In Situ, Nonlinear Optical Probe of Surfactant Adsorption on the Surface of Microparticles in Colloids

The demonstration of a nonlinear optical technique for directly monitoring adsorption of surfactants on the surface of microparticles in colloids is reported. In this approach, dye molecules with strong hyperpolarizability are first adsorbed on the particle surface to give detectable second-harmonic generation. The surfactant is then added to the colloidal solution in competition with dye for adsorption on the surface. The displacement of the dye molecules on the surface results in a decrease of the second-harmonic signal, indicating the adsorption of the surfactant molecules. A continuous flow/titration system in combination with a high-repetition-rate femtosecond laser allows the adsorption to be monitored in real time. This approach was first demonstrated on a methacrylate polymeric surfactant on latex and talc particles in an aqueous solution. The adsorption free energy and surface density of this surfactant on these particles have been determined.