La situation durable de volatilité des prix du pétrole est considérée à la fois comme une menace et un défi par l'industrie pétrolière. Au cours de cette crise, les compagnies pétrolières ont l’opportunité de se recentrer sur la recherche de solutions de production rentables, ce qui implique souvent l’apport des nouvelles technologies, en plus de l'amélioration des processus.Ce travail présente une avancée pour la synthèse d’une nouvelle génération de fluides de forage pétrolier sans surfactants/émulsifiants pour des applications dans le forage des puits profonds et ultra profonds. Cette nouvelle génération repose sur l’introduction des émulsions de Pickering dans la formulation des fluides de forage. Ces dernières sont des émulsions stabilisées uniquement par des particules solides (dans ce cas des particules de silice). Différents types de nano particules de silice de différentes hydrophobicités ont été utilisées pour stabiliser des fluides de forage de types huile-dans-eau et eau-dans-huile. Ces fluides ont été conçus pour être utilisés dans des conditions hostiles de température et de pression. Par conséquent, une caractérisation expérimentale de leur stabilité ainsi que de leurs propriétés rhéologiques sous ces conditions extrêmes étaient nécessaires. Au cours de ce travail, les profils rhéologiques de ces fluides reflétant leurs capacités de nettoyage du puits, leur coulabilité ainsi que leurs capacités à transporter les débris jusqu'à la surface, ont été établis. D’autre part, la stabilité électrique des émulsions ainsi que leur morphologie (distribution de taille des gouttelettes) ont été étudiées et une comparaison avec celles stabilisées par des agents tensioactifs a été établie. Les fluides ont été exposés à un processus de vieillissement qui permet d’étudier l'effet de l'environnement du réservoir hostile sur la stabilité et la rhéologie des nouveaux fluides préparés. Ces fluides de haute qualité se sont révélés très fiables, offrant une grande stabilité et une capacité à résister à des conditions extrêmes de réservoir. Ils représentent une nouvelle génération de fluides de forage ouvrant la voie à une exploitation optimisée de réservoirs profonds et ultra profonds. / This enduring situation of volatile oil prices has been seen as a decline and a challenge at the same time for the oil and gas industry. It is during this slump that the oil and gas companies own the opportunity to focus on cost-effective production solutions, which very often means bringing new technologies and further improving processes.This work presents a novel frontier of surfactant-free drilling and completion fluids for deep and ultra-deep wells. This new generation of drilling fluids is based on the principle of Pickering emulsions (emulsions stabilized solely by solid nano particles). Hydrophobic and hydrophilic silica nano particles were used to stabilize Oil-Based Mud and Water-Based Mud. These fluids were designed to be used under hostile conditions of temperature and pressure. Therefore, a concrete characterization of their stability as well as their rheological properties under HTHP conditions was mandatory. Rheological profiles reflecting the flowability, hole cleaning capacity as well as cutting transport ability of the fluids were established. On the other hand, the electrical stability as well as the morphology (Droplet Size Distribution) of the emulsions were studied and compared with surfactant-stabilized drilling fluids. The fluids were submitted to an aging process allowing one to study the effect of hostile reservoir environment on the stability and rheology of the new fluids prepared.These high quality fluids were seen very reliable offering high stability as well as high capacity to withstand extreme reservoir conditions giving rise to a new generation of drilling fluids allowing breaking the frontiers of deep and ultra-deep reservoirs.

Cellulose nanocrystals (CNCs) are bio-based nanoparticles with the ability to stabilize oil and water emulsions thanks to their intermediate wettability and nanometric size. These and other types of particle-stabilized emulsions, commonly referred to as Pickering emulsions, are of great academic and industrial interest due to their superior stability against drop coalescence compared to classical surfactant-stabilized emulsions. In addition, the presence of a densely packed layer of particles at the oil-water interface is expected to impact the encapsulation ability of the emulsion droplets opening up for the possibility to use these systems to modulate the release of active substances in the context of oral or topical delivery formulations used in pharmaceutical and cosmetic applications. In these types of applications, the use of emulsions with nano-sized drops is advantageous due to their longtermcolloidal stability, improved dermal and mucosal transport of actives, improved bioavailability and greater aesthetic appeal and skin feel. This study had two main objectives. The first one was to explore to possibility to produce o/w emulsions with submicron-size drops by means of microfluidization using a combination of CNCs and hydroxypropyl methylcellulose (HPMC), a surface-active cellulose derivative that has been shown to have the ability to modify the wettability of CNCs (thereby enhancing their ability to adsorb at the oil/water interface). An important aspect of this first part of the study also involved gaining better understanding on the separate contributions of CNCs and HPMC to the properties of the resulting emulsions. The second objective of the work was to assess the performance of selected o/w CNC/HPMC compared to that of surfactant-stabilised emulsions in terms of their ability to deliver lutein, a hydrophobic prototype active of interest for topical delivery applications. / Cellulosa-nanokristaller (CNC) är biobaserade nanopartiklar med förmågan att stabilisera emulsioner av olja i vatten (o/w) tack vare deras medelhöga vätbarhet och storlek i nanometerskalan. Dessa och andra typer av partikelstabiliserade emulsioner, så kallade Pickering-emulsioner, är av stort akademiskt och industriellt intresse på grund av deras överlägsna stabilitet mot droppkoalescens jämfört med klassiska tensidstabiliserade emulsioner. Det tätt packade skiktet av partiklar vid gränsytan mellan olja och vatten påverkar också inkapslingsförmågan hos emulsionsdropparna vilket kan utnyttjas för att reglera frisättning av aktiva substanser i läkemedel eller kosmetiska produkter. I dessa typer av applikationer är användningen av emulsioner med droppar i nano-storlek fördelaktig på grund av deras långsiktiga kolloidala stabilitet, förbättrad hud- och slemhinnetransport, förbättrad biotillgänglighet och hudkänsla. Denna studie hade två huvudmål. Det första var att undersöka möjligheten att producera o/w emulsioner med droppar av submikron-storlek med hjälp av mikrofluidisering och genom att använda en kombination av CNC och hydroxypropylmetylcellulosa (HPMC), ett ytaktivt cellulosa-derivat som har visat sig ha förmågan att modifiera vätbarheten hos CNC och därigenom förbättra dess förmåga att adsorbera vid olja/vatten-gränsytan. En viktig aspekt av denna första del av studien var att få bättre förståelse för hur CNC och HPMC var för sig påverkar egenskaperna hos emulsionerna. Det andra målet med arbetet var att bedöma prestandan hos o/w CNC/HPMC-emulsioner för frisättning av lutein, ett hydrofob aktivt ämne, och jämföra med tensidstabiliserade emulsioner. / nanocellulosa, hydroxipropylmetylcellulosa, Pickering emulsioner, microfluidization, drogleverans

[pt] Alguns óleos crus brasileiros formam emulsões estáveis, mesmo contendo baixo teor de asfaltenos, os quais são reconhecidos como os principais surfactantes naturais do petróleo. Este trabalho visou compreender os fatores que contribuem na formação e estabilização dessas emulsões através da caracterização de frações com atividade interfacial: os materiais interfaciais (IM) e os ácidos naftênicos (NA). Para isso, tais frações foram extraídas de três óleos crus brasileiros com API entre 21 e 30 graus, permitindo a caracterização da sua composição química e estrutura coloidal. Além disso, estas frações e os óleos residuais de suas extrações foram usados para preparar emulsões água-em-óleo (A/O). A caracterização química realizada por análise elementar, espectroscopia de infravermelho, ressonância magnética nuclear e espectrometria de massas, mostrou que os IM podem ser compostos por saturados, aromáticos, resinas e asfaltenos e NA por saturados e aromáticos. Porém, são enriquecidos em compostos aromáticos e com grupos polares, como ácidos carboxílicos, aminas, sulfóxidos e sulfônicos, em relação aos seus óleos de origem. Ainda assim, a fração de NA não apresentou um papel relevante nas emulsões. Já os compostos anfifílicos presentes nos IM são capazes de formar agregados coloidais caracterizados pela técnica de espalhamento de raios X a baixos ângulos (SAXS) e promover a formação de emulsões, mas não são suficientes para garantir sua estabilização. A remoção dos IM aumentou a auto-organização dos agregados no óleo cru residual e a estabilidade das emulsões, o que parece ter mais relação com propriedades reológicas do que com a atividade interfacial dos compostos. / [en] Some Brazilian crude oils form stable emulsions, even containing alow content of asphaltenes, recognized as the main natural surfactants in petroleum. This work aimed to understand the factors contributing to theformation and stabilization of these emulsions through the characterization of fractions with possible interfacial activity: interfacial materials (IM) and naphthenic acids (NA). For this, these fractions were extracted from three Brazilian crude oils with API between 21 and 30 degrees, allowing the characterization of their chemical composition and colloidal structure. Furthermore, these fractions and the residual oils from their extractions were used to prepare water-in-oil (W/O) emulsions. Chemical characterization carried out by elemental analysis, infrared spectroscopy, nuclear magnetic resonance, and mass spectrometry, showed that IM can be composed of saturates, aromatics, resins, and asphaltenes and NA by saturates and aromatics. However, they are enriched in aromatic compounds and polar groups, such as carboxylic acids, amines, sulfoxides,and sulfonic acids, concerning their original oils. Nevertheless, the NAfraction did not play a relevant role in emulsions. The amphiphilic compounds present in IM can form colloidal aggregates characterized by the small-angle X-ray scattering (SAXS) technique and promote the formation of emulsions. Still, they are not sufficient to guarantee their stabilization. The removal of IM increased the self-organization of aggregates in the residual crude oil and the stability of emulsions, which seems to be more related to rheological properties than to the interfacial activity of the compounds.

Emulsões são sistemas formados quando dois componentes imiscíveis são misturados, na forma de gotículas dispersas numa fase contínua, estabilizados pela ação de emulsificantes, compostos anfifílicos, com afinidades por ambas as fases do sistema. No caso de emulsões de Pickering, o sistema é estabilizado por partículas coloidais sólidas, que adsorvem à interface das gotículas da emulsão. O objetivo desta dissertação foi produzir e caracterizar suspensões de celulose cristalina (CC), celulose amorfa (CA) e de partículas de quitosana (PQ) e avaliar seu potencial de aplicação como únicos compostos estabilizantes em emulsões óleo-em-água. As CC e CA foram produzidas por tratamentos térmico e ácido de celulose microcristalina, respectivamente, enquanto que as PQs foram produzidas por tratamento ácido de quitosana de média massa molecular. Em todos esses casos, os tratamentos foram seguidos de ultra-agitação: 0 (ST), 10000 (UT10), 15000 (UT15) ou 20000 rpm (UT20) por 3 minutos. As suspensões de CC, CA e PQ foram caracterizadas para determinação da distribuição do tamanho de partículas, do potencial zeta e da estabilidade física, e por microscopia eletrônica de varredura e/ou de força atômica. As partículas em pó, produzidas por liofilização, foram submetidas a análises de difração de raios-X, espectroscopia de infravermelho com Transformada de Fourier (FTIR) e de colorimetria instrumental. Em função dessas caracterizações, foi estudado o efeito do tipo de partícula estabilizadora (CC, CA ou PQ) sobre o tamanho de gotas, colorimetria instrumental e estabilidade física de emulsões com 20% (v/v) de óleo de soja, sem e com β-caroteno. Observou-se que os tratamentos UT10, UT15 e UT20 provocaram importantes alterações na distribuição de tamanho de partículas, com redução do tamanho médio das partículas, sem efeito significativo da velocidade de agitação. Em relação à PQ, os tratamentos por ultra-agitação não influenciaram o tamanho de partículas, nem quando comparado com suspensões ST. A CC apresentou-se em fragmentos de fibras celulósicas e altamente instáveis em suspensão, com índices de instabilidade próximos a 0,78. A CA apresentou-se em partículas coloidais e agregados irregulares, com estabilidade física razoável em suspensão (0,26). As suspensões de PQ apresentaram grandes estruturas cristalinas de acetato de sódio, junto a partículas coloidais de quitosana, mas altamente estáveis em suspensão aquosa (0,04). De forma geral, o potencial ζ e a estabilidade física das suspensões de CC, CA e PQ não variaram com o tratamento (ST, UT10, UT15 e UT20). Na caracterização das partículas liofilizadas, constatou-se alto índice de cristalinidade da CC (81%), e baixa cristalinidade da CA (42%) e da PQ (40%). Os tratamentos não provocaram modificações consideráveis na estrutura química, analisada por FTIR, e nem na cor instrumental da CC, CA e PQ. Por fim, apenas a PQ foi capaz de produzir e estabilizar emulsões óleo-em-água, não havendo formação de fase creme durante o armazenamento. A adição de 0,005% de β-caroteno à fase lipídica deixou as emulsões estabilizadas por PQ ligeiramente alaranjadas e aumentou sua estabilidade física, sem afetar o tamanho médio de suas gotas (29-32 µm). Portanto, apenas a PQ demonstrou potencial para estabilizar emulsões óleo-em-água, com ou sem β-caroteno. / Emulsions are systems formed when two immiscible components are mixed, presenting dispersed droplets in a continuous phase, stabilized by emulsifiers, amphiphilic compounds, with affinities for both phases of the system. In the case of Pickering emulsions, the system is stabilized by solid colloidal particles, which adsorb at the interface of the emulsion droplets. The objective of this dissertation was to produce and characterize suspensions of crystalline cellulose (CC), amorphous cellulose (CA) and chitosan particles (PQ) and to evaluate its potential as single stabilizing compounds in oil-in-water emulsions. CC and CA were produced by heat and acidic treatments of microcrystalline cellulose, respectively, whereas PQs were produced by acidic treatment of medium molecular weight chitosan, also followed by ultra-stirring treatment. In all cases, the treatments were followed by ultra-stirring: 0 (ST); 10,000 (UT10); 15,000 (UT15) or 20,000 rpm (UT20) for 3 minutes. The suspensions of CC, CA and PQ were characterized for determination of particle size distribution, zeta potential and physical stability, and by scanning electron microscopy and/or atomic force microscopy. The powder particles, produced by freeze-drying, were subjected to analysis by X-ray diffraction, Fourier Transform infrared spectroscopy (FTIR) and instrumental colorimetry. As a function of these characterizations, the effect of the stabilizing particle type (CC, CA or PQ) on droplet size, instrumental colorimetry and physical stability of emulsions with 20% (v/v) soybean oil, without and with β-carotene was studied. It was observed that the treatments UT10, UT15 and UT20 caused important changes in the particle size distribution, with reduction of the mean particle size, without significant effect of the agitation speed. Regarding chitosan particles, ultra-stirring treatments did not influence particle size, neither when compared to suspensions without pretreatment. CC was presented as highly unstable cellulosic fiber fragments in suspension, with instability indexes close to 0.78. CA was presented in colloidal particles and irregular aggregates, with reasonable physical stability in suspension (0.26). The suspensions of PQ showed large crystalline structures of sodium acetate, together with colloidal chitosan particles, but highly stable in aqueous suspension (0.04). In general, the potential ζ and the physical stability of CC, CA and PQ suspensions did not change with the treatment (ST, UT10, UT15 and UT20). In the characterization of the freezedried particles, a high crystallinity index of CC (81%) was observed, whereas CA (42%) and PQ (40%) showed low crystallinities. The treatments neither caused significant changes in the chemical structure, analyzed by FTIR, nor in the instrumental color of CC, CA and PQ. Finally, only PQ was able to produce and stabilize oil-in-water emulsions, with no cream phase formation during storage. Addition of 0.005% β-carotene to the oil phase left the emulsions stabilized by PQ slightly orange and increased the physical stability of the emulsions, without affecting the droplet size of the emulsions (29-32 µm). Therefore, only PQ demonstrated the potential to stabilize oil-in-water emulsions, with or without β-carotene.

Emulsões são sistemas formados quando dois componentes imiscíveis são misturados, na forma de gotículas dispersas numa fase contínua, estabilizados pela ação de emulsificantes, compostos anfifílicos, com afinidades por ambas as fases do sistema. No caso de emulsões de Pickering, o sistema é estabilizado por partículas coloidais sólidas, que adsorvem à interface das gotículas da emulsão. O objetivo desta dissertação foi produzir e caracterizar suspensões de celulose cristalina (CC), celulose amorfa (CA) e de partículas de quitosana (PQ) e avaliar seu potencial de aplicação como únicos compostos estabilizantes em emulsões óleo-em-água. As CC e CA foram produzidas por tratamentos térmico e ácido de celulose microcristalina, respectivamente, enquanto que as PQs foram produzidas por tratamento ácido de quitosana de média massa molecular. Em todos esses casos, os tratamentos foram seguidos de ultra-agitação: 0 (ST), 10000 (UT10), 15000 (UT15) ou 20000 rpm (UT20) por 3 minutos. As suspensões de CC, CA e PQ foram caracterizadas para determinação da distribuição do tamanho de partículas, do potencial zeta e da estabilidade física, e por microscopia eletrônica de varredura e/ou de força atômica. As partículas em pó, produzidas por liofilização, foram submetidas a análises de difração de raios-X, espectroscopia de infravermelho com Transformada de Fourier (FTIR) e de colorimetria instrumental. Em função dessas caracterizações, foi estudado o efeito do tipo de partícula estabilizadora (CC, CA ou PQ) sobre o tamanho de gotas, colorimetria instrumental e estabilidade física de emulsões com 20% (v/v) de óleo de soja, sem e com β-caroteno. Observou-se que os tratamentos UT10, UT15 e UT20 provocaram importantes alterações na distribuição de tamanho de partículas, com redução do tamanho médio das partículas, sem efeito significativo da velocidade de agitação. Em relação à PQ, os tratamentos por ultra-agitação não influenciaram o tamanho de partículas, nem quando comparado com suspensões ST. A CC apresentou-se em fragmentos de fibras celulósicas e altamente instáveis em suspensão, com índices de instabilidade próximos a 0,78. A CA apresentou-se em partículas coloidais e agregados irregulares, com estabilidade física razoável em suspensão (0,26). As suspensões de PQ apresentaram grandes estruturas cristalinas de acetato de sódio, junto a partículas coloidais de quitosana, mas altamente estáveis em suspensão aquosa (0,04). De forma geral, o potencial ζ e a estabilidade física das suspensões de CC, CA e PQ não variaram com o tratamento (ST, UT10, UT15 e UT20). Na caracterização das partículas liofilizadas, constatou-se alto índice de cristalinidade da CC (81%), e baixa cristalinidade da CA (42%) e da PQ (40%). Os tratamentos não provocaram modificações consideráveis na estrutura química, analisada por FTIR, e nem na cor instrumental da CC, CA e PQ. Por fim, apenas a PQ foi capaz de produzir e estabilizar emulsões óleo-em-água, não havendo formação de fase creme durante o armazenamento. A adição de 0,005% de β-caroteno à fase lipídica deixou as emulsões estabilizadas por PQ ligeiramente alaranjadas e aumentou sua estabilidade física, sem afetar o tamanho médio de suas gotas (29-32 µm). Portanto, apenas a PQ demonstrou potencial para estabilizar emulsões óleo-em-água, com ou sem β-caroteno. / Emulsions are systems formed when two immiscible components are mixed, presenting dispersed droplets in a continuous phase, stabilized by emulsifiers, amphiphilic compounds, with affinities for both phases of the system. In the case of Pickering emulsions, the system is stabilized by solid colloidal particles, which adsorb at the interface of the emulsion droplets. The objective of this dissertation was to produce and characterize suspensions of crystalline cellulose (CC), amorphous cellulose (CA) and chitosan particles (PQ) and to evaluate its potential as single stabilizing compounds in oil-in-water emulsions. CC and CA were produced by heat and acidic treatments of microcrystalline cellulose, respectively, whereas PQs were produced by acidic treatment of medium molecular weight chitosan, also followed by ultra-stirring treatment. In all cases, the treatments were followed by ultra-stirring: 0 (ST); 10,000 (UT10); 15,000 (UT15) or 20,000 rpm (UT20) for 3 minutes. The suspensions of CC, CA and PQ were characterized for determination of particle size distribution, zeta potential and physical stability, and by scanning electron microscopy and/or atomic force microscopy. The powder particles, produced by freeze-drying, were subjected to analysis by X-ray diffraction, Fourier Transform infrared spectroscopy (FTIR) and instrumental colorimetry. As a function of these characterizations, the effect of the stabilizing particle type (CC, CA or PQ) on droplet size, instrumental colorimetry and physical stability of emulsions with 20% (v/v) soybean oil, without and with β-carotene was studied. It was observed that the treatments UT10, UT15 and UT20 caused important changes in the particle size distribution, with reduction of the mean particle size, without significant effect of the agitation speed. Regarding chitosan particles, ultra-stirring treatments did not influence particle size, neither when compared to suspensions without pretreatment. CC was presented as highly unstable cellulosic fiber fragments in suspension, with instability indexes close to 0.78. CA was presented in colloidal particles and irregular aggregates, with reasonable physical stability in suspension (0.26). The suspensions of PQ showed large crystalline structures of sodium acetate, together with colloidal chitosan particles, but highly stable in aqueous suspension (0.04). In general, the potential ζ and the physical stability of CC, CA and PQ suspensions did not change with the treatment (ST, UT10, UT15 and UT20). In the characterization of the freezedried particles, a high crystallinity index of CC (81%) was observed, whereas CA (42%) and PQ (40%) showed low crystallinities. The treatments neither caused significant changes in the chemical structure, analyzed by FTIR, nor in the instrumental color of CC, CA and PQ. Finally, only PQ was able to produce and stabilize oil-in-water emulsions, with no cream phase formation during storage. Addition of 0.005% β-carotene to the oil phase left the emulsions stabilized by PQ slightly orange and increased the physical stability of the emulsions, without affecting the droplet size of the emulsions (29-32 µm). Therefore, only PQ demonstrated the potential to stabilize oil-in-water emulsions, with or without β-carotene.

Synthèse et étude de nouveaux NHC-Boranes pour leurs propriétés énergétiques et leurs rôles en tant que photo co-amorceurs pour la photopolymérisation en émulsion.Depuis la première synthèse de complexes N-Hétérocycliques Boranes (NHC-Borane) stables en 1993, une étude plus générale de propriétés et réactivité n’a débuté que dans le milieu des années 2000. Les domaines d’applications de ces composés qui sont des paires de Lewis vont de la synthèse organique (agent réducteur, hydroboration de liaisons multiples) en passant par la chimie radicalaire (remplacement de l’hydrure de tributylétain, hydroboration) ou même en tant qu’amorceur ou co-amorceur de polymérisations.L’objet de cette thèse était d’étendre l’application des NHC-Boranes dans deux domaines précis. Un premier axe porte sur les propriétés hypergoliques amenées par leurs structures inédites. Un second est consacré à l’amorçage de réactions de polymérisations en émulsion et l’obtention de particules hybrides sous irradiation visible.Nous avons choisi et synthétisé de nouvelles cibles polyazotées qui ont montré des propriétés énergétiques potentiellement intéressantes pour l’usage de NHC-Boranes en propulsion solide. L’étude mis en évidence des différentes de réactivités en fonction du squelette du carbène utilisé. De plus, un nouveau type de carbène borane pouvant être utilisé dans différents domaines a été synthétisé.Nous avons aussi amélioré la compréhension du système de photoamorçage déjà proposé en polymérisation en émulsion dans le visible. Des points clés, sur la conception du système et du réacteur ont été améliorés. Nous avons aussi pu remplacer le tensioactif utilisé pour proposer la première photopolymérisation en émulsion Pickering. Il en résulte des latex stables, composés de particules hybrides pouvant former des films potentiellement anti-UV. L’excitation dans le visible, pourrait être utilisée dans le but de réduire les coûts énergétiques et même former d’autres particules inédites en évitant la dégradation de composés thermo ou UV-sensibles / Study and synthesis of new NHC-Boranes usable as hypergolic fuels and as photo co-initiators for radical emulsion photopolymerizationsThe first N-Heterocyclic Carbene Borane complex (NHC-Borane) was synthetized in 1993, but we had to wait until the mid-2000s before chemists investigated their properties and reactivity. The applications of NHC-Boranes range from organic chemistry (where they are used as reducing agents or for the hydroboration of multiple bonds) to radical chemistry (as replacement of te tributyltin hydride) and radical polymerizations (initiators and co-initiators). We designed and synthetized new Nitrogen-rich NHC-Boranes. The latter are hypergolic and might serve as fuels for solid propulsion. We managed to synthetize several new classed of NHC-Borane which was or could be used in different fields. We also deepened our understanding of the visible light-induced emulsion polymerization, where the NHC-Boranes serve as co-initiators. We could optimize the process and then replaced the surfactant by an inorganic sol to propose the first Pickering emulsion photopolymerization. Stable latexes of hybrid particles have been generated which might be used as sunscreen films, to reduce the energetic footprint of the reactions and/or to access particles made of heat- or UV-sensitive materials

Les émulsions fluorées de Pickering sont étudiées et mises au point dans la technologie demicrofluidique en gouttes pour des applications d’études sur des cellules adhérentes isolées.Les principaux résultats de ce projet sont : l’établissement d’un lien entre la couverture desurface des nanoparticules et la fluidité de l’émulsion de Pickering ; l’établissement deslignes directrices pour la stabilisation des gouttes avec un débit de production élevé et unminimum de déchets de particules ; et la mise en oeuvre d’une plateforme technologiquecomplète pour l’étude des cellules RPE, pour mesurer leur hétérogénéité phénotypique auniveau de la cellule individuelle. / Fluorinated Pickering emulsions are studied and engineered within droplet-based microfluidicstechnology for adherent-cell studies applications. The main findings of this projectinclude: linking the nanoparticles surface coverage to the bulk flowability of the Pickeringemulsion; deriving guidelines for droplet stabilization with high production throughput andminimal particle waste; and implementing the full technological platform for the study ofRPE cells, while unraveling their phenotypic heterogeneity at the single cell level.

Les émulsions de Pickering ont suscité un intérêt croissant dans de nombreux domaines de la recherche en raison de leur grande stabilité et versatilité. Une attention particulière a été accordée à la fabrication des systèmes complexes et originaux qui peuvent être obtenus avec différentes particules. Cette étude a consisté dans l'analyse des différents paramètres physico-chimiques des particules, des milieux liquides et des systèmes dispersées, et leur relation avec le comportement mécanique et la structure des émulsions afin de prédire et de moduler les caractéristiques de ces dernières. Nous avons étudié plus particulièrement pour la première fois, le diagramme de phase concernant les inversions de phase du type catastrophique et transitionnelle des émulsions de Pickering. Nous avons utilisé des particules de silice avec des structures et hydrophobicités différentes. En particulier, nous avons montré que le mélange de particules de différente hydrophobicités peut moduler finement l'inversion de phase aussi bien que les propriétés rhéologiques et structurales des émulsions. La fabrication de membranes à partir des émulsions de Pickering précédentes a été proposée comme un exemple de l'utilisation de ces systèmes modèles pour la conception de matériaux complexes. / Pickering emulsions have gained interest in many fields of research due their properties like higher stability and versatility. Special attention has been given to the processing of complex and original systems which can be obtained by using different particles. This study consists in the analysis of the different physicochemical parameters of particles, liquid media as well dispersion systems, and their relationship with emulsions structural and mechanical behavior in order to predict and modulate the emulsions characteristics. We studied extensively for the first time the phase diagram of catastrophic and transitional phase inversion of Pickering emulsions. We used silica particles with different structure and hydrophobicity. In particular we showed that mixing particles with different hydrophobicity can finely modulate the phase inversion as well the rheological and structural properties of the emulsions. The manufacturing of emulsified membranes based on previous Pickering emulsions was proposed as an example of the use of these systems as templates for the design of complex materials.

L’objectif du présent projet est de développer une méthodologie pour la modélisation fondamentale de procédés de polymérisation en émulsion sans tensioactif stabilisés par des particules inorganiques, dénommées "polymérisation en émulsion Pickering". La modélisation des systèmes de polymérisation en émulsion nécessite la modélisation de la distribution de taille des particules (PSD), qui est une propriété importante d'utilisation finale du latex. Cette PSD comprend des sous-modèles dédiés à la nucléation des particules, le transfert de masse entre les différentes phases (monomère, radicaux, stabilisant) et la coagulation des particules. Ces modèles devraient de préférence être validés expérimentalement de manière individuelle. La première partie principale du travail est consacrée à l'étude expérimentale. Cette partie peut être divisée en trois parties. La première partie décrit l'adsorption de particules inorganiques sur le polymère sans réaction. Une adsorption multicouche a été observée et l’isotherme B.E.T. a été capable de décrire cette adsorption. L'adsorption se révèle être plus importante pour une force ionique plus élevée. La dynamique d'adsorption semple être rapide et par conséquent le partage peut être considéré à l'équilibre pendant la polymérisation. La deuxième partie concerne l'étude de différents paramètres de réaction sur le nombre de particules et la vitesse de réaction dans des polymérisations ab initio. L'effet du mélange, de la concentration initiale des monomères et de la concentration de l'initiateur a été étudié. L'optimisation de ces conditions a été utile pour la partie de modélisation. La dernière partie décrit les différences entre plusieurs Laponite® à travers la polymérisation en émulsion ab initio du styrène.La deuxième partie principale du manuscrit a porté sur la modélisation de la polymérisation en émulsion Pickering. Le modèle de bilan de population et le nombre moyen de radicaux par particule ont été calculés en fonction de l'effet des particules organiques. La croissance des particules de polymère a été optimisée en ajustant les modèles d'entrée et de désorption des radicaux décrits dans la littérature aux données expérimentales. Aucune modification n'a été nécessaire, ce qui nous a permis de conclure que l'argile n'avait aucune influence sur l'échange radical. Cependant, la stabilisation joue un rôle important dans la production de particules de polymère. Le modèle de nucléation coagulante a été capable de décrire le taux de nucléation et de prédire le nombre total de particules / The aim of the present project is to develop a methodology for fundamental modeling of surfactant-free emulsion polymerization processes stabilized by inorganic particles, referred to as “Pickering emulsion polymerization”. Modeling emulsion polymerization systems requires modeling the particle size distribution (PSD), which is an important end-use property of the latex. This PSD includes submodels dedicated to particle nucleation, mass transfer between the different phases (monomer, radicals, stabilizer), and particle coagulation. These models should preferably be individually identified and validated experimentally. The first main part of the work is dedicated to the experimental study. This part can be divided in three parts. The first part describes the adsorption of inorganic particles on polymer without reaction. Multilayer adsorption was observed and B.E.T. isotherm was able to describe this adsorption. The adsorption was found to be enhanced at higher ionic strength. The adsorption dynamics were found fast and therefore clay partitioning can be considered at equilibrium during polymerization. The second part concerned the investigation of different reaction parameters on the particles number and reaction rate in ab initio polymerizations. The effect of mixing, initial monomer concentration and initiator concentration were considered. Optimization of these conditions was useful for the modeling part. The last part described the differences between several LaponiteR_ grades through the ab initio emulsion polymerization of styrene. The second main part of the manuscript focused on the modeling of the Pickering emulsion polymerization. The population balance model and average number of radicals balance were adapted regarding the effect of inxi organic particles. The growth of the polymer particles was optimized by fitting the models of radicals’ entry and desorption described available in literature to the experimental data. No modification was needed, which allowed us to conclude that the clay had no influence on radical exchange. However, LaponiteR_ stabilization played an important role in polymer particles production. Coagulative nucleation model was able to describe the nucleation rate and predict the total number of particles

L’objectif de cette thèse consiste à mettre en place un système d’émulsion catalysé par des nanoparticules de Pickering afin de synthétiser des tensioactifs bio sourcés. Pour cela nous nous sommes intéressés à des matériaux mésoporeux fonctionnalisés (de type MCM-41). Ces matériaux favorisent la formation des émulsions tout en catalysant la réaction.Après une étude bibliographique sur le glycérol, les tensioactifs, les émulsions de Pickering et les matériaux mésoporeux, nous nous sommes intéressés à la synthèse et à la fonctionnalisation de ces matériaux. Puis après les avoir caractérisés, nous les avons testés dans des réactions modèles biphasiques (acétalysation et hydrolyse d’ester). Enfin, nous avons terminé cette étude en testant ces catalyseurs dans notre réaction cible (éthérification du glycérol par des alcools gras). La MCM-41 a été synthétisée en utilisant un chauffage micro-onde.Les fonctions greffées sur nos matériaux ont permis de faire varier la balance hydrophile hydrophobe de nos matériaux tout en leur fournissant une fonction catalytique. Les nanoparticules ont été caractérisées par leur ATG, BET, DRX, analyse élémentaire, acidité et tailles des particules.Des catalyseurs à base d’Aerosil® 200 et de Nanoparticules de carbone ont également été testés.Une longue chaine alkyke (C18) et des nanoparticules de petites tailles (Aerosil® 200 et nanoparticules de carbone) favorisent la stabilité des émulsions. Cependant la présence de pores dans nos matériaux n’apporte pas d’avantage catalytique déterminant. / The objective of this work is the conception of emulsion catalysed by Pickering nanoparticles inorder to synthetize biosurfactant. Our strategy was based on functionalised mesoporous materials(MCM-41). These materials combine both emulsion stabilisation and reaction catalysis.After a bibliographic study on glycerol, surfactants, Pickering emulsions and mesoporousmaterials; our strategy was to functionalise these materials. After charaterisation, these materialswere tested in bipohasic model reactions (acetalysation and ester hydrolysis). We come to the end of this study by testing these catalysts in our target reaction (glycerol etherifaction from fattyalcohol).The MCM-41 was synthetized by using a microwave heating. The grafted functions on our materials can both make several hydrophilic-hydrophobic materialsas possible and provided them some catalytic functions. The nanoparticles were characterized byTGA, BET, XRD, elemental analysis, acidity and particle size.Catalyst from Aerosil® 200 and carbon nanoparticles were also tested. A long alkyl chain (C18) and small nanoparticles (Aerosil® 200 and carbon nanoparticles) supportthe emulsion’s stability. Nevertheless, the porous inside our materials is not interesting on acatalytic point of view.