Polyelectrolyte-surfactant interactions at interfaces

Abstract

Interactions between negatively charged surfaces coated with cationic polyelectrolytes across solutions containing an anionic surfactant, sodium dodecyl sulphate (SDS) have been studied. Polyelectrolytes with charge densities between 100% and 10%, counted per monomer unit, were used. At low ionic strength the polyelectrolytes adsorb in a flat conformation to neutralize the negative mica surface charge. The higher the linear charge density of the polyelectrolyte, the thinner adsorbed layers are obtained. In no case could any desorption be detected when the polyelectrolyte containing solution was replaced with an aqueous polyelectrolyte-free solution. The presence of SDS at concentrations considerably below the critical micellar concentration (cmc) does in all cases result in a recharging and a considerable swelling of the adsorbed layer. This is due to a cooperative association of surfactants in the preadsorbed polyelectrolyte layer. In case of the 100% charged PCMA, the force versus distance profile displays clear oscillations. We interpret these oscillations as being caused by the spatial arrangement of SDS micelles induced by the polyelectrolyte. The oscillations in the force curve remain as the SDS concentration is increased to twice the cmc. No similar oscillations in the force distance curve are observed when the surfaces are precoated with less charged polyelectrolytes. In these cases a strong swelling of the polyelectrolyte layer is observed once the surfactant concentration reaches a critical value (well below the cmc).