Nonequilibrium glass transitions

Thermodynamic fluctuations inglass-forming liquids

The yield stress is a defining feature of amorphous materials which is difficult to analyze theoretically, because it stems from the strongly non-linear response of an arrested solid to an applied deformation. Mode-coupling theory predicts the flow curves of materials undergoing a glass transition, and thus offers predictions for the yield stress of amorphous solids. We use this approach to analyse several classes of disordered solids, using simple models of hard sphere glasses, soft glasses, and metallic glasses for which the mode-coupling predictions can be directly compared to the outcome of numerical measurements. The theory correctly describes the emergence of a yield stress of entropic nature in hard sphere glasses, and its rapid growth as density approaches random close packing at qualitative level. By contrast, the emergence of solid behavior in soft and metallic glasses, which originates from direct particle interactions is not well described by the theory. We show that similar shortcomings arise in the description of the vibrational dynamics of the glass phase at rest. We discuss the range of applicability of mode-coupling theory to understand the yield stress and non-linear rheology of amorphous materials.

We analyse numerically thermal fluctuations of the static overlap between equilibrium configurations in a glass-forming liquid approaching the glass transition. We find that the emergence of slow dynamics near the onset temperature correlates with the development of non-Gaussian probability distributions of overlap fluctuations, measured using both annealed and quenched definitions. Below a critical temperature, a thermodynamic field conjugate to the overlap induces a first-order phase transition, whose existence we numerically demonstrate in the annealed case. These results establish that the approach to the glass transition is accompanied by profound changes in the nature of thermodynamic fluctuations, deconstructing the view that glassy dynamics occurs with little structural evolution.

The shear rheology of soft particles systems becomes complex at large density because crowding effects may induce a glass transition for Brownian particles, or a jamming transition for non-Brownian systems. Here we successfully explore the hypothesis that the shear stress contributions from glass and jamming physics are 'additive'. We show that the experimental flow curves measured in a large variety of soft materials (colloidal hard spheres, microgel suspensions, emulsions, aqueous foams) as well as numerical flow curves obtained for soft repulsive particles in both thermal and athermal limits are well described by a simple model assuming that glass and jamming rheologies contribute linearly to the shear stress, provided that the relevant scales for time and stress are correctly identified in both sectors. Our analysis confirms that the dynamics of colloidal hard spheres is uniquely controlled by glass physics while aqueous foams are only sensitive to jamming effects. We show that for micron-sized emulsions both contributions are needed to successfully account for the flow curves, which reveal distinct signatures of both phenomena. Finally, for two systems of soft microgel particles we show that the flow curves are representative of the glass transition of colloidal systems, and deduce that microgel particles are not well suited to studying the jamming transition experimentally.