4 research outputs found
Sedimentation of binary mixtures of like- and oppositely charged colloids: the primitive model or effective pair potentials?
We study 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 spontaneous macroscopic
electric field [J. Zwanikken and R. van Roij, Europhys. Lett. {\bf 71}, 480
(2005)], 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 phenomenon when
the charge ratio of the colloids varies from large positive through zero to
large negative values
Volume terms for charged colloids: a grand-canonical treatment
We present a study of thermodynamic properties of suspensions of charged
colloids on the basis of linear Poisson-Boltzmann theory. We calculate the
effective Hamiltonian of the colloids by integrating out the ionic degrees of
freedom grand-canonically. This procedure not only yields the well-known
pairwise screened-Coulomb interaction between the colloids, but also additional
volume terms which affect the phase behavior and the thermodynamic properties
such as the osmotic pressure. These calculations are greatly facilitated by the
grand-canonical character of our treatment of the ions, and allow for
relatively fast computations compared to earlier studies in the canonical
ensemble. Moreover, the present derivation of the volume terms are relatively
simple, make a direct connection with Donnan equilibrium, yield an explicit
expression for the effective screening constant, and allow for extensions to
include, for instance, nonlinear effects.Comment: 16 pages, 6 figures, published in Phys.Rev.