Gegenstand der Dissertation ist die größen- und eigenschaftsoptimierte Synthese und Charakterisierung von anorganischen Nanopartikeln in einer geeigneten Polyelektrolytmodifizierten Mikroemulsion. Das Hauptziel bildet dabei die Auswahl einer geeigneten Mikroemulsion, zur Synthese von kleinen, stabilen, reproduzierbaren Nanopartikeln mit besonderen Eigenschaften. Die vorliegende Arbeit wurde in zwei Haupteile gegliedert. Der erste Teil befasst sich mit der Einmischung von unterschiedlichen Polykationen (lineares Poly (diallyldimethylammoniumchlorid) (PDADMAC) und verzweigtes Poly (ethylenimin) (PEI)) in verschiedene, auf unterschiedlichen Tensiden (CTAB - kationisch, SDS - anionisch, SB - zwitterionisch) basierenden, Mikroemulsionssysteme. Dabei zeigt sich, dass das Einmischen der Polykationen in die Wassertröpfchen der Wasser-in-Öl (W/O) Mikroemulsion prinzipiell möglich ist. Der Einfluss der verschiedenen Polykationen auf das Phasenverhalten der W/O Mikroemulsion ist jedoch sehr unterschiedlich. In Gegenwart des kationischen Tensids führen die repulsiven Wechselwirkungen mit den Polykationen zu einer Destabilisierung des Systems, während die ausgeprägten Wechselwirkungen mit dem anionischen Tensid in einer deutlichen Stabilisierung des Systems resultieren. Für das zwitterionische Tensid führen die moderaten Wechselwirkungen mit den Polykationen zu einer partiellen Stabilisierung. Der zweite Teil der Arbeit beschäftigt sich mit dem Einsatz der unterschiedlichen, Polyelektrolyt- modifizierten Mikroemulsionen als Templatphase für die Herstellung verschiedener, anorganischer Nanopartikel. Die CTAB-basierte Mikroemulsion erweist sich dabei als ungeeignet für die Herstellung von CdS Nanopartikeln, da zum einen nur eine geringe Toleranz gegenüber den Reaktanden vorhanden ist (Destabilisierungseffekt) und zum anderen das Partikelwachstum durch den Polyelektrolyt-Tensid-Film nicht ausreichend begrenzt wird. Zudem zeigt sich, dass eine Abtrennung der Partikel aus der Mikroemulsion nicht möglich ist. Die SDS-basierten Mikroemulsionen, erweisen sich als geeignete Templatphase zur Synthese kleiner anorganischer Nanopartikel (3 – 20 nm). Sowohl CdS Quantum Dots, als auch Gold Nanopartikel konnten erfolgreich in der Mikroemulsion synthetisiert werden, wobei das verzweigte PEI einen interessanten Templat-Effekt in der Mikroemulsion hervorruft. Als deutlicher Nachteil der SDS-basierten Mikroemulsionen offenbaren sich die starken Wechselwirkungen zwischen dem Tensid und den Polyelektrolyten während der Aufarbeitung der Nanopartikel aus der Mikroemulsion. Dabei erweist sich die Polyelektrolyt-Tensid-Komplexbildung als hinderlich für die Redispergierung der CdS Quantum Dots in Wasser, so dass Partikelaggregation einsetzt. Die SB-basierten Mikroemulsionen erweisen sich als günstige Templatphase für die Bildung von größen- und eigenschaftenoptimierten Nanopartikeln (< 4 nm), wobei insbesondere eine Modifizierung mit PEI als ideal betrachtet werden kann. In Gegenwart des verzweigten PEI gelang es erstmals ultrakleine, fluoreszierende Gold Cluster (< 2 nm) in einer SB-basierten Mikroemulsion als Templatphase herzustellen. Als besonderer Vorteil der SB-basierten Mikroemulsion zeigen sich die moderaten Wechselwirkungen zwischen dem zwitterionischen Tensid und den Polyelektrolyten, welche eine anschließende Abtrennung der Partikel aus der Mikroemulsion unter Erhalt der Größe und ihrer optischen Eigenschaften ermöglichen. In der redispergierten wässrigen Lösung gelang somit eine Auftrennung der PEI-modifizierten Partikel mit Hilfe der asymmetrischer Fluss Feldflussfraktionierung (aF FFF). Die gebildeten Nanopartikel zeigen interessante optische Eigenschaften und können zum Beispiel erfolgreich zur Modifizierung von Biosensoren eingesetzt werden. / This work is focused on the formation, recovery and characterisation of inorganic nanoparticles in a tailor-made polycation-modified reverse microemulsion. The main aim is the choice of an adequate microemulsion for the synthesis of small, uniform, reproducible nanoparticles with specialn characteristics. The first part is focused on the incorporation of two different polycations, low molecular weight linear poly(diallyldimethylammonium chloride) (PDADMAC) and low molecular weight branched poly(ethyleneimine) (PEI) in different surfactant-based (CTAB – cationic, SDS – anionic, SB - zwitterionic) w/o microemulsions. In principle the incorporation of the polycations in the small water droplets is possible, but the influence of the polycations on the phase behaviour is different. Repulsive interactions induce a destabilisation of the w/o microemulsion for cationic surfactant CTAB, while the distinctive interactions between the anionic surfactant SDS and the polycations induce an extension of the phase range and a considerable stabilisation. In case of zwitterionic surfactant SB a partial destabilisation can be observed, according to the lower interactions with the polycations. The second part is focused on the formation of different, inorganic nanoparticles in these polyelectrolyte-modified reverse microemulsions as a template phase. The CTAB-based microemulsion is not adequate for the formation of CdS nanoparticles, according to the low tolerance towards the reactants (destabilisation effect). Furthermore the particle growth cannot be limited by the surfactant-polycation-film and a recovery of the nanoparticles from the microemulsion is not possible. The results show that the SDS-based quaternary template phase consisting of water, toluene-pentanol (1:1), and the anionic surfactant SDS in presence of PEI or PDADMAC can be successfully used for the synthesis of polymer capped inorganic nanoparticles (3 – 20 nm). CdS quantum dots, as well as gold nanoparticles are successfully synthesised in the microemulsion droplets. Especially PEI acts as a reducing and stabilizing agent and shows an additional, interesting template effect in the microemulsion. Unfortunately a recovery of the nanoparticles without a particle aggregation is not possible due to the strong surfactant polycation interactions, which lead to polycation-surfactant complexes. The SB-based microemulsion can be successfully used as a tailor-made polycation-modifiedreverse microemulsion for the formation of small, uniform nanoparticles (< 4 nm) with special characteristics. Especially a modification with PEI is optimal and for the first time small, fluorescent gold cluster (< 2 nm) can be synthesised in a SB-based microemulsion as template phase. The results show that the electrostatic interactions between the polycation and the surfactant are of high relevance especially in the solvent evaporation and redispersion process. That means only in the case of moderate polycation-surfactant interactions a redispersion of the polymer capped particles without problems of aggregation is possible and the size and characteristics are unchanged in the redispersed solution. By means of asymmetric flow field flow fractionation (af-fff) it becomes possible to separate the two cluster fractions from each other as well as from the nanoparticle fraction with diameter > 5 nm. This opens a way to use the nanoparticles with their interesting, optical characteristics in different new fields of application for example for modification of biosensors.

In this study, pharmaceutical-grade and food-grade linker-based lecithin self-emulsifying delivery systems (SEDS) were developed with a combination of lipophilic and hydrophilic linkers. These additives at suggested concentrations are safe for pharmaceutical and food applications. The ratio of surfactant lecithin and linkers in these systems was optimized to develop surfactant in oil preconcentrates. The preconcentrates containing different surfactant concentrations and oil were diluted with fed state simulated intestinal fluid to produce pseudo-ternary phase diagrams and to identify the formulations that produced self-emulsifying or self-microemulsifying delivery systems. Optimal SEDS preconcentrates were evaluated using a dialyzer model to simulate intestinal uptake. An uptake of 39.6 mg/cm2 for the pharmaceutical-grade SEDS was obtained within 72 minutes, which promises substantial improvement in the bioavailability of hydrophobic actives. The optimal uptake of 12.2 mg/cm2 for food-grade SEDS suggests enhancement in the bioavailability of omega-3 fatty acids.

Ce travail de thèse traite de l’élaboration de nanoparticules luminescentes à based’organolanthanides pour des applications d’imagerie biomédicale ou de marquage pour la lutte anticontrefaçon. Les organolanthanides ont été incorporés sans liaison covalente afin de préserver leursremarquables propriétés de luminescence et leur stabilité chimique. Deux types de nanoparticulesont été étudiés, des particules de latex et des billes de silice qui ont toutes les deux été synthétiséesen milieu hétérogène.La silice a été synthétisée par un procédé sol-gel en microémulsion inverse. Deux organolanthanidesluminescents initialement dissous dans les micelles inverses ont été piégés physiquement dans lasilice amorphe pendant sa formation. Une nouvelle méthode basée sur la quantification de l’activitéd’un isotope radioactif de l’Eu(III) a été développée pour étudier l’incorporation desorganolanthanides. Les propriétés physico-chimiques des organolanthanides influencent directementleur localisation au sein des particules et l’efficacité d’incorporation. L’étude approfondie de cesnanoparticules a permis de mettre en évidence une amélioration de la relaxivité d’un complexe deGd(III) quand il est confiné dans la silice.Les particules de latex ont été synthétisées par polymérisation radicalaire en miniémulsion directe.Différents organolanthanides de structures ionique ou non ionique ont été incorporés efficacementpar simple dissolution dans le monomère. L’incorporation du complexe de structure ionique anécessité l’utilisation d’un tensioactif cationique afin de le maintenir à l’intérieur des gouttelettes etgarantir son incorporation dans les particules de latex. Ce système permet d’incorporer un grandnombre de complexes et aucun relargage n’est observé après plusieurs mois. Le ligand utilisé permeten plus d’exciter jusqu’à dix terre rares simultanément. En faisant varier la nature et la quantité desorganolanthanides incorporés, il est ainsi possible de générer des codes optiques complexes sousune excitation unique. / This work deals with the elaboration of luminescent nanoparticles based on organolanthanides forbioimaging and optical coding. The organolanthanides were embedded without covalent linking inorder to preserve their remarkable luminescent properties and chemical stability. Two differenttypes of nanoparticles have been studied: polymer latexes and silica particles that were bothsynthesized in dispersed media.The silica nanoparticles were synthesized by a reverse microemulsion-mediated sol-gel process. Twoluminescent lanthanide chelates originally dissolved into water droplets were physically trapped intothe amorphous silica during its formation. A novel method based on a radioactive Eu(III) probe hasbeen developed to study the incorporation process. The physicochemical properties of the differentchelates had a strong influence on their localization within the particles and on the measuredincorporation efficiencies. This study finally allowed us to investigate the effect of Gd(III) complexesconfinement into silica nanoparticles.Luminescent polymer latexes based on organolanthanides have been synthesized by miniemulsionpolymerization. Several organolanthanides exhibiting a ionic structure or a non-ionic structure havebeen efficiently embedded into latex particles by simple dissolution in the corresponding monomers.For the ionic lanthanide chelate, a cationic surfactant was used to maintain the organolanthanidecomplex inside the droplets and guaranty and efficient incorporation. The resulting polymericluminescent nanoparticles showed excellent stability over leakage and a high loading capacity. Thisparticular ligand is able to efficiently sensitize over ten luminescent lanthanides, emitting in thevisible, the NIR or both regions. This allowed us to generate a large variety of color codes based onluminescence by tuning the emission signal using several lanthanide ions.

Le projet de thèse, mené en collaboration avec le laboratoire Medesis Pharma, porte sur la mise au point de deux formulations pharmaceutiques, une microémulsion inverse et un gel colloïdal, à base de Pécéol®, lécithine, éthanol et eau. Le lithium indiqué dans le traitement de maladies neurodégénératives a été utilisé comme un modèle de principe actif hydrophile dans le cadre de ce projet. Ce travail a été initié par l’étude du comportement de phases du mélange quaternaire Pécéol®/lécithine/éthanol/eau, mettant essentiellement l’accent sur les différents paramètres impliqués dans les transitions de phases, dans le but de déterminer le rôle du Pécéol® et de la lécithine dans la structuration du système.- L’étude des propriétés structurales de la microémulsion, dans le domaine riche en Pécéol®, a montré que la structure du système n’est pas cohérente avec un modèle classique de micelles sphériques, l’hypothèse d’une structure localement lamellaire a été proposée. Les propriétés de solubilisation de la microémulsion ont été évaluées par l’élaboration d’une série de diagrammes de phases pseudo-ternaires, en faisant varier le rapport éthanol/lécithine. Une efficacité optimale a été obtenue pour un rapport éthanol/lécithine égal à 40/60. La formulation optimisée est capable d’incorporer efficacement le lithium (Li), à des concentrations acceptables sans altérer la stabilité du système. L’étude des propriétés d’incorporation du Li dans la microémulsion a montré que le mécanisme d’encapsulation est compatible avec un modèle d’interactions de type drug-surfactant. Les résultats des études de stabilité de la microémulsion vide et chargée en Li menées selon les conditions ICH sont satisfaisants.- La structuration du gel clair, dans le domaine riche en lécithine, a été suivie par des analyses de rhéologie et de microscopie en lumière polarisée en fonction du rapport lécithine/Pécéol®. Les résultats ont montré que les propriétés rhéologiques du gel peuvent être modifiées en ajustant le rapport lécithine/Pécéol®. La caractérisation de la structure du gel clair par diffraction de rayons X aux petits angles (SAXS) et cryofracture conjuguée à la microscopie électronique en transmission (FF-TEM) a mis en évidence une structure anisotrope hexagonale H2. Alors que dans le domaine riche en eau, une structure anisotrope hexagonale inverse H2 et lamellaire Lα a été mise en évidence. Les propriétés rhéologiques modulables du gel dans le domaine riche en lécithine ainsi que sa grande capacité de rétention d’eau, sont particulièrement intéressantes pour une application du gel clair dans le domaine de pharmaceutique et/ou cosmétique. / This thesis project, carried out in collaboration with Medesis Pharma laboratory, is about the development of two pharmaceutical formulations, a reverse microemulsion and a colloidal gel, based on Pécéol®, lécithine, ethanol and water. The indicated lithium in the treatment of neurodegenerative diseases has been used as a hydrophilic principal active model for this project. This work started with the study of the phase behavior of the four component system Pécéol®/lecithin/éthanol/water, focusing primarily on the various parameters involved in phase transitions in order to determine the role of Pécéol® and lecithin in the structuring of the system.- The study of the structural properties of the reverse microemulsion, in the Pécéol® rich domain, showed that the system structure is not coherent with a classical model of spherical micelles, a hypothesis of a local lamellar structure was proposed. The solubilization properties of the microemulsion were evaluated following the development of a series of pseudo-ternary phase diagrams, by varying the ethanol/lecithin ratio. Optimal efficiency was obtained for an ethanol/lecithin ratio of 40/60. The optimized formulation is capable of effectively incorporating lithium (Li) to acceptable concentrations without altering the stability of the system. The study of the incorporation properties of Li in the microemulsion has shown that the encapsulation mechanism is compatible with drug-surfactant binding model. The results of the stability studies of the free and Li loaded microemulsion, conducted according to ICH conditions, are satisfactory.- The gel structuring was followed, in the lecithin rich domain, through rheological and optical microscopy analyses, according to lecithin/Pécéol® ratio. Results showed that the rheological properties of the gel can be modified by adjusting the lecithin/Pécéol® ratio. Moreover, the characterization of the gel structure through Small Angle X-Ray Scattering (SAXS) and Freeze Fracture-Transmission Electron Microscopy (FF-TEM) showed an inverse hexagonal phase H2. While, in the water rich region, an inverse hexagonal H2 and lamellar Lα phases were identified. The adjustable rheological properties of the clear gel, and its great water solubilisation capacity, are particularly interesting for the application of the gel in pharmaceutical and/or cosmetic fields.

Made available in DSpace on 2014-12-17T15:01:26Z (GMT). No. of bitstreams: 1 LuizAN_DISSERT.pdf: 1380946 bytes, checksum: dc4e735e97a7eeceeab1f285f4673933 (MD5) Previous issue date: 2011-02-21 / The underground reservoirs of fuel retailing system represent an environmental threat, because once in bad conservation, these tanks allow fuel leakage and infiltration. For soil contaminated with fuel, such as diesel oil, the present study introduces the microemulsion systems used by the method of washing. In tests carried out in column with a sample of sandy soil artificially contaminated and previously characterized as to its void level to porosity, to permeability which is an important parameter concerning the study of the method of washing. While microemulsions were characterized for their viscosity and wettability, a variation of active matter was also done departing from the original formulation. The hydraulic diffusivity of the microemulsion was studied so as the injection of such fluid in a soil with sandy characteristics. The results of the extractions revealed the excellent performance of these systems which get to remove around 95% of diesel fuel. This proves the efficiency of the microemulsion in the process of removal of diesel fuel from the soil with the advantage of being a system easily obtainable and less aggressive to the environment when compared to organic solvents. / Os reservat?rios subterr?neos do sistema retalhista de combust?veis representam uma amea?a ambiental, pois em mau estado de conserva??o esses tanques permitem o vazamento e infiltra??o do combust?vel. Para solo contaminado com combust?veis como o ?leo diesel este trabalho apresenta os sistemas microemulsionados aplicados pelo m?todo de lavagem. Em ensaios feitos em coluna com amostra de solo arenoso contaminado artificialmente e previamente caracterizado quanto ao seu ?ndice de vazios, ? porosidade, ? permeabilidade que s?o par?metros importantes no tocante ao estudo do m?todo de lavagem. Enquanto as microemuls?es foram caracterizadas por sua viscosidade e sua molhabilidade, tamb?m foi realizada a varia??o de mat?ria ativa partindo da formula??o original. A difusividade hidr?ulica da microemuls?o foi estudada a fim de que seja avaliada a inje??o deste fluido num solo com as caracter?sticas de arenoso. Os resultados das extra??es mostraram excelente desempenho desses sistemas chegando a retirar em torno de 95% do ?leo diesel. O que comprova a efici?ncia da microemuls?o no processo remo??o do ?leo diesel do solo com a vantagem de ser um sistema de f?cil obten??o e menos agressivo ao meio ambiente quando comparado aos solventes org?nicos.

Made available in DSpace on 2014-12-17T15:01:36Z (GMT). No. of bitstreams: 1 LuisaCP.pdf: 1955160 bytes, checksum: 7051a33823820be485db53c8225425a3 (MD5) Previous issue date: 2007-02-09 / Petroleum exists in the nature in certain underground formations where it is adsorbed into the rocks pores. For the conventional recovery methods usually only 30% of the oil is extracted and this can be credited, basically, to three aspects: high viscosity of the oil, geology of the formation and high interfacial tensions between the reservoir s fluids. The enhanced recovery methods use the injection of a fluid or fluids mixture in a reservoir to act in points where the conventional process didn't reach the recovery rates. Microemulsion flooding, considered an enhanced method, has the purpose to desorb the oil from the rock formation and to attain an efficient displacement of the oil emulsion. With this in mind, this work was accomplished with two main objectives: the study of the parameters effect that influence a microemulsified system (surfactant and cosurfactant types, C/S rate and salinity) and the evaluation of displacement efficiency with the microemulsions that showed stability in the rich aqueous area. For the analyzed parameters it was chose the microemulsions composition used in the recovery stage: 25% water, 5% kerosene, 46.7% of butanol as cosurfactant and 23.3% of BC or SCO cosurfactant. The core plugs of Assu and Botucatu sandstones were appraised in porosity and permeability tests and then submitted to the steps of saturation with seawater and oil, conventional recovery with water and enhanced recovery with the selected microemulsions. The Botucatu sandstone presented better recovery parameters, and the microemulsion composed with BS surfactant had larger recovery efficiency (26.88%) / O petr?leo ocorre na natureza em determinadas forma??es subterr?neas onde ? adsorvido nos poros destas rochas. Pelos m?todos convencionais de recupera??o geralmente apenas 30% deste petr?leo ? extra?do e isto pode ser atribu?do, basicamente, a tr?s aspectos: alta viscosidade do petr?leo, geologia da forma??o e elevadas tens?es interfaciais entre os fluidos do reservat?rio. Os m?todos avan?ados de recupera??o envolvem a inje??o de um fluido ou de uma mistura de fluidos em um reservat?rio para atuar nos pontos onde o processo convencional n?o conseguiu atingir as taxas de extra??o desejadas. A inje??o de microemuls?o, considerado um m?todo avan?ado, tem por finalidade dessorver o ?leo da forma??o rochosa e obter um deslocamento eficiente da emuls?o de petr?leo. Dentro deste contexto, este trabalho foi realizado com dois objetivos principais: estudo dos par?metros que influenciam o sistema microemulsionado (tipo de tensoativo, cotensoativo, raz?o C/T e salinidade) e a avalia??o da efici?ncia de deslocamento do petr?leo com as microemuls?es que apresentaram estabilidade na regi?o rica em ?gua. Pelos par?metros analisados estipulou-se microemuls?es para serem submetidas ? etapa de recupera??o com composi??o: 25% ?gua, 5% querosene, 46,7% de n-butanol como cotensoativo e 23,3% de tensoativo BS ou SCO. Os testemunhos de arenitos Assu e Botucatu foram avaliados em ensaios de porosidade e permeabilidade posteriormente submetidos ?s etapas de satura??o com ?gua do mar e petr?leo, recupera??o convencional com ?gua do mar e avan?ada com as microemuls?es selecionadas. O arenito Botucatu apresentou os melhores par?metros f?sicos para a recupera??o, e a microemuls?o composta pelo tensoativo BS foi a que obteve maior efici?ncia de deslocamento (26,88%)

Made available in DSpace on 2015-05-14T13:21:11Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2503826 bytes, checksum: efc2f2118eacd06235948cf7c3c38d1f (MD5) Previous issue date: 2011-03-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work we have developed an automated methodology for the analysis of metals in gasoline and naphtha in the form of microemulsions using a flow-batch analyzer with piston propulsion for the preparation of microemulsions and quantification of analytes by GF AAS. Three studies were conducted, the first concerning the study of optimal composition of microemulsions made through the construction of phase diagrams for gasoline and naphtha. The second study sought to improve all operational parameters of the automatic system for the production of solutions and also in relation to their coupling to the instrument for analysis. Finally it was done to optimize the operating parameters of the GF AAS for the quantification of metals which have been quantized in two ways, the first quantification by a procedure manual preparation of microemulsions and the second by the same automatic preparation. The two results were then compared by paired t test at a 95% level of confidence, no significant differences between the two relevant procedures. Furthermore, recovery tests performed showed acceptable accuracy for the two methods investigated, with average recoveries in the ranges from 88 to 93% for the automatic method and between 86 to 92% without significant differences in both a 95% level of confidence. The characteristic masses obtained were 0.36pg for Cu, 0.29pg for Cr and 0.87pg for Pb, with limits of detection and quantification respectively of 0.073 and 0.22 for Cu, 0.024 and 0.72 for Cr and 0.115 and 0.346 for Pb. / Neste trabalho foi desenvolvida uma metodologia automática para a análise de metais em gasolina e nafta na forma de microemulsões utilizando um analisador em fluxo-batelada com propulsão a pistão para a preparação das soluções e posterior quantificação dos analitos por GF AAS. Três estudos foram realizados, sendo o primeiro referente ao estudo da composição ótima das microemulsões feito através da construção de diagramas de fases para a gasolina e para a nafta. O segundo estudo tratou de aperfeiçoar todos os parâmetros operacionais do sistema automático para a produção das soluções e também em relação ao seu acoplamento ao instrumento de análise. Por fim foi realizado a otimização dos parâmetros operacionais do GF AAS para a quantificação dos metais, que foram quantizados de dois modos, sendo a primeira quantificação através de um procedimento de preparação manual das microemulsões e a segunda pela preparação automática das mesmas. Os dois resultados obtidos foram então comparados através do teste t pareado a um nível de 95% de confiança, sem diferenças estatísticas relevantes entre os dois procedimentos. Além disso, testes de recuperação realizados indicaram precisão satisfatória para as duas metodologias investigadas, com recuperações médias nas faixas de 88 a 93% para o método automático e entre 86 a 92% ambos sem diferenças significativas a um nível de 95% de confiança. As massas características obtidas foram de 0,36pg para Cu, 0,29pg para Cr e 0,87pg para Pb, com limites de detecção e quantificação respectivamente de 0,073 e 0,22 para Cu, 0,024 e 0,72 para Cr e 0,115 e 0,346 para Pb.

Made available in DSpace on 2016-08-19T12:56:35Z (GMT). No. of bitstreams: 1 CASSIO DA SILVA DIAS.pdf: 1841610 bytes, checksum: 19960efa8e582ace78afd42034c3916a (MD5) Previous issue date: 2010-11-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In nature babassu oil can be applied as fuel in diesel engines. However, such practice is limited by its high viscosity and gum formation tendency. Conversely, vegetal oil-based microemulsions often have appropriated combustion and physicochemical properties. In such context, this work aims to evaluate microemulsions from vegetal oil, hydrated alcohol and fusel oil as an alternative fuel. Thus, the babassu chemical properties were determined by several analyses and its miscibility pattern was evaluated by means of phase diagrams. Based on such study, were selected microemulsion with high oil content. Among them, the 60% oil-based ternary system has presented desired characteristics, being evaluated as pure or binary diesel blended fuels. The combustion efficiency, for all samples, was evaluated according to fuel consumption, gaseous exhaust emission. In general, all microemulsified systems has presented low viscosities, being inferior to the initial oil and equivalent to diesel. Furthermore, it was observed a significant reduction of the gaseous releases for B5 microemulsion blend. / A utilização do óleo de babaçu in natura em motores do ciclo diesel é limitada, tendo em vista que sua alta viscosidade pode ocasionar a formação de gomas e entupimento dos bicos injetores do motor. Entretanto, a obtenção de microemulsões a partir do óleo vegetal, álcool hidratado e óleo fúsel constitui uma alternativa para redução da viscosidade do sistema, apresentando vantagens nos aspectos sociais, econômicos e ambientais. O objetivo desse trabalho é a obtenção de microemulsões combustíveis. Na primeira etapa foram avaliados os parâmetros físico-químicos do óleo de babaçu, sendo então, construído um diagrama de fases a partir dos componentes formadores das microemulsões. Posteriormente, fez-se a seleção da região de microemulsão dos sistemas com maior proporção de óleo vegetal nos quais foram realizados ensaios físico-químicos de caracterização, sendo escolhido um sistema com proporção de 60% do óleo vegetal para ser testado puro e misturado ao diesel em um motor. A eficiência da combustão das microemulsões e de suas misturas binárias com o diesel no motor, baseou-se na quantificação do consumo, vazão dos gases e emissões de CO, CO2 e NOx. Os sistemas microemulsionados apresentaram uma redução significativa da viscosidade, quando comparado ao óleo de babaçu degomado, ficando-as semelhantes ao diesel e atingindo valores equivalentes aos padrões de comercialização. Houve uma melhora nos índices de emissões gasosas para as misturas das microemulsões com o B5.

Made available in DSpace on 2016-08-19T12:56:48Z (GMT). No. of bitstreams: 1 Dissertacao ANA CRISTINA RIBEIRO FREITAS.pdf: 1794956 bytes, checksum: b673e072d214c0950503c73479be5486 (MD5) Previous issue date: 2014-07-25 / The metal corrosion manifests itself in different ways, however, the environment in which it occurs most often is aqueous. In between the mechanism of electrochemical corrosion is essentially. Considering that microemulsions containing pure Biodiesel and mixtures thereof, the water-in-oil (W/O) or oil in water (O/W), have higher electrical conductivity and lower viscosity, it may be possible to obtain electrochemical data of these systems. Thus, the paper aims to study the corrosion resistance of carbon steel in the presence of three micromeulsionados systems (EMS's) rightly C / T = 2, containing CTAB as surfactant, ethanol, isopropanol and butanol as co-surfactant, Biodiesel as Babaçu oil phase and water as the aqueous phase. The corrosion of steel was conducted by electrochemical tests of the open circuit potential, electrochemical impedance spectroscopy and polarization. The electrochemical results generated data and information which have allowed the objectives proposed for this work. Regarding immersion times, the surface of 1020 carbon steel showed better corrosion protection behaviors when the microemulsion system containing butanol / CTAB was used as expressed results from the experiments of electrochemical impedance spectroscopy, This good performance of corrosion protection can be attributed to surface passivation of 1020 carbon steel due to the formation of a film, ensuring a good resistance to corrosion of carbon steel. / A corrosão de metais normalmente manifesta-se na interface entre o metal e o meio corrosivo produzindo a degradação e perda de algumas propriedades físico-químicas e mecânicas do material metálico. Esta ação corrosiva pode ser provocada por diversos meios, entre eles: atmosfera, líquidos, meios orgânicos etc. Em meio aquoso o mecanismo da corrosão é essencialmente eletroquímico. Nesse meio o mecanismo da corrosão é essencialmente eletroquímico. Considerando-se que microemulsões contendo o Biodiesel puro e suas misturas, do tipo água em óleo (A/O) ou óleo em água (O/A), apresentam maior condutividade elétrica e menor viscosidade, pode ser possível obter dados eletroquímicos destes sistemas. Desta forma, o trabalho tem como objetivo estudar a resistência a corrosão do aço carbono na presença de três sistemas micromeulsionados (SME s), com razão Cotensoativo/Tensoativo (C/T) = 2, contendo o tensoativo brometo de cetiltrimetilamônio CTAB, etanol, isopropanol e o butanol como cotensoativos e o Biodiesel de Babaçu como fase oleosa e a água como fase aquosa. A corrosão do aço foi conduzida através de ensaios eletroquímicos de potencial de circuito aberto, impedância eletroquímica e polarização. Os resultados eletroquímicos obtidos geraram dados e informações que permitiram chegar aos objetivos propostos por este trabalho. Em relação aos tempos de imersão, a superfície do aço carbono 1020 apresentou melhores comportamentos de proteção à corrosão quando foi utilizado o sistema microemulsionado contendo Butanol/CTAB, conforme resultados expressos através dos experimentos de espectroscopia de impedância eletroquímica. O bom comportamento de proteção à corrosão pode ser atribuído à passivação da superfície do aço carbono 1020 que devido à formação de um filme, maximiza a resistência à corrosão do aço carbono.

In the Fischer-Tropsch (FT) synthesis, CO and H2 (synthesis gas) are converted into hydrocarbons that can be further upgraded to high-quality fuels and chemicals. Different carbon sources such as natural gas, coal and biomass can be used as feed-stocks for the synthesis gas. In commercial applications, supported cobalt catalysts are commonly used in the FT synthesis, especially when the synthesis gas emanates from natural gas and when the desired final product is diesel. The activity and selectivity of a cobalt catalyst is dependent on several parameters, one of them being the support. The present thesis is focused on the design, synthesis and characterization of alumina and silica materials (with and without Ce and Zr promoters) with non-conventional morphology, and evaluation of their feasibility as cobalt supports in the FT synthesis. Ce- and Zr-alumina nanoparticles were synthesized by co-precipitation in water-in-oil microemulsion. The obtained product is amorphous alumina with highly dispersed promoters, resulting in strong cobalt-support interactions and low cobalt reducibility. By increasing the calcination temperature of the Ce-promoted support, crystalline CeO2 is obtained which apparently increases the cobalt reducibility and thereby the catalytic activity (per gram catalyst). The small pore size of the materials may induce diffusion limitations on the reactants arrival and/or result in very small cobalt particles, which favour methane over long-chain hydrocarbons.  Successful preparations of pore expanded mesoporous silicas with 1D, 2D and 3D pore structures via the atrane route, combined with the addition of swelling agents, have been demonstrated. The advantage of this method is that pore expansion can be achieved at mild conditions and there is no need for a post-synthesis process using an autoclave system. In larger silica support pores, larger cobalt particles will be formed and the weaker the cobalt-support interactions will be. This generally results in a higher cobalt reducibility for larger-pore supports and thereby a higher catalytic activity. / <p>QC 20171004</p>