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Afin de mieux comprendre les spécificités de l'écoulement des fluides en seuil en géométries confinées, nous avons opté pour une approche multi-échelle expérimentale et/ou numérique dans des milieux poreux complexes et modèles. Nous montrons qu'il est possible d'utiliser la RMN pour visualiser des écoulements de fluides à seuil en géométrie complexe. Dans un milieu poreux, il est également possible de mesurer la distribution statistique des vitesses, ceci sans problème de résolution spatiale, grâce à la méthodologie de réglage d'une expérience d'injection sous IRM que nous avons mise en place. A l'aide de ces techniques, nous montrons que l'écoulement d'un fluide à seuil dans un pore modèle (une expansion-contraction axisymétrique) se localise dans la partie centrale du pore, dans le prolongement du tube d'entrée, tandis que les régions extérieures restent dans le régime solide. Des simulations numériques confirment ces résultats et montrent que la localisation de l'écoulement provient du confinement engendré par la géométrie. A l'inverse, nous montrons que pour un fluide à seuil s'écoulant dans un milieu poreux réel (en trois dimensions), il n'existe pas de zones au repos. De plus, la distribution de vitesse est identique à celle d'un fluide newtonien. Une analyse de ces résultats nous permet de prédire la forme de la loi de Darcy pour les fluides à seuil et de comprendre l'origine physique des paramètres déterminés par des expériences d'injection « macroscopiques » / To better understand the specifics of the flow of yield stress fluids in confined geometries, we opted for a multi-scale experimental and / or numerical approach in complex and model porous media. We show the usefulness of NMR for the study of yield stress fluid's flows in complex geometry. In a porous medium, we can also measure the true probability density function of fluid velocities without spatial resolution problem thanks to a complete optimisation of the design process of a NMR-PGSE experiment. Using these measurement technics, we find that the flow of a yield stress fluid in a model pore (an axisymetric expansion-contraction) is localised in the central part of the pore, i.e. in the continuity of the entry duct, and the external region stay at rest in the solid regime. Numerical simulations confirm those results and point out that the flow localisation is due to the confinement caused by the geometry. On the contrary, no region at rest exists for a yield stress fluid flowing through a real porous media (in 3D). Furthermore, the velocity distribution is the same as a newtonian fluid. The analysis of the results makes it possible to deduce the form of the Darcy's law for yield stress fluids and provides an insight in the physical origin of the coefficients found by “macroscopical” injection experiments

La investigación y desarrollo de líquidos iónicos a temperatura ambiente (RTILsl va cobrando mayor importancia, como una necesidad de contar con materiales y sustancias químicas apropiados para diversos procesos químico-industriales, así como al creciente uso de ciertas fuentes alternativas de energía, más llevaderos con nuestro medio ambiente. En este artículo se hace una reseña sobre los líquidos iónicos, sus propiedades físicas y de transporte, aplicaciones presentes y futuras. / Room temperature ionic liquids (RTILs): Properties, applieations and future prospeetsResearch and development of room-temperatureionic I iquids (RTILs) is becoming more important, as a need to count with materials and chemical substances suitable for several processes in chemical industries, as well as for the growing use of alternative sources of energy, much more friendly with our environment. In this paper is presented a review on ionic liquids, their physical and transport properties, current and future applications

<p>A new kind of lipid/polymer composite particle, consisting of a biodegradable polymer matrix with well-defined lipid domains, has been created. The lipid used is the water-swelling lipid monoolein (MO), which forms a reversed bicontinuous cubic diamond structure in aqueous solutions. The polymer is poly(d,l-lactide-co-glycolide) (PLG), which degrades into water-soluble monomers through hydrolysis. This new particle might be a good alternative for encapsulation of active substances intended to be released over a longer period of time, i.e. sustained/retained/controlled release.</p><p>To prepare such particles can be difficult. Suitable phase behaviour and a solvent with the right properties are needed. For this reason, the phase behaviours of several different lipid/polymer/solvent/water systems have been explored. From the phase behaviour of a suitable system (i.e. MO/PLG/ethyl acetate/water), a route for formation of lipid/polymer composite particles has been deduced. Particles have been formed and distinct, water-swelling, lipid domains have been confirmed by characterization by means of confocal laser scanning probe microscopy (CLSM). </p><p>The sample preparation process has been automated and a method based on using a robotic liquid handler has been developed. Phase diagrams have been determined by examination of macroscopic behaviours and the microstructures of the phases have been studied by small- and wide-angle X-ray scattering (L₃, V₂, L_α, L), nuclear magnetic resonance self-diffusion (L, L₃), viscosimetry (L) and rheology (L). Several different theoretical models have been applied for interpretation of the results. For example, the swelling of the reversed bicontinuous cubic phases and the sponge phase have been modelled by applying the theory of infinite periodical minimal surfaces, the sponge phase has been shown to be bicontinuous according to the theory of interconnected rods and the phase behaviour of the polymer has been described by the Flory-Huggins theory. The main focus of this work (4/5) concerns phase studies in multicomponent systems from a physical-chemical point of view.</p>

A new kind of lipid/polymer composite particle, consisting of a biodegradable polymer matrix with well-defined lipid domains, has been created. The lipid used is the water-swelling lipid monoolein (MO), which forms a reversed bicontinuous cubic diamond structure in aqueous solutions. The polymer is poly(d,l-lactide-co-glycolide) (PLG), which degrades into water-soluble monomers through hydrolysis. This new particle might be a good alternative for encapsulation of active substances intended to be released over a longer period of time, i.e. sustained/retained/controlled release. To prepare such particles can be difficult. Suitable phase behaviour and a solvent with the right properties are needed. For this reason, the phase behaviours of several different lipid/polymer/solvent/water systems have been explored. From the phase behaviour of a suitable system (i.e. MO/PLG/ethyl acetate/water), a route for formation of lipid/polymer composite particles has been deduced. Particles have been formed and distinct, water-swelling, lipid domains have been confirmed by characterization by means of confocal laser scanning probe microscopy (CLSM). The sample preparation process has been automated and a method based on using a robotic liquid handler has been developed. Phase diagrams have been determined by examination of macroscopic behaviours and the microstructures of the phases have been studied by small- and wide-angle X-ray scattering (L3, V2, Lα, L), nuclear magnetic resonance self-diffusion (L, L3), viscosimetry (L) and rheology (L). Several different theoretical models have been applied for interpretation of the results. For example, the swelling of the reversed bicontinuous cubic phases and the sponge phase have been modelled by applying the theory of infinite periodical minimal surfaces, the sponge phase has been shown to be bicontinuous according to the theory of interconnected rods and the phase behaviour of the polymer has been described by the Flory-Huggins theory. The main focus of this work (4/5) concerns phase studies in multicomponent systems from a physical-chemical point of view.

The existence of hydrodynamically developed, laminar Viscoelastic Secondary Flows (VSFs) of non-Newtonian fluids in straight ducts of non-circular cross-section was proposed in the 1950's. VSFs have since been observed sporadically, and only once with a velocimetric technique. Using axial and transverse full flow-field velocity-position raster maps made with Rheological Nuclear Magnetic Resonance (Rheo-NMR), Newtonian and non-Newtonian fluid flows were quantified in Hagen-Poiseuille and Power Law contexts, over more than two orders of magnitude of flow rate, in ducts of circle, square, triangle, and pentagon cross-section. VSF was reliably and repeatedly observed to occur at between one part in 130 and one part in 600 of the primary axial flow velocity. Velocity measurements ranged from <10 µm/s to approximately 30 cm/s, suggesting a velocity dynamic range >3E4 without optimization. To obtain VSF flow direction information, a novel flow directional phantom was developed and characterized. Aqueous solutions of Polyethylene Oxide (PEO), Viscarin GP-109NF, Viscarin GP-209NF (V209), Hyaluronan (HA) in a Phosphate-Buffered Saline-like solvent, and an aqueous Polyethylene Glycol/PEO-based Boger fluid were investigated. Axial data was corroborated with related data gathered by an independent method. Basic simulations corroborated the VSF observations. Duct hydraulic diameters (>= 1.6 mm) approached the micro-channel regime. VSF detections in HA --- synovial fluid's principal component --- and V209 were novel, as were observations of some artifacts which were subsequently characterized and corrected. The detection of VSF in HA represents the first experimental evidence suggesting that its second normal stress (N_2) is comparable to that of better-characterized fluids. In the first application of a new VSF-based method, a particular Boger fluid's constant viscosity and, in the square duct, its lack of VSF were used with established criteria to suggest that the fluid's N_2 approached zero. The development of a rudimentary, but versatile and inexpensive home-built velocimetric spectrometer is detailed, as are several new components. An exhaustive VSF literature review is included. The remarkable transverse velocimetric ability of Rheo-NMR in both optically opaque and transparent system is highlighted, suggesting that perhaps the technique might represent, in both micro-channels and conventional ducts, the gold-standard in flow velocimetry.

Afin de mieux comprendre les spécificités de l'écoulement des fluides en seuil en géométries confinées, nous avons opté pour une approche multi-échelle expérimentale et/ou numérique dans des milieux poreux complexes et modèles. Nous montrons qu'il est possible d'utiliser la RMN pour visualiser des écoulements de fluides à seuil en géométrie complexe. Dans un milieu poreux, il est également possible de mesurer la distribution statistique des vitesses, ceci sans problème de résolution spatiale, grâce à la méthodologie de réglage d'une expérience d'injection sous IRM que nous avons mise en place. A l'aide de ces techniques, nous montrons que l'écoulement d'un fluide à seuil dans un pore modèle (une expansion-contraction axisymétrique) se localise dans la partie centrale du pore, dans le prolongement du tube d'entrée, tandis que les régions extérieures restent dans le régime solide. Des simulations numériques confirment ces résultats et montrent que la localisation de l'écoulement provient du confinement engendré par la géométrie. A l'inverse, nous montrons que pour un fluide à seuil s'écoulant dans un milieu poreux réel (en trois dimensions), il n'existe pas de zones au repos. De plus, la distribution de vitesse est identique à celle d'un fluide newtonien. Une analyse de ces résultats nous permet de prédire la forme de la loi de Darcy pour les fluides à seuil et de comprendre l'origine physique des paramètres déterminés par des expériences d'injection " macroscopiques "