Destructed double-layer and ionic charge separation near the oil-water interface

We study suspensions of hydrophobic charged colloidal spheres dispersed in a demixed oil-water mixture by means of a modified Poisson-Boltzmann theory, taking into account image charge effects and partitioning of the monovalent ions. We find that the ion's aversion for oil can destroy the double layers of the oil-dispersed colloids. This affects the salt-concentration dependence of the colloidal adsorption to the oil-water interface qualitatively. The theory also predicts a narrow range of the oil-dielectric constant in which micron-sized water-in-oil droplets acquire enough charge to crystallize at volume fractions as small as $\sim 10^{-3}$ in the absence of colloids. These findings explain recent observations [M.E. Leunissen {\em et al.}, Proc. Nat. Ac. Sci {\bf 104}, 2585 (2007)].

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