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Stuttgart, Univ., Diss., 2006.

Submitted by Marco Antônio de Ramos Chagas (mchagas@ufv.br) on 2018-07-12T12:02:47Z No. of bitstreams: 1 texto completo.pdf: 9092047 bytes, checksum: 974ae7db880ee66c1f42778fd4204373 (MD5) / Made available in DSpace on 2018-07-12T12:02:47Z (GMT). No. of bitstreams: 1 texto completo.pdf: 9092047 bytes, checksum: 974ae7db880ee66c1f42778fd4204373 (MD5) Previous issue date: 2018-04-16 / Fundação de Amparo à Pesquisa do Estado de Minas Gerais / O amadurecimento de Ostwald é um processo de crescimento controlado por difusão onde partículas maiores crescem em detrimento da diminuição, e eventualmente do desaparecimento, de partículas menores. Nesse processo ocorre o aumento do raio médio e a diminuição do número total de partículas. A descrição teórica desse fenômeno é dada pela teoria LSW, que descreve o crescimento de partículas em soluções sólidas supersaturadas. Há um grande número de trabalhos teóricos e experimentais sobre o amadurecimento de Ostwald, todavia existe uma carência de trabalhos experimentais com bolhas de gás em escala macroscópica (10-100μm). Com isso, fica evidente a necessidade de realizar um estudo experimental preciso da atuação do amadurecimento de Ostwald em bolhas de gás em líquido. Os resultados foram obtidos a partir do processamento de imagens geradas por videomicroscopia óptica. É apresentado os resultados da evolução temporal do raio médio das bolhas R(t), do número de bolhas N (t), da fração volumétrica ocupado pelas bolhas φ(t) e das distribuições de tamanhos f (R, t) para três frentes de experimento com bolhas de gás em um fluido: fluido em repouso, fluido sob fluxo macroscópico e fluido em repouso com adição de surfactante. Confrontando os resultados com as previsões teóricas verificou-se que o raio médio pode, em algumas condições, se comportar de acordo com a lei de crescimento segundo a teoria LSW (R ∼ t1/3 ), mas que na maioria dos casos a evolução é a mais lenta do que o previsto. O número de bolhas N(t) decai mais devagar do que o previsto pela teoria (N (t) ∼ t-¹). Há uma discussão sobre o sistema estar em um regime transiente, migrando para o regime de validade dos modelos teóricos, e sobre a teoria LSW não ser suficiente para descrever um sistema real de bolhas de gás. Todas as etapas foram realizadas no Laboratório de Microfluídica e Fluidos Complexos, coordenado pelo professor Alvaro Vianna N. C. Teixeira, utilizando-se dos recursos do mesmo e do Departamento de Física da UFV, como programas apropriado para processamento de imagens, microscópio óptico, câmera integrada ao computador, mesa de deslocamento dentre outros. / Ostwald ripening is a diffusion-controlled growth process where larger particles grow at the expense of the shrinking, and eventual disappearance, of smaller particles. In this process the mean radius increases and the total number of particles decreases. The theoretical description of this phenomenon is given by the LSW theory, which describes the growth of particles in supersaturated solid solutions. There is a large number of theoretical and experimental works about the of Ostwald ripening, however there is a lack of experimental works with gas bubbles on a macroscopic scale (10-100μm). Thus, it is evident the need to carry out a precise experimental study of the performance of Ostwald ripening of gas bubbles in liquid. The results were obtained by image processing generated by optical videomicroscopy. It is shown the results of the temporal ̄ evolution of the average bubble radius R(t), the number of bubbles N (t), the volume fraction occupied by the bubbles φ(t) and the size distributions f (R, t) for three types of experiment with gas bubbles in a fluid: resting fluid, fluid under macroscopic flow and resting fluid with addition of surfactant. Comparing the results with the theoretical predictions, it has been found that the average radius can, under some conditions, behave according to the growth law predicted ̄ ∼ t 1/3 ), but that in most cases the evolution is slower than expected. by the LSW theory ( R The number of bubbles N (t) decreases more slowly than predicted by the theory (N (t) ∼ t −1 ). There is a discussion about the system being in a transient regime, migrating to the validity regime of the theoretical models, and about the LSW theory not being enough to describe a real system of gas bubbles. All steps were carried out in the Microfluidics and Complex Fluids Laboratory, led by professor Alvaro Vianna N.C. Teixeira, using either the resources or those of and the Department of Physics at UFV, as appropriate softwares for image processing, optical microscope, integrated camera to computer, displacement table etc.

The experiment successfully established the mathematical correlations between the logarithm of retention time of illegal drugs with GC system and the solute descriptor L from the Abraham model. the experiment used the method of Gas Chromatography to analyze the samples of illegal drugs and obtain the retention time of each one. Using the Abraham model to calculate and analyze the sorption coefficient of illegal drugs is an effective way to estimate the drugs. Comparison of the experimental data and calculated data shows that the Abraham linear free energy relationship (LFER) model predicts retention behavior reasonably well for most compounds. It can calculate the solute descriptors of illegal drugs from the retention time of GC system. However, the illegal drugs chosen for this experiment were not all ideal for GC analysis. HPLC is the optimal instrument and will be used for future work. HPLC analysis of the illegal drug compounds will allow for the determination of all the solute descriptors allowing one to predict the illegal drugs behavior in various Abraham biological and medical equations. the results can be applied to predict the properties in biological and medical research which the data is difficult to measure. the Abraham model will predict more accurate results by increasing the samples with effective functional groups.

Die vorliegende Arbeit behandelt Aspekte der Verschlackung von MgO in sekundärmetall-urgischen Schlacken. Mittels FactSage© wird eine Berechnung der Löslichkeit von MgO in Kalksilikat- und Kalkaluminatschlacke bei 1600, 1650 und 1700°C durchgeführt. Die Ergebnisse werden leicht handhab- und ablesbar dargestellt. Die Verschlackung eines porösen MgO-Probekörpers in einer an MgO ungesättigten und an MgO gesättigten Kalkaluminat-schlacke wird bei 1600°C thermogravimetrisch verfolgt. Der Verschlackungsvorgang wird maßgeblich durch die Mechanismen der Teilchendesintegration und Ostwald-Reifung in der infiltrierten Mikrostruktur beeinflusst. Das komplexe Zusammenspiel von Zerfall und Auflösung wird nach einem Modell von W. Gans an feuerfestes Material (MgO) angepasst und modelliert. Der Einfluss von Teilchendesintegration und Ostwald-Reifung auf den voreilenden Verschleiß im 3-Phasenkontakt (Marangoni-Konvektion) wird quantifiziert. Ferner wird ein einfaches Modell zur Abschätzung des voreilenden Verschleißes dargelegt.

Die vorliegende Arbeit behandelt Aspekte der Verschlackung von MgO in sekundärmetall-urgischen Schlacken. Mittels FactSage© wird eine Berechnung der Löslichkeit von MgO in Kalksilikat- und Kalkaluminatschlacke bei 1600, 1650 und 1700°C durchgeführt. Die Ergebnisse werden leicht handhab- und ablesbar dargestellt. Die Verschlackung eines porösen MgO-Probekörpers in einer an MgO ungesättigten und an MgO gesättigten Kalkaluminat-schlacke wird bei 1600°C thermogravimetrisch verfolgt. Der Verschlackungsvorgang wird maßgeblich durch die Mechanismen der Teilchendesintegration und Ostwald-Reifung in der infiltrierten Mikrostruktur beeinflusst. Das komplexe Zusammenspiel von Zerfall und Auflösung wird nach einem Modell von W. Gans an feuerfestes Material (MgO) angepasst und modelliert. Der Einfluss von Teilchendesintegration und Ostwald-Reifung auf den voreilenden Verschleiß im 3-Phasenkontakt (Marangoni-Konvektion) wird quantifiziert. Ferner wird ein einfaches Modell zur Abschätzung des voreilenden Verschleißes dargelegt.

La tension interfaciale est une grandeur physico-chimique d'intérêt pour de nombreuses industries et notamment l'industrie pétrolière. Cette grandeur est l'un des paramètres qui permet d'optimiser le rendement d'un puits de pétrole. La difficulté liée à sa mesure dans les conditions réservoirs a amené à étudier les systèmes eau/tensioactif/huile par simulation moléculaire. Ce travail a permis de montrer que la Dynamique Particulaire Dissipative (DPD) était un outil adapté pour l’étude de systèmes eau/tensioactif/huile sous différents aspects, de la caractérisation de la structure des interfaces au calcul de la tension interfaciale. Cette thèse a permis la démonstration de l’influence non-négligeable de la variation des paramètres de la force harmonique, l’amplitude K et la distance d’équilibre r0 , sur le calcul de la tension interfaciale et sur la structure des interfaces à forte concentration en tensioactif. En effet, la structure des tensioactifs aux interfaces est le résultat d’une balance subtile entre les forces intra et inter moléculaire. L’étude d’une population modèle de tensioactifs non chargés a permis de montrer que la DPD reproduit bien l'évolution de la tension interfaciale en fonction de la concentration en tensioactif en solution et en fonction du coefficient de partage de tensioactifs modèles non chargés. Une méthodologie est proposée pour caractériser les systèmes contenant des interfaces et où la tension interfaciale est calculée.Des travaux prospectifs ont permis de montrer que la DPD permettait d'étudier des phénomènes liés à la tension interfaciale comme le mûrissement d'Ostwald dans les émulsions d'huile dans l'eau. Ces derniers travaux ouvrent la voie à l’étude d’autres systèmes d’intérêt pour le milieu pétrolier comme le décollement de gouttes de pétroles adsorbées sur des parois ou l’étude d’émulsions pétrolières. / The interfacial tension is a physical-chemical property that numerous industrial areas have an interest of especially the petroleum industry. This property is one of the many which helps to optimize production wells' rate of return. Measuring that property in reservoir's conditions (high pressure and temperature) is highly difficult and led to study water/surfactant/oil systems using molecular modeling. The difficulty to measure that specific physical-chemical property linked to the pressure and temperature conditions in the reservoirs led the scientists to study water/surfactant/oil systems using molecular modeling. This thesis establishes that the Dissipative Particle Dynamics (DPD) is able to study water/surfactant/oil systems. The study of the effect of the variation of the harmonic force's parameters, namely the force constant K and the equilibrium distance r0, demonstrated that their variation can heavily influence the interfacial tension computation. Actually, a subtle balance exists between the intra and inter-molecular interactions, which influences the local structure of the surfactants at the oil-water interface, modifies the interfacial tension and influences the interface stability. It was demonstrated that DPD reproduces the variation of interfacial tension with the bulk surfactant concentration and the effect of the variation of hydrophobicity of models of un-charged surfactants on interfacial tension by mean of their coefficient partition. We established a method to properly study systems containing interfaces where interfacial tension is computed. Prospective work showed that DPD was a good tool to study microscopic phenomenon which can be observed macroscopically like the Ostwald ripening in oil in water emulsions. This is a first step before studying others systems of interest for the petroleum industry such as oil/water emulsion or the adsorption of oil droplets on rock wall.

Nanoemulsões são emulsões especiais com glóbulos de tamanho na faixa de 20 a 500 nm. São sistemas que apresentam transparência ou fluidez, favorecendo o aspecto sensorial de espalhabilidade e umectação muito interessantes para produtos cosméticos destinados aos cuidados da pele e produtos para a saúde, atuando como sistemas de liberação de fármacos, além da característica nanométrica, que previne processos de instabilidade física. A queimadura da pele é o quadro resultante da ação direta ou indireta do calor sobre o organismo humano causando inflamação proporcionando intensa ação de radicais livres. A presente pesquisa teve como objetivo desenvolver nanoemulsões à base de óleo de gergelim aditivadas de óleo de framboesa para aplicação em queimaduras de pele. Os óleos de gergelim e framboesa apresentaram atividade antioxidante nos testes de DPPH e Xantina Oxidase. No desenvolvimento das dispersões o método de preparo por baixa energia, fundamentado na mudança de curvatura da molécula do tensoativo, foi induzido pela temperatura de inversão de fase. O resultado desta pesquisa foram duas nanoemulsões utilizando dois tensoativos derivados do óleo de rícino com diferentes etoxilações. A avaliação da estabilidade foi realizada pelo cálculo do principal mecanismo de instabilidade das nanoemulsões, chamado Ostwald ripening. O projeto também propõe uma nova metodologia para a avaliação in vitro- HET-CAM e, in vivo do eritema através da medida pelo Chroma Meter e transformação em escala dos resultados. A pesquisa demonstrou que as nanoemulsões não preveniram o processo de queimadura da pele dos camundongos hairless, mas sugere uma tendência mais rápida à redução do eritema. / Nanoemulsions are special systems with uniform and extremely small droplet size, in the range of 20500 nm. Due to their characteristic size, some nanoemulsions are optically transparent or translucent and have kinetic stability, low viscosity, that result in excellent espalhability and humectation making them of increasing use in many applications, for example, in cosmetics as personal care formulations, and in pharmaceutical field as drug delivery systems. The skin burn is the result of direct or indirect hot effect over human organism. This situation provokes an inflammatory process with intense action of reactive oxygen species. The aim of this research was the development of sesame indicum oil-based nanoemulsions with raspberry oil for application in skin burn. The sesame and raspberry oils presented antioxidant activity in DPPH test and Oxidase Xantine system. The dispersions were obtained by low energy method, that was based on curvature change of surfactant molecule induced for temperature. It was obtained two nanoemulsions using different surfactant castor oil derivative etoxilated. The stability assessement was realized with the calculation of main instability mechanism, the Oswald ripening rate. This Project has been carried out with an in vitro method to evaluate the toxicity (HET-CAM) and antioxidant activity (DPPH and Xantine Oxidase), and in vivo erytem evaluation with Chroma Meter. The results of in vivo test was transformed in a score, that reflected the level of erythema. This work demonstred nanoemulsion hasn´t prevented the skin burn in hairless rats, but there was a tendency to decrease the erythema.

Nanoemulsões são emulsões especiais com glóbulos de tamanho na faixa de 20 a 500 nm. São sistemas que apresentam transparência ou fluidez, favorecendo o aspecto sensorial de espalhabilidade e umectação muito interessantes para produtos cosméticos destinados aos cuidados da pele e produtos para a saúde, atuando como sistemas de liberação de fármacos, além da característica nanométrica, que previne processos de instabilidade física. A queimadura da pele é o quadro resultante da ação direta ou indireta do calor sobre o organismo humano causando inflamação proporcionando intensa ação de radicais livres. A presente pesquisa teve como objetivo desenvolver nanoemulsões à base de óleo de gergelim aditivadas de óleo de framboesa para aplicação em queimaduras de pele. Os óleos de gergelim e framboesa apresentaram atividade antioxidante nos testes de DPPH e Xantina Oxidase. No desenvolvimento das dispersões o método de preparo por baixa energia, fundamentado na mudança de curvatura da molécula do tensoativo, foi induzido pela temperatura de inversão de fase. O resultado desta pesquisa foram duas nanoemulsões utilizando dois tensoativos derivados do óleo de rícino com diferentes etoxilações. A avaliação da estabilidade foi realizada pelo cálculo do principal mecanismo de instabilidade das nanoemulsões, chamado Ostwald ripening. O projeto também propõe uma nova metodologia para a avaliação in vitro- HET-CAM e, in vivo do eritema através da medida pelo Chroma Meter e transformação em escala dos resultados. A pesquisa demonstrou que as nanoemulsões não preveniram o processo de queimadura da pele dos camundongos hairless, mas sugere uma tendência mais rápida à redução do eritema. / Nanoemulsions are special systems with uniform and extremely small droplet size, in the range of 20500 nm. Due to their characteristic size, some nanoemulsions are optically transparent or translucent and have kinetic stability, low viscosity, that result in excellent espalhability and humectation making them of increasing use in many applications, for example, in cosmetics as personal care formulations, and in pharmaceutical field as drug delivery systems. The skin burn is the result of direct or indirect hot effect over human organism. This situation provokes an inflammatory process with intense action of reactive oxygen species. The aim of this research was the development of sesame indicum oil-based nanoemulsions with raspberry oil for application in skin burn. The sesame and raspberry oils presented antioxidant activity in DPPH test and Oxidase Xantine system. The dispersions were obtained by low energy method, that was based on curvature change of surfactant molecule induced for temperature. It was obtained two nanoemulsions using different surfactant castor oil derivative etoxilated. The stability assessement was realized with the calculation of main instability mechanism, the Oswald ripening rate. This Project has been carried out with an in vitro method to evaluate the toxicity (HET-CAM) and antioxidant activity (DPPH and Xantine Oxidase), and in vivo erytem evaluation with Chroma Meter. The results of in vivo test was transformed in a score, that reflected the level of erythema. This work demonstred nanoemulsion hasn´t prevented the skin burn in hairless rats, but there was a tendency to decrease the erythema.

La règle des phases d'Ostwald classiquement utilisée pour justifier la cristallisation d'un système polymorphique, stipule que la phase métastable apparait en premier puis subit une transition polymorphique vers la phase stable. Les modèles classiques, qui ne considèrent que la nucléation et la croissance, ne permettent pas de refléter l'avantage cinétique de la phase métastable formulé par la règle d'Ostwald. Cette étude propose d'étudier et de mieux comprendre la cristallisation d'un système polymorphe en prenant en compte le mécanisme de mûrissement d'Ostwald, habituellement négligé. Un produit modèle, l'acide L-Glutamique, est choisi pour l'étude expérimentale menée en milieu agité et stagnant. Deux modèles, l'un basé sur les bilans de population, l'autre basé sur les équations cinétiques, sont développés et qualitativement comparés pour simuler le comportement expérimental des phases polymorphes. Alors que le modèle de bilan de population s'avère limité, le modèle des équations cinétiques a permis de souligner l'effet du mécanisme de mûrissement sur la compétition entre les phases polymorphes et de valider, ainsi, une nouvelle explication pour la règle des phases d'Ostwald / The Ostwald rule of stages is conventionally used to explain the crystallization behavior of a polymorphic system. It states that the metastable phase first appears and undergoes a polymorphic transition toward the stable phase, in a second step. The Classical models, which only consider nucleation and growth, fail to reflect the kinetic advantage of the metastable phase formulated by Ostwald’s rule. Hence, this work intends to study and better understand the crystallization of a polymorphic system, taking into account the Ostwald ripening mechanism, usually neglected. A model compound, L-Glutamic acid, is chosen for the experimental study in agitated and stagnant conditions. Two numerical models, one based on the population balance equation and the other based on the kinetic equations, are developed to simulate the behavior of that polymorphic system, observed experimentally. A qualitative comparison between these two models is proposed. The model that relates the population balance equation does not permit correct implementation of all the mechanisms. Conversely, the model based on the kinetic equations highlights the effect of the ripening mechanism on the competition between the two polymorphic phases and allows us to propose a new explanation of the Ostwald rule of stages