In this work, the nano-structured components of solid oxide fuel cells have been produced, using radio frequency (RF) solution or suspension plasma spraying processes. The emerging technology of suspension plasma spraying was explored to produce thin and gas tight nano-structured solid oxide fuel cells electrolytes, which in an effort to develop a cost-effective and scalable fabrication technique for high performance solid oxide fuel cells (SOFCs). Glycine-nitrate process (GNP) produced cerium oxide (CeO[subscript 2]) and gadolinium oxide (Gd[subscript 2]O[subscript 3]) nano-powders were used to prepare suspensions and then separately injected to form composite GDC electrolyte coatings. A dynamic mask system has been developed to control the heating effects of a high-temperature plasma deposition process. The experimental results of the nano-structured SOFCs GDC electrolytes production by means of a RF suspension plasma spraying process using the newly proposed mask were compared to the ones without mask. The potential of this deposition technique to improve the electrolyte coating uniformity and to reduce the coating porosity was demonstrated. SOFCs anodes require long triple phase boundary (TPB) and appropriate gas diffusion pass for the fast transport of both fuel and exhaust gases, but the area where gas diffusion passes are especially required would be different from the area suitable for electrochemical reaction in the anodes. Functionally graded anodes in both composition and porosity have been proposed to fulfill the anodic functions in adequate anodic areas. On the basis of the optimized spraying conditions and the laboratory-developed solution feeding system, NiO-GDC functionally graded nanostructure anodes were prepared using solution plasma spraying (SolPS) process. Then the microstructure and material composition of the anodes were analyzed. A graded distribution in contents of both nickel and GDC was confirmed in the coating. Field emission scanning electron microscopy (FESEM) observation exhibited a continuous variation in porosity from 35% to 9% along the direction across the coating thickness. The functionally graded anodes deposited by SolPS process may minimize the thermal expansion mismatch between SOFC components and increase the length of triple phase boundary, which should lead to the improvement of the anodic performances. The successful fabrication of the functionally graded nano-structural electrodes as well as dense electrolyte coatings represents an opportunity for the Centre de Recherche en Énergie, Plasma et Électrochimie (CREPE) to fabricate the fully integrated nano-structured SOFC using solution and suspension plasma spraying processes.

In Abhängigkeit von der Suspensionszusammensetzung und der jeweiligen Scherrate können konzentrierte Kaolinsuspensionen ungewöhnliche rheologische Phänomene wie Oszillationen der scheinbaren Viskosität oder eine negative 1.~Normalspannungsdifferenz zeigen. In dieser Arbeit wurde die Abhängigkeit der 1.~Normalspannungsdifferenz, des Speicher- und des Verlustmoduls im linear-viskoelastischen Bereich sowie der Fließgrenze von der Oberflächenbeladung des Kaolins, von der Kaolinfeststoffkonzentration, vom pH-Wert und von der Ionenstärke untersucht. Weiterhin wurde eine Methode entwickelt, die die Fixierung der scherinduzierten Mikrostruktur der Suspensionen und deren anschließende Charakterisierung mittels Röntgenbeugung gestattet. Außerdem wurde ein rheologisches Modell abgeleitet, das den Zusammenhang zwischen den Aussagen zur scherinduzierten Mikrostruktur und dem Auftreten negativer 1.~Normalspannungsdifferenzen herstellt.

Les nanotubes de carbone mono-paroi (SWNT) sont souvent dilués dans un solvant afin de les purifier, les fonctionnaliser ou les transformer. Le contrôle de ces processus requiert une compréhension profonde de la rhéologie de leurs suspensions. Cependant, les bases physiques de leur comportement rhéologique ne sont pas absolument claires. Cette thèse a permis d'apporter des réponses au travers de la modélisation de la viscoélasticité linéaire des suspensions diluées de SWNTs en utilisant une approche par la Dynamique Brownienne (DB). Les SWNTs sont modélisés par des filaments semi-flexibles dont la configuration est naturellement courbée due à la présence de défauts structuraux. Le modèle continu de filament semi-flexible est discrétisé en un système multibarre en flexion non-libre ayant une configuration non-droite à l'équilibre. Une redéfinition du potentiel de flexion est effectuée afin de prendre en compte les cas des configurations non-rectilignes. Le comportement en viscoélasticité linéaire de leurs suspensions diluées a été modélisé par DB en mode dynamique et de relaxation. Des nouveaux processus de relaxation caractérisés par l'activation d'une élasticité à fréquences intermédiaires sont constatés en dynamique. D'autre part, une relaxation quasi-instantanée du module de relaxation est obtenue lors de l'application d'un échelon de cisaillement. Les spectres de relaxation de l'énergie de flexion sont en accord avec les réponses dynamiques, ce qui prouve la cohérence du modèle en viscoélasticité linéaire. Les différences non négligeables par rapport au comportement rhéologique des systèmes multibarre droits à l'équilibre démontrent que la flexibilité couplée avec la présence de défauts structuraux de courbure joue un rôle important dans la dynamique d'un SWNT en suspension.

Hollow fiber membranes offer the opportunity to dramatically reduce the energy required to perform gas separations in the chemical industry. The membranes are fabricated from highly non-Newtonian precursor materials, including concentrated polymer solutions that sometimes also contain dispersed particles. These materials are susceptible to shear-induced microstructural changes during processing, which can affect the characteristics of the resulting membrane. This thesis explores several shear-related effects using materials and flow conditions that are relevant for fiber spinning. The findings are discussed as they relate to membrane processing, and also from the standpoint of enhancing our fundamental understanding of the underlying phenomena. First, the effect of shear on polymeric dope solutions was investigated. Shear-induced demixing—a phenomenon not previously studied in membrane materials—was found to occur in membrane dopes. Phase separation experiments also showed that shear-induced demixing promotes macrovoid formation. The demixing process was found to depend not only on the instantaneous shear conditions, but also on the shear history of the solution. This suggests that low-shear flow processes that occur in the upstream tubing and channels used for fiber spinning can affect macrovoid formation. The effect of viscoelastic media on dispersed particles was also explored. Shear-small-angle light scattering results showed that particles suspended in membrane dope solutions formed aggregated, vorticity-oriented structures when shear rates in the shear-thinning regime of the polymer solution were applied. Shear rates well below the shear-thinning regime did not produce any structure. In fact, the application of a Newtonian shear rate to a sample already containing the vorticity structure caused the sample to return to isotropy. Measurements using a highly elastic, constant-viscosity Boger fluid showed that strong normal forces alone are not sufficient to form the vorticity structures, but that shear thinning is also required. Lastly, a study was conducted examining cross-stream migration of particles dispersed in viscoelastic media. Fluids exhibiting varying degrees of shear thinning and normal forces were found to have different effects on the particle distribution along the shear gradient axis in Poiseuille flow. Shear thinning was found to promote migration toward the channel center, while normal stresses tended to cause migration toward the channel walls. In addition to hollow fiber spinning, many other industrially relevant applications involve polymer solutions and suspensions of particles in viscoelastic media. Often, the properties and performance of the material depend strongly on the internal microstructure. The results from the research described in this thesis can be used to guide the design of materials and processing conditions, so that the desired microstructural characteristics can be achieved.

L'objectif de cette étude est de comprendre et de modéliser la phénoménologie du transport vertical dense descendant de particules de la classe A de la classification de Geldart. Dans un premier temps, une étude expérimentale est réalisée sur une maquette en statique (absence de circulation de solide) dans le but de déterminer expérimentalement l'effet des paramètres opératoires sur les grandeurs caractéristiques de la défluidisation des particules de FCC : vitesses de sédimentation, porosité de la phase dense, temps caractéristiques…. Ces données sont nécessaires pour l'étude de l'écoulement gaz/solide dense vertical descendant. La simulation numérique en 2D de la défluidisation est effectuée et les prédictions sont comparées aux données expérimentales. Dans un deuxième temps, des essais sur une maquette permettant de reproduire les phénomènes observés industriellement dans les écoulements denses verticaux descendants de particules sont entrepris. Les observations visuelles complètent les mesures de pressions locales obtenues le long de l'écoulement à différentes conditions avec et sans injection de gaz d'aération. L'étude expérimentale consiste à : - déterminer les limites des différents régimes en termes de débit surfacique de solide et de débit d'aération ; - établir les propriétés de l'écoulement dans les différents régimes. Dans un troisième temps, les propriétés des écoulements de différents régimes sont étudiées et modélisées par une approche monodirectionnelle du type bulle-émulsion. / The objective of this study is to understand and model the phenomenology of the vertical downward dense transport of class A particles of the Geldart classification. Initially, an experimental study is conducted on a static fluidized bed (no flow of solid) in order to determine experimentally the effect of operating parameters on the defluidization properties of FCC particles, such as, sedimentation rates, dense phase porosity, characteristic times ... These data are needed to study gas/solid dense downward flow. 2D numerical simulations of defluidization are performed and the predictions are compared with experimental data. In a second step, experiments are undertaken in a pilot unit able to reproduce the gas/solid dense downward flow phenomena observed in industrial units. Visual observations complement the local pressure measurements profile obtained for the different flow conditions with and without external injection of gas. The experimental study is conducted to: - determine the boundaries of different flow patterns in terms of solid mass flux and gas flowrate; - establish flow properties in different flow patterns. Finally, flow properties of the different patterns are studied and modelled by a monodimensional bubble/emulsion approach.

Nous étudions expérimentalement l'effondrement d'une colonne granulaire dans un liquide visqueux. Contrairement au cas sec, la morphologie des dépôts n'est principalement plus contrôlée par le rapport d'aspect initial du tas mais par la fraction volumique initiale de la masse granulaire. Deux régimes différents sont identifiés selon l'empilement initial. L'empilement lâche donne lieu à des dépôts minces et longs et la dynamique est rapide. Une surpression du liquide est mesurée sous de la colonne. Pour l'empilement dense, l'étalement final est deux fois moindre, le mouvement est lent et une dépression interstitielle est mesurée. Ces observations suggèrent que la dynamique de l'effondrement granulaire dans un fluide est fortement affectée par le comportement de la dilatance du milieu granulaire.Nous développons ensuite un modèle théorique basé sur des équations diphasiques moyennées dans l’épaisseur prenant en compte les mécanismes de dilatance. L’étude dimensionnelle de notre modèle permet de montrer que l’effondrement d’une colonne est contrôlé par trois paramètres sans dimension : le rapport d’aspect de la colonne, la fraction volumique initiale, et le nombre de grains dans l’épaisseur. On montre également que le temps caractéristique met en compétition le frottement visqueux et la gravité.De ce modèle, nous développons un algorithme de résolution lagrangien. Cette approche, grossière mais robuste, permet d’implanter s sans trop de difficulté. Le code est validé sur des configurations simples sur plan incliné avant de simuler l’effondrement de colonnes granulaires immergées dans la même gamme de paramètres que nos expériences. / Nous étudions expérimentalement l'effondrement d'une colonne granulaire dans un liquide visqueux. Contrairement au cas sec, la morphologie des dépôts n'est principalement plus contrôlée par le rapport d'aspect initial du tas mais par la fraction volumique initiale de la masse granulaire. Deux régimes différents sont identifiés selon l'empilement initial. L'empilement lâche donne lieu à des dépôts minces et longs et la dynamique est rapide. Une surpression du liquide est mesurée sous de la colonne. Pour l'empilement dense, l'étalement final est deux fois moindre, le mouvement est lent et une dépression interstitielle est mesurée. Ces observations suggèrent que la dynamique de l'effondrement granulaire dans un fluide est fortement affectée par le comportement de la dilatance du milieu granulaire.Nous développons ensuite un modèle théorique basé sur des équations diphasiques moyennées dans l’épaisseur prenant en compte les mécanismes de dilatance. L’étude dimensionnelle de notre modèle permet de montrer que l’effondrement d’une colonne est contrôlé par trois paramètres sans dimension : le rapport d’aspect de la colonne, la fraction volumique initiale, et le nombre de grains dans l’épaisseur. On montre également que le temps caractéristique met en compétition le frottement visqueux et la gravité.De ce modèle, nous développons un algorithme de résolution lagrangien. Cette approche, grossière mais robuste, permet d’implanter s sans trop de difficulté. Le code est validé sur des configurations simples sur plan incliné avant de simuler l’effondrement de colonnes granulaires immergées dans la même gamme de paramètres que nos expériences.

Les objectifs de cette thèse visent le développement d’un traitement inédit dans un repère spatiale tridimensionnel, pour le problème de la dynamique de collisions diffusives d’objets macromoléculaires en solution en écoulement hydrodynamique à l'intérieur des pores de largeur variable, soumis aux forces hydrodynamiques, du mouvement brownien et des collisions diffusifs aux parois des pores, en utilisant la modélisation théorique et les simulations numériques. L’approche par simulation numérique est nécessaire car il est extrêmement complexe d’utiliser des outils analytiques à présent pour traiter le problème de ces collisions diffusives aux parois solides. Les algorithmes que nous avons développés et les simulations correspondantes sont suffisamment généraux et avancés pour être directement appliquée à l'étude de la dynamique d'une grande variété de polymère et des particules biologiques dans des solutions diluées sous diverses conditions physiques et hydrodynamiques à l'intérieur des pores. Par ailleurs, les mécanismes conduisant à l'adhésion de nano particules et de particules macromoléculaires sous conditions de non-équilibre, en raison de l'influence contradictoire des collisions mécaniques diffusifs et les forces attractives de Hamaker aux parois solides, sont d'un intérêt majeur. Nous avons donc développé un modèle théorique pour calculer le coefficient de restitution. L'objectif est de quantifier le bilan énergétique pendant le processus de collision diffusive de ces particules aux parois, sous l'influence des forces de répulsion d'une part et les forces attractives de Hamaker. Cela se fait par l'élaboration d'un modèle, basé sur le JKR et les théories d’Hertz, pour tenir compte des pertes d'énergie lors des collisions et des gains d'énergie en raison des interactions Hamaker. L’adhésion arrive si le bilan énergétique le permet. Notre modèle théorique est développé en proposant une approche particulière basée sur le potentiel Hamaker. Nous démontrons ce bilan par le biais d'une équation caractéristique non linéaire pour le coefficient de restitution, et analysons ses propriétés qui déterminent l'adhésion ou non pour diverses conditions physiques initiales. / The purpose of this thesis is to develop a comprehensive model analysis in a three-dimensional spatial frame for the dynamics of molecular particles in dilute colloidal suspensions in solutions flowing inside pores of variable width, subject to hydrodynamic forces, Brownian motion and diffusive collisions at the rough pore boundaries, by using numerical simulations. The approach by simulations is necessary because it is extremely complex to use analytical tools at present to deal with the problem of diffusive collisions of the particles at the solid pore boundaries. The algorithms which we have developed and the corresponding simulations are sufficiently general and refined to be directly applied to the study of the dynamics of a wide variety of polymer and biological particles in dilute solutions under diverse physical and applicable hydrodynamic conditions inside pores. Moreover, the mechanisms leading to the adhesion of particles of nano sizes under what would be non-equilibrium conditions, due to the conflicting influence of the mechanical diffusive collisions and the attractive Hamaker forces at the boundaries, are of major interest. We have hence investigated a theoretical model to calculate the restitution coefficient from basic physical principles. The objective is to quantify the energy balance during the process of a diffusive collision of a nano particle under the influence of the repulsive forces on one hand, and the attractive Hamaker forces acting on the nano particle on the other. This is done by developing a model, based on the JKR and Hertz theories, to account for the energy losses during collisions, and for the energy gains due to the Hamaker interactions. Adhesion becomes an outcome if the energy balance permits this. Our theoretical model is developed by proposing a special analytic approach based on the Hamaker potential. We derive from the theoretical analysis a characteristic nonlinear equation for the restitution coefficient, and analyze its properties which determine under given physical conditions the outcome for adhesion or not.

L'utilisation de fluides au comportement rhéologique complexe (seuil d'écoulement, thixotropie) est de plus en plus courante dans notre quotidien. Une description globale du comportement n'est pas suffisante et c'est pourquoi ce travail se focalise sur la détermination locale des propriétés de ces matériaux complexes. Pour cela nous nous appuyons sur des méthodes optiques pour obtenir des informations sur la contrainte et la vitesse de cisaillement. Nous avons choisi d'opter pour la PIV (Particle Image Velocimetry) pour l'obtention du gradient de vitesse et la photoélasticimétrie pour la mesure de contrainte. L'emploi de ces deux techniques de mesure oblige que les fluides étudiés soient transparents et biréfringents. Nous étudions alors une solution de Milling Yellow (fluide au comportement rhéologique simple) pour valider nos techniques de mesure et des suspensions de Laponite qui sont des fluides à seuil et thixotropes. La première étape de ce travail consiste à avoir une idée générale du comportement rhéologique des fluides d'où leur caractérisation à l'aide d'un rhéomètre. Ensuite, dans une géométrie où la répartition de contrainte est connue (géométrie à cylindres coaxiaux), nous déterminons les lois rhéo-optiques nous permettant de relier la contrainte dans le matériau à sa réponse optique. Enfin, dans une géométrie plan-plan, nous couplons les deux techniques de mesure optiques (PIV et photoélasticimétrie) afin de reconstruire un rhéogramme local des différents fluides étudiés pouvant être comparé à celui issu de mesures classiques de rhéométrie. / The use of fluids with a complex rheological behavior (yield stress, thixotropy) is becoming more common in our daily lives. However, a global description of this behavior is not satisfactory even if it is quickly and easily accessible. The aim of this work is to advance in the understanding of complex behaviors at a local scale. Optical methods are the best way to do that. In our case, we need to get information about the shear stress and the shear rate. So we need a measurement technique for each of these variables. A PIV (Particle Image Velocimetry) technique is used to obtain the shear rate and the shear stress is determined by photoelasticimetry. The use of these two techniques requires that the studied fluids are transparent and birefringent. Then, our measurement techniques are validated using a Milling Yellow solution (a simple rheological fluid) before studying Laponite suspensions which are thixotropic yield stress fluids. Firstly, a rheometer is used to have a general idea of the rheological behavior of our fluids. Secondly, in a geometry where the shear stress distribution is known (a coaxial cylinders geometry), rheo-optical laws connecting the shear stress within the material to its optical response are determined. Finally, in a plate-plate geometry, the two optical measurement techniques (PIV and photoelasticimetry) are coupled to reconstruct a local rheogram for the studied fluids that can be compared to the one obtained from conventional Rheometric measurements.

Os solos ácidos recobrem, cerca de 40% da área terrestre, constituindo-se em um dos principais fatores limitantes à população à produção vegetal do planeta. No Brasil, os solos ácidos abrangem cerca de dois terços do território nacional. De um modo geral, a acidez do subsolo reduz a profundidade do sistema radicular, aumentando a susceptibilidade à seca e diminuindo o uso de nutrientes pelas plantas. Além da alta atividade de íon hidrogênio (H+), os solos ácidos geralmente apresentam níveis tóxicos de alumínio, sendo que a toxicidade por AI tem sido intensivamente investigada nos últimos anos. No entanto, a toxicidade por AI ocorre apenas a pH baixo e em condições onde a toxicidade por prótons geralmente também se manifesta. Apesar disto, trabalhos envolvendo a toxicidade por prótons são escassos. A sensibilidade de células a pH baixo depende da fase de crescimento e desenvolvimento em que estas se encontram. Em raízes, as células mais sensíveis são as da região de alongamento e em suspensões celulares as células na fase log de crescimento são mais sensíveis do que as células na fase estacionária. Este trabalho faz parte de uma linha de pesquisa que procura explorar as diferenças que existem entre células quanto à sensibilidade a pH baixo para melhor entender a toxicidade e tolerância a prótons. Foram utilizadas células da cultura de tabaco cv. BY-2, um sistema modelo que apresenta diversas vantagens sobre o uso de raízes para a realização deste trabalho. Os objetivos deste estudo foram de a) determinar condições apropriadas para a exposição destas células a acidez; b) caracterizar a resposta destas células a pH baixo, sob influência de diferentes fatores ambientais, quando se encontram em estados distintos de sensibilidade ao pH baixo; e c) verificar se mudanças na sensibilidade das células a pH baixo podem ser decorrentes de alterações na composição da membrana plasmática ou na atividade das ATPases. Vários testes iniciais foram realizados com o intuito de se definir algumas condições experimentais - o tempo de exposição, a composição do meio e o tampão a ser empregado. Optou-se por lavar as células e depois incubá-las por 1h em meio simples com pH desejado e contendo apenas Ca \'Cl IND. 2\' 2mM, KCl 10mM. E o tampão MES ou biftalato (10 mM). O biftalato foi testado porque o tampão MES, usado normalmente no meio de cultura completo, não é eficiente na faixa de pH abaixo de 5,0. O biftalato (pKa = 4,1) praticamente não afetou a viabilidade celular avaliada pela permeabilidade a trypan blue, mas inibiu o crescimento celular no meio de cultura completo. Mesmo assim, os dois tampões foram utilizados em paralelo em diversos experimentos e verificou-se que os resultados foram semelhantes. A viabilidade das células na fase log (2 dias) foi reduzida quando se abaixou o pH de 5,6 a 3,8, sendo que caiu mais acentuadamente até o pH de 4,8. As células da fase estacionaria (7d) foram insensíveis ao baixo pH. A um pH fixo de 4,2 aumentando-se a concentração de Ca \'Cl IND. 2\' para cerca de 8 a 16 mM praticamente aboliu o efeito deletério do pH baixo. Para se ter o mesmo efeito com a adição de KCl, foi necessário adicionar entre 80 e 160 mM. A adição de sacarose também amenizou os efeitos do pH\'sendo praticamente revertido a uma concentração de 100 Mm. Os resultados indicam a importância da força iônica e da osmolaridade da solução, mas o efeito de Ca não parece depender apenas destas duas propriedades. A inibição de ATPases, pelo uso de DCCD, não pareceu ter qualquer relação com a sensibilidade a pH baixo. Tanto células de tabaco na fase log quanto estacionárias foram sensíveis à aplicação de ortovanadato de sódio. Em células da fase estacionária, este efeito mais acentuado a pH 4,2, sugerindo que nestas células, as H+ ATPases do tipo P da membrana plasmática podem ter algum papel na tolerância destas células ao baixo pH. Encontrou-se diferenças no perfil protéico de frações enriquecidas em membrana plasmática entre células da fase log e estacionárias e entre células tratadas ou não a pH baixo. Estas diferenças precisam ser melhor estudadas. / Acid soils account for about 40 % of the surface area of the world and are one of the major factors limiting plant productivity. In Brazil, these soils comprise roughly two-thirds of its total territory. In general, soil acidity is detrimental because it limits the depth of the root system, increasing susceptibility to drought and decreasing the use of nutrients. In addition to the high levels of hydrogen ion activity, acid soils usually have Al toxicity hazards, a topic which has been intensely studied in the past years. However, Al toxicity only occurs at low pH, under conditions in which proton toxicity is also a problem. Despite this, studies of proton toxicity are lacking. The sensitivity of cells to low pH depends on their growth and developmental status. In roots, the most sensitive cells are those of the elongation zone and in cell cultures, cells in the log phase are more sensitive than those of the stationary phase. This study is part of a larger attempt to explore the differences that exist between cells with respect to their sensitivity to low pH to further understand toxicity and tolerance to protons. Cells of tobacco BY-2, a plant cell model system which has several advantages over the use of roots, was used in this study. The objectives were a) to determine the appropriate conditions to expose these cells to low pH; b) characterize the response of these cells to low pH, when different environmental factors are varied and at different stages of cellular sensitivity to acidity; and c) examine if changes in the sensitivity of cells to low pH are due to changes in the composition of plasma membranes or in the activity of ATPases. Several preliminary tests were performed to define the experimental conditions to be used ? the duration of exposure to low pH, the composition of the medium and the buffer to be used. A simple solution containing only CaCl2 2mM, KCl 10 mM and MES or phthalate buffer (10 mM) was chosen to wash and incubate the cells at the pH of interest. Phthalate was tested because MES, the buffer normally used in the culture medium, is not effective at pH values below 5.0. Phthalate (pKa = 4,1) had very little effects on cell viability as evaluated by membrane permeability to trypan blue, but it severely inhibited the growth of the cell culture in complete medium. Nevertheless, both buffers were used in several subsequent experiments, the results of which were found to be similar between both buffers. The viability of log-phase cells (2 day-old) was reduced when the pH was lowered from pH 5,6 to 3.8, but this was sharper down to pH 4,8. Cells in stationary phase (7 day-old) were insensitive to low pH. At a fixed pH of 4,2, increases in the concentration of CaCl2 up to 8 or 16 mM abolished most of the deleterious effects of low pH. To generate the same effect, KCl had to be added at concentrations between 80 and 160 mM. The addition of sucrose also alleviated the effects of low pH. The results suggest the importance of solution ionic strength and osmolarity on sensitivity to low pH, but the effects of Ca do not appear to depend only on these two properties. The inhibition of ATPases, by DCCD, did not appear to bear any relation to cellular sensitivity to low pH. Both log-phase and stationary-phase cells were affected by the addition of sodium orthophosphate. In stationary-phase cells, this effect was more pronounced at pH 4,2, suggesting that in these cells, P-type H+-ATPases of the plasma membrane may play a role in the tolerance of these cells to lo pH. Differences were found in the protein profile of enriched plasma membrane fractions both between log-phase and stationary-phase cells and between cells treated or not with low pH. These differences, however, need to be better examined.

O presente projeto de trabalho buscou avaliar e estabelecer relações de causa e efeito que justificassem a ocorrência de singularidades no comportamento reológico de formulações complexas contendo elevada carga de sólidos em suspensão incorporada. O mecanismo de estabilização coloidal empregado para preparação das formulações e posterior análise foi o mecanismo de estabilização eletroestérico. O caso particular estudado correspondeu à dispersão de cargas inorgânicas (óxido de alumínio) em meio aquoso auxiliada pela incorporação de conteúdo orgânico com ação dispersante (poliacrilato de amônio) e ligante (emulsão acrílica) respectivamente. A implementação de técnicas analíticas complementares permitiu o estudo detalhado de uma singularidade associada ao comportamento reológico do sistema, exclusivamente evidenciada em função da elevada carga de sólidos, oferecendo, portanto, subsídios para elaboração de um modelo supramolecular fundamentado em possíveis alterações de configuração das cadeias poliméricas para justificativa do fenômeno. A contribuição referente ao pleno entendimento do fenômeno, considerando-se suas causas e efeitos, reside na possibilidade de se estabelecer diretrizes de formulação que propiciem a otimização das quantidades de aditivos incorporados e o respectivo controle do estado de dispersão e estabilidade do sistema. Considerou-se, para efeitos práticos de engenharia de formulação, que o mínimo secundário de viscosidade corresponda ao ponto ótimo de estabilidade do sistema mesmo que a condição de máxima dispersão já tenha sido alcançada para uma concentração de dispersante equivalente ao mínimo primário de viscosidade. A contribuição do efeito estérico associada à reduzida distância de separação entre as partículas (IPS) mostrou-se de vital importância para assegurar a viabilidade de uma dada formulação. A proposta aqui apresentada fundamentou-se no mecanismo de depleção como principal força motriz para desencadear possíveis mudanças de conformação espacial das cadeias poliméricas implicando, portanto, em alterações do raio hidrodinâmico, da fração volumétrica efetiva ocupada e da intensidade de interação (repulsão) entre as partículas. O efeito da dinâmica configuracional sofrida pelo sistema refletiu-se diretamente no comportamento reológico do mesmo. O caráter de inovação do presente trabalho reside na utilização não convencional da técnica de espectroscopia eletroacústica, empregada para avaliação de mudanças do raio hidrodinâmico de partículas em suspensão (sistemas concentrados), integrada com a técnica de turbidimetria dinâmica de varredura para avaliação de desempenho (cinética de sedimentação) de formulações complexas (suspensões). / The present research project pretended to evaluate and establish cause and effect relationships able to justify the singularities evidenced when exploring the rheological behaviour of complex formulations containing elevated solids loading. The stabilization mechanism used for the preparation of the dispersed systems and subsequent analyses corresponded to the electrosteric mechanism. The particular case studied herein corresponded to the dispersion of inorganic colloidal particles (aluminun oxide) in aqueous media assisted by the incorporation of organic components acting respectively as dispersant (ammonium polyacrylate) and binder agent (acrylic emulsion). The implementation of complementary analytical techniques enabled the detailed study of a singularity related to the rheological behaviour of the system that could only be evidenced for high solids loading condition. The results obtained provided the fundamental concepts necessary to propose a supramolecular model based on possible conformational changes associated with the adsorbed polymeric chains and sufficient to justify the phenomenon. Considering the practical aspects related to formulation engineering, it was determined that the secondary minimum viscosity corresponds to the optimum stablity condition although the maximum dispersion condition was achieved for dispersant concentrations equal to the primary minimum viscosity. The contribution of the steric effect associated with the reduced interparticle separation distance (IPS) showed itself to be of vital importance to ensure the viability of a stable formulation. The proposal here presented suggests that the depletion mechanism corresponds to the major cause that imparts possible configurational changes related to the adsorbed polymer chains. As a result of, significant alterations of the hydrodynamic radius, effective volume fraction occupied by and interaction intensity (repulsion) between the particles are expected. The effect of the configurational dynamics experienced by the system reflected directly on the associated rheological behaviour.The innovation character of the present work relies on the employment of the electrosacoustic spectroscopy technique to evaluate possible changes of the hydrodynamic radius of the suspended particles (concentrated systems) integrated with the dynamic turbidimetry technique to evaluate the performance (sedimentation kinetics) of the complex formulations.