Cationic Amphiphilic Polyelectrolytes and Oppositely Charged Surfactants at the Silica−Aqueous Interface

Abstract

The influence of sodium dodecyl sulfate (SDS) on the interfacial behavior of two amphiphilic polyelectrolytes, which are copolymers of the cationic monomers triethyl(vinylbenzyl)ammonium chloride and dimethyldodecyl(vinylbenzyl)ammonium chloride, at the silica-aqueous interface was studied. The fraction of amphiphilic monomers was varied, where 0DT, 40DT, and 80DT contained 0, 40, and 80 mol % monomers with dodecyl side chains, respectively. We used in situ ellipsometry to follow the kinetics of adsorption, in terms of adsorbed amount and adsorbed layer thickness, as well as the response of the adsorbed layers to changes in ionic strength and surfactant concentration. Different results were obtained when surfactant was added to the preadsorbed layers compared to the cases when complexes were preformed in the solution prior to the adsorption. In the whole range of concentrations studied, SDS interacts with 40DT and 80DT noncooperatively, whereas for 0DT cooperativity of binding is observed. The amount adsorbed increased significantly as the SDS concentration was close to the cmc. At high SDS concentrations, a lowering of the layer density was observed. For the amphiphilic polyelectrolytes, 40 DT and 80DT, no desorption from the interface was detected for the range of SDS concentrations studied, while 0DT features a maximum in adsorbed amount at concentrations close to the cmc of SDS. Adsorption of 40DT and 80DT from their mixtures with SDS is found to be path dependent with respect to the variation in SDS concentration, where the reversibility decreases with increasing SDS concentration above the expected charge neutralization point. The coadsorption of 80DT and SDS is highly irreversible with respect to changes in the ionic strength within the time scale of the experiment. In this study, we attempt to illustrate both general mechanisms and specific effects. With regard to the general behavior, it is important to note the charge regulation of both the silica surfaces and the polyion/surfactant complexes; an interplay between the two charge-regulating effects is the key to understanding our observations.