darker, redder, and more yellow because of the presence of the nanoparticles, iron and degradation. These results agreed with the changes observed by infrared spectroscopy, which generally showed low occurrence of the degradation rates of carbonyl and unsaturation, concluding that the greatest degradation occurred by the reduction in molar mass due to the β -scission process, confirming the reduction the values of complex viscosity. It was possible to monitor via rheology by different modes narrowing of the distribution of molar masses and the reduction in molar mass. Along with this information the values and behaviors of the slopes of the curves allowed us to infer the possible microstructure formed state of dispersion and distribution. XRD results indicated the formation of only a sample with an increase in the interlayer spacing, while the rheological results suggest that there is more than one sample with intercalated structure. Thus, there was a little difficulty using just one technique among them to state what actually occurred, concluding that it is essential to perform the technique of transmission electron microscopy. Addition of MMT and MMT / PP - g-MA afforded more thermally stable samples compared to pure PP, this was attributed to the effect of labyrinth. Finally, the impact resistance by the addition of montmorillonite was greater, it means that the clay did not act as stress concentrators, but as energy absorbers and hindered propagation of microcracks. But with PP-g-MA had a fracture behavior intermediate between PP and PP/MMT, with intermediate values of impact resistance. The fracture analysis was possible via SEM and allows to observe the morphology of the different samples. / Nanocompósitos poliméricos são materiais bem estabelecidos do ponto de vista da sua importância, mas ainda há um longo caminho a ser investigado, desde seus métodos de obtenção, processamento e caracterização, pois existem muitas variáveis a serem alteradas para otimização das respostas apresentadas por esses materiais. Há também uma necessidade em compreender o comportamento de tais materiais quando submetidos a processos degradativos, como as nanocargas influenciam o comportamento, bem como maximizar ou minimizar determinados desempenhos. Neste trabalho, foi estudado o comportamento das composições de polipropileno puro, polipropileno com montmorilonita, com e sem agente compatibilizante (polipropileno graftizado com anidrido maleico) quando submetidos a múltiplas extrusões em extrusora dupla rosca; investigando ainda o efeito da massa molar da matriz polimérica. Para tanto, três tipos de polipropilenos com diferentes massas molares (baixa, média e alta) foram processados uma, ou em até cinco vezes. As composições elaboradas foram puras ou com 5% de montmorilonita em peso, com e sem a presença de agente compatibilizante na razão 3:1. Em seguida, as amostras foram investigadas por meio das técnicas de difração de raios X, microscopia eletrônica de varredura, reometria de placas paralelas, espectroscopia de infravermelho por transformada de Fourier, termogravimetria, ensaios de impacto Izod com entalhe e colorimetria. Primeiramente comprovou-se a presença de ferro na nanoargila, o qual afetou a coloração das amostras, devido à oxidação do cátion de ferro. Verificou-se que as amostras tornaram-se mais escuras, mais vermelhas e mais amarelas, por causa da presença das nanopartículas, do ferro e da degradação. Estes resultados concordaram com as variações observadas por espectroscopia de infravermelho, que em geral revelou pouca ocorrência de degradação pelos índices de carbonila e insaturação, concluindo que a maior degradação ocorreu pela redução na massa molar, devido ao processo de cisão-β, comprovado pela redução nos valores de viscosidade complexa. Foi possível via reologia acompanhar por diferentes modos o estreitamento da distribuição de massas molares e a redução na massa molar. Juntamente com essas informações os valores das inclinações e comportamentos das curvas permitiram inferir sobre a possível microestrutura formada, estado de dispersão e distribuição. Os resultados de DRX indicaram a formação de apenas uma amostra com aumento no espaçamento interlamelar, enquanto que os resultados reológicos apresentaram indícios de haver mais de uma amostra com estrutura intercalada. Deste modo, ocorreu uma pequena dificuldade em utilizar apenas uma técnica entre elas para afirmar o que de fato ocorreu, concluindo que é imprescindível a realização da técnica de microscopia eletrônica de transmissão. A adição de MMT ou MMT/PP-g-AM permitiu obter amostras termicamente mais estáveis em relação ao PP puro, isso se atribuiu ao efeito de labirinto. Finalmente, a resistência ao impacto com a adição de montmorilonita foi maior, ou seja, não atuaram como concentradores de tensão, mas auxiliaram na absorção de energia e dificultando a propagação de microfissuras. Já com PP-g-AM ocorreu um comportamento de fratura intermediário entre PP e PP/MMT, apresentando valores intermediários de resistência ao impacto. A análise da fratura foi possível via MEV, além de permitir observar a morfologia das diferentes amostras.

Made available in DSpace on 2017-07-21T20:42:43Z (GMT). No. of bitstreams: 1 Nayana Reggiani Peres.pdf: 6432613 bytes, checksum: 9c46ae14abc57b5978dfcd678165787b (MD5) Previous issue date: 2013-12-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The development of new materials takes into account factors such as need and sustentabilidade.Novas trends in modifying properties of polymeric materials have been observed due to increasing concern about the environment and the constant search by the use of fillers in polymeric materials. Among them, there are the lignocellulosic fibers, which in addition to reinforcing the polymer, are biodegradable low cost, low density and have no abrasive characteristic. The agro-industrial residues are a great source of raw materials, especially in the case of soybean hulls, which is a waste in abundance in our region ( Paraná ). However, it is not always possible to obtain the best features with the Shell Soy Gross ( CSB ) . Thus , in a first step we sought to obtain microfibrillated pulp from the CSB . Conducted to obtain microfibrillated pulp by grinding the colloid mill, proven by analysis of Zeta Potential . And then be obtained twin screw extruder via nanocomposites with the incorporation of 1, 3 and 5% of microfibrillated cellulose. Finally, the nanocomposites were characterized by analysis of tensile test scanning electron microscopy, atomic force microscopy, X-ray diffraction, rheological analysis, thermogravimetry, and mechanical impact tests. Through the zeta potential was proved that the dimensions were namometricas the SEM and AFM demonstrated good adhesion of the microfibrillated cellulose, XRD confirmed the crystallinity. According to rheological analysis showed an increase in molecular weight , with the incorporation of cellulose microfibrillated there was a slight increase in impact strength, and an increase in the stiffness of nanocomposites. / O desenvolvimento de novos materiais leva em conta fatores como necessidade e sustentabilidade. Novas tendências na modificação de propriedades dos materiais poliméricos têm sido observadas devido à crescente preocupação com o meio ambiente e a constante busca pela utilização de cargas em materiais poliméricos. Entre elas, destacam-se as fibras lignocelulósicas, que além de reforçar o polímero, são biodegradáveis, de baixo custo, baixa massa específica e não possuem característica abrasiva. Os resíduos agroindustriais são uma ótima fonte de matériaprima, principalmente no caso da casca de soja, que é um resíduo em abundância em nossa região (Paraná). No entanto, nem sempre é possível obter as melhores características com a Casca de Soja Bruta (CSB). Deste modo, em uma primeira etapa buscou-se a obtenção de celulose microfibrilada, a partir da CSB. Realizou-se a obtenção da celulose microfibrilada através da moagem no moinho coloidal, comprovada pela análise de Potencial Zeta. E em seguida, obtiveram-se via extrusora dupla rosca os nanocompósitos com a incorporação de 1, 3 e 5% de celulose microfibrilada. Finalmente, os nanocompósitos foram caracterizados através das análises de microscopia eletrônica de varredura, microscopia de força atômica, difração de raios X, analise reológica, termogravimetria, ensaios mecânicos de impacto e ensaios mecânicos de tração. Através do potencial zeta provou-se que as dimensões são namometricas, o MEV e MFA comprovou a boa adesão da celulose microfibrilada, o DRX comprovou a cristalinidade. Segundo, a analise reológica houve aumento da massa molar. Com a incorporação da celulose microfibrilada houve um ligeiro aumento na resistência ao impacto, e um aumento na rigidez dos nanocompositos,

[pt] No intuito de desenvolver novas abordagens para a redução do coeficiente de expansão térmica (CTE) em PEAD, um polímero termoplástico largamente usado em geomembranas onde seu alto CTE contribui para a redução de seu desempenho, titanatos em camadas na forma de nanofolhas foram testados pela primeira vez como os aditivos com esta função. Nanofolhas de titanatos foram sintetizadas a partir de tratamento hidrotérmico alcalino de areias ilmeníticas e foram funcionalizadas com viniltrimetoxisilano (VTMS), visando melhorar a compatibilidade com a matriz PEAD, ou organofilizadas com cloreto de dimetildioctadecilamonio (2C18), para promover a esfoliação/intercalação destas nanocargas no polímero. Posteriormente, estas nanocargas modificadas foram caracterizadas por termogravimetria, espectroscopia de infravermelho, análise de área superficial, análise de CHN, difração de raios-X e microscopia eletrônica de transmissão. Os nanocompósitos foram fabricados por microextrusão e microinjeção com porcentagens mássicas de carga de 0,5 por cento a 10 por cento, em séries denominadas BRANCA, VTMS, VTMS reativa e 2C18. Finalmente os nanocompósitos foram caracterizados através de ensaios de tração, termogravimetria, dilatometria e microscopia eletrônica de transmissão. Os resultados obtidos na caracterização das nanofolhas permitiram verificar a incorporação do VTMS na superfície por meio de ligações primárias. A modificação com 2C18 foi realizada pela primeira vez neste tipo de material, como foi conferido por difração de raios-X pelo incremento no espaçamento da distância interlamelar. As séries BRANCA e VTMS apresentaram um incremento no módulo de elasticidade e na ductilidade, porém a tensão no escoamento incrementou apenas para o compósito com 0,5 por cento da série BRANCA e para o compósito com 2 por cento da série VTMS. As séries VTMS reativa e 2C18 mostraram redução no módulo de elasticidade e ductilidade. A tensão no escoamento aumentou para o compósito da série VTMS Reativa 0,5 por cento, diminuiu para os compósitos 0,5 e 2 por cento da série 2C18 e permaneceu similar ao PEAD para os outros compósitos destas séries. O compósito que apresentou melhores propriedades foi o VTMS 2 por cento com um aumento em torno de 14 por cento no módulo de elasticidade, de aproximadamente 3 por cento na tensão no escoamento e de aproximadamente 16 por cento na ductilidade. A adição das nanofolhas não alterou significativamente as propriedades de estabilidade térmica da matriz e apresentou decréscimo do CET para a série VTMS 2 por cento. O grau de cristalinidade variou apresentando aumento máximo de aproximadamente 14 por cento na série VTMS 0,5 por cento e redução máxima de aproximadamente 20 por cento na série 2C18 2 por cento. / [en] In order to develop new approaches to the reduction of the coefficient of thermal expansion (CTE) in HDPE, a thermoplastic polymer widely used in geomembranes where its high CTE contributes to the reduction of his performance, in the form of layered titanates nanosheets were tested for the first time as additives with this function. Titanates nanosheets were synthesized from hydrothermal treatment of alkaline ilmenitic sands and were funcionalizated with vinyl trimethoxy silane (VTMS), to improve compatibility with the HDPE matrix, or organofilizated with dimethyl dioctadecyl amonio chloride (2C18), to promote the exfoliation/intercalation of these nanofiller in the polymer. Subsequently, these modified nanofiller were characterized by infrared spectroscopy, thermogravimetry, surface area analysis, CHN analysis, x-ray diffraction and transmission electron microscopy. The nanocomposites were manufactured by microextrusion and microinjection with mass percentages of 0,5 percent to charge 10 percent, in weigth, denominated series VTMS, reactive VTMS and 2C18. Finally the nanocomposites were characterized by tensile, thermogravimetry, dilatometry and transmission electron microscopy. The results obtained in the characterization of nanosheets allowed to check the incorporation of VTMS on the surface by means of primary links. The modifications with 2C18 was performed for the first time this type of material, as was conferred by x-ray diffraction by the increase in the distance interlamelar spacing. The series BRANCA and VTMS presented an increase in modulus of elasticity and ductility, however the voltage in outlets increased only to composite with 0,5 percent BRANCA and series for the composite with 2 percent VTMS series. VTMS series reactive and 2C18 showed a reduction in ductility and modulus. The tension in the flow increased to the series VTMS Reactive composite 0,5 percent, decreased to the composites 2 and 0,5 percent 2C18 series and remained similar to HDPE for the other composites of these series. Composite who presented best properties was the VTMS 2 percent with an increase around 14 percent in modulus, approximately 3 percent on voltage in outlets and approximately 16 percent on ductility. The addition of nanofolhas did not alter significantly the thermal stability properties of the array and fell of the CET for the series VTMS 2 percent. The degree of crystallinity ranged showing maximum increase of approximately 14 percent on 0,5 percent VTMS series and maximum reduction of approximately 20 percent in 2 percent 2C18 series.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho foram sintetizados nanocompósitos à base de poliuretanos em dispersão aquosa (NWPUs) e argilas hidrofílicas do tipo montimorilonita (MMT) de natureza sódica e cálcica. Os monômeros empregados na síntese foram: poli(glicol propilênico) (PPG); copolímero em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), com teor de 7% de EG; ácido dimetilolpropiônico (DMPA) e diisocianato de isoforona (IPDI). Os NWPUs tiveram as argilas, previamente deslaminadas em água e incorporadas à formulação no momento da dispersão do prepolímero. Dispersões aquosas (WPUs), sem a presença de argila, foram sintetizadas como base, nas quais foram variadas a razão NCO/OH e a proporção de copolímero em relação ao PPG. Nas formulações NWPUs, foram variados também o teor de argila em relação à massa de prepolímero e o tipo de argila sódica e cálcica. As dispersões foram avaliadas, quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade. Os filmes vazados a partir das dispersões foram caracterizados por espectrometria na região do infravermelho (FTIR), difração de raios-x (XRD) e microscopia eletrônica de varredura (SEM). A resistência térmica dos filmes foi determinada por termogravimetria (TG) e a resistência mecânica dos filmes foi avaliada por ensaios mecânicos em dinamômetro. O grau de absorção de água dos filmes também foi determinado. A formação de nanocompósitos à base de água foi confirmada pela ausência do pico de XRD, característico das argilas empregadas na maioria dos filmes analisados. As micrografias obtidas por SEM confirmam uma dispersão homogênea das argilas na matriz poliuretânica. Os filmes à base de nanocompósitos (NWPUs) apresentaram propriedades superiores às apresentadas por aqueles obtidos a partir das dispersões sem argilas (WPUs). Os revestimentos formados a partir da aplicação das dispersões aderiram à maioria dos substratos testados (metal, vidro, madeira e papel) formando superfícies homogêneas / In this work nanocomposites (NWPUs) based on waterborne polyurethanes and hydrophilic montimorillonite clays (MMT) were synthesized. Polypropyleneglycol (PPG), poly(ethylene glycol-b-propylene glycol) (EG-b-PG) containing 7% of ethylene glycol (EG), dimethylolpropionic acid (DMPA) and isophorone diisocyanate (IPDI) were employed in polyurethane synthesis. The NWPUs were prepared with calys previously exfoliated in water, and were added at the moment of dispersion. Different formulations were obtained from WPUs, without clays, by varying the NCO/OH ratio, and the proportions of PPG and EG-b-PG. For NWPUs formation was varied the content of clays with different cations (Na+ and Ca+2). The properties of the dispersions were evaluated in terms of their solid content, particle size and viscosity. The cast films obtained were characterized by infrared spectrometry (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM). The thermal stability of the films was evaluated by thermogravimetry (TG) and mechanical properties in a dynamometry. X-ray diffraction and scanning electron microscopy examinations were determined confirming the nanocomposite formation. NWPUs films showed improved properties in comparison with WPUs Coatings obtained by the application of the dispersions in substrates as wood, metals, paper and glass were homogeneous and showed good adherence