Intermolecular and Surface Forces, 3rd Edition

15 Solvation, Structural, and Hydration Forces

15.1 Non-DLVO Forces

When two surfaces or particles approach closer than a few nanometers, continuum theories of attractive van der Waals and repulsive double-layer forces often fail to describe their interaction. This is either because one or both of these continuum theories breaks down at small separations or because other non-DLVO forces come into play. These additional forces can be monotonically repulsive, monotonically attractive, or oscillatory, and they can be much stronger than either of the two DLVO forces at small separations.

As we saw in Chapter 7 short-range oscillatory solvation forces can arise when spherical liquid molecules are induced to order or “structure” into quasi-discrete ...