Ce travail de thèse est une contribution à l’étude des émulsions de Pickering qui ont vu unregain d’intérêt ces dernières années. Bien que l’effet Pickering ait été décrit depuis plus d’un siècle,des études plus systématiques pour comprendre l’activité des particules solides aux interfacesliquide/liquide n’est que partiellement entrepris, surtout en cours de déformation. Plusieurs questionsrestent d’actualité et, en premier, la localisation même des particules à l’interface et le mécanismed’adsorption associé.L’approche proposée dans ce travail de thèse s’inscrit dans cette optique avec en particulier laconsidération d’un événement élémentaire d’une émulsion : une goutte isolée dans une matrice etexaminée suite à un saut de déformation en cisaillement dans un dispositif de cisaillement contrarotatifdéveloppé à PCI. De manière générique, le but est de comprendre la relation entre le comportement dela goutte et la rhéologie complexe (en volume ou en surface) apportée par la dynamique de particulessolides aux interfaces liquide/liquide mobiles. Plusieurs paramètres ont été étudiés en commençant parl’affinité chimique des particules solides avec les phases liquides, la rhéologie des phases liquides, laconcentration et la taille des particules solides ; et pour finir, une attention particulière a été portée àl'effet de la déformation macroscopique et l’âge de la goutte.Plus particulièrement, la mise en évidence de la synergie entre la déformation macroscopiqueet l’âge de la goutte, sur la dynamique d’adsorption des particules à l’interface liquide/liquide et lastructuration de l’interface composée, a permis de proposer une méthodologie pour la modulation de« l’effet mémoire induite par la déformation » lors de la relaxation de la goutte en modifiant lasurface des particules par adsorption de tensioactifs choisis. Ainsi, il a été possible de figer les gouttesliquides dans des formes anisotropes contrôlées. Ce phénomène a été corrélé à une transition liquidesolidede l’interface composée mise en évidence par des mesures des modules rhéologiquesinterfaciaux. Ces derniers ont été, par ailleurs, reliés quantitativement à l’anisotropie des gouttesfigées. / This thesis is a contribution to the study of Pickering emulsions that have seen a renewedinterest in recent years. Although the effect Pickering has been described for over a century, moresystematic studies to understand the activity of solid particles at liquid/liquid interfaces is onlypartially undertaken, especially during flow. Several issues are still relevant and, in particular, thelocation of particles at the interface and the involved adsorption mechanism.The approach proposed in this thesis is to consider an elementary event of an emulsion: asingle droplet in a matrix undergoing a strain jump in a shear flow. This experiment was performed ina counter-rotating shear device developed at PCI. Generically, the aim is to understand the relationshipbetween the behavior of the droplet and the bulk and interfacial rheology induced by the dynamics ofsolid particles at a liquid/liquid interfaces. Several parameters were studied starting with the chemicalaffinity of solid particles with the liquid phases, the rheology of the liquid phases, the concentrationand the size of solid particles, and finally, special attention was paid to the effect of macroscopicdeformation and the age of the interface.More specifically, the demonstration of synergy between the macroscopic strain and the age ofthe interface, the dynamic adsorption of particles at the liquid/liquid interface and the structure of theinterface, allowed to propose a methodology for the modulation of the "memory effect induced by thedeformation" during the relaxation of the droplet by changing the particle surface using the adsorptionof a selected surfactants. Thus, it was possible to freeze the liquid drops in a controlled anisotropicshapes. This phenomenon was correlated to a liquid-solid transition of the interface demonstrated byrheological measurements of the interfacial moduli. These were, moreover, quantitatively related tothe anisotropy of frozen droplets.

The first part of this thesis is concerned with thestructure-property relationships in nonionic surfactantsystems. The main aim was to investigate how the surfactantstructure influences the adsorption at interfaces andinteractions between surfactant coated interfaces.Particularly, the effect of the structure of the surfactantheadgroups was investigated. These were sugar-based headgroupwith varying size and flexibility and poly(ethylene oxide)based headgroups with or without an additional amide or estergroup. The hydrophobic part of the surfactant consisted mostlyof straight alkyl chains, except for one type of poly(ethyleneoxide) based surfactant with a dehydroabietic hydrophobe. The main technique that was used is the surface forcetechnique, with which the forces acting between two adsorbedsurfactant layers on hydrophilic or hydrophobic surfaces can bemeasured. These forces are important for e.g. the stability ofdispersions. The hydrophilic surfaces employed were glass andmica, whereas the hydrophobic surfaces were silanized glass andhydrophobized mica. The adsorption behavior on hydrophilicsurfaces is highly dependent on the type of headgroup andsurface, whereas similar results were obtained on the two typesof hydrophobic surfaces. To better understand how the surfaceforces are affected by the surfactant structure, measurementsof adsorbed amount and theoretical mean-field latticecalculations were carried out. The results show that the sugarsurfactant layers and poly(ethylene oxide) surfactant layersgive rise to very different surface forces, but that the forcesare more similar within each group. The structure-propertyrelationships for many other physical properties have beenstudied as well. These include equilibrium and dynamicadsorption at the liquid-vapor interface, micelle size, micelledynamics, and wetting. The second part in this thesis is about the aggregationbetween cationic polyelectrolytes and an anionic surfactant.The surface force technique was used to study the adsorption ofa low charged cationic polyelectrolyte on mica, and theaggregation between the adsorbed polyelectrolyte with theanionic surfactant. The aggregation in bulk was studied withturbidimetry, small angle neutron scattering (SANS), and smallangle x-ray scattering (SAXS). An internal hexagonal aggregatestructure was found for some of the bulk aggregates. <b>Keywords:</b>nonionic surfactant, sugar surfactant,poly(ethylene oxide), amide, ester, polyelectrolyte, SDS,hydrophobic surface, glass surface, mica, adsorption,aggregation, micelle size, surface forces, wetting, dynamicsurface tension, NMR, TRFQ, SANS, SAXS, mean-field latticecalculations.

<p>The first part of this thesis is concerned with thestructure-property relationships in nonionic surfactantsystems. The main aim was to investigate how the surfactantstructure influences the adsorption at interfaces andinteractions between surfactant coated interfaces.Particularly, the effect of the structure of the surfactantheadgroups was investigated. These were sugar-based headgroupwith varying size and flexibility and poly(ethylene oxide)based headgroups with or without an additional amide or estergroup. The hydrophobic part of the surfactant consisted mostlyof straight alkyl chains, except for one type of poly(ethyleneoxide) based surfactant with a dehydroabietic hydrophobe.</p><p>The main technique that was used is the surface forcetechnique, with which the forces acting between two adsorbedsurfactant layers on hydrophilic or hydrophobic surfaces can bemeasured. These forces are important for e.g. the stability ofdispersions. The hydrophilic surfaces employed were glass andmica, whereas the hydrophobic surfaces were silanized glass andhydrophobized mica. The adsorption behavior on hydrophilicsurfaces is highly dependent on the type of headgroup andsurface, whereas similar results were obtained on the two typesof hydrophobic surfaces. To better understand how the surfaceforces are affected by the surfactant structure, measurementsof adsorbed amount and theoretical mean-field latticecalculations were carried out. The results show that the sugarsurfactant layers and poly(ethylene oxide) surfactant layersgive rise to very different surface forces, but that the forcesare more similar within each group. The structure-propertyrelationships for many other physical properties have beenstudied as well. These include equilibrium and dynamicadsorption at the liquid-vapor interface, micelle size, micelledynamics, and wetting.</p><p>The second part in this thesis is about the aggregationbetween cationic polyelectrolytes and an anionic surfactant.The surface force technique was used to study the adsorption ofa low charged cationic polyelectrolyte on mica, and theaggregation between the adsorbed polyelectrolyte with theanionic surfactant. The aggregation in bulk was studied withturbidimetry, small angle neutron scattering (SANS), and smallangle x-ray scattering (SAXS). An internal hexagonal aggregatestructure was found for some of the bulk aggregates.</p><p><b>Keywords:</b>nonionic surfactant, sugar surfactant,poly(ethylene oxide), amide, ester, polyelectrolyte, SDS,hydrophobic surface, glass surface, mica, adsorption,aggregation, micelle size, surface forces, wetting, dynamicsurface tension, NMR, TRFQ, SANS, SAXS, mean-field latticecalculations.</p>

Thermal and chemical recovery processes are important EOR methods used often by the oil and gas industry to improve recovery of heavy oil and high viscous oil reservoirs. Knowledge of underlying mechanisms and their modeling in numerical simulation are crucial for a comprehensive study as well as for an evaluation of field treatment. EOS-compositional, thermal, and blackoil reservoir simulators can handle gas (or steam)/oil/water equilibrium for a compressible multiphase flow. Also, a few three-phase chemical flooding reservoir simulators that have been recently developed can model the oil/water/microemulsion equilibrium state. However, an accurate phase behavior and fluid flow formulations are absent in the literature for the thermal chemical processes to capture four-phase equilibrium. On the other hand, numerical simulation of such four-phase model with complex phase behavior in the equilibrium condition between coexisting phases (oil/water/microemulsion/gas or steam) is challenging. Inter-phase mass transfer between coexisting phases and adsorption of components on rock should properly be modeled at the different pressure and temperature to conserve volume balance (e.g. vaporization), mass balance (e.g. condensation), and energy balance (e.g. latent heat). Therefore, efforts to study and understand the performance of these EOR processes using numerical simulation treatments are quite necessary and of utmost importance in the petroleum industry. This research focuses on the development of a robust four-phase reservoir simulator with coupled phase behaviors and modeling of different mechanisms pertaining to thermal and chemical recovery methods. Development and implementation of a four-phase thermal-chemical reservoir simulator is quite important in the study as well as the evaluation of an individual or hybrid EOR methods. In this dissertation, a mathematical formulation of multi (pseudo) component, four-phase fluid flow in porous media is developed for mass conservation equation. Subsequently, a new volume balance equation is obtained for pressure of compressible real mixtures. Hence, the pressure equation is derived by extending a black oil model to a pseudo-compositional model for a wide range of components (water, oil, surfactant, polymer, anion, cation, alcohol, and gas). Mass balance equations are then solved for each component in order to compute volumetric concentrations. In this formulation, we consider interphase mass transfer between oil and gas (steam and water) as well as microemulsion and gas (microemulsion and steam). These formulations are derived at reservoir conditions. These new formulations are a set of coupled, nonlinear partial differential equations. The equations are approximated by finite difference methods implemented in a chemical flooding reservoir simulator (UTCHEM), which was a three-phase slightly compressible simulator, using an implicit pressure and an explicit concentration method. In our flow model, a comprehensive phase behavior is required for considering interphase mass transfer and phase tracking. Therefore, a four-phase behavior model is developed for gas (or steam)/ oil/water /microemulsion coexisting at equilibrium. This model represents coupling of the solution gas or steam table methods with Hand’s rule. Hand’s rule is used to capture the equilibrium between surfactant, oil, and water components as a function of salinity and concentrations for oil/water/microemulsion phases. Therefore, interphase mass transfer between gas/oil or steam/water in the presence of the microemulsion phase and the equilibrium between phases are calculated accurately. In this research, the conservation of energy equation is derived from the first law of thermodynamics based on a few assumptions and simplifications for a four-phase fluid flow model. This energy balance equation considers latent heat effect in solving for temperature due to phase change between water and steam. Accordingly, this equation is linearized and then a sequential implicit scheme is used for calculation of temperature. We also implemented the electrical Joule-heating process, where a heavy oil reservoir is heated in-situ by dissipation of electrical energy to reduce the viscosity of oil. In order to model the electrical Joule-heating in the presence of a four-phase fluid flow, Maxwell classical electromagnetism equations are used in this development. The equations are simplified and assumed for low frequency electric field to obtain the conservation of electrical current equation and the Ohm's law. The conservation of electrical current and the Ohm's law are implemented using a finite difference method in a four-phase chemical flooding reservoir simulator (UTCHEM). The Joule heating rate due to dissipation of electrical energy is calculated and added to the energy equation as a source term. Finally, we applied the developed model for solving different case studies. Our simulation results reveal that our models can accurately and successfully model the hybrid thermal chemical processes in comparison to existing models and simulators. / text

No description available.

Les fluorocarbures ont un fort potentiel en médecine. Cependant, et en dépit du fait que certaines formulations employant des fluorocarbures sont utilisées en clinique, il n’existe que relativement peu d’études visant à déterminer les interactions entre un fluorocarbure et une membrane de phospholipides. Notre étude concentre à l’interface fluorocarbure/phospholipide, qui représente d’une part un modèle simplifié du surfactant pulmonaire natif dont le composant majoritaire est la dipalmitoylphosphatiylcholine (DPPC), et d’autre part la paroi de microbulles développées comme nouveaux agents théranostiques.Tout d’abord, nous montrons que les fluorocarbures abaissent considérablement la tension interfaciale d’équilibre d’une série de phospholipides et accélèrent fortement leur adsorption. Nous montrons que des oscillations périodiques appliquées à la bulle induisent une transition du film de DPPC vers un état d’organisation plus dense. L’application d’oscillations périodiques permet aussi à la DPPC d’expulser du film interfacial une protéine, l’albumine, dont la présence est souvent liée aux troubles dus au mauvais fonctionnement du surfactant pulmonaire. L’effet des fluorocarbures, qui accélère considérablement l’expulsion de l’albumine par la DPPC, est également étudié. D’autre part, nous avons obtenu des microbulles exceptionnellement stables grâce à une série homologue de phosphates perfluoroalkylés. Nous avons également réussi à former des microbulles couvertes par des nanoparticules magnétiques, tout en gardant les propriétés échogènes des bulles. De telles microbulles offrent un potentiel comme des agents de contraste bimodaux pour l’IRM et l’échosonographie. / Fluorocarbons have a great potential in medicine. However, and despite the fact that some formulations using fluorocarbons are used clinically, only a few studies are reported that aim to determining the interactions between a fluorocarbon and a membrane of phospholipids. Our work concentrated on the fluorocarbon/phospholipid interface, which represents, on one hand, a simplified model of the lung surfactant, the major component of which is dipalmitoylphosphatiylcholine (DPPC), and on the other hand, the shell of microbubbles developed as new theranostic agents. In a first part, we show that fluorocarbons significantly reduce the equilibrium interfacial tension of a series of phospholipids and greatly accelerate their adsorption rate. We also show that periodical oscillations applied to the bubble induce a transition of DPPC film to state with a denser organization. The application of periodical oscillations also allows DPPC to expel from the interfacial film a protein, albumin, whose presence is often associated with disorders caused by dysfunction of the lung surfactant. The impact of fluorocarbons, which considerably accelerate the expulsion from the interfacial film of albumin, is also studied. In a second part, we have obtained exceptionally stable microbubbles with a homologous series of perfluoroalkylated phosphates. We were also able to form microbubbles covered by magnetic nanoparticles, while preserving the echogenicity of the bubbles. Such microbubbles offer a potential as bimodal contrast agents for MRI and echography.

Ce travail est consacré à l’étude des propriétés de systèmes à base de tensioactifs non ioniques hydrogéné et fluoré dans le but de préparer des matériaux poreux silicatés. L’effet de la solubilisation d’hexadécane ou de décane dans des micelles de C12H25CO(OC2H4)9OCH3 conduit à la formation de silices mésoporeuses à plus larges pores, tandis qu’aucun effet de gonflement n’est observé avec l’ajout de cyclohexane. Lorsque les matériaux sont préparés avec des micelles de C8F17C2H4(OC2H4)9OH, l’ajout de perflorooctylbromure (PFOBr) augmente la taille des mésopores. Par ailleurs, l’incorporation de grandes quantités de PFOBr ou de perfluorodécaline conduit à la formation de macropores. Avec C7F15C2H4(OC2H4)8OH, l’incorporation de (C4F9CH)2 permet d’élargir les mésopores et de créer un réseau de macropores, tandis que l’ajout de PFOBr ne conduit ni à la formation de mésopore, ni à la formation de macropore. Les résultats mettent en évidence que la formation de matériaux macroporeux à partir d’émulsions hydrogénées ou fluorées est favorisée avec les systèmes qui présentent des valeurs de PIT (Température d’Inversion de Phase) élevées. Pour finir, l’effet de l’addition de différents alcools dans le système à base de C8F17C2H4(OC2H4)9OH a été étudié. La détermination des paramètres structuraux de la phase cristal liquide hexagonal, indique que les alcools à courte ou moyenne chaîne jouent le rôle de solvant, tandis que le fluoro-octanol joue celui d’un co-tensioactif. L’addition d’alcools courts provoque la destruction progressive des micelles qui perturbe le mécanisme d’auto-assemblage et les matériaux obtenus présentent des structures vermiformes / This work deals with the study of the properties of nonionic hydrogenated and fluorinated surfactant based systems which are related to the synthesis of porous silica. The effect of the solubilization of low fraction of hexadecane or decane in the micelles of C12H25CO(OC2H4)9OCH3 leads to the formation of large mesoporous silica, whereas no swelling effect was noted with cyclohexane. When the materials are templated by fluorinated micelles of C8F17C2H4(OC2H4)9OH, large pore mesoporous materials are obtained with perfluorooctyl bromide (PFOBr). Both PFOBr and perfluorodecalin give rise to macropores at high oil concentrations. With C7F15C2H4(OC2H4)8OH, the fluorocarbon (C4F9CH)2 is not only an effective expander to enlarge the pore size of mesoporous materials, but also very favourable for the design of macropore network. On the contrary, with PFOBr, there is neither mesopore nor macropore. Therefore, both hydrogenated and fluorinated systems obey to the same rule: the formation of macroporous materials template by emulsions is favoured with systems which exhibit a high value of the PIT. Lastly, alcohols used as additives in the C8F17C2H4(OC2H4)9OH -water system to tune the characteristics of the recovered materials. The structural parameters of the hexagonal liquid crystal show the short and medium alcohols behaved like solvent, while the long chain and fluorinated octanol acted as co-surfactant. The short alcohols provoke a micelle breaking effect. Thus, the self-assembly mechanism is disturbed and wormhole-like structures are recovered

No description available.

This research thesis reports experimental work done to design a stable magneticmicroemulsion of ionic liquid in 2-ethylhexyl laurate with the help of an ionic surfactant andan alcohol co-surfactant. The ionic liquids tested were based on a 1,3-dialkylimidazoliumcation with different alkyl chain lengths and a tetrachloroferrate anion ([FeCl4]+) to ensure theemulsion is sensitive to applied magnetic fields. Tests of solubility of these ionic liquids havebeen performed in different solvents and oils. Emulsification tests have been done withdifferent dispersing medium, surfactants as well as with different components quantities tofind the best composition possible. Polarity and chain length of alkyl radicals in ionic liquidsand hydrocarbons in alcohol co-surfactants were proved to affect the emulsification process.Shorter chains, and higher polarity of [C1C2im]+ [FeCl4]- (at 1wt%) combined with [C1C12im]+[FeCl4]- surfactant (between 3 and 5wt%) and non-polar 1-Hexanol co-surfactant (at 10 wt%)were the best combination to create a stable magnetic microemulsion in 2-ethylhexyl laurate. Applications for this microemulsion could vary from improved oil recovery to transport ofmaterials in liquid medium for examples and have all in common a better and tunablecontrollability of the used liquid via magnetic fields. / Denna forskningsuppsats rapporterar experimentellt arbete som gjorts för att designa enstabil magnetisk mikroemulsion av jonisk vätska i 2-EtylHexyllaurat med hjälp av ett jonisktytaktivt ämne och ett alkoholsamverkande ytaktivt ämne. De joniska vätskorna som testadesvar baserade på en 1,3-dialkylimidazoliumkatjon med olika alkylkedjelängder och entetraklorferratanjon ([FeCl4]+) för att säkerställa att emulsionen är känslig för applicerademagnetfält. Tester av lösligheten av dessa joniska vätskor har utförts i olika lösningsmedel ocholjor. Emulgeringstester har gjorts med olika dispergeringsmedium, ytaktiva ämnen samt medolika mängd komponenter för att hitta bästa möjliga sammansättning. Polaritet ochkedjelängd för alkylradikaler i joniska vätskor och kolväten i alkoholsamverkande ytaktivaämnen visade sig påverka emulgeringsprocessen. Kortare kedjor och högre polaritet för[C1C2im]+[FeCl4]- (vid 1 wt%) kombinerat med [C1C12im]+[FeCl4]- ytaktivt ämne (mellan 3 och 5 wt%) och opolär 1-hexanol medytaktivt medel (vid 10 wt% var den bästa kombinationen föratt skapa en stabil magnetisk mikroemulsion i 2-EtylHexyllaurat. Tillämpningar för denna mikroemulsion kan variera från förbättrad oljeutvinning tilltransport av material i flytande medium till exempel och har alla gemensamt en bättre ochavstämbar styrbarhet av den använda vätskan via magnetfält.

As easy target reservoirs are depleted around the world, the need for intelligent enhanced oil recovery (EOR) methods increases. The first part of this work is focused on modeling aspects of novel chemical EOR methods for naturally fractured reservoirs (NFR) involving wettability modification towards more water wet conditions. The wettability of preferentially oil wet carbonates can be modified to more water wet conditions using alkali and/or surfactant solutions. This helps the oil production by increasing the rate of spontaneous imbibition of water from fractures into the matrix. This novel method cannot be successfully implemented in the field unless all of the mechanisms involved in this process are fully understood. A wettability alteration model is developed and implemented in the chemical flooding simulator, UTCHEM. A combination of laboratory experimental results and modeling is then used to understand the mechanisms involved in this process and their relative importance. The second part of this work is focused on modeling surfactant/polymer floods using a fully implicit scheme. A fully implicit chemical flooding module with comprehensive oil/brine/surfactant phase behavior is developed and implemented in general purpose adaptive simulator, GPAS. GPAS is a fully implicit, parallel EOS compositional reservoir simulator developed at The University of Texas at Austin. The developed chemical flooding module is then validated against UTCHEM. / text