O surfactante pulmonar é uma mistura complexa de fosfolipídios e proteínas, e encontra-se presente na interface ar-líquido dos alvéolos pulmonares. O seu papel principal é reduzir a tensão superficial para manter os alvéolos estáveis. A deficiência ou disfunção do surfactante leva ao colapso alveolar, provocando a falta de oxigenação que ocorre devido ao edema ou a resposta inflamatória nos pulmões. Em recém-nascidos, a imaturidade pulmonar, pela deficiência do surfactante, pode causar a Síndrome de Desconforto Respiratória (SDR). Nos adultos, a Síndrome de Desconforto Respiratório Agudo (SDRA) é a manifestação mais grave da Lesão Pulmonar Aguda (LPA), o tratamento para estas doenças inclui a utilização de surfactantes exógenos. Para entender a funcionalidade do surfactante é necessário caracterizá-lo biofisicamente. A principal característica observada neste estudo foi o espalhamento e recuperação do surfactante na subfase, para a interface ar-líquido. O espalhamento e recuperação foram quantificadas observando o trabalho feito em sucessivos ciclos de compressão e expansão na balança de Wilhelmy. Analisou-se o decaimento do trabalho ao longo dos ciclos até a sua estabilização. Os parâmetros obtidos neste ajuste do decaimento exponencial foram utilizados para a caracterização de dois surfactantes exógenos, o Curosurf® e o Survanta®. As comparações entre eles foram segundo a concentração, as subfases e das velocidades de barreira. O decaimento exponencial do trabalho nos ciclos só ocorreu para concentrações menores de surfactante. Quando em subfase de solução salina ocorreu a melhora na recuperação do surfactante para a interface ar-líquido, em comparação a subfase de água ultrapura. A melhor velocidade de barreira encontrada para otimização da recuperação do surfactante foi 120 mm/min. Foi observado nesse estudo que as propriedades de recuperação do Curosurf® foram melhores em relação ao Survanta®, os parâmetros se mostraram de acordo com os dados clínicos encontrados na literatura, a caracterização da dinâmica do surfactante foi feita de forma diferente de todos os métodos encontrados / Lung surfactant is a complex mixture of phospholipids and proteins, found at the airliquid interface of pulmonary alveoli. The main role is to reduce the surface tension to keep alveoli stable. Surfactant deficiency, or dysfunctional, leads to alveolar collapse, causes a lack of oxygen and it may be due to edema or inflammatory response in the lungs. In newborn babies, pulmonary immaturity, caused by surfactant deficiency, may cause Respiratory Distress Syndrome (RDS). In adults, the Acute Respiratory Distress Syndrome (ARDS) is the gravest manifestation of Acute Lung Injury (ALI), and the treatment includes Mechanical Ventilation (MV) and exogenous surfactants. To understand surfactant functionality, it is necessary to characterize them biophysically. The main characteristic observed in this work was the mobility and recovery of surfactant in the subphase to the air-liquid interface. The mobility and recover were quantified observing the work done in successive cycles of compression and expansion in a Wilhelmy plate tensiometer. The work decay was analyzed over cycles until its stabilization. The parameters obtained for the exponential fitting of decay were used for characterization of two exogenous surfactants, Curosurf® and Survanta®. The comparisons between them were done under concentration, subphases and barrier speeds. The exponential decay of the cycle work only happened for lower concentrations of surfactant. Saline solution subphase improved the surfactant recovery to the air-liquid interface over ultrapure water subphase. A suitable barrier speed founded to optimize surfactant recovery was 120 mm/min. In this study were observed that recovery properties of Curosurf® were better than Survanta®, the parameters agrees with clinical data from the literature, and the dynamic characterization of surfactant was done of different way than founded methods

This thesis presents a framework for history matching and model calibration of surfactant-polymer (SP) flooding. At first, a high-fidelity mechanistic SP flood model is constructed by performing extensive lab-scale experiments on Berea cores. Then, incorporating Sobol based sensitivity analysis, polynomial chaos expansion based surrogate modelling (PCE-proxy) and Genetic algorithm based inverse optimization, an optimized model parameter set is determined by minimizing the miss-fit between PCE-proxy response and experimental observations for quantities of interests such as cumulative oil recovery and pressure profile. The epistemic uncertainty in PCE-proxy is quantified using a Gaussian regression process called Kriging. The framework is then extended to Bayesian calibration where the posterior of model parameters is inferred by directly sampling from it using Markov chain Monte Carlo (MCMC). Finally, a stochastic multi-objective optimization problem is posed under uncertainties in model parameters and oil price which is solved using a variant of Bayesian global optimization routine. <br>

<div>The House Cricket (Acheta domesticus) is a promising alternative to traditional protein sources, as these insects produce over 12 times the mass of protein for a given mass of food/water when compared to cattle, while also producing lower amounts of greenhouse gases and NH3 emissions (Kim et al. 2017, Hanboonsong, Jamjanya and Durst 2013, Van Huis 2013). Additionally, previous studies have demonstrated significant emulsification and gelling properties of insect flours, such as from cricket, which has been attributed to the functional properties of the protein (Kim et al. 2017). Ground cricket flours contain significant quantities of both protein and fibrous polysaccharides, particularly chitin. Since chitin particles are also capable of preparing emulsions as a Pickering stabilizer, there remains a question on the relative role of the protein and chitin components in crickets for stabilizing emulsion products. Relative contributions of each component was identified by first isolating the water-soluble protein and water-insoluble chitin fractions from ground cricket flour and then determining their interfacial properties and stability of prepared oil-in-water emulsions. Dynamic interfacial tension measurements indicated significant surface activity of the protein fraction, while there was minimal evidence of significant surface pressure development in the presence of 5-10 μm chitin particles. 10 % (w/w) canola oil-in-water emulsions were prepared with 0.5-2% (w/w) of the water-soluble protein fraction and 5.29% (w/w) canola oil-in-water emulsions were prepared with 0.688% of the chitin fraction. Stability of the emulsions against creaming was between 75% and 90% for emulsions stabilized by the protein fraction over three weeks of storage and between 93% and 96% for emulsions stabilized by chitin over 24 hours of storage. Significant fractions of precipitate- and oil-layers found in chitin-stabilized dispersions was attributed to the presence of large chitin particles (79 μm volume weighted mean diameter) and inefficient adsorption to droplet interfaces during homogenization, respectively. Volume-weighted mean diameter of emulsified oil droplets remained at 17-24 μm among protein-stabilized (>1.5 wt%) emulsions over three weeks of storage but only 60 μm over 24 hours among chitin-stabilized emulsions. Light micrographs of emulsion droplets showed successful adsorption of chitin fractions to oil droplets in the emulsion layer, verifying their potential as Pickering stabilizers. These findings demonstrated that both water-soluble protein and chitin particles obtained from ground cricket flours are legitimate emulsion stabilizers, yet the chitin fraction is much less effective without a more intensive approach to reduce their particle size.</div>

Spent oil based drilling fluid and cutting wastes are global liabilities due to their hazardous hydrocarbon content which impacts negatively on flora, fauna, and global carbon footprint. The formulation of two demulsifiers to ensure chemically enhanced phase separation of this waste into oil, water and solid components was successfully carried out in addition to recycling the solid phase into PA6 nanocomposite materials. Initial characterisation of the untreated waste was carried out by Fourier Transform Infra Red (FTIR) for total petroleum hydrocarbon (TPH) analysis, Inductively coupled plasma optical emission spectrometry (ICPOES) for quantitative elemental analysis and Energy dispersive xray analysis (EDXA) for qualitative elemental composition amongst other characterisation methods. The analysis showed that the sample had a high hydrocarbon load of 662,500mg/kg and a high heavy metal load for Pb of 122mg/kg. No As, Cd, Hg were detected. The demulsifier formulations were composed of isopropanol, sodium dodecyl sulphate, poloxamer, sodium chloride, chitosan in 0.2M acetic acid and deionised water for demulsifier S4 and addition of phosphoric acid for demulsifier S3. Hydrocarbon reduction on the extracted solid phase nanofiller S3 and nanofiller S4 was 98.6% and 98.5% respectively after demulsification. The demulsified spent oil based drilling fluid solid extracts were below OSPAR regulation of < 1% oil on cutting by weight. However, recycling of the recovered solid was carried out in order to achieve environmentally sustainable management of the waste in Polyamide 6 (PA6) nanocomposite manufacture/fabrication. The formulation of different blends of PA6 nanocomposite materials from untreated, demulsifier treated and thermally treated drilling fluid and cuttings was successfully achieved. Nanocomposite leaching test showed Pb immobilisation. The flexural and compressive - modulus and strength of the PA6 were markedly improved in the presence of the nanofillers and glass fibre. This was attributed to the reinforcement, exfoliating, stiffening, rigidity effect of the nanofillers. S6 (untreated drilling fluid) nanofillers significantly improved the mechanical properties of PA6. This was attributed to the increased interfacial bonding between the fillers and the polymer matrix as a result of the petroleum hydrocarbon present in the sample. The Thermogravemetric analysis (TGA) results showed that nanocomposites PA6/S3 and PA6/S3/GF30 had improved the thermal stability of PA6 by 13.6% and 38.8% respectively compared to PA6/S2 and PA6/S2/GF30 (simulated commercial nanocomposite materials) that improved PA6 by 9.7% and 35.8% respectively.

In the automotive industry, a kind of fuel additives, known as surfactant, is used to protect metallic surfaces. Its efficiency strongly depends on factors such as temperature, solvent properties and the presence of other surfactants in the system. In this thesis, both classical and ReaxFF molecular dynamics (MD) simulations are used in studying the impacts of these factors on the adsorption of organic surfactants at the fluid-solid interface. Firstly, a classical MD simulation study of competitive adsorption is carried out on a multi-functional phenol and amine surfactant model with ethanol at the oil/iron oxide interface. As the concentration of ethanol increases, the ethanol molecules effectively compete for the adsorption sites on the iron oxide surface. This observation concurs with the experimental findings of similar oil/iron oxide systems. Unlike most MD interfacial studies, ReaxFF MD uses a fully flexible and polarizable solid surface. The second part of the thesis includes a study on the effect of polarity of organic molecules on the structure of iron oxide using ReaxFF-based MD simulations. The simulation results suggest that care must be taken when parameterising empirical and transferable force fields because the fixed charges on a solid slab may not be a perfect representation of the real system, especially when the solid is in contact with polar compounds. Lastly, but not the least, missing ReaxFF interaction parameters for Fe/N have been developed to simulate the adsorption of amine based surfactant on iron oxide. The parameterisation of the force field is done by fitting these interaction parameters to a set of quantum mechanical data involving iron-based clusters. These newly developed parameters are able to capture chemisorption and proton transfer between hexadecylamine and iron oxide.

A exploração indiscriminada dos combustíveis fósseis vem alertando para o colapso próximo do suprimento de energia. Fontes alternativas vêm sendo exploradas com o propósito de apresentarem-se como combustíveis com o mesmo potencial, além de estarem inseridas em um contexto de desenvolvimento sustentável. O Brasil, por consolidar sua posição com forte mercado agroindustrial e dispor de uma grande variedade de unidades agrícolas possui como subprodutos uma alta quantidade de resíduos, como o sabugo de milho. Assim, buscam-se viabilizar metodologias que tornem a exploração desta fonte economicamente vantajosa para a obtenção de etanol de segunda geração (2G). Novas metodologias vêm propondo o emprego de tensoativos como aditivos tanto no prétratamento quanto na hidrólise enzimática de materiais lignocelulósicos. Neste contexto, o presente trabalho objetivou estudar a hidrólise enzimática do sabugo de milho pré-tratado por ácido diluído na presença de diferentes concentrações do tensoativo Tween 80 em associação com a dosagem do complexo enzimático Cellic CTec2 para a obtenção de um hidrolisado rico em glicose para obtenção de etanol pela levedura Scheffersomyces stipitis CBS 6054 através do processo SHF (Separate Hydrolysis and Fermentation). Os ensaios foram conduzidos de acordo com planejamento experimental 23 com face centrada e 3 repetições no ponto central. As variáveis estudadas foram: concentração de surfactante no pré-tratamento e na hidrólise enzimática e dosagem do complexo enzimático. Os resultados mostraram que o uso do surfactante no pré-tratamento com ácido sulfúrico diluído surtiu maior efeito na remoção de lignina e hemicelulose quando empregado na concentração de 10% (m/m). Nesta condição foi possível observar um aumento (21,1%) na perda de celulose em relação ao pré-tratamento sem a presença de surfactante. A maior diminuição na cristalinidade (81,23%) foi com o uso de 10% do tensoativo. A análise da superfície de resposta permitiu determinar as condições ótimas do processo SHF para obtenção de máximo rendimento em glicose (entre 80 e 90 %) que foi quando a concentração de surfactante no pré-tratamento aumentou de 0 a 10 % (m/m) mantendo-se constante em seu nível superior a concentração de surfactante na hidrolise enzimática (10 % m/m) com redução na dosagem de enzima (25,50 FPU/gmaterial lignocelulósico seco). Nestas condições experimentais obteve-se favorecimento no rendimento em glicose (80,54%) e concentração em glicose (61,98 g/L) no meio reacional concomitantemente com o favorecimento no rendimento em xilose (70,66%). Esta levedura fermentou concomitantemente os açúcares (glicose, xilose e celobiose) a etanol com elevados fator de conversão (0,37 g/g) e produtividade volumétrica (1,02 getanol/L.h). A velocidade especifica máxima de consumo destes açúcares foi favorecida na seguinte ordem: glicose, celobiose e xilose. Após esta fermentação foi obtido um material com uma superfície mais porosa e fragmentada. Este fato evidenciou que o complexo enzimático agiu eficientemente quebrando a celulose cristalina obtendo um material amorfo. Espera-se que este trabalho tenha contribuído para o desenvolvimento de uma tecnologia alternativa para a produção de etanol por via biotecnológica a partir da fração lignocelulósica do sabugo de milho, a fim de mitigar os impactos ambientais intrínsecos ao processo. / The indiscriminate exploitation of fossil fuels has been warning of the near collapse of the energy supply. Alternative sources have been explored with the purpose of presenting themselves as fuels with the same potential, besides being inserted in a context of sustainable development. Brazil, by consolidating its position with a strong agroindustrial market and having a wide variety of agricultural units, has as a by-product a high amount of waste, such as corn cob. Thus, we seek to make feasible methodologies that make the exploitation of this source economically advantageous to obtain second generation etanol (2G). New methodologies have proposed the use of surfactants as additives in both pretreatment and enzymatic hydrolysis of lignocellulosic materials. In this context, the present work aimed to study the enzymatic hydrolysis of diluted-acid pretreated corn cob in the presence of different concentrations of the Tween 80 surfactant in combination with the dosage of the Cellic CTec2 enzymatic complex to obtain a glucose rich hydrolysate to produce ethanol by the yeast Scheffersomyces stipitis CBS 6054 in SHF (Separate Hydrolysis and Fermentation) process. The experiments were conducted according to experimental design 23 with centered face and 3 repetitions at the central point. The variables studied were: concentration of surfactant in the pretreatment and in the enzymatic hydrolysis and dosage of the enzymatic complex. The results showed that the use of surfactant in the pretreatment with diluted sulfuric acid had a greater effect on the removal of lignin and hemicellulose when used at the concentration of 10% (w/w). In this condition, the cellulose content was decreased by 21.1% as compared with the amount presents in the diluted-acid corn cob pretreatment without surfactant. The greatest decrease in crystallinity (81.23%) was with the use of 10% of the surfactant. The response surface analysis allowed to determine the optimum conditions of the SHF process to obtain maximum glucose yield (between 80 and 90%), when the pre-treatment surfactante concentration increased from 0 to 10% (w/w) with a reduction in the enzyme dosage (25,50 FPU/g dry lignocellulosic material) at a higher level than the surfactant concentration in the enzymatic hydrolysis. In these experimental conditions, glucose yield (80.54%) and glucose concentration (61.98 g/L) in the reaction medium were favored concomitantly with xylose yield (70.66%). This yeast concomitantly fermented the sugars (glucose, xylose and cellobiose) to ethanol with high conversion factor (0.37 g/g) and volumetric productivity (1.02 getanol/L.h). The maximum specific velocity of consumption of these sugars was favored in the following order: glucose, cellobiose and xylose. After this fermentation was obtained a material with a more porous and fragmented surface. This fact evidenced that the enzymatic complex acted efficiently breaking down the crystalline cellulose obtaining an amorphous material. It is hoped that this work had contributed to the development of an alternative technology to produce ethanol by Biotechnological route from the corn cob lignocellulosic fraction in order to mitigate the environmental impacts intrinsic to the process.

A prática da troca de óleo lubrificante usado, particularmente óleos automotivos, representa um grave problema ambiental em função de sua natureza perigosa, do manuseio incorreto e do descarte indiscriminado no meio ambiente. A investigação quanto à remediação de áreas contaminadas por esse resíduo torna-se necessária, particularmente para solo de natureza argilosa. O presente estudo teve por objetivo avaliar a biorremediação de um solo argiloso contaminado por óleo lubrificante utilizando biorreatores de fase semi-sólida. Frascos tipo Erlenmeyer, contendo 20 g de solo contaminado com 3% (m/m) de óleo lubrificante, em triplicata, foram mantidos em temperatura e agitação constantes, segundo as seguintes estratégias de tratamento: (i) Bioestímulo com ajuste de nutrientes (BIOE); (ii) Bioaumento com adição de inóculo microbiano aclimatado (BIOA); (iii) Bioestímulo e adição de surfactante sintético Tween-80 (BIOES); (iv) Bioaumento, bioestímulo e surfactante sintético Tween-80 (BIOAS) e (iv) controle, com água destilada purificada (CONT). A eficiência de remoção do contaminante foi avaliada após 68 dias de tratamento por análises de evolução de CO2, redução de COT, decaimento de HTP, de n-alcanos e frações de hidrocarbonetos saturados, aromáticos e compostos polares. O tratamento BIOAS resultou na maior produção de CO2 acumulada (1247,0 mg.20g-1 de solo) seguida pelo tratamento BIOES (1077,6 mg.20g-1 de solo). Ao final do experimento, todos os tratamentos reduziram significativamente os teores de HTPs quando comparados ao controle (11,14,2%). Os tratamentos BIOAS e BIOES não apresentaram diferenças significativas quanto à redução de HTPs (42,03,7% e 37,46,3%, respectivamente). Tanto o bioestímulo quanto o bioaumento mostraram-se estratégias com potencial para aumentar a eficácia da biorremediação de solos argilosos, sendo que a adição de surfactante foi o fator mais importante, tendo aumentado significativamente a capacidade de remoção em ambas as estratégias. O uso de biorreatores em fase semi-sólida na biorremediação de solo argiloso contaminado com óleo lubrificante mostrou-se bastante promissor e tal estratégia pode ser aplicada em escala imediatamente superior / The practice of exchange of used lubricating oil, automotive oils in particular, represents a serious environmental problem due to its hazardous nature, the misuse and its indiscriminate disposal of same in the environment. Strategies for remediation of contaminated areas by this waste are necessary, particularly in case of soils with clayey nature. This study aimed to evaluate the bioremediation of a clayey soil contaminated by lubricating oil using bioreactors of semi-solid phase. Erlenmeyer flasks containing 20 g of contaminated soil with 3% (w / w) of lubricating oil, in triplicate, were kept at constant temperature and agitation, according to the following treatment strategies: (i) biostimulation with nutrient adjustment (BIOE), (ii) addition of bioaugmentation with microbial inoculum acclimated (BIOA), (iii) addition of biostimulation and synthetic surfactant Tween-80 (BIOES) (iv) bioaugmentation, biostimulation and synthetic surfactant Tween-80 (BIOAS) and (iv) control with purified distilled water (CONT). The contaminant removal efficiency was evaluated after 68 days of treatment by analysis of evolution of CO2, reduction of TOC, decay of HTP, n-alkanes, and fractions of saturated hydrocarbons, aromatics and polar compounds. The BIOAS treatment resulted in increased accumulated production of CO2 (1247.0 mg.20g-1 soil) followed by BIOES treatment (1077.6 mg.20g-1 soil). At the end of the experiment, all treatments significantly reduced the levels of HTP as compared to control (11.1 4.2%). The BIOAS and BIOES treatments presented no significant differences in the reduction of HTP (42.0 3.7% and 37.4 6.3%, respectively). Both biostimulation and bioaugmentation were shown to be strategies with potential to increase the effectiveness of bioremediation in a clayey soil, and the addition of surfactant being the most important factor, increasing significantly the capacity of removal in both strategies. The use of bioreactors in semi-solid phase bioremediation in a clayey soil contaminated by lubricating oil proved to be very promising, and this strategy can be applied to at higher scales

Made available in DSpace on 2014-12-17T15:41:59Z (GMT). No. of bitstreams: 1 JoseFCM_DISSERT.pdf: 2061310 bytes, checksum: 67b7e2ece769fac61927cbbd2bd5769a (MD5) Previous issue date: 2012-01-31 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Combating pollution of soils is a challenge that has concerned researchers from different areas and motivated the search for technologies that aim the recovery of degraded soils. Literature shows numerous processes that have been proposed with the intent of remediating soils contaminated by oils and other by-products of the oil industry, considering that the processes available have, generally, high operating costs, this work proposes a costeffective alternative to the treatment of Diesel-contaminated soils. The washing solutions were prepared using water as aqueous phase, the saponified coconut oil (OCS) as surfactant and n-butanol as co-surfactant. In this study, the soil was characterized by physical and chemical analyses. The study of diesel desorption from the soil was held in bath, using hexane and washing solutions, which had 10 and 20 wt.% active matter (AM - co-surfactant/surfactants) respectively. The study of the influence of active matter concentration and temperature in bath agitated used an experimental planning. The experiment also developed a system of percolation in bed to wash the soil and studied the influence of the concentration of active substance and volume of washing solution using an experimental planning. The optimal times to achieve hexane extraction were 30 and 180 min, while the best results using a 10% AM was 60 min and using a 20% AM was 120 min. The results of the experimental planning on bath showed that the maximum diesel removal was obtained when at a 20 wt.% of AM and under 50 ?C, removing 99.92% of the oil. As for experiments in the system of percolation soil bed, the maximum diesel removal was high when the volume of the washing solution was of 5 L and the concentration of 20% AM. This experiment concluded that the concentration of AM and the temperature were vital to bath experiments for diesel removal, while in the system of percolation soil bed only concentration of AM influenced the soil remediation / O combate ? polui??o do solo ? um desafio que tem envolvido pesquisadores de diferentes ?reas na busca de tecnologias que permitam a recupera??o do solo degradado. V?rios processos de remedia??o de solos contaminados por ?leos, e outros produtos da ind?stria do petr?leo, t?m sido propostos na literatura, por?m, estes processos geralmente t?m elevados custos operacionais. Este trabalho tem como objetivo propor uma metodologia eficaz para o tratamento de solos contaminados por ?leo diesel atrav?s de lavagem com solu??o precursora de microemuls?o de baixo custo. As solu??es de lavagem foram preparadas utilizando ?gua como fase aquosa, ?leo de coco saponificado (OCS) como tensoativo e n-butanol como cotensoativo. Neste estudo o solo foi caracterizado atrav?s de an?lises qu?micas e f?sicas. Realizou-se em banho termostatizado com agita??o, o estudo do tempo de dessor??o do diesel do solo com hexano e com as solu??es de lavagem, as quais tinham 10% e 20% de mat?ria ativa (cotensoativo/tensoativo). Foi realizado um estudo planificado da influ?ncia da concentra??o de mat?ria ativa e da temperatura, em banho agitado. Tamb?m foi desenvolvido um sistema de percola??o em leito para lavagem o solo, e estudou-se a influ?ncia da concentra??o de mat?ria ativa (MA) e volume da solu??o de lavagem utilizando um planejamento experimental. Os melhores tempos de dessor??o do diesel no do solo para o hexano foram de 30 e 180 min, enquanto que para a solu??o contendo 10% de MA foram necess?rios 60 min e para a solu??o com 20% de MA os melhores resultados foram obtidos com 120 min. Os resultados do planejamento experimental em banho agitado mostraram que a remo??o do diesel foi m?xima quando se utilizou 20% de MA na temperatura de 50?C, removendo 99,92% e para os experimentos no sistema de percola??o em leito de solo, a remo??o foi m?xima quando o volume da solu??o foi de 5 L e a concentra??o de 20% de MA. Conclui-se que a concentra??o de MA e a temperatura foram par?metros importantes nos experimentos em banho agitado para a remo??o do diesel, enquanto que no sistema de percola??o em leito de solo apenas a concentra??o de MA teve influencia na remedia??o do solo. O trabalho realizado apresenta-se como uma boa alternativa para remedia??o de solo contaminado por Diesel

Made available in DSpace on 2014-12-17T15:42:14Z (GMT). No. of bitstreams: 1 RosemiroMB_DISSERT.pdf: 2340991 bytes, checksum: c71ab28274a335ce511c0a85fd6c1157 (MD5) Previous issue date: 2014-01-07 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The knowledge of the rheological behavior of microemulsionated systems (SME) is of fundamental importance due to the diversity of industrial applications of these systems. This dissertation presents the rheological behavior of the microemulsionated system formed by RNX 95/alcohol isopropyl/p-toulen sodium sulfonate/kerosene/distilled water with the addition of polyacrylamide polymer. It was chosen three polymers of the polyacrylamide type, which differ in molar weight and charge density. It was studied the addition of these polymers in relatively small concentration 0,1% in mass and maximum concentration of 2,0%. It was made analysis of flow to determine the appearing viscosities of the SME and rheological parameters applying Bingham, Ostwald de Waale and Herschell-Buckley models. The behavior into saline environment of this system was studied for a solution of KCl 2,0%, replacing the distilled water. It was determined the behavior of microemulsions in relation with the temperature through curves of flow in temperatures of 25 to 60?C in variations of 5?C. After the analysis of the results the microemulsion without the addition of polymer presented a slight increase in its viscosity, but it does not mischaracterize it as a Newtonian fluid. However the additive systems when analyzed with low concentration of polymer adjusted well to the applied models, with a very close behavior of microemulsion. The higher concentration of the polymer gave the systems a behavior of plastic fluid. The results of the temperature variation point to an increase of viscosity in the systems that can be related to structural changes in the micelles formed in the own microemulsion without the addition of polymer / O conhecimento do comportamento reol?gico de sistemas microemulsionados (SME) ? de fundamental import?ncia, devido ? diversidade de aplica??es industriais desses sistemas. Esse trabalho apresenta o comportamento reol?gico do sistema microemulsionado formado por RNX 95/?lcool isoprop?lico/p-tolueno sulfonato de s?dio/Querosene/?gua destilada com a adi??o do pol?mero poliacrilamida. Foram escolhidos tr?s pol?meros do tipo poliacrilamida, que diferem quanto a massa molar e sua densidade de carga. Estudou-se a adi??o desses pol?meros em concentra??o relativamente baixa 0,1% em massa e concentra??o m?xima de 2,0%. Foram realizadas an?lises de escoamento para a determina??o das viscosidades aparente dos SME e par?metros reol?gicos aplicando os modelos de Bingham, Ostwald de Waale e Herschell-Buckley. O comportamento em meio salino desse sistema foi estudado para uma solu??o de KCl 2,0%, em substitui??o ? ?gua destilada. Foi determinado o comportamento das microemuls?es em rela??o ? temperatura atrav?s de curvas de escoamento a temperaturas de 25 a 60?C com varia??es de 5?C. Ap?s an?lise dos resultados a microemuls?o sem adi??o de pol?mero apresentou um ligeiro aumento em sua viscosidade, mas o que n?o a descaracteriza como um fluido newtoniano. Os sistemas aditivados quando analisados com concentra??o baixa de pol?mero ajustaram-se bem aos modelos aplicados, com comportamento muito pr?ximo da microemuls?o. J? a concentra??o mais elevada de pol?mero deu aos sistemas comportamento de fluido pl?stico. Os resultados da varia??o de temperatura apontam para um aumento na viscosidade dos sistemas que pode estar relacionado a mudan?as estruturais nas micelas formadas na pr?pria microemuls?o sem adi??o de pol?mero

L'objectif de cette thèse était le développement d'un tensioactif organométallique pour catalyser la cycloaddition entre un alcyne et un azoture. Le but d'un tel système est de compartimenter le catalyseur et les réactifs dans deux phases différentes : le catalyseur dans une phase organique ou fluorée et les réactifs dans une phase aqueuse, afin de simplifier la purification en fin de réaction. D'abord, le complexe [Cu(TF6)(3-benzoylbenzoate)2] a été synthétisé. Puis, il a été montré que ce complexe non soluble dans l'eau présente de bonnes propriétés tensioactives à l'interface des systèmes DIPE-eau et PFD-eau, grâce à ces chaînes fluorées. Il est aussi photoréductible pour obtenir un complexe de cuivre (I). Enfin, il a été utilisé comme catalyseur dans des émulsions. Le complexe [Cu(TF6)(3-benzoylbenzoate)2], une fois réduit, montre une bonne activité en catalyse. Cependant, à la fin de la réaction, une quantité importante de cuivre est détectée dans la phase aqueuse pour des raisons encore non déterminées. Par ailleurs, il s'avère que c'est le cuivre présent dans l'eau qui est responsable de la catalyse et non le complexe à l'interface. / The aim of this thesis was to develop a new metallosurfactant for the catalysis between an alkyne and an azide. The goal of such a system was to keep separated the reactants and the catalyst in two different phases to facilitate the purification of the reaction mixture. The first step was to synthetized the complex [Cu(TF6)(3-benzoylbenzoate)2]. Then it was shown that this complex, insoluble in water and DIPE-water. This complex is also photoreductible to form a copper(I) complex. Finally, it was tested as catalyst in emulsion. When reduced, it showed good activity. However at the end of the reactions a certain amount of copper was found in the water phase for still unknown reason. Besides, it appeared that mainly the copper in the water phase was responsible for the reaction and not the complex at the interface.