Polyelectrolytes, such as Poly(Styrene Sulfonate), Poly(Acrylic Acid), DNA, and a myriad of similar polymeric materials, are commonly used in stimuli-responsive or self-assembling materials due to their strong coupling between chemical functionality (i.e. charged groups) and molecular architecture. Despite the ubiquity of these chemical features, fundamental and conceptual understanding of the physical ramifications of these systems still requires significant further development. We present, in a conceptual fashion, thermodynamic attributes of charged interfaces in polymeric systems. In particular, we consider the effect of charge ordering using a novel combined SCFT-liquid state theory calculation that allows the consideration of strongly coupled (high-valency, low-dielectric) systems, hard-sphere repulsions, and spatially inhomogenous polymers in a rigorous statistical-mechanical fashion.  This investigation uses the simplified geometry of a polymer blend interface to elucidate novel effects such as valency-dependent interfacial stiffening, ion exluded-volume pressures due to hard sphere repulsions, and the effects of local structure arising from ion-ion correlations. We provide conceptual arguments to supplement the numerical theory presented in order to develop an intuitive understanding of the ramifications of ion correlations in multiphase systems, which will inform the development of more complicated polyelectrolyte materials.

Effect of ion correlations on the thermodynamics of polymer interfaces

246th National Meeting (2013)

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