Interference between the glass, gel, and gas-liquid transitions

Abstract

Recent experiments and computer simulations have revealed intriguing phenomenological fingerprints of the interference between the ordinary equilibrium gas-liquid phase transition and the non-equilibrium glass and gel transitions. We thus now know, for example, that the liquid-gas spinodal line and the glass transition loci intersect at a finite temperature and density, that when the gel and the glass transitions meet, mechanisms for multistep relaxation emerge, and that the formation of gels exhibits puzzling latency effects. In this work we demonstrate that the kinetic perspective of the non-equilibrium self-consistent generalized Langevin equation (NE-SCGLE) theory of irreversible processes in liquids provides a unifying first-principles microscopic theoretical framework to describe these and other phenomena associated with spinodal decomposition, gelation, glass transition, and their combinations. The resulting scenario is in reality the competition between two kinetically limiting behaviors, associated with the two distinct dynamic arrest transitions in which the liquid-glass line is predicted to bifurcate at low densities, below its intersection with the spinodal line.

Glass-liquid and glass-gel transitions of soft-shell particles

“…Together with the coincidence with the glass-gel transition at larger weight fractions this results suggests a manifestation (or reminder) of the glass-gel transition in the supercooled liquid state. This is rationalized by the interference of glass and gel dynamics that results in anomalous dynamics such as subdiffusion [55] and multiple relaxation processes [56][57][58]. Both may result in a reduction of γ and increase of p which matches our data.…”

Light-Controlled Aggregation and Gelation of Viologen-Based Coordination Polymers

“…This pathway is driven by an arrested phase separation. Such a scenario is new to supramolecular systems but has already been observed in colloidal dispersions, polymers, and protein solutions , and has also been investigated with simulations. − It opens up new perspectives in the field of viologen-based responsive supramolecular gels. − This work provides a physical analysis of a highly complex chemical system. The chemical evolution in terms of interactions and reaction pathways remains to be elucidated and compared to the physical pathway proposed in this article.…”

“Inner clocks” of glass-forming liquids

“…For example, for simple liquids with purely repulsive interparticle interactions, this theoretical framework accurately describes the non-stationary and non-equilibrium process of the formation of high-density hard-sphere-like glasses, [30][31][32] whereas for liquids with repulsive plus attractive interactions at low densities and temperatures, it predicts the formation of sponge-like gels and porous glasses by arrested spinodal decomposition. [33][34][35][36] The NE-SCGLE was formulated in Ref. 29 and can be summarized in terms of a set of equations that describe the non-equilibrium evolution of the structural and dynamical properties of a simple glass-forming liquid [we refer here for simplicity to a generic system of N identical spherical particles in a volume V that interact through a radially symmetric pair potential U(r)].…”