Zeta Potential of Poly(methyl methacrylate) (PMMA) in Contact with Aqueous Electrolyte–Surfactant Solutions

The addition of surfactants can considerably impact the electrical characteristics of an interface, and the zeta potential measurement is the standard method for its characterization. In this article, a comprehensive study of the zeta potential of poly­(methyl methacrylate) (PMMA) in contact with aqueous solutions containing an anionic, a cationic, or a zwitterionic surfactant at different pH and ionic strength values is conducted. Electrophoretic mobilities are inferred from electrophoretic light scattering measurements of the particulate PMMA. These values can be converted into zeta potentials using permittivity and viscosity measurements of the continuous phase. Different behaviors are observed for each surfactant type, which can be explained with the various adsorption mechanisms on PMMA. For the anionic surfactant, the absolute zeta potential value below the critical micelle concentration (CMC) increases with the concentration, while it becomes rather constant around the CMC. At concentrations above the CMC, the absolute zeta potential increases again. We propose that hydrophobic-based adsorption and, at higher concentrations, the competing micellization process drive this behavior. The addition of cationic surfactant results in an isoelectric point below the CMC where the negative surface charge is neutralized by a layer of adsorbed cationic surfactant. At concentrations near the CMC, the positive zeta potential is rather constant. In this case, we propose that electrostatic interactions combined with hydrophobic adsorption are responsible for the observed behavior. The zeta potential in the presence of zwitterionic surfactant is influenced by the adsorption, because of hydrophobic interactions between the surfactant tail and the PMMA surface. However, there is less influence, compared to the ionic surfactants. For all three surfactant types, the zeta potential changes to more-negative or less-positive values for alkaline pH values, because of hydroxide adsorption. An increase of the ionic strength decreases the absolute value of the zeta potential, because of the shielding effects.