Three stage multilayer formation kinetics during adsorption of an anionic fluorinated surfactant onto germanium: Solution pH and salt effects

The effects of solution pH, salt type and its concentration on the adsorption kinetics and the structural evolution of an anionic fluorinated surfactant, tetraethylammonium perfluorooctylsulfonate (TEA-FOS), at the hydroxylated Ge/aqueous solution interface are investigated by using Fourier transform infrared spectroscopy in attenuated total reflection mode (ATR-FTIR). The surface excess, the adsorption rate, the durations of three-stage adsorption and the molecular orientation of adsorbed TEA-FOS are all dependent on the pH of the solution. Consistent with the expected effects of solution pH on surface charge of the germanium oxide crystal surface, the most surfactant adsorbs at acidic pH 3.4 although a considerable amount still adsorbs at pH 10.0. Linear dichroism measurements suggest that the adsorbed surfactants prefer to form less-curved (flattened) multilayer admicelles, which pack more closely on the solid surface as the solution pH decreases. Under both acidic (pH 3.4) and basic (pH 10.0) conditions, the equilibrium surface excess first passes through a maximum as NaCl concentration increases, followed by a decrease. This suggests that excessive NaCl concentration is not favorable for multilayer formation due to increased electrostatic shielding which reduces the ion-pairing ability between TEA⁺ and FOS^-. In addition, infrared dichroism measurements of CF₂ stretching show that salt type and its concentration influence the structural evolution of adsorbed surfactants. A moderate amount of NaCl favors the assembly of adsorbed micelles into ordered flattened aggregates, but an excess of NaCl makes adsorbed surfactants assemble randomly like spherical aggregates. Compared to Na⁺ and K⁺ ions, Ca²⁺ ions cause the adsorbed surfactants to pack more closely on the solid surface into flattened micellar aggregates. All of the effects of solution pH and salt can be rationalized based on Coulombic interactions between the substrate surface, surfactants and counter-ions.