Gravitational collapse of colloidal gels: non-equilibrium phase separation driven by osmotic pressure

P Padmanabhan and R Zia, SOFT MATTER, 14, 3265-3287 (2018).

DOI: 10.1039/c8sm00002f

Delayed gravitational collapse of colloidal gels is characterized by initially slow compaction that gives way to rapid bulk collapse, posing interesting questions about the underlying mechanistic origins. Here we study gel collapse utilizing large-scale dynamic simulation of a freely draining gel of physically bonded particles subjected to gravitational forcing. The hallmark regimes of collapse are recovered: slow compaction, transition to rapid collapse, and long-time densification. Microstructural changes are monitored by tracking particle positions, coordination number, and bond dynamics, along with volume fraction, osmotic pressure, and potential energy. Together these reveal the surprising result that collapse can occur with a fully intact network, where the tipping point arises when particle migration dissolves strands in a capillary-type instability. While it is possible for collapse to rupture a gel network into clusters that then sediment, and hydrodynamic interactions can make interesting contributions, neither is necessary. Rather, we find that the `` delay'' arises from gravity-enhanced coarsening, which triggers the reemergence of phase separation. The mechanism of this transition is a leap toward lower potential energy of the gel, driven by bulk negative osmotic pressure that condenses the particle phase: the gel collapses in on itself under negative osmotic pressure allowing the gel, to tunnel through the equilibrium phase diagram to a higher volume fraction `` state''. Remarkably, collapse stops when condensation stops, when gravitational advection produces a positive osmotic pressure, re-arresting the gel.

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