Aging, Jamming, and the Limits of Stability of Amorphous Solids
Wolynes, Peter G.
Apart from not having crystallized, supercooled liquids can be considered as being properly equilibrated and thus can be described by a few thermodynamic control variables. In contrast, glasses and other amorphous solids can be arbitrarily far away from equilibrium and require a description of the history of the conditions under which they formed. In this paper we describe how the locality of interactions intrinsic to finite-dimensional systems affects the stability of amorphous solids far off equilibrium. Our analysis encompasses both structural glasses formed by cooling and colloidal assemblies formed by compression. A diagram outlining regions of marginal stability can be adduced which bears some resemblance to the quasi-equilibrium replica meanfield theory phase diagram of hard sphere glasses in high dimensions but is distinct from that construct in that the diagram describes not true phase transitions but kinetic transitions that depend on the preparation protocol. The diagram exhibits two distinct sectors. One sector corresponds to amorphous states with relatively open structures, the other to high density, more closely packed ones. The former transform rapidly owing to there being motions with no free energy barriers; these motions are string-like locally. In the dense region, amorphous systems age via compact activated reconfigurations. The two regimes correspond, in equilibrium, to the collisional or uniform liquid and the so-called landscape regime, respectively. These are separated by a spinodal line of dynamical crossovers. Owing to the rigidity of the surrounding matrix in the landscape, high-density part of the diagram, a sufficiently rapid pressure quench adds compressive energy which also leads to an instability toward string-like motions with near vanishing barriers. Conversely, a dilute collection of rigid particles, such as a colloidal suspension leads, when compressed, to a spatially heterogeneous structure with percolated mechanically stable regions. This jamming corresponds to the onset of activation when the spinodal line is traversed from the low density side. We argue that a stable glass made of sufficiently rigid particles can also be viewed as exhibiting sporadic and localized buckling instabilities that result in local jammed structures. The lines of instability we discuss resemble the Gardner transition of meanfield systems but, in contrast, do not result in true criticality owing to being short-circuited by activated events. The locally marginally stable modes of motion in amorphous solids correspond to secondary relaxation processes in structural glasses. Their relevance to the low temperature anomalies in glasses is also discussed.