Ce mémoire présente une étude physicochimique sur la réutilisation des fluides de mobilisation pour le traitement de sols contaminés. Cette recherche a été menée afin d’étudier l’efficacité de cette réutilisation et d’évaluer la réduction des coûts opérationnels et des impacts environnementaux. La première partie de ce travail est consacrée au traitement d’hydrocarbures lourds issus de créosote ou de goudrons dans des sols moyennement à fortement contaminés. Plusieurs stratégies ont été développées et évaluées tant pour la réutilisation et l’optimisation d’agents chimiques que pour l’efficacité du fluide de lavage. L’étude du mécanisme d’oxydation des hydrocarbures avec du persulfate a permis d’entrevoir la possibilité de réactions en cascades. Les procédés membranaires d’ultra- et de nano-filtration se sont révélés particulièrement attractifs car préservant l’activité des fluides de traitement après utilisation; Des mesures ont permis d’optimiser à la fois la récupération des substances actives et l’abattement des contaminants. L’étude du mécanisme de mobilisation des hydrocarbures par des mousses de surfactant a montré que les hydrocarbures lourds sont majoritairement extraits dans la phase gazeuse de l’émulsion eau-air. Ces différentes stratégies ont été évaluées au cours de campagnes de terrain. La deuxième partie concerne la réutilisation de solutions diluées d’agents chélatants pour extraire, puis immobiliser des cations métalliques divalents. Plusieurs agents chélatants de la famille des polyaminocarboxylates ont été évalués. La régénération des ligands à partir de résines chélatantes ou de FeS a été évaluée à travers de nombreux cycles de réutilisation / This thesis presents a physico-chemical study devoted to the reuse of remediation fluids for contaminated soil treatment. The aim of this research project was to study the reuse efficiency and to evaluate the reduction of operational costs and environmental impacts. The first part was focused on the treatment of moderately to highly contaminated soils by heavy hydrocarbons from creosote or tar. Several strategies have been developed and evaluated for reuse and optimization of chemical agents. The oxidation mechanism of hydrocarbons with persulphate highlights possible cascade reactions. Ultra- and nanofiltration processes were particularly attractive for activity safe of used treatment fluids; Measurements have been optimized for both active substances recovery and contaminants reduction. The study of hydrocarbons mobilization mechanism by surfactant foams showed that the heavier hydrocarbons are mainly extracted into gaseous phase of water-air emulsion. The different strategies were evaluated during field campaigns. The second part deals with the reuse of chelating agents dilute solutions to extract and then immobilize divalent metal cations. Several chelating agents of polyaminocarboxylates family were evaluated. Regeneration of ligands from chelating resins or FeS was evaluated for many reuse cycles.

A successful Chemical Enhanced Oil Recovery (CEOR) program starts with a proper process selection for a given field, followed by a formulation of the batch components and a representative simulation step. Also, lab studies, field data, pilot testing, and economic analyses are required before project implementation. This work discusses the state of the art of the Surfactant-Polymer flood (SP) EOR technique, specifically for carbonate reservoirs, and states a methodology mixing laboratory, literature and reservoir simulation, to assess its applicability under economic and geological uncertainties. First, it is explained concepts related to the research, such as polymer, surfactant, microemulsion, functionalities of each chemical injected, advantages, and disadvantages. Second, a state of the art is developed about recent SP advances. Third, it is described the laboratory method being used to evaluate some properties of the chemicals injected for the Polymer flooding (PF) and SP flooding. Later, the simulation study step being conducted is explained, which will define the volume recovered and Net Present Value (NVP) obtained for the PF, SP injections and water flooding, in different economic and geological scenarios for two models resembling carbonate Brazilian reservoirs. Finally, it is discussed the results obtained, future researches that could be performed, and the respective bibliography. As part of this research, it was verified the Xanthan gum shows adequate results at different concentrations; that a surfactant specifically selected for a carbonate rock with low Interfacial tension and low adsorption is required; also that for the Lula based model although the polymer flooding and Surfactant-Polymer simulation brought some benefits, when compared with the waterflooding, on different economic scenarios and geological models, the high cost associated to the chemical handling facilities and volume spent do not make favorable its application in any scenario. On the contrary for the Cerena I field model, it was found the SP and Polymer flooding on all cases brought better results when compared with the water injection. Concluding that the performance and success of a CEOR program require finding the correct slug characteristics for the unique conditions of each reservoir. In this research the reservoir with higher production rates made possible the use of Chemical EOR presenting better results than a water injection however in the smaller model they were not economically viable due to the additional associated prices. / Um programa bem-sucedido de recuperação melhorada de petróleo por método químico (CEOR) começa com uma seleção precisa do processo para um determinado campo, seguido pela formulação dos componentes e uma etapa de formulação representativa. Adicionalmente, testes laboratoriais, dados de campos, testes pilotos e análises econômicas são necessárias antes da implementação de um projeto. Este trabalho discute o estado da arte da técnica de recuperação melhorada de petróleo (EOR) pela injeção de surfactante-polímero (SP), especificamente para reservatórios carbonáticos e, utilizada uma metodologia baseada em dados de laboratório, literatura e de simulação de reservatório para avaliar sua aplicabilidade sob incertezas econômicas e geológicas. Primeiramente, são explicados conceitos necessários a este trabalho relacionados com polímero, surfactante, microemulsão, funcionalidades de cada produto químico injetado, vantagens e desvantagens. Em segundo lugar, um estado da arte é desenvolvido sobre os avanços recentes do SP. Após, descreve-se os métodos laboratoriais utilizados para avaliar algumas propriedades dos produtos químicos usados nas injeções de Polímeros (PF) e SP. Posteriormente, é explicada a etapa do estudo de simulação, que definirá o volume recuperado e o valor presente líquido (NVP), obtidos para injeções PF, SP e água, em diferentes cenários econômicos e geológicos, para dois modelos semelhantes a reservatórios carbonáticos brasileiros. Por fim, são discutidos os resultados obtidos, sugestões de trabalhos futuros e apresentação da bibliografia. Como parte desta pesquisa, verificou-se que a goma xantana apresenta resultados consistentes em diferentes concentrações e que é necessário um surfactante especificamente selecionado para uma rocha carbonática, possuindo baixa tensão interfacial e baixa adsorção. Para o modelo baseado em Lula, embora a simulação de injeção de polímero e surfactante-polímero tenham trazido alguns benefícios, quando comparados com a injeção de água, em diferentes cenários econômicos e modelos geológicos, o alto custo associado às instalações de manipulação química e volume gasto não favorece sua aplicação em qualquer cenário. Por outro lado, no modelo de campo Cerena I, verificou-se que as injeções de SP e de polímero, em todos os casos, trouxeram melhores resultados quando comparadas com a injeção de água. Concluindo, o desempenho e o sucesso de um programa de CEOR exige encontrar as corretas características de slugs para condições únicas de cada reservatório. Neste trabalho, o reservatório com maiores taxas de produção infere que o método químico de EOR apresente melhores resultados quando comparado com a injeção de água.

Les matériaux méso-structurés sont des matériaux à porosité contrôlée, issus de synthèses de chimie sol/gel entre micelles de tensioactifs et précurseur inorganique, le plus souvent de silice. Parmi ces matériaux, le SBA-15, formé en milieu super-acide à partir de P123 (un copolymère tribloc) comme tensioactif et de TEOS comme précurseur inorganique de silice, est un des plus étudiés. La synthèse de ce matériau a été étudiée par diffusion des rayons X à petits angles (SAXS) in situ, et a permis de décrire qualitativement et quantitativement les mécanismes d’auto-assemblages entre micelles de tensioactifs et particules silicatées. Spécifiquement, nos résultats ont montré que l’hydrolyse-condensation du TEOS en solution a permis la formation d’oligomères de silice, qui interagissent avec la couronne des micelles sphériques de P123, pour progressivement former des micelles hybrides cylindriques organiques/inorganiques, qui vont ensuite précipiter en une mésophase hybride 2D-hexagonale. Ce modèle de synthèse est appelé « transition sphères-cylindres ». De plus, afin de comprendre les mécanismes de formation du matériau à toutes les échelles, nous avons étudié l’influence des conditions de synthèse sur la morphologie des grains de matériau méso-structurés. En effet, nous avons montré que sans agitation pendant la synthèse, les grains de matériaux présentent une forme d’équilibre qui dépend fortement de la température de synthèse. En fonction de la température, il est donc possible de former des matériaux hybrides de forme grains de riz, bâtons (courts ou longs) ou mêmes sous forme de tores. Nous proposons un modèle théorique qui permet d’expliquer l’ensemble des morphologies observées, en fonction des tensions de surfaces et des énergies de courbures de cristal-liquide 2D-hexagonal lors de la précipitation de la mésophase hybride. Nous appuyons ce modèle théorique sur des études en diffusion des rayons X à très petits angles (USAXS), qui permettent d’étudier la croissance des grains. Grâce à ces études, nous proposons une description très complète de la formation du matériau SBA-15. Fort de ces connaissances, nous avons pu, grâce à de nouvelles études de SAXS in situ, appliquer le modèle de précipitation de type « transition sphères-cylindres » à d’autres matériaux, issus de tensioactifs non-ioniques fluorés, et ainsi expliquer la formation de matériaux dits « bimodaux », c’est-à-dire issus d’un mélange entre P123 et un tensioactif fluoré(Rf₈(EO)₉ et qui présentent deux ordres poreux bien définis. Enfin, nous avons cherché à utiliser nos connaissances pour la fabrication de matériaux innovants, en remplaçant la solution micellaire par des émulsions dopées en nanoparticules d’or (NPs), afin de fabriquer des matériaux hybrides dopés en NPs. / Meso-structured materials are materials with a well-controlled porosity, designed from sol/gel syntheses between surfactant micelles and an inorganic precursor, most often a silica precursor. Among them, the SBA-15 material, formed in super-acid solution from P123 (a tri-block copolymer) as surfactant and TEOS a silica precursor, is one of the most studied. Synthesis of this material has been studied by in situ Small Angle X-Ray Scattering (SAXS), which allowed to describe both qualitatively and quantitatively the self-assembly mechanisms between surfactant micelles and silica particles. In details, our results showed that TEOS hydrolysis-condensation allow the formation of silica oligomers that interact with the corona of the spherical micelles of P123, and progressively the micelles reshape in hybrid organic/inorganic cylindrical micelles. The hybrid micelles, first free in solution, eventually precipitate in a hybrid 2D-hexagonal mesophase. This model of synthesis is called “sphere-to-rod transition”. Moreover, in order to understand the material mechanisms of formation at every length scales, we studied the influence of the synthesis conditions on the morphology of the meso-structured material grains. Indeed, in agreement with a previous study, our results show that if the synthesis is made without stirring, the material grains has an equilibrium shape that strongly depends on the synthesis temperature. By changing the temperature, one can form hybrid materials with a “rice grain” shape, or a (short or long) rod shape, or even a torus shape. We propose a theoretical model to explain all the observed morphologies, model that takes into account surface tensions and curvature energy of the newly formed 2D-hexagonal liquid-crystal at the precipitation of the hybrid mesophase. We measured the nucleation and growth of the grains by Ultra Small Angle X-Ray Scattering (USAXS). Thanks to all these studies, we present a complete description of the formation of the SBA-15 material. Our knowledge were used to describe new in situ SAXS measurements of new materials: our “sphere-to-rod transition” model was able to describe the formation of two materials, form two fluorinated surfactants and allowed to explain the formation of a “bimodal” material, which means a material with two well-defined porous order, that is synthesized from a mix of two surfactant (P123 and (Rf₈(EO)₉). Finally, we tried to use our knowledge to form innovative materials, by replacing the micellar solution as template by an emulsion doped in gold nanoparticles (NPs) to form hybrid materials doped in NPs.

Pigmentary titanium dioxide (TiO2) is the most important white pigment used in several industries, including those that manufacture plastic, coatings and paper. To achieve maximum efficiency in light scattering and to deliver the required opacity to the medium in which the TiO2 is present, the TiO2 particles must be fully dispersed throughout this medium. The particle dispersion in a cured, dry, or solid medium depends on the dispersion efficiency in the wet state, which depends on the effectiveness of the deagglomeration process. Based on the existing technical knowledge, the objective of this study is to investigate fundamental aspects in the dispersion process and to understand the effect of these processes on the required energy to deagglomerate pigmentary TiO2 particles in water. The fundamental aspects of particle wetting, dispersion and stability are reviewed as well as the theories of the tensile strength of agglomerates, particle roughness and liquid surface tension and viscosity. Although liquid surface tension and viscosity are the main factors that influence deagglomeration, some particle-related properties (particle radius, particle shape factor, agglomerate pore volume and specific surface area) play an important role in wetting behavior. The maximum mass of water adsorbed by the agglomerates is proportional to the liquid surface tension. The liquid adsorption rate is a function of the ratio between the liquid and solid surface tensions as well as the shape factor. In the present study, for any shape factor value, the lower the liquid surface energy is in relation to the solid surface tension, the larger the water adsorption rate. After characterizing the particles, the agglomerates and the liquid medium, and obtaining correlations between all properties and the energy to achieve maximum dispersion, a predictive model is proposed to describe the influence of liquid surface tension and the particle roughness on the energy required to produce liquid dispersions with minimum particle size. This model applies to different particles with similar surfaces and to particles with different surfaces but similar sizes. / Dióxido de titânio é o pigmento branco mais importante de diversas indústrias incluindo as de tintas, plásticos e papel. Para atingir sua máxima eficiência no espalhamento de luz, prover a opacidade requerida ao meio em que se encontra presente, as partículas devem estar completamente dispersas neste meio. A dispersão no meio sólido, seco ou curado dependerá da eficiência de dispersão no estado úmido, a eficiência da dispersão no estado úmido dependerá de quão efetivo foi o processo de desaglomeração. O objetivo deste trabalho é compreender como as propriedades do líquido e do sólido impactam a energia requerida para desaglomerar às partículas de dióxido de titânio pigmentário em um meio líquido. As teorias de umectação de partículas, dispersão e estabilidade foram revisadas assim como as teorias de tensão de coesão de aglomerados, rugosidade da partícula e viscosidade e tensão superficial de líquidos. O objetivo destas revisões foi determinar os fatores que influenciam o processo de desaglomeração e a energia requerida para que isso ocorra. Apesar das propriedades do líquido serem os principais fatores que influenciam o processo de desaglomeração (viscosidade e tensão superficial do líquido), as propriedades da partícula, ainda que sempre associadas a propriedades do líquido, desempenham um papel importante no comportamento de umectação (raio da partícula, rugosidade, volume dos poros do aglomerado e área superficial específica). Após a caracterização das propriedades das partículas, dos aglomerados e do meio, e analisar as correlações entre as propriedades e a energia necessária para atingir o máximo da dispersão um modelo preditivo foi desenvolvido para descrever a influencia da tensão superficial e da rugosidade na energia necessária para atingir o tamanho de partícula mínimo. Este modelo se aplica a diferentes partículas com superfícies similares e partículas com superfícies diferentes com tamanhos similares.

Nesse trabalho foi estudado a degradação anaeróbia do alquilbenzeno linear sulfonado (LAS), um surfactante amplamente utilizado na fabricação de detergentes e presente em esgoto doméstico e águas residuárias industriais. Para isso foi utilizado reator anaeróbio de leito fluidificado em escala de bancada (1,2 L) preenchido com material suporte para imobilização da biomassa. Quatro diferentes suportes foram testados previamente em reatores de leito fluidificado em menor escala (350 ml): carvão ativado (R1), argila expandida (R2), pérolas de vidro (R3) e areia (R4). Todos os reatores foram inoculados com lodo proveniente de reator UASB utilizado no tratamento de dejetos de suinocultura e alimentados com substrato sintético acrescido de LAS. Os reatores foram mantidos a 30°C e operados com tempo de detenção hidráulica (TDH) de 18 horas. Foi possível constatar que os quatro reatores foram aptos na remoção de matéria orgânica (acima de 84%) e LAS (acima de 81%), respectivamente para concentração inicial média de 550 mg/L e 16,5 mg/L. No entanto, carvão ativado e argila expandida sofreram processo de fragmentação durante a operação do reator. Assim, areia foi o material escolhido para preencher o reator em escala de bancada devido aos bons resultados de remoção do LAS (99%), menor custo e facilidade de aquisição, quando comparada a pérola de vidro. Após 270 dias de operação, com concentrações crescentes de LAS e média de 32,3 mg/L, constatou-se que o reator em escala de bancada removeu 93% de LAS. Todos os suportes adsorveram pouco LAS (máximo de 0,43 mgLAS/gargila) não interferindo significativamente no processo de remoção biológica. Exames microscópicos realizados durante a operação dos reatores mostraram que estiveram presentes microrganismos com morfologias semelhantes a espiroquetas, bacilos, bactérias filamentosas e cocos, entre outros. A biomassa presente no final da operação do reator em escala de bancada e nos reatores menores preenchidos com pérolas de vidro (R3) e areia (R4) foi submetida à técnica de clonagem e sequenciamento do gene 16S RNAr para o Domínio Bacteria. Observou-se que os reatores apresentaram clones relacionados a diversos Filos como Bacteroidetes, Proteobacteria, Verrucomicrobia e Firmicutes, entre outros. / This work presents the anaerobic degradation of linear alkylbenzene sulphonate (LAS), a surfactant widely used in the production of detergents and present in domestic and industrial wastewaters. It was used an anaerobic fluidized bed reactor in bench scale (1,2L) filled with support material for biomass immobilization. Four different supports were previously tested in small scale fluidized bed reactors (350 ml): activated charcoal (R1), expanded clay (R2), glass beads (R3) and sand (R4). All reactors were inoculated with sludge from a UASB reactor treating swine wastewater and were fed with a synthetic substrate supplemented with LAS. The reactors were kept at 30ºC and operated with a hydraulic retention time (HRT) of 18 h. It was possible to note that the four tested reactors were able to remove organic matter (higher than 84%) and LAS (higher than 81%), respectively, to initial mean value of 550 mg/L and 16.5 mg/L. However, activated charcoal and expanded clay both produced shearing during reactor operation. Thus, sand was the chosen material to fill the bench scale reacto because of good results of LAS removal (99%) and smaller cost and affordability compared to glass beads. After 270 days of operation, with crescent LAS concentrations and average of 32,3 mg/L, it was found that the bench scale reactor was able to remove LAS in 93%. All supports adsorb a few LAS (maximun of 0.43 mgLAS/gclay). This value does not interfere in biologic removal process. Microscopic tests done during the reactor´s operation presented microorganisms with morphologies similar to spirochetes, bacillus, filamentous, cocci and others. 16S rRNA gene sequencing and phylogenetic analysis of samples from the bench scale reactor and smaller reactor filled with glass beads (R3) and sand (R4) revealed that these reactors gave rise to broad microbial diversity, with microorganisms belonging to the phyla Bacteroidetes, Proteobacteria, Verrucomicrobia and Firmicutes, and others.

As emulsões múltiplas mostram-se como veículos promissores em várias áreas das ciências cosmética e farmacêutica. O estudo do método de obtenção de emulsões múltiplas em etapa única é ferramenta útil para elucidação de seus aspectos físico-químicos e para viabilizar sua aplicação tecnológica. O objetivo da pesquisa foi desenvolver e caracterizar os aspectos físico-químicos do processo de emulsificação em etapa única, das emulsões múltiplas A/O/A obtidas e dos tensoativos empregados. Testes preliminares de estabilidade e avaliação do seu perfil de liberação (cafeína) foram realizados. Nanoemulsões foram inicialmente obtidas pela metodologia proposta, resultado de processo de emulsificação por inversão de fases. Suas características físico-químicas foram determinadas (valores de pH, potencial zeta e granulometria) e a influência de aditivos avaliada. Para o desenvolvimento da emulsão múltipla foram realizadas análises qualitativas e quantitativas das variáveis relevantes à composição (tipo de fase oleosa, de tensoativo hidrofílico, valor de EHL, emprego de diagrama ternário) e ao método de emulsificação (temperatura de aquecimento das fases e de emulsificação, ordem de adição e velocidade de agitação). Os estudos das propriedades físico-químicas dos tensoativos e do filme interfacial formado (cloud point, tensão superficial, CMC, reologia interfacial, reologia de fluxo e isotermas de Langmuir) foram primordiais para compreensão dos fenômenos envolvidos e relevantes ao processo de emulsificação proposto. As emulsões múltiplas foram caracterizadas quanto aos aspectos macro e microscópico, granulometria, valores de pH, potencial zeta, viscosidade relativa, perfil reológico e influência da adição de macromoléculas. A temperatura de manipulação e de emulsificação (78±2grausC) foram parâmetros fundamentais para obtenção destes sistemas em etapa única. Seus aspectos macro e microscópico foram extremamente dependentes da temperatura de emulsificação. Os resultados indicam glóbulos múltiplos consideravelmente menores do que os relatados pela literatura. Foi possível observar, no intervalo de temperatura considerado crítico para o processo, valores de tensão superficial/interfacial mínimos. Os resultados de elasticidade superficial sugerem que o comportamento das moléculas de tensoativos, em associação ou não, foi marcadamente influenciado pela temperatura e que o aumento do número de moléculas do tensoativo hidrofólico na superfície foi desfavorável as interações intramoleculares. A isoterma para os tensoativos em associação e em função da temperatura exibiu marcante inflexão para a faixa de temperatura crítica. Este comportamento indica uma dramática alteração na microestrutura do filme interfacial. O processo de encapsulação foi considerado eficiente. Os resultados obtidos indicam que, no atual estágio de desenvolvimento, não foi possível definir um perfil de liberação para a emulsão múltipla em análise. O método de emulsificação escolhido permitiu a obtenção de sistema múltiplo em etapa única, determinado pelas características físico-químicas dos tensoativos empregados, em especial do tensoativo hidrofílico derivado do óleo de rícino e do processo proposto. A formação de emulsões múltiplas anormais não ocasionais ou momentâneas sugere uma combinação dos processos de inversão de fases transicional, influência do emprego de tensoativos não-iônicos etoxilados, e catastrófica, influência da razão entre o volume da fase dispersa e dispersante. As emulsões múltiplas obtidas apresentaram difícil reprodutibilidade microestrutural; entretanto podem ser consideradas estáveis frente às metodologias de avaliação e análise empregadas. / Multiple emulsions are potential vehicles not only for the cosmetic science, but also for the pharmaceutical science. Study the manufacture process of multiple emulsions by one step is a useful tool for understanding their physical-chemistry aspects and making their technological application practicable as well. The goals of this research were to development and characterize the physical chemistry features of the emulsification process by one step, the W/O/W multiple emulsions produced and the surfactants employed. Preliminary stability tests and evaluation of the release profile (caffeine) were carried out. Initially, nano-emulsions were produced by the proposed methodology, resulting from phase inversion emulsification process. Their physical chemistry aspects (pH and zeta potential values and size distribution) and electrolytes addition influence were evaluated. In order to develop the multiple emulsions, noteworthy qualitative and quantitative variables related to the composition (oil phase and hydrophilic surfactant types, HLB values, phase diagram) and to emulsification process (heating and emulsification temperatures, addition order and agitation speed) were analyzed. Analyses of the physical chemistry aspects of the surfactants in solution and their interfacial film (cloud point, surface tension, CMC, interfacial and flux rheology, and Langmuir isotherms) were essential in order to understand the phenomena related to proposed emulsification process. Multiple emulsion analyses (macroscopic, microscopic, size distribution, pH and zeta potential values, relative viscosity, rheological profile and macromolecule addition influence) were carried out. Production and emulsification temperatures (78±2grausC) were fundamental parameters in order to obtain multiple droplets by one step. Their macro and microscopic aspects were completely conditioned by the emulsification temperature. The sizes of the multiple droplets obtained were significantly smaller than those reported in the literature. For the critical temperature range, the minimum surface tension values were reached. Surface elasticity results suggest that the behavior of the surfactant molecules, in association or not, was fundamentally influenced by the temperature. Increasing surfactant molecule moieties on the surface, the intra molecular interactions were misplaced. The Langmuir isotherm as a function of the temperature demonstrated distinctive behavior for the critical temperature range, where the transition phase into solid state and soon afterwards some collapse could be observed. This phenomenon indicated some dramatic alteration of the surface film microstructure. The encapsulation process was regarded as efficient. The release profile studies demonstrated that the dispersed system in analysis was not ready yet for this research stage. The proposed emulsification process was able to produce multiple droplets by one step; moreover this result presented direct influence of the surfactant physical chemistry features, particularly the hydrophilic one, castor oil derivate, and of the methodology employed. The abnormal, non-occasional and non-transitory, multiple emulsion formation suggest a combination of transitional (ethoxylated non ionic surfactant influence), and catastrophic (dispersed/dispersant ratio influence) phase inversion processes. The obtained multiple emulsions presents microstructure aspects were not easily reproducible; however those were regarded stable for the analysis methodology employed.

Die vorliegende Arbeit präsentiert eine erste umfassende Wachstumsstudie, und erste quantitative Wachstumsmodelle, von Gruppe-III und IV Oxiden synthetisiert mit sauerstoffplasmaunterstützter Molekularstrahlepitaxie (MBE). Diese entwickelten Modelle beinhalten kinetische und thermodynamische Effekte. Die erworbenen Erkenntnisse sind auf fundamentale Wachstumsprozesse in anderen Syntheseverfahren übertragbar, wie zum Beispiel der Laserdeposition oder metallorganische Gasphasenepitaxie. Die Wachstumsraten und Desorptionsraten werden in-situ mit Laser-Reflektometrie bzw. Quadrupol-Massenspektrometrie (QMS) bestimmt. Es werden die transparenten halbleitenden Oxide Ga2O3, In2O3 und SnO2 untersucht. Es ist bekannt, dass sich das Wachstum von Gruppe-III und IV Oxiden, aufgrund der Existenz von Suboxiden, fundamental von anderen halbleitenden Materialien unterscheidet. Es stellt sich heraus, dass die Wachstumsrate der untersuchten binären Oxide durch die Formierung und Desorption von Suboxiden flussstöchiometrisch und thermisch limitiert ist. Es werden die Suboxide Ga2O für Ga2O3, In2O für In2O3 und SnO für SnO2 identifiziert. Ein Suboxid ist ein untergeordneter Oxidationszustand, und es wird gezeigt, dass die untersuchten Oxide über einen Zwei-Stufen-Prozess gebildet werden: vom Metall zum Suboxid, und weiterer Oxidation vom Suboxid zum thermodynamisch stabilen festen Metalloxid. Dieser Zwei-Stufen-Prozess ist die Basis für die Entwicklung eines ersten quantitativen, semiempirschen MBE-Wachstumsmodells für binare Oxide die Suboxide besitzen. Dieses Model beschreibt und erklärt die gemessenen Wachstumsraten und Desorptionsraten. Es wird die Kinetik und Thermodynamik des ternären Oxidsystems (InxGa1−x)2O3 untersucht. Die gemittelten Einbauraten von In und Ga in ein makroskopisches Volumen von (InxGa1−x)2O3 Dünnschichten werden ex-situ mit energiedispersiver Röntgenspektroskopie gemessen. Diese Einbauraten werden systematisch analysiert und im Rahmen kinetischer und thermodynamischer Grenzen beschrieben. Es wird gezeigt, dass Ga den In-Einbau in (InxGa1−x)2O3 aufgrund seiner stabileren Ga–O Bindungen thermodynamisch verhindert. In diesen Zusammenhang wird ein neuer katalytisch-tensidischer Effekt des In auf den Einbau von Ga gefunden. Eine Folge dieses katalytisch-tensidischen Effektes ist die Formierung der thermodynamisch, metastabilen hexagonalen Ga2O3 phase mit sehr hoher Kristallqualität. Ein thermodynamisch induziertes, kinetisches Wachstumsmodel für (InxGa1−x)2O3 wird entwickelt, mit dem sich alle makroskopischen Metall-Einbauraten und Desorptionsraten vorhersagen lassen. Mögliche (InxGa1−x)2O3 Strukturen gewachsen mit MBE werden mittels Röntgenkristallographie bestimmt. Mit Hilfe der Röntgenstrukturanalyse wird ein erster makroskopischer Ansatz zur Bestimmung der mikroskopischen In Konzentration X in möglichen (InXGa1−X)2O3 Phasen hergeleitet. Es werden Löslichkeitsgrenzen von In bzw. Ga in monoklinem und kubischem (InXGa1−X)2O3 bestimmt. / The present thesis presents a first comprehensive growth investigation and first quantitative growth models of group-III and IV oxides synthesized by oxygen plasma-assisted molecular beam epitaxy (MBE). The developed models include kinetic and thermodynamic effects. The obtained findings are generally valid for fundamental growth processes in other growth techniques, such as pulsed laser deposition and metal-organic vapor phase-epitaxy. The growth rates and desorption rates are measured in-situ by laser reflectometry and quadrupole mass spectrometry (QMS), respectively. The binary transparent semiconducting oxides Ga2O3, In2O3, and SnO2 are investigated. It is known that the growth of group-III and IV oxides is fundamentally different as compared to other semiconductor compounds and due to the existence of suboxides. It is found that the growth rate of the binary oxides investigated is flux-stoichiometrically and thermally limited by the formation and desorption of their respective suboxide. These suboxides are identified as Ga2O for Ga2O3, In2O for In2O3, and SnO for SnO2. A suboxide is a lower oxidation state, and it is shown, that the investigated oxides grow via a two-step oxidation process. That means, all metal oxidizes to the suboxide, and the suboxide can be further oxidized to the thermodynamic stable solid metal-oxide. This two-step oxidation process is the basis for the development of a first quantitative semi-empirical MBE growth model which predicts and explains the measured growth rates and desorption rates, for binary oxides possessing suboxides. The kinetics and thermodynamics of the ternary oxide system (InxGa1−x)2O3, grown by MBE, is investigated. The average In and Ga incorporation rates into a macroscopic volume of (InxGa1−x)2O3 are measured ex-situ by energy dispersive X-ray spectroscopy. These incorporation rates are systematically analyzed and explained in the framework of kinetic and thermodynamic limitations. It is shown that Ga thermodynamically inhibits the incorporation of In into (InxGa1−x)2O3 due to its stronger Ga–O bonds. In this context, a new catalytic-surfactant effect of In on the formation of Ga2O3 is found. As a consequence of this catalytic-surfactant effect the metastable hexagonal Ga2O3 with very high crystal quality is formed. A thermodynamically induced kinetic growth model for (InxGa1−x)2O3 MBE is developed. It predicts all macroscopic metal incorporation rates and desorption rates. Possible (InxGa1−x)2O3 phases grown by MBE are investigated by X-ray crystallography. By means of X-ray diffraction analysis, a first macroscopic approach to determine the microscopic In concentration X in possible (InXGa1−X)2O3 phases is derived. The solubility limits of In and Ga in monoclinic and cubic (InXGa1−X)2O3 phases, respectively, are identified.

Nesse trabalho foi estudado a degradação anaeróbia do alquilbenzeno linear sulfonado (LAS), um surfactante amplamente utilizado na fabricação de detergentes e presente em esgoto doméstico e águas residuárias industriais. Para isso foi utilizado reator anaeróbio de leito fluidificado em escala de bancada (1,2 L) preenchido com material suporte para imobilização da biomassa. Quatro diferentes suportes foram testados previamente em reatores de leito fluidificado em menor escala (350 ml): carvão ativado (R1), argila expandida (R2), pérolas de vidro (R3) e areia (R4). Todos os reatores foram inoculados com lodo proveniente de reator UASB utilizado no tratamento de dejetos de suinocultura e alimentados com substrato sintético acrescido de LAS. Os reatores foram mantidos a 30°C e operados com tempo de detenção hidráulica (TDH) de 18 horas. Foi possível constatar que os quatro reatores foram aptos na remoção de matéria orgânica (acima de 84%) e LAS (acima de 81%), respectivamente para concentração inicial média de 550 mg/L e 16,5 mg/L. No entanto, carvão ativado e argila expandida sofreram processo de fragmentação durante a operação do reator. Assim, areia foi o material escolhido para preencher o reator em escala de bancada devido aos bons resultados de remoção do LAS (99%), menor custo e facilidade de aquisição, quando comparada a pérola de vidro. Após 270 dias de operação, com concentrações crescentes de LAS e média de 32,3 mg/L, constatou-se que o reator em escala de bancada removeu 93% de LAS. Todos os suportes adsorveram pouco LAS (máximo de 0,43 mgLAS/gargila) não interferindo significativamente no processo de remoção biológica. Exames microscópicos realizados durante a operação dos reatores mostraram que estiveram presentes microrganismos com morfologias semelhantes a espiroquetas, bacilos, bactérias filamentosas e cocos, entre outros. A biomassa presente no final da operação do reator em escala de bancada e nos reatores menores preenchidos com pérolas de vidro (R3) e areia (R4) foi submetida à técnica de clonagem e sequenciamento do gene 16S RNAr para o Domínio Bacteria. Observou-se que os reatores apresentaram clones relacionados a diversos Filos como Bacteroidetes, Proteobacteria, Verrucomicrobia e Firmicutes, entre outros. / This work presents the anaerobic degradation of linear alkylbenzene sulphonate (LAS), a surfactant widely used in the production of detergents and present in domestic and industrial wastewaters. It was used an anaerobic fluidized bed reactor in bench scale (1,2L) filled with support material for biomass immobilization. Four different supports were previously tested in small scale fluidized bed reactors (350 ml): activated charcoal (R1), expanded clay (R2), glass beads (R3) and sand (R4). All reactors were inoculated with sludge from a UASB reactor treating swine wastewater and were fed with a synthetic substrate supplemented with LAS. The reactors were kept at 30ºC and operated with a hydraulic retention time (HRT) of 18 h. It was possible to note that the four tested reactors were able to remove organic matter (higher than 84%) and LAS (higher than 81%), respectively, to initial mean value of 550 mg/L and 16.5 mg/L. However, activated charcoal and expanded clay both produced shearing during reactor operation. Thus, sand was the chosen material to fill the bench scale reacto because of good results of LAS removal (99%) and smaller cost and affordability compared to glass beads. After 270 days of operation, with crescent LAS concentrations and average of 32,3 mg/L, it was found that the bench scale reactor was able to remove LAS in 93%. All supports adsorb a few LAS (maximun of 0.43 mgLAS/gclay). This value does not interfere in biologic removal process. Microscopic tests done during the reactor´s operation presented microorganisms with morphologies similar to spirochetes, bacillus, filamentous, cocci and others. 16S rRNA gene sequencing and phylogenetic analysis of samples from the bench scale reactor and smaller reactor filled with glass beads (R3) and sand (R4) revealed that these reactors gave rise to broad microbial diversity, with microorganisms belonging to the phyla Bacteroidetes, Proteobacteria, Verrucomicrobia and Firmicutes, and others.

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2018-02-07T12:42:14Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Rolf de Campos.pdf: 5588727 bytes, checksum: d81ab37d8cd335285d51711794fbbc44 (MD5) / Made available in DSpace on 2018-02-07T12:42:14Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Rolf de Campos.pdf: 5588727 bytes, checksum: d81ab37d8cd335285d51711794fbbc44 (MD5) Previous issue date: 2017-07-05 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / Esta tese descreve as interações entre o surfactante não iônico p-(1,1,3,3 tetrametilbutil) fenil polietilenoglicol (denominado Triton X) e dodecil sulfato de sódio (SDS) com o polímero catiônico 3-cloreto-n-propilpiridínio silsesquioxano (SiPy) na presença da ftalocianina tetrasulfonada de níquel (NiTsPc), as quais foram avaliadas utilizando medidas de tensão superficial e viscosidade. Os efeitos dessas interações também foram estudados quando estes polieletrólitos foram transferidos para filmes finos pela técnica LbL sobre substrato condutor (óxido de estanho dopado com índio – ITO), quartzo e silício. Observou-se, por meio de técnica espectroscópica de absorção na região do UVVis, que há um efeito sinérgico proporcionado pela interação dos polieletrólitos catiônico (SiPy/surfactante) e aniônico (NiTsPc) nos filmes LbL. Por técnicas espectroscópicas FTIR e Raman, e técnicas eletroquímicas tais como impedância eletroquímica e voltametria cíclica, foi constatado que há coexistência de micelas mistas e puras e que a adsorção destes agregados tem um papel importante na superfície dos filmes LbL. Foi também realizada a síntese e a caracterização de nanopartículas de hidróxido de níquel, em sua fase α, estabilizadas pelo polímero SiPy, e pelo surfactante zwiteriônico 3-(1- alquil-3-imidazólio)propano-sulfonado. O surfactante ImS3-14 foi escolhido por sua interação preferencial com ânions, tornando-o um excelente limitante para o crescimento das nanopartículas de Ni(OH)2. A formação dos agregados foi caracterizada por espalhamento dinâmico de luz e potencial zeta, para determinar tamanho e carga das nanopartículas, respectivamente. Após a síntese das nanopartículas, estas foram depositadas através da técnica LbL em vários substratos. O crescimento dos filmes foi acompanhado por UV-VIS e sua caracterização foi realizada pelas técnicas de FTIR, Raman, AFM e MEV-FEG. As características eletroquímicas dos filmes foram estudadas por voltametria cíclica (VC) e espectroscopia de impedância eletroquímica (EIE). / This thesis describes the interactions between the nonionic surfactant p-(1,1,3,3- tetramethylbutyl)phenyl-polyethylene glycol (Triton X) and sodium dodecyl sulfate (SDS) with the cationic polymer 3-chloride-n-propylpyridinium silsesquioxane (SiPy) in the presence of nickel phthalocyanine tetrasulfonate (NiTsPc), which they were evaluated using surface tension and viscosity measurements. The effects of these interactions were also studied when these polyelectrolytes were transferred to thin films by the LbL technique on conductive substrate (indium doped tin oxide - ITO), quartz and silicon. It has been observed by UV-Vis absorption spectroscopy there is a synergistic effect provided by the interaction of the cationic polyelectrolytes (SiPy / surfactant) and anionic (NiTsPc) polyelectrolytes in the LbL films. Spectroscopic techniques, such as, FTIR and Raman, and electrochemical techniques, electrochemical impedance and cyclic voltammetry, it was observed that there is a coexistence of mixed and pure micelles. The adsorption of these aggregates plays an important role on the surface of the LbL films. The synthesis and characterization of nickel hydroxide nanoparticles, in their α phase, stabilized by the SiPy polymer, and by the zwitterionic surfactant 3- (1-alkyl-3 - imidazolium) propane sulfonate was realized. The surfactant ImS3-14 was chosen for its preferential interaction with anions, making it an excellent stabilizer for the growth of the Ni(OH)2 nanoparticles. The formation of the aggregates was characterized by dynamic scattering of light (DLS) and zeta potential to determine size and charge, respectively. After the synthesis of the nanoparticles, they were deposited by the LbL technique on several substrates. The growth of the films was accompanied by UV-VIS and their characterization was evaluated by FTIR, Raman, AFM and MEV-FEG techniques. The electrochemical characteristics of the films were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).

Control and analysis of protein aggregation is an increasing challenge to biopharmaceutical research and development. Therefore it is important to understand the interactions, causes and analysis of particles in order to control protein aggregation to enable successful biopharmaceutical formulations. This work investigates the role of different non-ionic surfactants on protein conformational stability, as assessed by HSDSC, and on protein size stability as assessed by Dynamic Light Scattering (DLS), HIAC and MFI. BSA and IgG2 were used as model proteins. Thermal unfolding experiments indicated a very weak surfactant-immunoglobulin IgG2 interaction, compared to much stronger interactions for the BSA surfactant systems. The DLS results showed that BSA and IgG2 with different surfactants and concentration produced different levels of particle size growth. The heat treatment and aging of samples in the presence of Tween 20, Tween 80, Brij 35 and Pluronic F-68 surfactants led to an increase in the populations of larger particles for BSA samples, whereas IgG2 systems did not notably aggregate under storage conditions MFI was shown to be more sensitive than HIAC technique for measuring sub-visible particles in protein surfactant systems. Heat treatment and storage stress showed a significant effect on BSA and IgG2 protein sub-visible particle size stability. This work has demonstrated that both proteins with different Tween 20, Tween 80, Brij 35 and Pluronic F-68 concentrations, have different level of conformational and size stability. Also aging samples and heating stress bears the potential to generate particles, but this depends on surfactant type. Poor predictive correlations between the analytical methods were determined.