This thesis explored how asphaltene and naphthenic amphiphile species influence the formation (morphology and size) and stability of heavy crude oil (bitumen) emulsions. It was experimentally shown that asphaltenes produce water-in-oil emulsions. Naphthenic amphiphiles on the other hand flip the emulsion morphology to oil-in-water. It was further demonstrated that the size and stability of these emulsions is influenced by physicochemical effects such as the pH, solvent-bitumen-water ratios, solvent aromaticity, and temperature. In view of these findings, the hydrophilic-lipophilic deviation (HLD) and net-average curvature (NAC) models were looked at as potential means for predicting the formation and stability of emulsions. Owing to the complexity of bitumen emulsions, however, the HLD and NAC models were instead tested against well-defined sodium dihexyl sulfosuccinate-toluene-water emulsions. The morphologies of these emulsions were predicted as a function of the formulation salinity whereas corresponding droplet sizes were predicted as a function of the continuous phase density and interfacial tension (γow). Emulsion stability trends were in turn predicted using a collision-coalescence-separation assumption. From this assumption, emulsion stability was expressed as a function of the emulsion droplet collision frequency and activation energy. The key parameters of the highly scrutinized activation energy term included the γow, interfacial rigidity, and critical film thickness. In applying the same modeling approach to the stability of other emulsions already published in the literature, it was found that the rigidity of adsorbed multilayer/liquid crystal films cannot yet be fully accounted for. This shortcoming was the reason for which only minimum stability times were reported for bitumen emulsions.

This thesis explored how asphaltene and naphthenic amphiphile species influence the formation (morphology and size) and stability of heavy crude oil (bitumen) emulsions. It was experimentally shown that asphaltenes produce water-in-oil emulsions. Naphthenic amphiphiles on the other hand flip the emulsion morphology to oil-in-water. It was further demonstrated that the size and stability of these emulsions is influenced by physicochemical effects such as the pH, solvent-bitumen-water ratios, solvent aromaticity, and temperature. In view of these findings, the hydrophilic-lipophilic deviation (HLD) and net-average curvature (NAC) models were looked at as potential means for predicting the formation and stability of emulsions. Owing to the complexity of bitumen emulsions, however, the HLD and NAC models were instead tested against well-defined sodium dihexyl sulfosuccinate-toluene-water emulsions. The morphologies of these emulsions were predicted as a function of the formulation salinity whereas corresponding droplet sizes were predicted as a function of the continuous phase density and interfacial tension (γow). Emulsion stability trends were in turn predicted using a collision-coalescence-separation assumption. From this assumption, emulsion stability was expressed as a function of the emulsion droplet collision frequency and activation energy. The key parameters of the highly scrutinized activation energy term included the γow, interfacial rigidity, and critical film thickness. In applying the same modeling approach to the stability of other emulsions already published in the literature, it was found that the rigidity of adsorbed multilayer/liquid crystal films cannot yet be fully accounted for. This shortcoming was the reason for which only minimum stability times were reported for bitumen emulsions.

Made available in DSpace on 2014-12-17T15:01:26Z (GMT). No. of bitstreams: 1 JosilmaFF_DISSERT_Parcial.pdf: 436034 bytes, checksum: 128f71801f48233150a514d2629a577b (MD5) Previous issue date: 2011-02-11 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The constant search for biodegradable materials for applications in several fields shows that carnauba wax can be a viable alternative in the manufacturing of biolubricants. Carnauba wax is the unique among the natural waxes to have a combination of properties of great importance. In previous studies it was verified the presence of metals in wax composition that can harm the oxidative stability of lubricants. Considering these factors, it was decided to develop a research to evaluate iron removal from carnauba wax, using microemulsion systems (Me) and perform the optimization of parameters, such as: extraction pH, temperature, extraction time, among others. Iron concentration was determined by atomic absorption and, to perform this analysis, sample digestion in microwave oven was used, showing that this process was very efficient. It was performed some analysis in order to characterize the wax sample, such as: attenuated total reflectance infrared spectroscopy (ATR-IR), thermogravimetry (TG), differential scanning calorimetry (DSC), energy dispersive X-ray fluorescence (EDXRF), scanning electron microscopy (SEM) and melting point (FP). The microemulsion systems were composed by: coconut oil as surfactant, n-butanol as cosurfactant, kerosene and/or heptanes as oil phase, distilled water as water phase. The pH chosen for this study was 4.5 and the metal extraction was performed in finite experiments. To evaluate Me extraction it was performed a factorial design for systems with heptane and kerosene as oil phase, also investigating the influence of temperature time and wax/Me ratio, that showed an statistically significant answer for iron extraction at 95% confidence level. The best result was obtained at 60?C, 10 hours contact time and 1: 10 wax/Me ratio, in both systems with kerosene and heptanes as oil phase. The best extraction occurred with kerosene as oil phase, with 54% iron removal / Em virtude da constante busca por materiais biodegrad?veis para diversas aplica??es, a cera de carna?ba pode ser uma alternativa vi?vel na fabrica??o de biolubrificantes. A carna?ba ? a ?nica entre as ceras a possuir uma combina??o de propriedades de grande import?ncia. Em estudos preliminares verificaram-se na composi??o da cera alguns metais que podem prejudicar a estabilidade oxidativa do lubrificante. Diante desses fatores, decidiu-se desenvolver um trabalho sobre a remo??o de ferro, da cera de carna?ba, atrav?s de sistemas microemulsionados (Me) e realizar uma otimiza??o de par?metros, como: ajuste de pH, temperatura, tempo de extra??o, entre outros. A concentra??o de ferro foi determinada por absor??o at?mica e, para essa an?lise, a digest?o da amostra em forno de micro-ondas se mostrou bastante eficiente. Foram realizadas algumas an?lises de caracteriza??o da amostra como: espectroscopia de infravermelho por reflet?ncia total atenuada (IV-ATR), termogravimetria (TG), calorimetria explorat?ria diferencial (DSC), fluoresc?ncia de raios-X por energia dispersiva (EDXRF), microscopia eletr?nica de varredura (MEV) e ponto de fus?o (PF). O sistema de microemuls?o utilizado teve como tensoativo: ?leo de coco saponificado, cotensoativo: n-butanol, fase ?leo: querosene e/ou heptano, fase aquosa: ?gua destilada. O pH escolhido para o estudo foi de 4,5 e a extra??o do metal foi realizada em banho finito. Para tanto, foi realizado um planejamento experimental fatorial para o sistema com fase ?leo heptano e fase ?leo querosene. Em ambos os planejamentos foram investigadas as vari?veis temperatura, tempo e raz?o cera/microemuls?o, que se mostraram estatisticamente significativas para a resposta extra??o de ferro a 95% de confian?a. Tanto para o sistema em que a fase ?leo foi o heptano quanto para o querosene, o melhor resultado obtido foi em 60?C, 10 horas e raz?o cera/Me 1:10. A melhor extra??o se deu com sistemas microemulsionados com fase ?leo querosene, extraindo cerca de 54% de ferro / 2020-01-01

[pt] Um estudo foi realizado visando avaliar nova abordagem analítica para a determinação de um hidrocarboneto poliaromático nitrogenado (carbazol, CBZ) e um sulfurado (dibenzotiofeno, DBT) em amostras orgânicas líquidas usando fosforimetria na temperatura ambiente. Para isto, microemulsões sem detergente foram usadas para viabilizar a determinação destes compostos em solução. Um estudo preliminar das propriedades fosforescentes desses dois analitos foi realizado, sendo este dividido em duas etapas: (i) definição da composição da microemulsão (ME) e (ii) estudo do efeito da concentração da ME sobre o sinal fosforescente do analito. Como resultado, sinais fosforescentes com potencial analítico e em ambiente livre de interferências de fluorescência foram obtidos para várias das composições testadas. As condições experimentais foram otimizadas usando planejamento fatorial visando à maximização desses sinais fosforescentes para o CBZ (292/436 nm) e para o DBT (286/442 nm). A concentração de I- (íon de átomo pesado indutor de fosforescência), concentração de Na2SO3, pH e tipo de ME foram avaliadas. Essa abordagem permitiu que, na ME diluída, os valores de LD e de LQ para o CBZ fossem 2,6 ng mL-1 e 8,6 ng mL-1 e para o DBT de 7,4 ng mL-1 e 24,5 ng mL-1. As faixa lineares estenderam-se até 800 ng mL-1 (CBZ) e até 1400 ng mL-1 (DBT). Amostras orgânicas líquidas (frações combustíveis do petróleo e extratos orgânicos de amostras ambientais) fortificadas com os analitos foram usadas para testar os métodos. Estratégias apropriadas para cada tipo de amostra são apresentadas. Porcentuais de recuperação para CBZ e para o DBT ficaram dentro da faixa de 90 a 110 %. Interferências mútuas e de outras substâncias foram avaliadas. / [en] A new approach for the determination of one nitrogen- containing PAH (carbazole, CBZ) and one sulfur-containing PAH (dibenzothiophene, DBT) in organic liquid samples using room-temperature phosphorimetry was evaluated. Detergentless microemulsions were used to allow the determination of these compounds in aqueous solution. A preliminary study of the phosphorescent properties of the analytes was made in two steps: (i) definition of the ME composition and (ii) effect of the concentration of the ME on the analyte phosphorescent signal. As a result, phosphorescent signals with analytical potential, in a fluorescence free environment, were obtained for several tested compositions. Experimental conditions were optimized using a factorial design aiming the maximization of the phosphorescence from CBZ (292/436 nm) and DBT (286/442 nm). The concentration of I- (phosphorescence inducer heavy atom ion), concentration of Na2SO3, pH and ME type were evaluated. The method allowed, in the diluted ME, values for LD and for LQ of 2,6 ng mL-1 and 8,6 ng.mL-1for CBZ and of 7,4 ng mL-1 and 24,5 ng mL-1 for DBT. Linear dynamic ranges extended up to 800 ng mL-1 (CBZ) and up to 1400 ng mL-1 (DBT). Organic liquid samples (petroleum fuel fractions and organic extracts of environmental samples) spiked with the analytes of interest were used to test the methods. Proper strategies for analyzing each type of sample were described. Recoveries for CBZ and for DBT were within the 90 to 110 % range. Mutual interferences and interferences from other substances were evaluated.

A pre-eminent emulsion-based micellar drug delivery system, "microemulsion", comprising drug in oil or water phase, stabilized by surfactants and co-surfactants, has been evidenced to have a phenomenal role in a number of applications. Oils play an important role in the formation of ME and increase the drug absorption at the site of action. Oils employed in microemulsion formulation solubilize lipophilic drug. As the concept of "natural" therapies is recently gaining importance amongst researchers all over the world, scientists are employing essential oil as an organic component in this system. The active components of essential oils include flavonoids, phenylpropanoids, monoterpenes and polyunsaturated mega-6-fatty acids. These oils are enriched with characteristic intrinsic properties such as anti-oxidant, anti-bacterial, anti-viral, etc., bestowing enhanced supremacy to the whole microemulsion system. This mini-review is the first to document various types of essential oils employed in microemulsion systems and highlight their therapeutic potential and applications as drug delivery vehicles. Key inferences from this study suggest: 1) Clove oil is the most explored oil for incorporation into a microemulsion based system, followed by peppermint and Tea Tree Oil (TTO). 2) Penetration enhancing effects of these oils are due to the presence of terpenic constituents. 3) Essential oil based microemulsions protect volatility of ethereal oils and protect them from degradation in the presence of light, air, temperature. 4) These systems may also be explored for their applications in different industries like aromatherapy, food, drink, fragrance, flavour, cosmeceutical, soap, petroleum and pharmaceutical industry.

Le développement de nanomatériaux à propriétés optiques et fonctionnalisés pour un marquage spécifique est en plein essor dans le domaine de l'imagerie biologique. Parmi les agents de contraste exogènes déjà utilisés, les marqueurs fluorescents tels que les nanocristaux semi-conducteurs (CdSe/ZnS,…) et les molécules organiques naturelles (GFP,…) ou synthétiques (fluorescéine,…) souffrent respectivement de clignotements (blinking) et de photo-blanchiment (bleaching) c'est-à-dire d'une faible tenue au rayonnement lumineux incident. Récemment, la microscopie de Génération de Second Harmonique (GSH) à partir de structures non-centrosymétriques de certains matériaux ou molécules optiquement non linéaires (ONL), s'est révélée un outil particulièrement prometteur. Les inconvénients du clignotement et du photo-blanchiment sont en effet absents pour le processus non linéaire de GSH. De plus, le principe de fonctionnement des marqueurs ONL repose sur un processus non résonant, contrairement aux marqueurs fluorescents, ce qui est un avantage décisif pour le choix de la longueur d'onde d'excitation des nanosondes. Pour des illuminations dans le proche infrarouge, cela permet de limiter l'énergie déposée dans le milieu biologique, d'augmenter la profondeur d'imagerie et enfin de bien séparer spectralement les signaux des marqueurs ONL de l'auto-fluorescence naturelle de certains échantillons. Notre objectif, dans ce contexte, était la synthèse et la caractérisation de nouvelles nanosondes ONL de forme sphérique et de taille inférieure à 100nm. Le matériau de structure cristalline non centrosymétrique retenu est l'iodate de fer (Fe(IO3)3) car ses éléments chimiques sont peu toxiques et que ses propriétés paramagnétiques peuvent également donner un contraste en imagerie par résonance magnétique (IRM) ce qui est potentiellement intéressant par rapport à d'autres cristaux ONL tels que ZnO, KNbO3, BaTiO3 et KTP. D'un point de vue synthèse, les microémulsions inverses sont bien référencées dans la littérature pour leur rôle de gabarit permettant un bon contrôle de la taille et de la morphologie des nanomatériaux obtenus par co-précipitation. Dans ce travail, les nano-réacteurs ont été préparés à partir des systèmes AOT/alcane/eau et Triton/1-hexanol/cyclohexane/eau. De manière très originale et pratique, le développement d'un banc optique de diffusion Hyper-Rayleigh (HRS) a permis de suivre in-situ et en temps réel les cinétiques de cristallisation des nanoparticules de Fe(IO3)3 en fonction de conditions expérimentales variables. Les mécanismes de croissance et de cristallisation des nano-bâtonnets de Fe(IO3)3 ont été élucidés en combinant d'autres techniques physico-chimiques usuelles comme la diffraction des rayons X, la diffusion dynamique de la lumière et la microscopie électronique en transmission. Nous avons démontré que la température et la nature du tensioactif influencent les forces d'interaction à l'interface organique-inorganique ce qui permet, pour certaines conditions expérimentales, de réduire la taille et la polydispersité des nanocristaux en fin de processus. Toutefois, avant d'envisager l'utilisation de ces derniers en tant que marqueurs optiques spécifiques, il est nécessaire d'encapsuler ces nanocristaux en raison de la faible stabilité du composé aux pH physiologiques. Les premiers essais de stabilisation en microémulsions par une couche de silice ont permis d'obtenir des nanoparticules de taille ~ 10 nm avec une forte réponse ONL. La caractérisation complète et la fonctionnalisation de ces nanostructures ainsi qu'une optimisation des interactions à l'interface particules – films de tensioactifs constituent les perspectives de ce travail. / The development of functionalized nanomaterials with optical properties for a site-specific labeling or conjugation has undergone a rapid growth in the biological imaging field. Among the exogenous contrast agents which are already used, fluorescent nanocrystals such as semi-conductor (CdSe / ZnS, ...) and natural organic molecules (GFP, ...) or synthetic molecules (fluorescein, ...) suffer from blinking and photobleaching, respectively. Recently, Second Harmonic Generation (SHG) from acentric structures of some Non-Linear Optical (NLO) materials or organic molecules appeared to be particularly promising. Indeed, the major disadvantages of blinking and photobleaching are absent in the SHG process. Additionally, imaging of NLO probes is based on a non-resonant process, contrary to traditional fluorescent probes, which is key in terms of excitation wavelength. Near infrared illumination can limit the energy deposited in the biological tissues, increase the imaging depth and, finally, the SHG signal can be more readily spectrally resolved from the natural auto-fluorescence. The main objectives of this thesis were the synthesis and characterization of new NLO nanoprobes with a spherical shape and a size lower than 100 nm. The non-centrosymmetric material of interest is iron iodate (Fe(IO3)3). Its chemical elements are non toxic and its paramagnetic response may also provide a contrast in Magnetic Resonance Imaging (MRI) which is not the case of the other NLO crystals such as ZnO, KNbO3, BaTiO3 and KTP. From a synthesis point of view, reverse microemulsions are well documented in the literature as good templates for the size and shape control of nanomaterials obtained by a coprecipitation reaction. In this work, nanoreactors were prepared from the AOT/alkane/water and Triton/1-hexanol /cyclohexane/water systems..A very original and convenient setup based on the Hyper-Rayleigh Scattering (HRS) was implemented so that the real-time crystallization kinetics of the growing acentric iron iodate nanocrystals in microemulsions could be measured according to different experimental conditions. We demonstrate that HRS is a fast, valuable and nondestructive alternative to probe in-situ the crystallization and growth dynamics of Fe(IO3)3 nanorods whereas the growth mechanism was elucidated by a combination of Dynamic Light Scattering, X-ray diffraction and Transmission Electron Microscopy experiments. The binding interaction between surfactant molecules and colloidal particles was studied as a function of the synthesis temperature as well as the surfactant nature. In some experimental conditions the size and polydispersity of the final nanorods can be thus reduced. However, the use of iron iodate as specific NLO optical probes is so far restricted due to its low stability at physiological pH. Preliminary encapsulation tests by a thin silica-coating in reverse microemulsions show the presence of ~ 10nm nanocparticles with a strong NLO response. The complete characterization and functionalization of these nanostructures as well as the optimization of the binding interactions at the organic-inorganic interface are the prospects of this work

Le développement de nouveaux capteurs, transducteurs et de dispositifs intégrés optoélectroniques et piézo-électriques nécessite l'élaboration de nouveaux matériaux avec des propriétés mécaniques, optiques et électriques couplées. Dans cette perspective, les nanocomposites à base de nanocristaux inorganiques non centrosymétriques dispersés dans une matrice polymère peuvent donner à la fois des propriétés piézoélectriques et optiques non-linéaires. Cependant, la dispersion et l’orientation des nanocristaux dans la matrice sont primordiales si on souhaite un comportement collectif des nanocristaux individuels et des propriétés résultantes significatives. Dans ce travail, nous avons utilisé des cristaux d’iodate de fer (Fe(IO3)3) comme nano-charges inorganiques et le PMMA/ PTMPTA comme matrice polymère. La réponse optique non-linéaire du Fe(IO3)3 est comparable à celle des cristaux les plus efficaces tels que BaB2O4 et LiNbO3. Le comportement piézoélectrique du matériau massif n’étant pas référencé, sa structure cristalline laisse toutefois envisager des propriétés piézoélectriques intéressantes. Par ailleurs, la matrice polymère a été choisie pour sa simplicité d'utilisation et de production, son coût relativement faible, sa versatilité et sa facilité de mise en forme. Les nanocomposites peuvent être élaborés par deux voix différentes : la première consiste à disperser mécaniquement des nanocristaux fonctionnalisés dans un polymère ou dans un solvant de polymère approprié et la deuxième concerne la polymérisation in-situ de microémulsions composées du monomère liquide. Les synthèses en microémulsions inverses ont été privilégiées pour d’une part élaborer des nanocristaux d’iodate de fer de taille et de forme contrôlées puis, d’autre part, photo-polymériser des couches minces déposées à la tournette. Un aspect très original de ce travail consiste en l’utilisation de la Diffusion Hyper-Rayleigh pour étudier in-situ les cinétiques de cristallisation des particules d’iodate de fer en fonction des conditions expérimentales de synthèse à savoir, la température et la composition des microémulsions. Cette technique qui consiste à détecter les réponses optiques non-linéaires des suspensions de nanoparticules en microémulsions a été combinée avec d’autres méthodes expérimentales plus classiques comme la diffraction des rayons X, la diffusion dynamique de la lumière et la microscopie électronique en transmission. Cela a permis d’élucider les mécanismes de croissance des nanocristaux d’iodate de fer en microémulsions inverses. Par la suite, des couches minces nanocomposites ont été préparées après orientation sous champs électriques des nanocristaux polaires dispersés dans le MMA. Les caractérisations mécaniques, optiques non linaires et piézoélectriques de ces couches sont encourageantes. / The development of new sensors, transducers and integrated optoelectronic and piezoelectric devices requires the preparation of new materials that link mechanical, optical and electrical properties. In this perspective, it is expected that nanocomposite materials with inclusions of acentric inorganic nanocrystals in a polymer matrix will give rise to both piezoelectric and nonlinear optical (NLO) properties. Dispersion and orientation of nanocrystals in the polymer matrix are however crucial to obtain a collective response of individual nanocrystals and significant resultant properties. In this work, iron iodate (Fe(IO3)3) nanocrystals were used as nanofillers of a PMMA / PTMPTA polymer matrix. The nonlinear optical response of Fe(IO3)3 is comparable to the most effective NLO crystals such as LiNbO3 and BaB2O4. Good piezoelectric properties are also expected due to the material crystalline structure. Moreover, the polymer matrix was chosen for its ease of use and production, its relatively low cost, versatility and ease in shaping. Elaboration of nanocomposites is usually based on two different experimental procedures: mechanical dispersion of functionalized nanocrystals in a suitable polymer or polymer solvent is a first route whereas in-situ polymerization of reverse microemulsions for which a liquid monomer is the oil phase is the second one. Water-in-Oil (W/O) microemulsions were preferred in order to control the size and shape of as-obtained iron iodate nanocrystals and then to polymerize spin-coated thin films. A very original aspect of this work is the implementation of the Hyper-Rayleigh Scattering technique to probe in-situ the crystallization kinetics of iron iodate nanoparticles according to the experimental conditions (synthesis temperature and microemulsions composition). Detection of the second-harmonic scattered light combined with more conventional experimental techniques such as X-ray diffraction, dynamic light scattering and Transmission Electron Microscopy allowed us to understand the growth mechanisms of iron iodate naocrystals in W/O microemulsions. Nanocomposite thin films were then spin-coated after electric fields orientation of dispersed polar nanocrystals in MMA.

Made available in DSpace on 2014-12-17T15:01:22Z (GMT). No. of bitstreams: 1 MariaCPAM.pdf: 984936 bytes, checksum: 2ad822e0048cda570ce57a014ed42a7c (MD5) Previous issue date: 2006-05-19 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The tanning industries are those which transform animal hide or skin into leather. Due to the complexity of the transformation process, greater quantities of chemicals are being used which results in the generation of effluents with residual solids. The chromium in the residual waters generated by tanning tend to be a serious problem to the environment, therefore the recovery of this metal could result in the reduction of manufacturing costs. This metal is usually found in a trivalent form which can be converted into a hexavalent compound under acidic conditions and in the presence of organic matter. The present study was carried out with the objective to recover chromium through an extraction/re-extraction process using micro emulsions. Micro emulsions are transparent and thermodynamically stable system composed of two immiscible liquids, one forming the continuous phase and the other dispersed into micro bubbles, established by an interfacial membrane formed by surface active and co-surface active molecules. The process of recovering the chromium was carried out in two stages. The first, an extraction process, where the chromium was extracted in the micro emulsion phase and the aqueous phase in excess was separated. In the second stage, a concentrated acid was added to the micro emulsion phase rich in chromium in order to obtain a Winsor II system, where the water that formed in the micro emulsion phase separates into a new micro emulsion phase with a higher concentration of chromium, due to the lowering of the hydrophiles as well as the ionisation of the system. During the experimental procedure, a study was initiated with a synthetic solution of chromium sulphate passing onto the effluent. A Morris extractor was used in the extraction process. Tests were carried out according to the plan and the results were analysed by statistical methods in order to optimise the main parameters that influence the process: the total rate of flow (Q), stirring speed (w) and solvent rate (r). The results, after optimization, demonstrated that the best percentuals in relation to the chromium extraction (99 %) were obtained in the following operational conditions: Q= 2,0 l/h, w= 425 rpm and r= 0,375. The re-extraction was carried out at room temperature (28 ?C), 40 ?C and 50?C using hydrochloric acid (8 and 10 M) and sulphuric acid (8 M) as re-extracting agents. The results obtained demonstrate that the process was efficient enough in relation to the chromium extraction, reaching to re-extraction percentage higher than 95 %. / Os Curtumes s?o ind?strias que transformam peles em couro. Devido a complexidade do processo de transforma??o s?o utilizadas grandes quantidades de agentes qu?micos e gerados grandes volumes de efluentes e res?duos s?lidos. O cromo presente nas ?guas residu?rias geradas pelos curtumes constitui um s?rio problema ambiental e sua recupera??o poder? representar uma redu??o nos custos do processo. Normalmente encontra-se na forma trivalente podendo ser convertido a cromo hexavalente sob condi??es ?cidas e na presen?a de mat?ria org?nica. Este estudo foi realizado com o objetivo de recuperar o cromo atrav?s de um processo de extra??o/reextra??o utilizando microemuls?es. As microemuls?es s?o sistemas transparentes, termodinamicamente est?veis, constitu?dos por dois l?quidos imisc?veis, um formando a fase cont?nua e o outro disperso na forma de microgot?culas, estabilizadas por uma membrana interfacial formada por mol?culas de tensoativo e cotensoativo. O processo de recupera??o do cromo ocorre em duas etapas. Na primeira, a extra??o, o cromo ? extra?do para a fase microemuls?o e a fase aquosa em excesso ? separada. A segunda etapa, ? realizada adicionando-se a fase microemuls?o, rica em cromo, um ?cido concentrado visando a obten??o de um sistema Winsor II, em que parte da ?gua que formava a fase microemuls?o, devido a diminui??o da hidrofilia e ioniza??o do sistema, se desloca formando uma nova fase aquosa, mais concentrada em cromo. Durante o procedimento experimental, iniciou-se o estudo com uma solu??o sint?tica de sulfato de cromo passando-se, em seguida, ao efluente. No processo de extra??o do cromo em escala semi-piloto utilizou-se o extrator Morris. Os ensaios foram efetuados seguindo um planejamento experimental e os resultados obtidos foram analisados, atrav?s de m?todos estat?sticos, visando a otimiza??o dos principais par?metros que influenciam no processo: vaz?o total (Q), velocidade de agita??o (w) e taxa de solvente (r). Os resultados obtidos, ap?s a otimiza??o, demonstraram que os maiores percentuais de extra??o (99 %) s?o obtidos nas seguintes condi??es operacionais: Q=2,0 l/h, w= 425 rpm e r= 0,375. A reextra??o foi realizada a temperatura ambiente (28 ?C) e a 40?C e 50?C utilizando-se como agente reextratante ?cido clor?drico (8 e 10 M) e ?cido sulf?rico (8 M). Os resultados obtidos demonstraram que o processo foi eficiente com rela??o ao cromo, obtendo-se percentuais de reextra??o acima de 95%

Made available in DSpace on 2014-12-17T15:01:43Z (GMT). No. of bitstreams: 1 AnaCMS.pdf: 1022234 bytes, checksum: 6525fbcf6f201d09af59285b78bcba6b (MD5) Previous issue date: 2006-12-18 / Naphthenic lubricating oils are used in transformers with the purpose of promoting electrical insulation and dissipating heat. The working temperature range of these oils typically lies between 60?C and 90?C and their useful life is 40 years in average. In that temperature range, the oils are decomposed during operation, whereby a small fraction of polar compounds are formed. The presence of these compounds may induce failure and loss of physical, chemical and electrical properties of the oil, thus impairing the transformer operation. By removing these contaminants, one allows the oxidized insulating oil to be reused without damaging the equipment. In view of this, an investigation on the use of surfactants and microemulsions as extracting agents, and modified diatomite as adsorbent, has been proprosed in this work aiming to remove polar substances detected in oxidized transformer oils. The extraction was carried out by a simple-contact technique at room temperature. The system under examination was stirred for about 10 minutes, after which it was allowed to settle at 25?C until complete phase separation. In another experimental approach, adsorption equilibrium data were obtained by using a batch system operating at temperatures of 60, 80 and 100?C. Analytical techniques involving determination of the Total Acidity Number (TAN) and infrared spectrophotometry have been employed when monitoring the decomposition and recovery processes of the oils. The acquired results indicated that the microemulsion extraction system comprising Triton? X114 as surfactant proved to be more effective in removing polar compounds, with a decrease in TAN index from 0.19 to 0.01 mg KOH/g, which is consistent with the limits established for new transformer oils (maximal TAN = 0.03 mg KOH/g). In the adsorption studies, the best adsorption capacity values were as high as 0.1606 meq.g/g during conventional adsoprtion procedures using natural bauxite, and as high as 0.016 meq.g/g for the system diatomite/Tensiofix? 8426. Comparatively in this case, a negative effect could be observed on the adsorption phenomenon due to microemulsion impregnation on the surface of the diatomite / ?leos lubrificantes naft?nicos s?o usados em transformadores tem com a finalidade de promover um isolamento el?trico e agir como fonte dissipadora de calor. A temperatura de trabalho destes ?leos est? entre 60 a 90?C e sua vida ?til ? de em m?dia 40 anos. Nesta temperatura, durante o servi?o, ocorre a degrada??o do ?leo, onde uma pequena fra??o de compostos polares ? formada. A presen?a desta fra??o pode provocar falhas e a perda das propriedades f?sicas, qu?micas e el?tricas do ?leo, impossibilitando o uso do transformador. A remo??o destes compostos permite que o ?leo isolante oxidado possa ser novamente utilizado, sem causar preju?zo ao equipamento. Nestes contexto, este trabalho prop?e-se a investigar a utiliza??o de tensoativos e microemuls?es, como extratantes, e a diatomita modificada, como adsorvente, na remo??o dos compostos polares existentes nos ?leos oxidados de transformador. A extra??o foi realizada pelo m?todo de contato simples ? temperatura ambiente. O sistema em estudo foi agitado por cerca de 10 minutos, em seguida mantido em repouso ? 25?C at? completa separa??o das fases. Por outro lado, os dados de equil?brio de adsor??o foram obtidos utilizando um sistema em batelada para as temperaturas de 60, 80 e 100oC. As t?cnicas anal?ticas de IAT (?ndice de Acidez Total) e espectrofotometria no infravermelho foram utilizadas no acompanhamento dos processos de degrada??o e recupera??o dos ?leos degradados. Os resultados obtidos indicam que o sistema de extra??o por microemuls?o utilizando triton X114 mostrou-se ser o m?todo mais eficiente na remo??o dos compostos polares, com redu??o no ?ndice de acidez total (IAT) de 0,19 para 0,01 mg KOH/g. Este valor se encontra dentro dos limites especificados para um ?leo de transformador novo (IAT m?ximo = 0,03 mg KOH/g). Nos estudos de adsor??o, os maiores valores de capacidade de adsor??o foram de 0,1606 meq.g/g na adsor??o convencional usando bauxita natural e de 0,016 meq.g/g para o sistema diatomita/tensiofix 8426. Comparativamente, neste caso, observou-se um forte efeito negativo apresentado sobre o fen?meno adsortivo devido ao processo de impregna??o com microemuls?o

Im Raman dieser Arbeit wurden binäre und ternäre Stoffgemische in einem Mikrokapillarsystem (MKS) mittels optischer Messtechnik hinsichtlich ihrer molekularen Strukturierung untersucht. Dies wurde durch die Kombination unterschiedlicher Auswertemethoden ermöglicht, welche alle gemeinsam haben, dass sie auf der Auswertung des Schwerpunktes des isolierten Raman-Spektrums der OH-Streckschwingung basieren. Für die Auswertung der binären Stoffgemische W/MeOH, W/EtOH und W/Acn konnten durch die kombinierte Auswertung von molaren-, partiellen molaren- und idealen molaren Raman Spektren, unterschiedliche Regime der molekularen Strukturierung identifiziert werden. Insbesondere für die beiden Stoffgemische W/MeOH und W/EtOH erlaubte die Berechnung partieller molarer Raman-Spektren und deren Interpretation umfassendere Rückschlüsse als es über die direkte Auswertung der Raman-Spektren möglich gewesen wäre. Durch die Berechnung der partiellen molaren Raman-Spektren konnte die Raman-Intensität der OH-Streckschwingung des Gemisches in die der einzelnen Komponenten – Wasser und MeOH/EtOH – aufgeteilt werden.:Formelzeichen mit Indizes und Abkürzungen I 1 Einleitung und Motivation 1 2 Stand der Technik und Zielsetzung der Arbeit 5 2.1 Molekular strukturierte Stoffgemische 5 2.1.1 Binäre Stoffgemische und der Einfluss von Wasserstoffbrückenbindungen 5 2.1.2 Ternäre Stoffgemische und die Ausbildung von CO2-basierten Surfactant-freien Mikroemulsionen 10 2.2 Zielsetzung der Arbeit 13 3 Anwendungsbezogene Grundlagen 14 3.1 Wasserstoffbrückenbindungen 14 3.1.1 Wasserstoffbrückenbindungen allgemein 14 3.1.2 Wasserstoffbrückenbindungen in Wasser und wasserenthaltenden Lösungen 15 3.2 CO2-basierte Surfactant-freie Mikroemulsionen 19 3.3 Analyse molekular strukturierter Stoffgemische mittels Strahlung 21 3.4 Raman-Spektroskopie 24 3.4.1 Raman-Spektroskopie allgemein 24 3.4.2 Raman-Spektroskopie zur Analyse molekular strukturierter Stoffgemische 28 3.5 Partielle molare Größen 28 4 Materialien und Methoden 31 4.1 Chemikalien 31 4.2 Mikrokapillarsystem und Peripherie 31 4.3 Versuchsdurchführung 35 5 Auswertemethodik 38 5.1 Isolierung der OH-Streckschwingung 39 5.1.1 Binäre Stoffgemische 39 5.1.2 Ternäres Stoffgemisch 41 5.2 Berechnung molarer-, partieller molarer- und idealer molarer Raman-Spektren 42 5.2.1 Molare Raman-Spektren 43 5.2.2 Partielle molare Raman-Spektren 45 5.2.3 Ideale molare Raman-Spektren 47 5.3 Schwerpunktbestimmung isolierter OH-Steckschwingungen 48 6 Ergebnisse und Diskussion 51 6.1 Binäre Stoffgemische 51 6.2 Ternäres Stoffgemisch 66 7 Zusammenfassung und Ausblick 72 8 Literaturverzeichnis 75 Anhang A83 Auflistung der untersuchten Stoffgemische und deren Zusammensetzungen A83 Zusammenfassung der Auswertemethodik der binären Stoffgemische A87