Complexes of surfactants with oppositely charged polymers at surfaces and in bulk

Addition of surfactants to aqueous solutions of polyelectrolytes carrying an opposite charge causes the spontaneous formation of complexes in the bulk phase in certain concentration ranges. Under some conditions, compact monodisperse multichain complexes are obtained in the bulk. The size of these complexes depends on the mixing procedure and it can be varied in a controlled way from nanometers up to micrometers. The complexes exhibit microstructures analoguous to those of the precipitates formed at higher concentrations. In other cases, however, the bulk complexes are large, soft and polydisperse. In most cases, the dispersions are only kinetically stable and exhibit pronounced non-equilibrium features.Association at air-water interfaces readily occurs, even at very small concentrations. When the surfactant concentration is small, the surface complexes are usually made of a surfactant monolayer to which the polymer binds and adsorbs in a flat-like configuration. However, under some conditions, thicker layers can be found, with bulk complexes sticking to the surface. The association at solid-water interfaces is more complex and depends on the specific interactions between surfactants, polymers and the surface. However, the behaviour can be understood if distinctions between hydrophilic surfaces and hydrophobic surfaces are made. Note that the behaviour at air-water interfaces is closer to that of hydrophobic than that of hydrophilic solid surfaces.The relation between bulk and surface complexation will be discussed in this review. The emphasis will be given to the results obtained by the teams of the EC-funded Marie Curie RTN “SOCON”.