Dans ce travail de thèse, nous avons préparées des émulsions de Pickering innovantes, stabilisées par des nanoparticules (NP) biocompatibles et biodégradables de poly (acide lactique-co-glycolique) (PLGA), en utilisant du Miglyol comme phase huileuse. Ces systèmes permettent de s’affranchir de l’ajout de tensioactifs synthétiques, utilisés pour stabiliser les émulsions classiques, et qui sont souvent à l’origine d’irritations lors de traitements topiques chroniques. Dans ces émulsions ont été co-encapsulées deux substances actives, la première, un agent immunosuppresseur, dans les NP PLGA, la seconde, un agent anti-inflammatoire, dans les gouttelettes de Miglyol.Dans un premier temps, une étude physicochimique approndie a permis de mieux comprendre les mécanismes de stabilisation de ces émulsions, en fonction du type de NP utilisé. Aussi, l’influence de l’ajout de substances actives a été évaluée sur les structures macroscopique, microscopique et interfaciale des émulsions, mais également sur leur stabilité. Dans un deuxième temps, nous avons démontré que l’ajout de Carbopol, un polymère épaississant, permettait d’améliorer la stabilité, la texture et le pH des émulsions. Enfin, le potentiel thérapeutique d’un tel système à été évalué de manière préliminaire, notamment sa cytotoxicité sur des cultures de kératinocytes, mais aussi son activité immunosuppressive sur des cellules immunitaires activées et leur production de cytokines. Un tel système peut donc s’avérer intéressant pour le traitement de pathologies cutanées chroniques. / In this thesis work, we formulated innovative Pickering emulsions, stabilized by biocompatible and biodegradable poly (lactic-co-glycolic acid) nanoparticles (NP), using Miglyol as the oil phase. These systems could be an alternative to conventional emulsions, often stabilized with synthetic surfactants that can be responsible for irritation in particular during long-term topical treatments. Two active pharmaceutical ingredients (API) were successfully co-encapsulated, the first one, an immunosuppressant agent, entrapped in PLGA NP, the second one, an anti-inflammatory agent, incorporated in Miglyol droplets.Firstly, a thorough physicochemical characterization allowed to better understand the stabilization mechanism of these emulsions, depending on the type of NP used. Moreover, the influence of the addition of API was evaluated on the macroscopic, microscopic and interfacial structures of the emulsions, also on their stability. Secondly, we demonstrated that the addition of Carbopol, a thickening agent, improved the stability, texture and pH of emulsions. Finally, the therapeutic potential of such system was investigated through preliminary evaluation of its cytotoxicity on keratinocyte cells, but also its immunosuppressive activity on activated immune cells and their cytokine production. Such a system could be interesting for the treatment of chronical skin diseases.

Cette thèse est consacrée à la fabrication et à l’étude d’une nouvelle classe de matériaux à gradient d’indice acoustique (GRIN) pour la manipulation des ondes acoustiques ultrasonores dans l’eau. Comme en optique, les « GRIN acoustiques » sont des matériaux non homogènes, dans lesquels l'indice de réfraction acoustique n =C_(L,eau/air)/C_(L,matériau) varie en fonction de la position à l'intérieur du matériau. Ici, C_(L,eau/air) and 〖 C〗_(L,matériau) sont respectivement les vitesses des ondes acoustiques dans un milieu de référence (l’eau pour l'acoustique sous-marine dont il est question ici) et dans le matériau. Nous décrivons ici la fabrication de matériaux GRIN ultra-minces (c’est-à-dire sub-longueur d’onde) que nous désignons de fait sous le terme de métasurfaces acoustiques « molles » à gradient d’indice, conçues à partir de silicone poreux à indice acoustique élevé. Nous montrons que ces matériaux permettent a priori la génération de tous types de fronts d’onde en milieu sous-marin, et ce sur une très large bande de fréquence des ondes ultrasonores. / This thesis is devoted to the fabrication and the study of a novel class of acoustic gradient index (GRIN) materials for the manipulation of waterborne acoustic waves. As in optics, acoustic GRIN are inhomogeneous materials, in which the acoustic refractive index n =C_(L,water/air)/C_(L,material) varies as a function of the position inside the material. Here, C_(L,water/air) and 〖 C〗_(L,material) are the acoustic wave speeds in a reference medium (water for underwater acoustics) and in the material respectively. We here describe the fabrication of ultrathin (i.e. sub-wavelength) GRIN materials named “Soft acoustic gradient index metasurfaces” engineered from soft graded-porous silicone rubbers with a high acoustic index for broadband ultrasonic three-dimensional wave-front shaping in water.

Atualmente, tem se dado grande importância à criação de novos sistemas de liberação de princípios ativos. Na área cosmética, os sistemas em destaque são nanoemulsões, emulsões múltiplas e emulsões contendo cristais líquidos/fase gel lamelar. Nas emulsões múltiplas coexistem emulsões dos tipos O/A e A/O. Elas possuem inúmeras vantagens sobre outros sistemas de liberação, como por exemplo, a possibilidade de veicular dois ativos incompatíveis em compartimentos diferentes e controlar o perfil de liberação dos mesmos. Além disso, possuem biocompatibilidade, completa biodegradabilidade e podem ser usados diferentes óleos e tensoativos. Outra tendência recente em cosmetologia é o emprego de matérias-primas vegetais associadas a sistemas de liberação de princípios ativos, para formulação de novos produtos com apelo comercial e sustentável. O objetivo deste trabalho foi desenvolver um novo sistema de emulsão múltipla, por etapa única, que tivesse estabilidade características diferenciadas. Para tanto, elegeu-se dois óleos vegetais: girassol e gergelim, que foram usados separadamente no desenvolvimento dessas emulsões. O método de emulsificação utilizado foi o método de inversão de fases (EPI). Foi determinado o EHL crítico para cada um dos óleos, 6,5 para o óleo de girassol e 5,0 para o óleo de gergelim. Os pares de tensoativos escolhidos para o estudo foram Steareth 2 - Steareth 20 para óleo de girassol e Span® 60 - R400 para óleo de gergelim. Foram construídos dois diagramas pseudoternários, um para cada sistema, com o objetivo de definir variáveis relevantes à composição (fração aquosa, fração oleosa, porcentagem de tensoativo). Foram selecionadas as melhores emulsões para prosseguimento dos estudos de estabilidade, avaliada por meio dos seguintes testes físico-químicos: medições de pH, condutividade elétrica, granulometria e medidas reológicas. O método de emulsificação em etapa única por inversão de fases se mostrou eficiente na produção de emulsões múltiplas estáveis. Foi desenvolvida uma emulsão múltipla com características diferenciadas a partir do óleo de girassol: emulsão múltipla contendo fase gel-lamelar, um sistema ainda não descrito na literatura. As características das emulsões múltiplas descritas nesse trabalho, a saber: o uso de óleos vegetais como os óleos de girassol e gergelim; baixas concentrações de tensoativos; multiplicidade dos glóbulos e fase gel lamelar no mesmo sistema; são características desejáveis para a indústria cosmética, o que as tornam potenciais sistemas de liberação de ativos. / Currently, it has been given great importance to the creation of new delivery systems for active ingredients. In the cosmetic area, the highlighted systems are nanoemulsions, multiple emulsions and liquid crystal/lamellar gel phase emulsions. In multiple emulsions coexist O/W and W/O types of emulsions. They have several advantages over other delivery systems, such as the possibility of carry out two incompatible active ingredients in different compartments and the control of the release of the same. Moreover, they have biocompatibility, biodegradability and different oils and surfactants can be used. Another recent trend in cosmetology is the use of vegetable raw materials associated with the delivery systems for active ingredients, to formulate new products with commercial and sustainable appeal. The objective of this study was to develop a new system of multiple emulsion, in one step emulsification, which have stability and distinctive features. It was selected two vegetable oils: sunflower and sesame, which were used separately in the development of the multiple emulsions. The method of emulsification used was emulsion phase inversion (EPI). The critical HLB of oils was, 6.5 for sunflower oil and 5.0 for sesame oil, respectively. The pairs of surfactants chosen for the study were Steareth 2 - Steareth 20 for sunflower oil and Span® 60 - R400 for sesame oil. We constructed two pseudo-ternary diagrams, one for each system, in order to define variables relevant to the composition (water and oil fraction, percentage of surfactant). We selected the best emulsions for further investigation. Stability of the emulsions was evaluated by the following physico-chemical tests: measurements of pH, electrical conductivity, particle size and rheological measurements. The method of one-step emulsification was efficient in producing stable multiple emulsions. A multiple emulsion from sunflower oil was developed with distinctive features: gel-lamellar phase multiple emulsion, a system not described yet. The characteristics of multiple emulsions described in this work, to know: use of vegetable oils, as sunflower and sesame oils; low concentrations of surfactants; multiplicity of droplets and lamellar gel phase at same system; they are desirable characteristics for the cosmetic industry, and they make these multiple emulsion potential delivery systems.

Atualmente, tem se dado grande importância à criação de novos sistemas de liberação de princípios ativos. Na área cosmética, os sistemas em destaque são nanoemulsões, emulsões múltiplas e emulsões contendo cristais líquidos/fase gel lamelar. Nas emulsões múltiplas coexistem emulsões dos tipos O/A e A/O. Elas possuem inúmeras vantagens sobre outros sistemas de liberação, como por exemplo, a possibilidade de veicular dois ativos incompatíveis em compartimentos diferentes e controlar o perfil de liberação dos mesmos. Além disso, possuem biocompatibilidade, completa biodegradabilidade e podem ser usados diferentes óleos e tensoativos. Outra tendência recente em cosmetologia é o emprego de matérias-primas vegetais associadas a sistemas de liberação de princípios ativos, para formulação de novos produtos com apelo comercial e sustentável. O objetivo deste trabalho foi desenvolver um novo sistema de emulsão múltipla, por etapa única, que tivesse estabilidade características diferenciadas. Para tanto, elegeu-se dois óleos vegetais: girassol e gergelim, que foram usados separadamente no desenvolvimento dessas emulsões. O método de emulsificação utilizado foi o método de inversão de fases (EPI). Foi determinado o EHL crítico para cada um dos óleos, 6,5 para o óleo de girassol e 5,0 para o óleo de gergelim. Os pares de tensoativos escolhidos para o estudo foram Steareth 2 - Steareth 20 para óleo de girassol e Span® 60 - R400 para óleo de gergelim. Foram construídos dois diagramas pseudoternários, um para cada sistema, com o objetivo de definir variáveis relevantes à composição (fração aquosa, fração oleosa, porcentagem de tensoativo). Foram selecionadas as melhores emulsões para prosseguimento dos estudos de estabilidade, avaliada por meio dos seguintes testes físico-químicos: medições de pH, condutividade elétrica, granulometria e medidas reológicas. O método de emulsificação em etapa única por inversão de fases se mostrou eficiente na produção de emulsões múltiplas estáveis. Foi desenvolvida uma emulsão múltipla com características diferenciadas a partir do óleo de girassol: emulsão múltipla contendo fase gel-lamelar, um sistema ainda não descrito na literatura. As características das emulsões múltiplas descritas nesse trabalho, a saber: o uso de óleos vegetais como os óleos de girassol e gergelim; baixas concentrações de tensoativos; multiplicidade dos glóbulos e fase gel lamelar no mesmo sistema; são características desejáveis para a indústria cosmética, o que as tornam potenciais sistemas de liberação de ativos. / Currently, it has been given great importance to the creation of new delivery systems for active ingredients. In the cosmetic area, the highlighted systems are nanoemulsions, multiple emulsions and liquid crystal/lamellar gel phase emulsions. In multiple emulsions coexist O/W and W/O types of emulsions. They have several advantages over other delivery systems, such as the possibility of carry out two incompatible active ingredients in different compartments and the control of the release of the same. Moreover, they have biocompatibility, biodegradability and different oils and surfactants can be used. Another recent trend in cosmetology is the use of vegetable raw materials associated with the delivery systems for active ingredients, to formulate new products with commercial and sustainable appeal. The objective of this study was to develop a new system of multiple emulsion, in one step emulsification, which have stability and distinctive features. It was selected two vegetable oils: sunflower and sesame, which were used separately in the development of the multiple emulsions. The method of emulsification used was emulsion phase inversion (EPI). The critical HLB of oils was, 6.5 for sunflower oil and 5.0 for sesame oil, respectively. The pairs of surfactants chosen for the study were Steareth 2 - Steareth 20 for sunflower oil and Span® 60 - R400 for sesame oil. We constructed two pseudo-ternary diagrams, one for each system, in order to define variables relevant to the composition (water and oil fraction, percentage of surfactant). We selected the best emulsions for further investigation. Stability of the emulsions was evaluated by the following physico-chemical tests: measurements of pH, electrical conductivity, particle size and rheological measurements. The method of one-step emulsification was efficient in producing stable multiple emulsions. A multiple emulsion from sunflower oil was developed with distinctive features: gel-lamellar phase multiple emulsion, a system not described yet. The characteristics of multiple emulsions described in this work, to know: use of vegetable oils, as sunflower and sesame oils; low concentrations of surfactants; multiplicity of droplets and lamellar gel phase at same system; they are desirable characteristics for the cosmetic industry, and they make these multiple emulsion potential delivery systems.

Different scenarios for assembling rod-like and spherical colloidal particles using binary mixtures of partially miscible liquids were investigated experimentally. Suitable rod-like colloids were developed first. The subsequent studies of colloids in binary liquids consisted, on one hand, of systems where particles were partially wetted by both phases and, on the other hand, of systems where particles were completely wetted by the minority phase. A simple method to prepare large quantities of micrometer-sized akagan eite-silica core-shell rods was developed. These were proven to be very versatile, with the possibility of modifying their properties on different levels. The aspect ratio is simply controlled by a gradual growth of the silica shells. From them, hollow silica rods and rods with an increased responsiveness to a magnetic field could be obtained in straightforward ways. Bijels were prepared by trapping rod-like particles on a percolating liquid-liquid interface. The familiar bicontinuous organization of liquid domains was observed after structural arrest. At a fixed volume per particle it is demonstrated that for rod-like particles the domain size decreases faster with increasing quantity of particles than in the case of spherical particles. Additionally, the packing of the rods at the interface was elucidated, revealing several characteristic features. In particle-stabilized droplet emulsions rapid evaporation of the continuous phase and eventual full mixing of the liquid phases can leave a cellular network of particles. The formation and eventual stability of these networks were investigated in detail with confocal microscopy. When colloids are completely wetted by the minority component of an asymmetric binary mixture there can be substantial temperature and composition regimes outside the binodal where shear-induced aggregation can take place. This happens as adsorbed layers present at the particle surfaces coalesce and bind particles through a liquid bridge. Depending on particle concentration, percolating networks can form of rods wetted by the minority phase after temperature quenching such a system just across the binodal.

Des émulsions particulièrement stables peuvent être formulées à l’aide de particules colloïdales (émulsions dites de Pickering). L’objectif de cette étude est d’accéder à la compréhension des mécanismes de stabilisation des interfaces, ainsi que du lien entre propriétés interfaciales et propriétés macroscopiques des émulsions. Dans ce cadre, la stratégie adoptée repose sur l’utilisation de particules colloïdales dont les caractéristiques peuvent être variées continûment à la fois en amont par la chimie de synthèse (variation de la mouillabilité, de la déformabilité) et in situ par un stimulus (pH, sel, température...). De plus,les émulsions stabilisées par de telles particules deviennent, elles aussi, sensibles aux stimuli et la déstabilisation des émulsions peut être déclenchée à la demande. Les mécanismes d’adsorption, les interactions entre particules aux interfaces et les propriétés résultantes des émulsions sont étudiés. L’établissement de concepts généraux régissant la stabilisation/déstabilisation des émulsions permet d’en contrôler, via la formulation ou le procédé (température, cisaillement), les propriétés d’usage. Enfin les émulsions stabilisées par des particules colloïdales peuvent être utilisées en tant que précurseurs dans la formulation de matériaux plus complexes : ceci est illustré par l’élaboration de capsules à libération thermostimulée / Highly stable emulsions can be formulated using colloidal particles as stabilizers (so-calledPickering emulsions). This study aims at understanding the interfacial stabilizationmechanisms as well as the links between the interfacial properties and the macroscopicproperties of emulsions. In this context, our strategy consists in using colloidal particles forwhich characteristics can be continuously tuned either during the synthesis (variation of theparticles’ wettability or deformability) or in situ by using a stimulus (pH, salt, temperature…).Emulsions stabilized by such particles are stimuli responsive and their destabilization can betriggered on demand. We study and report the mechanisms of particle adsorption, theinteractions between particles anchored at interfaces and the resulting properties of emulsions.Such study allows us to draw general concepts governing the emulsionsstabilization/destabilization and to control their end-use properties via formulation oremulsification process (temperature, shear). Colloidal particle stabilized-emulsions can beused as templates to synthesize more complex materials as illustrated by the elaboration ofcapsules allowing a thermally controlled delivery of their content.

[pt] A presença de emulsões durante a produção de óleo causa vários problemas e traz desafios tecnológicos a serem vencidos, já que afeta a produtividade dos poços, a elevação artificial, o tempo de vida dos equipamentos e o processo de separação do óleo produzido. Existe incerteza em relação à origem das emulsões geradas durante a produção de petróleo, podendo resultar do escoamento no meio poroso, do fluxo turbulento no fundo do poço, nas bombas, ou nas instalações de superfície. Este trabalho é focado na geração de emulsões no meio poroso e em alguns aspectos das emulsões produzidas em escoamentos turbulentos. Emulsões podem ser formadas no escoamento bifásico em um meio poroso através de diversos mecanismos. A quebra de gotas da fase não molhante durante a passagem por uma garganta é um dos mecanismos mais importantes. Este fenômeno foi estudado em detalhe através da visualização do escoamento de grandes gotas de óleo suspensas em água através de uma garganta de poro. Foi obtido o mapeamento numa única curva das condições que levam à quebra de gota dentro de um capilar com garganta. Os resultados obtidos determinam as condições nas quais o processo de emulsificação ocorre em um meio poroso. O estudo de geração de emulsões no escoamento turbulento foi focado no estudo do tipo de emulsão (distribuição de tamanho de gotas e fase externa) obtida através de mistura de óleo e água em um misturador, em função da concentração e propriedades das fases. Especial atenção é dada às condições necessárias para a inversão da fase externa e formação de água livre. Os resultados obtidos permitem conhecer a influência das propriedades e concentração das fases no tipo de emulsão produzida, alem de proporcionar ferramentas que permitem o monitoramento remoto da morfologia das emulsões que escoam em algum ponto específico dos processos de produção, desde o fundo de poço até as instalações de superfície. / [en] Emulsion formation during oil production may take place in the flow inside the reservoir or in the two-phase flow down hole in production wells, and through pipelines and valves in surface facilities. Emulsions can cause a number of operational problems such as tripping of equipment in gas-oil separations plants and high pressure drops in flow lines. Flow conditions responsible for generation of emulsions present at the surface, going from porous media, turbulence down hole, through pumps, or in surface facilities, are uncertain, and their effects on the drop size, are not well understood. The present work is focused on emulsion generation inside reservoirs and in some aspects of the produced emulsions in turbulent flow. Emulsions can be formed in the two-phase flow inside a porous media by different mechanism. Snap-off of the non-wetting phase drops as there flow through pore throats is one of these mechanisms. This phenomenon is analyzed in this work by visualizing the flow of large oil drops suspended in water through a glass micro-capillary with a constriction. The conditions at which the snap-off occurs were mapped as a function of the operating parameters. The results define the conditions at which emulsification by snap-off occurs inside a porous media. Study of emulsion formation in a turbulent flow was focused on the characteristics of the produced emulsion (external phase and diameter size distribution) as a function of the phase concentration and properties. Conditions for emulsion inversion were analyzed as a function of the phases properties and concentration. The results can be used to estimate the state of emulsification as a function of process conditions at different locations, from the reservoir to the surface facilities.

A cinética plasmática de uma emulsão lipídica, que se liga aos receptores de LDL, foi estudada em 23 pacientes com Doença Arterial Coronariana (DAC) e em 16 indivíduos sadios (não apresentaram lesões obstrutivas, nem irregularidades, após serem submetidos à cineangiocoronariografia). Foram selecionados 39 participantes, sendo 30 do sexo masculino e 9 do sexo feminino, na faixa etária de 30 a 84 anos, com índice de Massa Corpórea (IMC) entre 21 e 41 ( kg/m2 ) , divididos em 2 grupos: DAC e Sadio. Após jejum de 12 horas, foram coletadas amostras de sangue total para determinação dos níveis séricos de lipídios e apolipoproteínas. A seguir foram injetadas, endovenosamente, emulsões com marcação radioativa, constituídas por lípides puros (40 mg), trioleína (TG) 1 mg, oleato de colesterol (CE) 20 mg, colesterol (CL) 0,5 mg e os isótopos radioativos 14C-oleato de colesterol e 3H-colesterol. 3H-colesterol. A cada participante foi administrado um volume da emulsão, correspondente à atividade de 37 kBq para o isótopo 14C e de 74 kBq para o isótopo 3H. Amostras de sangue foram colhidas nos intervalos 0,08 , 1, 4, 10 e 24 h , após a aplicação da emulsão. O colesterol-éster e o colesterol livre foram isolados e tiveram suas radioatividades medidas em cintilador. As taxas fracionais de remoção do 14C-oleato de colesterol e do 3H-colesterol livre, foram estimadas por análise compartimental, com auxílio de um programa computacional. Observou-se que: - não há diferença entre os dois grupos, em relação à idade, porcentagem de indivíduos do sexo masculino e feminino e o IMC. Pacientes do grupo DAC apresentam níveis de HDL-colesterol (p=0,0005) e de apolipoproteína A 1 ( p=0,009), reduzidos em relação aos indivíduos do grupo Sadio. As taxas fracionais de remoção do 14C-oleato de colesterol não diferiram entre os grupos DAC e Sadio (0,107± 0,026 horas -1VS 0,064± 0,009 horas -1, p=ns ). A taxa fracional de remoção do 3H-colesterol livre foi maior no grupo DAC do que no Sadio (0,152±0,014 horas -10,096± 0,019 horas-1, p=0,032). A taxa fracional de remoção do 3H-colesterol livre correlacionou-se diretamente com os níveis plasmáticos de triglicérides (r=0,37, p=0,002) e inversamente com os de HDL-C(r=-0,47, p=0,002) e LDL-C (r= -0,35, p = -0,03). Não houve diferença significativas entre os perfis lipídicos e de apolipoproteínas dos pacientes do grupo DAC e os dos indivíduos do grupo Sadio / The plasma kinetics of a lipidic emulsion that binds to LDL receptors was studied in patients with coronary artery disease (CAD) and in control subjects without CAD as documented by coronary angiography. CAD group consistent in 23 subjects (20 male and 3 of female sex , 37-70 year 21-37 body mass index), whereas the healthy control group had 16 subjects (10 male,30-84 aged, 21-41 body mass index). The emulsion was prepared by ultrassonic irradiation of a lipid mixture in aqueous buffer and purified by a two-step ultracentrifugation procedure. The emulsion composition was lipids (40 mg), triglycerides (1 mg), cholestero! (0,5 mg), cholesterol oleate( 20 mg) and was labeled with C14 and 3H . The emulsion vvas injected intravenously into the subjects after a 12 h fast and plasma samples were colected at 0.08, 1, 4, 10 and 24 hour time periods after the injection for determination of the plasma decaying curves of the radioactive lipids. \\/\\lith this purpose, the plasma samp!es were lipid extracted and the lipids were separated by thin-Iayer chromatography. Radioactivity was counted in a liquid scintillation solution. The plasma Fractional Clearance Rate (FC R, in h -1 ) was estimated from the decaying curves by the method of minimum squares, with the aid of a computational software. The two study groups did not differ regarding age, sex, and BMI. The CAD group had smaller plasma HDL cholesterol and apolipoprotein (apo) A1 values, but LDL and VLDL cholesterol as well as apo B, were similar between the two groups. 14C-cholesteryl ester FCR-of the CAD group was not different from the controls (CAD: and Healthy:,p). However, 3H-cholesteroi FCR was greater in the CAD group than in the controls (0,152 ±0,014 h -1 vs 0,096± 0,019 h -1 ,p=0,032 ). 3H cholesterol FCR was positively correlated with triglyceride plasma concentration ( r=0,37, p=0,002) and negatively correlated with HDL (r= -0,47, p=0,002) and LDL (r= -0,35, p=0,03). Therefore, the emulsion particles were similarly removed from the circulation in both CAD and healthy groups. Disturbances of cholesterol esterification and removaI from the plasma of free-cholesterol are related with presence od CAD.

<div>Fluid interfaces containing surface-active species (e.g., surfactants, polymers, and particles) have rheological properties that are vital to the kinetic stability of emulsions. Many practical applications of emulsions necessitate superb stability during storage, such as in emulsion-based therapeutic delivery systems. While in other cases, stabilized systems are entirely unwanted (e.g., separating oil and aqueous phases in enhanced oil recovery and bilge water applications).</div><div><br></div><div>Techniques for modulating emulsion stability are highly desired and are largely determined by the mechanics of the interfacially-trapped species. However, the utility of these techniques is often limited by difficulties in measuring and interpreting the rheological characteristics of complex fluid interfaces. Lack of control over interface formation during emulsification magnifies this problem, further obscuring relationships between interfacial rheology and bulk emulsion stability. Thus, the objectives of this research were to (1) elucidate these fundamental relationships through emulsion stability and interfacial rheological measurements, and (2) present innovative methodologies for modulating the kinetic stability of model oil-in-water emulsions using physical chemistry principles.</div><div><br></div><div>Objective 1 was addressed by studying correlations between the dilatational rheology of single- and multi-component oil-water interfaces and the susceptibility to coalescence of the bulk systems they comprised. Oscillating pendant drop tensiometry was used to probe interfacial viscoelastic behavior, while dynamic light scattering and optical microscopy were used to characterize coalescence susceptibility in bulk oil-in-water emulsions. The magnitude of the low-frequency dilatational elastic modulus was shown to positively correlate with oil droplet coalescence resistance over time. Objective 2 was addressed by analyzing how physical chemistry principles can be applied to control various emulsion droplet destabilization phenomena and produce desirable bulk behavior. To this aim, two emulsion destabilization studies were performed; one related to the nanoparticle-induced flocculation of oil droplets in a dilute, electrostatically-stabilized emulsion and one related to the convective flows generated by the asymmetric dilatational rheology of coalescing droplets. <br></div><div><br></div><div>The knowledge garnered from this body of work is highly relevant to academic and industrial emulsion formulators who seek inexpensive, yet robust methods for predicting, characterizing and tailoring the kinetic stability of oil-in-water emulsions.</div>

The better understanding of the behavior of emulsions and suspensions is important in many applications. In general, emulsions allow the delivery of insoluble agents to be uniformly distributed in a more efficient way. At the same time suspensions of rigid particles are used as “smart materialsâ€� as their properties can be changed by the interaction with a magnetic or electric field. In the first part of the talk we consider a periodic emulsion formed by two Newtonian fluids in which one fluid is dispersed under the form of droplets of arbitrary shape, in the presence of surface tension. We assume the droplets have fixed centers of mass and are only allowed to rotate. We are interested in the time-dependent, dilute case when the characteristic size of the droplets aε, of arbitrary shape, is much smaller than the period length ε. We obtain a Brinkman type of fluid flow for the critical size aε = O(ε3) as a replacement of the Stokes flow of the emulsion. Additionally, using Mosco convergence and semigroup theory we extend the convergence to the parabolic case. For the case when the droplets convect with the flow, it can be shown again using Mosco-convergence that, as the size of the droplets converges to zero faster than the distance between the droplets, the emulsion behaves in the limit like the continuous phase and no “strangeâ€� term appears. Moreover, we determine the rate of convergence of the velocity field for the emulsion to that of the velocity for the one fluid problem in both the H1 and L2 norms. Additionally, a second order approximation is determined in terms of the bulk and surface polarization tensors for the cases of uniform and non-uniform surface tension. The second part of the talk is devoted to the study of MR fluids. We consider a suspension of rigid magnetizable particles in a non-conducting, viscous fluid with an applied external magnetic field. Thus, we use the quasi-static Maxwell equations coupled with the Stokes equations to capture the magnetorheological effect. We upscale using two scale asymptotic expansions to obtain the effective equations consisting of a coupled nonlinear system in a connected phase domain as well as the new constitutive laws. The proposed model generalizes the model of Rosenweig by coupling the velocity of the fluid and the magnetic field intensity. Using the finite element method we compute the effective coefficients for the MR fluid. We analyze the resulting MR model for Poiseuille and Couette flows and compare with experimental data for validation.