Les mousses aqueuses sont des fluides complexes constitués de dispersions concentrées de bulles de gaz dans une solution de tensioactifs. A l'instar d'autres fluides complexes comme les émulsions ou les pâtes, une mousse se comporte comme un solide viscoélastique lorsque la fraction volumique de la phase continue est suffisamment faible pour que l'empilement des bulles soit bloqué. Ses propriétés mécaniques résultent de couplages entre processus se produisant à plusieurs échelles de temps et d'espace : celles des tensioactifs adsorbés aux interfaces liquide-gaz, celles d'une bulle de gaz ou de mouvements collectifs à une échelle mésoscopique. A partir de trois expériences, nous avons mis en évidence l'impact du désordre de leur structure d'une part, et celui des tensioactifs d'autre part, sur les propriétés viscoélastiques des mousses. Nous avons mis au point un rhéomètre oscillatoire qui permet de mesurer la relation contrainte-déformation-fréquence d'une monocouche de bulles confinées entre deux parois planes parallèles tout en contrôlant sa pression osmotique. Nous avons montré que les relaxations de ces mousses de structure modèle sont pilotées par la rhéologie interfaciale de cisaillement que nous avons caractérisée indépendamment. Nous proposons un modèle quantitatif de ce couplage. Dans une deuxième expérience, nous avons sondé la réponse viscoélastique des mousses de structure 3D désordonnées. Nos résultats montrent que selon la rigidité des interfaces, le facteur de perte d'une mousse est décrit par une loi d'échelle en fréquence. Son évolution avec la taille des bulles et la viscosité du liquide permet de déterminer le mécanisme à l'origine de la dissipation. Dans une troisième expérience, Nous avons élaboré des mousses monodisperses de structure 3D ordonnées et de pression osmotique contrôlée. De manière remarquable, la variation de leur facteur de perte en fonction de la fréquence est similaire à celle des mousses désordonnées de même composition chimique. Ces résultats démontrent que le désordre de l'empilement des bulles n'est pas à l'origine des relaxations viscoélastiques linéaires des mousses, comme l'avaient suggéré plusieurs modèles théoriques, et ouvrent la voie à une modélisation quantitative du lien entre la viscoélasticité des interfaces et celle des mousses 3D / Aqueous foams are constituted of concentrated gas bubble dispersions in a surfactant solution. Like other complex fluids, such as emulsions or pastes, foam behaves as a viscoelastic solid if the volume fraction of the continuous phase is sufficiently small for the bubble packing to be jammed. The mechanical properties of the foam are due to couplings between processes at a wide range of time and length scales: The ones of the surfactant molecules that are adsorbed to the gas-liquid interfaces, the ones of the bubbles or collective motions at a mesoscopic scale. On the basis of three experiments, we have evidenced the impact of structural disorder and surfactant properties on foam viscoelasticity. We have constructed an oscillatory rheometer to measure the frequency and strain dependent stress response of a bubble monolayer confined between two parallel plates, subjected to an imposed osmotic pressure. We have shown that the relaxation of these model foams are governed by the interfacial shear rheology which we have probed in independent experiments and, we present a quantitative model of this coupling. In a second experiment, we have probed the viscoelastic response of disordered 3D foams. Our results show that, depending on interfacial rigidity, the mechanical loss factor of a foam is described by a scaling law depending on frequency. Its dependence on bubble size and liquid viscosity helps to determine the origin of the dissipation. In our third experiment, we have produced monodispersed ordered foams, subjected to a controlled osmotic pressure. Remarkably, the frequency scaling of their loss factor is similar to the one of disordered foams of the same chemical composition. These results demonstrate that the linear viscoelastic response of foams is not the consequence of disorder on the bubble scale as suggested by several previous theories, and they thus open the way for quantitative models linking the viscoelasticity of the interfaces to that of 3D foams

L’étude des fluides complexes présente un grand intérêt de par la richesse des phénomènes que font intervenir leur écoulement. Une étude de rhéologie locale de systèmes de micelles géantes en microcanal droit est effectuée. L’expérience montre que les propriétés du fluide soumis à un fort gradient de contrainte ne peuvent être décrites que par une équation rhéologique comportant des termes non locaux. Nous montrons alors l’influence du système de micelles géantes, du confinement ainsi que de la nature des surfaces du microcanal sur ces effets non locaux. Une étude des phénomènes temporels intervenant dans ces écoulements en microcanaux est alors proposée, ainsi qu’une étude préliminaire concernant les écoulements dans des milieux poreux modèles. / The study of complex fluids flows is of great interest according to the diversity of phenomenon it involves. A study of the local rheology of wormlike micelles flowing in a simple straight microchannel is proposed. Experiments show that the properties of such a fluid undergoing a strong shear stress gradient can only be described by an equation including non local terms. We thereafter show the influence of the wormlike micelles system, of the confinement and of the nature of the microchannel walls on those non local effects. A study of the temporal phenomenon occurring in microfluidic flows of wormlike micelles is then proposed, as well as a preliminary study concerning flows in porous media.

Consideramos o modelo de Maier-Saupe com a discretização de Zwanzig para as possíveis orientações das moléculas de cristais líquidos nemáticos. Esse modelo reproduz a transição de fases nemático-isotrópica dos cristais líquidos termotrópicos em acordo com a teoria fenomenológica de Maier e Saupe. Introduzimos variáveis desordenadas de forma a fim de descrever uma eventual estrutura biaxial em uma mistura binária de moléculas uniaxiais oblatas e prolatas. Para uma desordem do tipo quenched, o diagrama de fases do modelo possui uma fase nemática biaxial estável. Para uma desordem do tipo annealed, a estrutura biaxial é termodinamicamente instável. Esses resultados são confirmados realizando um contato com a teoria de Landau-de Gennes. Para ganhar intimidade com os cálculos estatísticos estudamos também um modelo para uma mistura binária de magnetos de Ising na rede. Para ir além dos resultados de campo médio, formulamos o modelo de Maier-Saupe discretizado na rede de Bethe. A análise desse problema é realizada através das relações de recorrência para a função de partição. A transição nemático-isotrópica é localizada através de uma expressão para a energia livre obtida pelo engenhoso método de Gujrati. Considerando o problema das misturas binárias de moléculas nemáticas e utilizando o formalismo adequado à fluidez das partículas annealed, tanto uma análise de estabilidade linear das relações de recorrência quanto uma análise termodinâmica proibem a existência da fase nemática biaxial. / We consider the Maier-Saupe model with the Zwanzig restriction for the orientations of the liquid-crystalline molecules. This model describes the nematic-isotropic phase transition of the thermotropic liquid-crystals. In order to study an elusive biaxial structure on a binary mixture of rods and discs, we add new disordered shape variables. For a quenched distribution of shapes, the system displays a stable biaxial nematic phase. For a thermalized distribution of shapes, however, the biaxial structure is forbidden. These results are confirmed through a connection with the Landau-de Gennes theory. To gain confidence in the use of these techniques, we also studied a model for a binary mixture of Ising magnets on a lattice. In order to go beyond the mean-field calculations, we consider the discretized Maier- Saupe (-Zwanzig) model on a Bethe lattice. The analysis of the problem is performed by the iteration of some recurrence relations. The isotropic-nematic phase transition is determined through the free energy that comes from the Gujrati method. For the problem of a binary mixture of prolate and oblate molecules, using a formalism suitable for the fluidity of the nematic molecules, we show that both thermodynamic and dynamic analyses of stability preclude the existence of a nematic biaxial phase.

Etudier le séchage est un moyen original de caractériser les propriétés de fluides complexes. Cette technique permet de concentrer continûment des fluides : d'un état dilué à un état sec. A l'échelle microfluidique, la manipulation, les observations et les processus qui entrent en jeu sont simplifiés. Ce travail de thèse s'attache à décrire le séchage de ces fluides et plus particulièrement le cas de dispersions colloïdales. Ces travaux présentent deux méthodes pour étudier l'extraction du solvant d'un fluide à l'échelle microfluidique : la micropervaporation et la goutte confinée. Ces techniques ont notamment permis de réaliser des estimations précises de coefficients de diffusion collective sur toute la gamme de concentrations pour un mélange eau/glycérol et pour une dispersion colloïdale de nanoparticules de silice chargées. Par ailleurs, le séchage induit des contraintes mécaniques conséquentes. Ces contraintes peuvent générer des déformations importantes, des phénomènes de délamination ou de fracturation du matériau solidifié. Une méthode originale de mesure in situ de contraintes a été mise en place pendant ces travaux. Les mesures réalisées avec une dispersion colloïdale modèle permettent de mettre en évidence expérimentalement l'apparition de contraintes mécaniques au moment de la transition sol/gel de la dispersion. L'augmentation de la contrainte est ensuite associée au séchage d'un gel poroélastique. / Drying complex fluids is an original technique to study their properties. Solvent extraction enables the continuous concentration of fluids from a dilute to a solid state. The use of the microfluidic scale allows one to limit side effects and simplify experiments, observations and modeling. This project mainly describes the drying of colloidal dispersions in two confined geometries: microfluidic channels and confined droplets between two plates. With these two techniques, we estimate collective diffusion for a water/glycerol mixture and a model dispersion of charged silica nanoparticles over the whole concentration range. Moreover, the drying of complex fluids often induces mechanical stresses which are the root for deformation, delamination phenomena and cracks. We developed an original technique to measure these stresses in situ. For a model colloidal dispersion, we evidenced experimentally that these forces arise from a liquid to solid state transition. The increase of these stresses is then associated with the drying of a poroelastic gel.

Nanofluidos magnéticos formados por partículas de ferrite de manganês eletricamente carregadas foram estudados sob o ponto de vista estrutural, magnético e óptico. Características estruturais foram analisadas por meio da técnica de espalhamento de raios X a baixos ângulos (SAXS), que permitiu a determinação da distribuição de diâmetros de nanopartículas em solução. Assim, foi possível determinar o comportamento lognormal da distribuição de tamanhos nas amostras, bem como o diâmetro médio das soluções estudadas, Mn3, Mn4 e Mn6, como 2.8nm, 3.4nm e 6.2nm, respectivamente. Ademais, foi investigada a magnetização das diferentes soluções em função da temperatura sob o protocolo ZFC/FC, permitindo a determinação da distribuição de temperaturas de bloqueio, grandeza que depende do volume das partículas. Ao comparar as distribuições obtidas, foi constatado que aquela determinada por medidas magnéticas era mais estreita do que a por SAXS, indicando interações dipolares entre partículas. Essa hipótese foi corroborada por medidas de suscetibilidade ac, que resultaram em tempos de relaxação muito curtos, incompatíveis com modelos de partículas únicas, levando à conclusão da existência de um comprimento de correlação com N partículas interagindo no volume de correlação 3. Tais grupos de partículas não correspondem a aglomerados físicos, uma vez que alterações de densidade eletrônica não foram verificadas nas curvas de espalhamento de raios X, mas sim a clusters magnéticos, que respondem ao campo externo em conjunto. A análise dos resultados de magnetização ac e dc, simultaneamente, evidenciou ainda alterações na anisotropia das partículas, efeitos de superfície devido à redução de tamanho do cristal. O estudo de propriedades ópticas lineares permitiu a determinação do espectro de absorção em função da concentração de nanopartículas em solução. Desse modo, foi verificada a validade da lei de Beer-Lambert em uma região do espectro, para 300nm < < 600nm. O gap óptico foi determinado para as transições diretas e indiretas como EgapDir = 3.07 ± 0.15eV e EgapInd = 2.06 ± 0.11eV, respectivamente. Por fim, propriedades ópticas não lineares foram estudadas por meio da técnica de z-scan na escala de femto-segundo, a fim de estudar efeitos de origem eletrônica. Curvas foram obtidas e, por meio de ajustes de equações teóricas, foi possível a determinação dos parâmetros não lineares. Contudo, estudos adicionais evidenciaram que tais sinais não eram de origem eletrônica, mas sim térmica, como formação de lente térmica e termodifusão. Assim, os coeficientes não lineares dos ferrofluidos não puderam ser determinados com precisão, de maneira que apenas valores máximos desses coeficientes foram obtidos independentemente do tamanho das nanopartículas, sendo max = 3.9x10-2cm/GW o valor máximo para o coeficiente de absorção de dois fótons e |n2max| = 5.3x10-16cm2/W, para o índice de refração não linear. / Magnetic nanofluids formed by electrically charged manganese ferrite particles were studied under the structural, magnetic and optical point of view. Structural characteristics were analyzed by small angle X-rays scattering (SAXS) technique, which allowed determining the nanoparticles\' size distribution. Thus, it was possible to determine the lognormal behavior of the size distribution, as well as the particles\' mean diameter of the studied solutions, Mn3, Mn4 and Mn6, as 2.8nm, 3.4nm and 6.2nm, respectively. Also, the magnetization of the different solutions was investigated as a function of the temperature under the ZFC/FC protocol, allowing the determination of the blocking temperature distribution, quantity that depends on the nanoparticles\' volume. Comparing the distributions obtained it was noted that the obtained by magnetic measurements was narrower than the one obtained by SAXS, which indicates dipolar interactions between nanoparticles. This hypothesis was supported by ac susceptibility measurements, which resulted in very short relaxation times, incompatible with single particles models, leading to the conclusion of the existence of a correlation length with N interaction particles in the correlation volume 3. Those particles groups do not correspond to physical clusters, since electron density changes were not observed in X-rays scattering curves, but to magnetic clusters that responds collectively to the external field. The simultaneous analysis of ac and dc magnetization results showed changes in the anisotropy of the particles, surface effects due to reduction of crystal size. The study of linear optical properties allowed the determination of the absorption spectrum as a function of the nanoparticles\' concentration in solution. Thus, the validity of the Beer-Lambert law was verified for the wavelength range 300nm < < 600nm was determined for direct and indirect transitions as EgapDir = 3.07 ± 0.15eV and EgapInd = 2.06 ± 0.11eV, respectively. Finally, nonlinear optical properties were studied by the z-scan technique in the femto-second time scale. Curves were obtained and, by means of theoretical equations adjustments to the data, it was possible to determine nonlinear parameters. However, additional studies have shown that such effects were not of electronic origin, but thermal, as thermal lens and thermodiffusion. Thus, the nonlinear coefficient of ferrofluids could not be determined accurately, only maximum values of these coefficients were obtained regardless of the size of the nanoparticles, as max = 3.9x10-2cm/GW the maximum value of the two photon absorption coefficient and |n2max| = 5.3x10-16cm2/W for the nonlinear refraction index.

Neste trabalho, construímos um arranjo óptico para realizar medidas de espalhamento de luz dinâmico (Dynamic Light Scattering - DLS). Após o processo de montagem, o experimento foi calibrado por meio de soluções padrão de nanoesferas de poliestireno dispersas em água deionizada. Após a calibração, investigamos sistemas mais complexos como cristais líquidos nemáticos uniaxias, bem como misturas ferronemáticas. A primeira etapa dos estudos teve como objetivo investigar o comportamento das difusividades dos modos hidrodinmicos splay e twist, em função da concentração iônica das misturas. As amostras preparadas se diferenciavam apenas pela quantidades de sal em suas composições. Observamos um aumento em Dsplay e diminuição de Dtwist com o aumento na concentração de sal. Esses efeitos são multifatoriais e podem estar relacionados à blindagem eletrostática intermicelar, favorecendo a aproximaao entre micelas vizinhas. O efeito de backflow também é um fenômeno relevante que minimiza os efeitos dissipativos e está associado as distorções de splay. Por fim, foram realizadas medidas de DLS em misturas ferronemáticas liotrópicas uniaxiais, com o objetivo de investigar o comportamento das difusividades dos modos hidrodinâmicos em função da concentração de nanopartículas magnéticas (ferrofluido FF). O alinhamento do diretor é bastante favorecido com a presença das nanopartículas, como previsto na literatura [32]. Além disso, em baixas concentrações (< 10^13 grãos/mL) as nanopartículas não interferem nos espectros de autocorrelação, sendo possível observar as flutuações orientacionais do diretor nemático. Dessa forma, a incorporação de grãos magnéticos auxiliou nas medidas de DLS, principalmente no que diz respeito à seleção dos modos hidrodinâmicos. Os resultados mostraram que, em fase NC , as difusividades Dsplay e Dbend diminuíram com o aumento da concentração de FF. Por outro lado, a difusividade Dtwist praticamente não foi afetada com a incorporação de FF. No entanto, na fase ND, foi possível observar quedas nos valores de Dsplay e Dtwist , comparando com a mistura sem FF (Nd3). / In the present dissertation we made a Dynamic Light Scattering (DLS) experimental setup as well as their clalibration. We use standard aqueous solution with polystyrene nanospheres, with 20 nm and 200 nm of mean diameter, for system calibation. After this process we investigated more complex systems as uniaxial lyotropic liquid crystals mixtures and ferronematic samples. Firstly, we investigate the behaviour of hydrodynamic modes as a function of ionic concentration. The experiments showed that D splay increases and D twist decreases when ionic concentration increases. There are many factors around this behaviour, one of them is the electrostatic shielding forming between nearby micelles that may favours the approximation between tham. The backflow effect also is a relevante phenomenon that minimize the viscous dissipation process of splay distortion. This effect tends to increase with ionic concentration. We also investigated the hydrodynamic behaviour of uniaxial lyotropic mixtures doped with magnetic nanoparticles (ferrofluid - FF). They were characterized by DLS measure-ments to investigated the role of dopping concetration on splay, twist, and bend distortions. According to our results the nanoparticles favours the director alignment by magnetic field as we can found in the literature [32]. Thus, the DLS measurements had been favored by addition of magnetics grains, particularly with regard to the selection role of hydrodynamic modes. Moreover, we have seen that the director relaxation process is not abruptly affected with incorporation of nanoparticles, at low quantities (< 10^13 grain/mL). In NC phase, Dsplay and Dbend tends to decreases when the FF concetrations increases. However the behavior of Dtwist is not completly clear. In ND phase, the addition of nanoparticles further decreases Dsplay and Dtwist , comparing with the free nanoparticles sample (Nd3).

Les mécanismes de fracture dans les matériaux solides ont été activement étudiés. Dans les fluides complexes, les fractures ont déjà été observées et sont jusqu'à présent beaucoup moins bien documentées. Nous avons choisi d'analyser les phénomènes de fracturation dans une classe particulière de fluides complexes : les gels transitoires auto-assemblés. Ces gels, viscoélastiques, possèdent la propriété de s'écouler aux temps longs et de se comporter de manière élastique aux temps courts. Nous avons axé cette thèse autour de trois systèmes modèles : des microémulsions connectées, des solutions de micelles géantes, ainsi qu'un système « hybride » constitué de solutions de micelles de morphologie contrôlable et connectées. Tous ces systèmes, qui sont à l'équilibre thermodynamique, se comportent comme des fluides de Maxwell, néanmoins leurs microstructures sont très différentes. Les microémulsions connectées sont formées de gouttelettes d'huile, stabilisées par des tensioactifs, dispersées dans de l'eau et connectées par des polymères téléchéliques. Les solutions de micelles géantes sont des agrégats allongés et semi-flexibles, enchevêtrés, résultant de l'auto-assemblage de tensioactifs en solution dans l'eau. Enfin, le système de micelles pontées est constitué d'agrégats de tensioactifs dont on peut contrôler la morphologie (sphères -> cylindres -> vers) et qui sont pontés par un polymère téléchélique. Ces trois systèmes ont été étudiés dans une géométrie confinée : une cellule de Hele-Shaw radiale. Elle est constituée de deux plaques de verre séparées par des espaceurs de taille contrôlée (500 µm) et percée d'un trou en son centre permettant l'injection de fluides.Nos expériences consistent en l'injection, à débit contrôlé, d'une huile faiblement visqueuse dans le gel. Le contraste de viscosité entre l'huile injectée et le gel étant important, l'interface huile/gel n'est pas stable. En fonction du débit d'injection d'huile, nous avons observé différents phénomènes. A bas débits d'injection, une instabilité visco-capillaire se développe : l'interface huile/gel se déforme et forme des motifs appelés doigts visqueux. Cette instabilité de Saffman-Taylor est bien connue pour des fluides visqueux. A plus haut débit en revanche, un autre type d'instabilité se développe, d'origine élasto-capillaire : les fractures.Nous avons quantifié les différences entre les deux types d'instabilité. En utilisant des techniques complémentaires, visualisation directe à l'aide d'une caméra rapide et vélocimétrie par corrélation d'images, nous avons montré qu'il existe une discontinuité entre la vitesse de l'interface huile/gel et la vitesse du gel à la pointe de fracture. Cette discontinuité est inexistante dans le cas de la digitation. Nous avons montré que la structure du gel influe sur la transition entre ces deux types d'instabilité. En étudiant les champs de déplacement des microémulsions connectées, nous avons caractérisé les déplacements du gel autour de la pointe, notamment la manière dont l'amplitude des déplacements du gel décroit quand on s'éloigne de la pointe de fracture. Quand la structure du gel peut se réorganiser sous écoulement, nous avons mesuré un signal de biréfringence associé à ces réorganisations. En étudiant ce signal, qui apparait à la pointe d'une fracture, nous avons pu réaliser une première mesure macroscopique de la taille d'une « zone de process ». Nous avons montré que cette zone est d'autant plus grande que la vitesse de la fracture est petite.Lors d'expériences consistant à injecter des solutions de micelles géantes dans elles-mêmes, nous avons découvert l'existence d'une instabilité d'écoulement inconnue jusqu'à aujourd'hui. Elle se caractérise par la perte transitoire de la symétrie radiale de l'écoulement et l'apparition de «branches » biréfringentes se propageant à de très hautes vitesses dans le gel et qui, au final, déforment l'interface air/gel. / Fracture mechanisms in solid materials have been extensively studied. Although cracks are also commonly seen in soft solids, the fracture process is still not very well understood for these materials. In this thesis we choose to study fracture on a particular class of materials: complex fluids. We will focus on one particular family of complex fluids which are self-assembled transient gels. These viscoelastic gels have the property to flow at long timescale while behaving as an elastic solid at short timescales. We have investigated three model systems: a bridged micro emulsion and a entangled solution of wormlike micelle, and a “hybrid” system made of bridged micelles of tunable morphology. These systems are at thermodynamic equilibrium and behave as Maxwell fluids but they differ in microscopic structures. Bridged micro emulsions are made of surfactant-stabilzed oil droplet dispersed in water and bridged by telechelic polymers. Wormlike micelles are long semi flexible aggregates made from the self-assembly of surfactant in a water solution. Lastly, bridged micelles are made of surfactant aggregates of controllable shape (sphere -> cylinder -> worm) in water bridged by telechelic polymers. We choose to study these different systems in a confined geometry: a radial Hele-Shaw cell. The Hele-Shaw cell is made of two glass plates separated by spacers of controllable thickness. A hole is pierced in the center of the cell for injecting the fluids. The experiments consist in the injection at a controlled rate of low viscosity oil inside the highly viscous gel. Because of the high viscosity contrast between the two fluids, the oil/gel interface is unstable. Depending of the injection rate, we observed different instabilities. At lowest rates, an instability of visco-capillary origins appears and the oil/gel interface is deformed leading to a viscous fingering pattern. This instability called Saffman Taylor instability is widely known and has been extensively studied for Newtonian fluids. At highest rates another instability patterns arise of elasto capillary origin where the patterns are vastly different from the previous one and are made of cracks propagating through the gel. We have quantified the difference between the two types of instability. By combining direct visualization using high speed imaging and digital image correlation techniques we have characterized the displacement field of the gel around the crack tip, and in particular how its amplitude decays away from the tip. For bridged microemulsion, we have also evidenced the existence of a velocity discontinuity between the crack velocity and the velocity of the gel near the crack tip whereas no discontinuity occurs in the case of viscous fingering. Using bridged micelles of tunable morphologies we have also shown that the transition between the two instabilities is controlled by the viscoelasticity of the gel. Finally, for gel that can reorient under flow we have measured a birefringence signal associated to these reorganization. By studying this signal at the crack tip we were able to perform a measurement of the size of the “process zone” which could be considered as the first macroscopic quantitative analysis of the ductility of a crack in complex fluids. During complementary experiments which consist of the injection of wormlike micelles in themselves we have reported a new kind of flow instability. This instability is characterized by the transient loss of the radial symmetry during flow and by the apparitions of typical “branches” which propagates at very high speed through the sample and finally distort the air/gel interface.

Pour augmenter les performances de nos composants électroniques, les fabricants ont recourt à de nouveaux matériaux tels que les terres rares. Malgré leur nom, les terres rares sont présentes en quantité sur le globe terrestre mais de façon diluée dans les minerais extraits. L’extraction de ces éléments est peu effectuée en Europe mais majoritairement en Asie où les procédés chimiques de séparations employés sont parfois peu respectueux de l’environnement. De plus les industriels européens sont contraints économiquement par le marché asiatique pour l’achat de ces matières premières. En revanche l’Europe dispose d’une grande quantité de déchets électroniques contenant les éléments d’intérêts. Les procédés de recyclage sont donc primordiaux pour réduire notre dépendance économique et répondre aux besoins d’une économie circulaire. Des procédés de recyclage comme par exemple, l’extraction liquide-liquide existent déjà, mais la diversité des déchets présents nécessite d’adapter le procédé en fonction du lot de déchets afin d’améliorer le rendement. Mais l’optimisation d’un procédé nécessite des expérimentations qui peuvent prendre plusieurs années. L’objectif de la thèse est de trouver des moyens innovants pour réduire le temps nécessaire à l’étude d’un système d’extraction liquide-liquide de quelques années à quelques semaines. Pour cela le domaine a besoin d’une instrumentation dédiée pouvant analyser de façon automatique et rapide les procédés. Les travaux de cette thèse ont donc porté sur le développement d’un dispositif microfluidique d’extraction liquide-liquide associé à deux techniques principales d’analyses en ligne. La première technique d’analyse est basée sur une méthode de fluorescence des rayons X (XRF) pour déterminer la performance d’extraction. La seconde méthode est basée sur de la spectrométrie infrarouge à transformée de Fourrier (FTIR) afin d’étudier l’activité des solvants (aqueux et organiques), informant sur les mécanismes d’extraction. / To increase the performance of our electronic components, manufacturers are using new materials such as rare earth elements (REE). Despite their name, the REE are present in quantity on Earth but in a diluted way in the ores extracted. The extraction of these elements is little carried out in Europe but mainly in Asia where the chemical processes of separations employed are sometimes not very respectful of the environment. Moreover European manufacturers are economically constrained by the Asian market for the purchase of these raw materials. On the other hand, Europe has a large quantity of electronic waste containing the elements of interest. Recycling processes are therefore essential to reduce our economic dependence and meet the needs of a circular economy. Recycling processes such as, for example, liquid-liquid extraction already exist, but the diversity of the present waste requires to adapt the process according to the batch of waste in order to improve the yield. But the optimization of a process requires experiments that can take several years. The aim of the thesis is to find innovative ways to reduce the time needed to study a liquid-liquid extraction system from a few years to a few weeks. For this the domain needs a dedicated instrumentation that can analyse processes automatically and quickly. The work of this thesis is focused on the development of a microfluidic liquid-liquid extraction device associated with two main online analysis techniques. The first analytical technique is based on an X-ray fluorescence (XRF) method to determine the extraction performance. The second method is based on Fourier transform infrared spectrometry (FTIR) in order to study the activity of solvents (aqueous and organic), informing about extraction mechanisms.

L’écoulement et la stabilité des rideaux liquides viscoélastiques sont étudiés pour des solutions de polymères flexibles et semi rigides. Ces liquides viscoélastiques sont extrudés à partir d’une fente à débit constant et s’écoulent à l’air libre sous l’effet de la gravité. L’écoulement de ces liquides se caractérise par un équilibre initial entre la gravité et les forces élastiques causées par les déformations des chaînes de polymère, jusqu’à ce que l’inertie du liquide finisse par dominer et que l’on retrouve le comportement classique de chute libre. Nous montrons que l’écoulement est principalement influencé par la valeur du temps de relaxation extensionnel mesuré par une méthode de filamentation. Un nouvel éclairage sur l’écoulement des rideaux liquides Newtoniens nous permet de trouver une courbe maîtresse de l’écoulement dans le cas viscoélastique par analogie. En ce qui concerne la stabilité du rideau, nous observons que le débit critique de formation du rideau n’est pas affecté par la présence de polymères, tandis que le débit minimum en deçà duquel le rideau se rompt diminue après ajout de polymères, ce qui révèle une plus grande résistance de la nappe à l’initiation de trous. Par ailleurs, nous observons une instabilité de l’écoulement pour les solutions les plus rhéofluidifiantes, où des bandes épaisses (où la vitesse du liquide est supérieure à la moyenne) sont formées au sein du rideau. Une visualisation de l’écoulement à l’intérieur de la filière d’extrusion révèle que ce phénomène est lié à une instabilité de l’écoulement de contraction en amont de la fente, où l’écoulement est de nature instationnaire et tridimensionnelle. / The flow and the stability of viscoelastic liquid curtains are investigated using solutions of flexible and semi-rigid polymer chains. These viscoelastic liquids are extruded from a slot at constant flow rate and fall in ambient air under gravity. We show that the curtain flow of polymer solutions is characterized by an initial balance between gravity and the elastic stresses arising from the stretching of polymer molecules, until inertia finally dominates and the classical free-fall behavior is recovered. We show that the flow is mostly influenced by the value of the extensional relaxation time of the solution measured by a filament thinning technique. New insights on the theoretical description of Newtonian curtains allow us to find the master curve of the viscoelastic curtain flow by analogy. Concerning the curtain stability, we show that the critical flow rate for curtain formation is not affected by the presence of polymers whereas the minimum flow rate below which the curtain rapidly breaks is reduced by polymer addition, thus revealing a greater resistance of the sheet to hole initiations. Furthermore, we observe the onset of a flow instability for the most shear-thinning solutions, where thick bands (where the liquid velocity is larger than average) are formed within the curtain. Visualizations of the flow inside the die reveal that this phenomenon is linked to a flow instability at the contraction plane upstream of the slot where the flow is unsteady and three-dimensional in nature

La transplantation de microcapsules contenant des îlots de Langerhans, amas de cellules pancréatiques régulant la glycémie, montre des résultats prometteurs dans le traitement du diabète de type 1. A l’heure actuelle, il existe encore de nombreux challenges pour augmenter la durabilité d’une greffe fonctionnelle. Le manque de standardisation des technologies d’encapsulation actuelles a suscité un intérêt pour les technologies d’encapsulation microfluidique permettant d’apporter précision et automatisation. Cette thèse s’est attachée à faire progresser deux points de limitations actuelles de ces techniques : la productivité du système et l’état de surface des capsules obtenues.Dans la première partie, nous nous sommes concentrés sur la caractérisation d’un système microfluidique de génération de gouttes à focalisation d’écoulement (MFFD), contrôlé en pression. Des modèles analytiques et numériques ont été développés afin de déterminer les écoulements dans le système. Ensuite, la formation de gouttes a été caractérisée en fonction des paramètres d’entrée du système. Cette étude a abouti à l’obtention de lois permettant de prédire ces paramètres d’entrée afin d’optimiser la fréquence de production de microcapsules d’alginate.Dans la deuxième partie, nous avons développé un système microfluidique permettant de former des capsules de type cœur-couche, afin d’optimiser l’état de surface des capsules. Des premiers essais d’encapsulation d’îlots de Langerhans ont montré le potentiel de ce système dans la minimisation d’une réaction immunitaire vis-à-vis de ces capsules.Ce travail est un premier pas vers l’optimisation du système d’encapsulation, qui à terme, permettra de fournir aux cliniciens des capsules répondant à tous les critères exigés pour la transplantation. / Transplantation of microcapsules containing pancreatic islets, cell clusters regulating blood sugar, show promising results for type 1 diabetes therapy. However, many challenges remain to improve long-term graft functionality. The lack of standardization of current encapsulation technologies has aroused interest in microfluidic systems that enable more precision and automation.This thesis focuses on two of the current encapsulation technologies stakes: improving system productivity and microcapsules surface.In the first part of this thesis, we characterized a pressure-driven microfluidic flow focusing device (MFFD) droplet generation system. Analytical and numerical models were developed in order to determine and predict flow rates. Droplet formation was characterized as a function of the system input parameters. This study led to scaling laws enabling to predict these system input parameters in order to optimize alginate microcapsules production frequency.In the second part of this thesis, a microfluidic system enabling the production of core-shell microcapsules was developed. First experiments of pancreatic islets encapsulation have shown the ability of this system to minimize the immune reaction towards these capsules.This work is a first step towards encapsulation system optimization, which eventually, may provide capsules that meet all the capsule requirements for transplantation.