Multilayering of Surfactant Systems at the Air-Dilute Aqueous Solution Interface

In the last 15 years there have been a number of observations of surfactants adsorbed at the air-water interface with structures more complicated than the expected single monolayer. These observations, mostly made by neutron or X-ray reflectivity, show structures varying from the usual monolayer to monolayer plus one or two additional bilayers to multilayer adsorption at the surface. These observations have been assembled in this article with a view to finding some common features between the very different systems and to relating them to aspects of the bulk solution phase behavior. It is argued that multilayering is primarily associated with wetting or prewetting of the air-water interface by phases in the bulk system, whose structures depend on an overall attractive force between the constituent units. Two such phases, whose formation is assumed to be partially driven by strong specific ion binding, are a concentrated lamellar phase that forms at low concentrations and a swollen lamellar phase that is not space-filling. Multilayering phenomena at the air-water interface then offer a delicate and easy means of studying the finer details of the incompletely understood attraction that leads to these two phases, as well as an interesting new means of self-assembling surface structures. In addition, multilayering is often associated with unusual wetting characteristics. Examples of systems discussed, and in some cases their bulk phase behavior, include surfactants with multivalent metal counterions, surfactants with oligomers and polymers, surfactant with hydrophobin, dichain surfactants, lung surfactant, and the unusual system of ethanolamine and stearic acid. Two situations where the air-water surface is deliberately held out of equilibrium are also assessed for features in common with the steady-state/equilibrium observations.