Kinetics of localized adsorption of colloid particles

Methods of analyzing localized adsorption of colloid particles at solid/liquid interfaces were extensively reviewed. First, the initial adsorption fluxes calculated using the Levich-Smoluchowski approximation were discussed. The uniformly, and nonuniformly accessible interfaces were distinguished and the superiority of the former in experimental studies was pointed out. A criterion was introduced for estimating the relative significance of the bulk transfer and surface adsorption steps. It was shown that for the majority of experimental and practical situations the surface mass balance equation can be decoupled from the bulk continuity equation. Thus, in due course attention was focused on theoretical and experimental methods of determining the surface blocking parameter B. It was shown that for low and moderate surface concentration range the statistical mechanic approach can be effectively used for predicting B. By introducing the equivalent hard sphere radius r∗ it became possible to analyze quantitatively blocking effects of interacting as well as nonspherical particles. The analytical solutions were compared with numerical simulation methods valid for the entire range of surface concentrations. The Monte-Carlo algorithm based on the random sequential adsorption (RSA) concept was compared with the sequential Brownian-Dynamics (SBD) method. Theoretical results obtained using these approaches were extensively discussed especially the role of repulsive electrostatic interaction among adsorbing particles. It was shown that these interactions diminish profoundly both the particle adsorption rate and the maximum surface concentration of particles forming “random” monolayers. When the electrostatic forces were operating (lower ionic strength) two distinctive adsorption regimes were predicted (i) fast Langmuir-type adsorption for short times and then (ii) very slow RSA-type approach to the maximum surface concentrations. As discussed such long lasting transient adsorption states could erroneously be interpreted as equilibrium adsorption isotherms. Then, the indirect and direct experimental methods aimed at a quantitative determination of particle adsorption kinetics were described. Illustrative experimental results performed for model latex suspensions were evoked. A satisfactory agreement with theoretical predictions was found for a variety of important physicochemical parameters studied. The RSA approach was found useful for describing particle adsorption kinetics for low and moderate surface concentrations in the case when the flow induced effects could be neglected. On the other hand, the SBD method was found of general validity especially in describing the hydrodynamic scattering effect observed experimentally for higher shear rates. Finally, the theoretical and experimental results concerning structure formation in adsorption processes were presented. The experimentally measured two-dimensional (2D) pair correlation function g12 of adsorbed particles suggested a liquid-like short range ordering occurring for larger surface concentrations. The extent of the 2D ordering was influenced by the adsorption mechanisms of particles, especially the presence of external field of forces.