Nous avons étudié la dynamique de particules rigides et sphériques immergées dans un écoulement de cisaillement simple et oscillant à bas nombre de Reynolds. Les particules, au delà d’une déformation critique, se comportent de façon irréversible. La particules suivent alors un processus diffusif appelé: diffusion induite par cisaillement. Dans cette thèse, nous avons montré, par une approche numérique et expérimentale, que les collisions solides entre particules sont à l’origine de ce phénomène. Des simulations numériques ont été effectués afin d’évaluer l’importance relative des forces hydrodynamiques longues portées, des forces de lubrifications et des forces de contact. Deux expériences ont été effectuées afin de mettre en évidence l’influence des contacts solides entre particules. Nous avons étudié la dynamique de 3 particules soumises à un écoulement de cisaillement périodique. Les trajectoires des particules sont irréversibles durant le premier cycle et réversible pour les cycles suivants. En montrant que l’amplitude de l’irréversibilité est corrélée à la rugosité des particules, nous fournissons une preuve évidente que des collisions solides entre particules ont bien lieu et que ces collisions influencent la dynamique des particules. Effectuée dans une suspension homogène, le rôle des contacts a aussi été mis en évidence en montrant que l’amplitude critique de déformation dépend de la rugosité des particules. Un modèle géométrique simple qui considère des `particules effectives’ ayant un volume dépendant de l’amplitude de déformation et de la rugosité des particules, nous a permis de quantitativement reproduire les mesures expérimentales. / Even at low Reynolds number, particles within a shear flow exhibit irreversible dynamics. Many theories have been put forth to explain this phenomenon, the origin of irreversibility remains unclear. An integrated program of experimental and computational studies has been performed to assess the origin of the irreversible behavior of particles. Numerical simulations were used to evaluated the relative importance of long-range hydrodynamic interactions, lubrication, and contact forces. By isolating contribution of these interactions, we have shown that neither the long-range hydrodynamic interactions nor the lubrication are responsible for irreversibility. Solid contacts between particles largely dominate this phenomenon. However, producing realistic results requires both contact interactions and lubrication. Two different experiments were performed to address the role of contacts between particles in sheared suspensions. In the first experiment, the particle trajectories are irreversible during the first cycle but reversible for the next cycles. By showing that the magnitude of irreversibility increases with the particle roughness, we provide direct evidence that contacts occur in viscous flow. Experimental particle trajectories are well captured by the numerical model. In the second experiment, performed in a homogeneous suspension, the role of solid collisions was also revealed by showing that the critical strain amplitude depends on the particle roughness. A geometrical model based on the assumption that colliding particles produce irreversibility was derived. The model successfully reproduces the measured values of the critical strain amplitude.

Hydrocracking of plastic wastes offers the best value in terms of quality of its process oil product among other feedstock recycling methods capable of recycling mixed plastic waste; a paraffin-rich synthetic crude similar in composition to gasoline and diesel is produced. Additional benefits of the process include heteroatom removal, catalyst conservation as well as a lower process temperature. However PVC content in mixed plastics waste and the high viscosity of plastics are prominent issues in relation to subjecting plastics to petrochemical processes such as hydrocracking. A 5ppm chlorine limit and maximum feedstock viscosity of 0.5 Pas at 200oC is tolerable in the petrochemical industry. Although dechlorination of mixed plastic waste has been studied exhaustively, viscosity studies in relation to process improvement or efficiency in the pyrolysis or hydrocracking of plastics haven’t received as much attention. Viscosity has been identified as being inhibitive to heat and mass transfer, and transport into reactors, as well as being a major problem in relation to designing reactors for feedstock recycling. In this research, four of the main polymer types; high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), Polypropylene (PP), Polystyrene (PS) and Polyethylene Terephthalate (PET) were rheological characterised to establish the extent to which they exceed the recommended viscosity in the petroleum industry. Viscosities 400 – 1200 times the feedstock viscosity in the petrochemical industry at a shear rate of 500s-1, which is typical for pumping and atomisation operations, were obtained during the characterisation of the plastic samples in a conventional capillary rheometer. Saturated chain hydrocarbon solvents (iso-octane, decane, tetradecane, pentadecane and hexadecane) were investigated for treating HDPE, in a range of HDPE-solvent mixtures, in order to reduce its viscosity. Preliminary results of differential scanning calorimetry tests carried out on the solvent-treated HDPE revealed a 12 – 16% drop in the melting peak temperature of the pure HDPE (129 oC) using tetradecane (108 oC), pentadecane (110 oC) and hexadecane (113 oC) for the 20:80 PE-solvent mixtures. iso-octane and decane however only produced a viscosity drop of 3% and 4% respectively for the same 20:80 PE-solvent mixtures. Thermal stability of HDPE was largely unaffected by the solvent treatment except in the case of pentadecane which showed a reducing trend on the decomposition onset temperature as solvent concentration in the starting mixtures was increased, albeit marginal (from 441oC to 437oC). A custom built sealed-vessel impeller viscometer designed to facilitate the treatment of the HDPE via solvent refluxing and in situ viscosity measurement was calibrated by determining constants which enable the conversion of machine data to viscosity and shear rate using Newtonian and non-Newtonian calibration fluids. These constants, the shape factor and shear rate conversion factor, were determined to be 81.03 and 22.08, respectively, with corresponding 95% confidence limits of 79.21 and 86.26, and 21.47 and 24.00. Viscosity measurements of a 40:60 PE-nC15 mixture carried out in the sealed-vessel impeller viscometer at a shear rate of between 71s-1 and 80s-1 at 95% confidence level and 250oC was 7 Pas representing approximately 200 fold reduction from the virgin HDPE measured in the conventional capillary rheometer.

Metronidazole is a synthetic, nitroimidazole-derivative antibacterial and antiprotozoal agent (ed. McEvoy, 2001). It has been reported that crystallization occurs in aqueous suspensions of metronidazole benzoate, a bland-tasting prodrug of metronidazole, as a result of conversion from the anhydrous to the monohydrate form, thereby compromising the stability and clinical efficacy of the substance due to the particle size growth (Hoelgaard & Moller, 1983). A generic South African based pharmaceutical company commenced formulation of an aqueous metronidazole benzoate suspension and experienced problems with crystallization that occurred in products stored at 2 to 8 °C. This study aimed to continue development of the product in order to identify a formulation that prevents formation of the hydrate form of metronidazole benzoate and the accompanying crystal growth. A variety of metronidazole benzoate suspensions were manufactured on a laboratory scale using a number of natural and synthetic suspending agents, including magnesium aluminium silicate, povidone K90, xanthan gum and Avicel® RC-591 (microcrystalline cellulose and carboxymethylcellulose sodium), over a range of concentrations. Analytical quantification methods were developed and validated, and the physicochemical properties of the raw material and finished products were fully characterized. Rheological tests were performed in order to characterize the suspension flow properties. Real-time and accelerated stability studies and a temperature cycle study were conducted in accordance with the International Conference on Harmonization (ICH) guidelines. Conversion of metronidazole benzoate to the monohydrate form took place in suspensions containing xanthan gum 0.65 percent m/v under real-time and accelerated storage conditions. The suspensions containing Avicel® RC-591 were found to be physically and chemically stable after the temperature cycle and over the 12-week period whilst stored at 25 ºC / 60 percent RH and 5 ºC. The suspensions were chemically stable whilst stored at 40 ºC / 75 percent RH but showed sedimentation at this accelerated condition. The metronidazole benzoate contained in these products remained in the anhydrous state under all storage conditions and were consequently concluded to be the most stable formulations out of all the products analyzed in the current study. The suspending agent system consisting of microcrystalline cellulose and carboxymethylcellulose sodium thus shows promise in preventing the conversion of metronidazole benzoate from the anhydrate to the monohydrate form, thereby inhibited the subsequent increase in particle size due to crystal growth.

Materials can flow down a slope in a wide range of geophysical and industrial contexts, including lava flows on volcanoes and thin films on coated surfaces. The aim of my research is to provide quantitative insight into these forms of motion and their dependence on effects of the topography, the volume and the rheology of the flowing structure. Numerous different problems are investigated through mathematical models, which are developed analytically and confirmed by laboratory experiments. The initial advance of long lava flows is studied by considering the flow of viscous fluid released on sloping channels. A scaling analysis, in agreement with analog experiments and field data, offers a practical tool for predicting the advance of lava flows and conducting hazard analysis. A simple and powerful theory predicts the structure of flows resulting from any time-dependent release of fluid down a slope. Results obtained by the method of characteristics reveal how the speed of the advancing front depends importantly on the rate of fluid supplied at an earlier time. Viscous flows on surfaces with different shapes are described by similarity solutions to address problems motivated by engineering as well as geophysical applications. Pouring viscous fluid out of a container can be a frustratingly slow process depending on the shape and the degree of tipping of the container. The discharge rate of the fluid is analysed in simple cases, shedding light on how containers can be emptied most quickly in cosmetic and food industries. In a separate study motivated by coating industries, thin films are shown to evolve with uniform thickness as they drain near the top of a horizontal cylinder or sphere. The leading edge eventually splits into rivulets as predicted theoretically and confirmed by experiments. Debris flows can develop levees and trigger avalanches which are studied by considering dense granular flows down a rough inclined plane. Granular materials released down a slope can produce a flowing structure confined by levees or trigger avalanches at regular intervals, depending on the steady rate of supply. The experimental results are discussed using theoretical ideas of shallow granular flows. Finally, materials flowing in long and slender ducts are investigated theoretically to better understand the digestive and urinary systems in biology. The materials are pumped in an elastic tube by translating waves of muscular contraction and relaxation. The deformation of the tube is predicted by solving a free-boundary problem, a similar mathematical exercise to predicting the moving boundaries of materials spreading on slopes.

The purpose of this project has been to investigate potential correlations between rheological properties and jetting quality of solder paste. The project was carried out for Mycronic AB. Data from previously obtained measurements for both rheological properties and jetting quality were used in the analysis. We were only able to suggest preliminary correlations. One reason for this was that the jetting data was not designed for correlation work. It was performed to set parameters for new fluids. The data was inconsistent and difficult to work with in a correlation studie. However, the work led to a framework for future studies and correlation work.

Les adhésifs sensibles à la pression (PSAs) sont constitués de matériaux polymères mous qui collent presque instantanément sur presque tout type de surface. Les propriétés adhésives de ces matériaux sont principalement contrôlées par leurs propriétés rhéologiques et ainsi, par la structure moléculaire des polymères utilisés dans leur formulation. La nature des monomères, la distribution des masses molaires et le degré de réticulation sont des exemples de paramètres habituellement définis par les ingénieurs pour l’optimisation des adhésifs commerciaux. La singularité de notre projet est d’étudier les propriétés adhésives de matériaux polymères modèles fonctionnalisés par des groupements urée.Ces groupements fortement interactifs par liaison hydrogène renforcent les propriétés élastiques et dissipatives de la matrice polymère constituée de chaînes non enchevêtrées, tout en gardant une très faible viscosité dans les solvants non polaires. Inspiré de l’étude récente sur le PIBUT (Courtois et al, Adv .Func. Mater. 2010), nos systèmes modèle sont constitués de chaînes linéaires polybutylacrylate fonctionnalisées en leur milieu. La méthode de synthèse utilisée dans notre projet permet un très bon contrôle de la longueur des chaînes, tout en permettant d’utiliser une grande diversité de groupements interactifs. La caractérisation systématique de nos matériaux nous a permis d’identifier les paramètres structuraux qui gouvernent la rhéologie et l’adhésion. Des structures supramoléculaires plus complexes ont aussi été explorées dans notre projet et montrent clairement le fort potentiel de la chimie supramoléculaire pour le domaine de l’adhésion. / Pressure Sensitive Adhesives (PSA) are soft polymer materials which stick on almost any surface due to their particular rheological properties. Engineers adjust polymers molecular structure to optimize adhesion properties for each application. The nature of the monomers, molecular weight distribution and degree of crosslinking are classical tunable parameters for acrylic adhesives. The specificity of our project is to investigate the adhesive properties of model polymers functionalized by urea groups. The presence of strong hydrogen bonds inside the polymeric matrix allows to dramatically increase the viscosity and dynamic modulus of short polymer chains (M<20kg/mol) reducing the need for crosslinking while reducing dramatically the viscosity when dissolved in polar solvents. Inspired by the recent study on PIBUT (Courtois et al, Adv .Func. Mater. 2010), our model systems are linear center-functionalized polybutylacrylate chains synthesized with a highly controlled but versatile synthesis method. In our work, the extensive characterization of these materials allowed us to identify the key structural parameters governing their rheology and their adhesive properties. More complex structures were also investigated and showed clearly the potential of the supramolecular chemistry for the science of adhesion.

Orientadores: Florencia Cecilia Menegalli, Rosiane Lopes da Cunha / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-14T14:28:38Z (GMT). No. of bitstreams: 1 CiroVelasquez_HectorJose_D.pdf: 3600504 bytes, checksum: efd0571f00b5ea398f5836590f0165bb (MD5) Previous issue date: 2009 / Resumo: Suspensões de gomas xantana e de l-carragena foram secas usando um secador de leito de jorro fluidizado com partículas inertes de vidro e plásticas de ABS (acrylonitrile butadine styrene). O processo de secagem foi avaliado quanto ao desempenho do secador (eficiência de produção de pó e retenção de sólidos), características fluidodinâmicas (velocidades da partícula inerte no jorro e ânulo, queda de pressão no leito, largura da fonte, altura máxima de jorro, distribuição de temperaturas no leito) e qualidade do produto final obtido (propriedades reológicas e teor de umidade). Um planejamento fatorial 23 com 2 pontos centrais e 6 pontos axiais e superfícies de resposta foi usado para determinar o efeito das condições de secagem (temperatura de ar, vazão de suspensão e vazão de ar no jorro e ânulo) sobre o processo e na qualidade do produto final. Os resultados mostraram que foi possível obter produto reconstituído de pó de xantana usando vidro ou ABS como inerte. No entanto, para suspensões de l- carragena não foi possível a secagem com partículas esféricas de vidro devido à alta tensão superficial e baixo ângulo de contato. De acordo com os resultados do planejamento experimental, a eficiência de produção média de pó de goma xantana usando vidro como inerte foi de 28% com uma retenção de sólidos de 65%, enquanto que usando ABS a produção média foi de 45% e a retenção de sólidos de 49%, ou seja, o melhor desempenho do secador ocorreu quando ABS foi empregado como partícula inerte. Para a secagem de suspensões de l-carragena com partículas de ABS a eficiência de produção média de pó foi de 23% e a retenção media foi de 71%. A variável mais relevante na secagem das suspensões de gomas xantana e carragena foi a vazão de suspensão, sendo que um aumento desta variável produziu um baixo rendimento de pó e aumentou a retenção de sólidos dentro do leito. A queda de pressão do leito apresentou uma variação periódica indicando uma instabilidade fluidodinâmica. A distribuição de temperatura no leito mostrou uma operação quase isotérmica e que o processo evaporativo ocorreu principalmente na zona do jorro e base do ânulo. A velocidade da partícula no jorro foi dependente da vazão de ar na região do jorro, enquanto que a velocidade da partícula dentro no ânulo foi função da vazão de suspensão e também da vazão de ar que passava pelo jorro. A xantana obtida pela secagem em jorro fluidizado formou suspensões de natureza altamente pseudoplástica e com propriedades viscoelásticas de gel fraco. A vazão de alimentação da suspensão (=1 g/min) foi um fator importante para a preservação da qualidade reológica. A secagem de suspensões de goma xantana realizada em condições ótimas, tanto em leitos com partículas de ABS quanto de vidro, não mostrou efeito na qualidade reológica do produto. O produto reconstituído de l-carragena obtido nas condições otimizadas de secagem também formou suspensões de natureza altamente pseudoplástica, porém com propriedades viscoelásticas características de suspensões altamente diluídas (G''>G'), mostrando valores de viscosidade, módulos elástico (G') e de perda (G'') menores que o produto comercial e portanto uma perda de qualidade do produto. Nas condições de melhor desempenho do secador, as suspensões de l-carragena foram mais susceptíveis a sofrer mudanças em sua estrutura molecular que a goma xantana / Abstract: Xanthan and l-carrageenan suspensions were dried using a two dimensional spouted fluidized bed dryer with inert particles of glass and ABS (acrylonitrile butadine styrene).The dryer performance (powder production and solid retention), fluid flow characteristics (particle velocity in the spout and annulus, pressure drop, fountain width, maximum spout height, distribution of temperatures inside the bed) and quality properties of final product (rheological properties and moisture content) were evaluated. A complete 23 factorial design with 2 central points and 6 axial points together with response surfaces analysis was used to determine the effect of the drying conditions (drying temperature, suspension mass flow and air flow in the spout and annulus) on the drying process and final product. The results showed that it is possible obtain a reconstituted powder of xanthan gum using glass and ABS as inert particles. However, for suspensions of l- carrageenan was not possible the drying with glass spherical particles due to high superficial tension (low angle of contact). According to results of experimental design the mean powder production of xanthan gum using glass as inert was of 28% with a solid retention of 65%, whereas using ABS the mean powder production was of 45% with a solid retention of 49%, thus the best performance of the drier occurs when the bed with ABS is operated. In addition, the drying of l carrageenan suspensions with ABS particles showed a me n production of 23% with a solids retention of 71%. The most significant variable in the drying of the suspensions of xanthan and l carragena gum was the suspension mass flow rate where an increases produces a diminishing of the powder production increasing the solids retention in the bed. The pressure drop in the bed presented a periodic variation with the processing time indicating a hydrodynamics instability. The temperature distribution in the bed showed that annulus zone operated almost isothermally and that the spout zone and the annulus base are the zones where occurs the evaporative process. The particle velocity in the spout depends upon of the air flow in the spout, whereas the particle velocity in the annulus is function of the aeration and suspension mass flow rate. The reconstituted xanthan powder produced suspensions of highly pseudoplastic nature and with viscoelastic weak gel properties. The suspension mass flow rate (=1 g/min) was a factor important to preserve its rheological quality. To xanthan gum the drying operating conditions evaluated in the optimum point showed that the inert particle (ABS and glass) not influenced on the rheological quality of the reconstituted product. The l-carrageenan suspensions evaluated in the drying optimum conditions formed suspensions of highly pseudoplastic nature with viscoelastic properties of suspensions highly diluted (G''>G'). Also, the rheological and viscoelastic characteristics as viscosity, storage (G') and loss moduli (G'') are lower than commercial gum indicating a severe loss of product quality. In the conditions of better performance of the dryer, the suspensions of l- carrageenan were more sensitive to suffer changes in its molecular structure than the xanthan gum / Doutorado / Doutor em Engenharia de Alimentos

Orientador: Edvaldo Sabadini / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T01:55:14Z (GMT). No. of bitstreams: 1 Simoes_ThiagoAugusto_M.pdf: 2543594 bytes, checksum: 7e559c17b32f95f43db82455a855492b (MD5) Previous issue date: 2014 / Resumo: Materiais nanoestruturados apresentam-se em muitas formas diferentes. Um grupo de compostos ainda pouco investigado é o grupo dos organogéis, especialmente aqueles cuja estrutura tridimensional de rede é baseada na auto-organização de compostos orgânicos de baixa massa molecular, capazes de promover a gelificação no meio em que se encontram. São os chamados "Low Molecular Organic Gelators ¿ LMOG". Esses materiais termorreversíveis consistem de uma pequena quantidade de LMOG e um líquido orgânico. O presente trabalho visa esclarecer os mecanismos de auto-organização dos LMOG na escala supramolecular. Os LMOG estudados são derivados em moléculas que podem ser divididas em três partes. A parte central é constituída por um anel fenílico. Em uma das partes está ligado um grupo glicosídeo, e em outro ponto do anel uma cadeia alquílica. Procurou-se estudar as características estruturais e cinéticas de géis formados em um solvente aromático (para-xileno) e em um solvente formador de ligações de hidrogênio (n-propanol). Avaliaram-se, então, os efeitos relacionados com o balanço polar-apolar da molécula de LMOG, analisando os géis com 8, 4 e 3 unidades metilênicas da cadeia alquílica, bem como os efeitos de solvatação. A investigação dos fenômenos foi realizada utilizando a reologia rotatória e oscilatória nos regimes diluído e concentrado, aliada às técnicas de microscopia eletrônica de varredura (MEV), difratografia de raios-X e difusão dinâmica da luz (DDL) / Abstract: Nanostructured materials exist in many different ways. A group of compounds which has not been much investigated is the group of organogels, especially those whose three-dimensional network structure is based on the self-assembly of low molecular weight organic compounds. They promote gelation in the medium in which they are. These compounds are titled as "Low Molecular Mass Organic Gelator - LMOG" and they form thermoreversible materials constituted by a small amount of a LMOG and an organic liquid. The work presented in this dissertation aimed to clarify the mechanisms of self-assembly in a supramolecular scale. The LMOG molecules studied have a phenyl ring with a glycoside group bonded in one side and an alkyl chain bonded in the other part of the aromatic ring. The kinetic and structural characteristics of the gel formed in an aromatic solvent (para-xylene) and in a solvent donator of hydrogen bonding (propanol) were investigated. Therefore, the effects emerged from the polar-nonpolar balance of the LMGO molecule with 8, 4 and 4 methyl groups in the alkyl chain, as well as the solvation effect. The investigations were performed using the rotational and oscillatory rheology in dilute and concentrated regimes combined with the techniques of Scanning Electron Microscope (SEM), X-RAY diffraction and Dynamic Light Scattering (DLS) / Mestrado / Físico-Química / Mestre em Química

Orientador: Eugênio José Zoqui / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-27T09:38:07Z (GMT). No. of bitstreams: 1 Peluso_TomaisGoncalves_M.pdf: 4698944 bytes, checksum: 3430f71d5bf40358338cef1d992df4fc (MD5) Previous issue date: 2015 / Resumo: O objetivo desse estudo é avaliar a tixoconformabilidade da liga A318 sob três pontos de vista: o termodinâmico, o metalúrgico, e o reológico. Esse trabalho é motivado pela falta de estudos sobre a tixoconformabilidade desse material em ambientes industriais. Foram realizadas análises DSC e simulações utilizando o software Thermo-calc® para verificar a viabilidade do ponto de vista termodinâmico. Foram feitas comparações entre o material fundido com e sem agitação eletromagnética para decidir qual seria usado como material de estudo para o tratamento térmico de globularização, e em seguida análises para determinar tamanhos de glóbulo de fase primária, tamanhos de grão e fatores de forma, o que resultou no material fundido com agitação sendo escolhido. O material então passou pelo tratamento térmico de globularização, a fim de observar a evolução morfológica do material. Foram utilizadas micrografias para determinar os tamanhos de glóbulo primário e fator de forma, e micrografias coloridas para determinar os tamanhos de grão, para cada condição de ensaio proposta. O tratamento térmico globularizou com sucesso a microestrutura do material, obtendo fatores de forma de até 0,64, e tamanhos de glóbulo e grão de apenas 76 e 115 µm respectivamente. O material tratado termicamente passou então por ensaios de compressão a quente, para que fosse observado seu comportamento reológico. O maior valor de tensão obtido durante os ensaios foi de apenas 1,95 MPa, e a viscosidade aparente se manteve na ordem de grandeza de 105 Pa.s, o que de acordo com a literatura é semelhante à do vidro fundido, e apresentam ótima conformabilidade. De maneira geral, observou-se pouca variação na morfologia e na reologia do material para as condições de estudo propostas, mostrando que o material é viável para ser utilizado no estado semissólido em ambientes industriais / Abstract: The objective of this study is to evaluate the thixoformability of the A318 alloy under three points of view: the thermodynamic one, the metallurgic one, and the rheologic one. This work is motivated by the lack of that support the thixoformability of this material in industrial environment. DSC analyses, and simulations using the Thermo-calc® software were run in order to verify the viability from the thermodynamical point of view. Comparisons were made between the materials as-cast and electromagnetically stirred in order to decide which would be the feedstock material for the globularization heat treatment, analyzes to determine globule size, grain size and shape factor resulted in the stirred material being chosen. Material then went into globularization heat treatment in order to observe the evolution of the material¿s microstructure. The heat treated material then went through hot pressing tests in order to observe its rheologic behavior. Micrographs were used to determine average primary globule size and shape factor, and macrographs to determine grains size. The heat treatment successfully globularized the microstructure, giving shape factors as high as 0.64, and primary globule and grains sizes only as high as 76µm and 115µm respectively. The material then went through hot pressing tests in order to observe its rheologic behavior. The highest stress shown during the tests was only as high 1,95 MPa, and the apparent viscosity was in the order of magnitude of 105 Pa.s, which according to specialized literature is similar to that of the molten glass, which shows great conformability. In general, there was close to no variation in morphologic and rheologic behavior for the intended test conditions, showing the material¿s processing in the semisolid state in industrial environments to be viable / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Orientador: Edvaldo Sabadini / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T18:09:34Z (GMT). No. of bitstreams: 1 Creatto_EduardoJose_M.pdf: 2495128 bytes, checksum: 6912961c15614521a8e45f4e9139f99f (MD5) Previous issue date: 2015 / Resumo: A química supramolecular envolve estruturas mantidas por interações intermoleculares. Neste contexto, sistemas que apresentam estruturas auto organizadas são de interesse devido importância como ciência de base bem como aplicabilidade. Neste trabalho foram utilizadas micelas de brometo de hexadeciltrimetilamônio (CTAB) como reticulantes de hidroxietilceluloses hidrofobicamente modificadas. Como as micelas estão em constante quebra e recombinação, reticulações transientes são obtidas. Tais sistemas apresentam comportamento reológico característico, dependente da concentração do surfactante. Obervou-se que a celulose que apresenta maior ramificação hidrofóbica resulta em aumento mais efetivo da viscosidade como consequência do maior grau de reticulação. A Técnica de calorimetria de titulação isotérmica (ITC) foi utilizada de modo a compreender os processos energéticos envolvidos na agregação. Com esta pôde-se obter parâmetros do sistema como cmc, cac e ?H°mic . Elucidou-se também que as interações polímero-surfactante são de origem hidrofóbica. A adição de salicilato de sódio (NaSal) em solução de CTAB leva a formação de micelas gigantes. Determinou-se por ITC a razão, [CTAB]/[NaSal], em que ocorre a formação de micelas gigantes, bem como a variação de entalpia deste processo. Sistemas contendo micelas gigantes e na presença de celulose hidrofóbicamente modificada foram estudados por reologia. Variações em seu comportamento foram claramente observadas / Abstract: Supramolecular chemistry involves structures maintained by the intermolecular interactions. In this context, systems that have self-assembled structures are of interest because of importance as basic science as well as applicability. In this study, we used micelles formed by hexadecyltrimethylammonium bromide (CTAB) as crosslinking agents of hydrophobically modified hydroxyethylcelluloses. As the micelles are constantly breaking and recombination, transient crosslinks are obtained. Such systems have characteristic rheological behavior, dependent on the surfactant concentration. It was observed that the cellulose which is more hydrophobic branching results in more effective increase in viscosity as a result of the higher degree of crosslinking. Isothermal titration Calorimetry (ITC) technique was used to understand the energy involved in the aggregation process. With this it was possible to obtain system parameters such as cmc, cac and ?H°mic. It is also elucidated that the interaction polymer-surfactant are of hydrophobic origin. The addition of sodium salicylate (NaSal) into CTAB solutions leads to formation of giant micelles. It was determined by ITC the ratio [CTAB]/[NaSal] in what occurs the formation of giant micelle, and the enthalpy change of the process. Systems containing giant micelles in the presence of hydrophobically modified cellulose were studied by rheology. Variations in their behavior were clearly observed / Mestrado / Físico-Química / Doutor em Ciências