O reator de FAD deve propiciar condições adequadas para contato entre as micro-bolhas e os flocos formados no pré-tratamento e também condições para que o conjunto floco/bolha possa ser direcionado ao topo do reator, e assim ser removido. O projeto de pesquisa visou estudar condições hidrodinâmicas proporcionadas pela variação da Velocidade Cross-Flow (VCF) e assim verificar a influência na eficiência de uma estação piloto de flotação por ar dissolvido. A VCF é importante parâmetro para concepção de unidades de FAD e é função da vazão de entrada no tanque de flotação e da área entre o nível d\'água no tanque de flotação e o anteparo que separa a zona de contato da zona de separação. A velocidade cross-flow constitui um parâmetro de grande importância para projetos de unidades de flotação. Nesta região de transição entre a zona de contato e a zona de separação, ocorre a passagem do conjunto floco/bolha, e turbulência excessiva pode causar o rompimento do conjunto e assim comprometer a eficiência da flotação. Além disso, o padrão de escoamento observado na zona de separação dos flotadores, onde ocorre a separação dos aglomerados \"flocos + bolhas\", depende fortemente do valor médio da velocidade cross-flow, conforme comentado por Lundh et al. (2000 e 2002) e por Reali e Patrizzi (2007). Daí a necessidade de se investigar mais profundamente a influência da VCF na eficiência da clarificação por flotação. O projeto de pesquisa foi dividido em duas etapas. Para realização das etapas foi estudado um tipo de água preparada em laboratório, através da adição de substância húmica e caulinita, para obtenção de cor aparente e turbidez, respectivamente. A água estudada possui cor aparente e turbidez moderada (1 mg/L de substância húmica e 8,5 mg/L de caulinita) resultando em valores de turbidez por volta de 7 NTU e cor aparente por volta de 40 UH. A etapa 1 consistiu na determinação do par, pH de coagulação e dosagem de coagulante (sulfato de alumínio), gradiente médio de floculação e tempo médio de floculação adequado para a água de estudo. Para realização da etapa 1 foi utilizado equipamento de flotação de bancada de regime de batelada (Flotateste), que se encontra nas dependências do Laboratório de Tratamento Avançado e Reuso de Águas - LATAR/SHS/EESC/USP. Foram mantidos fixos os seguintes parâmetros: \'T IND.MR\', \'G IND.MR\', \'T IND.F\', \'G IND.F\', \'P IND.SAT\', \'T IND.REC\', \'V IND.FLOT\'. Conforme preconizado por Reali et al (2007), foi variada a dosagem de coagulante. Após determinado o melhor par pH e dosagem de coagulante foram realizados ensaios visando determinar o melhor \'G IND.F\' e \'T IND.F\' para a água em estudo. Para a água de estudo foram escolhidas duas condições de potencial Zeta, determinados na etapa 1 do projeto de pesquisa. A primeira condição o potencial Zeta permaneceria com valor próximo de 0 mV e na segunda condição o potencial Zeta seria positivo, por volta de +12 mV. A etapa 2 consistiu em variar a velocidade cross-flow, através da variação da altura do vertedor de saída da água flotada de uma unidade piloto de flotação, de forma a se obter diferentes valores de VCF (mantendo-se constantes os valores de tempo de contato e taxa de aplicação superficial na zona de contato), para dois valores de Taxas de Aplicação Superficial (TAS) (7,67 m/h e 15 m/h) na zona de separação e os dois valores de potencial Zeta (PZ), e com isto avaliar a sua influencia na eficiência de remoção de sólidos suspensos totais, cor e turbidez da instalação piloto retangular de FAD. / The reactor DAF should provide adequate conditions for contact between the micro-bubbles and the flakes formed in the pretreatment conditions and also for the aggregate flocs/bubble can be directed to the top of the reactor, and thus be removed. The research project aimed at studying hydrodynamic conditions provided by the variation of Cross-Flow Velocity (VCF) and thus checks the influence on the efficiency of a pilot plant of dissolved air flotation. The VCF is an important parameter to design units of DAF and is a function of input flow in the flotation tank and the area between the water level in the flotation tank and the bulkhead that separates the contact zone of the zone of separation. The cross-flow velocity is a parameter of great importance to projects of flotation units. In this region of the transition zone between the contact zone and the separation zone, occurs the passage of the aggregate flocs/bubble, and excessive turbulence can cause disruption of the aggregate and thereby harm the flotation efficiency. Moreover, the pattern of flow observed in the flotation separation zone, which occurs the separation of aggregates \"flakes + bubbles\", depends strongly on the average value of cross-flow velocity as described by Lundh et al. (2000 and 2002) and Reali and Patrizzi (2007). Hence the needs to investigate further the influence of VCF on the clarification efficiency by flotation. The research project was divided into two steps. To perform the steps has been studied a type of water prepared in the laboratory, through the addition of humic substances and kaolin, to obtain apparent color and turbidity, respectively. The study water has moderate turbidity and apparent color (1 mg/L of humic substance and 8.5 mg/L of kaolin) resulting in turbidity values around 7 NTU and color apparent by 40 HU. Step 1 consisted in the determination of the pair, coagulation pH and coagulant dosage (aluminum sulfate), flocculation gradient and time flocculation suitable for the study water. For the implementation of step 1 was used bench batch flotation system equipment (Flotatest), located on the Laboratory for Advanced Treatment and Reuse Water - LATAR / SHS / EESC / USP. Were kept fixed the following parameters: \'T IND.MR\', \'G IND.MR\', \'T IND.F\', \'G IND.F\', \'P IND.SAT\', \'T IND.REC\', \'V IND.FLOT\'. As predicted by Reali et al (2007), was varied the dosage of coagulant. After determined the best pair of coagulant dosage and pH coagulation the tests were performed to determine the best \'G IND.F\' and \'T IND.F\' for the study water. For the study water were chosen two conditions of Zeta potential values, determined in the step 1 of the research project, where the first condition the Zeta potential value kept near 0 mV and the second condition kept a positive value of Zeta potential, around +12 mV. The step 2 consisted of varying the cross-flow velocity, by varying the height of the outlet weir of the clarified water of the flotation pilot plant to obtain different values of VCF (keeping constant the values of time contact and application rate on the contact zone) for two values of superficial application rates (7.67 m/h and 15 m/h) in the zone of separation and the two values of Zeta potential (PZ) and then was availed the influence on removal efficiency of total suspended solids, colour and turbidity of the rectangular pilot plant of DAF.

Este estudo reúne os principais resultados de fluorescência estática e resolvida no tempo sobre a interação da porfirina meso-tetrakis (4-metilpiridil), na forma de base livre (TMPyP) e complexada com Zn2+ (ZnTMPyP), com vesículas de fosfolipídio. Adicionalmente foram utilizadas as técnicas de potencial zeta e espalhamento de luz dinâmico (DLS, do inglês \"dynamic light scattering\"). As vesículas de fosfolipídio foram formadas por dois conjuntos de fosfolipídios: saturados e insaturados. O primeiro grupo é formado pela mistura dos fosfolipídios zwiteriônico 1,2-dipalmitoil-sn-glicero-3-fosfocolina (DPPC) e aniônico 1,2-dipalmitoil-sn-3-glicero-[fosfo-rac-(1- glicerol)] (DPPG), a diferentes razões molares. Os estudos utilizando tais sistemas foram realizados abaixo (25oC) e acima (50oC) da temperatura de transição de fase gel-líquido cristalino destes fosfolipídios (~ 41oC). O segundo grupo é formado pela mistura dos fosfolipídios zwiteriônico 1-palmitoil-2-oleoil-sn-glicero-3-fosfocolina (POPC) e aniônico 1-palmitoil-2-oleoil-sn-glicero-3-fosfo(1-rac-glicerol) (POPG). Como a transição de fase destes dois fosfolipídios ocorre a temperaturas negativas, todos os experimentos foram realizados a 25oC (vesículas no estado líquido cristalino). Todos os sistemas foram preparados através do método de extrusão para a obtenção de vesículas grandes unilamelares (LUV, do inglês \"large unilamellar vesicles\"). As análises dos dados de fluorescência indicaram que a atração eletrostática entre os substituíntes (positivamente carregados) das porfirinas TMPyP e ZnTMPyP e o grupo das cabeças polares (camada de Stern) das vesículas de fosfolipídio desempenha um papel fundamental na associação da porfirina. A distribuição da TMPyP entre o meio aquoso (tampão) e as vesículas de fosfolipídio foi evidenciada pela coexistência de um tempo de vida de fluorescência mais curto (~ 5 ns) e outro mais longo (~ 9-11 ns), respectivamente. Baseado nos valores das constantes pré-exponenciais, estudos adicionais mostram que a distribuição acima é afetada pela concentração de sal na solução. Os resultados de supressão de fluorescência com o supressor iodeto de potássio (KI) indicaram que ambas porfirinas estão localizadas, preferencialmente, na região da camada de Stern. Este resultado foi confirmado pelos estudos de potencial zeta e de DLS, os quais mostraram uma neutralização parcial das cargas negativas na superfície das vesículas devido à associação da porfirina. / This study presents time-resolved and steady-state fluorescence results on the interaction of the meso-tetrakis (4-methylpyridil) porphyrin, in free base form (TMPyP), and complexed with Zn2+ (ZnTMPyP), with phospholipid vesicles. Zeta potential and dynamic light scattering (DLS) techniques were also used. Phospholipid vesicles were formed by two phospholipid systems: saturated and unsaturated. The first group is a mixture of zwiterionic dipalmitoyl-sn-glycero-3-phosphocoline (DPPC) and anionic 1,2-dipalmitoyl-sn-3-glycero-[phospho-rac-(1-glycerol)] (DPPG) phospholipids, at different molar ratios. Measurements were performed bellow (25oC) and above (50oC) the main gel-liquid crystalline phase transition temperature (~ 41oC). The second group is constituted by a mixture of zwiterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocoline (POPC) and anionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho(1-rac-glycerol) (POPG) phospholipids, at different molar ratios. Since the gel-liquid crystalline phase transition of these phospholipids occurs at a very low temperature value, all experiments were performed at 25oC (liquid crystalline state vesicles). All phospholipid systems were prepared through the extrusion method in order to obtain large unilamellar vesicles (LUV). The fluorescence data analyses indicated that the electrostatic attraction between the porphyrin substituents (positively charged) and the polar head groups of the phospholipid vesicles (Stern layer) plays an important role on the porphyrin binding affinity. The distribution of TMPyP between the aqueous medium (buffer) and the phospholipid vesicles was characterized by the coexistence of a shorter (~ 5 ns) and a longer (~ 9-11 ns) fluorescence lifetimes, respectively. Based on the pre- exponential values, additional time-resolved experiments showed a redistribution of the porphyrin at increasing salt concentration. The quenching studies, using potassium iodide (KI) as quencher, indicated that both TMPyP and ZnTMPyP are preferentially located at the Stern layer region. This result is in agreement with the zeta potential and DLS findings, which demonstrated a partial neutralization of the negative charges at the vesicle surface due to the porphyrin association.

Les charges à l'interface liquide/solide sont un élément originel majeur des phénomènes électrocinétiques observés en micro/nanofluidique. Elles sont donc la colonne vertébrale de mon manuscrit de thèse, qui se décompose en trois parties : Dans la première partie, un rappel des concepts de base sur les interfaces liquides/solides est proposé au lecteur. Il est suivi d'une description des différentes méthodes expérimentales permettant de mesurer le potentiel zeta de couples solide/électrolyte, puis d'une présentation des travaux de la littérature exploitant les charges aux interfaces pour la préconcentration de molécules biologiques dans des systèmes Micro-Nano-Micro (MNM) fluidiques. Ensuite, une deuxième partie est consacrée à la mesure du potentiel zeta par la méthode des courants d'écoulement. Nous y présentons l'amélioration du banc expérimental issu des travaux antérieurs à ma thèse, ainsi que le développement de nouveaux protocoles de préparation des surfaces permettant de rationaliser et de stabiliser les mesures. Une application à un détecteur original de molécules biologiques clos cette deuxième partie. Enfin, la troisième et dernière partie s'intéresse à la préconcentration de molécules biologiques. Une méthode originale de fabrication des dispositifs MNM et les résultats de préconcentration obtenus, très encourageants, sont décrits. Des premiers modèles numériques et phénoménologiques sont proposés, qui mettent en avant l'originalité de notre travail / The charges at liquid/solid interfaces are a key element for both understanding and exploiting the electrokinetic phenomena in micro/nanofluidics. The manuscript of my Ph.D thesis is dedicated to these phenomena, which is divided into three main parts: Above all, a simple overview of charges at the liquid/solid interface is proposed. Then, several common methods for measuring the zeta potential at the liquid/solid interface are described. Next, various effective methods to preconcentrate the biological molecules is presented with the help of the surface charges. Secondly, the streaming current, which is a standard method to measure the zeta potential in our laboratory, is detailed. It contains the upgrade of the experimental setup from the previous version and the development of new protocols, which improve dramatically the stabilization and the reproducibility of the measurements. In addition, an original biological sensor is briefly presented based on these advancements. Lastly, in the final part, we describe a method which is primitively utilised in the fabrication of Micro-Nano-Micro fluidic system. Based on this system, some favorable preconcentration results is obtained. Moreover, numerical simulations are presented to prove the originality of our work

Organic materials are ubiquitous in the geologic environment, and can exert significant influence over the interfacial properties of minerals. However, due to the complexity in their structure and interaction with soil solids, their impact has remained relatively unquantified. This study investigated the engineering behaviors of organoclays, which were synthesized in the laboratory using naturally occurring clay minerals and quaternary ammonium compounds of controlled structure and density of loading. Organic cations were chosen to study the effects of functional group structure and size. The laboratory investigation showed that the presence of the organic cations on the mineral surfaces led to increased hydrophobicity of all clays tested. Conduction studies on the electrical, hydraulic, and thermal properties of the organoclay composites suggested that increasing the total organic carbon content resulted in decreased electrical and thermal conductivity, but increased hydraulic conductivity, due to the reduced swelling of the base clay mineral phase. Electrokinetic properties of the organoclays illustrated that compared with the clay's naturally occurring inorganic cations, exchanged quaternary ammonium cations were more likely bound within a particle's shear plane. Consequently, organoclays had less negative zeta potential than that of unmodified bentonite. Increasing the length of one carbon tail was more effective at binding organic cations within the shear plane than increasing the size of the cation, when compared on the basis of total organic carbon content. In terms of large strain strength, the modified organic clays exhibited increased shear strength, in part owing to the reduction in water content caused by the presence of the hydrophobic organic layering. Shear strength increased with single carbon tail length or with cation size, although the latter effect tended to reach a plateau as the length of the four short cation tails increased from 2 to 4. In terms of small strain behavior, the shear modulus was shown to be a function of the total organic carbon content. It is believed that number of particle contacts increased as the organic carbon content increased. Stiffness increased as either the size of the cation or the total organic carbon content was increased. Damping also increased as the organic loading was increased, with the organic phase acting as an energy dissipation mechanism.

Résumé : Au Québec, les ouvrages hydrauliques représentent une source indéniable pour la production d’énergie et la gestion hydraulique, et par conséquent un moteur nécessaire pour le développement socioéconomique. De ce fait, une conception adéquate et des inspections continues sont nécessaires pour assurer la stabilité et la sécurité de ces ouvrages. Ainsi, les anomalies dans les barrages doivent être localisées dans le plus court délai. L’érosion interne est la cause principale de la rupture des ouvrages en remblai. En conséquence, l’infiltration de l’eau dans les barrages, qui engendre le phénomène d’érosion interhe, doit être détectée. Quelques méthodes non destructives ont été développées pour ausculter ces ouvrages et déterminer le niveau piézométrique dans les ouvrages en remblai. Dans le cadre de ce projet, la méthode de la polarisation spontanée a été adoptée. Cette méthode consiste à mesurer de façon passive un champ électrique généré à la surface des particules du sol par électrofiltration. Le phénomène d’électrofiltration est défini par la circulation hydrique dans la matrice poreuse d ’un matériau qui engendre un champ électrique mesurable à la surface du sol. Des essais au laboratoire de l’Université de Sherbrooke ont été réalisés pour déterminer l’effet de la circulation de l’eau sur les propriétés électriques de différents matériaux. Un dispositif d’essai a été développé et utilisé pour les essais et le modèle théorique est celui de Helmholtz-Smoluchowski. Durant les essais, l’influence de la charge hydraulique, de la température et de la granulométrie sur les propriétés électriques des matériaux ont été vérifiées. Les expériences ont pour objectif primaire de déterminer le rapport entre le coefficient de couplage et le potentiel zêta en utilisant la méthode de la polarisation spontanée. Les résultats expérimentaux obtenus ont été comparés avec des valeurs tirées de la littérature pour tester le modèle et le protocole utilisés. Étant donné que les données expérimentales correspondent avec les valeurs acceptées dans la communauté scientifique, le modèle expérimental adopté peut être considéré fiable. Ce projet est un préalable pour une recherche future qui permettra de développer un algorithme d’inversion pour déterminer et localiser les anomalies dans les ouvrages en remblai. Les études expérimentales ont démontrées que la charge hydraulique a eu un effet considérable sur les propriétés électriques des différents matériaux. Le coefficient de couplage et le potentiel zêta varie proportionnellement avec la charge hydraulique. De plus, les propriétés électriques ont subi une variation en fonction de la température du fluide. Enfin, le coefficient de couplage et le potentiel zêta des différents matériaux ont subi des variations proportionnelles à l’uniformité de chacun des matériaux. Pour un matériau plus uniforme, le coefficient de couplage est plus faible et le potentiel zêta est plus élevé. // Abstract : In Quebec, hydraulic represents an undeniable source for energy production and therefore needed an engine for economie development. Therefore, proper design and ongoing inspections are necessary to ensure the stability and safety of these structures. Thus, abnormaiities in embankment dams should be located in the shortest time. The internai erosion is the main cause of the failure of embankment dams. Consequently, the infiltration of water in dams, which generates the internai erosion, should be detected. Several non-destructive methods have been developed to auscultate these structures and determine the groundwater level in the embankment works. In this project, the self-potential (SP) method was adopted. This method consists in measuring a passive electric field at the surface of the soil. The phenomenon is defined by the electrofiltration circulation water into the porous matrix of a material which generates a measurable electric current to the ground surface. Laboratory tests at the Université de Sherbrooke were performed to determine the effect of water flow on the electrical properties for different materials. Plexiglas pipe was used for testing and the theoretical model is the Helmholtz-Smoluchowski. During the tests, the influence of hydraulic loading and temperature on the electrical properties of the materials has been checked. The experiments aim at determining the primary relationship between the coupling coefficient and zeta potential using the self-potential (SP) method. The experimental results were compared with values from the literature to confirm the model and protocol used. Thus since that the experimental data are consequent with those theoretical, experimental model adopted can be considered as reliable. This project is a prerequisite for future research that will develop an inversion algorithm to identify and locate anomalies in the embankment dams. Experimental studies have demonstrated that the hydraulic load had a significant effect on the electrical properties of different materials. The coupling coefficient and the zeta potential vary proportionally to the hydraulic load. In addition, the electrical properties underwent change depending on the fluid temperature. Finally, the coupling coefficient and zeta potential of different materials have fluctuated proportionally to the uniformity of each material. For a more uniform material, the coupling coefficient is lower and the zeta potential is higher.

Microbiological water quality monitoring of bathing waters does not account for faecal bacteria in sediments. Intertidal deposits are a significant reservoir of faecal bacteria and this indicates there is a risk to human health through direct contact with the sediment, or through the resuspension of bacteria to the water column. This project investigated factors influencing the relative abundance of faecal indicator organisms (FIOs) in intertidal estuarine sediments. The effects of physical, biogeochemical and biological sediment characteristics, environmental variables and native microbial communities were explored through field campaigns on the Ythan and Eden estuaries, Scotland. The contributory role of sediments to adverse water quality was investigated by combining FIO abundance and measurements of sediment stability. The importance of strain and sediment characteristics in the adhesion of E. coli to suspended sediments was also examined using laboratory experiments. E. coli concentrations up to 5.9 log₁₀ CFU 100 g dry wt⁻¹ were observed, confirming that intertidal sediments are an important reservoir of faecal bacteria. The variability of E. coli abundance in estuarine sediments was successfully explained with multiple stepwise linear regression (Adjusted R² up to 87.4) using easily-obtainable measurements of sediment characteristics and environmental variables, with variability most heavily influenced by salinity and particle size gradients. Native microbial community population metrics and community constituent composition correlated with environmental gradients, but did not influence FIO abundance. The amount of E. coli adhering to suspended sediments ranged from 0.02 to 0.74 log₁₀ CFU ml⁻¹, and was dependant on strain characteristics and sediment type rather than zeta potential, with higher cell-particle adhesion at 2 and 3.5 PSU than 0 and 5 PSU. Monitoring of sediment characteristics will lead to more informed bathing water quality advisories to protect public health. Future research should focus on applying the findings here to the modelling of bacterial fate and transport on a catchment scale.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Os nanotubos de carbono apresentam extraordinÃrias propriedades fÃsico-quÃmicas que tÃm sido exploradas para aplicaÃÃes que vÃo desde a ciÃncia de materiais atà a biologia. No entanto, a maioria das aplicaÃÃes requer modificaÃÃes quÃmicas dos nanotubos de modo a explorar ao mÃximo seu potencial. Neste contexto, o desenvolvimento de protocolos de tratamento e de purificaÃÃo à muito importante. O objetivo deste estudo à contribuir para o entendimento de como a mudanÃa de uma variÃvel especÃfica, a temperatura, afeta as propriedades fÃsico-quÃmicas dos nanotubos de carbono de paredes mÃltiplas (MWNTs) durante a purificaÃÃo. Um grama (1g) de MWNTs (Ctube 100, CNT Co. Ltd., Incheon - CorÃia do Sul) foram submetidos a um refluxo de Ãcido nÃtrico 9 mol/L por 12 horas em temperaturas de 25ÂC, 75ÂC, 125ÂC e 175ÂC. ApÃs o refluxo, as amostras foram resfriadas em um banho tÃrmico, filtradas em condiÃÃes de vÃcuo com uma membrana de PTFE de 0, 2 Âm e lavadas com Ãgua deionizada atà que o pH neutro do filtrado foi atingido. Por Ãltimo, os MWNTs oxidados foram secos em vÃcuo durante 48 h. As tÃcnicas utilizadas neste trabalho para a realizaÃÃo das caracterizaÃÃes forneceram resultados que tratam desde caracterÃsticas macro e de superfÃcie atà as associadas ao nÃvel atÃmico. A estabilidade tÃrmica foi analisada por meio de medidas de TGA, uma vez que muitos dos grupos funcionais criados no tratamento sÃo termicamente instÃveis. A oxidaÃÃo resultante do tratamento introduz grupos polares na superfÃcie dos MWNTs e assim cria a estabilidade eletrostÃtica necessÃria para uma dispersÃo estÃvel em meio aquoso. A estabilidade foi avaliada para cada amostra por meio de medidas de potencial zeta. A quantidade e o tipo de resÃduos catalÃticos presentes nas amostras antes e depois do tratamento foram analisados atravÃs de medidas de EDX e UV-VIS. Medidas de espectroscopia Raman Confocal permitiram a anÃlise especÃfica dos defeitos estruturais criados sobre a superfÃcie dos tubos, em conseqÃÃncia do processo de oxidaÃÃo. Constatou-se que os experimentos Raman devem ser realizados sobre muitos pontos para poder acessar as propriedades mÃdias das amostras. A capacidade de adsorÃÃo da superfÃcie de cada amostra apÃs o tratamento foi inspecionada atravÃs de medidas de Ãrea superficial especÃfica (mÃtodo BET). Ao comparar os resultados de diferentes tÃcnicas, foi possÃvel acessar os efeitos da temperatura do tratamento sobre as propriedades fÃsico-quÃmicas relevantes, permitindo assim a obtenÃÃo de amostras bem caracterizadas que serÃo Ãteis para futuros estudos em Ãreas bio-relacionadas. / Carbon nanotubes exhibit remarkable physico-chemical properties which have been exploited for applications ranging from materials science to biology. However, most of the aplications requires the chemical modification of the nanotubes in order to exploit their maximum potential. In this context, the development of protocols for treatment and purification is very important. The purpose of this study is to contribute for the understand on how the change of a particular purification parameter, temperature, affects the physico-chemical properties of multi-walled carbon nanotubes (MWNTs) during the purification. One gram (1g) of MWNTs (Ctube 100, CNT Co. Ltd., Incheon - South Korea) were subjected to a reflux with nitric acid 9 mol/L for 12 hours at temperatures 25ÂC, 75ÂC, 125ÂC and 175ÂC. After refluxed, the samples were cooled down in a heat bath, filtered in vacuum condition using a PTFE membrane of 0, 2 Âm and washed with deionized water until the neutral pH of the filtrate was reached. Afterwards, the oxidized MWCNTs were dried in vacuum for 48 h. The experimental techniques used in this work to perform the samples characterization provide results that allow to get information from macro and surface characteristics to those associated with the atomic level. Thermal stability was analyzed by TGA measurements, since many of the functional groups created during the treatment are thermally unstable. Oxidation resulting from treatment introduces polar groups on the surface of MWNTs thus creating the electrostatic stability required for a stable dispersion in aqueous medium. The stability was evaluated for each sample by zeta potential measurements. The amount and type of catalytic residues present in the samples before and after treatment were analyzed by means of EDX and UV-VIS. Techniques confocal Raman spectroscopy measurements allowed the specific analysis of the structural defects created on the surface of the tubes as a consequence of oxidation process. It was found that Raman experiments should be performed on may points of the sample in order to access their average properties. The adsorption capacity of the surface of each sample after treatment, were inspected through specific surface area measurements (BET method). By comparing the results of different techniques it was possible to access the effects of temperature on the treatment on the relevant physico-chemical properties thus allowing us to have well characterized samples that will be useful for further studies in biorelated areas.

Este estudo reúne os principais resultados de fluorescência estática e resolvida no tempo sobre a interação da porfirina meso-tetrakis (4-metilpiridil), na forma de base livre (TMPyP) e complexada com Zn2+ (ZnTMPyP), com vesículas de fosfolipídio. Adicionalmente foram utilizadas as técnicas de potencial zeta e espalhamento de luz dinâmico (DLS, do inglês \"dynamic light scattering\"). As vesículas de fosfolipídio foram formadas por dois conjuntos de fosfolipídios: saturados e insaturados. O primeiro grupo é formado pela mistura dos fosfolipídios zwiteriônico 1,2-dipalmitoil-sn-glicero-3-fosfocolina (DPPC) e aniônico 1,2-dipalmitoil-sn-3-glicero-[fosfo-rac-(1- glicerol)] (DPPG), a diferentes razões molares. Os estudos utilizando tais sistemas foram realizados abaixo (25oC) e acima (50oC) da temperatura de transição de fase gel-líquido cristalino destes fosfolipídios (~ 41oC). O segundo grupo é formado pela mistura dos fosfolipídios zwiteriônico 1-palmitoil-2-oleoil-sn-glicero-3-fosfocolina (POPC) e aniônico 1-palmitoil-2-oleoil-sn-glicero-3-fosfo(1-rac-glicerol) (POPG). Como a transição de fase destes dois fosfolipídios ocorre a temperaturas negativas, todos os experimentos foram realizados a 25oC (vesículas no estado líquido cristalino). Todos os sistemas foram preparados através do método de extrusão para a obtenção de vesículas grandes unilamelares (LUV, do inglês \"large unilamellar vesicles\"). As análises dos dados de fluorescência indicaram que a atração eletrostática entre os substituíntes (positivamente carregados) das porfirinas TMPyP e ZnTMPyP e o grupo das cabeças polares (camada de Stern) das vesículas de fosfolipídio desempenha um papel fundamental na associação da porfirina. A distribuição da TMPyP entre o meio aquoso (tampão) e as vesículas de fosfolipídio foi evidenciada pela coexistência de um tempo de vida de fluorescência mais curto (~ 5 ns) e outro mais longo (~ 9-11 ns), respectivamente. Baseado nos valores das constantes pré-exponenciais, estudos adicionais mostram que a distribuição acima é afetada pela concentração de sal na solução. Os resultados de supressão de fluorescência com o supressor iodeto de potássio (KI) indicaram que ambas porfirinas estão localizadas, preferencialmente, na região da camada de Stern. Este resultado foi confirmado pelos estudos de potencial zeta e de DLS, os quais mostraram uma neutralização parcial das cargas negativas na superfície das vesículas devido à associação da porfirina. / This study presents time-resolved and steady-state fluorescence results on the interaction of the meso-tetrakis (4-methylpyridil) porphyrin, in free base form (TMPyP), and complexed with Zn2+ (ZnTMPyP), with phospholipid vesicles. Zeta potential and dynamic light scattering (DLS) techniques were also used. Phospholipid vesicles were formed by two phospholipid systems: saturated and unsaturated. The first group is a mixture of zwiterionic dipalmitoyl-sn-glycero-3-phosphocoline (DPPC) and anionic 1,2-dipalmitoyl-sn-3-glycero-[phospho-rac-(1-glycerol)] (DPPG) phospholipids, at different molar ratios. Measurements were performed bellow (25oC) and above (50oC) the main gel-liquid crystalline phase transition temperature (~ 41oC). The second group is constituted by a mixture of zwiterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocoline (POPC) and anionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho(1-rac-glycerol) (POPG) phospholipids, at different molar ratios. Since the gel-liquid crystalline phase transition of these phospholipids occurs at a very low temperature value, all experiments were performed at 25oC (liquid crystalline state vesicles). All phospholipid systems were prepared through the extrusion method in order to obtain large unilamellar vesicles (LUV). The fluorescence data analyses indicated that the electrostatic attraction between the porphyrin substituents (positively charged) and the polar head groups of the phospholipid vesicles (Stern layer) plays an important role on the porphyrin binding affinity. The distribution of TMPyP between the aqueous medium (buffer) and the phospholipid vesicles was characterized by the coexistence of a shorter (~ 5 ns) and a longer (~ 9-11 ns) fluorescence lifetimes, respectively. Based on the pre- exponential values, additional time-resolved experiments showed a redistribution of the porphyrin at increasing salt concentration. The quenching studies, using potassium iodide (KI) as quencher, indicated that both TMPyP and ZnTMPyP are preferentially located at the Stern layer region. This result is in agreement with the zeta potential and DLS findings, which demonstrated a partial neutralization of the negative charges at the vesicle surface due to the porphyrin association.

O reator de FAD deve propiciar condições adequadas para contato entre as micro-bolhas e os flocos formados no pré-tratamento e também condições para que o conjunto floco/bolha possa ser direcionado ao topo do reator, e assim ser removido. O projeto de pesquisa visou estudar condições hidrodinâmicas proporcionadas pela variação da Velocidade Cross-Flow (VCF) e assim verificar a influência na eficiência de uma estação piloto de flotação por ar dissolvido. A VCF é importante parâmetro para concepção de unidades de FAD e é função da vazão de entrada no tanque de flotação e da área entre o nível d\'água no tanque de flotação e o anteparo que separa a zona de contato da zona de separação. A velocidade cross-flow constitui um parâmetro de grande importância para projetos de unidades de flotação. Nesta região de transição entre a zona de contato e a zona de separação, ocorre a passagem do conjunto floco/bolha, e turbulência excessiva pode causar o rompimento do conjunto e assim comprometer a eficiência da flotação. Além disso, o padrão de escoamento observado na zona de separação dos flotadores, onde ocorre a separação dos aglomerados \"flocos + bolhas\", depende fortemente do valor médio da velocidade cross-flow, conforme comentado por Lundh et al. (2000 e 2002) e por Reali e Patrizzi (2007). Daí a necessidade de se investigar mais profundamente a influência da VCF na eficiência da clarificação por flotação. O projeto de pesquisa foi dividido em duas etapas. Para realização das etapas foi estudado um tipo de água preparada em laboratório, através da adição de substância húmica e caulinita, para obtenção de cor aparente e turbidez, respectivamente. A água estudada possui cor aparente e turbidez moderada (1 mg/L de substância húmica e 8,5 mg/L de caulinita) resultando em valores de turbidez por volta de 7 NTU e cor aparente por volta de 40 UH. A etapa 1 consistiu na determinação do par, pH de coagulação e dosagem de coagulante (sulfato de alumínio), gradiente médio de floculação e tempo médio de floculação adequado para a água de estudo. Para realização da etapa 1 foi utilizado equipamento de flotação de bancada de regime de batelada (Flotateste), que se encontra nas dependências do Laboratório de Tratamento Avançado e Reuso de Águas - LATAR/SHS/EESC/USP. Foram mantidos fixos os seguintes parâmetros: \'T IND.MR\', \'G IND.MR\', \'T IND.F\', \'G IND.F\', \'P IND.SAT\', \'T IND.REC\', \'V IND.FLOT\'. Conforme preconizado por Reali et al (2007), foi variada a dosagem de coagulante. Após determinado o melhor par pH e dosagem de coagulante foram realizados ensaios visando determinar o melhor \'G IND.F\' e \'T IND.F\' para a água em estudo. Para a água de estudo foram escolhidas duas condições de potencial Zeta, determinados na etapa 1 do projeto de pesquisa. A primeira condição o potencial Zeta permaneceria com valor próximo de 0 mV e na segunda condição o potencial Zeta seria positivo, por volta de +12 mV. A etapa 2 consistiu em variar a velocidade cross-flow, através da variação da altura do vertedor de saída da água flotada de uma unidade piloto de flotação, de forma a se obter diferentes valores de VCF (mantendo-se constantes os valores de tempo de contato e taxa de aplicação superficial na zona de contato), para dois valores de Taxas de Aplicação Superficial (TAS) (7,67 m/h e 15 m/h) na zona de separação e os dois valores de potencial Zeta (PZ), e com isto avaliar a sua influencia na eficiência de remoção de sólidos suspensos totais, cor e turbidez da instalação piloto retangular de FAD. / The reactor DAF should provide adequate conditions for contact between the micro-bubbles and the flakes formed in the pretreatment conditions and also for the aggregate flocs/bubble can be directed to the top of the reactor, and thus be removed. The research project aimed at studying hydrodynamic conditions provided by the variation of Cross-Flow Velocity (VCF) and thus checks the influence on the efficiency of a pilot plant of dissolved air flotation. The VCF is an important parameter to design units of DAF and is a function of input flow in the flotation tank and the area between the water level in the flotation tank and the bulkhead that separates the contact zone of the zone of separation. The cross-flow velocity is a parameter of great importance to projects of flotation units. In this region of the transition zone between the contact zone and the separation zone, occurs the passage of the aggregate flocs/bubble, and excessive turbulence can cause disruption of the aggregate and thereby harm the flotation efficiency. Moreover, the pattern of flow observed in the flotation separation zone, which occurs the separation of aggregates \"flakes + bubbles\", depends strongly on the average value of cross-flow velocity as described by Lundh et al. (2000 and 2002) and Reali and Patrizzi (2007). Hence the needs to investigate further the influence of VCF on the clarification efficiency by flotation. The research project was divided into two steps. To perform the steps has been studied a type of water prepared in the laboratory, through the addition of humic substances and kaolin, to obtain apparent color and turbidity, respectively. The study water has moderate turbidity and apparent color (1 mg/L of humic substance and 8.5 mg/L of kaolin) resulting in turbidity values around 7 NTU and color apparent by 40 HU. Step 1 consisted in the determination of the pair, coagulation pH and coagulant dosage (aluminum sulfate), flocculation gradient and time flocculation suitable for the study water. For the implementation of step 1 was used bench batch flotation system equipment (Flotatest), located on the Laboratory for Advanced Treatment and Reuse Water - LATAR / SHS / EESC / USP. Were kept fixed the following parameters: \'T IND.MR\', \'G IND.MR\', \'T IND.F\', \'G IND.F\', \'P IND.SAT\', \'T IND.REC\', \'V IND.FLOT\'. As predicted by Reali et al (2007), was varied the dosage of coagulant. After determined the best pair of coagulant dosage and pH coagulation the tests were performed to determine the best \'G IND.F\' and \'T IND.F\' for the study water. For the study water were chosen two conditions of Zeta potential values, determined in the step 1 of the research project, where the first condition the Zeta potential value kept near 0 mV and the second condition kept a positive value of Zeta potential, around +12 mV. The step 2 consisted of varying the cross-flow velocity, by varying the height of the outlet weir of the clarified water of the flotation pilot plant to obtain different values of VCF (keeping constant the values of time contact and application rate on the contact zone) for two values of superficial application rates (7.67 m/h and 15 m/h) in the zone of separation and the two values of Zeta potential (PZ) and then was availed the influence on removal efficiency of total suspended solids, colour and turbidity of the rectangular pilot plant of DAF.

Les travaux présentés dans ce mémoire ont pour but de mieux comprendre l’électrodéposition de revêtements nanocomposites et d’approfondir leur caractérisation. Le système étudié est un revêtement de zinc renforcé par des nanoparticules de cérine. Les dépôts de zinc sont élaborés par électrodéposition en courant continu et pulsé dans un bain ammonium chlorure dans lequel sont introduites des nanoparticules de cérine commerciales de 50 nm de diamètre. A l’issue d’une phase d’optimisation, des conditions de bain particulières caractérisées par un pH basique et l’utilisation d’un surfactant anionique ont ainsi été sélectionnées afin de s’assurer d’une suffisante stabilité de la suspension. L’influence des nanoparticules sur les mécanismes et rendements d’électrodéposition est étudiée. Une caractérisation précise des revêtements élaborés en courant continu a été développée au moyen de diverses techniques (MEB-EDS, DRX, SIMS, SDL, MET). Cette approche multi-disciplinaire a pour but d’évaluer l’incorporation de cérine dans le composite et localiser celle-ci dans l’épaisseur, approche originale et novatrice dans le domaine des revêtements composites à matrice zinc. Les nanoparticules influencent les propriétés des revêtements, avec une augmentation de dureté jusqu’à quarante pourcents. L’impact sur le comportement à la corrosion est mineur mais une amélioration en immersion longue durée est observée. Dans le but d’augmenter plus drastiquement l’incorporation et donc les propriétés, une modification de la morphologie du zinc parait indispensable. Dans cette optique, une démarche d’élaboration en courants pulsés a été conduite avec des résultats limités du fait de la forte influence des particules sur les mécanismes de germination/croissance en pulsés. L’utilisation d’un élément d’alliage tel le nickel est une perspective encourageante pour obtenir des revêtements composites aux propriétés optimisées. / The work presented within this thesis aims to better understand the electrodeposition of nanocomposite coatings and to improve their characterization. The system studied is a zinc coating reinforced by nanoparticles of ceria (50 nm in size). Zinc coatings are produced by DC and PC electroplating from an ammonium chloride bath in which the commercial ceria nanoparticles were introduced. Following an optimization stage, specific bath conditions with a alcaline pH and the use of an anionic surfactant have been selected to ensure sufficient stability of the suspension. The influence of nanoparticles on the mechanisms and plating efficiency is studied. A deep characterization of coatings was performed using various techniques (SEM-EDS, XRD, SIMS, GDOES, TEM). This plural approach aims to assess the dispersion of ceria in the composite surface and bulk, which leads to an original and innovative approach in the field of zinc matrix composite coatings. Nanoparticles influence the properties of coatings, increasing hardness up to forty percent. The impact on the corrosion behavior is minor but a slight improvement in long-term immersion is observed. In order to increase more drastically the incorporation of ceria and therefore properties of the resulting coating, change in the morphology of the zinc seems essential. In this context, an approach developed towards pulsed currents was conducted with limited results because of the strong influence of particles on the mechanisms of germination / growth. The use of an alloying element such as nickel is a promising prospect for composite coatings with optimal properties.