No / Pure anhydrous polymorphs of carbamazepine were prepared by solution-enhanced dispersion with supercritical fluids (SEDSTM). Crystallization of the polymorphs was studied. Mechanisms are proposed that consider the thermodynamics of carbamazepine, supersaturation in the SEDSTM process, and the binary phase equilibria of organic solvents and the carbon dioxide antisolvent. -Carbamazepine was crystallized at high supersaturations and low temperatures, -carbamazepine crystallized from a methanol-carbon dioxide phase split, and -carbamazepine crystallized via nucleation at high temperatures and low supersaturation.

Mixing of miscible gas with oil in a reservoir decreases the effective strength of the gas, which can adversely affect miscibility and recovery efficiency. The mixing that occurs in a reservoir, however, is widely debated and often ignored in reservoir simulation, where very large grid blocks are used. Large grid blocks create artificially large mixing that can cause errors in predicted oil recovery. Reservoir mixing, or dispersion, is caused by diffusion of particles across streamlines of varying velocities. Mixing is enhanced by any mechanism that increases the area of contact between the gas and the oil, thereby allowing the effects of diffusion to be magnified. This is, in essence, the cause of scale-dependent dispersion. The contact area grows primarily because of variations in streamlines and their velocities around grains and through layers of various permeabilities (heterogeneity). Mixing can also be enhanced by crossflow, such as that caused by gravity and by the effects of other neighboring wells. This dissertation focuses on estimation of the level of effective local mixing at the field scale and its impact on oil recovery from miscible gas floods. Pore-level simulation was performed using the Navier-Stokes and convection-diffusion equations to examine the origin of scale dependent dispersion. We then estimated dispersivity at the macro scale as a function of key scaling groups in heterogeneous reservoirs. Lastly, we upscaled grid blocks to match the level of mixing at the pattern scale. Once the contact area ceases to grow with distance traveled, dispersion has reached its asymptotic limit. This generally occurs when the fluids are well mixed in transverse direction. We investigated a variety of pore-scale models to understand the nature of scale dependency. From the pore-scale study, we found that reservoir mixing or dispersion is caused by diffusion of particles across streamlines. Diffusion can be significantly enhanced if the surface area of contact between the reservoir and injected fluid are increased as fluids propagate through the reservoir. Echo and transmission dispersivities are scale dependent. They may or may not reach an asymptotic limit depending on the scale of heterogeneities encountered. The scale dependence results from an increase in the contact area between solute (gas) and resident fluid (oil) as heterogeneities are encountered, either at the pore or pattern-scale. The key scaling groups for first-contact miscible (FCM) flow are derived and their impact on mixing is analyzed. We examine only local mixing, not apparent mixing caused by variations in streamline path lengths (convective spreading). Local mixing is important because it affects the strength of the injected fluid, and can cause an otherwise multicontact miscible (MCM) flood to become immiscible. We then showed how to upscale miscible floods considering reservoir mixing. The sum of numerical dispersion and physical dispersion associated with the reservoir heterogeneities, geometry and fluid properties must be equal at both the fine- and large-scales. The maximum grid-block size allowed in both the x- and z-directions is determined from the scaling groups. Small grid-blocks must be used for reservoirs with uncorrelated permeabilities, while larger grid blocks can be used for more layered reservoirs. The predicted level of mixing for first-contact miscible floods can be extended with good accuracy to multicontact miscible (MCM) gas floods. / text

Parmi tous les plastiques, les polyuréthanes (PUs) représentent la sixième classe de polymères la plus utilisée au monde. Ils sont synthétisés industriellement par réaction entre un diol et un diisocyanate, en présence d'un catalyseur métallique et d’un solvant organique.Néanmoins, cette synthèse présente d’importants problèmes environnementaux et de santé.Afin de s’affranchir de ces composés toxiques, les progrès dans ce domaine ont conduit à un certain nombre de procédés sans isocyanates. Néanmoins, ces procédés doivent faire face à de nombreux défis (propriétés physiques, masses molaires, réactions secondaires, etc.), afin de concurrencer les polyuréthanes classiques. Par conséquent, une partie de ce manuscrit est dédiée à une étude rationnelle de l'influence de catalyseurs organiques, tels que le TBDou P4, non seulement sur la cinétique de polymérisation de l’aminolyse de carbonates biscycliques,mais aussi sur la structure et les propriétés des PUs résultants. Par la suite, et afin de limiter l’utilisation de composés organiques volatiles, des dispersions aqueuses de polyuréthanes sans isocyanates ont été obtenues en adaptant : 1) le procédé acétone à l’aminolysis de carbonates bis-cycliques et 2) la polymérisation interfaciale à la polycondensation de dicarbonates linéaires avec des diamines. / Among all plastic materials, polyurethanes (PUs) represent the 6th most popularly usedpolymers in the World. They are industrially synthesized by the reaction between a diol and adiisocyanate, in the presence of a metal catalyst and an organic solvent. Nevertheless, thissynthesis presents important environmental and health problems. In order to replace thesetoxic compounds, advances in this field have led to a number of isocyanate-free processes.However, these processes have to face many challenges (physical properties, molarmasses, side reactions, etc.), in order to compete with conventional polyurethanes.Therefore, part of this manuscript is dedicated to a rational study of the influence oforganocatalysts, such as TBD or P4, not only on the polymerization kinetics of the aminolysisof bis-cyclic carbonates, but also on the structure and properties of the resulting PUs.Subsequently, and in order to limit the use of volatile organic compounds, aqueousdispersions of non-isocyanate PUs were obtained by adapting: 1) the acetone process to theaminolysis of bis-cyclic carbonates and 2) the interfacial polymerization to thepolycondensation of linear dicarbonates with diamines.

Depuis quelques années, les nanomatériaux sont de plus en plus utilisés dans les processus industriels. Afin de protéger la population et l'environnement des possibles conséquences lors de rejets accidentels de ces produits dans l'atmosphère, des analyses de risques ont permis d'identifier des scénarios accidentels dans le cas du transport, de la manipulation et du stockage. Parmi les cas de fuite non intentionnelle dans l'atmosphère libre, la fuite accidentelle sur un convoyeur peut générer un relargage massif de nanoparticules. Afin d’évaluer les conséquences de ce type de scénario accidentel, notre étude s’intéresse à la prédiction des propriétés du nuage de particules dispersées dans l’air, par exemple la concentration en nombre et la distribution des diamètres. La première étape de l’étude consiste à synthétiser les phénomènes physiques des nanoparticules dans l’air afin de choisir les phénomènes physiques les plus pertinants à modéliser. Les phénomènes physiques à modéliser sont la forme complexe des agglomérats, la force de traînée des agglomérats, la fragmentation des agglomérats par le fluide, la collision et l'agglomération des agglomérats. Ensuite, la modélisation des phénomènes physiques est développée dans l'outil CFD Code\_Saturne. Pour chaque phénomène physique, un cas de simulation numérique est réalisé pour vérifier le développement de la modélisation dans l'outil CFD. Une bonne comparaison des résultats CFD avec les résultats de modèle 0D de Scilab et les modèles dans la littérature est obtenue. Egalement dans notre étude, un nouveau modèle de la probabilité de collision des agglomérats est proposé. Ces nouveaux modèles sont validés par les expérimentations numériques. Ensuite, l'outil CFD développé est appliqué dans une simulation d'une fuite de canalisation de transport. La zone proche de la fuite est simulée par Code\_Saturne. Les résultats du Code\_Saturne sont utilisés comme les données entrées pour ADMS, un outil numérique de la dispersion des particules à grande échelle. Les résultats montrent que les particules sont dispersées plus de 1 km par rapport au terme source, ce qui est en accord avec la distance observée. En perspective, l'influence de plusieurs paramètres comme la vitesse du vent, les propriétés des particules comme la distribution de taille ou la concentration en agglomérats pourrait être testé. Une expérimentation de rejet des microparticules est réalisée à l'INERIS pour ensuite pouvoir étudier les rejets des nanoparticules à l'échelle laboratoire. / Since a few years, nanomaterials are more and more used in industrial process. In order to protect the population and the environment from the consequences of an accidental release into the atmosphere, the risk assessment allowed to identify the accidental scenario in transport, manipulation and storage of those products. The accidental leakage of the conveying pipe may lead to a massive release of nanoparticles. In order to evaluate the consequences of this type of accident, our study focuses on the prediction of particles properties dispersed into the air, for example the particle number concentration and the particle diameter distribution. The first step of the study consists in the analyse of physical phenomena related to nanoparticles in order to choose the most predominant physical phenomena to model. The relevant physical phenomena in the present configuration are the agglomerate complex shape, the drag force on agglomerates, the agglomerate breakage by gas, the agglomerate collision and the agglomeration. After that, the modelling of physical phenomena chosen is developed in CFD tool Code\_Saturne. For each physical phenomenon, a simulation test case is realized in order to verify the development in CFD tool. A good agreement between CFD tool Code\_Saturne and 0D tool from Scilab and model in the literature is obtained. Also in the present study, new model for the collision probability of agglomerates is proposed. This new model is validated with the numerical experiment. After that, the numerical tool developed is applied in a simulation of an accidental pipe leakage. The field near the leakage is simulated by Code\_Saturne. The results from Code\_Saturne is used as the input data for ADMS tool, a simulation tool for the particle dispersion in large scale. The results show that the particles are dispersed more than 1 km from the release source, which is in agreement with the distance observed. In perspective, the influences of different parameters as the wind field and the particle properties, on the agglomerate size and number distribution can be tested. An experiment of the microparticle jet is realized at INERIS in order to be able to assess the nanoparticle jet experiment in the laboratory scale.

Long distance repeaterless optical fiber communications systems are currently used to transmit most internet and telephone information worldwide. The growth of photonic telecommunications technology has produced systems with very high bit-rate per fiber, but this still falls short of its potential capacity. Currently systems that are able to transmit even higher bit-rates are being developed utilizing dense wavelength-division-multiplexing (WDM) to maximally utilize the bandwidth potential of optical fibers. One of the most important factors that limits the bit-rate achievable in a such a WDM optical communications system is the cross-talk between channels caused by pulse collisions. In this thesis a consistent mathematical theory is used to analyze the frequency and timing shifts caused collisions between two WDM channels. This theory is applied to the systems currently most promising for next-generation photonic telecommunications; the dispersion managed (DM) soliton and 'quasi-linear' systems. Self-contained formulae are obtained which accurately predict the timing shifts suffered in these systems with a wide range of parameters. These formulae require an order of magnitude less computational time that direct numerical simulations. Several mathematical techniques are introduced to obtain computationally efficient formulae for complete and incomplete collisions in both systems. For complete collisions we use the Poisson sum transform to change the calculation to a sum in the Fourier domain. For incomplete collisions we use asymptotic integration to obtain approximate formulae. For quasi-linear systems we simplify the Laplace method even further to obtain elementary formulae. We show that using a combination of these methods the timing shift for incomplete and complete collisions in a wide range of system configurations can be obtained in comparatively small computational times. We find that for systems with small DM map strength the timing shift from widely separated channels is significant. For quasi-linear systems with large DM map strength this is negligable and the timing shift decreases with the square of the channel frequency separation. We also find the timing shift from closely spaced channels is higher for quasi-linear systems than for DM soliton systems operating at the same average dispersion.

Impact of odour emissions from livestock operation sites on the air quality of neighboring areas has raised public concerns. A practical means to solve this problem is to set adequate setback distance. Air dispersion modeling was proved to be a promising method in predicting proper odour setback distance. Although a lot of air dispersion models have been used to predict odour concentrations downwind agricultural odour sources, not so much information regarding the capability of these models in odour dispersion modeling simulation could be found because very limited field odour data are available to be applied to evaluate the modeling result. A main purpose of this project was evaluating AERMOD and CALPUFF air dispersion models for odour dispersion simulation using field odour data.<p> Before evaluating and calibrating AERMOD and CALPUFF, sensitivity analysis of these two models to five major climatic parameters, i.e., mixing height, ambient temperature, stability class, wind speed, and wind direction, was conducted under both steady-state and variable meteorological conditions. It was found under steady-state weather condition, stability class and wind speed had great impact on the odour dispersion; while, ambient temperature and wind direction had limited impact on it; and mixing height had no impact on the odour dispersion at all. Under variable weather condition, maximum odour travel distance with odour concentrations of 1, 2, 5 and 10 OU/m3 were examined using annual hourly meteorological data of year 2003 of the simulated area and the simulation result showed odour traveled longer distance under the prevailing wind direction.<p> Evaluation outcomes of these two models using field odour data from University of Minnesota and University of Alberta showed capability of these two models in odour dispersion simulation was close in terms of agreement of modeled and field measured odour occurrences. Using Minnesota odour plume data, the difference of overall agreement of all field odour measurements and model predictions was 3.6% applying conversion equation from University of Minnesota and 3.1% applying conversion equation from University of Alberta between two models. However, if field odour intensity 0 was not considered in Minnesota measured odour data, the difference of overall agreement of all field odour measurements and model predictions was 3.1% applying conversion equation from University of Minnesota and 1.6% applying conversion equation from University of Alberta between two models. Using Alberta odour plume data, the difference of overall agreement of all field odour measurements and model predictions was 0.7% applying conversion equation from University of Alberta and 1.2% applying conversion equation from University of Minnesota between two models. However, if field odour intensity 0 was not considered in Alberta measured odour data, the difference of overall agreement of all field odour measurements and model predictions was 0.4% applying conversion equation from University of Alberta and 0.7% applying conversion equation from University of Minnesota between two models. Application of scaling factors can improve agreement of modeled and measured odour intensities (including all field odour measurements and field odour measurements without intensity 0) when conversion equation from University of Minnesota was used.<p> Both models were used in determining odour setback distance based on their close performance in odour dispersion simulation. Application of two models in predicting odour setback distance using warm season (from May to October) historical annul hourly meteorological data (from 1999 to 2002) for a swine farm in Saskatchewan showed some differences existed between models predicted and Prairie Provinces odour control guidelines recommended setbacks. Accurately measured field odour data and development of an air dispersion model for agricultural odour dispersion simulation purpose as well as acceptable odour criteria could be considered in the future studies.

Impact of odour emissions from livestock operation sites on the air quality of neighboring areas has raised public concerns. A practical means to solve this problem is to set adequate setback distance. Air dispersion modeling was proved to be a promising method in predicting proper odour setback distance. Although a lot of air dispersion models have been used to predict odour concentrations downwind agricultural odour sources, not so much information regarding the capability of these models in odour dispersion modeling simulation could be found because very limited field odour data are available to be applied to evaluate the modeling result. A main purpose of this project was evaluating AERMOD and CALPUFF air dispersion models for odour dispersion simulation using field odour data.<p> Before evaluating and calibrating AERMOD and CALPUFF, sensitivity analysis of these two models to five major climatic parameters, i.e., mixing height, ambient temperature, stability class, wind speed, and wind direction, was conducted under both steady-state and variable meteorological conditions. It was found under steady-state weather condition, stability class and wind speed had great impact on the odour dispersion; while, ambient temperature and wind direction had limited impact on it; and mixing height had no impact on the odour dispersion at all. Under variable weather condition, maximum odour travel distance with odour concentrations of 1, 2, 5 and 10 OU/m3 were examined using annual hourly meteorological data of year 2003 of the simulated area and the simulation result showed odour traveled longer distance under the prevailing wind direction.<p> Evaluation outcomes of these two models using field odour data from University of Minnesota and University of Alberta showed capability of these two models in odour dispersion simulation was close in terms of agreement of modeled and field measured odour occurrences. Using Minnesota odour plume data, the difference of overall agreement of all field odour measurements and model predictions was 3.6% applying conversion equation from University of Minnesota and 3.1% applying conversion equation from University of Alberta between two models. However, if field odour intensity 0 was not considered in Minnesota measured odour data, the difference of overall agreement of all field odour measurements and model predictions was 3.1% applying conversion equation from University of Minnesota and 1.6% applying conversion equation from University of Alberta between two models. Using Alberta odour plume data, the difference of overall agreement of all field odour measurements and model predictions was 0.7% applying conversion equation from University of Alberta and 1.2% applying conversion equation from University of Minnesota between two models. However, if field odour intensity 0 was not considered in Alberta measured odour data, the difference of overall agreement of all field odour measurements and model predictions was 0.4% applying conversion equation from University of Alberta and 0.7% applying conversion equation from University of Minnesota between two models. Application of scaling factors can improve agreement of modeled and measured odour intensities (including all field odour measurements and field odour measurements without intensity 0) when conversion equation from University of Minnesota was used.<p> Both models were used in determining odour setback distance based on their close performance in odour dispersion simulation. Application of two models in predicting odour setback distance using warm season (from May to October) historical annul hourly meteorological data (from 1999 to 2002) for a swine farm in Saskatchewan showed some differences existed between models predicted and Prairie Provinces odour control guidelines recommended setbacks. Accurately measured field odour data and development of an air dispersion model for agricultural odour dispersion simulation purpose as well as acceptable odour criteria could be considered in the future studies.

Thesis (Ph.D.)--Auburn University, 2005. / Abstract. Vita. Includes bibliographic references (ℓ. 156-170)

Ces travaux de thèse visent à améliorer la densification et la résistance à la rupture de céramiques silicatées élaborées principalement à partir de kaolin. Cette amélioration est effectuée en substituant une partie du kaolin par de l’halloysite. En effet, cette voie permet également de mettre en évidence l’influence de la morphologie et de l’organisation des particules sur les propriétés microstructurales. Premièrement, la dispersion des suspensions contenant soit du kaolin soit un mélange de kaolin et d’halloysite, a été optimisée en réduisant la taille des agglomérats et en augmentant la valeur absolue du potentiel zêta. Deuxièmement, les paramètres (broyage, rapport liant/plastifiant…) contrôlant le procédé de mise en forme de coulage en bande ont également été optimisés. Enfin, l’influence de deux types de traitement thermique à 1200°C (frittage conventionnel et par voie micro-ondes) sur les propriétés mécaniques (contrainte à la rupture en flexion biaxiale) des matériaux finis a été mise en évidence. Les résultats obtenus montrent que plusieurs compromis entre le taux de porosité, l’organisation de la microstructure et les propriétés mécaniques ont été obtenus i) soit avec un taux d’halloysite de 10 % en masse associée à un traitement thermique par voie micro-ondes à 1200°C ii) soit avec un taux de substitution d’halloysite égal à 50 % en masse associé à un frittage conventionnel à la même température. / This thesis is devoted to improve both densification and stress to rupture values of silicate ceramics mainly elaborated from kaolin. This improvement is achieved by replacing a proportion of kaolin by halloysite. Indeed, this way also allows to highlight the influence of the shape of particles and their organization on microstructural properties. First, the dispersion of suspensions containing only kaolin or a mixture of kaolin and halloysite was optimized by reducing the size of agglomerates and by increasing the absolute value of zeta potential. Second, parameters (milling, ratio binder/plasticizer...) controlling the tape casting shaping process were also optimized. Finally, the influence of two types of thermal treatment at 1200°C (conventional and micro-waves sintering) mechanical properties (stress to rupture determined by bixial bending tests) of final products was studied. Results obtained show that several compromises regarding porosity, the organization of microstructure and mechanical properties i) a proportion equals to 10 mass % of halloysite combined with a micro-waves thermal treatment at 1200°C ii) a substitution content equals to 50 mass % of halloysite combined with a conventional thermal treatment at the same temperature.

Le BUT de ma thèse est d’étudier les mécanismes fondamentaux du mélange d’une poudre avec un liquide : Au début du mélange, la poudre et le liquide sont versés dans le mélangeur, des agrégats de poudre communément appelés grumeaux se forment. Ensuite chaque agrégat va évoluer par l’action de plusieurs phénomènes : l’imbibition, phénomène spontané qui désigne l’infiltration d’un liquide dans un milieu poreux par capillarité ; et le phénomène forcé de rupture sous contraintes d’écoulement. A l’état final la poudre est dispersée finement et de façon homogène dans le liquide. Ma thèse est alors structurée en deux parties : l’étude de la cinétique d’imbibition d’un agrégat sphérique immergé ; et l’étude de la rupture d’un agrégat sous contrainte extérieure. La REUSSITE de l’étude provient des expériences approfondies: de la création d’un nouveau procédé de fabrication d’un agrégat grâce à l’impression 3D, jusqu’à la détermination de lois empiriques de nouveaux phénomènes mis en évidence. / The GOAL of my PhD is to study the fundamental mechanisms of mixing a powder with a liquid. The mix of focus proceeds as follows:At start, as the powder and the liquid are filled in the mixer, powder aggregates form.Then each powder aggregate evolves under the influence of several phenomena: imbibition, spontaneous phenomenon corresponding to the infiltration of a liquid inside a porous medium by capillarity; and the forced phenomenon of rupture under flow. At last the powder is finely and homogeneously dispersed in the liquid. My PhD is thus organized in two parts: the study of the imbibitions kinetics of a spherical aggregate, and the study of the rupture of an aggregate under flow.The SUCCESS of the study relies on the thorough experiments: from creating a new aggregate manufacturing process using 3D printing, to determining empirical laws corresponding to new phenomena.