Effect of Surface Freezing on Stability of Oil-in-Water Emulsions

Penetration of alkane molecules into the adsorbed film of a cationic surfactant gives rise to a surface freezing transition at the alkane–water interface upon cooling. In this paper, we show that surface freezing of hexadecyltrimethylammonium chloride (CTAC) at the tetradecane–water interface stabilizes oil-in-water (OW) emulsions. For concentrations of CTAC near the critical micelle concentration, an OW emulsion coalesced readily above the surface freezing transition whereas the OW emulsion was stable in the surface frozen state. There was a discontinuous change in the stability of the OW emulsion at a temperature very close to the surface phase transition temperature as determined by interfacial tensiometry and ellipsometry on a planar oil–water interface. The mechanical elasticity of the surface frozen layer opposes film drainage and density fluctuations that could lead to rupture and is the most likely cause of the enhanced emulsion stability.