No description available.

High speed and/or high efficiency separations can be realized using small particles (~ 1 µm) in liquid chromatography (LC). However, due to the large pressure drop caused by small particles, conventional LC pumping systems cannot satisfy the pressure requirements needed to drive the mobile phase through the column. Use of ultrahigh pressure, elevated temperature, or both can overcome these pressure limitations and allow the use of very small particles for high speed and/or high efficiency separations. In this dissertation, the use of ultrahigh pressures with and without elevated temperatures in capillary LC is described. Very fast separations of various samples on silica-based stationary phases were achieved using optimized equipment and conditions. Great reduction in separation time, while maintaining high efficiency, is the most significant result of this work. Mechanically, chemically and thermally stable new packing materials were required for this research. Polybutadiene encapsulated nonporous zirconia particles, which are chemically and thermally more stable than silica, were evaluated for fast separations of pharmaceuticals and herbicides at temperatures and pressures as high as 100 °C and 30 kpsi, respectively. Safety is a concern when extremely high pressures are used in LC. Column rupture and system component failure can lead to the creation of high speed liquid jets and capillary projectiles. The use of a plexiglass shroud to cover the initial section of the installed capillary column can eliminate any safety-related concerns about these liquid jets or capillary projectiles. An ultrahigh pressure sample injector, with small dwell volume is critical for sample injection and gradient operation at high pressures. A novel injection assembly, composed of six small needle valves, withstood pressures as high as 30 kpsi. A new capillary connector was designed to hold the capillary by “two-point” holding forces under high pressures. With this new injector and capillary connector, gradient elution was easily achieved for the high resolution separation of a protein tryptic digest.

Ces travaux de recherche portent sur le développement d'un système original de fusion de données de diffusion électromagnétique et optique par des milieux denses et complexes. La méthode, à la fois théorique, numérique et expérimentale, permet la fusion des signatures de diffusion hyperspectrales, polarimétriques et angulaires d'un milieu d'étude. Un système expérimental multi-capteurs comprenant une source laser supercontinuum est présenté pour mesurer les signatures de diffusion de différentes cibles. Des modèles directs de simulation physique ont aussi été développés via : (i) une approche dite « top-down » qui modélise les signatures à partir de paramètres macroscopiques (ex. rugosité, indices optiques effectifs) ou (ii) une approche dite « bottom-up » qui modélise les signatures à partir de paramètres microscopiques (ex. distribution en taille, géométrie, concentration, indices optiques et structuration des diffuseurs) en résolvant soit l'équation de transfert radiatif ou directement les équations de Maxwell. Des méthodes inverses appliquées sur les signatures mesurées sont développées pour retrouver simultanément les paramètres d’intérêt du milieu analysé. Les avancées de ces travaux permettent une amélioration de la compréhension des phénomènes de diffusion électromagnétiques et optiques par des milieux denses et complexes tels que les surfaces rugueuses, les revêtements, les nanomatériaux, les suspensions colloïdales ou les agrégats fractals d'aérosols ultrafins. Les domaines d'applications de ces travaux sont l'aéronautique (ex. peintures d'aéronefs), l'imagerie aéroportée ou satellite (ex. imagerie active hyperspectrale ou polarimétrique), la sécurité et la défense (ex. matériaux pour la furtivité) ou bien les sciences de l'atmosphère (ex. systèmes LiDAR, suivi de pollution, suies), l'industrie chimique (ex. suspensions colloïdales) ou le biomédical (ex. diagnostic de tumeurs et mélanomes). / This work reports the development of an original data fusion system dedicated to electromagnetic and light scattering by dense and complex media. The dissertation encompasses the theoretical, numerical and experimental studies. The output of the data fusion system is a fused hyperspectral, polarimetric and angular scattering signature. An experimental multi-sensor and supercontinuum laser-based system is presented to measure the scattering signatures for various targets. Direct physical simulation models were developed using a two-level modelling scheme: (i) a top-down approach is used to model signatures from macro-physical parameters, e.g. the surface roughness or the effective refractive index and, (ii) a bottom-up approach is used to model signatures from microphysical parameters, e.g. the size distribution, the geometry, the concentration, the refractive index and the structuration of the scatterers, by solving the radiative transfer equation or directly the Maxwell's equations. Inversion schemes are deployed to retrieve these parameters by inverting the experimental signatures. The advancements described throughout this dissertation will serve to improve understanding of electromagnetic and light scattering by dense and complex media such as rough surfaces, coatings, nanomaterials, colloidal suspension and fractal aggregates of ultrafine aerosols. This study has relevant applications in fields as diverse as aeronautics (e.g. aircraft paint coatings), remote-sensing (e.g. hyperspectral, polarimetric, active or passive imaging), security and defense (e.g. furtive materials), atmospheric science (e.g. black carbon or soot characterization, LiDAR systems), chemical engineering (e.g. colloidal suspensions), or biomedical (e.g. tumor and melanoma diagnostic).