[pt] Os compósitos de matriz polimérica reforçados com fibras se destacam em diversas aplicações industriais, devido as suas características, como baixo custo, baixa densidade e boa resistência mecânica. Porém, o ambiente ao qual o compósito será exposto e a variação de temperatura a qual o compósito é submetido, irão exercer influência no comportamento do material. Estudos sobre as características microestruturais e o comportamento mecânico de compósitos poliméricos com fibras de luffa (Luffa cylindrica) e híbridos (fibra de vidro/luffa) em ambientes úmidos são recentes e, para os compósitos de luffae, principalmente, para os híbridos poucas pesquisas foram realizadas. Assim, com a finalidade de obter materiais com diferentes propriedades e comportamentos, foram fabricados e estudados compósitos com matriz epóxi reforçada com fibras de vidro, fibra de luffae híbridos vidro-luffa. O ensaio de envelhecimento foi realizado em amostras submersas em água destilada em duas temperaturas de envelhecimento (25°C e 60°C). O tempo total de envelhecimento foi de 4 meses (120 dias). Para a avaliação da degradação mecânica foram realizados ensaios não-destrutivos (termografia e ensaio sonoro) e ensaios destrutivos (impacto). O processo de absorção de água nos compósitos também foi avaliado. O presente estudo tem como relevância o preenchimento de lacunas de conhecimento do comportamento de híbridos vidro/luffa, notadamente em ambiente úmido com variação de temperatura. Como resultado, observou-se que o ensaio de envelhecimento indicou que os valores de absorção máxima dos compósitos de fibra de vidro, luffa e híbrido, assim como, seus respectivos coeficientes de difusão mostraram-se condizentes com os valores encontrados na literatura. Os compósitos de fibra de luffa foram os que apresentaram maior valor de absorção. Já os resultados do ensaio de impacto, permitiram identificar os modos de falha e avaliar o efeito entre as temperaturas de envelhecimento. Os compósitos de fibra de vidro tiveram pouca variação da resistência ao impacto antes e após o envelhecimento a 25ºC e a 60ºC. Já os compósitos de fibra de luffa e híbrido apresentaram uma variação considerável antes e após o envelhecimento a 25ºC e 60ºC. O ensaio sonoro permitiu avaliar o efeito do envelhecimento sobre o módulo de elasticidade e o fator de perda. O resultado do ensaio sonoro dos compósitos híbridos mostrou que o módulo de elasticidade e o fator de perda não tiveram diferenças significativas entre os tempos de envelhecimento indicando que a hibridização atuou de modo eficiente para proteger as fibras de luffa. O ensaio de termografia foi usado como uma nova abordagem para avaliar a condutividade térmica dos compósitos. Por fim, conclui-se que a hibridização foi eficiente, pois os compósitos híbridos apresentaram características em relação a absorção, resistência ao impacto e condutividade térmica, intermediárias aos compósitos de fibra de vidro e fibra de luffa e, principalmente a hibridização reduziu de modo significativo a degradação do compósito de luffa quando exposto a ambiente úmidos, além de proporcionar uma alternativa de projeto mais ambientalmente amigável. / [en] Polymer matrix composites reinforced with fibers stand out in various industrial applications due to their characteristics such as low cost, low density, and good mechanical strength. However, the environment to which the composite will be exposed and the temperature variation to which the composite is subjected will influence the material s behavior. Studies on the microstructural characteristics and mechanical behavior of polymer composites with Luffa cylindrica fibers and hybrid fibers (glass/luffa) in humid environments are recent, and few studies have been carried out for the Luffa and, especially, the hybrid composites. Thus, in order to obtain materials with different properties and behaviors, composites were fabricated and studied with an epoxy matrix reinforced with glass fibers, Luffa fibers, and glass-Luffa hybrids. The aging test was carried out on samples submerged in distilled water at two aging temperatures (25°C and 60°C). The total aging time was 4 months (120 days). Non-destructive tests (thermography and sound test) and destructive tests (impact) were performed to evaluate mechanical degradation. The water absorption process in the composites was also evaluated. The present study is relevant to filling knowledge gaps in the behavior of glass/luffa hybrids, especially in a humid environment with temperature variation. As a result, it was observed that the aging test indicated that the maximum absorption values of the glass, Luffa, and hybrid fiber composites, as well as their respective diffusion coefficients, were consistent with the values found in the literature. The Luffa fiber composites had the highest absorption value. The results of the impact test allowed for the identification of failure modes and the evaluation of the effect between aging temperatures. The glass fiber composites had little variation in impact strength before and after aging at 25°C and 60°C. The Luffa and hybrid fiber composites showed considerable variation before and after aging at 25°C and 60°C. The sound test allowed for the evaluation of the aging effect on the modulus of elasticity and loss factor. The sound test results for the hybrid composites showed that the modulus of elasticity and loss factor had no significant differences between aging times, indicating that hybridization efficiently protected the luffafibers. The thermography test was used as a new approach to evaluate the thermal conductivity of the composites. Finally, it is concluded that hybridization was efficient because the hybrid composites had characteristics regarding absorption, impact resistance, and thermal conductivity that were intermediate between glass and Luffa fiber composites, and mainly hybridization significantly reduced the degradation of the Luffa composite when exposed to humid environments, as well as providing a more environmentally friendly design alternative.

No / An extensive study of the fibre orientation structures developed in a transverse ribbed plate during injection moulding, and the use of these structures to investigate the effect of local fibre orientation state on crack initiation resistance, is reported. The fibre orientation results for the ribbed plate, measured using large area image analysis system developed at Leeds University, showed that after an initial settling down period, the central core region, where the fibres are aligned perpendicular to the flow direction, decreased in size monotonically, with an associated monotonic increase in the outer shell regions, where the fibres are aligned preferentially along the injection direction. Interestingly, the level of orientation in the two regions remained almost constant: only the proportions of the two regions were found to change with flow length. Across the plate, close to the gate, the central core region was found to have a lens-like shape, while at the other end of the plate the core was thinner and also consistent in thickness across the sample width. The transverse rib was found to cause little disturbance to the fibre orientation of the base plate. The different proportions of the shell and core regions at different locations over the ribbed plate provided an ideal case to test the proposition of Friedrich that the crack resistance of a short fibre reinforced material depends on the number of fibres that are perpendicular to the crack tip. The impact test results gathered in this way confirmed this hypothesis of Friedrich.

No presente trabalho, tanino (macromolécula de origem natural) foi utilizado como substituinte de fenol na formulação de matriz fenólica usada na preparação de compósitos, o que é possível devido à presença de anéis fenólicos sua estrutura. Os compósitos de matriz taninofenólica (50% em massa de tanino) apresentaram propriedades mecânicas superiores aquelas dos compósitos de matriz fenólica, quando reforçados pelo mesmo tipo de fibra, mostrando que a substituição de material obtido em larga escala a partir de fonte fóssil (fenol) é viável e pode ser feita por material obtido de fonte renovável (tanino) sem comprometimento de propriedades. Ainda, avaliou-se para propriedades de compósitos com diferentes tipos de reforços (fibras e cargas) através de caracterizações via análise térmica (TG e DSC), análise dinâmico-mecânica, espectroscopia na região do infravermelho, resistência ao impacto, absorção de água e microscopia eletrônica de varredura. Os ensaios de resistência ao impacto indicaram uma melhora de propriedades mecânicas quando da incorporação de fibras vegetais (juta e coco) nos termorrígidos fenólico e taninofenólico, além de mostrar que as fibras de juta reforçam as matrizes taninofenólicas mais eficientemente que as fibras de coco. As cascas da árvore de Acácia Negra, ricas em taninos, também foram utilizadas como agentes de reforço em compósitos na forma de fibras e cargas, obtidos através de desfibramento e pulverização, respectivamente. A utilização destes reforços, em diferentes proporções de massa, em compósitos de matriz taninofenólica (50% de tanino) levou a diferenças nas propriedades do compósito, com destaque para baixa absorção de água. Provavelmente, a presença de taninos no reforço e na matriz levou a intensas interações na interface fibra/matriz, diminuindo o número de vazios que podem alojar moléculas de água. As fibras de coco foram tratadas por ultra-som, a fim de avaliar a influência deste tratamento nas propriedades da fibra e dos compósitos reforçados por elas. As fibras de coco tratadas e não-tratadas foram caracterizadas quanto à composição química, índice de cristalinidade, ensaio de tração e microscopia eletrônica de varredura. Os resultados obtidos mostraram que o ultra-som é um tratamento promissor, pois modifica a morfologia da superfície das fibras sem levar à degradação química, sendo que a separação dos feixes de fibra que ocorre permite melhor interação fibra/matriz na interface, obtendo-se assim compósitos mais resistentes à água. Outros tratamentos utilizados em trabalhos anteriores a este, como mercerização, diminuem absorção de água dos compósitos por ela reforçados, ao custo de parcial degradação das fibras lignocelulósicas. No presente trabalho, materiais preparados a partir de matéria-prima oriunda de fontes renováveis foram processados, o que vem de encontro aos anseios atuais. Os compósitos obtidos têm potencial para aplicações não estruturais, por exemplo, em partes internas de veículos automotivos. / In the present work, tannin (macromolecule obtained from natural source) was used as substitute of phenol in the formulation of phenolic matrix composites, due to the presence of phenolic rings in its structure. The tanninphenolic matrix composites (50% w/w of tannin) presented mechanical properties better than those of phenolic matrix composites showing that substitution of material obtained in large scale from non-renewable source (phenol) can be done by material obtained from natural source (tannin) without compromising the properties of the composite. The tanninphenolic matrix composites reinforced by different reinforcing agents (fibers and particules) were characterized by different techniques: Izod impact strength, thermogravimetry (TG), differential scanning calorymetry (DSC), infrared spectroscopy (IV), dynamic-mechanical analysis (DMA) and scanning electron microscopy (SEM). The Izod impact strength showed an improvement of mechanical properties due to the incorporation of natural fibres (jute and coir) in the phenolic and tanninphenolic matrices and also the better reinforcement of these matrices by jute fibres, when compared to coir fibres. The barks of Acacia Mimosa (high content of tannin) were also used as reinforcing agents of the tanninphenolic matrices in the forms of fibres and particules. The presence of these reinforcing agents in the matrix led to differences in the properties of the composites, highlighted by its lower water uptake. The presence of tannins in both reinforcing agents and matrix enhanced the fiber/matrix interactions, lowering the voids that increase water uptake. The coir fibres were treated by ultrasound, in order to evaluate the influence of this treatment in the properties of the fibres and, therefore, the composites reinforced with them. Besides chemical composition, all the fibres were characterized by the following techniques: X-ray diffraction, tensile strengh, infrared spectroscopy (IV), and scanning electron microscopy (SEM). The results revealed that the ultrasound is a promising treatment of fibres for the processing of composites, because it modifies the morphology of the surface of fibres without leading them to chemical degradation. The separation of fiber beams allows enhancement of the fiber/matrix interactions, leading to composites with lower water absorption capacity. Other treatments, such as mercerization, for example, improved the impregnation of the fibres by the pre-polymer, leading to composites with better properties, at expenses of partial degradation of lignocellullosic fibres. In the present work, composites were prepared using material obtained from renewable source, according to the purpose of this work. The obtained composites presents potential for non-structural applications, such as, internal panels of cars, for example.

Materiais odontológicos inovadores que apresentem propriedades antimicrobianas são altamente desejáveis na cavidade oral. O objetivo deste estudo foi avaliar a atividade antimicrobiana do vanadato de prata nanoestruturado (&beta;-AgVO3) incorporado em duas resinas acrílicas frente a Candida albicans, Streptococcus mutans, Staphylococcus aureus e Pseudomonas aeruginosa, além de examinar as propriedades mecânicas e o padrão de incorporação do nanomaterial nas resinas. O nanomaterial foi caracterizado por difração de raios X (DRX), espectroscopia no infravermelho por transformada de Fourier (FTIV), análise elementar por energia dispersiva (EDS) e microscopia eletrônica de varredura (MEV). As propriedades antimicrobianas das resinas acrílicas incorporadas com diferentes porcentagens de &beta;-AgVO3 foram investigadas pelo método de redução do XTT, unidades formadoras de colônias (UFC) e microscopia confocal à laser e o comportamento mecânico por meio de ensaios de dureza e rugosidade superficial, resistência à flexão, à compressão e ao impacto. O padrão de incorporação do &beta;-AgVO3 nas resinas foi analisado por microscopia eletrônica de varredura (MEV) e análise elementar por energia dispersiva (EDS). Os dados foram analisados por ANOVA, Tukey e pelo teste Generalized Linear Models (&alpha;=0,05). Para ambas as resinas, em relação ao grupo controle, a incorporação de 5% e 10% de &beta;-AgVO3 reduziram significantemente a atividade metabólica de C. albicans e P. aeruginosa (p<0,05), enquanto que para S. mutans houve redução significante apenas com a incorporação de 10% (p<0,05). Não houve diferença na atividade metabólica pelo método do XTT frente a S. aureus (p> 0,05). Para ambas as resinas, observou-se uma redução significativa no número de UFC/mL de C. albicans para o grupo incorporado com 10% de &beta;-AgVO3 e de S. mutans para os grupos com 2,5%, 5% e 10% do nanomaterial (p<0,05). Para S. aureus e P. aeruginosa, houve redução significante com a incorporação de 5% e 10% (p<0,05). A dureza superficial da resina termopolimerizável permaneceu inalterada pela incorporação do nanomaterial (p>0,05) e da autopolimerizável aumentou com 0,5% (p<0,05). Concentrações maiores que 1% promoveram redução na resistência flexural das resinas (p<0,05) enquanto que a rugosidade superficial permaneceu inalterada (p>0,05). A resistência à compressão da resina autopolimerizável permaneceu inalterada (p>0,05) e da termopolimerizável reduziu com a incorporação de 0,5% e 10% (p<0,05). As concentrações de 5% e 10% promoveram redução significante na resistência ao impacto das resinas, em relação ao controle (p<0,05). A caracterização das resinas quanto a dispersão da carga utilizada mostrou a presença de domínios de &beta;-AgVO3 ao longo da matriz polimérica seguindo um padrão circular. Conclui-se que o método proposto foi capaz de promover atividade antimicrobiana às resinas acrílicas frente aos micro-organismos avaliados, sendo a mesma dependente da concentração do nanomaterial. Porém, alterações na dispersão do &beta;-AgVO3 na matriz dos polímeros são necessárias para não sacrificar as propriedades mecânicas e para potencializar o efeito antimicrobiano / Innovative dental materials that have antimicrobial properties are highly desirable in the oral cavity. The aim of this study was to evaluate the antimicrobial activity of nanostructured silver vanadate (&beta;-AgVO3) incorporated into two acrylic resins against Candida albicans, Streptococcus mutans, Staphylococcus aureus and Pseudomonas aeruginosa, while examining the mechanical properties and the pattern of nanomaterial incorporation into resins. The nanomaterial was characterized by X-ray diffraction (XRD), infrared spectroscopy Fourier transform (FTIR), elemental analysis by energy dispersive (EDS) and scanning electron microscopy (SEM). The antimicrobial properties of acrylic resins incorporated with different percentages of &beta;-AgVO3 were investigated by the reduction of XTT method, colony forming units (CFU) and confocal laser microscopy and the mechanical behavior through hardness, surface roughness, flexural, compression and impact tests. The pattern of incorporation of &beta;-AgVO3 resins was analyzed by scanning electron microscopy (SEM) and elemental analysis by energy dispersive (EDS). Data were analyzed by ANOVA, Tukey test and the Generalized Linear Models (&alpha; = 0.05). For both resins, compared to the control group, the incorporation of 5% and 10% &beta;-AgVO3 caused a significantly reduced in the metabolic activity of C. albicans and P. aeruginosa (p <0.05), while for S. mutans significant reduction was observed only with the incorporation of 10% (p <0.05). There was no difference in metabolic activity by XTT method against S. aureus (p> 0.05). For both resins, there was a significant reduction in the number of CFU / mL for C. albicans incorporated group with 10% &beta;-AgVO3 and S. mutans in groups with 2.5%, 5% and 10% of nanomaterial (p <0.05). For P. aeruginosa and S. aureus, there was a significant decrease with the incorporation of 5% to 10% (p <0.05). The surface hardness of the heat-cured resin was unchanged by the incorporation of the nanomaterial (p <0.05) and increased self-cured with 0.5% (p <0.05). Concentrations above 1% promote the reduction in flexural strength of the resins (p <0.05) while the surface roughness remained unchanged (P> 0.05). The compressive strength of the self-cured resin remained unchanged (P> 0.05) and heat-cured reduced with the incorporation of 0.5% and 10% (p <0.05). Concentrations of 5% and 10% caused a significant reduction in impact strength of resins, compared to control (p <0.05). The characterization of the resins as the dispersion of the filler used showed the presence of &beta;-AgVO3 domains along the polymer matrix following a circular pattern. It was concluded that the proposed method was able to promote antimicrobial activity to acrylic resins against microorganisms evaluated, with the same concentration dependent of the nanomaterial. However, changes in the &beta;-AgVO3 dispersion in the polymer matrix are necessary to do not sacrifice the mechanical properties and to enhance the antimicrobial effect

The main objective of this thesis was to improve the understanding of some aspects on wood and fibre mechanics related to conditions in the thermomechanical pulping process. Another objective was to measure the power distribution between the rotating plates in a refiner.   The thesis comprises the following parts: –A literature review aimed at describing fracture in wood and fibres as related to the thermomechanical pulping process –An experimental study of fracture in wood under compression, at conditions similar to those in feeding of chips into preheaters and chip refiners –An experimental study of the effect of impact velocity on the fracture of wood, related to conditions of fibre separation in the breaker bar zone in a chip refiner –A micromechanical model of the deterioration of wood fibres, related to the development of fibre properties during the intense treatment in the small gap in the refining zone –Measurements of the power distribution in a refiner.   The fracture in wood under compression was investigated by use of acoustic emission monitoring. The wood was compressed in both lateral and longitudinal directions to predict preferred modes of deformation in order to achieve desired irreversible changes in the wood structure. It was concluded that the most efficient compression direction in this respect is longitudinal. Preferable temperature at which the compression should be carried out and specific energy input needed in order to achieve substantial changes in the wood structure were also given.   The fibre separation step and specifically the effect of impact velocity on the fracture energy were studied by use of a falling weight impact tester. The fracture surfaces were also examined under a microscope. An increase in impact velocity resulted in an increase in fracture energy. In the thermomechanical pulping process the fibres are subjected to lateral compression, tension and shear which causes the creation of microcracks in the fibre wall. This damage reduces the fibre wall stiffness. A simplified analytical model is presented for the prediction of the stiffness degradation due to the damage state in a wood fibre, loaded in uni-axial tension or shear. The model was based on an assumed displacement field together with the minimum total potential energy theorem. For the damage development an energy criterion was employed. The model was applied to calculate the relevant stiffness coefficients as a function of the damage state. The energy consumption in order to achieve a certain damage state in a softwood fibre by uniaxial tension or shear load was also calculated. The energy consumption was found to be dependent on the microfibril angle in the middle secondary wall, the loading case, the thicknesses of the fibre cell wall layers, and conditions such as moisture content and temperature. At conditions, prevailing at the entrance of the gap between the plates in a refiner and at relative high damage states, more energy was needed to create cracks at higher microfibril angles. The energy consumption was lower for earlywood compared to latewood fibres. For low microfibril angles, the energy consumption was lower for loading in shear compared to tension for both earlywood and latewood fibres. Material parameters, such as initial damage state and specific fracture energy, were determined by fitting of input parameters to experimental data. Only a part of the electrical energy demand in the thermomechanical pulping process is considered to be effective in fibre separation and developing fibre properties. Therefore it is important to improve the understanding of how this energy is distributed along the refining zone. Investigations have been carried out in a laboratory single-disc refiner. It was found that a new developed force sensor is an effective way of measuring the power distribution within the refining zone. The collected data show that the tangential force per area and consequently also the power per unit area increased with radial position. The results in this thesis improve the understanding of the influence of some process parameters in thermomechanical pulping related wood and fibre mechanics such as loading rate, loading direction, moisture content and temperature to separate the fibres from the wood and to achieve desired irreversible changes in the fibre structure. Further, the thesis gives an insight of the spatial energy distribution in a refiner during thermomechanical pulping.

Materiais odontológicos inovadores que apresentem propriedades antimicrobianas são altamente desejáveis na cavidade oral. O objetivo deste estudo foi avaliar a atividade antimicrobiana do vanadato de prata nanoestruturado (&beta;-AgVO3) incorporado em duas resinas acrílicas frente a Candida albicans, Streptococcus mutans, Staphylococcus aureus e Pseudomonas aeruginosa, além de examinar as propriedades mecânicas e o padrão de incorporação do nanomaterial nas resinas. O nanomaterial foi caracterizado por difração de raios X (DRX), espectroscopia no infravermelho por transformada de Fourier (FTIV), análise elementar por energia dispersiva (EDS) e microscopia eletrônica de varredura (MEV). As propriedades antimicrobianas das resinas acrílicas incorporadas com diferentes porcentagens de &beta;-AgVO3 foram investigadas pelo método de redução do XTT, unidades formadoras de colônias (UFC) e microscopia confocal à laser e o comportamento mecânico por meio de ensaios de dureza e rugosidade superficial, resistência à flexão, à compressão e ao impacto. O padrão de incorporação do &beta;-AgVO3 nas resinas foi analisado por microscopia eletrônica de varredura (MEV) e análise elementar por energia dispersiva (EDS). Os dados foram analisados por ANOVA, Tukey e pelo teste Generalized Linear Models (&alpha;=0,05). Para ambas as resinas, em relação ao grupo controle, a incorporação de 5% e 10% de &beta;-AgVO3 reduziram significantemente a atividade metabólica de C. albicans e P. aeruginosa (p<0,05), enquanto que para S. mutans houve redução significante apenas com a incorporação de 10% (p<0,05). Não houve diferença na atividade metabólica pelo método do XTT frente a S. aureus (p> 0,05). Para ambas as resinas, observou-se uma redução significativa no número de UFC/mL de C. albicans para o grupo incorporado com 10% de &beta;-AgVO3 e de S. mutans para os grupos com 2,5%, 5% e 10% do nanomaterial (p<0,05). Para S. aureus e P. aeruginosa, houve redução significante com a incorporação de 5% e 10% (p<0,05). A dureza superficial da resina termopolimerizável permaneceu inalterada pela incorporação do nanomaterial (p>0,05) e da autopolimerizável aumentou com 0,5% (p<0,05). Concentrações maiores que 1% promoveram redução na resistência flexural das resinas (p<0,05) enquanto que a rugosidade superficial permaneceu inalterada (p>0,05). A resistência à compressão da resina autopolimerizável permaneceu inalterada (p>0,05) e da termopolimerizável reduziu com a incorporação de 0,5% e 10% (p<0,05). As concentrações de 5% e 10% promoveram redução significante na resistência ao impacto das resinas, em relação ao controle (p<0,05). A caracterização das resinas quanto a dispersão da carga utilizada mostrou a presença de domínios de &beta;-AgVO3 ao longo da matriz polimérica seguindo um padrão circular. Conclui-se que o método proposto foi capaz de promover atividade antimicrobiana às resinas acrílicas frente aos micro-organismos avaliados, sendo a mesma dependente da concentração do nanomaterial. Porém, alterações na dispersão do &beta;-AgVO3 na matriz dos polímeros são necessárias para não sacrificar as propriedades mecânicas e para potencializar o efeito antimicrobiano / Innovative dental materials that have antimicrobial properties are highly desirable in the oral cavity. The aim of this study was to evaluate the antimicrobial activity of nanostructured silver vanadate (&beta;-AgVO3) incorporated into two acrylic resins against Candida albicans, Streptococcus mutans, Staphylococcus aureus and Pseudomonas aeruginosa, while examining the mechanical properties and the pattern of nanomaterial incorporation into resins. The nanomaterial was characterized by X-ray diffraction (XRD), infrared spectroscopy Fourier transform (FTIR), elemental analysis by energy dispersive (EDS) and scanning electron microscopy (SEM). The antimicrobial properties of acrylic resins incorporated with different percentages of &beta;-AgVO3 were investigated by the reduction of XTT method, colony forming units (CFU) and confocal laser microscopy and the mechanical behavior through hardness, surface roughness, flexural, compression and impact tests. The pattern of incorporation of &beta;-AgVO3 resins was analyzed by scanning electron microscopy (SEM) and elemental analysis by energy dispersive (EDS). Data were analyzed by ANOVA, Tukey test and the Generalized Linear Models (&alpha; = 0.05). For both resins, compared to the control group, the incorporation of 5% and 10% &beta;-AgVO3 caused a significantly reduced in the metabolic activity of C. albicans and P. aeruginosa (p <0.05), while for S. mutans significant reduction was observed only with the incorporation of 10% (p <0.05). There was no difference in metabolic activity by XTT method against S. aureus (p> 0.05). For both resins, there was a significant reduction in the number of CFU / mL for C. albicans incorporated group with 10% &beta;-AgVO3 and S. mutans in groups with 2.5%, 5% and 10% of nanomaterial (p <0.05). For P. aeruginosa and S. aureus, there was a significant decrease with the incorporation of 5% to 10% (p <0.05). The surface hardness of the heat-cured resin was unchanged by the incorporation of the nanomaterial (p <0.05) and increased self-cured with 0.5% (p <0.05). Concentrations above 1% promote the reduction in flexural strength of the resins (p <0.05) while the surface roughness remained unchanged (P> 0.05). The compressive strength of the self-cured resin remained unchanged (P> 0.05) and heat-cured reduced with the incorporation of 0.5% and 10% (p <0.05). Concentrations of 5% and 10% caused a significant reduction in impact strength of resins, compared to control (p <0.05). The characterization of the resins as the dispersion of the filler used showed the presence of &beta;-AgVO3 domains along the polymer matrix following a circular pattern. It was concluded that the proposed method was able to promote antimicrobial activity to acrylic resins against microorganisms evaluated, with the same concentration dependent of the nanomaterial. However, changes in the &beta;-AgVO3 dispersion in the polymer matrix are necessary to do not sacrifice the mechanical properties and to enhance the antimicrobial effect

No presente trabalho, tanino (macromolécula de origem natural) foi utilizado como substituinte de fenol na formulação de matriz fenólica usada na preparação de compósitos, o que é possível devido à presença de anéis fenólicos sua estrutura. Os compósitos de matriz taninofenólica (50% em massa de tanino) apresentaram propriedades mecânicas superiores aquelas dos compósitos de matriz fenólica, quando reforçados pelo mesmo tipo de fibra, mostrando que a substituição de material obtido em larga escala a partir de fonte fóssil (fenol) é viável e pode ser feita por material obtido de fonte renovável (tanino) sem comprometimento de propriedades. Ainda, avaliou-se para propriedades de compósitos com diferentes tipos de reforços (fibras e cargas) através de caracterizações via análise térmica (TG e DSC), análise dinâmico-mecânica, espectroscopia na região do infravermelho, resistência ao impacto, absorção de água e microscopia eletrônica de varredura. Os ensaios de resistência ao impacto indicaram uma melhora de propriedades mecânicas quando da incorporação de fibras vegetais (juta e coco) nos termorrígidos fenólico e taninofenólico, além de mostrar que as fibras de juta reforçam as matrizes taninofenólicas mais eficientemente que as fibras de coco. As cascas da árvore de Acácia Negra, ricas em taninos, também foram utilizadas como agentes de reforço em compósitos na forma de fibras e cargas, obtidos através de desfibramento e pulverização, respectivamente. A utilização destes reforços, em diferentes proporções de massa, em compósitos de matriz taninofenólica (50% de tanino) levou a diferenças nas propriedades do compósito, com destaque para baixa absorção de água. Provavelmente, a presença de taninos no reforço e na matriz levou a intensas interações na interface fibra/matriz, diminuindo o número de vazios que podem alojar moléculas de água. As fibras de coco foram tratadas por ultra-som, a fim de avaliar a influência deste tratamento nas propriedades da fibra e dos compósitos reforçados por elas. As fibras de coco tratadas e não-tratadas foram caracterizadas quanto à composição química, índice de cristalinidade, ensaio de tração e microscopia eletrônica de varredura. Os resultados obtidos mostraram que o ultra-som é um tratamento promissor, pois modifica a morfologia da superfície das fibras sem levar à degradação química, sendo que a separação dos feixes de fibra que ocorre permite melhor interação fibra/matriz na interface, obtendo-se assim compósitos mais resistentes à água. Outros tratamentos utilizados em trabalhos anteriores a este, como mercerização, diminuem absorção de água dos compósitos por ela reforçados, ao custo de parcial degradação das fibras lignocelulósicas. No presente trabalho, materiais preparados a partir de matéria-prima oriunda de fontes renováveis foram processados, o que vem de encontro aos anseios atuais. Os compósitos obtidos têm potencial para aplicações não estruturais, por exemplo, em partes internas de veículos automotivos. / In the present work, tannin (macromolecule obtained from natural source) was used as substitute of phenol in the formulation of phenolic matrix composites, due to the presence of phenolic rings in its structure. The tanninphenolic matrix composites (50% w/w of tannin) presented mechanical properties better than those of phenolic matrix composites showing that substitution of material obtained in large scale from non-renewable source (phenol) can be done by material obtained from natural source (tannin) without compromising the properties of the composite. The tanninphenolic matrix composites reinforced by different reinforcing agents (fibers and particules) were characterized by different techniques: Izod impact strength, thermogravimetry (TG), differential scanning calorymetry (DSC), infrared spectroscopy (IV), dynamic-mechanical analysis (DMA) and scanning electron microscopy (SEM). The Izod impact strength showed an improvement of mechanical properties due to the incorporation of natural fibres (jute and coir) in the phenolic and tanninphenolic matrices and also the better reinforcement of these matrices by jute fibres, when compared to coir fibres. The barks of Acacia Mimosa (high content of tannin) were also used as reinforcing agents of the tanninphenolic matrices in the forms of fibres and particules. The presence of these reinforcing agents in the matrix led to differences in the properties of the composites, highlighted by its lower water uptake. The presence of tannins in both reinforcing agents and matrix enhanced the fiber/matrix interactions, lowering the voids that increase water uptake. The coir fibres were treated by ultrasound, in order to evaluate the influence of this treatment in the properties of the fibres and, therefore, the composites reinforced with them. Besides chemical composition, all the fibres were characterized by the following techniques: X-ray diffraction, tensile strengh, infrared spectroscopy (IV), and scanning electron microscopy (SEM). The results revealed that the ultrasound is a promising treatment of fibres for the processing of composites, because it modifies the morphology of the surface of fibres without leading them to chemical degradation. The separation of fiber beams allows enhancement of the fiber/matrix interactions, leading to composites with lower water absorption capacity. Other treatments, such as mercerization, for example, improved the impregnation of the fibres by the pre-polymer, leading to composites with better properties, at expenses of partial degradation of lignocellullosic fibres. In the present work, composites were prepared using material obtained from renewable source, according to the purpose of this work. The obtained composites presents potential for non-structural applications, such as, internal panels of cars, for example.

Les Déchets d'Equipement Electriques et Electroniques (DEEE) constituent un volume important de déchets dont le constituant majoritaire est l’ABS. C’est pour cela que nous avons travaillé principalement avec des polymères provenant d’un gisement réel (carters d’ordinateurs). Puis, des mélanges ABS/PC ont été élaborés (le PC étant un des constituants d’un gisement de carters), dans le but d’obtenir un matériau avec une résilience au moins équivalente à celle d’un ABS neuf. Même si l’ABS a montré une bonne aptitude à être recyclé seul, après vieillissement et recyclage, sa résilience connaît une chute due à la dégradation de la phase élastomère et à la présence d’ignifugeants. Il est important pour le recyclage de l’ABS et de ses mélanges de séparer les polymères ignifugés de ceux qui ne le sont pas. La voie mélange pour le recyclage de l’ABS par l’ajout de PC a l’avantage de simplifier le tri et de recycler un maximum des polymères présents dans les DEEE. Nous avons tout d’abord réalisé des mélanges ABS/PC neufs pour bénéficier d’une mise en œuvre et d’une composition optimales. L’influence des paramètres du procédé de recyclage (température et vis d’extrusion) et des propriétés des matériaux (taux et viscosité du PC, retardateurs de flamme de l’ABS) sur les propriétés du mélange a été étudiée. Nous avons effectué essentiellement des essais de résistance au choc Charpy et des études morphologiques. Les résultats ont montré qu’une morphologie fibrillaire ou co-continue est favorable à la meilleure résilience des mélanges ABS/PC. Nous avons obtenu pour des mélanges neufs ABS neuf FR/PC neuf réalisés avec 70% d’ABS une résilience supérieure à celle de l’ABS neuf. Mais, à composition égale, ce résultat n’a pas été atteint pour les mélanges majoritaires en ABS recyclé. Souhaitant réaliser des mélanges performants majoritaires en ABS recyclé, la compatibilisation semble nécessaire. Un mélange recyclé majoritaire en ABS, compatibilisé avec du PP-g-MA, est montré plus résilient que l’ABS neuf seul. Toutefois, les compatibilisants ont une efficacité limitée lorsqu’ils sont en présence de retardateurs de flamme ou soumis à un temps de séjour élevé dans la presse à injecter. Nous avons voulu utiliser des nanocharges minérales (montmorillonites), ajoutées en faible quantité, en tant qu'ignifugeants et compatibilisants. Elles se sont avérées inefficaces dans les études préliminaires réalisées. Le choix des nanoargiles minérales doit être optimisé. / WEEE constitute a huge waste volume in which ABS is the major component. So, we focused on polymers from a real deposit (casing of computers); such a deposit contains ABS, PC, PS, ABS-PC. In a first step, recycling of aged ABS was studied. The decrease in the C=C content induces an impact strength drop. Nevertheless, ABS proved to be recyclable given that optimized processing conditions are found. The role of flame retardants was shown to be crucial on the recyclability. Separating polymers with or without flame retardants is the key point of the ABS recycling. However, recycled aged ABS do not recover the impact strength of neat virgin ABS. Then, ABS/PC blends were elaborated in order to obtain a material with an impact strength at least equivalent to the neat ABS. The use of ABS/PC blends for this recycling facilitates the sorting and the utilization of most of WEEE polymers. We first made ABS/PC blends from virgin polymers to have optimal processability and composition. Performing Charpy impact strength tests and morphological studies allowed to evaluate the influence of recycling process parameters (temperature and screw extrusion) and material properties (rate and viscosity of PC and ABS flame retardants). Experimental results indicate that the impact strength of the ABS/PC blends is higher when the morphology is fibrillar or co-continuous. We obtained ABS virgin FR/PC virgin blends (70/30) with an impact strength greater than the neat ABS. But, with equal composition, this result was not reached for the blends. So to achieve reliable blends rich in recycled ABS, compatibilisation is necessary. Recycled ABS/PC blends compatibilised with PP-g-MA is more resilient than the ABS. However, the compatibilising agents have a limited efficiency when they are used in the presence of flame retardants or subjected to a high residence time. Finally, nanoclays were attemptively used as both FR and compatibiliser. Tough they proved uneffective in the very first experiments carried out (the choice of clay need to be optimized).

Tato Diplomová práce se zabývá vlivem vyztužení na mechanické vlastnosti materiálu pro přípravu snímatelných náhrad. Pro testování byly použity tři sady vzorků: PMMA pryskyřice, PMMA pryskyřice s Dentapreg Mesh výztuží a PMMA pryskyřice vyztužena zesilující síťkou z nerezové oceli.Pro měření chování vzorků při statickém a dynamickém namáhání byl použit třibodový ohybový test a Charpy rázové kladivo. Viskoelastické vlastnostzi byly měřeny dynamicko-mechanickou analýzou (DMA). Skenovací elektronová mikroskopie (SEM) byla použita k charakterizaci lomových ploch. Během statického namáhání vzorků výztuž nehraje důležitou roli v porovnání s nevyztuženou pryskyřicí. Nicméně byl pozorován opačný trend při dymanickém namáhání, kde efekt výzruže rostl v řadě PMMA pryskyřice – síťka z nerezové oceli – Dentapreg Mesh.

In this article the correlation between the average molar mass and the melt flow rate (MFR) is achieved. Based on the example of Polyoxymethylene (POM) it is shown that a high average molar mass is associated with a low MFR (high viscosity). On the basis of this dependency, the mechanical properties of static and dynamic tensile strength, elastic modulus, hardness and notched impact strength are investigated. It was found that the characteristic values of static tensile strength, elastic modulus and hard-ness increase with increasing MFR (decreasing viscosity). On the other hand the dynamic long-term properties and notched impact strengths decrease with increasing MFR. / Im Beitrag wird der Zusammenhang zwischen der mittleren molaren Masse und des Schmelzfließindex (MFR) hergestellt. Dabei wird am Beispiel von Polyoxymethylen (POM) ersichtlich, dass eine hohe mittlere molare Masse mit einem geringen MFR (hochviskos) einhergeht. Basierend auf dieser Abhängigkeit werden die mechanischen Eigenschaften statische und dynamische Zugfestigkeit, E-Modul, Härte sowie Kerbschlagzähigkeit untersucht. Dabei konnte festgestellt werden, dass die Kenngrößen statische Zugfestigkeit, E-Modul und Härte mit steigendem MFR (abnehmende Viskosität) zunehmen. Die dynamischen Langzeiteigenschaften und Kerbschlagzähigkeiten sinken hingegen mit zunehmendem MFR.