Adsorption of Anionic Surfactants in a Nonionic Polymer Brush: Experiments, Comparison with Mean-Field Theory, and Implications for Brush−Particle Interaction

Abstract

The adsorption of the anionic surfactants sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS) in poly(ethylene oxide) (PEO) brushes was studied using a fixed-angle optical flow-cell reflectometer. We show that, just as in solution, there is a critical association concentration (CAC) for the surfactants at which adsorption in the PEO brush starts. Above the critical micelle concentration (CMC) the adsorption is found to be completely reversible. At low brush density the adsorption per PEO monomer is equal to the adsorption of these surfactants in bulk solution. However, with increasing brush density, the number of adsorbed surfactant molecules per PEO monomer decreases rapidly. This decrease is explained in terms of excluded volume interactions plus electrostatic repulsion between the negatively charged surfactant micelles. Experimentally, a plateau value in the total adsorption is observed as a function of grafting density. The experimental results were compared to the results of an analytical self-consistent field (aSCF) model, and we found quantitative agreement. Additionally, the model predicts that the plateau value found is in fact a maximum. Both experiments and model calculations show that the adsorption scales directly with the polymerization degree of the polymers in the brush. They also show that an increase in the ionic strength leads to an increase in the adsorbed amount, which is explained as being due to a decrease in the electrostatic penalty for the adsorption of the SDS micelles. The adsorption of SDS micelles changes the interactions of the PEO brush with a silica particle. This is illustrated by atomic force microscopy (AFM) measurements of the pull-off force of a silica particle from a PEO brush: at high enough PEO densities, the addition of SDS leads to a very strong reduction in the force necessary to detach the colloidal silica particle from the PEO brush. We attribute this effect to the large amount of negative charge incorporated in the PEO brush due to SDS adsorption.