Die Methode der Reaktiven Abscheidung wurde benutzt, um zu untersuchen ob und in welcher Weise das Silicidwachstum mittels einer Monolage aus Sb, d.h. mittels eines surfactant (surface active agent), gesteuert werden kann. Hierzu wurden unter UHV-Bedingungen die Metalle Mn, Ti und Ni auf geheizte Si(001) bzw. Si(001)-Sb Substrate abgeschieden. Die Probenanalyse erfolgte durch LEED, RBS, XRD, SEM, TEM und AFM. Die Theorie zum surfactant-gesteuerten Wachstum wird vorgestellt und auf das System des reaktiven Silicidwachstums übertragen. Die Probenanalysen zeigen, dass eine Monolage von Sb in der Lage ist das Wachstum der drei untersuchten Silicide zu beeinflussen. Für das System der Höheren Mangansilicide kommt es zu einer Erhöhung der Inseldichte um bis zu zwei Größenordnungen und zu Änderungen in den Orientierungsbeziehungen der Silicidinseln. Beim Wachstum der Titansilicidschichten konnte durch das surfactant die pinhole-Bildung unterdrückt werden. Das dritte untersuchte Silicid ist das Nickeldisilicid. In diesem Fall wird der Ort der Keimbildung von der Si-Oberfläche in das Volumen des Si-Substrates verschoben, d.h. die Oberfläche wird vollständig passiviert, zusätzlich treten neue Orientierungsbeziehungen auf.

Cette thèse vise à contribuer à la caractérisation, à l’aide de modélisation et d’expérience, de la dynamique de bulle en microfluidique. Deux régimes d’écoulements rencontrés en microfluidique sont étudiés, le régime bubbly flow et le régime Taylor flow. En particulier, la première partie de cette thèse traite de la dynamique d’un écoulement de type bubbly flow dans un microcanal rectiligne de section circulaire en présence de surfactants. Le code de calcul numérique JADIM est utilisé. Une méthode numérique permettant, d’une part, de simuler le transport de surfactants le long d’une interface qui bouge et qui se déforme, et d’autre part, de simuler l’effet Marangoni crée par une distribution inhomogène de ces surfactants sur cette interface, est implémentée et validée. Les simulations effectuées avec ce code concernant la dynamique d’un écoulement de type bubbly flow montrent par exemple que, le confinement créé par les parois du microcanal résulte en une distribution des surfactants sur la surface des bulles qui est fondamentalement différente d’une distribution rencontrée dans le cas d’une bulle qui se déplace dans un liquide de dimension infinie. En effet, les surfactants s’accumulent en des locations spécifiques sur la surface des bulles et créent des forces de Marangoni locale, qui influencent drastiquement la dynamique des bulles. Dans certains cas, les surfactants peuvent même engendrer une désintégration de la bulle, un mécanisme qui est rationalisé par un bilan de force à l’arrière de la bulle. La méthode numérique implémentée dans cette thèse est également utilisée pour un problème pratique concernant la production artisanale de Mezcal, une boisson alcoolisée produite au Méxique. La seconde partie de cette thèse traite de la dynamique d’un écoulement de type Taylor flow, à l’aide d’expérience et de modélisation. Une méthode expérimentale permettant de mesurer l’épaisseur du film de lubrification qui se forme entre une bulle de Taylor et les parois du microcanal est développée. Cette méthode requiert uniquement une image « brightfield » de la bulle. En plus de la mesure de l'epaisseur du film de lubrification, la méthode permet aussi de mesurer la profondeur du microcannal. Enfin, l'utilisation de la méthode proposée couplée à la mesure de la vitesse de translation de la bulle permet de déduire la tension de surface de celle-ci. Dans le dernier chapitre de cette thèse, l'influence des effets gravitaires sur la dynamique des écoulements de Taylor est quantifiée. Quoique souvent négligée en microfluidique, il est montré que les effets gravitaires peuvent avoir un impact significatif sur la dynamique des écoulements de Taylor. Ces impacts sont quantifiés à l'aide d'expériences et de modélisations. Ce travail a été réalisé à la Princeton University avec Professeur Howard A. Stone pendant un séjour de 7 mois. / This thesis aims at contributing to the characterization of the dynamics of bubbles in microfluidics through modeling and experiments. Two flow regimes encountered in microfluidics are studied, namely, the bubbly flow regime and the Taylor flow regime (or slug flow). In particular, the first part of this thesis focuses on the dynamics of a bubbly flow inside a horizontal, cylindrical microchannel in the presence of surfactants using numerical simulations. A numerical method allowing to simulate the transport of surfactants along a moving and deforming interface and the Marangoni stresses created by an inhomogeneous distribution of these surfactants on this interface is implemented in the Level set module of the research code. The simulations performed with this code regarding the dynamics of a bubbly flow give insights into the complexity of the coupling of the different phenomena controlling the dynamics of the studied system. Fo example it shows that the confinement imposed by the microchannel walls results in a significantly different distribution of surfactants on the bubble surface, when compared to a bubble rising in a liquid of infinite extent. Indeed, surfactants accumulate on specific locations on the bubble surface, and create local Marangoni stresses, that drastically influence the dynamics of the bubble. In some cases, the presence of surfactants can even cause the bubble to burst, a mechanism that is rationalized through a normal stress balance at the back of the bubble. The numerical method implemented in this thesis is also used for a practical problem, regarding the artisanal production of Mezcal, an alcoholic beverage from Mexico. The second part of the thesis deals with the dynamics of a Taylor flow regime, through experiments and analytical modeling. An experimental technique that allows to measure the thickness of the lubrication film forming between a pancake-like bubble and the microchannel wall is developed. The method requires only a single instantaneous bright-field image of a pancake-like bubble translating inside a microchannel. In addition to measuring the thickness of the lubrication film, the method also allows to measure the depth of a microchannel. Using the proposed method together with the measurment of the bubble velocity allows to infer the surface tension of the interface between the liquid and the gas. In the last chapter of this thesis, the effect of buoyancy on the dynamics of a Taylor flow is quantified. Though often neglected in microfluidics, it is shown that buoyancy effects can have a significant impact on the thickness of the lubrication film and consequently on the dynamics of the Taylor flow. These effects are quantified using experiments and analytical modeling. This work was performed at Princeton University with Professor Howard A. Stone during a seven month stay.

The intercalation of surfactant anions, namely sodium dodecyl sulphate, sodium benzene sulphonate and lauric acid, into commercial layered double hydroxides (LDH-CO3) with approximate composition [Mg0.654AI0.346 (OH)2](CO3)0.173.0.5H2O] was explored. LDH-CO3 is commercially available in bulk form owing to its large scale applications as a PVC stabiliser and acid scavenger in polyolefins. It is therefore of interest to investigate intercalation methods using LDH-CO3 as starting material. The intercalation method used was compared with the pre existing procedures, for instance the co-precipitation, ion exchange and regeneration methods. Due to the tenacity with which the carbonate ion is held in LDH-CO3, direct ion exchange is an intricate matter. Hence, in the regeneration method the carbonate ion is removed by thermal treatment and the LDH-surfactant is obtained by reaction of the LDH and surfactant in an aqueous medium. Nevertheless, the resulting products are impure and poorly crystallised, and only partial intercalation is achieved. The underlying principle of the current method is protonation of the carbonate anion to a monovalent anion that is easily exchanged with surfactant anions. Improved results were obtained when water-soluble organic acids were used, the most suitable being lower aliphatic carboxylic acids, e.g. acetic, butyric and hexanoic acid. In contrast, higher linear aliphatic carboxylic acids are preferentially intercalated to the anionic surfactants. In both cases the carboxylic acids are assumed to assist intercalation by facilitating the elimination of the carbonate ions present in the anionic clay galleries. X-ray diffraction analysis, thermal analysis and infrared spectroscopy confirmed the monolayer intercalation of LDH-dodecyl sulphate and LDH-dodecylbenzene sulphonate. In contrast, LDH-laurate featured a bilayer structure. / Dissertation (MSc)--University of Pretoria, 2009. / Chemistry / unrestricted

Warfarin is a well-known anticoagulant drug that is used to prevent cardiovascular disease and blood coagulation such as thrombosis. In this study, the main aim was to investigate the photo physical characteristics of warfarin in the different molecular environments provided by sodium dodecyl sulfate (SDS) micelles by using ultraviolet absorption and fluorescence emission spectroscopic techniques. Warfarin and a structural analogue not existing in solution as a cyclic hemiketal, phenprocoumon, were mixed with different concentrations of SDS and spectral changes for these warfarin and phenprocoumon were recorded. Interestingly, results demonstrated, based on an evident increase in the absorption intensity at 273 nm and an evident blue shift in the fluorescence emission spectrum after the addition of an increasing concentration of SDS, that primarily the cyclic hemiketal isomer of warfarin was found to be solvated by SDS micelles at an apparent recorded critical micelle concentration of ~8mM.  Altogether these observations suggest that warfarin may be used as a molecular probe to explore the polarities of complex colloidal mixtures. Moreover, the possibility of using micelles for controlling the isomeric state of warfarin is interesting and can potentially be used for better controlling dosage of warfarin thereby reducing side effects.

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[pt] O uso de surfactantes zwitteriônicos em projetos de recuperação avançada de petróleo está limitado à adsorção na superfície da rocha-reservatório, que deve ser prevista para determinar a viabilidade econômica desses projetos. Porém, existe uma falta de modelos capazes de estimar essa adsorção e explicar os mecanismos envolvidos. O objetivo do trabalho foi providenciar modelos que pudessem estimar a adsorção de um surfactante zwitteriônico (CAPB), e explicar seus mecanismos de adsorção. Os experimentos foram realizados em rochas do tipo carbonato e arenito, através de testes com rocha particulada (estáticos) e no interior de núcleos de rocha (dinâmicos). Foi desenvolvida uma metodologia para quantificar o CAPB em salmoura utilizando a cromatografia líquida de alta eficiência. Como um diferencial, a adsorção foi normalizada pela área superficial específica da rocha, através de análise BET (testes estáticos) e microtomografia com (micro)CT-scan (testes dinâmicos). Os resultados foram interpretados com modelos empíricos e teóricos integrados às estimativas de potencial de superfície. Verificou-se para o carbonato, que a primeira camada de adsorção segue um padrão homogêneo, limitada por repulsão eletrostática com a superfície, enquanto a segunda camada segue uma adsorção heterogênea, onde são formados agregados de surfactante mediados por interações hidrofóbicas entre as caudas. Para o arenito, as duas camadas têm uma distribuição heterogênea, explicando a maior adsorção entre as duas rochas. Concluiu-se que os modelos de dupla camada são capazes de explicar e estimar a adsorção em condições de fluxo de forma confiável e a área superficial foi o fator mais relevante na diferença de adsorção dinâmica entre rochas, favorecida no arenito. / [en] The use of zwitterionic surfactants in enhanced oil recovery projects is limited to adsorption on the surface of the reservoir rock, which must be predicted to determine the economic feasibility of these projects. However, there is a lack of models capable of estimating this adsorption and explaining the involved mechanisms. The objective of this study was to provide models that could estimate the adsorption of a zwitterionic surfactant (CAPB) and explain its adsorption mechanisms. Experiments were conducted on carbonate and sandstone rocks using static tests with particulate rock and dynamic tests within rock cores. A methodology was developed to quantify CAPB in brine using high-performance liquid chromatography. As a distinguishing feature, the adsorption was normalized by the specific surface area of the rock, determined through BET analysis (static tests) and microtomography with (micro)CT-scan (dynamic tests). The results were interpreted with empirical and theoretical models integrated with surface potential estimates. For carbonate, it was observed that the first layer of adsorption follows a homogeneous pattern, limited by electrostatic repulsion with the surface, while the second layer follows heterogeneous adsorption, forming surfactant aggregates mediated by hydrophobic interactions between the tails. For sandstone, both layers exhibit a heterogeneous distribution, explaining the higher adsorption between the two rocks. It was concluded that bilayer models are capable of reliably explaining and estimating adsorption under flow conditions, and the surface area was the most relevant factor in the difference of dynamic adsorption between rocks, favored in sandstone.

The use of nanofluids as heat transfer fluids has received a lot of attention from the heat transfer research community. Due to the increased thermal conductivity of nanofluids over their base fluids, the number of nanofluids scientific publications increased significantly in the past decade. The effects of the heated surface roughness, nanoparticles and surfactant concentrations on pool boiling of nanofluids have been thoroughly investigated. However, contradicting findings have been observed under what appeared to similar test conditions. In this experimental investigation, two boiling surfaces have been prepared with an average surface roughness of 6 and 60 nm using high precision machining. Alumina Oxide-Water based nanofluids have been used in this investigation. The initial nanoparticle size reported by the manufacturer is 10 nm. The nanoparticles concentration has been kept at 0.05 wt. %. A Sodium Dodecylbenzenesulfonate (SDBS) surfactant has been added to the nanofluids in order to improve its stability. Results showed that the nanofluids boiling performance depended on the boiling surface roughness. The heat transfer coefficient (HTC) obtained in the case of the smooth, mirror finished surface showed an enhancement of 205% with respect to pure water. This trend was reversed in the case of the rough surface which is believed to be due to significant nanoparticles deposition. The HTC obtained with the rough surface was 12% lower than that of pure water. The effect of the surfactant concentration on nanoparticles deposition has been investigated by changing the surfactant concentration from 0.1 to 1.0 wt. %. In the case of the rough surface, the increase of surfactant concentration was found to reduce the formation of the nanoparticles deposition layer. The HTC obtained with the higher surfactant concentration was increased by 46 %. The effect of nanoparticles concentration on the smooth surface shows an unexpected trend of 20 % reduction of the transfer rate of the nanofluids coupled with the increase of the nanoparticle concentration from 0.05 to 0.1 wt. %. However all concentrations showed heat transfer enhancement with respect to pure water. The minimum heat transfer coefficient ratio enhancement was 11 % using 0.1 wt. % nanofluids with respect to pure water. Since nanoparticles deposition has been observed and attributed to micro-layer evaporation, an investigation has been carried out to examine the nucleation process during the pure water and nanofluids pool boiling. The bubble growth rate in both cases was analyzed at different wall degrees of superheat ranging from 104.3 to 105.9 ºC. In addition, the bubble departure diameter and frequency have been measured and compared for both cases. The nanofluid bubble size was about 80 % smaller than that of pure water. The nanofluid bubble departure had almost constant frequency of 500 Hz over the range of wall superheats whereas the maximum bubble frequency in the case of pure water was 22.72 Hz. / Thesis / Master of Applied Science (MASc)

The surfactant protein-G (SP-G) has recently been discovered in the brain and linked to fluid balance regulations. Stroke is characterized by impaired vessel integrity, promoting water influx and edema formation. The neurovascular unit concept (NVU) has been generated to cover not only ischemic affections of neurons or vessels but also other regionally associated cells. This study provides the first spatio-temporal characterization of SP-G and NVU elements after experimental stroke. Immunofluorescence labeling was applied to explore SP-G, vascular and cellular markers in mice (4, 24, and 72 h of ischemia), rats (24 h of ischemia), and sheep (two weeks of ischemia). Extravasated albumin indicated vascular damage within ischemic areas. Quantifications revealed decreasing SP-G signals in the ischemia-affected neocortex and subcortex. Inverse immunosignals of SP-G and vascular elements existed throughout all models. Despite local associations between SP-G and the vasculature, a definite co-localization was not seen. Along with a decreased SP- G-immunoreactivity in ischemic areas, signals originating from neurons, glial elements, and the extracellular matrix exhibited morphological alterations or changed intensities. Collectively, this study revealed regional alterations of SP-G, vascular, and non-vascular NVU elements after ischemia, and may thus stimulate the discussion about the role of SP-G during stroke.