Cette thèse est une contribution à la modélisation du comportement d'une suspension de bulles dans un fluide non newtonien du type fluide à seuil. Elle comprend trois parties. La première partie est une étude bibliographique recensant les travaux théoriques et expérimentaux pour des bulles cisaillées dans un matériau newtonien. La seconde partie est consacrée à l'étude expérimentale de cisaillement simple d'une bulle suspendue dans un fluide à seuil. La dernière partie présente une approche par changement d'échelle du comportement macroscopique d'une suspension de bulles dans un fluide à seuil. Pour le travail expérimental, nous avons développé un premier prototype de dispositif permettant de cisailler d'une bulle suspendue dans un fluide à seuil. Pour cela, une bulle d'air est injectée au sein d'un grand volume de Carbopol cisaillé loin de la bulle par un dispositif à bandes parallèles. Une première série d'essais a permis de montrer l'efficacité du dispositif et d'obtenir quelques résultats sur la déformabilité d'une bulle cisaillée par un fluide à seuil. Pour le travail théorique, d'abord nous avons proposé des estimations du comportement de la suspension dans le cas des schémas dilué, Mori-Tanaka, autocohérent et motifs morphologiques. Ces modèles nous ont permis de trouver que dans le régime élastique le module élastique macroscopique de la suspension dépend du nombre capillaire Caelast défini comme le rapport entre le module de cisaillement du fluide porteur et la pression capillaire de la bulle. Ensuite en utilisant une méthode d'homogénéisation sécante modifiée (Suquet 1997), nous avons estimé des caractéristiques non linéaires globales de la suspension. Le modèle prédit que le seuil d'écoulement de la suspension est égal au seuil d'écoulement du fluide porteur quelle que soit la taille des bulles. La validation de ces modèles micromécanique a été réalisée par comparaison aux résultats expérimentaux obtenus au laboratoire (Ducloué 2014).Mots clés : suspension de bulles, fluide à seuil, rhéologie, nombre capillaire, approche par changement d'échelle / This thesis contributes to characterizing the behavior of a suspension of bubbles dispersed in a non-Newtonian fluid (yield stress fluid type).It consists of three parts. The first part is a literature review identifying the theoretical and experimental works for bubbles sheared in a Newtonian material. The second part is dedicated to the experimental study of the simple shear of a bubble suspended in a yield stress fluid. The last part consists in developing an upscaling approach to study the macroscopic behavior of a suspension of bubbles in a yield stress fluid. For experimental work, we developped a first prototype of device for the study of the shearing of a bubble in a yield stress fluid. For that purpose, an air bubble is injected in a big volume of Carbopol sheared far from the bubble by a system in two parallel bands. A fist series of tests allowed to show the efficiency of the device and to obtain some results on the deformability of a sheared bubble in a yield stress fluid. For theoretical work, first we proposed estimates of the behavior of the suspension in the case of diluted scheme, Mori-Tanaka, autocoherent and morphological patterns. These models have allowed us to find that in the elastic regime the macroscopic elastic modulus of the suspension depends on the capillary number Caelast defined as the ratio of the shear modulus of the fluid suspended over the capillary pressure of the bubble. Then using a modified secant homogenization method (Suquet 1997), we estimated the overall nonlinear properties of the suspension. The model predicts that the overall yield stress of the suspension is that of the suspending fluid regardless of the size of bubbles. The validation of these micromechanical models was achieved thanks to the experimental results obtained in the laboratory (Ducloué 2014).Keywords: bubbles suspensions, yield stress fluid, rheology, capillary number, upscaling approach

Les suspensions de grains rigides dans un fluide constituent une classe de fluides complexes présentant une rhéologie riche. Même dans les cas simples où le fluide est Newtonien, et les grains sphériques, non Browniens et non colloïdaux, les comportements macroscopiques observés restent mal compris, en particulier dans le cas de suspensions concentrées. Dans ces matériaux, la complexité de la dynamique provient de l'équilibre subtil qui se met en place entre les interactions de nature hydrodynamiques portées par le fluide interstitiel et les forces de contact entre les grains. Dans ce travail, nous abordons ces questions sous l'angle de la simulation numérique discrète, dans le cadre du cisaillement simple de suspensions concentrées 2D. Nous modélisons les efforts hydrodynamiques par des interactions de lubrification de paires, couplées à un modèle de contact éventuellement frottant. L'inertie des grains n'est pas négligée. Nous accédons à tous les coefficients du tenseur des contraintes, ce qui permet de mesurer pression, contrainte de cisaillement, et différence des contraintes normales, ainsi que les viscosités associées. L'étude du cisaillement à volume constant nous permet de mettre en évidence l'existence d'une transition de rhéo-épaississement entre un régime visqueuse à bas taux de cisaillement (contrainte proportionnelle au taux de cisaillement) et un régime inertiel à haut taux de cisaillement (contrainte proportionnelle au carré du taux de cisaillement), selon que la contrainte soit dominée par les interactions de lubrification ou par l'inertie des grains. Le taux de cisaillement de transition mesuré est compatible avec un argument d'échelle pour la contrainte, tenant compte de sa divergence avec la fraction volumique. Des simulations du cisaillement à pression constante nous permettent ensuite d'explorer le comportement de suspensions très concentrées (jusqu'à 1% de la fraction volumique de blocage théorique) dans leur domaine d'écoulement visqueux. Nous montrons que la rhéologie du mélange peut se décrire sous la forme d'une loi d'écoulement dépendante du seul nombre visqueux, construit comme le rapport entre un temps caractéristique de réarrangement local des grains sous l'effet des forces visqueuses et un temps typique de convection imposé par l'écoulement. Cette description nous permet de caractériser précisément la divergence de la contrainte avec la concentration en particules. Enfin, nous mesurons la microstructure stationnaire développée dans l'écoulement. Nous mettons en évidence une anisotropie importante des contacts générés, et discutons l'évolution de cette distribution avec la concentration du mélange / Suspensions of rigid grains in a fluid constitute a class of complex fluids that present a rich rheology. Even simpler cases of non-Brownian, non-colloidal spherical grains suspended in a Newtonian fluid feature macroscopic behaviours that are still not completely understood, especially when the concentration of particles is high. In these materials, the complexity of the dynamic is the result of the subtle balance that occurs between hydrodynamic interactions mediated by the interstitial fluid, and contact forces between grains. In this work, we tackle those questions from the point of view of discrete numerical simulations, in the context of the simple shear of 2D concentrated suspensions. Hydrodynamic interactions are modelled by pair lubrication, coupled with a possibly frictional contact law. Grains inertia is not neglected. We have access to the whole stress tensor, allowing the measure of pressure, shear stress, and normal stress difference, as well as their associated viscosities. The study of constant volume simple shear shows the existence of a shear-thickening transition between a viscous regime at low shear rate (stress proportional to the shear rate) and an inertial regime at high shear rate (stress proportional to the shear rate squared), depending on whether the stress is dominated by lubrication interactions or grains inertia. The position of the measured transition shear rate is consistent with a scaling argument for the stress that takes its divergence with concentration into account. Constant pressure simple shear simulations then let us explore the behaviour of very concentrated suspensions (up to 1% to the theoretical jamming fraction) in their viscous flow domain. We show that the rheology of the mix can then be described by a flow law that is only function of the viscous number, constructed as the ratio of a typical time for the local rearrangement of grains subjected to viscous forces, and a convection time consistent with the imposed flow. This allows a precise characterization of the divergence of stress with particles concentration. At last, we measure the stationary microstructure that develops within the flow. We show an important anisotropy of contacts, and discuss the evolution of this distribution with the concentration of the suspension

No description available.

This work presents theoretical and experimental findings pertaining to the possible replacement of conventional, automotive fuels by solid, light alkaline-metal borohydrides (EM+,B3+/H-). On a complete oxidation basis, and under certain arrangements, the latter fuels have volumetric energy capacities that exceed the most recognized, automotive constraints; furthermore, the solid metal oxide products (EM+,B3+/02-) have the potential to be regenerated off-board to their respective hydrides via electrolytic reverse complete oxidation processes. Electrolytic reverse complete oxidation processes are conceptualized as water electrolysis and electrolytic reverse combustion or electrolytic reverse hydrolysis unit operations in series. To more clearly express these mostly electrochemical fuel-cycles, a thermodynamic reaction model was contrived. To investigate the electrolytic reverse hydrolysis hypothesis, attempts were made to prepare metal-supported, electrolytic reverse hydrolysis anode compartments. The glycine nitrate process facilitated the synthesis of nickel iron oxide (anode) and select doped ceria fluorite and double-doped LaGaO3 perovskite (solid oxygen anion electrolytes) powders. Hydridic electrolyte compositions belonging to the Na2BH5-Na413205 quasi-binary system were synthesized from NaH, NaBH4 and NaB02. Analyses for the materials' compatibilities and solubilities studies (823 + 10 °K, 1.00 f 0.01 MPa) included induction coupled plasma, inert x-ray diffraction, and scanning electron microscopy. NaH reduces magnetite to austenite; hence, the most promising solid oxygen anion electrolyte, Lao7Sro3GauFeo3Mgo 103.6 (LSGFM), cannot be in direct contact with these hydridic electrolytes. The other oxides of Lao8Sro2Ga08Mg0203.6 are significantly soluble in these melts, but either a quenching or an electrochemical technique will be required to more accurately assess their values. For the preparation of small, metal-supported, electrolytic reverse hydrolysis anode compartments, suspension plasma spraying was used for the depositions of the anode and solid oxygen anion electrolyte layers. Energy dispersive x-ray spectroscopy, scanning electron microscopy, and x-ray diffraction were used for the analyses of the resultant coatings' characteristics. In consequence of LSGFM's remarkable specific conductivity at — 673 °K, a solid oxygen anion electrolyte-supported, electrolytic reverse combustion or electrolytic reverse hydrolysis anode compartment design may be considered, but this will require the addition of a protective, solid oxygen anion electrolyte layer. The thermodynamic analyses has identified scandia stabilized zirconia as the most auspicious solid oxygen anion electrolyte; hence, understanding the nature of the anhydrous Sc)+,Zr4*,B3+,Na+,H+/H",02" system at 723 ± 50 °K and < 1.0 MPa is paramount to further efforts regarding electrolytic reverse hydrolysis or electrolytic reverse combustion proof-of-concept studies. [symboles non conformes]

Cette thèse a pour objectif l'étude du comportement vibratoire des suspensions à joint de ferrofluide utilisées dans un nouveau type de haut-parleur. Le moteur de ce haut-parleur, conçu pour réduire les non-linéarités d'origine magnétique, permet l'utilisation de joints de ferrofluide comme alternative aux suspensions viscoélastiques traditionnelles : sous la forme de deux joints annulaires, ils réalisent la liaison entre la partie fixe et la partie mobile du système. L'originalité du travail présenté a trait aux forts niveaux du champ magnétique présent dans le haut-parleur et à la caractérisation en dynamique des joints en terme de masse, raideur et amortissement. La première partie est une analyse expérimentale de la raideur radiale statique d'un joint au sein d'un moteur magnétique. La connaissance de cette raideur est nécessaire pour dimensionner le guidage de l'équipage mobile. Elle est étudiée en fonction du volume et de la saturation magnétique du ferrofluide. Les résultats sont en bon accord avec les simulations. Dans une deuxième partie, nous présentons une étude expérimentale sur le comportement visqueux des ferrofluides en condition de cisaillement oscillatoire et sous champ magnétique homogène et stationnaire. Cette étude s'élargie dans la suite aux conditions magnétiques du moteur, où le champ n'est plus homogène. Les propriétés sont étudiées en fonction du volume, de la viscosité et de la saturation magnétique. Un modèle pour les pertes du haut-parleur est proposé en fonction des propriétés magnétovisqueuses du ferrofluide.

No description available.

Laboratory studies conducted at 5, 15, 25, and 35 C measured changes in gilling rates and oxygen consumption of green sunfish in response to exposure to bentonite clay suspensions. The tests indicate that gilling rates are not affected by bentonite clay suspensions below 2125 FTU at 5 C, 1012 FTU at 15 C, and 898 FTU at 25 C. At turbidity levels exceeding 1012 FTU at 15 C and 898 at 25 C, gilling rates increased 50-70%. Tests were inconclusive at 35 C. Oxygen consumption rates were found to be unaffected by turbid suspensions below 3500 FTU at all four temperatures. Evidence suggests that increased gilling rates under highly turbid conditions are a means of compensating for reduced respiratory efficiency and a strategy for maintaining a constant oxygen uptake. Evidence indicates that the cost of increased gilling rates is probably met by a reduction in activity.

O estudo da dispersão e estabilização de barbotinas de porcelana de cinza de ossos é uma etapa muito importante no processo de conformação de peças cerâmicas, assim como também a etapa de obtenção da sua principal matéria-prima que é a cinza de ossos, devido a que constitui 50% em peso da porcelana e por ser uma matéria-prima renovável, reciclável e com alto valor agregado na fabricação de porcelana. Neste trabalho se investigou a influência das temperaturas de calcinação dos ossos (700, 800, 900 e 1000 °C) moídos e lavados, no seu tamanho, forma das partículas, composição química, comportamento elétrico superficial das partículas com o meio líquido, grupos funcionais e possíveis contaminantes nas superfícies das partículas dos ossos calcinados, que poderiam prejudicar a preparação de barbotinas de porcelana de ossos. Mostra-se também a dispersão, preparação e a estabilização da mistura de porcelana de ossos (50% cinza de ossos, 25% de caulim, 25% de feldspato) por meio dos ensaios de viscosidade e mobilidade eletroforética, conseguindo dispersar, homogeneizar e estabilizar as suspensões de porcelana de ossos aplicando tempos de envelhecimentos apropriados. / The study of the dispersion and stabilization of slip casting of bone porcelain is a very important stage in the process of preparation of suspensions ceramic, as well as the obtaining of its main material, that it is the bone ash, so that it constitutes 50% in weight of dry mass, and also that is one raw material renewable, recyclable and with high value added in the porcelain production. In the present research, the influence from the calcination of bovine bones to different temperatures (700, 800, 900 and 1000 °C) was investigated besides the size and form of the particles, variation in its chemical compositions, variations in its electric superficial behavior of the particles in contact with the liquid medium and also the groups present functional in the particles of ash of bones, kaolin and feldspar. Reveals the behavior of the particles during the dispersion and stabilization of the bone porcelain (50% ash of bones, 25% kaolin, 25 % feldspar) by means of the tests of viscosity and electrophoretic mobility, being able to disperse, to homogenize and to stabilize the suspensions of bone china with appropriate ageing time.

A estabilização de suspensões de alumina é essencial para a fabricação de vários produtos, especialmente na indústria cerâmica e com o controle das propriedades que se pode atingir usando polímeros como agentes estabilizantes. Na busca de processos industriais que preservem o meio ambiente, polímeros sintéticos podem ser substituídos por biopolímeros, com a vantagem adicional de encontrar usos nobres para rejeitos, como quitina, da qual se obtêm a quitosana e ligninas. Nesta tese, os derivados carboximetilados de celulose, a carboximetilcelulose (CMC) e quitosana, a carboximetilquitosana (CMQ) foram preparados e caracterizados por Espectroscopia de Ressonância Magnética Nuclear de Próton (1HRMN), Espectroscopia na Região do Infravermelho (FTIR), Termogravimetria (TG), Calorimetria Diferencial Exploratória (DSC), Difração de raios X, Cromatografia de Exclusão por Tamanho (SEC). O derivado obtido da lignina, a carboximetil-lignina, (CML) foi caracterizado por Espectroscopia na Região do Infravermelho (FTIR), Termogravimetria (TG), Calorimetria Diferencial Exploratória (DSC). Os três derivados obtidos foram usados como agentes estabilizantes para suspensões aquosas de alumina. A reação de carboximetilação ocorreu em meio heterogêneo, gerando derivados solúveis em água. O grau de substituição (GS) para as carboximetilceluloses foi determinado por 1HRMN, obtendo-se valores de 0,7; 1,3 e 1,8 para as três amostras analisadas nesse trabalho. Para as carboximetilquitosanas, o GS foi determinado por FTIR e análise elementar sendo obtidos valores de 0,6 e 0,8 para duas amostras de CMQ. O valor de GS de 0,5 para carboximetil-lignina foi obtido por titulação potenciomêtrica. Os derivados CMC, CMQ e CML permitiram a estabilização de suspensões de alumina, como demonstrado em medidas de tamanho de partículas, potencial zeta e viscosidade. De relevância especial foi a estabilização em altos valores de pHs, incluindo o ponto de carga zero, pcz, no qual a atração entre as partículas de alumina, de cargas opostas, é máxima, levando a aglomeração de partículas em suspensões sem agentes de estabilização. A distribuição de tamanhos de partícula também foi afetada positivamente com a incorporação dos derivados. De maneira geral, os resultados com os derivados foram promissores em termos de potencial zeta e tamanho de partícula no pcz da alumina, o intervalo de interesse deste trabalho. O destaque é para o derivado de celulose, a CMC GS 1,3 que obteve a melhor performance dentre todos do derivados levando aos menores valores de viscosidade para a suspensão, salientando que esta foi preparada com alto teor de sólidos, nas mesmas condições de suspensões utilizadas em processamentos cerâmicos,. Foi importante também a estabilização ao longo do tempo das suspensões contendo CMC, CMQ e CML, pois o tamanho médio de partícula permaneceu invariável por períodos de até 2 horas, tempo suficiente para processos de moldagem de cerâmicos como extrusão, injeção, tap-casting. O uso de derivados carboximetilados de lignina, quitosana e celulose, como agentes estabilizantes de suspensões de alumina, abre caminho para novas aplicações de produtos obtidos a partir de fontes naturais e renováveis, em substituição aos tradicionalmente usados, oriundos de fontes fósseis. / The stabilization of alumina suspensions is crucial for the fabrication of various products, especially in the ceramic industry, with fine control of materials properties being reached using polymers as stabilizing agents. In this context, in the search for environmentally-friendly industrial processes, synthetic polymers may be replaced with biopolymers, with the added advantage of providing noble uses for waste materials such as those deriving from lignins and chitosans. In this thesis, carboxymethylated cellulose (CMC) and chitosan (CMQ) were prepared and characterized with proton nuclear magnetic resonance (1HNMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), differential scanning calorimetry (DSC), X-ray diffraction and size exclusion chromatography (SEC). Carboxymethylated lignin (CML) was characterized with Fourier Transform infrared (FTIR) spectroscopy, thermogravimetry (TG) and DSC. These three derivatives were used as stabilizing agents in aqueous solutions of alumina. The carboxymethylation reaction was carried out in a heterogeneous medium yielding water-soluble derivatives. GS values of 0.7, 1.3 and 1.8 for CMC were obtained with 1HNMR measurements, while values of 0.6 and 0.8 for CMQ were determined using FTIR and elemental analysis. For CML, GS = 0.5 was found using potentiometric titration. The success of the carboxymethylation was confirmed via 1HNMR measurements. The effectiveness of the derivatives CMC, CMQ and CML as stabilizing agents was proven by measuring the size distribution of particles, viscosity and zeta potential of alumina suspensions. Of particular relevance was the stabilization at high pHs, including the point of zero charge (pcz) for which attraction between oppositely charged particles is maximum, where alumina particles normally agglomerate in the absence of stabilizing agents. The particle size distributions were also affected positively by incorporation of the derivatives. Overall, the data presented indicated that CML was responsible for optimized results for the zeta potential and mean particle size at the pzc of alumina suspensions. The CMC with GS = 1.3 exhibited the best performance with the lowest viscosity values at the pcz, even in dispersions with high contents of solid materials which are the conditions prevailing in ceramic processes. Also worth mentioning was the stability over time of the alumina suspensions incorporating CMQ, CML and CMC, with the average particle size remaining the same for 1-2 hours, which is a sufficient period of time for ceramic molding processes such as extrusion, injection and tap-casting. The use of carboxymethylated derivatives of lignin, chitosan and cellulose as stabilizing agents opens the way for the development of new products from natural and renewable sources, to replace those materials traditionally used which are obtained from fossil sources.

Este trabalho teve por finalidade desenvolver um método para a caracterização do perfil de dissolução de suspensões de mebendazol (MBZ), discriminatório para as formas polimórficas do fármaco. Pertencendo a classe II do Sistema de Classificação Biofarmacêutica (SCB), além da baixa solubilidade, o MBZ é bastante crítico por apresentar-se comercialmente disponível em duas formas polimórficas (A e C) e misturas destas. Além disso, pouca informação é encontrada acerca de métodos de dissolução de suspensões. O material apresentado está dividido em três capítulos, sendo o primeiro deles uma revisão da literatura sobre a dissolução de suspensões de fármacos que apresentam polimorfismo. Neste capítulo é feita uma abordagem sobre questões relacionadas ao desenvolvimento de métodos, como inserção das amostras na cuba de dissolução, agitação, uso de tensoativos no meio e a quantificação do fármaco. No segundo capítulo é apresentado o desenvolvimento do método de dissolução, com ênfase no estudo da solubilidade das formas polimórficas A e C de MBZ e sua interação com tensoativos. Foram realizados ensaios de solubilidade pelo método do equilíbrio, cálculo de concentração micelar crítica para os tensoativos lauril sulfato de sódio e polissorbato 80, sendo ao final realizado delineamento experimental (DOE) para o desenvolvimento do método. Pela avaliação do DOE, o local de inserção da amostra não influencia a dissolução de MBZ, por outro lado, a presença de tensoativo, assim como a forma polimórfica empregada, exercem efeito nos resultados apresentados. A partir destas informações, o método indicado para avaliação das suspensões de MBZ com potencial discriminatório de suas formas polimórficas foi definido pela utilização do aparato 2 (pá) a 75 rpm, com 2 litros de HCl 0,1 M sem tensoativo, como meio de dissolução. No último capítulo, o método desenvolvido foi utilizado na avaliação de especialidades farmacêuticas adquiridas no Brasil e em alguns países da América Latina, sendo os respectivos perfis de dissolução, comparados por meio de uma análise multivariada de componentes principais, com formulações contendo o MBZ em diferentes proporções de polimorfos. A partir dos resultados, foi possível observar que grande parte das formulações comercializadas não apresentaram perfil de dissolução satisfatório, isso pode estar relacionado com a presença considerável de polimorfo A nas matérias-primas utilizadas, comprometendo assim a sua solubilidade. / The aim of this work was to develop a method for characterization of the dissolution profile of mebendazole (MBZ) suspensions, being discriminatory for the polymorphic forms of the drug. MBZ belongs to class II of the Biopharmaceutics Classification System (BCS), besides its low solubility, it is very critic, being commercially available in two polymorphic forms (A and C) and their mixtures. Moreover, there is low information about dissolution methods for suspensions. The text presented herein is divided into three chapters, the first chapter is a literature review about dissolution of suspensions containing drugs that present polymorphism. In this chapter is made a discussion about the variables of the method, as sample insertion in the dissolution vessel, rotation speed, use of surfactants in the dissolution medium and drug quantification. The development of the dissolution method, focused on the solubility study of MBZ polymorphic forms A and C and their interaction with surfactants is presented in the chapter 2. Some tests were performed: solubility using shake flask method, calculation of micellar critical concentration for the surfactants sodium lauryl sulphate and polysorbate 80, and an experimental design (DOE) was done for developing the method. By DOE evaluation, the sample insertion site does not influence on MBZ dissolution, but the presence of surfactant and the polymorphic form used, show effect on the results. Based on these information, the method indicated for evaluation of MBZ suspensions, with discriminatory power for its polymorphic forms was defined by using apparatus 2 (paddle) at 75 rpm and 2 L of 0.1M HCl without surfactant as dissolution medium. In chapter 3, the method developed was used to evaluate pharmaceutical suspensions from Brazil and from some countries of Latin America. The respective dissolution profiles were compared by means of multivariate analysis of principal components with formulations containing MBZ in different polymorphs ratios. From the results, it was possible to observe that a great part of the commercially available formulations do not presented a satisfactory dissolution profile, and this fact can be related to a considerable amount of the crystalline form A in the raw material, which compromises its solubility.