No abstract

Aggregation and breakage of aggregates of fully destabilized polystyrene latex particles in turbulent flow was studied experimentally in both batch and continuous stirred tanks. Small-angle static light scattering (SASLS) was used to monitor the time evolution of two independent moments of the cluster mass distribution (CMD), namely, the mean radius of gyration and the zero angle scattered light intensity. In addition, information about the structure of the aggregates was obtained in terms of the static light scattering structure factor. It was observed that decreasing the solid volume fraction over more than one order of magnitude resulted in monotonically decreasing steady-state values of both moments of the CMD. Using a combination of batch operation and continuous dilution with particle-free solution in the stirred tank, it was found that the steady-state distributions were fully reversible upon changing the solid volume fraction. These observations indicate that the steady-state CMD in this system is controlled by the dynamic equilibrium between aggregation (with the second-order kinetics in cluster concentration) and breakage (with the first-order kinetics in cluster concentration). In addition, by dilution to very low solid volume fractions, we demonstrate the existence of a critical aggregate size below which breakage is negligible.

Interactions between colloidal particles are strongly affected by the particle surface chemistry and composition of the liquid phase. Further complexity is introduced when particles are exposed to shear flow, often leading to broad variation of the final properties of formed clusters. Here we discover a new dynamical effect arising in shear-induced aggregation where repeated aggregation and breakup events cause the particle surface roughness to irreversibly increase with time, thus decreasing the bond adhesive energy and the resistance of the aggregates to breakup. This leads to a pronounced overshoot in the time evolution of the aggregate size, which can only be explained with the proposed mechanism. This is demonstrated by good agreement between time evolution of measured light-scattering data and those calculated with a population-balance model taking into account the increase in the primary particle nanoroughness caused by repeated breakup events resulting in the decrease of bond adhesive energy as a function of time. Thus, the proposed model is able to reproduce the overshoot phenomenon by taking into account the physicochemical parameters, such as pH, till now not considered in the literature. Overall, this new effect could be exploited in the future to achieve better control over the flow-induced assembly of nanoparticles.