Adsorption of Oppositely Charged Polyelectrolyte/Surfactant Complexes at the Air/Water Interface: Formation of Interfacial Gels

The adsorption and complexation of polystyrene sulfonate (a highly charged anionic polyelectrolyte) and dodecyltrimethylammonium bromide (a cationic surfactant) at the air−water interface can lead to interfacial gels that strongly influence foam-film drainage and stability. The formation and characteristics of these gels have been studied by combining surface tension, ellipsometry, and foam-film drainage experiments. Simultaneously, the solution electromotive force is measured and used to track the polymer−surfactant interactions in the bulk solution. We find that surface gelation occurs above the critical aggregation concentration in solution but before bulk precipitation of the polymer−surfactant complexes. Furthermore, we reveal that strong readsorption of polymer−surfactant complexes occurs during the resolubilization of the precipitated complexes at high surfactant concentrations (i.e., ≫critical micelle concentration). Seemingly overlooked in the past, this readsorption significantly influences the surface rheological properties and foam-film drainage of these systems.