Kinetics and Mechanism of Cationic Surfactant Adsorption and Coadsorption with Cationic Polyelectrolytes at the Silica−Water Interface

Abstract

We used scanning angle reflectometry to measure the adsorption isotherm, adsorption kinetics, and desorption kinetics for cetyltrimethylammonium bromide (CTAB) surfactants on negatively charged silica surfaces. The initial adsorption rate increased with increasing CTAB concentrations between approximately 0.2 × cmc and 10 × cmc, displaying a discontinuous increase at the critical micelle concentration. The initial desorption rate was a monotonically increasing function of the bulk concentration of the surfactant solution from which the adsorbed layer was formed, both above and below the cmc. Combining equilibrium and kinetic information, we conclude that the adsorption mechanism and the structure of the adsorbed layer both change abruptly at the cmc. Below the cmc, monomeric surfactants adsorb to an extent that is consistent with a defective bilayer structure. Above the cmc, micelles adsorb directly to the surface, to an extent that is consistent with a close-packed monolayer of micelles. The adsorption rate was apparently limited by slow rearrangements within the adsorbed layer. CTAB adsorption was significantly hindered by coadsorption with polylysine, in terms of both the rate and extent of adsorption. The effect of polylysine on CTAB adsorption was very sensitive to the ionic strength and the order in which the surfactant and the polyelectrolyte were exposed to the surface. Different pathways to the same final bulk solution composition produced much different adsorption results. This demonstrates that coadsorption of CTAB and polylysine is inherently a nonequilibrium process dominated by kinetic traps. Although it had an overall hindering effect, coadsorption with polylysine did not alter the basic difference in CTAB adsorption mechanisms above and below the cmc.