Les polyuréthanes segmentés thermoplastiques (TPUs) sont des matériaux élastomères thermoplastiques qui couvrent une large gamme d’applications. Ces matériaux possèdent intrinsèquement une aptitude à la nano-structuration car ils présentent dans leur structure macromoléculaire une alternance de segments rigides et de segments souples thermodynamiquement immiscibles en dessous d’une certaine température (température de micro-mélange). Ainsi, en refroidissant à partir de l’état fondu, une micro-séparation de phase, dont la cinétique dépend de la température, se produit. De plus, l’application d’une déformation avant cette structuration modifie sa cinétique. Ainsi, en vue d’appréhender l’effet de la mise en oeuvre sur certaines propriétés de ces matériaux, il s’avère intéressant d’étudier l’influence de l’histoire thermomécanique sur la structuration. Cette étude repose sur l’observation du comportement de cristallisation et/ou de séparation de phase de cinq polyuréthanes commerciaux de nature chimique différente, en fonction de différentes conditions thermiques et mécaniques appliquées en milieu modèle ou en conditions de mise en oeuvre réelles. Les techniques utilisées sont principalement rhéologiques, rhéo-optiques et par diffusion de rayons X aux petits angles (SAXS). Ces différentes analyses permettent d’affirmer que les contraintes appliquées dans le fondu des matériaux avant leur solidification modifient de façon drastique la cinétique de structuration mais aussi leur morphologie résultante. En effet, une orientation particulière des entités structurées au sein des matériaux peut être engendrée par des contraintes appliquées en fonction de leur intensité. Cette morphologie résultante particulière joue également un rôle sur les propriétés mécaniques finales des matériaux. / Thermoplastic segmented polyurethanes are an important class of thermoplastic elastomers which cover a wide range of applications. These materials are multi-block copolymers composed of alternating “hard” and “soft” segments which are respectively below and above their glass transition temperature under ambient conditions. TPUs exhibit a twophase microstructure which arises from the thermodynamic incompatibility between the hard and soft segments. This microphase separation is often combined with the crystallization of either or both segments. The mechanical properties of these polymers will depend upon the overall multiblock length and the hard block sequence length and how they affect the material morphology. Our goal is to understand how the polyurethane final properties can be affected by the processing stresses (extrusion, injection…). In this scope, experiments were performed using a rheometer or an optical microscope coupled with a shearing hot stage. A preshear controlled treatment was applied and its effect on the material structuration was followed. These characterizations highlighted the enhancement of phase separation kinetics by the shear. For instance, for presheared samples, phase separation and/or crystallization of the hard segments occur ten times faster than for non-sheared ones. Moreover, SAXS experiments carried out on samples structured from several conditions illustrated perpendicular arrangements of crystalline domains perpendicularly to the flow direction. Finally, this particular morphology induced by shear modifies the materials final mechanical properties

Hollow fiber membranes offer the opportunity to dramatically reduce the energy required to perform gas separations in the chemical industry. The membranes are fabricated from highly non-Newtonian precursor materials, including concentrated polymer solutions that sometimes also contain dispersed particles. These materials are susceptible to shear-induced microstructural changes during processing, which can affect the characteristics of the resulting membrane. This thesis explores several shear-related effects using materials and flow conditions that are relevant for fiber spinning. The findings are discussed as they relate to membrane processing, and also from the standpoint of enhancing our fundamental understanding of the underlying phenomena. First, the effect of shear on polymeric dope solutions was investigated. Shear-induced demixing—a phenomenon not previously studied in membrane materials—was found to occur in membrane dopes. Phase separation experiments also showed that shear-induced demixing promotes macrovoid formation. The demixing process was found to depend not only on the instantaneous shear conditions, but also on the shear history of the solution. This suggests that low-shear flow processes that occur in the upstream tubing and channels used for fiber spinning can affect macrovoid formation. The effect of viscoelastic media on dispersed particles was also explored. Shear-small-angle light scattering results showed that particles suspended in membrane dope solutions formed aggregated, vorticity-oriented structures when shear rates in the shear-thinning regime of the polymer solution were applied. Shear rates well below the shear-thinning regime did not produce any structure. In fact, the application of a Newtonian shear rate to a sample already containing the vorticity structure caused the sample to return to isotropy. Measurements using a highly elastic, constant-viscosity Boger fluid showed that strong normal forces alone are not sufficient to form the vorticity structures, but that shear thinning is also required. Lastly, a study was conducted examining cross-stream migration of particles dispersed in viscoelastic media. Fluids exhibiting varying degrees of shear thinning and normal forces were found to have different effects on the particle distribution along the shear gradient axis in Poiseuille flow. Shear thinning was found to promote migration toward the channel center, while normal stresses tended to cause migration toward the channel walls. In addition to hollow fiber spinning, many other industrially relevant applications involve polymer solutions and suspensions of particles in viscoelastic media. Often, the properties and performance of the material depend strongly on the internal microstructure. The results from the research described in this thesis can be used to guide the design of materials and processing conditions, so that the desired microstructural characteristics can be achieved.

Une « boue » est constituée de particules submillimétriques immergées dans un fluide. Nous étudions des boues concentrées (ou « pâtes granulaires »), où la concentration en particules est proche du maximum réalisable. Les particules peuvent être plus denses que le fluide, et sédimenter, ou être équilibrées en densité. Ces deux cas sont examinés, à l’aide d’une boue modèle. Nous étudions les écoulements de ces boues dans une cellule de Couette. Les expériences utilisent des méthodes innovantes, permettant de mesurer les vitesses des grains individuellement et collectivement, et les profils de concentration sous cisaillement. Les expériences apportent des informations nouvelles sur les écoulements, comme l’existence de courants de re-circulation. Les résultats sur les vitesses azimutales et concentrations sont en accord avec la théorie de Morris et Boulay d’équilibre des forces normales, pour un rapport convenable des coefficients viscométriques des forces tangentielle et normales. / Wet granular materials are made of solid particles in high concentration, immersed in a viscous fluid. We investigated particle dynamics in a model granular suspension in Couette geometry, at low Reynolds/Taylor numbers for density and non density matched suspension. We used innovated techniques such as: Single Particle Tracking (SPT), Multi Particles Video Trajectography (MPVT) and Concentration Photometry (CP). These experiments allow us to provide information about single and collective motion of grains as well as particle repartition (local volume fraction). We investigated fully 3D velocity profiles in concentrated suspensions, diffusion coefficients, particle fluctuations and recirculation motion, also differential flows. We observe that the flow of non density matched suspensions is localized near the inner cylinder in the low shear rate regime, resulting in a sheared layer only a few particle diameters in thickness, in a way very similar to sheared dry granular materials. At high enough angular velocity, the initially localized flow crosses over to full fluidization: in this regime the granular suspension nearly behaves as a density-matched suspension. Dependence between particles’ velocity and associated fluctuation amplitude is evidenced. Experiments as velocity and concentration profiles were compared with theoretical prediction based on the force balance model and different viscometric laws were investigated for normal and shear forces.

Les suspensions non browniennes présentent un comportement rhéologique très différent en fonction de leur concentration. L'écoulement de suspensions semi-diluées est newtonien et montre une migration des particules provoquant des hétérogénéités de concentration. Au contraire, les suspensions concentrées présentent un large éventail de phénomènes rhéologiques non linéaire. Ce travail cherche à mieux comprendre les écoulements de suspensions dans différente gamme de concentration. A basse concentration,une étude de la migration est réalisée afin de quantifier les forces responsables de ce phénomène. Pour cela, les forces de migration sont comparées aux forces de sédimentation,grâce à un écoulement unidirectionnel et confiné. Des techniques de suivi de particules avancées et la microscopie confocale, permettent une mesure systématiquement à la fois des profils de fraction volumique et des profils de vitesse. Plusieurs systèmes sont comparés afin de mettre en évidence que les forces hydrodynamiques jouent un rôle important dans la migration. La seconde partie de ce travail consiste à caractériser l'écoulement d'un système rhéoépaississant. Des techniques de rhéologie locale, tel que la vélocimétrie ultrasonore et la tomographie RX sont utilisées dans différentes cellules de Couette. Ces techniques permettent de mesurer les profils de fraction volumique et les profils de vitesse. Nous soulevons que les propriétés rhéologiques dépendent fortement du confinement et de la rugosité, et parfois, nous avons observé instabilités dues aux interfaces. / Flows of non-Brownian suspensions are present in different fields, and exhibitdifferent behavior in function of concentration. Flows of semi-dilute suspensions aremainly governed by the spatial repartition of the particles. At low Reynolds numbers,it is indeed generally non-uniform due to cross-stream migration towards low shearedregions of the flow. In this work we aim at testing the idea that interactions betweenparticles could also be involved in the shear induced migration phenomenon. In orderto quantify the strength of shear induced migration, we take advantage of horizontalflow of buoyant particles in slits, where viscous resuspension is in competitionwith buoyancy.Using advanced particle imaging velocimetrie techniques and confocalmicroscopy, we measure systematically both volume fraction and velocity profiles.We compare two systems with and without interaction and any different was found.Concentrated suspensions exhibit a wide range of non linear rheological phenomena.This work characterizes the local rheology of a continuous shear thickening. We areused ultrasonic rheology and tomography RX in Couette cell for measured the volumefraction profile and velocity profile. We report that the rheological properties dependstrongly of the confinement and roughness, and sometimes we observed instabilitiesdue to the interface.

Thickened tailings production and disposal continue to grow in importance in the mining industry. In particular, the transport of oil sands tailings is of interest in this study. These tailings must be in a homogeneous state (non-segregating) during pipeline flow and subsequent discharge. Tailings are often transported in an open channel or flume. Slurries containing both clay and coarse sand particles typically exhibit non-Newtonian rheological behaviour. The prediction of the flow behaviour of these slurries is complicated by the limited research activity in this area. As a result, the underlying mechanisms of solids transport in these slurries are not well understood. To address this deficiency, experimental studies were conducted with kaolin clay slurries containing coarse sand in an open circular channel.<p> A numerical model has been developed to predict the behaviour of coarse solid particles in laminar, open channel, non-Newtonian flows. The model involves the simultaneous solution of the Navier-Stokes equations and a scalar concentration equation describing the behaviour of coarse particles within the flow. The model uses the theory of shear-induced particle diffusion (Phillips et al., 1992) to provide a number of relationships to describe the diffusive flux of coarse particles within laminar flows. A sedimentation flux has been developed and incorporated into the Phillips et al. (1992) model to account for gravitational flux of particles within the flow. Previous researchers (Gillies et al., 1999) have shown that this is a significant mechanism of particle migration.<p> The momentum and concentration partial differential equations have been solved numerically by applying the finite volume method. The differential equations are non-linear, stiff and tightly coupled which requires a novel means of analysis. Specific no-flux, no-slip and no-shear boundary conditions have been applied to the channel walls and free surface to produce simulated velocity and concentration distributions. The results show that the model is capable of predicting coarse particle settling in laminar, non-Newtonian, open channel flows. The results of the numerical simulations have been compared to the experimental results obtained in this study, as well as the experimental results of previous studies in the literature.

Thickened tailings production and disposal continue to grow in importance in the mining industry. In particular, the transport of oil sands tailings is of interest in this study. These tailings must be in a homogeneous state (non-segregating) during pipeline flow and subsequent discharge. Tailings are often transported in an open channel or flume. Slurries containing both clay and coarse sand particles typically exhibit non-Newtonian rheological behaviour. The prediction of the flow behaviour of these slurries is complicated by the limited research activity in this area. As a result, the underlying mechanisms of solids transport in these slurries are not well understood. To address this deficiency, experimental studies were conducted with kaolin clay slurries containing coarse sand in an open circular channel.<p> A numerical model has been developed to predict the behaviour of coarse solid particles in laminar, open channel, non-Newtonian flows. The model involves the simultaneous solution of the Navier-Stokes equations and a scalar concentration equation describing the behaviour of coarse particles within the flow. The model uses the theory of shear-induced particle diffusion (Phillips et al., 1992) to provide a number of relationships to describe the diffusive flux of coarse particles within laminar flows. A sedimentation flux has been developed and incorporated into the Phillips et al. (1992) model to account for gravitational flux of particles within the flow. Previous researchers (Gillies et al., 1999) have shown that this is a significant mechanism of particle migration.<p> The momentum and concentration partial differential equations have been solved numerically by applying the finite volume method. The differential equations are non-linear, stiff and tightly coupled which requires a novel means of analysis. Specific no-flux, no-slip and no-shear boundary conditions have been applied to the channel walls and free surface to produce simulated velocity and concentration distributions. The results show that the model is capable of predicting coarse particle settling in laminar, non-Newtonian, open channel flows. The results of the numerical simulations have been compared to the experimental results obtained in this study, as well as the experimental results of previous studies in the literature.

A suspension flow model based on the "suspension balance" approach has been developed. This work modifies the model to allow the solution of suspension flows under general flow conditions. This requires the development of a frame-invariant constitutive model for the particle stress which can take into account the spatially-varying local kinematic conditions. The mass and momentum balances for the bulk suspension and particle phase are solved numerically using a finite volume method. The particle stress is based upon the computed rate of strain and the local kinematic conditions. A nonlocal stress contribution corrects the continuum approximation of the particle phase for finite particle size effects. Local kinematic conditions are accounted through the local ratio of rotation to extension in the flow field. The coordinates for the stress definition are the local principal axes of the rate of strain field. The developed model is applied to a range of problems. (i) Axially-developing conduit flows are computed using both the full two-dimensional solution and the more computationally efficient "marching" method. The model predictions are compared to experimental results for cross-stream particle concentration profiles and axial development lengths. (ii) Model predictions are compared to experiments for wide-gap circular Couette flow of a concentrated suspension in a shear-thinning liquid. With minor modification, the suspension flow model predicts the major trends and results observed in this flow. (iii) Comparisons are made to experiments for an axisymmetric contraction-expansion. Model predictions for a two-dimensional planar contraction flow test the influence of model formulation. The variation of the magnitude of an isotropic particle normal stress with local kinematic conditions and anisotropy in the in-plane normal stresses are both explored. The formulation of the particle phase stress is found to have significant effects on the solid fraction and velocity. (iv) Finally, for a rectangular piston-driven flow and an obstructed channel flow, a "computational suspension dynamics" study explores the effect of particle migration on the bulk flow field, system pressure drop and particle phase composition.

The correlation between concrete rheological parameters and its pumping behavior under consideration of the so-called lubricating layer has been investigated for decades. In this thesis, flow-induced particle migration (FIPM) was studied in-depth, as the main underlying mechanism for the formation of the lubricating layer. Conventionally vibrated and self-compacting concretes were chosen as the target mixtures. Furthermore, cementitious model concretes, containing colored glass beads, were proposed to obtain further insights into the FIPM and its impact on pumping. The mixtures were differentiating with regard to particle volume fractions, mortars composition, maximum particle size and particle size distributions. In the experiments, various established methods were used to characterize the rheological properties and the pumping behavior of the concretes. New methodologies for estimating the thickness of the lubricating layer and the particle distribution in pumped cross-sections were proposed as well. The rheological properties and pumping behavior of real and model concretes were in agreement with the state-of-the-art literature. Based on the radial particle distributions, it was illustrated that the particle migration intensifies by increasing the particle size and decreasing the total volume fraction of solid particles. Furthermore, in highly-concentrated poly-dispersed model concretes, the particle concentration curves consist of a sudden jump close to the pipe wall and a relatively uniform distribution in the inner zone of the pipe. In these cases, the influence of FIPM on overall flow behavior cannot be neglected. Moreover, it was shown that the lubricating layer thickness is not constant for all concrete mixtures. For poly-dispersed suspensions, the shear-induced particle migration (SIPM) has a stronger impact than the wall for forming the lubricating layer. Finally, it was concluded that a solid-liquid threshold of 1 to 2 mm is a reliable choice when investigating concrete pipe flow. The faster the concrete is pumped or the lower the yield stress of the constitutive mortar is, the smaller is the solid-liquid threshold. Based on the experimental findings, a first-order physical correlation between pumping parameters (pressure and discharge rate), particle properties (volume fraction and packing properties) and lubricating layer properties (thickness and viscosity) was proposed. Accordingly, for a simple flow topology with a shearing lubricating layer and an extruding yield stress concrete, the lubricating layer thickness was computed from the competition between shear-induced fluxes of particles. In agreement with the driving equations of SIPM, it was assumed that the first flux correlates with the internal stress gradient in the plug concrete whereas the counteracting particle flux correlates with the shear rate in the lubricating layer. The model was validated for two flow types, pipe flow in the Sliper and Couette flow in a co-axial tribometer. The proposed model can capture the observed main features and their evolutions despite the absence of any fitting parameters.

La cellulose étant l'un des biopolymères les plus abondants, elle est employée dans ce travail de thèse sous sa forme nano-fibrille (2 à 5nm de diamètre et plusieurs microns de long) pour préparer des nanomatériaux durables. Les microfibrilles de cellulose (MFC) chargées positivement ou négativement sont assemblées en couches minces dans ces nanomatériaux par la méthode « Layer by Layer » (LbL) par trempage, pulvérisation ou spin assisté. Les différences entre ces films LbL à base de MFC et les films LbL à base de polymères standards sont discutées brièvement et sont reliées à la forme nanofibrillaire de la cellulose. Les MFC réagissent comme des nano-objets anisotropes et rigides. Les films LbL de MFC sont ensuite intégrés à des membranes de séparation, entre la couche polymérique de séparation et le support poreux, pour améliorer le débit à travers ces membranes. Ces films minces sont également déposés sur des aérogels de cellulose pour améliorer la stabilité de ces aérogels en milieu aqueux. Dans les deux applications, les résultats était encouragent et montre une validation de principe. / Cellulose, one of the most abundant biopolymers, is used in this PhD work in its nanofibrillated form, 2-5 nm in diameter and microns long, to prepare sustainable nanomaterials. Both positively and negatively charged microfibrillated celluloses (MFC) are assembled in these nanomaterials using the versatile Layer by Layer (LbL) assembly methods: dipping, spray assisted-deposition and spin-assisted deposition. A brief comparison between the MFC based LbL assembled films and the standard polymeric LbL films is carried out. Thedifferences between the two species are related to the fibrillar form of cellulose. MFC behaves like rigid anisotropic nano-objects. MFC LbL assembled films are then integrated in separation membranes between active polymeric separation layers and a mechanically stable porous support to improve the flux through these membranes. MFC LbL assembled films are also coated on cellulosic aerogels to improve the wet stability of these aerogels. In both cases, results were encouraging and showed a proof of concept.

The self-assembly of polystyrene-stabilized cadmium sulfide nanoparticles (PS-CdS) with amphiphilic stabilizing chains of polystyrene-block-poly(acrylic acid) (PS-b-PAA) into colloidal quantum dot compound micelles (QDCMs) is studied on two-phase gas-liquid segmented microfluidic reactors. The resulting particle sizes are found to arise from the interplay of shear-induced coalescence and particle breakup, depending on a combination of chemical and flow conditions. Variation of water content, gas-to-liquid ratio, and total flow rate, enable control of QDCM sizes in the range of 140 – 40 nm. The flow-variable shear effect on similar microfluidic reactors is then applied to direct the solution self-assembly of a PS-b-PAA block copolymer into various micelle morphologies. The difference between off-chip and on-chip morphologies under identical chemical conditions is explained by a mechanism of shear-induced coalescence enabled by strong and localized on-chip shear fields, followed by intraparticle chain rearrangements to minimize local free energies. Time-dependent studies of these nanostructures reveal that on-chip kinetic structures will relax to global equilibrium given sufficient time off-chip. Further investigations into the effect of chemical variables on on-chip shear-induced morphologies reveal a combination of thermodynamic and kinetic effects, opening avenues for morphology control via combined chemical (bottom-up) and shear (top-down) forces. An equilibrium phase diagram of off-chip micelle morphologies is constructed and used in conjunction with kinetic considerations to rationalize on-chip mechanisms and morphologies, including cylinders and vesicles, under different chemical conditions. Finally, we extend our strategy of two-phase microfluidic self-assembly of PS-b-PAA to the loading of fluorescent hydrophobic probes (pyrene and naphthalene) with different affinities for the PS core. The on-chip loading approach provides a fast alternate to the slow off-chip method, with implications for the potential development for point-of-care devices for drug loading. On-chip loading results indicate that loading efficiencies are dependent on water content and, to a lesser extent, on flow rate; the results also suggest that the on-chip morphologies of the PS-b-PAA micelles are an important factor in the loading efficiencies. / Graduate