Heterogeneous Adsorbed Film Formation and Line Tension at Oil/Water Interfaces

Abstract

Condensed domain formation of surface active substances in adsorbed films at alkane/water interfaces was investigated by interfacial tensiometry, X-ray reflectometry, and BAM observation. The results obtained are explained by the effects of contact energy and dipole-dipole interaction, which are competitive contributions to the line tension acting at the domain boundary. It was suggested that the contact energy is predominant in the domains formed during the phase transition in the adsorbed film of cationic surfactant. In the mixed adsorbed film of cationic surfactant and cholesterol, small domain formation due to the effects of low contact energy and dipole-dipole interaction was observed. In the adsorbed films of fluorinated alcohol, F8H2OH, at alkane/water interfaces, the domain formation was suppressed with increasing alkane chain length due to an increase in contact energy. The mixing of hybrid alcohol with fluorocarbon and hydrocarbon chains of the same carbon number, F6H6OH, in adsorbed film reduces contact energy. This stabilizes the dispersion of many domains with small size. On the other hand, when F8H2OH molecules are mixed with a cationic surfactant, C12TAB, in the adsorbed film, an attractive dipole-ion interaction between the hydrophilic groups relaxes the repulsive dipole-dipole interaction between F8H2OH molecules, resulting in the formation of domains with smooth boundary and large size. Furthermore, fluorinated ester, FC12Me molecules form flower shaped domains with intricate boundary mainly due to a larger dipole moment of FC12Me than F8H2OH.