Densified network glasses and liquids with thermodynamically reversible and structurally adaptive behaviour

If crystallization can be avoided during cooling, a liquid will display a substantial increase of its viscosity, and will form a glass that behaves as a solid with a relaxation time that grows exponentially with decreasing temperature. Given this ‘off-equilibrium’ nature, a hysteresis loop appears when a cooling/heating cycle is performed across the glass transition. Here we report on molecular dynamics simulations of densified glass-forming liquids that follow this kind of cycle. Over a finite pressure interval, minuscule thermal changes are found, revealing glasses of ‘thermally reversible’ character with optimal volumetric or enthalpic recovery. By analysing the topology of the atomic network structure, we find that corresponding liquids adapt under the pressure-induced increasing stress by experiencing larger bond-angle excursions. The analysis of the dynamic behaviour reveals that the structural relaxation time is substantially reduced in these adaptive liquids, and also drives the reversible character of the glass transition. Ultimately, the results substantiate the notion of stress-free (Maxwell isostatic) rigidity in disordered molecular systems, while also revealing new implications for the topological engineering of complex materials.