Many materials and biological systems in nature are suspensions composed of disks, such as clay, asphaltenes, and red blood cells. Despite their natural abundance and wide industrial application, disks are least studied compared to spheres and rods, due to the lack of model systems. In our research, disks at micro-scale were mass-produced with unprecedented uniformity in size and shape, and unique flexibility in the control of lateral size, lateral size polydispersity, shape, and aspect ratio (ξ = diameter/thickness). This dissertation focuses on two main areas: the study of the discotic colloidal liquid crystal phase transitions and the application of disk-like colloidal systems as Pickering emulsion and Pickering foam stabilizers. First, we engineered two discotic colloidal systems made from organic and inorganic materials. The former is made of α-eicosene, which is an alkene of 20 carbons. The latter is composed of nano-sheets from exfoliated zirconium phosphate (α-ZrP). Both discotic systems were used to experimentally investigate the liquid crystalline phase transitions (Isotropic-Nematic, Isotropic-Cubic and Isotropic-Columnar). Also, the nematic crystalline phase was studied in detail by embedding it in a translucent and thermo-sensitive hydrogel. This was possible since nematic textures could be formed instantly by ZrP nano-sheets due to their high diameter-thickness ratio. Second, we developed Pickering emulsions and Pickering foams stabilized by high-aspect-ratio nano-sheets. We have also demonstrated for the first time the fabrication of the thinnest amphiphilic Janus and Gemini nano-sheets, which are either surface- or edge-modified plates with a thickness at atomic scale. These nano-sheets were obtained by exfoliating α-ZrP crystals grafted with a coupling agent of hydrophobic molecules on their edges and outer surfaces. Extending this work, we studied crucial fundamental mechanisms that allow Pickering interfacial stabilization, including the effect on the adsorption properties of particle aspect ratio, concentration, and hydrophobicity. Our study is of great interest in the scientific community due to the difficulty in generating a discotic colloidal system of controllable parameters.

Particle stabilized emulsions, also known as Pickering emulsions, have been widely used in many industry applications. While the breadth of potential applications for Pickering emulsions keeps growing, our fundamental understanding of Pickering emulsions is still poor. My thesis work addresses both fundamentals and applications of particle stabilized emulsions. In the fundamental part of this thesis work, we investigated the effects of particle charge on particle adsorption and the particle contact angle, and to investigate their ensuing consequences for the stability of Pickering emulsions. We provided the first experimental hint that the widely overlooked image charge repulsion can hinder the adsorption of particle to the oil-water interface and prevent the formation of Pickering emulsions. Consistently with the experimental suggestion, our theoretical model also confirmed that the image charge repulsion has the right order of magnitude, relative to the other forces acting on the particle, to impede particle adsorption and Pickering emulsification. For the conditions in which particle adsorption to the liquid interface does occur, the particle contact angle will play an important role in influencing the stability and type of Pickering emulsions. Our experimental work showed that the equilibrium contact angle of particles at interfaces and the type of emulsions preferentially stabilized by these particles can be strongly affected by the particles' charging state, which we attribute to a free energy contribution from the electric field set up by the charged particle and its asymmetric counterion cloud. A very simplistic calculation considering only the dipole field as the leading contribution and treating the water phase as a perfect conductor, found that the energy stored in the field is indeed strong enough and shows sufficient variation with the particle position to shift the equilibrium position significantly from where it would be based on interfacial tension alone. In a separate, more application oriented part of this thesis work, we have fabricated microcapsules from double Pickering emulsions and demonstrated that the combined use of hard silica particles and pH-responsive dissoluble polymer particles at the emulsion interface imparts a combination of pH-responsiveness (stimulated pore opening) and structural integrity to resulting capsules. We have further demonstrated the first double Pickering emulsion templated capsules in which interfacial polymerization was carried out at both emulsion interfaces, yielding a capsule with two composite shells, composed of polyurethane and silica particles, and characterized the transport of a model cargo through the capsules walls as well as the capsules' mechanical properties.

Cette étude s’inscrit dans le cadre du projet de recherche collaboratif FOMOTEX (FOnctionnalisation de MOusses et TEXtiles innovants). Son objectif est le développement d’un procédé d’encapsulation de produits actifs lipophiles et notamment de retardateurs de flamme pour la fonctionnalisation de textiles. Pour permettre leur liage aux fibres textiles, leur préparation est basée sur la synthèse d’une double membrane dont la première a un rôle protecteur et dont la deuxième, thermofusible, permet la fixation sur le support lors de la mise en œuvre. Ce mémoire porte ainsi sur la sélection des matériaux utilisés pour préparer les particules, sur leur mise en œuvre et sur la compréhension des mécanismes de synthèse ainsi que sur la caractérisation des particules permettant l’optimisation des paramètres de synthèse. Une première partie de ce travail traite de l’utilisation de nanoparticules de silice pour la stabilisation prolongée de l’émulsion, dite de Pickering et la limitation des phénomènes d’exsudation de l’actif. Leur influence sur l’encapsulation par des procédés sol-gel est également étudiée. Une seconde partie concerne l’étude de l’influence des paramètres de formulation et de synthèse sur les caractéristiques de microparticules et l’optimisation de l’encapsulation par des procédés sol-gel. Enfin, dans une dernière partie, le concept de microcoencapsulation double membrane avec la membrane externe thermoliante aux fibres textiles a été validé. / This study was performed as a part of FOMOTEX collaborative research project (functionalization foams and Innovative textiles). The purpose is the development of an encapsulation process of lipophilic product as flame retardants for the functionalization of textiles. To allow the bonding to textile fibers, their preparation is based on the synthesis of a double wall particles, the first wall having a protective role and the second, melt, allowing the linkage on the textile support during processing . This thesis focuses on the selection of materials to prepare the particles, on their processing and on the understanding of the synthesis mechanisms of particle and on their characterization to enable the optimization of synthesis parameters. A first part deals with the use of silica nanoparticles to extend the stabilization of the emulsion, called Pickering emulsion, and to limit the exudation phenomena of the active substance. Their influence on the encapsulation by sol-gel processes is studied. A second part concerns the study of the influence of formulation and synthesis parameters on micropaticules characteristics and the optimization of the encapsulation by sol-gel processes. Finally, in a last part, the concept of double wall microcoencapsulation, the outer membrane allowing bonding to textile fibers, has been validated.

archives@tulane.edu / 1 / Azeem Farinmade

A produção de filmes biodegradáveis à base de amido representa um desafio tecnológico, pois estas matrizes são altamente sensíveis à água. Neste sentido, as pesquisas estão sendo realizadas a fim de melhorar as caraterísticas de hidrofobicidade sem afetar a integridade estrutural das matrizes. Dentre os compostos comumente empregados para melhorar as características de filmes biodegradáveis, pode-se mencionar os óleos e ácidos graxos. O óleo de sementes de melancia apresenta alto potencial de aplicação em matrizes filmogênicas, pois além da possibilidade de melhorar as propriedades de barreira, apresenta compostos fitoquímicos com atividade antioxidante, que podem conferir um caráter ativo aos materiais produzidos. Neste contexto, o objetivo deste trabalho foi desenvolver e caracterizar filmes à base de amido modificado de mandioca e óleo de sementes de melancia. O óleo de sementes de melancia foi extraído por batelada com etanol pressurizado, sob diferentes temperaturas de extração (40, 60 e 80°C) e diferentes comprimentos de leito de extração (L1 = 4,2 cm, L2 = 9,8 cm e L3 = 15,8 cm). A cinética de extração foi matematicamente descrita utilizando-se o modelo de Peleg e os óleos caraterizados quanto à atividade antioxidante. Posteriormente foram testados quatro amidos modificados de mandioca (amido reticulado, AR; amido acetilado, AA; amido não modificado, ANM e amido duplamente modificado, AAR) com a finalidade de selecionar o que apresentasse melhores caraterísticas na produção de filmes quanto ao caráter hidrofóbico. Os filmes foram produzidos pela técnica de casting, utilizando - se concentrações fixas de amido e sorbitol (4 e 1,2 g/100g de solução filmogênica, respectivamente). O caráter hidrofóbico das matrizes foi avaliado pela determinação da solubilidade, grau de inchamento, permeabilidade ao vapor de água e ângulo de contato. Adicionalmente, foram produzidas emulsões através da técnica de Pickering, com diferentes concentrações de óleo e amido e caraterizadas quanto à estabilidade, tamanho de partículas e polidispersidade. A emulsão com maior estabilidade foi incorporada na formulação de filmes à base de AR em concentrações de 0 a 0,5 g de óleo na emulsão/100 g de solução filmogênica. Todos os filmes foram caracterizados quanto às propriedades mecânicas, microscopia, espectroscopia de infravermelho (FTIR), difração de raios X, cor, solubilidade, inchamento, permeabilidade ao vapor de água e ângulo de contato. Os resultados da extração de óleos mostraram rendimentos superiores sob temperaturas de 80°C e melhor atividade antioxidante a 60°C. O modelo de Peleg apresentou um bom ajuste, observando-se coeficientes de correlação altos (R2 > 0,90). A caraterização dos filmes produzidos com diferentes amidos modificados mostrou que o AR formou matrizes com maior ângulo de contato, menor grau de inchamento e maior resistência mecânica. As emulsões com maior de estabilidade foram produzidas com altas concentrações de óleo e amido (15 e 12 g/100 g de emulsão, respectivamente). Os filmes produzidos com incorporação de óleo na forma de emulsão Pickering apresentaram caráter mais hidrofóbico, sendo também alteradas as caraterísticas estruturais com o aumento da concentração de óleo. Os filmes produzidos com a incorporação de óleo em forma de emulsão apresentaram conteúdos de fenólicos totais de 0,19 a 5,68 mg equivalente de ácido gálico/100g de filmes. No entanto, os filmes não apresentaram atividade antioxidante frente ao radical DPPH•. / The production of biodegradable films based on starch represents a technological challenge because these matrices are highly sensitive to water. In this sense, the research is being carried out in order to improve the characteristics of hydrophobicity without affecting the structural integrity of the matrices. Among the compounds commonly used to improve the characteristics of biodegradable films, the oils and fatty acids can be highlighted. The oil of the watermelon seeds presents high potential of application in filmogenic matrices because in addition to the possibility of improving the barrier properties, it presents phytochemical compounds with antioxidant activity, which can impart an active characteristic to the produced materials. In this context, the objective of this work was to develop and characterize films based on modified cassava starch and watermelon oil. The watermelon oil was extracted in batches with pressurized ethanol under different extraction temperatures (40, 60, and 80°C) and different extraction bed lengths (L1 = 4.2 cm, L2 = 9.8 cm, and L3 = 15.8 cm). The kinetics of extraction were mathematically described using the Peleg model and the oils characterized for antioxidant activity. Four modified starches of cassava (reticulated starch, AR, acetylated starch, AA, unmodified starch, ANM, and doubly modified starch, AAR) were then tested in order to select the material with the best hydrophobic characteristics. The films were produced by the casting technique, using fixed concentrations of starch and sorbitol (4 and 1.2 g/100 g of film-forming solution, respectively). The hydrophobic characteristic of the matrices was evaluated by determining the solubility, degree of swelling, permeability to water vapor, and contact angle. In addition, emulsions were produced using the Pickering technique with different concentrations of oil and starch and then, characterized for stability, particle size, and polydispersity. The results of the extraction showed higher yields under temperatures of 80°C and better antioxidant activity at 60°C. The Peleg model presented a good fit, observing high correlation coefficients (R2> 0.90). The characterization of the films produced with different modified starches showed that AR formed matrices with higher contact angle, lower degree of swelling, and higher mechanical resistance. Emulsions with the highest degree of stability were produced with high concentrations of oil and starch (15 and 12 g/100 g of emulsion, respectively). The films produced with oil incorporation in the form of Pickering emulsion presented a more hydrophobic characteristic, and the structural characteristics were also altered with the increase of oil concentration. The films produced with the incorporation of oil in emulsion form presented total phenolic contents of 0.19 to 5.68 mg of gallic acid equivalent/100 g of films. However, the films did not present antioxidant activity against the DPPH• radical.

Ce travail de thèse examine une nouvelle méthode prometteuse pour la dépollution efficace des eaux contaminées par des polluants organiques insolubles de type toluène, 1-méthylnaphtalène, nitrobenzène,…. Cette méthode d’oxydation avancée repose sur la photocatalyse hétérogène dans des émulsions de Pickering. Dans ce type d’émulsions, les tensioactifs stabilisants des gouttelettes huileuses sont remplacés par des nanoparticules solides à propriétés photocatalytiques élevées. Par ailleurs, ces nanoparticules solides doivent remplir les conditions de mouillabilité partielle dans les deux phases aqueuse et huileuse grâce à un équilibre hydrophile-hydrophobe à leur surface. Pour cette raison, le dioxyde de titane (TiO2) anatase a été préparé par la méthode sol-gel puis modifié par fluoration pour obtenir le catalyseur TiO2-F. L’objectif est de formuler des émulsions de Pickering de type huile dans l’eau (H/E) à partir de polluants organiques de faible solubilité dans l’eau. Les catalyseurs synthétisés ont été caractérisés par XRD, BET, SEM, DRS, XPS, et TG-TD-MS. Il a été montré que la fluoration apporte des changements importants dans les propriétés optiques du TiO2 et a amélioré l’équilibre hydrophile/hydrophobe à sa surface de façon significative. Par ailleurs, les résultats obtenus indiquent que des émulsions de Pickering stables peuvent être formulées en utilisant des particules de TiO2 ou TiO2-F de taille nanométrique. Le type et la stabilité des émulsions dépendent de la mouillabilité des nanoparticules stabilisantes évaluées par des mesures d'angle de contact. La mouillabilité des nanoparticules a été trouvée fortement dépendante du type d’huile en raison des contributions de la polarité et des interactions spécifiques avec les polluants. L'étude des émulsions de Pickering par conductivité électrique, microscopie optique et diffusion de la lumière a montré qu'une stabilité élevée a été obtenue dans des conditions de mouillage partiel : angle de contact dans l'eau compris entre 70 et 110°. L’évolution de la taille des gouttelettes d'huiles avec le rapport de masse huile/photocatalyseur a confirmé une forte adsorption des nanoparticules de catalyseur sur les gouttelettes d'huiles. Finalement, les émulsions jugées stables ont été photodégradées sous rayonnement UV. La cinétique de photodégradation des polluants organiques mesurée par HPLC a montré que la dégradation a été intensifiée en utilisant les émulsions de Pickering par rapport aux systèmes non émulsionnés. Ces résultats ont prouvé que l’utilisation des émulsions de Pickering stabilisées par des nanoparticules de dioxyde de titane constituait un moyen efficace et innovateur pour intensifier la dégradation photocatalytique des polluants organiques / This thesis examines a promising new method for the effective depollution of water contaminated by insoluble organic pollutants such as toluene, 1-methylnaphthalene, nitrobenzene, etc. This advanced oxidation method is based on heterogeneous photocatalysis in Pickering emulsions. In this type of emulsion, the stabilizing surfactants of the oily droplets are replaced by solid nanoparticles having high photocatalytic properties. Moreover, these solid nanoparticles must fulfill the conditions of partial wettability in both aqueous and oily phases thanks to a hydrophilic-hydrophobic balance on their surface. For this reason, the titanium dioxide (TiO2) anatase was prepared by the sol-gel method and then modified by fluorination to obtain the TiO2-F catalyst. The objective is to formulate Pickering oil-in-water (O/W) emulsions from organic pollutants of low water solubility. The synthesized catalysts were characterized by XRD, BET, SEM, DRS, XPS, and TG-TD-MS. It has been shown that fluorination brings about important changes in the optical properties of TiO2 (change in band gap) and improves the hydrophilic / hydrophobic balance at its surface significantly. Moreover, the obtained results indicate that stable Pickering emulsions can be formulated using TiO2 or TiO2-F nanoparticles. The type and stability of the emulsions depend on the wettability of the stabilizing nanoparticles evaluated by contact angle measurements. The wettability of the nanoparticles has been found to be highly dependent on the type of oil due to the contributions of polarity and specific interactions with pollutants. The study of Pickering emulsions by electrical conductivity, optical microscopy and light scattering showed that high stability was obtained under partial wetting conditions: contact angle in water between 70 and 110°. The change in the size of the oil droplets with the oil/photocatalyst mass ratio confirmed a strong adsorption of the catalyst nanoparticles on the oil droplets. Finally, the judged stable emulsions were photodegraded under UV radiation. The photodegradation kinetics of organic pollutants measured by HPLC showed that degradation was intensified using Pickering emulsions compared to non-emulsified systems. These results have shown that the use of Pickering emulsions stabilized by titanium dioxide nanoparticles is an effective and innovative way to intensify the photocatalytic degradation of organic pollutants

A produção de filmes biodegradáveis à base de amido representa um desafio tecnológico, pois estas matrizes são altamente sensíveis à água. Neste sentido, as pesquisas estão sendo realizadas a fim de melhorar as caraterísticas de hidrofobicidade sem afetar a integridade estrutural das matrizes. Dentre os compostos comumente empregados para melhorar as características de filmes biodegradáveis, pode-se mencionar os óleos e ácidos graxos. O óleo de sementes de melancia apresenta alto potencial de aplicação em matrizes filmogênicas, pois além da possibilidade de melhorar as propriedades de barreira, apresenta compostos fitoquímicos com atividade antioxidante, que podem conferir um caráter ativo aos materiais produzidos. Neste contexto, o objetivo deste trabalho foi desenvolver e caracterizar filmes à base de amido modificado de mandioca e óleo de sementes de melancia. O óleo de sementes de melancia foi extraído por batelada com etanol pressurizado, sob diferentes temperaturas de extração (40, 60 e 80°C) e diferentes comprimentos de leito de extração (L1 = 4,2 cm, L2 = 9,8 cm e L3 = 15,8 cm). A cinética de extração foi matematicamente descrita utilizando-se o modelo de Peleg e os óleos caraterizados quanto à atividade antioxidante. Posteriormente foram testados quatro amidos modificados de mandioca (amido reticulado, AR; amido acetilado, AA; amido não modificado, ANM e amido duplamente modificado, AAR) com a finalidade de selecionar o que apresentasse melhores caraterísticas na produção de filmes quanto ao caráter hidrofóbico. Os filmes foram produzidos pela técnica de casting, utilizando - se concentrações fixas de amido e sorbitol (4 e 1,2 g/100g de solução filmogênica, respectivamente). O caráter hidrofóbico das matrizes foi avaliado pela determinação da solubilidade, grau de inchamento, permeabilidade ao vapor de água e ângulo de contato. Adicionalmente, foram produzidas emulsões através da técnica de Pickering, com diferentes concentrações de óleo e amido e caraterizadas quanto à estabilidade, tamanho de partículas e polidispersidade. A emulsão com maior estabilidade foi incorporada na formulação de filmes à base de AR em concentrações de 0 a 0,5 g de óleo na emulsão/100 g de solução filmogênica. Todos os filmes foram caracterizados quanto às propriedades mecânicas, microscopia, espectroscopia de infravermelho (FTIR), difração de raios X, cor, solubilidade, inchamento, permeabilidade ao vapor de água e ângulo de contato. Os resultados da extração de óleos mostraram rendimentos superiores sob temperaturas de 80°C e melhor atividade antioxidante a 60°C. O modelo de Peleg apresentou um bom ajuste, observando-se coeficientes de correlação altos (R2 > 0,90). A caraterização dos filmes produzidos com diferentes amidos modificados mostrou que o AR formou matrizes com maior ângulo de contato, menor grau de inchamento e maior resistência mecânica. As emulsões com maior de estabilidade foram produzidas com altas concentrações de óleo e amido (15 e 12 g/100 g de emulsão, respectivamente). Os filmes produzidos com incorporação de óleo na forma de emulsão Pickering apresentaram caráter mais hidrofóbico, sendo também alteradas as caraterísticas estruturais com o aumento da concentração de óleo. Os filmes produzidos com a incorporação de óleo em forma de emulsão apresentaram conteúdos de fenólicos totais de 0,19 a 5,68 mg equivalente de ácido gálico/100g de filmes. No entanto, os filmes não apresentaram atividade antioxidante frente ao radical DPPH•. / The production of biodegradable films based on starch represents a technological challenge because these matrices are highly sensitive to water. In this sense, the research is being carried out in order to improve the characteristics of hydrophobicity without affecting the structural integrity of the matrices. Among the compounds commonly used to improve the characteristics of biodegradable films, the oils and fatty acids can be highlighted. The oil of the watermelon seeds presents high potential of application in filmogenic matrices because in addition to the possibility of improving the barrier properties, it presents phytochemical compounds with antioxidant activity, which can impart an active characteristic to the produced materials. In this context, the objective of this work was to develop and characterize films based on modified cassava starch and watermelon oil. The watermelon oil was extracted in batches with pressurized ethanol under different extraction temperatures (40, 60, and 80°C) and different extraction bed lengths (L1 = 4.2 cm, L2 = 9.8 cm, and L3 = 15.8 cm). The kinetics of extraction were mathematically described using the Peleg model and the oils characterized for antioxidant activity. Four modified starches of cassava (reticulated starch, AR, acetylated starch, AA, unmodified starch, ANM, and doubly modified starch, AAR) were then tested in order to select the material with the best hydrophobic characteristics. The films were produced by the casting technique, using fixed concentrations of starch and sorbitol (4 and 1.2 g/100 g of film-forming solution, respectively). The hydrophobic characteristic of the matrices was evaluated by determining the solubility, degree of swelling, permeability to water vapor, and contact angle. In addition, emulsions were produced using the Pickering technique with different concentrations of oil and starch and then, characterized for stability, particle size, and polydispersity. The results of the extraction showed higher yields under temperatures of 80°C and better antioxidant activity at 60°C. The Peleg model presented a good fit, observing high correlation coefficients (R2> 0.90). The characterization of the films produced with different modified starches showed that AR formed matrices with higher contact angle, lower degree of swelling, and higher mechanical resistance. Emulsions with the highest degree of stability were produced with high concentrations of oil and starch (15 and 12 g/100 g of emulsion, respectively). The films produced with oil incorporation in the form of Pickering emulsion presented a more hydrophobic characteristic, and the structural characteristics were also altered with the increase of oil concentration. The films produced with the incorporation of oil in emulsion form presented total phenolic contents of 0.19 to 5.68 mg of gallic acid equivalent/100 g of films. However, the films did not present antioxidant activity against the DPPH• radical.

Les microgels sont des particules colloïdales polymères faiblement réticulées, capables de se gonfler d’un solvant, de se déformer et de s’adsorber à des interfaces liquides. Parmi eux, les microgels de poly(N-isopropylacrylamide) (pNIPAM) sont thermosensibles et présentent une contraction en volume lorsque la température est supérieure à la température de transition de phase volumique, notée VPTT. De précédents travaux ont montré leur capacité à stabiliser des émulsions de Pickering : les émulsions peuvent être stables à des températures inférieures à la VPTT et être déstabilisées sur demande au-dessus de celle-ci. Afin d’approfondir la compréhension du mécanisme de stabilisation des émulsions, nous discutons le rôle de la structure des microgels sur leur adsorption, leur organisation à des interfaces modèles, les propriétés mécaniques des interfaces et les propriétés des émulsions résultantes en terme de stabilité (cinétique, mécanique) et de propriétés d’écoulement. Le rôle de la réticulation, de la présence de charges et de la taille est étudié pour le modèle du pNIPAM. Nous démontrons le lien existant entre conformation et propriétés macroscopiques des émulsions. En prenant en considération à la fois la structure des microgels et les procédés de formulation (voies d’émulsification), des émulsions avec des propriétés rhéologiques et des états de floculation variés peuvent être obtenues. Fort de ces connaissances, les concepts établis à l’aide des microgels de pNIPAM seront généralisés à d’autres familles de microgels, d’une part des systèmes biocompatibles avec des dérivés comportant des chaînes pendantes oligo(éthylène oxyde), d’autre part des microgels sensibles à des stimuli biologiques tels que la reconnaissance de sucre. / Microgels are soft and deformable colloidal particles that are swollen by a solvent and display the ability to deform and adsorb at liquid interfaces. The poly(N-isopropylacrylamide) (pNIPAM) microgels are thermo-sensitive and exhibit a volume contraction when the temperature is raised above the volume phase transition temperature (VPTT). These particle have shown high potential as Pickering emulsions stabilizers: emulsions could be stable at ambiant temperature, below the VPTT and destabilize on-demand above it. To get insight into understanding of the emulsion stabilization mechanism, we systematically discuss the relation between the microgel structure, their adsorption, their organization at model interfaces, the viscoelastic behavior of the interface and the resulting emulsions properties in terms of stability and flow behavior. In the present work, using pNIPAM as model microgels, we investigate the effect of their cross-linking density, their size and their charge density. Varying the microgels structures and the formulation conditions (emulsification process), we could control the emulsions flocculation state and rheological behavior. Based on this knowledge, we propose to synthesize new biocompatible microgels as emulsion stabilizers. Using ligand-modified microgels sucrose-sensitive emulsions may be obtained, enlarging the possible application domains.

La stabilisation des émulsions peut être assurée par des particules solides plutôt qu'avec des molécules d'émulsifiant. Les émulsions stabilisées par des particules solides sont aussi appelées “les émulsions de Pickering”. Ce travail est divisé en deux parties : <br />1) l'étude des aspects physico-chimiques des émulsions ; 2) l'évaluation des émulsions stabilisées par des solides pour l'application cutanée. <br />Les émulsions ont été stabilisées avec des nanoparticules de silice de caractère hydrophobe varié. Les émulsions huile-dans-eau obtenues avec de la silice partiellement hydrophobe ont été caractérisées en termes de stabilité, rhéologie et de quantité optimale de particules nécessaires pour la stabilisation. Les particules de silice hydrophile stabilisent les émulsions H/E avec des huiles très polaires. Le rôle de l'agrégation des particules en présence d'huile et d'électrolyte dans la stabilisation des émulsions a été souligné. Dans un deuxième temps, nous avons étudié l'absorption de principes actifs dans la peau, à partir des émulsions de Pickering, et nous avons comparé les résultats avec les émulsions classiques stabilisées par les tensioactifs. Les émulsions H/E et E/H avec des principes actifs modèles (rétinol comme molécule lipophile et caféine comme molécule hydrophile) ont été étudiées en terme d'absorption dans la peau. L'absorption des principes actifs a été significativement différente pour les émulsions stabilisées par des particules solides et pour les émulsions stabilisées par des molécules de tensioactif. Les émulsions de Pickering constituent une nouvelle formulation pour l'application cutanée.

The interfaces of bubbles and droplets imbue foams and emulsions with extraordinary mechanical and chemical properties. The remarkably large interfacial area of these structures controls their thermodynamics and makes them practical and functional materials. When these interfaces are forced to touch, they can turn a dispersion of one fluid in another into a solid. These solid-like properties are evident in common household products such as shaving foam and mayonnaise, and our ability to control the fluid and solid properties of these materials is essential to their function. / Physics