Nature of amine-surfactant interactions at the air-solution interface

The surface tension and adsorption behavior of polymer/surfactant mixtures of polyethyleneimine (PEI)/sodium dodecyl sulfate (SDS) is strongly dependent on pH. At both low and high pH, a strong PEI/SDS interaction gives rise to surface polymer/surfactant complex formation that results in significantly enhanced SDS adsorption at very low SDS concentrations and in multilayer formation at the interface. At low pH, this strong PEI/SDS interaction is dominated by the electrostatic attraction between the two oppositely charged species. However, at high pH the PEI is essentially neutral, and the origin of the "hydrophobic" interaction, or interaction of nonelectrostatic origin, is less clear. To investigate the origins of this interaction further, we have used neutron reflectivity and surface tension to study the pH dependence of the surface adsorption of different anionic surfactants-SDS, lithium dodecyl sulfate (LiDS), and sodium dodecyl benzene sulfonate (LAS)--in the presence of a range of small amine molecules (from ethylenediamine to pentaethylenehexamine). Analogous to that observed in PEI/SDS mixtures, the presence of amine molecules induces a strong enhancement in the surfactant adsorption at both low and high pH, which can result in extreme cases in multilayer formation at the interface. At high pH, the adsorption is highly dependent upon the amine molecular weight and is equivalent to that observed at low pH by the time the molecular weight of the amine has increased to that of pentaethylenehexamine. We attribute this nonelectrostatic interaction observed at high pH to the combined effect of a dipole-dipole interaction between the sulfate (or sulfonate) headgroup and the amine nitrogens and a cooperative hydrophobic interaction between the chains of the attached surfactants. At high pH and when there are at least six amine groups present, this effect appears to be equivalent in strength to the electrostatic attraction that dominates at low pH. These results are significant in the context of understanding the unusual nature of the PEI/surfactant interaction and of using small molecular weight additives rather than much larger molecular weight polymers to manipulate adsorption properties.