No description available.

No description available.

<p>Three chiral selectors (diketogulonic acid, benzoxycarbonylglycylproline and ketopinic acid) have been introduced for enantioseparation of pharmacologically active amines in non-aqueous capillary electrophoresis. The use of organic solvents, instead of aqueous buffers in the background electrolyte facilitated ion-pair formation between the analytes and the chiral selectors. The enantioresolution was strongly affected by the choice of selector and organic solvent but also depended on the other electrolytes. The most important parameter for the enantioresolution, apart from the choice of chiral selector, was the direction and magnitude of the electro-osmosis. Thus, covalently coated capillaries were used to suppress and to reverse this flow. Furthermore, the alkali metal hydroxide added to the background electrolyte had a great influence on the electro-osmosis. Exchanging LiOH for NaOH, was found to decrease the electro-osmotic flow. Interestingly, the flow was altered from cathodic to anodic, with KOH, RbOH or CsOH added to the ethanolic BGE. The occurrence of a reversed electro-osmosis had a great positive effect on the enantioresolution. An appropriate choice of solvent and electrolytes promoted also fast chiral separations, e.g., the enantiomers of isoprenaline were resolved within one minute. </p><p>The capillary electrophoresis systems developed within this work were applied for enantiomeric purity determinations of different pharmaceutical forms of drug products. A detection limit of 0.033 % was achieved for <i>1S,2R</i>-ephedrine, the enantiomeric impurity in Efedrin®, when diketogulonic acid was used as the selector. </p><p>By using the pre-concentration technique, transient isotachophoresis, the peak efficiency was enhanced for the enantiomers of timolol. This facilitated the introduction of a higher concentration of the sample into the capillary electrophoretic system containing ketopinic acid as the selector, and lowered the detection limit from 2.5 % to 0.2 % for the enantiomeric impurity <i>R</i>-timolol compared with injection without transient isotachophoresis.</p><p>The volatility of the non-aqueous media in capillary electrophoresis facilitated the hyphenation to mass spectrometry. The partial filling technique ensured that the selector did not contaminate the mass spectrometer, and the separated enantiomers of e.g., pronethalol were detected in the selector-free zone. </p>

Three chiral selectors (diketogulonic acid, benzoxycarbonylglycylproline and ketopinic acid) have been introduced for enantioseparation of pharmacologically active amines in non-aqueous capillary electrophoresis. The use of organic solvents, instead of aqueous buffers in the background electrolyte facilitated ion-pair formation between the analytes and the chiral selectors. The enantioresolution was strongly affected by the choice of selector and organic solvent but also depended on the other electrolytes. The most important parameter for the enantioresolution, apart from the choice of chiral selector, was the direction and magnitude of the electro-osmosis. Thus, covalently coated capillaries were used to suppress and to reverse this flow. Furthermore, the alkali metal hydroxide added to the background electrolyte had a great influence on the electro-osmosis. Exchanging LiOH for NaOH, was found to decrease the electro-osmotic flow. Interestingly, the flow was altered from cathodic to anodic, with KOH, RbOH or CsOH added to the ethanolic BGE. The occurrence of a reversed electro-osmosis had a great positive effect on the enantioresolution. An appropriate choice of solvent and electrolytes promoted also fast chiral separations, e.g., the enantiomers of isoprenaline were resolved within one minute. The capillary electrophoresis systems developed within this work were applied for enantiomeric purity determinations of different pharmaceutical forms of drug products. A detection limit of 0.033 % was achieved for 1S,2R-ephedrine, the enantiomeric impurity in Efedrin®, when diketogulonic acid was used as the selector. By using the pre-concentration technique, transient isotachophoresis, the peak efficiency was enhanced for the enantiomers of timolol. This facilitated the introduction of a higher concentration of the sample into the capillary electrophoretic system containing ketopinic acid as the selector, and lowered the detection limit from 2.5 % to 0.2 % for the enantiomeric impurity R-timolol compared with injection without transient isotachophoresis. The volatility of the non-aqueous media in capillary electrophoresis facilitated the hyphenation to mass spectrometry. The partial filling technique ensured that the selector did not contaminate the mass spectrometer, and the separated enantiomers of e.g., pronethalol were detected in the selector-free zone.

Dans cette thèse, on a étudié l’évolution de l’interface par électro-osmose entre deux couches de fluides dans un canal microfluidique. Les applications de ce problème concernent le mélange et le transport, sans contact avec des actionneurs, de fluides en micro-canal. De nombreuses questions restent toutefois posées lorsque le champ est oscillant en temps, notamment vis à vis de la stabilité de l'interface entre les deux fluides. Une analyse de stabilité linéaire basée sur une perturbation à l’interface a été réalisée pour un film mince d'électrolyte sous des champs électriques continus (constants) et alternatifs (dépendant du temps). Une analyse asymptotique avec une hypothèse de grande longueur d’onde des équations d'Orr-Sommerfeld a été appliquée afin de déterminer les seuils de stabilité paramétriques d'un film mince aqueux. L’accent a été mis sur les effets de la tension de surface, de la pression de disjonction pour l'interaction gaz-liquide-substrat, de l'amplitude et de la fréquence du champ électrique appliqué, ainsi que du potentiel zêta du substrat et de la surface libre. Une analyse comparative des profils de vitesse de l’état de base avec et sans contraintes de Maxwell à l’interface, a montré que les gradients de vitesse étaient importants à l'interface liquide-liquide avec les contraintes de Maxwell. De tels gradients sont essentiels à l'instabilité interfaciale sous l’action d’un champ électrique périodique car ils peuvent atténuer ou amplifier les ondes à l’interface. Parallèlement, un dispositif expérimental a été conçu et monté afin de caractériser l’écoulement électroosmotique dans un micro-canal rectangulaire. Avec l'aide d'une analyse PTV (« Particle Tracking Velocimetry »), les distributions de vitesse ont été obtenues et comparées aux prédictions théoriques. Cette comparaison a permis d’estimer le potentiel zêta du PDMS utilisé, valeur conforme à la valeur indiquée dans la littérature. / Since the past decade, use of electro-osmotic flow (EOF) as an alternative flow mechanism in microdevices is becoming more popular due to its less bulky and low maintenance system design. However, one of the biggest shortcomings for its usage in mainstream applications is that it requires the concerned liquid to be electrically conductive. One idea can be to use the flow of conductive fluids to transport non-conductive liquids passively via interfacial shear transfer. Such an idea can has numerous applications in a wide range of fields like bio-chemical processing (e.g. lab-on-a-chip reactors, mixers, etc.), to oil extraction from porous rock formations. One of the significant characteristics of micro-scale flows is high surface to volume ratio, which significantly highlights the role of multi-phase interfaces in such dynamics. The presence of a fluid-fluid interface in an EOF necessitates the characterization of the parameters responsible for hydrodynamic instability of such systems. The present work focuses on the role of steady and time-dependent electric stress (Maxwell stress), capillary force and disjoining pressure on fluid-fluid interfacial instability. A linear stability analysis of interfacial perturbation was performed for a thin film of electrolyte under DC and AC electric fields. Through long wave asymptotic analysis of the Orr-Sommerfeld equations, parametric stability thresholds of a thin aqueous film explored. Further, a set of experiments were performed in order to characterize the EOF in a rectangular microchannel. With the help of a Particle Tracking Velocimetry analysis, velocity distributions were obtained which agreed well to the theoretical values. This was further used to estimate PDMS zeta potential, which was found to be within the reported values in the existing literature. Liquid-liquid interfacial deformation was also explored under a time-periodic EOF and a wide range of the magnitudes of capillary force, and diffusive and convective transport.

No description available.

En el caso del almacenamiento de los residuos radioactivos los flujos osmóticos pueden ser relevantes y requieren un análisis en detalle. El residuo nuclear bituminizado (BW) será almacenado mediante contenedores en cavidades excavadas en la Boom Clay, que es una arcilla marina que presenta propiedades favorables para limitar y retrasar la migración de los contaminantes radioactivos. La interacción entre los dos materiales es un proceso acoplado químico-hidro-mecánico y depende de la respuesta hidromecánica de la Boom Clay y del BW. En condiciones de almacenamiento, el contacto del BW, que contienen cantidades importantes de NaNO3, con el agua subterránea induce la hidratación por gradientes osmóticos y el consiguiente hinchamiento, además de la difusión de la sal disuelta hacia la Boom Clay. Se pueden distinguir dos tipos de afecciones: la perturbación geomecánica causada por el hinchamiento del BW y el aumento de presión en el BW y cambio de las distribución de tensiones en la roca, y la perturbación físico química por la migración de grandes cantidades de sales. El objetivo de esta tesis es: (i) Mejorar la comprensión de los procesos que controlan la absorción de agua y el consecuente hinchamiento del BW que contengan sales (NaNO3), y (ii) Investigar los posibles efectos de la concentración de fluidos de los poros sobre el hinchamiento, la compresibilidad y comportamiento de corte de la Boom Clay. En primer lugar, se ha desarrollado una formulación para el análisis de la deformación inducida por la disolución de sales en medio poroso con contacto con agua. Las ecuaciones planteadas incluyen los flujos acoplados de agua y soluto. Se presenta también un trabajo teórico que ayuda a la comprensión del comportamiento mecánico del BW. Se considera este material como una mezcla de bitumen y cristales de NaNO3. Se ha desarrollado un modelo elasto-viscoplástico que describe el comportamiento de fluencia del BW considerando el comportamiento de fluencia de sus constituyentes. El modelo constitutivo elasto-viscoplástico ha sido implementado en el programa CODE_BRIGHT. Los resultados se han comparado con observaciones experimentales. Se ha estudiado el comportamiento a largo plazo del BW en contacto con agua al simular ensayos de hinchamiento por absorción de agua bajo condiciones confinadas. El análisis numérico ha demostrado ser capaz de proporcionar una representación satisfactoria de los principales patrones observados en su comportamiento. En lo que respecta al segundo objetivo de la tesis, se ha propuesto una formulación para el análisis de las deformaciones inducidas por procesos osmóticos en un medio poroso de doble estructura. Esta formulación distingue dentro del material un nivel micro-estructural y otro macro-estructural con cambios químicos que tienen un efecto significativo en la micro-estructura. Se han obtenido las ecuaciones básicas que describen los flujos acoplados de agua y solutos y el transporte de sus componentes a través de los macroporos así como las ecuaciones de balance de masa para agua y soluto en los macroporos y microporos. La formulación propuesta ha sido aplicada particularmente para analizar cualitativamente el efecto de la succión osmótica sobre el hinchamiento de los suelos arcillosos. Se han analizado los efectos a corto y largo plazo. Se ha investigado también la influencia del aumento de la concentración del fluido en los poros sobre las propiedades geotécnicas y el comportamiento de la Boom Clay no saturada. Se ha llevado a cabo un programa sistemático de investigación experimental, con control de succión osmótica y matricial, con el fin de investigar el efecto del incremento de la concentración del fluido de poros sobre la resistencia de corte y el cambio volumétrico bajo condiciones edométricas. Se ha observado, que bajo condiciones parcialmente saturadas, un cambio en la salinidad provoca una disminución en la compresibilidad y en la resistencia de corte del material. / For deep storage of high-level nuclear waste osmotic flows can be significant and so require a careful analysis. In Belgium, The bituminized nuclear waste (BW) named Eurobitum contained in metallic drums will be placed inside a tunnel or a shaft excavated in the Boom Clay, which is 100 m thick marine clay presenting favourable properties to limit and delay the migration of the leached radionuclides over extended periods of time. In Geological disposal conditions, contact of the bituminized radioactive waste which contains high amounts of highly soluble salt (NaNO3) with groundwater will result in water uptake and swelling of the waste and in subsequent diffusion of the dissolved salt through the host clay formation. Basically, two types of disturbance can be distinguished: A geo-mechanical perturbation, caused by the swelling of the waste and the increase of the pressure in and around the waste and a physico-chemical perturbation by the release of large amounts of NaNO3 and other soluble salts. In this context the aim of this thesis is: (i) to improve the understanding of the processes controlling the water uptake and the subsequent swelling of bituminized waste containing soluble salts (NaNO3), and (ii) to investigate of the possible effects of the increase of pore fluid concentration on swelling, compressibility and shear behaviour of Boom Clay. A formulation has been proposed for the analysis of deformation induced by dissolution of salts in porous media in contact with water. The equations include the effect of coupled transport phenomena and the formulation has been included as an extension in the coupled THM program CODE_BRIGHT. A theoretical and experimental work aiming at understanding the mechanical behaviour of the Bituminized Waste has been presented.This material is considered for this purpose as a mixture of bitumen and crystals of NaNO3. An elasto-viscoplastic model has been developed that describes the creep behaviour of BW considering the constituents' creep behaviour. The elasto-viscoplastic constitutive model has been implemented into CODE_BRIGHT. The modelling results have been compared with the experimental data. The impact of osmotic forces on the swelling of the material has been investigated by simulating water uptake swelling tests under confined conditions and comparing the predictions with experimental results. The numerical analysis has proven to be able to furnish a satisfactory representation of the main observed patterns of the behaviour. In regard to the second objective of this thesis, a formulation has been proposed for the analysis of deformations induced by osmotic processes in double structure porous media. The formulation is based on the distinction within the material of a microstructural and a macrostructural levels with chemical changes having a significant effect on the microstructure. A macroscopic description of the system is provided. Then the basic equations describing coupled flows of water and solutes and the transport of its components through macropores and mass balance equations for water and solute in macro and micro pores have been obtained. The proposed formulation has been particularly applied to analyze qualitatively the effect of osmotic suction on swelling of clayey soils. Transient and long term effects have been analyzed. The influence of pore fluid concentration on the geotechnical properties and behavior of Boom Clay under partially saturated conditions has been investigated. A systematic experimental research program involving osmotic suction and matric suction controlled experiments has been carried to investigate the effect of the increase of pore fluid concentration on shear strength and on the volume change behaviour under odometer stress state conditions. It has been observed that under partially saturated conditions a change in salinity causes a decrease in compressibility and shear strength.

Since the past decade, use of electro-osmotic flow (EOF) as an alternative flow mechanism in microdevices is becoming more popular due to its less bulky and low maintenance system design. However, one of the biggest shortcomings for its usage in mainstream applications is that it requires the concerned liquid to be electrically conductive. One idea can be to use the flow of conductive fluids to transport non-conductive liquids passively via interfacial shear transfer. Such an idea can has numerous applications in a wide range of fields like bio-chemical processing (e.g. lab-on-a-chip reactors, mixers, etc.), to oil extraction from porous rock formations. One of the significant characteristics of micro-scale flows is high surface to volume ratio, which significantly highlights the role of multi-phase interfaces in such dynamics. The presence of a fluid-fluid interface in an EOF necessitates the characterization of the parameters responsible for hydrodynamic instability of such systems. The present work focuses on the role of steady and time-dependent electric stress (Maxwell stress), capillary force and disjoining pressure on fluid-fluid interfacial instability. A linear stability analysis of interfacial perturbation was performed for a thin film of electrolyte under DC and AC electric fields. Through long wave asymptotic analysis of the Orr-Sommerfeld equations, parametric stability thresholds of a thin aqueous film explored. Further, a set of experiments were performed in order to characterize the EOF in a rectangular microchannel. With the help of a Particle Tracking Velocimetry analysis, velocity distributions were obtained which agreed well to the theoretical values. This was further used to estimate PDMS zeta potential, which was found to be within the reported values in the existing literature. Liquid-liquid interfacial deformation was also explored under a time-periodic EOF and a wide range of the magnitudes of capillary force, and diffusive and convective transport.