In simulations and experiments, we study the drying of films containing mixtures of large and small colloidal particles in water. During drying, the mixture stratifies into a layer of the larger particles at the bottom with a layer of the smaller particles on top. We developed a model to show that a gradient in osmotic pressure, which develops dynamically during drying, is responsible for the segregation mechanism behind stratification.

The stabilization of o/w Pickering emulsions in cases of weak adsorption of solid particles at the surface of oil droplets is addressed. Though the adsorption is usually very strong and irreversible when partial wetting conditions are fulfilled, electrostatic repulsions between charged solid particles act against the adsorption. The regime of weak adsorption was reached using charged silica nanoparticles at high pH and low ionic strength. O/w Pickering emulsions of the diisopropyl adipate oil were stabilized by colloidal nanoparticles of Ludox® AS40 consisting of non-aggregated particles of bare silica (hydrophilic). The combination of stability assessment, droplet size and electrokinetic potential measurements at various pH values, adsorption isotherms and cryo-SEM observations of the adsorbed layers disclosed the specificities of the stabilization of Pickering emulsions by adsorption of solid nanoparticles against strong electrostatic repulsions. Not only the long-term stability of emulsions was poor under strong electrostatic repulsions at high pH, but emulsification failed since full dispersion of oil could not be achieved. Emulsion stability was ensured by decreasing electrostatic repulsions by lowering the pH from 9 to 3. Stable emulsions were stabilized by a monolayer of silica particles at 54% coverage of the oil droplet surface at low silica content and an adsorption regime as multilayers was reached at higher concentrations of silica although there was no aggregation of silica in the bulk aqueous phase.