Insight into Kinetics and Mechanisms of AOT Vesicle Adsorption on Silica in Unfavorable Conditions.

The structure of adsorbed surfactant layers at the equilibrium state has already been investigated using various experimental techniques. However, the comprehension of the formation of structural intermediates in nonequilibrium states and the resulting adsorption kinetics still remain a challenging task. The temporal characterization of these intermediate structures provides further understanding of the layer structure at equilibrium and of the main interactions involved in the adsorption process. In this article, we studied the adsorption kinetics of AOT vesicles on silica at different pHs at ambient temperature. The AOT vesicles were formed in a brine solution. Quartz crystal microbalance with dissipation monitoring (QCM-D) was used to obtain information on the kinetics of surfactant adsorption and on the structure of the adsorbed layer at the equilibrium state. Additionally, neutron reflectivity experiments were performed to provide a detailed description of the mean surfactant concentration profile normal to the surface at equilibrium. Results suggest that vesicles in the bulk influence the adsorption mechanisms. In acidic conditions, after a time-dependent structural rearrangement step, followed by the rupture of initially adsorbed vesicles, the formation of a bilayer was observed. At an intermediate and basic pH, in spite of the electrostatic repulsion between the negatively charged surfactants and silica, results demonstrated the existence of an adsorbed layer composed of AOT vesicles. Vesicles are more or less closely packed depending on the pH of the solution. Results show a non-negligible influence of NaCl addition at pH values where adsorption is initially inhibited. Vesicle adsorption at the intermediate and basic pH is probably due to the combination of attractive van der Waals interactions promoted in high ionic strength systems and the formation of hydrogen bonds. Interpretation of adsorption kinetics gave insight into adsorption mechanisms in an electrostatic repulsion environment.