Switchable Oil-in-Water Emulsions Stabilized by Like-Charged Surfactants and Particles at Very Low Concentrations

Langmuir. 2019 Mar 19;35(11):4058-4067. doi: 10.1021/acs.langmuir.8b04159. Epub 2019 Mar 11.

Abstract

A novel CO2/N2 switchable n-decane-in-water emulsion was prepared, which is stabilized by a CO2/N2 switchable surfactant [ N'-dodecyl- N, N-dimethylacetamidine (DDMA)] in cationic form in combination with positively charged alumina nanoparticles at concentrations as low as 0.01 mM and 0.001 wt %, respectively. The particles do not adsorb at the oil-water interface but remain dispersed in the aqueous phase between surfactant-coated droplets. A critical zeta potential of the particles of ca. +18 mV is necessary for the stabilization of the novel emulsions, suggesting that the electrical double-layer repulsions between particles and between particles and oil droplets are responsible for their stability. By bubbling N2 into the emulsions, demulsification occurs following transformation of DDMA molecules from the surface-active cationic form to the surface-inactive neutral form and desorption from the oil-water interface. Bubbling CO2 into the demulsified mixtures, cationic DDMA molecules are re-formed, which adsorb to the droplet interfaces, ensuring stable emulsions after homogenization. Compared with Pickering emulsions and traditional emulsions, the amount of switchable surfactant and number of like-charged particles required for stabilization are significantly reduced, which is economically and environmentally benign for practical applications.