Macroscopic modeling of the surface tension of polymer-surfactant systems

Polymer-surfactant mixtures are increasingly being used in a wide range of applications. Weakly interacting systems, such as SDS/PEO and SDS/PVP, comprise ionic surfactants and neutral polymers, while strongly interacting systems, such as SDS/POLYDMDAAC and C12TAB/NaPSS, comprise ionic surfactants and oppositely charged ionic polymers. The complex nature of interactions in the mixtures leads to interesting and surprising surface tension profiles as the concentrations of polymer and surfactant are varied. The purpose of our research has been to develop a model to explain these surface tension profiles and to understand how they relate to the formation of different complexes in the bulk solution. In this paper we show how an existing model based on the law of mass action can be extended to model the surface tension of weakly interacting systems, and we also extend it further to produce a model for the surface tension of strongly interacting systems. Applying the model to a variety of strongly interacting systems gives remarkable agreement with the experimental results. The model provides a sound theoretical basis for comparing and contrasting the behavior of different systems and greatly enhances our understanding of the features observed.