Weak nonlinear surface-charging effects in electrolytic films.

Abstract

A simple model of soap films with nonionic surfactants stabilized by added electrolyte is studied. The model exhibits charge regularization due to the incorporation of a physical mechanism responsible for the formation of a surface charge. We use a Gaussian field theory in the film but the full nonlinear surface terms which are then treated at a one-loop level by calculating the mean-field Poisson-Boltzmann solution and then the fluctuations about this solution. We carefully analyze the renormalization of the theory and apply it to a triple-layer model for a thin film with Stern layer of thickness h. For this model we give expressions for the surface charge sigma(L) and the disjoining pressure P(d)(L) and show their dependence on the parameters. The influence of image charges naturally arises in the formalism, and we show that predictions depend strongly on h because of their effects. In particular, we show that the surface charge vanishes as the film thickness L-->0. The fluctuation terms in this class of theories contribute a Casimir-like attraction across the film. Although this attraction is well known to be negligible compared with the mean-field component for model electrolytic films with no surface-charge regulation, in the model studied here these fluctuations also affect the surface-charge regulation leading to a fluctuation component in the disjoining pressure which has the same behavior as the mean-field component even for large film thickness.