Pickering Emulsions of Hydrophilic Silica Particles and Symmetrical Organic Electrolytes

At high pH, bare silica particles are not an effective Pickering emulsion stabilizer of nonpolar oils with water due to their high surface charge. One way to promote particle adsorption to the oil-water interface is to add salt to the aqueous phase, although particle flocculation normally ensues. In most cases, inorganic salts are added, while little attention has been paid to the use of organic salts. Here, we describe the effects of adding tetraalkylammonium salts (R₄NX, X is an anion) to aqueous dispersions of silica nanoparticles at high pH and investigating the possibility of subsequently stabilizing octane-in-water (o/w) emulsions. The chain length of the R group is systematically increased from 1 (methyl) to 4 (butyl). Unlike inorganic electrolytes, the addition of these salts does not lead to particle flocculation in water, although the particle charge is reduced. No stable emulsion forms for the methyl analogue, but very stable o/w emulsions can be prepared with the other three members, with the minimum concentration of salt being required decreasing with R chain length to as low as 5 × 10^-5 M. The three-phase oil-water-solid contact angle increases with salt concentration and R chain length, confirming the increase in particle hydrophobicity on addition of salt. We show that the butyl analogue behaves similarly to that of cetyltrimethylammonium bromide surfactant with respect to promoting silica particles to emulsion drop interfaces. Finally, we compare the arrangement of micrometer-sized silica particles at both curved droplet interfaces and at a planar oil-water interface at different concentrations of the most hydrophobic salt.