The hydrodynamics of colloidal gelation

Colloidal gels are formed during arrested phase separation. Sub-micron, mutually attractive particles aggregate to form a system spanning network with high interfacial area, far from equilibrium. Models for microstructural evolution during colloidal gelation have often struggled to match experimental results with long standing questions regarding the role of hydrodynamic interactions. In nearly all models, these interactions are neglected entirely. In the present work, we report simulations of gelation with and without hydrodynamic interactions between the suspended particles executed in HOOMD-blue. The disparities between these simulations are striking and mirror the experimental-theoretical mismatch in the literature. The hydrodynamic simulations agree with experimental observations, however. We explore a simple model of the competing transport processes in gelation that anticipates these disparities, and conclude that hydrodynamic forces are essential. Near the gel boundary, there exists a competition between compaction of individual aggregates which suppresses gelation and coagulation of aggregates which enhances it. The time scale for compaction is mildly slowed by hydrodynamic interactions, while the time scale for coagulation is greatly accelerated. This enhancement to coagulation leads to a shift in the gel boundary to lower strengths of attraction and lower particle concentrations when compared to models that neglect hydrodynamic interactions. Away from the gel boundary, differences in the nearest neighbor distribution and fractal dimension persist within gels produced by both simulation methods. This result necessitates a fundamental rethinking of how dynamic, discrete element models for gelation kinetics are developed as well as how collective hydrodynamic interactions influence the arrest of attractive colloidal dispersions.