Phase Separation in Charge-Stabilized Colloidal Suspensions: Influence of Nonlinear Screening

Abstract

The phase behavior of charge-stabilized colloidal suspensions is modeled by a combination of response theory for electrostatic interparticle interactions and variational theory for free energies. Integrating out degrees of freedom of the microions (counterions, salt ions), the macroion-microion mixture is mapped onto a one-component system governed by effective macroion interactions. Linear response of microions to the electrostatic potential of the macroions results in a screened-Coulomb (Yukawa) effective pair potential and a one-body volume energy, while nonlinear response modifies the effective interactions [A. R. Denton, \PR E {\bf 70}, 031404 (2004)]. The volume energy and effective pair potential are taken as input to a variational free energy, based on thermodynamic perturbation theory. For both linear and first-order nonlinear effective interactions, a coexistence analysis applied to aqueous suspensions of highly charged macroions and monovalent microions yields bulk separation of macroion-rich and macroion-poor phases below a critical salt concentration, in qualitative agreement with predictions of related linearized theories [R. van Roij, M. Dijkstra, and J.-P. Hansen, \PR E {\bf 59}, 2010 (1999); P. B. Warren, \JCP {\bf 112}, 4683 (2000)]. It is concluded that nonlinear screening can modify phase behavior but does not necessarily suppress bulk phase separation of deionized suspensions.

14 pages of text + 9 figures

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• Modeling deswelling, thermodynamics, structure, and dynamics in ionic microgel suspensions
• Phase Separation of Charge-Stabilized Colloids: A Gibbs Ensemble Monte Carlo Simulation Study
• Electroneutrality and Phase Behavior of Colloidal Suspensions
• Charge Renormalization, Effective Interactions, and Thermodynamics of Deionized Colloidal Suspensions
• Yukawa potentials in systems with partial periodic boundary conditions I : Ewald sums for quasi-two dimensional systems
• Effective electrostatic interactions in mixtures of charged colloids
• Effective interactions, structure, and pressure in charge-stabilized colloidal suspensions: Critical assessment of charge renormalization methods