Recent study on counterion-mediated attraction between colloidal particles

摘要

Recent experimental results were reviewed. The 1D- and 2D-USAXS studies gave higher orders of Bragg diffraction for single crystals of colloidal silica particles, allowing more accurate determinations of the lattice constant, lattice symmetry, and direction. The closest interparticle spacing thus determined was confirmed to be smaller than the average spacing. The most closely packed planes ((110) planes for bcc) of negatively charged particles were found to be parallel to the likewise negatively charged capillary surface, inconsistently with the accepted double layer interaction theory but consistently with a recent experimental finding of positive adsorption. Shaking caused disruption of the single crystals but newly formed microcrystals retained the lattice constant and the preference of the (110) planes. The liquid-solid-liquid transition, a re-entrant phase transition, was found for silica particles and latex particles at given particle volume fraction and salt concentration, when the charge density of particles was varied. It was demonstrated that the purely repulsive Yukawa potential and the concept of renormalized charge cannot account for the re-entrant behavior. The Monte-Carlo simulation using the Sogami potential, which contains short-range repulsion and long-range attraction, was found to account for the fcc-bcc transition, which was earlier claimed to be explainable only be the Yukawa potential. Furthermore, the homogeneous-inhomogeneous phase transition and void formation could be accounted for by the simulation using the Sogami potential; the Yukawa potential could not reproduce the experiments. Attention was drawn to the experimental conditions in direct measurements of interparticle forces; only short interparticle distance and low charge density particles were covered, which make it practically impossible to detect the long-range counterion-mediated attraction. It is hoped that, by technical improvements, these shortcomings may be made up and quantitative argument become possible on the attraction.