The metastable states of foam films containing electrically charged micelles or particles: experiment and quantitative interpretation

The stepwise thinning (stratification) of liquid films containing electrically charged colloidal particles (in our case - surfactant micelles) is investigated. Most of the results are applicable also to films from nanoparticle suspensions. The aim is to achieve agreement between theory and experiment, and to better understand the physical reasons for this phenomenon. To test different theoretical approaches, we obtained experimental data for free foam films from micellar solutions of three ionic surfactants. The theoretical problem is reduced to the interpretation of the experimental concentration dependencies of the step height and of the final film thickness. The surface charges of films and micelles are calculated by means of the charge-regulation model, with a counterion-binding (Stern) constant determined from the fit of surface tension isotherms. The applicability of three models was tested: the Poisson-Boltzmann (PB) model; the jellium-approximation (JA), and the cell model (CM). The best agreement theory/experiment was obtained with the JA model without using any adjustable parameters. Two theoretical approaches are considered. First, in the energy approach the step height is identified with the effective diameter of the charged micelles, which represents an integral of the electrostatic-repulsion energy calculated by the JA model. Second, in the osmotic approach the step height is equal to the inverse cubic root of micelle number density in the bulk of solution. Both approaches are in good agreement with the experiment if the suspension of charged particles (micelles) represents a jellium, i.e. if the particle concentration is uniform despite the field of the electric double layers. The results lead to a convenient method for determining the aggregation number of ionic surfactant micelles from the experimental heights of the steps.