Surfactant monolayers at oil–water interfaces. Behavior upon compression and relation to emulsion stability

Abstract

Surfactant monolayers modify the surface tension of fluid surfaces, and they confer to the surfaces a resistance to mechanical perturbances, such as compression or dilatation. The resistance can be characterized by elastic and viscous moduli, that affect the phenomena involving the motion of liquid surfaces such as wetting, two-phase flow, foaming and emulsification, rheology and stability of foams and emulsions. Some of these phenomena, for instance coalescence of bubbles or drops, are extremely rapid, and although coalescence seems correlated with the elastic compression modulus, no quantitative comparison has been made. Indeed, this modulus is frequency dependent, and cannot be measured by most conventional devices at the short timescales during which coalescence events occur. In this paper, we first review the current understanding on foam and emulsion stability, highlighting the role of surface rheology in the stability of these systems, important for their formulation. We present tension measurements for various surfactant systems, nonionic and cationic, at oil–water interfaces. We show calculations of the high frequency elastic modulus using the Gibbs adsorption equation and compare the results to previous measurements at air–water interfaces. The moduli measured imposing a rapid expansion of the monolayers are consistently smaller, in particular at oil–water interfaces. We discuss the possible origin of the differences between the two types of interfaces.