is a major polysaccharide of the plant cell wall which is known to play a role in many mechanical functionalities, especially when a gel is formed in the presence of calcium. Understanding the gelling abilities of pectin is of great interest to the food industry also, since pectin is a widely used as a gelling agent and thickener. The aim of this study was to apply two complementary microrheological techniques to these systems, multiple particle tracking (MPT) and a light scattering technique called diffusing wave spectroscopy (DWS). While the first one provides fundamental information about the homogeneity of the studied gel, the second gives access to the high frequency behaviour, related to the nature of the basic strands of the network. Firstly, after verifying the validity of the experimental apparati and analysis approaches in a series of careful control experiments on archetypal systems, a regime where pectin gels exhibit the signatures of semi-flexible networks was identified in experiments carried out on gels made of pectin chains pre-engineered by enzymatic deesterification and subsequently assembled with the release of Ca2+. These results were the first showing that polysaccharides networks could be accommodated within the framework of semi-flexible networks, which have become a paradigm for biological gels, such as the well-known F-actin solutions present in the cell cytoskeleton. However, in the plant cell wall, where calcium is already present, the assembly mechanism could be controlled in a different manner, and a more biologically relevant system was studied where the action of the plant enzyme pectinmethylesterase was used to liberate ion-binding groups in the presence of Ca2+. Gels formed according to this alternative methodology were found to behave as punctually cross-linked flexible networks, strikingly different from the first results. This would be explained by the presence of short blocks of charged residues. Finally, experiments on pectins carried out with controlled blocky structures showed that a pectin made of short blocks can exhibit both sorts of network, depending on the polymer and Ca2+ concentrations. This lead naturally to the construction of a state diagram for the regimes of assembly, with proposed control parameters being the polymer concentration and the ratio of the amount of Ca2+ to the quantity of pectic residues which can effectively bind the calcium into cross-links, christened Reff.

In this thesis, the macroscopic phase separation of milk proteins and high molecular weight oat beta-glucan was investigated. A better knowledge of this model system will improve our ability to control structure in dairy gels containing nutritionally significant concentrations of dietary fiber. A phase behaviour diagram was obtained experimentally, and the results were then modelled using theoretical models based on thermodynamic incompatibility between casein micelles and beta-glucan and demonstrated that casein micelles are the main contributors to the instability of these mixtures. Water in water emulsion systems formed at high concentrations of protein and beta-glucan upon mixing, and were visualized using confocal scanning laser microscopy. For the first time, the dynamics of phase separation of these mixtures were followed using diffusing wave and ultrasonic spectroscopy, as well as with rheological methods. The work explored the formation of different bi-continuous networks by controlling the gelation of the protein phase using chymosin. This enzymatic reaction specifically destabilizes the casein micelles, allowing for a kinetic control of protein gelation within or between phase separated domains. The addition of -carrageenan and the effect of shear on the mixtures were evaluated as possible strategies for controlling the growth of the phase separated domains in dairy gels containing concentrations of beta-glucan high enough to be nutritionally significant. Results indicated that different structures could be obtained depending on the processing conditions, for example, the mode of addition of the polysaccharides or the pre-shearing conditions. This work represents a novel approach for incorporating nutritionally significant concentrations of beta-glucan in dairy foods, and serves as proof of concept for further development of an important application area linked to the development of reduced fat dairy products with additional health benefits. / Canadian Dairy Commission (CDC) and Natural Sciences and Engineering Research Council (NSERC)

This investigation evaluates the influences of optical property assumptions on nearinfrared diffuse correlation spectroscopy (DCS) flow index measurements. Independent variation is induced in optical properties, absorption coefficient (μa) and reduced scattering coefficient (μs’), of liquid phantoms with concurrent measurements of flow indices. A hybrid instrument is incorporated consisting of a dual-wavelength (785 and 830 nm) DCS flow device to obtain flow indices and a frequency-domain tissue-oximeter for optical properties. Flow indices are calculated with measured μa and μs’ or assumed constant μa and μs’. Inaccurate μs’ assumptions produced much larger flow index errors than inaccurate μa. Underestimated/overestimated μs’ from -35%/+175% lead to flow index errors of +110%/-80% and underestimated/overestimated μa from -40%/+150% lead to -20%/+40%, regardless of wavelength. Analysis of a clinical study involving human head and neck tumors indicates flow index errors due to inter-patient optical property variations up to +280%. Collectively, these findings suggest that studies involving significant μa and μs’ changes should measure flow index and optical properties simultaneously to accurately extract blood flow information. This study provides unique insight through the use of liquid phantoms, hybrid instrumentation, incorporation of measurement errors and a generalization into DCS flow index errors due to the influences of optical properties.

This thesis describes the development and applications of an extension of DWS which enables the recovery of ‘localized’ mechanical properties, in a specified region of a complex jelly-like object which is inhomogeneous, marked out by the focal volume of an ultrasound transducer, also called the region-of-interest (ROI). Introduction of the sinusoidal forcing creates a sinusoidal phase variation in the detected light in a DWS experiment which modulates the measured intensity autocorrelation, g2 (τ ). Decay in the modulation depth with τ is used to recover the visco-elastic spectrum of the material in the ROI. En route to this, growth of the mean-squared dis- placement (MSD) with time is extracted from the modulation depth decay, which was verified first by the usual DWS experimental data from an homogeneous object with properties matching those in the ROI of the inhomogeneous object and then those obtained by solving the generalized Langevin equation (GLE) modelling the dynamics of a typical scattering centre in the ROI. A region-specific visco-elastic spectral map was obtained by scanning the inhomogeneous object by the ultrasound focal volume. Further, the resonant modes of the vibrating ROI were measured by locating the peaks of the modulation depth variation in g2(τ ) with respect to the ultrasound frequency. These resonant modes were made use of to recover elasticity of the material of the object in the ROI. Using a similar strategy, it was also shown that flow in pipe can be detected and flow rate computed by ‘tagging’ the photons passing through the pipe with a focussed ultrasound beam. It is demonstrated, both through experiments and simulations that the ultrasound-assisted technique devel- oped is better suited to both detect and quantitatively assess flow in a background of Brownian dynamics than the usual DWS. In particular, the MSD of particles in the flow, which shows forth a super-diffusive dynamics with MSD growing following τ α with α < 2, is captured over larger intervals of τ than was possible using existing methods. On the theoretical front, the main contribution is the derivation of the GLE, with multiplicative noise modulating the interaction ‘spring constant’. The noise is derived as an average effect of the micropolar rotations suffered by the ‘bath’ particles on the ‘system’ particle modelled. It has been shown that the ‘local’ dynamics of the system particle is nontrivially influenced by the dynamics, both translation and rotation, of ‘nonlocal’ bath particles.

Quantifier l'impact des vibrations sur les propriétés rhéologiques des suspensions granulaires trouve son intérêt en géophysique et dans de nombreux secteurs industriels. Par exemple, les mécanismes de liquéfaction des sols sous l'effet d'une secousse demeurent mal connus à ce jour. L'objet de cette thèse est d'apporter une compréhension fondamentale des modifications induites par les vibrations sur les propriétés physiques et mécaniques d'un système modèle composé de billes de verre sphériques et monodisperses immergées dans un fluide newtonien en concentration dense (Φ≈0.61). Dans un premier temps, le comportement rhéologique macroscopique global des suspensions a été étudié à l'aide d'un rhéomètre couplé à une cellule vibrante. Les vibrations font disparaître la contrainte seuil du matériau et font apparaître un plateau newtonien contrôlé par une compétition entre les contraintes de lubrification et les contraintes frictionnelles. Un autre type d'expérience, la rhéométrie à chute de bille par Imagerie par Résonance Magnétique, montre des résultats similaires. Dans un second temps, la dynamique de réorganisation locale des grains a été sondée grâce à des expériences de diffusion de la lumière faisant appel à une caméra CCD et fondées sur l'analyse des fluctuations d'intensité des figures de speckle. Cette technique a permis de sonder la dynamique des particules aux temps longs. Il est apparu que le temps caractéristique de relaxation obtenu est relié à la viscosité au plateau newtonien de la suspension granulaire vibrée, ce qui a permis d'établir un lien entre le comportement rhéologique macroscopique des échantillons et la dynamique diffusionnelle à l'échelle du grain / Quantify the impact of vibrations on the rheological properties of granular suspensions is of paramount importance in many environmental or industrial areas. For example, the soil liquefaction mechanisms, as a result of an earthquake, remain poorly understood by now. The purpose of this thesis is to provide a fundamental understanding of the modifications induced by the vibrations on physical and mechanical properties of a model concentrated suspension (Φ≈0.61), made up of spherical monodisperse glass beads immersed in a Newtonian fluid. In a first step, the macroscopic rheological behavior of this system has been studied using a classical rheometer coupled with a vibrating cell. The vibrations induce the vanishing of the yield stress of the material and the emergence of a Newtonian plateau at low shear. Thus, it has been shown that the viscosity of the suspension is controlled by a competition between lubrication and frictional stresses. Another type of experiment, the falling ball rheometry by Magnetic Resonance Imaging, shows similar results. In a second step, the local dynamics of the grains was probed by diffusing wave spectroscopy using a CCD camera based on the analysis of the intensity fluctuations of speckle patterns. This technique allowed to probe the dynamics of particles at long times. It appears that the characteristic relaxation time obtained is related to the suspension viscosity, thereby linking the macroscopic rheological properties to the diffusional dynamics at the grain scale

Le chauffage des matériaux cosmétiques peut provoquer une exsudation de surface sous la forme de petites gouttes puis un retrait des gouttes associé à un processus de recristallisation. Des méthodes rhéologiques et de diffusion multiple de la lumière ont permis une étude des effets d’exsudation et de recristallisation en fonction de la température de chauffage, du vieillissement et de la plasticité du matériau. Des simulations numériques et un modèle phénoménologique basés sur la prolifération de fissures métastables et la croissance hors équilibre d’amas de défauts liquides susceptibles de crever la surface permettent de rendre compte des effets d’exsudation et de recristallisation variables selon la plasticité de la matrice semi-cristalline et la teneur en huile dans le matériau soumis à une perturbation thermique. / The heating of cosmetic materials can generate an external sweating phenomenon shown by the formation of droplets, followed by a withdrawal of the droplets due to the recrystallization process. Rheological methods and light scattering allowed to study the effects of sweating and re-crystallization in term of heating temperature, aging, and material’s elasticity. Numerical simulations and a phenomenological model based on the multiplication of metastable cracks and the growth outside of equilibrium state of liquid default pits able to burst the surface proves the sweating effects and the re-crystallization variable depending on the semi-crystalline matrix and the percentile of oil in the material under thermal fluctuation.

Au cours de ce travail, nous avons proposé une caractérisation "multi-échelle" des matériaux mous à travers des montages originaux permettant la mesure simultanée des quantités macroscopiques et microscopiques. Dans une première partie de nos travaux, nous avons associé une méthode optique introduite récemment, la diffusion multiple de la lumière résolue spatialement (PCI-DWS), avec une sollicitation thermique, afin de suivre l’évolution de la microstructure d’échantillons à base de corps gras lors d’une rampe de température. Ces expériences ont permis d’identifier des transitions de phase par PCI-DWS et de les localiser spatialement dans des échantillons hétérogènes.Dans une deuxième série d’expériences, la même méthode optique a été couplée à des essais mécaniques réalisés avec une machine de traction commerciale. Pour des éprouvettes de polymère semi-cristallin, nous avons mesuré la déformation de l’éprouvette par PCI-DWS, sans avoir recours à des marqueurs de surface, contrairement aux méthodes d’imagerie couramment utilisées. Pour le même polymère, nous avons suivi la dynamique microscopique lors d’essais de traction dans les deux régimes, élastique et plastique. Nous avons montré que la dynamique microscopique et la relaxation de la contrainte lors de tests de traction à déformation imposée sont liées par une relation étonnement simple, que nous avons pu modéliser. Dans une dernière partie de la thèse, nous avons conçu et réalisé un prototype d’instrument permettant de mesurer simultanément la dynamique microscopique, la force et le déplacement lors d’essais de traction sur des élastomères. Grâce à cet instrument, nous avons pu mettre en évidence l’existence de précurseurs dynamiques microscopiques qui précèdent de milliers de secondes l’apparition de signes macroscopiques de la défaillance du matériau. / In this thesis, we introduce a "multi-scale" characterization of soft matter based on novel setups that couple macroscopic measurements (temperature, force, deformation) to measurements of the microscopic dynamics. In a first series of experiments, we use a recently introduced optical method, space-resolved diffusion wave spectroscopy (PCI-DWS), to follow the microscopic dynamics of fat materials during a temperature ramp. This allows us to detect phase transitions and to localize them in space for heterogeneous samples. In a second series of experiments, the same optical method is coupled to mechanical measurements performed on a commercial universal traction machine. For a semi-crystalline polymer, we measure by PCI-DWS the mesoscopic deformation field under tension, with no need to pre-treat the sample surface as in conventional imaging methods. For the same polymer, we measure the microscopic dynamics during tensile stress relaxation tests, both in the linear and non-linear regime. We find a remarkably simple relationship between the microscopic dynamics and the macroscopic stress relaxation, and propose a simple model to rationalize it. In the last part of the thesis, we have designed and implemented a setup prototype to measure simultaneously the microscopic dynamics (by PCI-DWS), the force and the deformation during tensile tests on elastomers. Thanks to this apparatus, we unveil dynamic precursors preceding by thousands of seconds anymicroscopic sign of the incipient material failure.