Exceptionally Strong Double-Layer Barriers Generated by Polyampholyte Salt

Experiments using the surface force apparatus have found anomalously long-range interactions between charged surfaces in concentrated salt solutions. Ion clustering has been suggested as a possible origin of this behavior. In this work, we demonstrate that if such stable clusters indeed form, they are able to induce remarkably strong free energy barriers under conditions where a corresponding solution of simple salt provides negligible forces. Our cluster model is based on connected ions producing a polyampholyte salt containing a symmetric mixture of monovalent cationic and anionic polyampholytes. Ion distributions and surface interactions are evaluated utilizing statistical-mechanical (<i>classical</i>) polymer density functional theory, cDFT. In the Supporting Information, we briefly investigate a range of different polymer architectures (connectivities), but in the main part of the work, a polyampholyte ion is modeled as a linear chain with alternating charges, in which the ends carry an identical charge (hence, a monovalent net charge). These salts are able to generate repulsions, between similarly charged surfaces, of a remarkable strength, exceeding those from simple salts by orders of magnitude. The underlying mechanism for this is the formation of brush-like layers at the surfaces, i.e., the repulsion is strongly related to excluded volume effects, in a manner similar to the interaction between surfaces carrying grafted polymers. We believe our results are relevant not only to possible mechanisms underlying anomalously long-ranged underscreening in concentrated simple salt solutions but also for the potential use of synthesized polyampholyte salt as extremely efficient stabilizers of colloidal dispersions.