Is the configurational entropic model able to predict the final equilibrium state reached by Se glasses after very long ageing durations?

Abstract

This work compares the equilibrium states reached by glassy selenium (g-Se) after several ageing durations at temperatures lower than the glass transition temperature T _g, with the forecasts given by the configurational entropic model. The comparison is carried out through experimental data collected both on glassy samples after short-term ageing and on glassy samples older than 20 years, kept at room temperature. It is shown that the configurational entropic model is not able to describe the behaviour of g-Se, both at short- and long-ageing terms with the same set of fitting parameters. For short-term ageing, the forecasts given by the entropic model are in good agreement with the experimental data; the hypothesis that the heat capacities corresponding to the equilibrium state and to the state extrapolated from the liquid differ by an amount δ is therefore properly justified. For long-term ageing, the amount δ vanishes and the assumption does not hold any longer. Indeed, experimental results support the idea that at least two separate mechanisms of relaxation coexist in the physical ageing of g-Se, one with very fast kinetics and the other with much slower kinetics.

Keywords:

• chalcogenide glasses
• physical ageing
• selenium
• configurational entropic model
• DSC measurements