Charging of Oxide Nanoparticles in Media of Intermediate Dielectric Constant

The use of surfactants to charge colloidal particles in solvents of intermediate dielectric constants (5 < ε < 40) is investigated. While particle charging mechanisms in aqueous (ε = 80) and apolar (ε < 5) media are well understood, the interplay of these different charging mechanisms, which can all occur in solvents of intermediate dielectric constants (sometimes referred to as “leaky dielectrics”), remains to be fully explored. Conductometric titrations determining the critical micelle concentration (CMC) of the surfactant (aerosol-OT) confirm the existence of reverse micelles in intermediate dielectrics and show that as the solvent dielectric constant decreases, the CMC decreases as well. Electrophoretic mobility measurements of three oxide particles (SiO2, TiO2, and MgO) highlight various charging mechanisms that arise from particle–solvent, particle–surfactant, and solvent–surfactant interactions in a solvent series of alcohols and ketones. The results show that a combination of donor–acceptor particle–solvent interactions, surfactant ion adsorption, and reverse micelle-mediated acid–base interactions can all charge oxide particles in intermediate dielectrics. Furthermore, the results show that the dielectric constant of the solvent affects the relative magnitudes of each charging mechanism.