L’étuvage de poudre de protéines sériques (PS) de lait permet l’amélioration des propriétés techno-fonctionnelles des protéines : aptitude à la formation de gel, mousse, ou émulsion. L’objectif de cette thèse était d’étudier le mécanisme de formation et les propriétés physico-chimiques et rhéologiques d’assemblages de PS de taille micronique ou AMI produits par étuvage à 100 °C d’une poudre d’isolat de PS ajustée à pH 9.5 et à une activité d’eau proche de 0,2. Pour cela, la caractérisation morphologique des assemblages, la dénaturation des protéines, la diminution de lactose libre et la formation de produits de Maillard ont été suivies au cours du temps d’étuvageLe rôle de chacun des constituants de la poudre a aussi été étudié en faisant varier sa composition. Les résultats obtenus montrent que l’étuvage à pH 9.5 permet la formation d’assemblages de taille et de forme relatives à celle des particules de poudre étuvée. Dans un premier temps, des réactions de glycation des protéines s’opèrent, des agrégats solubles sont produits et les poudres brunissent, tandis que les produits terminaux de la réaction de Maillard se forment. Ensuite, la quantité d’agrégats solubles diminue avec la formation concomitante des AMI. Les AMI possèdent des propriétés de rétention d’eau très élevées ce qui leur confère des propriétés viscosifiantes. L’addition de lactose à la poudre d’isolat de PS permet d’accélérer la cinétique de formation des AMI et d’obtenir des AMI plus denses en protéines. Les caséines sont aussi intégrées dans les AMI, mais ont très peu d’effets sur leurs propriétés stru / The dry heating of whey protein powder increases the functional properties of proteins such as their ability to form gels, foams or emulsions. The aim of this PhD thesis was to study the mechanism of formation and the physicochemical and rheological properties of protein assemblies of micrometer sizes that were produced by dry heating at 100 °C a whey protein powder isolate adjusted at pH 9.5 at a water activity of 0.2. Thus, morphological properties, protein denaturation, lactose conjugation and products of the Maillard reaction were studied during the time course of the dry heating. The role of each compound of the powder has also been studied by modification of the powder composition. Dry heating at pH 9.5 was able to form large assemblies of size and shape related to the size of the dry heated powder particles.In the first step, the glycation of proteins increased. Soluble aggregates formed and the powder browning progressed, while advanced glycated end products of the Maillard reaction were found. Then, the content in soluble aggregates decreased and large protein assemblies of micrometer sizes formed. These large assemblies were highly hydrated, and had very high viscosity values. Addition of lactose to the whey protein isolate powder allowed increasing the speed of formation of these large assemblies, increasing their density, and reaching higher yields of production. Caseins were able to join to whey proteins in the large assemblies, and had very poor effects on their structural properties and ability to retain the aqueous phase.

Ces vingt dernières années, le développement de réseaux haute résolution sismologiques et géodésiques denses a permis la découverte de nouveaux signaux géophysiques parmi lesquels on trouve les trémors non-volcaniques (Non-volcanic tremor, NVT, Obara 2002) et les glissements lents épisodiques (Slow Slip Event, SSE, Dragert et al., 2001). La combinaison de NVT et de SSE est communément observée le long des frontières de plaques, entre la zone sismogénique bloquée à faible profondeur et la zone en fluage ductile à plus grande profondeur (Dragert et al., 2004). Cette association définie des glissements et trémors épisodiques (Episodic Tremor and Slip, ETS), systématiquement associés à des surpressions de fluides et à des conditions proches de la rupture. Dans cette thèse, nous proposons de combiner une étude microstructurale de roches exhumées avec une approche par modélisation numérique afin de reproduire et de mieux comprendre la mécanique des glissements et trémors épisodiques.Nous nous sommes concentrés sur des roches continentales provenant de la Zone de Cisaillement Est du Tende (Corse, France), correspondant à une zone de cisaillement Alpine kilométrique ayant enregistré une déformation dans la zone de subduction (10 kb / 400-450°C, Gueydan et al., 2003). Ces conditions pression-température sont cohérentes avec la localisation des ETS dans les zones de subduction. Les analyses microstructurales et EBSD de ces roches mettent en évidence des localisations de la déformation le long de zones de cisaillement centimétriques contrôlées par une rhéologie dépendante de la taille des grains. La microfracturation de la phase dure (ici du feldspath) et le colmatage de ces microfractures correspondent, respectivement, à de processus de réduction et d’augmentation de la taille des grains.La plupart des récentes modélisations des ETS sont basées sur une loi frictionnelle dite rate-and-state, associant les SSE et les NVT à un cisaillement sur un plan. Contrairement à ces modèles, nous souhaitons modéliser l’ensemble de la roche (et non pas uniquement un plan) avec une rhéologie ductile dépendante de la taille des grains directement guidée par nos observations microstructurales (avec microfracturation et colmatage), Nous faisons l’hypothèse que les SSE peuvent résulter d’une localisation ductile de la déformation et non d’un glissement sur des fractures. Durant la localisation de la déformation, le pompage des fluides peut déclencher une fracturation de la roche par surpression de fluide, ce qui pourrait être la signature des NVT. Le modèle numérique 1D présenté ici nous permettra de valider ces hypothèses. En suivant la loi de Darcy, notre approche nous permet également de prédire les variations de la pression de pore en fonction des variations de la porosité/perméabilité et du pompage des fluides.Les résultats numériques montrent que l’évolution dynamique des microstructures, dépendante des fluides, définie des cycles de localisation ductile de la déformation liés aux augmentations de la pression de fluide. Notre modèle démontre que la disponibilité des fluides et l’efficacité du pompage des fluides contrôlent l’occurrence des ETS. Nous prédisons également les conditions pression-température nécessaires au déclenchement des ETS : 400-500°C et 30-50 km de profondeur en subduction, et ~500°C et 15-30 km de profondeur le long des zones de décrochement. Ces conditions PT sont cohérentes avec les exemples naturels.Aussi simple soit-elle, notre modèle mécanique s’appuyant sur des observations de terrain décrit correctement la relation entre surpressions de fluides, rhéologie dépendant de la taille des grains et le déclenchement des ETS. Des travaux restent à entreprendre comme par exemple la comparaison directe de nos résultats avec des données géophysiques (GPS) ou bien l’introduction d’un nouvelle assemble minéralogique, comme par exemple des roches mafiques pour prendre en compte des minéralogies océaniques. / These last twenty years, the development of dense and highly sensitive seismologic and geodetic networks permits the discovery of new geophysical signals named non-volcanic tremor (Obara 2002) and slow slip events (Dragert et al., 2001). The combination of non-volcanic tremor and transient slow slip is commonly observed at plate interface, between locked/seismogenic zone at low depths and stable/ductile creep zone at larger depths (Dragert et al., 2004). This association defines episodic tremor and slip, systematically highlighted by over-pressurized fluids and near failure shear stress conditions. In this thesis we propose to combine a microstructural analysis of exhumed rocks with a modeling approach in order to accurately reproduce and understand the physics of episodic tremor and slip.We focus on continental rocks from the East Tenda Shear Zone (Corsica, France), a kilometer-wide localized Alpine shear zone that record HP/LT deformation (10kb / 400-450°C, Gueydan et al., 2003). Such pressure-temperature conditions are consistent with the location of episodic tremor and slip in subduction zone. Microstructural and EBSD analyses on these rocks describe a pattern of strain localization in centimeter-scale shear zones guiding by a grain size-sensitive creep. Microfracturing of the strong phase (feldspar here) and the sealing of these microfractures act, respectively, as grain size decrease and grain size increase processes.Most of recent modeling approaches of episodic tremor and slip are based on the rate-and-state variable friction law, describing slow slip event and non-volcanic tremor as slow shear slip on a plane. In contrast with such models, we wish to model the entire rock volume, with a ductile grain size-sensitive rheology guided by our microstructural observations (e.g. microfracturing and sealing as grain size variation processes). We hypothesize that slow slip events may result from ductile strain localization and not transient slip on fractures. Fluid pumping during strain localization may trigger whole rock fracturing at near lithostatic conditions that can be the signature of non-volcanic tremor. The 1D numerical model presented here will allow us to validate these assumptions.We also can predict pore fluid pressure variation as a function of changes in porosity/permeability and strain rate-dependent fluid pumping following the Darcy’s flow law. The fluid-enhanced dynamic evolution of microstructure defines cycles of ductile strain localization related to the increase in pore fluid pressure. We show that slow slip events can be ductile processes related to transient strain localization, while non-volcanic tremor can correspond to fracturing of the whole rock at peak of pore fluid pressure. Our model shows that the availability of fluids and the efficiency of fluid pumping control the occurrence of episodic tremor and slip. We also well predict the temperature and depth ranges of episodic tremor and slip: 400-500°C and 30-50 km in subduction zones and ~500°C and 15-30 km in strike slip settings, consistent with natural examples.As simplistic as it is, our field-guided mechanical model well describe, at first order, the relation between high pore fluid pressure, grain size-sensitive rheology and episodic tremor and slip. Some efforts remain to be done like a real fit of geophysical data (GPS) or the introduction of the new mineralogical assemblage, such as mafic rocks to reproduce oceanic environment.

Made available in DSpace on 2017-07-21T18:53:06Z (GMT). No. of bitstreams: 1 Fernanda Kubiaki.pdf: 1833486 bytes, checksum: 52af7c310dcf42579df3b3b6a0856799 (MD5) Previous issue date: 2016-02-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The chestnut (Castanea sativa, Mill) has lots of nutrients, including starch that is the main compound and is chemically composed of amylose and amylopectin. The starch is the main storage substance for plants and the main energetic source for humans, providing from 70 to 80% of the required daily calories. It is present in many botanical sources and can be used in various industrial sectors, being an important ingredient for processed foods. It can be used in natura or modified by chemical ways, physical, biological or combined techniques. The modified starch is an alternative under continuous development in order to overcome the limitation for some industrial applications of native starch such as low resistance and high tendency to retrogradation, which makes the starch like native. The objective of this study was the chestnut starch (Castanea sativa, Mill) extraction and to evaluate the modification with HCl in two concentrations (0,1 mol/L e 0,5 mol/L) diluted in alcoholic-acid solutions. The behavior of native and modified starch granules were analyzed by thermoanalytical techniques (TG-DTA and DSC), rheological (RVA), structural (XDR and SEM), and color. Furthermore, physical-chemical analyzes were performed on chestnut flour, like protein, ash, lipids, total dietary fiber, carbohydrates and moisture. The samples presented three major weight losses in the TG-DTA analysis, and showed only on native starch sample a strong oxidative character event. There was an increase in the gelatinisation enthalpy for modified samples if compared to the native one. On the other hand, the viscosity and impasting temperature decreased, this probable happened due to the structural weakening after the modification. The granules modification was observed in the scanning electron microscopy, but in the analysis by x ray diffraction the intensity of the samples had a low variation due to the treatments. In the physical-chemical analysis the chestnut flour presented a high content of fiber and low lipids content. This work by performing the chestnut starch modification allowed the knowledge of granules and noticed a change according to the performed modifications, becoming favorable for food industrial uses (marron glacé and candies), non-food and also as a raw material for futures studies of modified starches. / A castanha portuguesa (Castanea sativa, Mill) possui vários nutrientes, sendo o amido o componente principal quimicamente formado por amilose e amilopectina. O amido é a principal substância de reserva para as plantas e a principal fonte energética para o homem, fornecendo de 70 a 80% das calorias diárias necessárias. Está presente em diversas fontes botânicas e pode ser utilizado em diversos setores industriais, sendo um ingrediente importante para os alimentos processados. Pode ser utilizado in natura ou modificado por vias químicas, físicas, biológicas ou técnicas combinadas. O amido modificado é uma alternativa que está em contínuo desenvolvimento para superar as limitações para algumas aplicações industriais do amido nativo, como a baixa resistência e alta tendência a retrogradação. O objetivo deste trabalho foi realizar a extração do amido de castanha portuguesa (Castanea sativa, Mill) e avaliar a modificação com HCl em duas concentrações (0,1 mol/L e 0,5 mol/L) diluído em soluções ácido-alcoólica. O comportamento dos grânulos de amido nativo e modificados foram analisados por técnicas termoanalíticas (TG-DTA e DSC), reológicas (RVA), estruturais (DRX e MEV), e de cor. Ainda, análises físico-químicas foram realizadas na farinha da castanha, sendo elas proteína, cinzas, lipídios, fibra alimentar total, carboidratos e umidade. As amostras mostraram três principais perdas de massa na análise TG-DTA, e observou-se apenas na amostra de amido nativa um forte evento de caráter oxidativo. Houve um aumento da entalpia de gelatinização para as amostras modificadas se comparadas à amostra nativa. Por outro lado a viscosidade e temperatura de empastamento diminuíram, isso se deu provavelmente pelo enfraquecimento estrutural após a modificação. A modificação dos grânulos foi observada na análise da microscopia eletrônica de varredura, porém, na análise de difração por raios X a intensidade das amostras variou pouco a partir do tratamento. Nas análises físico-químicas a farinha da castanha apresentou um alto teor de fibras e um baixo teor de lipídios. O presente trabalho, a partir da realização da modificação de amido de castanha portuguesa permitiu o conhecimento dos grânulos e evidenciou uma alteração de acordo com as modificações realizadas, tornando-a favorável para o uso industrial alimentar (marrom glacé e doces), papel e também como uma matéria-prima para futuros estudos de amidos modificados.

Submitted by Eunice Novais (enovais@uepg.br) on 2018-08-28T18:42:12Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Guilherme - dissertação.pdf: 5842405 bytes, checksum: e65765aba951effa28bce4548159760a (MD5) / Made available in DSpace on 2018-08-28T18:42:12Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Guilherme - dissertação.pdf: 5842405 bytes, checksum: e65765aba951effa28bce4548159760a (MD5) Previous issue date: 2018-06-11 / Os objetivos dessa pesquisa foram desenvolver e avaliar fitomedicamentos para cicatrização de feridas contendo mucilagem de Ocoteapuberula (Rich) Nees. Materiais e métodos:a coleta e preparação das cascas foi realizada em espécies nativas da região dos Campos Gerais de Ponta Grossa PR, Brasil; sendo a mesma submetida a uma técnica hidroalcoólica para extração da mucilagem, através de técnicas distintas pela aplicação ou não de calor até 60°C. As amostras liofilizadas do extrato hidroalcoólico da Ocoteapuberula (EHOP) foram analisadas através de técnicas de DTG/TG, FTIR para análise dos extratos nas diferentes extrações, assim como quantificação de rendimento de extração do EHOP. Posteriormente foram formuladas membranas semipermeáveis de carboximetilcelulose (CMC)e acetato de polivinila (PVA) impregnadas com 10% de EHOP. Concomitante, foi realizado análise reológica e FTIR das membranas. As membranas de CMCe PVA puras e incorporadas com EHOP foram testadas em ratos através da aplicação em uma lesão no dorso do animal. Como controle positivo foi utilizado o curativo Megisorbr e negativo a água destilada. As lesões foram avaliadas quanto ao índice de retração da lesão, análise histológica das feridas quanto a inflamação, angiogênese e colagênese e análise laboratorial de amostra sanguínea dos animais quanto a toxicidade hepática ou renal. Resultados:a extração através do aquecimento a 60°C proporcionou melhor rendimento associado a maior concentração de compostos alcalóides, com similaridade em FTIR da extração sem emprego de calor e a análise reológica demonstrou potencial em absorção de forças de stress sem sofrer deformação. Os espectros de FTIR das membranas de CMC e PVA sugeriram melhor estabilidade do EHOP em PVA. As análises histológicas permitiram visualizar potencial cicatrizante aos grupos CMC/EHOP e o EHOP, sem toxicidade hepática ou renal em ambos os grupos, sugerindo assim um potencial fitoterápico na aplicação de EHOP em feridas. / The objectives of this research were to develop and evaluate one phytomedications for wound healing containing mucilage of Ocoteapuberula (Rich) Nees. Materials and method:The collection and preparation of the bark was carried out in native species of the “Campos Gerais” region of Ponta Grossa PR, Brazil, and it was submitted to a hydroalcoholic technique for extracting the mucilage, using different techniques for the application or not of heat up to 60 ° C. The lyophilized samples from the Ocoteapuberulahydroalcoholic extract (OPHE) were analyzed by DTG / TG, FTIR techniques for analysis of the extracts in the different extractions, as well as quantification of extraction yield of EHOP. Subsequently, semipermeable membranes of carboxymethylcellulose (CMC) and polyvinyl acetate (PVA) impregnated with 10% OPHE were formulated. At the same time, the rheological and FTIR analysis of the membranes was performed. Pure CMC and PVA membranes incorporated with OPHEwere tested in rats by application to a lesion on the animal's back. As a positive control the Megisorb dressing was used and negative the distilled water. The lesions were evaluated for lesion retraction index, histological analysis of wounds for inflammation, angiogenesis and collagenesis, and laboratory analysis of blood samples from animals for hepatic or renal toxicity. Results: Extraction through heating at 60 ° C provided a better yield associated with a higher concentration of alkaloid compounds, with FTIR similarity of the extraction without use of heat, and rheological analysis showed a potential for the absorption of stress forces without deformation. The FTIR spectra of CMC and PVA membranes suggested improved stability of EHOP in PVA. Histological analyzes allowed visualizing healing potential for the CMC / EHOP and EHOP groups, without hepatic or renal toxicity in both groups, thus suggesting a phytotherapeutic potential in the application of EHOP in wounds.

Dans ce manuscrit, nous mesurons la réponse mécanique à l’échelle nanométrique de divers systèmes issus de la matière molle en utilisant un microscope à force atomique basé sur un diapason à quartz. Utilisé comme un nano-rhéomètre, cet instrument permet une mesure quantitative des propriétés viscoélastiques des matériaux et des processus frictionnels et dissipatifs aux nanoéchelles. Nous montrons d’abord que les liquides ioniques confinés aux nanoéchelles peuvent subir un changement dramatique de leurs propriétés mécaniques, suggérant une solidification capillaire. Cette transition est favorisée par la nature métallique des interfaces confinantes, montrant la présence d’effets électrostatiques subtils dans ces électrolytes denses. Nous étudions ensuite les mécanismes de plasticité à l’échelle atomique en mesurant la réponse viscoélastique de jonctions d’or de quelques atomes de diamètre. Nous mettons en évidence une transition sous cisaillement entre un régime élastique, puis plastique, jusqu’à la liquéfaction complète de la jonction. Nous caractérisons ainsi de manière fine les mécanismes de plasticité dans ces systèmes moléculaires. Finalement, nous montrons les effets profonds que les interactions à l’échelle nanométrique peuvent avoir sur le comportement macroscopique de la matière molle. Nous mesurons le profil frictionnel entre paires de particules de suspensions de PVC et de maïzena. Nos mesures mettent en lumière le rôle dominant des interactions locales entre particules dans la rhéologie non-newtonienne des suspensions. / In this manuscript, we use a tuning fork based atomic force microscope to measure the mechanical response of various soft matter systems at the nanoscale. This instrument is used as a nano-rheometer, allowing quantitative measurements of viscoelastic material properties, and unprecedented characterization of friction and dissipation at the nanoscale. First, we show that ionic liquids can undergo a dramatic change in their mechanical properties when confined at the nanoscale, pointing to a capillary freezing transition. This transition is favored by the metallic nature of the confining substrates, suggesting the occurrence of subtle electrostatic effects in those dense electrolytes. Second, we probe plasticity at the individual atomic level, by measuring the viscoelastic rheological response of gold junctions of few atoms diameter. For increasing shear, we uncover a transition from a purely elastic regime to a plastic flow regime, up to the complete shear-induced melting of the junction. Our measurements give unprecedented insights on the plastic mechanisms at play in those molecular systems. Finally, we show that nanoscale interactions can have profound effects on the macroscopic behavior of soft materials. Focusing on the nonnewtonian flow behavior of concentrated suspensions of particles, we measure the nanoscale frictional force profile between pairs of particles of PVC and cornstarch suspensions. Our measurements highlight the dominant role of local interparticle interactions on the macroscale rheology of suspensions.

O emprego de compósitos na construção civil, como os de matriz cimentícia e pasta reforçada com fibras, tem se disseminado consideravelmente nos últimos anos. Uma grande variedade de fibras sintéticas, como o polipropileno, tem sido utilizada com sucesso para reforçar compósitos cimentícios. No entanto, o interesse mundial na utilização de produtos com menor impacto ambiental estimula a busca por materiais para substituir fibras sintéticas. As fibras vegetais, biodegradáveis, pode ser ótima alternativa devido à abundância, ao baixo custo, ao menor consumo de energia para sua produção e às propriedades mecânicas apropriadas. Fibra de curauá, planta nativa do estado do Amazonas, com plantações em escala comercial, é usada na fabricação de cordas, cestos ou como reforço em matrizes orgânicas. Suas propriedades mecânicas são semelhantes às de polipropileno. A tecnologia de extrusão é viável nas indústrias de fibrocimento, pois produz compósitos com matriz de alta densidade e ótimo empacotamento, baixa permeabilidade e boa adesão fibra matriz. No entanto, o processo de extrusão bem-sucedido de produtos cimentícios depende principalmente das propriedades reológicas do cimento fresco reforçado com fibras. As fibras vegetais podem promover o sequestro de água e interferir fortemente no escoamento, na coesão e no fluxo de pasta de cimento fresco. A incorporação de fibras vegetais influencia os materiais à base de cimento no estado fresco e afeta propriedades no estado endurecido. Neste contexto, o objetivo da pesquisa é avaliar a influência das fibras de curauá e de polipropileno em propriedades reológicas e em propriedades mecânicas da pasta de cimento fresco. Foram preparadas formulações sem fibras, como referência, e com 1 e 2% de reforço em massa, fibras com comprimento de 6 e 10 mm. Utilizaram-se duas técnicas reológicas: Squeeze flow e reômetro extrusor para analisar o fluxo de pastas cimentícias. Por meio de dados experimentais, como força/deslocamento, e de análise numérica da pressão do reômetro extrusor, foram determinados: tensão inicial de cisalhamento (σ0), limite de cisalhamento (τ0), tensão de escoamento (α) e tensão de cisalhamento (β). As propriedades mecânicas foram determinadas em máquina de ensaio MTS. Módulo de ruptura (MOR), tenacidade à fratura (TFT) e energia de fratura (EF) foram calculados. Os resultados reológicos indicam que a pasta cimentícia reforçada com fibras de curauá apresentou maior força, menor deslocamento e aumento da pressão de extrusão em fibras de curauá em relação às pastas cimentícias reforçadas com fibras de polipropileno. O comprimento das fibras influenciou mais o fluxo da mistura do que o teor de fibra. Compósitos cimentícios reforçados com fibra de polipropileno apresentaram melhores resultados mecânicos de MOR, TFT e EF em relação aos compósitos reforçados com curauá. Após os 200 ciclos de envelhecimento, os resultados mecânicos dos compósitos reforçados com as fibras de curauá diminuíram devido a mineralização das fibras. Os resultados de nanoindentação, como dureza e módulo elástico, aumentaram após os 200 ciclos. As metodologias aplicadas para avaliar o comportamento reológico e mecânico do fibrocimento durante a extrusão facilitará a futura transferência dessa tecnologia ao setor produtivo, com produtos potencialmente de melhor qualidade. / The use of composites in construction, as matrix and paste cement reinforced with fibers, has spread considerably in recent years. A wide variety of synthetic fibers such as polypropylene have been successfully used to reinforce cementitious composites. However, worldwide interest in the use of products with lower environmental impact stimulates the search for materials to replace synthetic fiber. Vegetable fiber, biodegradable, can be a great alternative because of the abundance, low cost, the lowest energy consumption for its production, appropriate mechanical properties. Curauá fiber, native plant from Amazon, with crops on a commercial scale, is used in the manufacture of ropes, baskets or as reinforcement in organic matrix. Its mechanical properties are similar to those of polypropylene. Extrusion technology is feasible in the fibercement industry, because it produces composites with high density matrix and great packaging, low permeability and good adhesion fiber matrix. However, successful extrusion process of cementitious products mainly depends on the rheological properties of fresh cement reinforced with fibers. The vegetable fibers can promote water kidnapping and strongly interfere in the flow, cohesion and fresh cement slurry flow. The incorporation of vegetable fibers influences the based cementitious materials in the fresh state and affects properties in the hardened state. In this context, the objective of the research is to evaluate the influence of curauá and polypropylene fiber in rheological and mechanical properties of fresh cement paste. Formulations without fiber, used as reference, 1 and 2% content by weight of reinforcement, fibers with a length of 6 to 10 mm were prepared. Two rheological techniques were used: Squeeze flow and extruder rheometer to analyze the flow of cement pastes. Through experimental data, as strength/displacement and numerical analysis of the pressure extruder rheometer were determined: yield stress corresponding to zero velocity (σ0), initial shear stress (τ0), effect of the velocity on yield stress (α) and effect of velocity in the shear stress (β). The mechanical properties were determined in MTS testing machine. Modulus of rupture (MOR), fracture toughness (TFT) and fracture energy (EF) were calculated. The rheological results indicate that the cement paste reinforced with curauá fiber showed higher strength, smaller displacement and increased extrusion pressure with curauá fibers compared to cementitious paste reinforced with polypropylene fibers. The length of the fibers influence the flow of the mixture more than the fiber content. Composites reinforced with polypropylene fibers presented higher values of MOR, TFT and EF compared to composites reinforced with curauá fiber. After 200 ageing cycles, the mechanical results of composites reinforced with curauá fibers decreased due to mineralization of the fibers. The nanoindentation results, as hardness and elastic modulus, increased after 200 cycles. The methodologies used to assess the rheological and mechanical behavior of fibercement during extrusion facilitate future transfer of this technology to the productive sector, with potentially higher quality products.

OBJETIVO: Comparar a viscosidade dinâmica da camada superficial da fáscia temporal com a de outros tecidos biológicos tradicionalmente utilizados em implantes de pregas vocais para o tratamento de rigidez de pregas vocais. DESENHO DO ESTUDO: Experimental. MÉTODO: Amostras de camada superficial da fáscia temporal, camada profunda da fáscia temporal e gordura abdominal de 12 cadáveres são submetidas a medição de viscosidade dinâmica. RESUTADOS: A viscosidade dinâmica das diferentes amostras apresenta-se na seguinte ordem crescente: camada superficial da fáscia temporal, camada profunda da fáscia temporal e gordura abdominal. Observa-se diferença estatística na comparação entre todas as amostras. DISCUSSÃO: Quanto maior for a viscosidade da mucosa da prega vocal, maior é a pressão subglótica necessária para se iniciar a fonação. Dessa maneira, um bom material implantável em lâmina própria de prega vocal deve ter baixa viscosidade. Por esse parâmetro, a camada superficial da fáscia temporal é um material promissor para implantação em pregas vocais. CONCLUSÃO: A viscosidade dinâmica da camada superficial da fáscia temporal é menor que a da camada profunda da fáscia temporal e que a da gordura abdominal. / OBJECTIVE: To compare the dynamic viscosity of superficial layer of temporalis fascia with that of other biological tissues traditionally used for vocal fold implants to treat vocal fold rigidity. STUDY DESIGN: Experimental. METHOD: Measurement of dynamic viscosity of samples of superficial layer of temporalis fascia, deep layer of temporalis fascia and abdominal fat of 12 cadavers are performed. RESULTS: Dynamic viscosity values of the different samples are presented in the following increasing order: superficial layer of temporalis fascia, deep layer of temporalis fascia and abdominal fat. There is statistical difference among all the samples. CONCLUSION: Dynamic viscosity of superficial layer of temporalis fascia is lower than the ones of deep layer of temporalis fascia and abdominal fat.

Grâce à leurs propriétés mécaniques et électroniques élevées, les NanoTubes de Carbone (NTC) semblent être les nanocharges idéales pour conférer des propriétés optimum à des matériaux composites, en particulier ceux qui sont élaborés à partir de matrices élastomères. Cependant, pour obtenir une amélioration significative des propriétés une bonne dispersion dans la matrice est nécessaire. La dispersion des NTC dans une matrice élastomère de type EPM est explorée ici en employant un copolymère statistique, le poly(éthylène-stat-acétate de vinyle) (EVA), comme agent dispersant. Les outils classiques de mélange des élastomères, mélangeur interne et mélangeur à cylindres, qui sont des techniques de mélange douces, ont été utilisés dans le cadre de cette étude. Nous avons montré qu’à faible taux de NTC dans la matrice leur dispersion était contrôlée par deux paramètres clés (i) la viscosité de la matrice EPM et (ii) la concentration en EVA. L’augmentation des concentrations de NTC a permis de mettre en évidence que les propriétés rhéologiques et électriques des nanocomposites variaient brusquement à partir de concentrations critiques (seuil de percolation) assez faibles permettant de justifier l’utilisation du système EPM-EVA sélectionné. Nous avons alors préparé un mélange maître EPM-EVA chargé à 20% en NTC possédant de très bonnes propriétés de conductivité. Des mélanges à base d’EPDM chargés par des nanotubes de carbone, du noir de carbone ou le mélange des deux ont également été analysés. Nous avons démontré que la dilution d’un mélange maître permet d’obtenir un élastomère chargé en NTC avec une viscosité Mooney constante et avec un impact fort sur la cinétique de vulcanisation de l’élastomère (accélération de la réaction). Un effet de synergie entre noir de carbone et NTC a été mis en évidence au niveau des propriétés mécaniques mais pas pour les propriétés électriques. / The outstanding properties of Carbon NanoTubes (CNTs) make them ideal candidates for use in nanocomposites, and particularly in those based on rubber matrix. However, to obtain an improvement of the properties, a good degree of dispersion of the CNT in the matrix is crucial. The CNT dispersion in an EPM rubber is investigated here by using a statistical copolymer, the ethylene-stat-vinyl acetate (EVA), as dispersing agent. In this study, we work with the classic methods used for rubber mixing, like an internal mixer and an open two roll mill, which are soft mixing techniques. At low CNT rate in the matrix, the dispersion is controlled by two parameters such as the EPM matrix viscosity and the EVA concentration. The rheological and electrical properties varied abruptly when the CNT concentration is increased in the matrix. The low values obtained for this percolation threshold justify the use of EPM-EVA system. We have prepared an EPM-EVA master batch loaded with 20% of CNT and possessing very good conductive properties. We studied EPDM compound filled with carbon nanotubes, carbon black or the blend of both. We have demonstrated that the dilution of the master batch allows us to obtain a rubber filled with a constant Mooney viscosity but with an important impact on the vulcanization kinetics of elastomers. The synergistic effect between carbon black and carbon nanotubes has been shown on the mechanicals properties but not on the electrical ones.

Nos travaux sont consacrés à la fabrication, à la mise en œuvre et aux caractérisations de mélanges de polymères thermoplastiques thermostables destinés à des applications aéronautiques hautes températures. Le Poly(éther cétone cétone) PEKK, polymère semi-cristallin, a été choisi pour sa température de transition vitreuse (Tg) et son point de fusion (Tf) élevés. Les polyimides amorphes utilisés pour leur Tg élevée, sont le Poly(éther imide) PEI et le (polyimide) PI. Le but de ces mélanges est d’augmenter la Tg du PEKK, sans augmenter sa température de fusion. Ces travaux ont abouti à la caractérisation thermique, mécanique et rhéologique de chacun des polymères purs ainsi qu’à la définition d’un protocole de fabrication des mélanges. Les propriétés des mélanges ont alors été caractérisées par analyses thermomécaniques, par balayage calorimétrique différentiel et par des essais de traction afin de faire ressortir les meilleurs candidats pour les applications visées. Les modèles empiriques classiques de variation de la Tg prennent en compte seulement la composition des mélanges. Dans ce travail, nous proposons de corriger ceux-ci par la prise en compte de la variation du taux de cristallinité qui influe sur la composition de la phase amorphe et ainsi permettre une prévision plus fine de ce paramètre. La tenue au vieillissement à court terme des différents polymères dans un fluide aéronautique a aussi été abordée, et a montré que le PEKK a un effet protecteur sur les mélanges. / This PhD work presents the fabrication, processing and characterizations of thermoplastic thermostable polymer blends. It aims at finding new materials useable at high temperatures for aeronautical applications. Poly(ether ketone ketone), PEKK, a semi-crystalline polymer, has been chosen for its high glass transition temperature (Tg) and high melting point (Tf). Amorphous polyimides, that have been used for their high Tg, are Poly(ether imide), PEI, and Polyimide, PI. The aim of these blends is to increase the Tg of the PEKK without increasing its Tf. We have measured the thermal, mechanical and rheological properties of each neat polymer and the processing conditions of the blends have been defined. The properties of the blends have been characterized by thermomechanical analyses, differential scanning calorimetry and tensile tests to focus on the better candidates for the aimed applications. The classical empirical models of the Tg composition dependence take only into account the blends composition. We propose to correct them taking into account the crystallinity level, that affects the blends composition and predict a better prediction of the Tg . The short term ageing of these polymer blends specimens in a commonly used aeronautic fluid has also been studied, and showed the protection effect of the PEKK polymer in the blends.

A ciência na qual se estuda a deformação de um fluido no qual é aplicada uma tensão de cisalhamento é conhecida como reologia e o equipamento utilizado para a realização dos ensaios é chamado de reômetro. Devido a impraticabilidade de uso de reômetros comerciais, diversos pesquisadores desenvolveram reômetros capazes de analisar suspensões de macropartículas, baseados nos mesmos princípios de funcionamento dos equipamentos já existentes. Em alguns casos, a medição do torque do motor é realizada pela aquisição da tensão, uma vez que esta é proporcional ao torque. Entretanto, para melhor compreensão do resultado e para evitar a possibilidade de conclusões precipitadas, vê-se necessária correta interpretação do sinal elétrico, precisando avaliar qual frequência do sinal é relevante para o ensaio e, também, qual a melhor taxa de amostragem. Além da aquisição, para que o ensaio reológico seja realizado com precisão, é indispensável ótimo controle da taxa ou tensão do motor e uma alternativa é a utilização de um servomotor e um servoconversor. No caso desse ser comercial é essencial saber configurá-lo. Para facilitar o usuário leigo, alguns pesquisadores desenvolveram softwares para controle do equipamento e análise dos dados. Assim, o presente trabalho tem como objetivo propor uma metodologia para compreender o sinal aquisitado de um reômetro servo controlado e desenvolvimento do software de análise para o tratamento dos dados obtidos a partir de ensaios reológicos. Verificou-se a melhor configuração do servocontrolador, a melhor taxa de amostragem, de no mínimo 20 amostras/segundo, e, também, desenvolveu-se um filtro digital passa-baixa do tipo FIR para remover a frequência indesejada. Além disso, foi desenvolvido um software utilizando uma rotina em Matlab e uma interface gráfica do usuário (Graphical User Interface - GUI), para o pós-processamento dos dados para auxiliar o usuário leigo no tratamento e interpretação do resultado, que se mostrou eficaz. / Rheology is the study of the behavior of material in fluid state. Rheometer is the equipment used to perform rheological measurements. Because of the impracticability of commercial rheometer, many researchers have developed rheometer able to analyze macro particles suspension, based on the principle of operation of the existing equipment. In some cases, measurement of the motor torque is performed by acquiring voltage signal, since is proportional to torque. However, for better understanding of the rheological results, it is necessary to understand the electrical signal, evaluating which signal frequency is relevant and what is the best sample rate. In addition, for an accurate rheological testing, it is essential a precise control of the shear rate or shear stress of the motor and a good alternative is the use of a servomotor and a drive. In the case of the drive being commercial, it is essential to know how to configure it. To turn rheometer user-friendly, some researchers have developed software to control the equipment and to analyze data. Thus, this dissertation propose a methodology to understand the electrical signal of a servo controlled rheometer and development of analysis software to process the data obtained from rheological tests. It has been found the best configuration of the servo drive, minimum sampling rate of 20 samples/second, and development of a low pass digital filter to remove unwanted frequency. In addition, was developed a software using a Matlab routine and a Graphical User Interface (GUI) to assist the user in the processing and interpretation of the result.