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Temperature dependence of aging dynamics in highly non-equilibrium model polymer glasses.

A central feature of the non-equilibrium glassy "state" is its tendency to age toward equilibrium, obeying signatures identified by Kovacs over 50 years ago. The origin of these signatures, their fate far from equilibrium and at high temperatures, and the underlying nature of the glassy "state" far from equilibrium remain unsettled. Here, we simulate physical aging of polymeric glasses, driven much farther from equilibrium and at much higher temperatures than possible in experimental melt-quenched glasses. While these glasses exhibit Kovacs' signatures of glassy aging at sufficiently low temperatures, these signatures disappear above the onset TA of non-Arrhenius equilibrium dynamics, suggesting that TA demarcates an upper bound to genuinely glassy states. Aging times in glasses after temperature up-jumps are found to obey an Arrhenius law interpolating between equilibrium dynamics at TA and at the start of the temperature up-jump, providing a zero-parameter rule predicting their aging behavior and identifying another unrecognized centrality of TA to aging behavior. This differs qualitatively from behavior of our glasses produced by temperature down-jumps, which exhibit a fractional power law decoupling relation with equilibrium dynamics. While the Tool-Narayanaswamy-Moynihan model can predict the qualitative single-temperature behavior of these systems, we find that it fails to predict the disappearance of Kovacs signatures above TA and the temperature dependence of aging after large temperature up-jumps. These findings highlight a need for new theoretical insights into the aging behavior of glasses at ultra-high fictive temperatures and far from equilibrium.