This dissertation explores the changes in structure of colloidal systems on the introduction of repulsive interactions. Colloidal gels are well understood when all particle interactions are attractive, but their structure is fundamentally changed when repulsive interactions compete with those attractive interactions, as in the case of a binary gel of oppositely charged particles. Similarly, colloidal crystals are well understood when interactions are approximately hard-sphere, but again, the structure and material properties change when a long-range repulsion is introduced, giving a colloidal `Wigner' crystal. My research quantitatively investigates these effects in experimental model systems. I use confocal microscopy to directly image in three dimensions suspensions of micron-scale colloidal particles which are monodisperse, index- and density-matched, fluorescent, and electrostatically charged. I use standard image-processing techniques to obtain the precise location of each particle in the imaging volume in order to analyze both global and local structure. In the case of the binary gel, I observe gelation of oppositely charged particles, controlled by varying the total particle volume fraction, the interaction strength, and the mixing ratio of the two particle species. I find that contrary to commonly studied purely attractive gels, in which weakly quenched gels are more compact and less tenuous, particles in these binary gels form fewer contacts and the gels become more tenuous as we approach the gel line, and the average attractive bond number emerges as a critical parameter for gelation. This suggests that a different mechanism governs gel formation and structure in binary gels, in which attractive and repulsive interactions compete. In the case of the long-range-repulsive colloidal `Wigner' crystals, I find a body-centered-cubic crystalline phase at particle volume fractions near 15%, in contrast to the face-centered-cubic crystalline phase found at volume fractions above 50% for hard spheres. The soft interactions in these repulsive crystals permit large fluctuations, with typical particle displacements up to 20% of the nearest-neighbor spacing. I determine the three independent crystalline elastic constants, and find that the crystals are very compliant (c ~ 5-40mPa), and strongly anisotropic at all volume fractions studied. I also observe a sharp interface between the fluid and crystalline phases. / Physics

Magnetic resonance (MR) is a highly versatile technique with great potential for use in industrial applications; from the in situ study of unit operations to the optimisation of product properties. This thesis, concerned with the latter, is divided into two parts. Firstly, dynamic MR is applied to characterise the flow behaviour, or rheology, of process fluids. Such characterisation is typically performed using conventional rheometry methods operating offline, with an online, or inline, method sought for process control and optimisation. Until recently, MR was an unlikely choice for this application due to the requirement of high-field MR hardware. However, recent developments in low-field MR hardware mean that the potential of MR in such applications can now be realised. Since the implementation of MR flow imaging is challenging on low-field MR hardware, two new approaches to MR rheometry are described using pulsed field gradient (PFG) MR. A cumulant analysis of the PFG MR signal is first used to characterise the rheology of model power-law fluids, namely xanthan gum-in-water solutions, accurate to within 5% of conventional rheometry, the data being acquired in only 6% of the time required when using MR flow imaging. The second approach utilises a Bayesian analysis of the PFG MR signal to characterise the rheology of model Herschel--Bulkley fluids, namely Carbopol 940-in-water solutions; data are acquired in only 12% of the time required for analysis using MR flow imaging. The suitability of the Bayesian MR approach to study process fluids is demonstrated through experimental study on an alumina-in-acetic acid slurry used by Johnson Matthey. Secondly, MR imaging is used to provide insights into the origins and mechanisms of colloidal gel collapse. Many industrial products are colloidal gels, a space-spanning network of attractive particles with a yield stress. Colloidal gels are, however, known to undergo gravitational collapse after a latency period, thus limiting the shelf-life of products. This remains poorly understood, with a more detailed understanding of both fundamental interest and practical importance. To this end, MR imaging is applied offline to investigate the phase behaviour of colloidal gels. In particular, a comparison of the simulated and experimental phase diagrams suggests gravitational gel collapse to be gravity-driven. Furthermore, measurement of the colloid volume fraction using MR imaging indicates the formation of clusters of colloids at the top of the samples. Whether such clusters initiate gravitational gel collapse is yield stress-dependent; the gravitational stress exerted by a cluster must be sufficient to yield the colloidal gel.

Ce travail est consacré à l'étude, par des techniques originales de diffusion dynamique de la lumière, de la dynamique lente de deux systèmes colloïdaux modèles. On a utilisée une technique de Corrélation Résolue dans le Temps (TRC) et des simulations numériques pour sonder, sur une grande plage de concentrations et sur sept décades en temps de relaxation, la dynamique d'un système de sphères dures colloïdales approchant de la transition vitreuse. A faible fraction volumique les temps de relaxation peuvent être représentés par une loi de puissance critique comme prévu par la Théorie de Couplage des Modes (MCT). A des concentrations élevées le temps de relaxation augmente selon une inattendue loi exponentielle critique avec une fraction volumique critique supérieure à celle prévue par MCT. L'étude des fluctuations de la dynamique confirme la présence d'un régime de dynamique activée: ce scénario est le même que l'on retrouve pour les systèmes vitreux moléculaires. Le deuxième sujet étudié est le comportement d'une suspension de colloïdes attractifs soumis à la contrainte gravitationnelle. Initialement, des agrégats de particules sédimentent en formant un gel sur le fond de la cellule. Les techniques spéciales employées nous ont permis de mesurer l'évolution des profils de concentration, des profils de vitesse et la dynamique locale dans la phase gel: la sédimentation peut être complètement décrite par le taux de déformation locale qui permet aussi une remise à l'échelle de la dynamique locale. Le rôle de la friction aux parois des cellules a été sondé par des expériences de polarimétrie et par la résolution numérique d'un modèle poroélastique pour la sédimentation du gel. / We investigated, using original light scattering techniques, the slow dynamics of two different model colloidal systems. We used a Time Resolved Correlation (TRC) technique and numerical simulations to study the dynamics of systems of colloidal hard spheres over a broad range of densities and seven decades in relaxation time. At low volume fraction the equilibrium relaxation time is described by the algebraic divergence predicted by mode-coupling theory (MCT). At higher density the relaxation time increases with an unexpected critical exponential form, whose the critical volume fraction is much larger then the MCT singularity. The fluctuations of the dynamics confirm the presence of an activated regime, as founded in molecular glass formers close to the glass transition. The second research subject concerns the behaviour of suspensions of attractive colloidal particles under gravitational stress. Initially, clusters fall forming a gelled deposit at the cell bottom. Our apparatus allows us to follow over time the concentration profile, the velocity profile and the local dynamics in the gel phase: the settling may be fully described by the local strain rate and dynamics exhibits remarkable scaling properties when time is normalized by strain rate. The role of the solid friction at the cell walls has been investigated by polarimetry experie nces and solving numerically a poroelastic model of gel sedimentation.

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