Surface freezing of cationic surfactant-adsorbed films at the oil-water interface: Impact on oil-in-water emulsion and pickering emulsion stability

When n-alkanes or n-alcohols coexist with surfactants that have similar chain lengths, they can form mixed surface-frozen films at the oil-water interface. In this review, we first explain the basic characteristics of this surface freezing transition mainly from a thermodynamic viewpoint. Then, we discussed the effect of surface freezing of a cationic surfactant (cetyltrimethylammonium chloride: CTAC) with tetradecane, hexadecane, or hexadecanol on the kinetic stability of the oil-in-water (O/W) emulsions. We show that the surface frozen film not only increases the kinetic stability of the O/W emulsions but also stably encapsulates coexisting organic molecules in the oil core. Finally, we will introduce one of our recent works in which we observed that the exchange between silica nanoparticles and CTAC molecules occurs at the surface of Pickering emulsions when the oil-water interfacial tension is lowered by the surface freezing. The resulting detachment of silica particles from the oil-water interface broke the Pickering emulsion. The advantages of controlling the stability of O/W emulsions via the use of surface-frozen film are discussed in comparison with normal surfactant emulsifiers in the conclusion part of the review.