Forces between solid surfaces in aqueous electrolyte solutions

This review addresses experimental findings obtained with direct force measurements between two similar or dissimilar solid surfaces in aqueous electrolyte solutions. Interpretation of these measurements is mainly put forward in terms of the classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). This theory invokes a superposition of attractive van der Waals forces and repulsive double layer forces. DLVO theory is shown to be extremely reliable, even in the case of multivalent ions. However, such a description is only successful, when appropriate surface charge densities, charge regulation characteristics, and ion pairing or complexation equilibria in solution are considered. Deviations from DLVO theory only manifest themselves at distances of typically below few nm. More long-ranged non-DLVO forces can be observed in some situations, particularly, in concentrated electrolyte solutions, in the presence of strongly adsorbed layers, or for hydrophobic surfaces. The latter forces probably originate from patch-charge surface heterogeneities, which can be induced by ion-ion correlation effects, charge fluctuations, or other types of surface heterogeneities.