Cette thèse de doctorat concerne l’étude de la distillation membranaire sous vide pour l’élimination de l’arsenic contenu dans les eaux souterraines. En effet, la contamination des nappes phréatiques par l’arsenic est une problématique majeure dans de nombreux pays, et en particulier au Vietnam. Dans ce pays, choisi comme cas d’étude pour ce travail, environ 13% de la population est empoisonnée par des eaux souterraines contaminées par l’arsenic. De plus, ces eaux souterraines présentent des salinités élevées (5-10 g.L-1) dues à des infiltrations d’eau de mer dans les nappes. Ce travail de thèse a permis de démontrer la faisabilité de la distillation membranaire sous vide (DMV) pour éliminer l’arsenic contenu dans ces eaux et réduire leur salinité afin de les rendre propres à la consommation humaine. Les concentrations en As(III) dans le perméat de DMV sont toujours inférieures aux limites de la norme en eau potable (10 μg.L-1), même pour de très fortes concentrations en As(III) dans l’alimentation (jusqu’à 2000 μg.L-1). La DMV ne nécessite pas de pré-oxydation de l’As(III) en As(V), étape nécessaire dans de nombreux procédés conventionnels de traitement. De plus, un couplage entre l’osmose inverse (OI) et la DMV a été étudié : l’étape d’OI permet une pré-concentration en NaCl et As(III), puis ce rétentat est alors sur-concentré grâce à laDMV. La DMV a montré de très bonnes performances pour traiter un concentrat contenant de très fortes concentrations en As(III) (7000 μg/L). La DMV permet toujours de limiter les teneurs en arsenic dans le perméat à des valeurs en-dessous de la norme. Enfin, unesimulation d’un procédé global, incluant OI et DMV, et fonctionnant à un taux de conversion global de 96%, a été effectuée. Ce couplage ouvre la voie vers un traitement global de l’arsenic permettant de générer de très faibles quantités d’effluents finaux / This PhD work deals with vacuum membrane distillation (VMD) for arsenic removal from groundwaters. Contamination of water resources with arsenic was identified in 105 countries. Approximately 150 million people are being exposed to arsenic contamination, and 147 million of these people live in Asia. In Vietnam, chosen as the case study of this work, 13% of the population is being in risk of arsenic poisoning. Drinking water resources present not only high arsenic concentration (1 – 3050 ppb) but also high salinity (5 – 15 g/L). This work allowed demonstrating the feasibility of VMD to remove arsenic and also salts contained in groundwaters. As(III) concentration in the permeate of VMD was always lower than the standard level for drinking water (10 μg.L-1), even for high As(III) concentrations in the feed (up to 2000 μg.L-1). With VMD, a pre-oxidation step was not necessary to convert As(III) into As(V), as it is the case for other conventional treatment processes. Moreover, a coupling between reverse osmosis (RO) and VMD was studied. RO was considered as a first step to concentrate NaCl and As(III) before this retentate stream was further concentrated by the VMD. VMD could work efficiently with 99.9% of As(III) andNaCl rejections at a very high RO retentate concentrations ([NaCl] = 300 g/L and [As(III)] = 7000 ppb). Arsenic in the permeate was still lower than the required standard for drinking water. Finally, a simulation of the coupling was performed. By coupling of RO and VMD, ahigh global recovery of 96% could be achieved

Submitted by Caroline Periotto (carol@ufscar.br) on 2016-09-21T12:53:09Z No. of bitstreams: 1 TeseVV.pdf: 2152205 bytes, checksum: cbcb3bfba1aaf9c801ac47859a7bd77a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-23T18:25:02Z (GMT) No. of bitstreams: 1 TeseVV.pdf: 2152205 bytes, checksum: cbcb3bfba1aaf9c801ac47859a7bd77a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-23T18:25:10Z (GMT) No. of bitstreams: 1 TeseVV.pdf: 2152205 bytes, checksum: cbcb3bfba1aaf9c801ac47859a7bd77a (MD5) / Made available in DSpace on 2016-09-23T18:25:16Z (GMT). No. of bitstreams: 1 TeseVV.pdf: 2152205 bytes, checksum: cbcb3bfba1aaf9c801ac47859a7bd77a (MD5) Previous issue date: 2016-05-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The use of lipases in large scale processes is limited due to their high cost. The reuse of the catalyst can contribute to make the enzymatic process more attractive. Hydrophobic supports are the mostly used for lipase immobilization, due to the mechanism of interfacial activation in the presence of hydrophobic interface. However, enzyme physically adsorbed to the support does not allow high operational stability. Therefore, in this work was evaluated the immobilization of commercial lipases from Candida antarctica type B (CALB), Thermomyces lanuginosus (LTL) e Pseudomonas fluorescens (LPF) on hybrid supports, that enable the hydrophobic adsorption, followed by covalent linkage between the adsorbed enzyme and the activated support. Silica was activated with trietoxy(octyl)silane (OCTES), (3-aminopropyl)trietoxysilane (APTES) e 3-glycidyloxypropyl)trimetoxysilane (GPTMS), aiming to produce supports with different functionality, as following: silica containing octyl groups (octyl-silica, OS), octyl and aldehyde groups (octyl-silica-glyoxyl and octyl-silicaaldehyde, OSGlx and OSGlu, respectively), and silica containing octyl and epoxy groups (octyl-silica-epoxy, OSEpx). From adsorption assays using the hydrophobic dye Rose of Bengal it was found that the modification of the silica with OCTES significantly increased the hydrophobicity of all the supports. Silica modified with OCTES groups showed to be 4 times more hydrophobic than non-modified silica. The support OSGlu yielded more active CALB biocatalyst, while OS yielded more active biocatalysts prepared with PFL and TLL. All the biocatalysts showed high stability in tert-butanol, specially CALB immobilized on OSGlu (OSGlu-CALB), maintaining 95% of its initial activity after 168 h at 60 ºC. CALB-OSGlu was successfully used in the synthesis of fructose oleate at 55ºC, yielding up to 70% conversion after 9 cycles of 6 hours, while the commercial biocatalyst Novozyme 435 retained around 53%. TLL and PFL were used in the synthesis of fructose oleate at 35ºC in presence of different amounts of water. All biocatalysts showed excellent performance in the ester synthesis when small amount of water (1%, v/v) was added to the organic phase, except for the lipases immobilized on silica modified with octyl and epoxy groups (OSEpx). Small amount of water increased around 5-times the ester productivity compared to reaction without water. Conversions around 70% were achieved at low temperature (35ºC) and short time of reaction (30 min). These results represent an advance in this field from of industrial point of view, where productivity is a relevant parameter for large-scale processes. Finally, porcine pancreatic lipase (PPL) immobilized on OS was used in the synthesis of xylose oleate and xylose caprilate, because it is the most inexpensive lipase commercially available. The results showed to be promising, because conversions around of 70% were achieved after 2 h of reaction at 60 oC. Generally, this work showed that the chemical modification of the silica surface with different active groups allowed the preparation of biocatalysts with different microenvironment, which exhibits an important role in the activity and stability of the immobilized enzymes. Besides, the biocatalysts prepared in this work showed excellent performance and operational stability in syntheses of sugar esters, showing to have potential for industrial application. / O uso de lipases em larga escala é limitado devido ao seu alto custo. O reuso do biocatalisador contribuiria para tornar o processo custo-efetivo. Suportes hidrofóbicos são os mais utilizados na imobilização de lipases, devido ao mecanismo de ativação interfacial na presença de interfaces hidrofóbicas. Entretanto, o fato da enzima ligar-se fisicamente ao suporte não garante maior estabilidade operacional. Portanto, nesse trabalho foi avaliada a imobilização de lipases comerciais de Candida antarctica tipo B (CALB), Thermomyces lanuginosus (LTL) e Pseudomonas fluorescens (LPF) em suportes híbridos, os quais possibilitam adsorção hidrofóbica, seguida de ligação covalente enzima-suporte. Sílica foi funcionalizada com trietoxi(octil)silano (OCTES), (3-aminopropil)trietoxisilano (APTES) e 3-glicidiloxipropil)trimetoxisilano (GPTMS), para produzir suportes com diferentes funcionalidades: sílica contendo grupos octil (octil-silica, OS), sílica contendo grupos octil e aldeídos (octil-sílica-glioxil e octil-sílica-glutaraldeído, OSGlx e OSGlu, respectivamente) e sílica contendo grupos octil e epóxi (octil-sílica-epóxi, OSEpx). A modificação da sílica com OCTES aumentou significativamente a hidrofobicidade de todos os suportes, observado a partir de ensaios de adsorção do corante hidrofóbico Rosa de Bengala. Sílica modificada com grupos OCTES apresentou hidrofobicidade cerca de quatro vezes superior à apresentada pela sílica não modificada. O suporte OSGlu rendeu biocatalisadores mais ativos para CALB, enquanto OS rendeu biocatalisadores mais ativos para LPF and LTL. Todos os biocatalisadores apresentaram boa estabilidade em terc-butanol, especialmente CALB imobilizada em OSGlu (CALB-OSGlu), retendo em torno de 95 % de sua atividade inicial após 168 h a 60 ºC. CALB-OSGlu foi usada com sucesso na síntese de oleato de frutose a 55ºC, mantendo mais de 70% de conversão após nove ciclos de 6 horas, enquanto para o biocatalisador comercial Novozyme 435 a conversão foi de aproximadamente 53%. LTL e LPF foram aplicados na síntese de oleato de frutose a 35ºC na presença de diferentes percentuais de água. Todos os biocatalisadores mostram excelente desempenho na síntese do éster adicionando-se uma pequena quantidade de água (1%, v/v) na fase orgânica, exceto para as enzimas imobilizadas em OSEpx. A presença de água contribuiu para aumentar em até cinco vezes a produtividade do éster em comparação à reação na ausência de água. Uma conversão de aproximadamente 70% foi alcançada à baixa temperatura (35ºC) e curto período de tempo (30 min). Esses resultados representam um avanço nesta área do ponto de vista industrial, onde a produtividade é um parâmetro relevante para processos em larga escala. Por fim, a lipase do pâncreas de porco (LPP) imobilizada em OS foi empregada na síntese de oleato de xilose e caprilato de xilose, devido ao seu menor custo dentre as lipases disponíveis comercialmente. Os resultados foram expressivos, obtendo-se uma conversão de aproximadamente 70% após 2 h de reação à 60ºC. De modo geral, esse trabalho mostrou que a modificação química da superfície da sílica com diferentes grupos ativos permitiu a preparação de biocatalisadores com diferentes microambientes, exercendo papel importante na atividade e estabilidade das lipases imobilizadas. Além disso, os biocatalisadores preparados neste trabalho apresentaram excelente desempenho e estabilidade operacional em reações de síntese de ésteres de açúcares, mostrando ter potencial para aplicação industrial.

Made available in DSpace on 2016-06-02T19:56:48Z (GMT). No. of bitstreams: 1 4556.pdf: 4130912 bytes, checksum: ce52d6d080c273997017ee16e040fc29 (MD5) Previous issue date: 2012-03-30 / Agência Nacional de Petróleo / Lipases (triacyl-glycerol-hydrolases) are enzymes that catalyze hydrolysis, esterification and transesterification reactions. Lipase can be obtained from animals, microbial and vegetable sources. Nowadays, commercial lipases are majority produced from microbial sources. The use of these enzymes in industrial scale is still limited because of its high cost of production, favoring then, the search for new sources of lipases. This work aimed the utilization of oilseeds as lipase sources, aiming its use in the synthesis of fatty esters and in the hydrolysis of vegetable oils. To achieve this goal, the protein content of seeds of sunflower, castor bean and soybean was solubilized in buffered medium. The oilseeds were crushed in the presence of sodium phosphate buffer pH 7.0 (50 mM), followed by 11 hconstant stirring at room temperature. Under these conditions, the average productivities were ca. 237, 100 and 81 U/g of dried seeds. The solids were withdrawal from the crude extract by filtration, followed by centrifugation. The clarified crude extract was purified by ultrafiltration in 100 kDa cut-off polypropylene membrane. This procedure allows an activity recovery of 40, 35 and 11% for soybean, sunflower and castor bean, respectively. The purified lipases from soybean, sunflower and castor bean seeds were immobilized on hydrophobic support (silica-octyl) by interfacial adsorption, yielding biocatalysts with recovered activities of 683%, 413% and 1494%, respectively. SDS-PAGE electrophoresis and activity assays during the immobilization of the purified lipases on silica-octil suggested the presence of two lipase isoforms with molecular weights around of 20 and 30 kDa. Soluble soybean lipase exhibited optimum pH and temperature for hydrolysis of olive oil around 8.0 and 47 °C, respectively, while for immobilized soybean lipase (derivative) were 6.0 and 57°C, respectively. The halflife of the immobilized lipase at 50oC and pH 7 was around 8 h. The synthesis of butyl butyrate at 40oC catalyzed by immobilized lipase yield a conversion of approximately 15% after 9 h of reaction. The productivity of lipases from soybean seeds can be increased by germination of the seeds for 12 h, followed by extraction at 25oC for 12 h with salt solution (sodium phosphate buffer pH 7.0) at 100 mM concentration, supplemented with 1% (m/v) Tris-HCl. / Lipases (glicerol éster hidrolases, EC 3.1.1.3) catalisam reações de hidrólise, esterificação e transesterificação. As lipases podem ser obtidas de fontes animais, microbianas e vegetais, sendo que as de origem microbiana representam a grande maioria das lipases produzidas atualmente. No entanto, o uso dessas enzimas em escala industrial ainda é restrito devido ao alto custo de produção, favorecendo, assim, a busca por novas fontes de lipase. Este trabalho teve por objetivo a utilização de sementes de oleaginosas como fontes de lipases, visando sua aplicação na síntese de ésteres de ácidos graxos e hidrólise de óleos vegetais. Inicialmente sementes de soja, girassol e mamona foram trituradas em tampão fosfato de sódio 50 mM, pH 7, seguida por agitação de 11 horas em temperatura ambiente. Sob essas condições, as produtividades médias foram de aproximadamente 237, 100 e 81 U/g de sementes secas. Os sólidos foram removidos do extrato enzimático bruto por filtração e o extrato enzimático foi clarificado por centrifugação. O extrato clarificado foi purificado por ultrafiltração em membrana de polipropileno com diâmetro de corte de 100 kDa. Esse procedimento permitiu a recuperação de 40, 35 e 11% da atividade inicialmente presente nos extratos enzimáticos brutos obtidos a partir de sementes de soja, girassol e mamona, respectivamente. Lipases de sementes de soja, girassol e mamona foram imobilizadas por adsorção hidrofóbica em sílica ativada com grupos octil (sílica-octil), obtendo-se biocatalisadores com atividades recuperadas de 683%, 413% e 1494%, respectivamente. Eletroforese SDS-PAGE do extrato enzimático da soja e ensaios de atividade durante a imobilização em sílica-octil sugeriram a presença de duas isoformas de lipases, com massas moleculares de aproximadamente 20 e 30 kDa. O pH e a temperatura de máximas atividades hidrolíticas do extrato enzimático da soja foram de 8,0 e 47ºC, respectivamente, enquanto para a enzima imobilizada foram de 6,0 e 57ºC, respectivamente. O tempo de meia-vida da enzima imobilizada a 50ºC e pH 7 foi de 8 h. Na síntese de butirato de butila, realizada a 40ºC, obteve-se uma conversão de aproximadamente 15% em 9 h de reação. A produtividade de lipases de sementes de soja pode ser aumentada por germinação das sementes por 12 h, seguida da extração a 25ºC por 12 h com solução salina (tampão fosfato de sódio, pH 7,0) com uma concentração de 100 mM e adição de Tris-HCl 1% (m/v).

Made available in DSpace on 2016-12-12T20:15:50Z (GMT). No. of bitstreams: 1 Jorge Batista - resumo.pdf: 37444 bytes, checksum: 8f8f7a4b6f5f96a5fc6085e5128c66c2 (MD5) Previous issue date: 2013-03-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The control of surface wettability is an issue of great scientific interest because of the large number of applications both as hydrophobic to hydrophilic surfaces, such as medical instruments, fluidic microdevices, coating for microdevices, manipulation of nanoparticles, microscale motors, lubricants, waterproofing surfaces and even instruments for domestic use. The objectives of this work are to compare the values obtained in experiments with surfaces of well-defined topography with available theoretical models and characterize the transition between hydrophobic and superhydrophobic surfaces with the proposition of configurations and criteria that lead to a better understanding of the wettability and superhydrophobic surfaces production, in the light of the energy minimization. / O controle da molhabilidade de superfícies é um tema de grande interesse científico em função da grande quantidade de aplicações, tanto para superfícies hidrofílicas quanto hidrofóbicas, como é o caso de instrumentos médicos, microdispositivos fluídicos, recobrimento para microdispositivos, manipulação de nanopartículas, motores em microescala, lubrificantes, impermeabilização de superfícies e mesmo em instrumentos de uso doméstico. Os objetivos deste trabalho são comparar os valores obtidos em experimentos com superfícies de topografia bem definida com os modelos teóricos disponíveis e caracterizar a transição entre superfícies hidrofóbicas e superhidrofóbicas, com a proposição de configurações e critérios que levem a um melhor entendimento da molhabilidade e da produção de superfícies superhidrofóbicas, sob a luz da minimização de energia.

A corrosão é um fenômeno de interface que deteriora um metal através de reações químicas ou eletroquímicas, sendo caracterizada como um processo espontâneo, onde os materiais são transformados do estado metálico para uma forma combinada, decorrente da interação dos compostos metálicos com as substâncias do meio que estão inseridos. Como os prejuízos oriundos de processos corrosivos são elevados (estimativas mostram que os valores variam em torno de 3% a 4% do PIB de uma nação), estudos que minimizem estes processos são de vital importância econômica. Nos últimos anos, diversas pesquisas foram realizadas com o intuito de estudar superfícies hidrofóbicas e super-hidrofóbicas devido à sua função de autolimpeza, baixa aderência de contaminantes e proteção contra os efeitos corrosivos. Estudos recentes propõem a utilização de ácidos carboxílicos como percussores à formação destas camadas protetoras, sendo que melhores resultados foram obtidos utilizando ácidos carboxílicos de cadeias longas (acima de 11 carbonos). O ácido n-tetradecanóico (CH3(CH2)12COOH) pode ser utilizado sobre cobre e, após 10 dias de imersão em solução alcoólica de 0,06 mol/L, uma película super-hidrofóbica é formada sob o substrato, porém as características superficiais do metal são afetadas e uma camada esverdeada de carboxilato de cobre é formada. O presente trabalho, além de comprovar o efeito protetor desta camada superhidrofóbica formada, propôs a utilização do ácido n-tetradecanóico em um tratamento superficial, de forma a atuar como uma película protetora contra processos corrosivos, considerando curtos períodos de imersão em solução de ácido mirístico de forma a preservar as características superficiais do metal utilizado e torná-lo comercialmente e esteticamente mais atrativo. Os metais avaliados foram: cobre, latão e aço carbono. As técnicas eletroquímicas empregadas para a avaliação da película formada foram: curva de polarização, resistência de polarização linear (Rp) e espectroscopia de impedância eletroquímica (EIE). Medidas de ângulo de contato foram realizadas a fim de comprovar a viii hidrofobicidade do filme formado e espectroscopia de infravermelho e Raman, além da difratometria de raios X, a fim de caracterizar sua composição química. Melhores resultados foram obtidos para cobre, onde os ensaios comprovaram um aumento da hidrofobicidade da superfície metálica à medida que se aumentava o tempo de imersão dos corpos-de-prova em solução alcoólica 0,06 mol/L de ácido ntetradecanóico, atingindo valores de 116,1o e 149,8o após, respectivamente, 12 horas e 5 dias de imersão. Além disso, através de medidas de espectroscopia de impedância eletroquímica, também foi avaliado o grau de proteção da película hidrofóbica formada com relação ao substrato puro, sendo observado um aumento na proteção da superfície após 12 horas de imersão. / Corrosion is an interface phenomenon that deteriorates a metal by chemical or electrochemical reactions. It is characterized as a spontaneous process, where materials are transformed from the metallic state to a combined form. As corrosive processes damages are high (estimates show that the values vary around 3% to 4% of a nation GDP), studies that minimize corrosion reactions are of vital economic importance. Recently, several studies were performed in order to study hydrophobic and superhydrophobic layers due to its self-cleaning function, low adherence of contaminants and protection against corrosive effects. Recent studies propose the use of carboxylic acids as precursors to the formation of such protective layers, with best results being obtained using long chain carboxylic acids (up to 11 carbons). Over copper, the usage of n-tetradecanoic acid (CH3(CH2)12COOH) has showed good results after 10 days immersion in 0.06 mol/L ethanolic solution. Experimental results proved that the super hydrophobic surface could improve significantly the corrosion resistance of copper, although the surfaces have been strongly modified and a green oxidation layer (which is a copper carboxylate) has been formed over the etched copper surface. Besides proving the protective effect of the super-hydrophobic layer formed, this work also studied the use of n-tetradecanoic acid as a temporary protective layer, considering short immersion periods. In this way, the metal surface characteristics were preserved. The metals studied were: copper, brass and carbon steel. The electrochemical techniques employed for evaluation of the formed film were: polarization curves, linear polarization resistance (Rp) and electrochemical impedance spectroscopy (EIS). Contact angle measurements were performed to prove the hydrophobicity of the film and X-ray diffraction, Raman and Infrared spectroscopy were also utilized to characterize its composition. x Test samples of these metals were immersed, at ambient temperature, in 0.06 mol/L of n-tetradecanoic ethanolic solution, for different immersion periods, in order to monitor the formation of the protective layer and its hydrophobicity. Furthermore, in order to study the formation and persistence of the formed film, electrochemical tests were also performed in 3.5 wt. % NaCl solution. The results obtained for copper demonstrate an increase of the metal surface hydrophobicity for longer immersion time in 0.06 mol/L n-tetradecanoic acid solution, reaching values of 116.1o and 149.8o after, respectively, 12 hours and 5 days of immersion. Furthermore, the degree of protection of hydrophobic film was also evaluated by electrochemical impedance spectroscopy measurements and the best results were obtained for 12hs of immersion.

Made available in DSpace on 2017-07-10T19:23:40Z (GMT). No. of bitstreams: 1 Ralpho.pdf: 2205542 bytes, checksum: 37ae4ee862cc62b72b5ed65409967739 (MD5) Previous issue date: 2013-05-17 / Collecting data on pesticide effects on the environment and several ecosystems is a slow and costly process. Therefore, significant research efforts have been focused on developing mathematical models to predict physical, chemical or biological properties of environmental interest. The soil sorption coefficient normalized to organic carbon content (Koc) is a physicochemical key parameter used in environmental risk assessments of substances released into the environment. Thus, several logKoc prediction models that use hydrophobic parameter (logP) or the logarithm of water solubility (logS) as descriptor have been reported in the last decades. Mostly, due to the lack of reliable experimental values of logP or logS, algorithms are used to calculate such properties. Despite the availability and easiness to access several algorithms for this purpose, scientific studies do not describe the procedure adopted to choose the algorithm used in quantitative structure-property relationship (QSPR) studies. Furthermore, the strong correlation between logP and logS prevents their application in the same mathematical equation obtained by multiple linear regression method. Since the sorption process of a chemical compound in soil is related both to its water solubility and its water/organic matter partition, it is expected models that are able to combine these two properties will can record more realistic results. This doctoral dissertation consists of two scientific papers. In the first one, a study was carried out to check the influence of choosing logP algorithm on logKoc modeling. Models were constructed to relate logKoc with logP according to different freeware algorithms. All models were assessed based on their statistic qualities and predictive power. The obtained results clearly showed that an arbitrary choice of the algorithm may not result in the best prediction model. On the other hand, a good choice can lead to obtaining simple models with statistic qualities and predictive power comparable to more complex models. The second paper aims at proposing an alternative approach for logKoc modeling, using simple descriptor of solubility, here referred as logarithm of corrected solubility by octanol/water partition (logSP). Thus, models were built with this descriptor and also with logP and logS conventional descriptors, which are isolated or associated with other explicative variables of easy physicochemical interpretation. The obtained models were validated and compared to other models previously published. The results showed that the use of logSP descriptor to replace the conventional ones led to obtaining simple models with statistic qualities and predictive power that are higher than other more complex models already found in literature. / A coleta de dados relativos aos danos causados pelos pesticidas sobre o meio ambiente e seus ecossistemas é lenta e onerosa. Desta maneira, grandes incentivos têm sido destinados às pesquisas que visam à construção de modelos matemáticos para predição de propriedades físicas, químicas ou biológicas de interesse ambiental. O coeficiente de sorção no solo normalizado para o conteúdo de carbono orgânico (Koc) é um importante parâmetro físico-químico utilizado nas avaliações de riscos ambientais das substâncias lançadas no meio ambiente. Assim, vários modelos para predição de logKoc, utilizando o parâmetro hidrofóbico (logP) ou o logaritmo da solubilidade em água (logS) como descritores, têm sido publicados nas últimas décadas. Muitas vezes, em virtude da ausência de valores experimentais confiáveis de logP ou logS, são usados algoritmos para o cálculo dessas propriedades. Apesar da disponibilidade e facilidade de acesso a diversos algoritmos para tal finalidade, os artigos científicos não descrevem o procedimento adotado para escolha do algoritmo usado nos estudos QSPR. Além disto, a forte correlação entre logP e logS impede que sejam usados em uma mesma equação obtida por regressão linear múltipla. Como o processo de sorção de um composto químico no solo está relacionado tanto com sua solubilidade em água como com sua partição água/matéria orgânica, espera-se que modelos que sejam capazes de combinar essas duas informações possam gerar resultados mais realistas. Este trabalho de tese é constituído de dois artigos. No primeiro artigo, foi feito um estudo para verificar a influência da escolha do algoritmo de logP na modelagem de logKoc. Foram construídos modelos que relacionam logKoc com logP a partir de diferentes algoritmos livres disponíveis. Todos os modelos foram avaliados quanto às suas qualidades estatísticas e poder de predição. Os resultados obtidos mostraram claramente que uma escolha arbitrária deste algoritmo pode não levar ao melhor modelo de predição. Por outro lado, uma boa escolha pode conduzir à obtenção de modelos simples com qualidades estatísticas e poder de predição comparáveis a de modelos mais complexos. No segundo artigo, o objetivo foi a proposição de uma abordagem alternativa para a modelagem de logKoc, utilizando um descritor simples de solubilidade, aqui designado como logaritmo da solubilidade corrigida pela partição octanol/água (logSP). Assim, foram construídos modelos com tal descritor e também com os descritores convencionais logP e logS, isolados ou associados com outras variáveis explicativas de fácil interpretação físico-química. Os modelos obtidos foram validados e comparados com outros modelos publicados anteriormente. Os resultados mostraram que o uso do descritor logSp em substituição aos descritores convencionais conduziu à obtenção de modelos simples com qualidades estatísticas e poder de predição superiores a de outros modelos mais complexos encontrados na literatura.

Desenvolvemos dois modelos estatísticos para água, nos quais diferentes aspectos de sua estrutura são considerados. O modelo geométrico permite diferentes números de coordenação. Em uma aproximação de campo médio mostramos que sob pressão o modelo apresenta linha de coexistência entre fases de baixa e alta densidade, e ponto crítico. A entropia das ligações de hidrogênio tem papel fundamental na definição da inclinação da linha de coexistência. O comportamento do modelo pode estar realcionado como segundo ponto crítico da água super resfriada e com transições líquido-líquido em geral.O modelo da água quadrada é uma versão térmica do modelo do gelo, no qual considera-se a direcionalidade das ligações de hidrogênio. O modelo foi estudado na rede de Bethe e através de simulações de Monte Carlo em três situações diferentes: para a água pura e na presença de solutos polares e apolares. A água quadrada pura não apresenta transição de fase. No modelo para solvente com solutos apolares, medidas de frequência relativa de ligações e do tempo de correlação mostram que o modelo apresenta estruturação da camada de hidratação. Medidas de correlação temporal no modelo de Ising mostram comportamento oposto. Em um estudo preliminar para uma solução com solutos que realizam ligações de hidrogênio não conseguimos encontrar diagramas de coexistência com círculo fechado, para o conjunto de parâmetros utilizados, possivelmente devido à ausência de buracos. / We have developed two statistical models for water in which different features of water structure are considered. In the geometrical model different coordination numbers are present and the model allows for translational disorder. A mean-field treatment shows that under pressure the model exhibits phases of different densities and a coexistence line ending in a critical point. Entropy of the hydrogen network plays an essential role in defining the slope of the coexistence line. The model behavior might be related with the second critical point in supercooled water and to liquid-liquid transitions in general. The square water model is a thermal version of the ice model, and takes into account the directionality of the hydrogen bonds. The model was studied on a Bethe lattice and through Monte Carlo simulations, for three different situations: as pure water and in the presence of polar and apolar solutes. Pure square water does not present a phase transition. In the presence of apolar solutes, first shell square water presents ordering, as shown from comparison of relative frequency of bonds, as well as from study of time correlations. The latter was shown to present opposite behavior in case of an Ising system. In a preliminary study for a solution of hydrogen bonding solutes we were unable to find a closed loop for the sets of parameters chosen. Vacancies might need to be included.

Dans le but d'améliorer la fiabilité des technologies utilisant l'électromouillage, l'objectif de cette thèse est d'étudier les mécanismes de vieillissement de matériaux diélectriques et hydrophobes utilisés en électromouillage et d'appliquer ensuite le protocole de caractérisation établi, à de nouveaux matériaux. Cette thèse s'articule en trois parties. Dans une première partie, afin de caractériser finement les propriétés d'hydrophobie de surfaces et de déterminer plus particulièrement leur polarité, nous avons mis au point une méthode de mesure de la polarité de surface basée sur le mouillage de deux liquides sur une surface, ce qui apporte une précision accrue avec un minimum de mesures. Dans une deuxième partie, nous avons étudié différents revêtements utilisés en électromouillage avant et après vieillissement. Nous nous sommes plus particulièrement intéressés aux films hydrophobes largement utilisés dans les systèmes optiques et de micro-laboratoires comme le Fluoropel©, le Cytop© et le parylène C. Cette étude montre une altération non négligeable des performances des matériaux de manière reproductible. L'hystérésis de mouillage, l'angle de contact au repos ainsi que les propriétés de cohésion des couches ont été étudiés afin de mettre en évidence les paramètres critiques à la durée de vie.Dans la dernière partie, nous avons cherché à mettre au point une méthode de dépôt d'un nouveau matériau hydrophobe par deux techniques de synthèse ; la voie sol-gel et la pulvérisation cathodique (PVD). Ainsi, un sol de précurseur à base du métal applicable pour la préparation de couches minces de son oxyde a été élaboré. La solution est obtenue à partir d'un précurseur synthétisé au laboratoire et stabilisée par des chélatants (acétylacétone). La stabilité de la solution ainsi que la procédure de dépôt sont présentées et les revêtements recuits déposés par sol-gel et PVD sont caractérisés par DRX et d'un point de vue morphologique (MEB, microscope optique…). Si, il fut possible de préparer par la méthode sol-gel des films de 300nm couvrants, leur forte rugosité n'a pas permis de les tester en électromouillage. Par la méthode PVD, nous avons pu réaliser des couches de 400 nm d'épaisseur, très lisses et utilisables en électromouillage. Ces films donnent de très bons résultats en électromouillage sur substrats plans et en lentilles liquides / In order to increase the technologies reliability using electrowetting, this work aims to study the mechanisms of ageing on dielectric and hydrophobic materials used in electrowetting as well and to apply this study to new materials. This thesis is composed of three parts.First, to be able to characterize precisely the hydrophobic properties of these surfaces and especially their surface polarity, we established a method to measure the surface polarity based on wettability of two liquids on a surface permitting a better precision with less measurements. In a second part, we studied different films used in electrowetting before and after ageing around 90°C for one week in order to simulate a long term ageing at an ambient temperature. Widely used hydrophobic coating used in optical systems and lab-on-chip will be mainly characterized such as Fluoropel©, Cytop© and parylène C. This work shows the visible alteration of material performances in a reproducible way. Wetting hysteresis and natural contact angle with the cohesive properties of the coatings are studied in order to establish critical parameters for the life time.Finally, we tried to establish a method to deposit a hydrophobic metal oxide coating by two ways, sol-gel technic with dip-coating deposition and by PVD. A precursor sol made of the metal usable to deposit its oxide thin films has been elaborated. The solution is prepared from the synthesized precursor and stabilized by chelatant (acetylacetone). The solution stability as well as the deposition method used are presented and the annealed coatings deposited by sol-gel and PVD are characterized by XRD and morphologically (SEM, optic microscope …). By the sol-gel method, covering coatings of about 300nm have been made. However, because of the roughness, no electrowetting experiments could have been achieved. By PVD, we have deposited coatings of 400nm thickness, very smooth and usable in electrowetting. These coatings give very good results in electrowetting on plane substrates and liquid lenses

Les contraintes techniques et économiques induites par la gestion des lixiviats de déchets ménagers et assimilés (LDMA) pourraient être minimisées en considérant le LDMA non plus comme un déchet mais comme un « co-produit » partiellement valorisable. Parmi la diversité des constituants des LDMA, la matière organique dissoute (MOD) présente 2 intérêts majeurs : une forte charge et des processus de transformations comparables à ceux de la matière organique naturelle (MON). Ce travail de thèse s’attache donc à extraire cette MOD des LDMA selon son caractère hydrophobe et à identifier des axes de valorisation. Seules les fractions de type hydrophobe (HPO*) et transphilique (TPH*), de par leurs caractéristiques et leur réactivité, ont été considérées dans cette étude et 2 voies de valorisation ont été testées : une valorisation énergétique et une valorisation matière par amendement sur un sol en déficit de carbone organique (Corg).La caractérisation des fractions de MOD anthropiques et leur comparaison à des fractions de MON a confirmé l’intérêt majeur de leur valorisation. En effet, elles sont (i) physiquement et chimiquement comparables à la MON, (ii) quantifiables à des concentrations jusqu’à plus de 1000 fois supérieures à la MON permettant ainsi un potentiel d’extraction conséquent en comparaison aux matrices environnementales telles que les eaux de surface, et (iii) plus facilement biodégradables que la MON, tout en ne présentant aucun caractère phytotoxique avéré.Un test BMP optimisé et adapté au LDMA a été développé via un plan d’expérience, puis utilisé pour mettre en évidence l’impact du caractère hydrophobe de la MOD du LDMA sur la digestion anaérobie, et notamment la production de méthane. Selon les résultats obtenus, les molécules organiques de type transphilique favorisent la production de biogaz. De plus, la fraction hydrophile, faiblement aromatique, diminue la teneur en méthane du biogaz, contrairement à la fraction hydrophobe.Enfin, l’amendement de fractions organiques extraites de LDMA présente un réel intérêt dans le cas d’un sol initialement pauvre en Corg. La fraction HPO* permet un apport de Corg plus important comparé à la fraction TPH*, tandis que les composés transphiliques favorisent l’activité biologique du sol.Ce travail de thèse a ainsi mis en évidence l’intérêt d’extraire les fractions hydrophobe (HPO*) et transphilique (TPH*) de la MOD de LDMA afin de les engager dans des processus de valorisation énergétique et agronomique. / The management of municipal solid waste leachates (MSWL) is technically and economically restrictive. It thus should be interesting to consider this effluent no more as a waste but rather as a partially valorizable “co-product”. The dissolved organic matter (DOM) is one of the major components of MSWL and presents a twofold interest: a high load and comparable processes of transformation to those of natural organic matter (NOM).This study thus aimed at extracting the DOM from MWSL according to its hydrophobic character and identifying ways of valorization. Only hydrophobic (HPO*) and transphilic (TPH*) fractions were considered because of their characteristics and reactivity. Two different ways of valorization were investigated: energetic valorization and enrichment of a soil with low content in organic carbon (Corg).The characterization of HPO* and TPH* fractions and their comparison with fractions of NOM confirmed their high valorizable potential. Indeed, they are physically and chemically comparable to NOM, they can be quantified at concentrations up to 1000 times higher than NOM (high extraction potential when compared to environmental matrices such as surface water), and they are more easily biodegradable than NOM without any phytotoxic character.An optimized BMP test was first developed by using an experimental design to adapt the experimental conditions to the digestion of MSWL. It was then applied in different conditions to highlight the impact of the hydrophobic character of the DOM of MSWL on the anaerobic digestion, and mainly on methane production. According to the results, the transphilic-like organic molecules improve the biogas production. Besides, the hydrophilic-like compounds with low aromatic character decrease the methane content of the produced biogas contrary to the hydrophobic fraction.Finally, organic fractions extracted from MSWL were relevant to enrich soil with low content in organic carbon. The HPO* fraction better improves the Corg content when compared to the TPH* fraction whereas transphilic-like molecules enhances the soil biological activity.With the results of this research study, the HPO* and TPH* fractions extracted from a MSWL can thus be considered both to produce biogas and particularly methane and to be amended on soils. Their extraction can thus be economically viable and their treatment no more highly costly.

In this thesis, we focused on the understanding of the synthesis and texturization processes of hydrophobic and (super)hydrophobic fluorinated surfaces by atmospheric plasmas.<p><p>First, we focused on the surface modifications of a model surface, the polytetrafluoroethylene (PTFE), by the post-discharge of a radio-frequency plasma torch. The post-discharge used for the surface treatment was characterized by optical emission spectroscopy (OES) and mass spectrometry (MS) as a function of the gap (torch-sample distance), and the helium and oxygen flow rates. Mechanisms explaining the production and the consumption of the identified species (N2, N2+, He, O, OH, O2m, O2+, Hem) were proposed. <p><p>The surface treatment was then investigated as a function of the kinematic parameters (from the motion robot connected to the plasma torch) and the gas flow rates. Although no change in the surface composition was recorded, oxygen is required to increase the hydrophobicity of the PTFE by increasing its roughness, while a pure helium plasma leads to a smoothing of the surface. Based on complementary experiments focused on mass losses, wettability and topography measurements coupled to the detection of fluorinated species on an aluminium foil by XPS, we highlighted an anisotropic etching oriented vertically in depth as a function of the number of scans (associated to the treatment time). Atomic oxygen is assumed to be the species responsible for the preferential etching of the amorphous phase leading to the rough surface, while the highly energetic helium metastables and/or VUV are supposed to induce the higher mass loss recorded in a pure helium plasma.<p><p>The second part of this thesis was dedicated to the deposition and the texturization of fluorinated coatings in the dielectric barrier discharge (DBD). The effects of the nature of the precursor (C6F12 and C6F14), the nature of the carrier gas (argon and helium), the plasma power, and the precursor flow rate were investigated in terms of chemical composition, wettability, topography and crystallinity by SIMS, XPS, WCA, AFM and XRD. We showed that hydrophobic surfaces with water contact angles (WCA) higher than 115° were obtained only in the presence of argon and were assumed to be due to the roughness created by the micro-discharges. Plasma-polymerized films in helium were smooth and no WCA higher than 115° was observed. We also studied the impact of the deposition rate and the layer thickness in the hydrophobic properties as well as the polymerization processes through the gas phase characterization.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished