Polymers of various types are added to crude oils and oil products to prevent wax deposition, break water-in-oil emulsions, reduce drag in pipelines and to stabilize asphaltenes. In mixtures where a polymer does not adsorb on colloids, two stable liquid phases can arise due to depletion flocculation. Asphaltenes in heavy oils and toluene mixtures form sterically stabilized colloidal particles. In this work, the addition of a non-adsorbing polymer (polystyrene) to C5 Maya asphaltene + toluene mixtures was investigated experimentally and theoretically. As concentrated asphaltene + toluene mixtures are opaque to visible light, phase volumes and compositions were detected using ultrasound. The sensors comprised two commercial 64 element phased-array acoustic probes. The operation of the view cell, and kinetic and equilibrium data processing procedures were validated using mixtures of methanol + alkanes. Acoustic speed and attenuation profiles were found to provide independent measures of phase separation. At equilibrium, acoustic speed profiles are uniform in each phase with a step change at the interface. Acoustic wave attenuation profiles exhibit a sharp peak/spike at liquid-liquid interfaces. Mixtures of asphaltenes + polystyrene + toluene are shown to exhibit liquid-liquid phase behavior over broad ranges of composition. This is the first report of liquid-liquid phase behavior for such mixtures. One phase is asphaltene rich and the other phase is polystyrene rich. Liquid-liquid critical points were also identified along the liquid-liquid/liquid phase boundary for mixtures with two mean molar masses of polystyrene. Compositions of co-existing phases were computed using phase volume variations along dilution lines, acoustic speed data and a mass balance model. A parameter was introduced to improve the agreement between calculated and experimental speeds of sound. The results of the model indicate that more than half of the asphaltenes, by volume, participate in the depletion flocculation process. Phase compositions were measured independently using UV-visible spectrophotometry. The nominal size of asphaltene colloidal particles participating in the phase separation mechanism was estimated by comparing calculated phase boundaries with the experimental phase diagram. The estimated size of asphaltene colloidal particles is in agreement with the expected size of asphaltenes in toluene mixtures obtained exogenously. / Chemical and Materials Engineering

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Cette thèse porte sur l'étude de la méthode d'imagerie photoacoustique, une nouvelle modalité hybride permettant de combiner la haute résolution de l'imagerie par ultrasons et le contraste de l'imagerie optique. Nous y étudions en particulier le problème inverse associé et sa résolution : il se décompose en l'inversion de l'équation d'ondes et en celle de l'équation de diffusion optique, dont le but est de retrouver les paramètres optiques du milieu. Dans la première partie de cette étude nous développons un modèle permettant de prendre en compte les variations de la vitesse acoustique dans le milieu biologique. En effet, la plupart des méthodes d'inversion supposent une vitesse acoustique constante, ce qui est à l'origine d'erreurs dans les reconstructions. La deuxième partie de la thèse porte sur une étude mathématique du phénomène de limitation de la profondeur de l'imagerie photoacoustique. Nous calculons une estimation de stabilité du problème inverse dans le cas d'un milieu stratifié et nous montrons que la reconstruction se dégrade avec la profondeur. Nous étudions dans la dernière partie le phénomène photoacoustique en présence de nanoparticules métalliques : ces marqueurs permettent d'amplifier par des résonances le signal photoacoustique généré autour d'elles. Elles permettent ainsi une meilleure visibilité des tissus en profondeur. Nous explicitons ici le modèle mathématique de génération du signal photoacoustique, ainsi que la résolution théorique du problème inverse photoacoustique dans ce contexte. / This thesis work is related to photoacoustic imaging techniques which are new multiwave modalities in medical imaging that combine both high resolution of ultrasounds and contrast of optical methods. Weprecisely studied the inverse problem that consists of determining the optical coefficients of biologicaltissues from measurement of acoustic waves generated by the photoacoustic effect. The photoacoustic inverse problem proceeds in two steps.We first retrieve the initial pressure from the measurement of the pressure wave on a part of the boundary of the sample. The first inversion takes then the form of a linear inverse source problem and provides internal data for the optical waves that are more sensitive to the contrast of the absorption and diffusion coefficients. In a second step we recover the optical coefficients from the acquired internal data.The aim of this work is to study the two inversions in different contexts. In the first part, we develop a model that takes into account the variations of the acoustic speed in the medium. Indeed, most of the inversion methods suppose that the acoustic speed is constant, and this assumption can lead to errors in the reconstruction of the optical coefficients. The second part of this work is the derivation of stability estimates for the photoacoustic inverse problem in a layered medium. We prove that the reconstruction is getting worse with depth. This is one of the main drawbacks of the photacoustic method, the imaging depth is limited to a few centimeters. The last part is about photoacoustic generation with plasmonic nanoparticles. They enhance the photoacoustic signal around them, so that we can investigate the tissue more deeply. We derive the mathematical model of the photoacoustic generation by heating nanoparticles, and we solve the photoacoustic inverse problem in this context.