Exceptionally strong double-layer barriers generated by polyampholyte salt

Abstract

Experiments using the Surface Force Apparatus (SFA) have found anomalously long-ranged interactions between charged surfaces in concentrated salt solutions. Ion clustering have been suggested as a possible origin of this behaviour. 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 provide 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 utilising statistical-mechanical (classical) 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 modelled 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 synthesised polyampholyte salt as extremely efficient stabilisers of colloidal dispersions.