Vitrification is a spontaneous non-equilibrium transition driven by osmotic pressure

Abstract

Persistent dynamics in colloidal glasses suggest the existence of a non-equilibrium driving force for structural relaxation during glassy aging. But the implicit assumption in the literature that colloidal glasses form within the metastable state bypasses the search for a driving force for vitrification and glassy aging and its connection with a metastable state. The natural relation of osmotic pressure to number-density gradients motivates us to investigate the osmotic pressure as this driving force. We use dynamic simulation to quench a polydipserse hard-sphere colloidal liquid into the putative glass region while monitoring structural relaxation and osmotic pressure. Following quenches to various depths in volume fraction φ (where φ RCP ≈ 0.678 for 7% polydispersity), the osmotic pressure overshoots its metastable value, then decreases with age toward the metastable pressure, driving redistribution of coordination number and interparticle voids that smooths structural heterogeneity with age. For quenches to 0.56 ≤ φ ≤ 0.58, accessible post-quench volume redistributes with age, allowing the glass to relax into a strong supercooled liquid and easily reach a metastable state. At higher volume fractions, 0.59 ≤ φ < 0.64, this redistribution encounters a barrier that is subsequently overcome by osmotic pressure, allowing the system to relax toward the metastable state. But for φ ≥ 0.64, the overshoot is small compared to the high metastable pressure; redistribution of volume stops as particles acquire contacts and get stuck, freezing the system far from the metastable state. Overall, the osmotic pressure drives structural rearrangements responsible for both vitrification and glassy age-relaxation. We leverage the connection of osmotic pressure to energy density to put forth the mechanistic view that relaxation of structural heterogeneity in colloidal glasses occurs via individual particle motion driven by osmotic pressure, and is a spontaneous energy minimization process that drives the glass off and back to the metastable state. This connection of energy, pressure, and structure identify the glass transition, 0.63 < φ g ≤ 0.64.

Glasses and gels: a crossroad of molecular liquids, polymers and colloids

“…Reference [10] challenges the conventional assumption that colloidal glasses form within a metastable state. The authors perform numerical simulations of hard-sphere colloidal suspensions quenched into the glass in the presence of Brownian motion and particle interactions, rather than artificially initialized into an amorphous dense configurations, as usually done.…”