Sedimentation of binary mixtures of like- and oppositely charged colloids: the primitive model or effective pair potentials?

Abstract

We study the sedimentation equilibrium of low salt suspensions of binary mixtures of charged colloids, both by Monte Carlo simulations of an effective colloids-only system and by Poisson–Boltzmann theory of a colloid–ion mixture. We show that the theoretically predicted lifting and layering effect, which involves the entropy of the screening ions and a spontaneousmacroscopic electric field (Zwanikken and van Roij 2005 Europhys. Lett. 71 480), can also be understood on the basis of an effective colloid-only system with pairwise screened-Coulomb interactions. We consider, by theory and by simulation, both repelling like-charged colloids and attracting oppositely charged colloids, and we find a re-entrant lifting and layering phenomenonwhen the charge ratio of the colloids varies from large positive through zero to large negative values.