Stabilization of Oil-in-Water Emulsions with Noninterfacially Adsorbed Particles

Classical (surfactant stabilized) and Pickering (particle stabilized) type emulsions have been widely studied to elucidate the mechanisms by which emulsion stabilization is achieved. In Pickering emulsions, a key defining factor is that the stabilizing particles reside at the liquid-liquid interface providing a mechanical barrier to droplet coalescence. This interfacial adsorption is achieved through the use of nanoparticles that are partially wet by both liquid phases, often through covalent surface modification of or surfactant adsorption to the nanoparticle surfaces. Herein, we demonstrate particle-induced stabilization of an oil-in-water emulsion with fully water wet nanoparticles (no interfacial adsorption) via synergistic interaction with low concentrations of surfactants. Laser scanning confocal microscopy analysis allows for unique and vital insights into the properties of these emulsions via both three-dimensional imaging and real-time monitoring of particle dynamics at the oil-water interface. Investigation of these "non-Pickering" particle stabilized emulsions suggests that the nonadsorbed particles impart stability to the emulsion primarily via entropic forces imparted by the accumulation of silica nanoparticles in the coherent phase between dispersed oil droplets.