Charge regulation of nonpolar colloids

Abstract

Individual colloids often carry a charge as a result of the dissociation (or adsorption) of weakly-ionized surface groups. The magnitude depends on the precise chemical environment surrounding a particle, which in a concentrated dispersion is a function of the colloid packing fraction $\eta$. Theoretical studies have suggested that the effective charge $Z_{\mathrm{eff}}$ in regulated systems could, in general, decrease with increasing $\eta$. We test this hypothesis for nonpolar dispersions by determining $Z_{\mathrm{eff}}(\eta )$ over a wide range of packing fractions ($10^{-5}\le \eta \le 0.3$) using a combination of small-angle X-ray scattering and electrophoretic mobility measurements. We find a complex dependence of the particle charge as a function of the packing fraction, with $Z_{\mathrm{eff}}$ initially decreasing at low concentrations before finally increasing at high $\eta$. We attribute the non-monotonic density dependence to a crossover from concentration-independent screening at low $\eta$, to a high packing fraction regime in which counterions outnumber salt ions and electrostatic screening becomes $\eta$-dependent. The efficiency of charge stabilization at high concentrations may explain the unusually high stability of concentrated nanoparticle dispersions which has been reported.

arXiv comment14 pages, 10 figures - published version

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• Surfactant Mediated Particle Aggregation in Nonpolar Solvent
• Charge regulation of colloidal particles in aqueous solutions
• Non-Monotonic Concentration Dependence of the Electro-Phoretic Mobility of Charged Spheres in Realistic Salt Free Suspensions
• Charge-, salt- and flexoelectricity-driven anchoring effects in nematics
• Surface Charge Relaxation Controls the Lifetime of Out-of-Equilibrium Colloidal Crystals