Hydrodynamic interactions enhance gelation in dispersions of colloids with short-ranged attraction and long-ranged repulsion

Abstract

We show that discrete element simulations of colloidal gelation must account for hydrodynamic interactions between suspended particles through investigation of gelation in a dispersion of colloids interacting pair-wise via short-ranged attraction and long-ranged repulsion (SALR). These dynamic simulations juxtapose self-assembly with and without hydrodynamic interactions between the particles. The long-ranged repulsion impacts the relative rates of coagulation and compaction of colloidal aggregates pre-gel, and introduces a surprising sensitivity to the nature of hydrodynamic interactions between the suspended colloids. For such SALR dispersions, we observe a significant disparity between the percolation boundaries predicted by simulations including and neglecting long-ranged hydrodynamic interactions. Additionally, we find that the percolation boundaries predicted by simulations including hydrodynamic interactions agree well with those measured experimentally. Long-ranged repulsion promotes gelation via growth of anisotropic clusters regardless of the hydrodynamic model employed. However, differences between the models, which persist far from the percolation boundary, are apparent via measurements of the fractal dimension, local bond order parameters, and the collective relaxation dynamics. Notably, the growth of elongated clusters is augmented in simulations that incorporate long-ranged hydrodynamic interactions due to the anisotropic diffusion of elongated bodies at low Reynolds numbers, which favors percolation over a transition of anisotropic clusters to their more isotropic ground states. It is only in relatively dense suspensions that a combination of hydrodynamic screening and significantly faster aggregation combine to bring the two simulation methods into agreement. These results demonstrate the necessity of long-ranged hydrodynamic forces in discrete element simulations of heterogeneous gelation at the colloidal scale.