A large variety of engaging phenomena, ranging from crystallization in protein solutions to the formation of colloidal gels and glasses via depletion forces, stems from the occurrence of very short-ranged attractive forces. From depolarized light scattering measurements of equilibrium sedimentation profiles, we obtain an accurate description of the equation of state and of the phase diagram of colloids where depletion forces are tuned by the addition of a surfactant. For weak depletion, a colloidal fluid fully described by Baxter’s “sticky” hard sphere model coexists with ultradense colloidal crystals. For stronger attractive interactions, kinetically arrested looser gels form, showing an elastic modulus that scales as a power law of the local particle concentration.
We use a combination of original light scattering techniques and particles with unique optical properties to investigate the behavior of suspensions of attractive colloids under gravitational stress, following over time the concentration profile, the velocity profile, and the microscopic dynamics. During the compression regime, the sedimentation velocity grows nearly linearly with height, implying that the gel settling may be fully described by a (time-dependent) strain rate. We find that the microscopic dynamics exhibit remarkable scaling properties when time is normalized by the strain rate, showing that the gel microscopic restructuring is dominated by its macroscopic deformation.
Alginate is a natural biopolymer that forms, in the presence of divalent cations, ionic-bound gels typifying a large class of biological gels stabilized by non-covalent cross-links, and displaying a consistent restructuring kinetics. We investigate the kinetics of formation and aging of alginate gels by slow permeation of a curing CaCl2 agent by means of photon correlation imaging, a novel optical technique that allows obtaining the microscopic dynamics of the sample, while retaining at the same time the spatial resolution of imaging techniques. Specifically, the gelling kinetics displays a peculiar non-diffusive behavior, and the subsequent restructuring of the gel structure shares several features in common with the aging of colloidal gels, in particular for what concerns the occurrence of heterogeneous dynamics effects. A comparative analysis of the gel macroscopic mechanical properties at different aging stages further highlights distinctive effects arising from the non-permanent nature of the bonds.
Particle settling is a pervasive process in nature, and centrifugation is a versatile separation technique. Yet, the results of settling and ultracentrifugation experiments often appear to contradict the very law on which they are based: Archimedes' principle – arguably, the oldest physical law. The purpose of this paper is delving into the very roots of the concept of buoyancy by means of a combined experimental–theoretical study on sedimentation profiles in colloidal mixtures. Our analysis shows that the standard Archimedes' principle is only a limiting approximation, valid for mesoscopic particles settling in a molecular fluid, and we provide a general expression for the actual buoyancy force. This “Generalized Archimedes' Principle” accounts for unexpected effects, such as denser particles floating on top of a lighter fluid, which in fact we observe in our experiments.
Depletion interactions and the critical Casimir effect are usually regarded as distinct phenomena in colloidal suspensions. By experimentally investigating how the Asakura-Oosawa picture, appropriate for a weakly correlated depletant, is modified when critical correlations develop within the depletion agent, we conversely show that the former merges continuously into the latter, leading to a distinctive scaling behavior solely dictated by the depletant correlation length. A model based on density functional theory provides a microscopic understanding of the phenomenon and properly accounts for the observed trends.