Effect of repulsive interactions on the rate of doublet formation of colloidal nanoparticles in the presence of convective transport

In this work, we have performed a systematic investigation of the effect of electrostatic repulsive interactions on the aggregation rate of colloidal nanoparticles to from doublets in the presence of a convective transport mechanism. The aggregation rate has been computed by solving numerically the Fuchs–Smoluchowski diffusion–convection equation. Two convective transport mechanisms have been considered: extensional flow field and gravity-induced relative sedimentation. A broad range of conditions commonly encountered in the applications of colloidal dispersions has been analyzed. The relative importance of convective to diffusive contributions has been quantified by using the Peclet number Pe. The simulation results indicate that, in the presence of repulsive interactions, the evolution of the aggregation rate as a function of Pe can always be divided into three distinct regimes, no matter which convective mechanism is considered. At low Pe values the rate of aggregation is independent of convection and is dominated by repulsive interactions. At high Pe values, the rate of aggregation is dominated by convection, and independent of repulsive interactions. At intermediate Pe values, a sharp transition between these two regimes occurs. During this transition, which occurs usually over a 10–100-fold increase in Pe values, the aggregation rate can change by several orders of magnitude. The interval of Pe values where this transition occurs depends upon the nature of the convective transport mechanism, as well as on the height and characteristic lengthscale of the repulsive barrier. A simplified model has been proposed that is capable of quantitatively accounting for the simulations results. The obtained results reveal unexpected features of the effect of ionic strength and particle size on the stability of colloidal suspensions under shear or sedimentation, which have relevant consequences in industrial applications.

Normalized doublet formation rate of colloidal nanoparticles as a function of Pe number in the presence of an extensional flow field, for different surface potential values..Figure optionsDownload high-quality image (109 K)Download as PowerPoint slideResearch Highlights
► Repulsive interactions effect colloidal doublet formation rate with convection.
► Sharp transition between interaction and convection-controlled regimes.
► Sedimentation and extensional flow show qualitatively similar behaviors.
► A simplified model can quantitatively predict the rigorous calculations results.