Surface Forces between Titanium Dioxide Surfaces in the Presence of Cationic Surfactant as a Function of Surfactant Concentration, Electrolyte Concentration, and pH

Titanium dioxide (titania) surfaces produced by atomic layer deposition (ALD) are suitable for surfactant adsorption and surface force measurements. Adsorption isotherms for cetyltrimethylammonium bromide (CTAB) on ALD titanium dioxide surfaces were measured using optical reflectometry (OR), and surface force measurements between ALD titanium dioxide surfaces in aqueous CTAB solutions were measured using the colloid probe technique at different pH and electrolyte concentrations. Measurements were performed at a range of concentrations below and above the common intersection point (CIP) where adsorption is dominated by electrostatic and hydrophobic interactions, respectively. An examination of surfactant adsorption above and below the isoelectric point (IEP) was performed. Interestingly, significant levels of adsorption were observed below the IEP where the electrostatic interactions are unfavorable. The adsorption results are used to interpret the force data, which is dependent upon the amount of surfactant adsorbed and the electrolyte concentration and pH. The surface force data is compared to DLVO theory. Poor fits are obtained when Lifshitz theory is used to describe the dispersion forces. However, all of the data are fit well with a dispersion force of reduced magnitude. The kinetics of adsorption was measured and reveals very slow adsorption kinetics below the critical micelle concentration as a result of the monomer-by-monomer formation of aggregates on the surface.