In this article, we present a general overview of the organization of colloidal charged clay particles in aqueous suspension by studying different natural samples with different structural charges and charge locations. Small-angle X-ray scattering experiments (SAXS) are first used to derive swelling laws that demonstrate the almost perfect exfoliation of clay sheets in suspension. Using a simple approach based on geometrical constraints, we show that these swelling laws can be fully modeled on the basis of morphological parameters only. The validity of this approach was further extended to other clay data from the literature, in particular, synthetic Laponite. For all of the investigated samples, experimental osmotic pressures can be properly described by a Poisson-Boltzmann approach for ionic strength up to 10(-3) M, which reveals that these systems are dominated by repulsive electrostatic interactions. However, a detailed analysis of the Poisson-Boltzmann treatment shows differences in the repulsive potential strength that are not directly linked to the structural charge of the minerals but rather to the charge location in the structure for tetrahedrally charged clays (beidellite and nontronites) undergoing stronger electrostatic repulsions than octahedrally charged samples (montmorillonites, laponite). Only minerals subjected to the strongest electrostatic repulsions present a true isotropic to nematic phase transition in their phase diagrams. The influence of ionic repulsions on the local order of clay platelets was then analyzed through a detailed investigation of the structure factors of the various clay samples. It appears that stronger electrostatic repulsions improve the liquidlike positional local order.
We explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time τ_{α} of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard spheres. Computer simulations confirm that the growth of τ_{α} on approaching the glass transition is independent of particle softness. By contrast, softness becomes relevant at very large packing fractions when the system falls out of equilibrium. In this nonequilibrium regime, τ_{α} depends surprisingly weakly on packing fraction, and time correlation functions exhibit a compressed exponential decay consistent with stress-driven relaxation. The transition to this novel regime coincides with the onset of an anomalous decrease in local order with increasing density typical of ultrasoft systems. We propose that these peculiar dynamics results from the combination of the nonequilibrium aging dynamics expected in the glassy state and the tendency of colloids interacting through soft potentials to refluidize at high packing fractions.
International audienceClay minerals, like beidellite or nontronite, spontaneously exfoliate in water and form colloidal suspensions of nanosheets. In a given range of concentration, these suspensions display a nematic liquid–crystalline phase whose structure and properties can be conveniently studied in detail by polarized-light microscopy and small-angle X-ray scattering (SAXS). Moreover, in situ SAXS investigations of sheared clay suspensions provide information about their flow properties, both in the isotropic and nematic phases. The colloidal nematic phase shows the classical properties of usual nematics, such as surface anchoring and electric-field and magnetic-field alignment. Thus, nematic single domains can be produced. The isotropic phase also displays strong electro-optic effects in moderate electric fields. Finally, we describe a few examples of applications of such systems and we show how these studies could be extended to suspensions of other types of nanosheets
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