Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2022 / Paper 2 / Section B / 23 / v

For like-charged plates, DLVO theory combines an attractive dispersion contribution and a screened electrostatic repulsion. A useful far-field schematic model isAt high salt concentration, ${\lambda }_D={\kappa }_D^{-1}$ is short. The repulsion then disappears over a short distance, leaving attraction across much of the accessible range. The usual high-salt sketch has a greatly reduced or absent repulsive energy barrier, so approach into a primary attractive minimum is easier. At very small separations, short-range repulsion cuts off the unphysical divergence of the simple $-d^{-2}$ continuum expression.

The large-distance tail of the stated model is attractive because an exponentially decaying repulsion eventually becomes smaller than the algebraic attraction. A barrier is not ruled out by the words “high salt” alone: its existence also depends on surface charge or potential, charge regulation, $A_H$ and the boundary conditions that determine $B$. The figure shows one declared barrier-free high-screening example rather than claiming a universal threshold concentration.

At lower salt concentration, the longer Debye–Hückel screening length allows the two diffuse layers to interact at greater separation. For sufficiently charged surfaces, this produces a positive free-energy barrier between separated plates and the short-range primary attractive region. Crossing a barrier costs free energy, so it can kinetically stabilize a dispersion even though a more attractive state exists at close approach. The relevant barrier in a finite object must be compared with thermal energy using the appropriate geometry and interaction area.

Over the experimentally relevant range of several screening lengths, the low-salt interaction can be predominantly repulsive, as drawn in the illustrative model. Strictly, at asymptotically infinite separation, the supplied nonretarded DLVO model still approaches zero from the attractive side, because $e^{-{\kappa }_{D}d}$ decays faster than $d^{-2}$ for any finite salt concentration. A shallow secondary minimum can therefore occur beyond the barrier. Calling the entire far field repulsive without specifying the distance range would conceal this distinction.

Lower salt alone does not guarantee a barrier: surface potential, charge regulation and attraction strength still matter. Extremely dilute or salt-free systems also require counterion and finite-cell constraints beyond blindly holding $B$ fixed while sending ${\kappa }_D$ to zero.