Glass transformation phenomena in bulk and film amorphous selenium via DSC heating and cooling scans

Abstract

Recently there has been an emphasis on the importance of using cooling scans in DSC experiments in studying the glass transformation kinetics of glasses. The physical interpretation of the apparent activation energy from DSC heating scans has been questioned as not being meaningful. The present paper reports glass transition temperature (T_g) measurements derived from Differential Scanning Calorimetry (DSC) experiments on bulk and film amorphous selenium samples subjected to heating, at constant rate r, and cooling, at constant rate q, scans. Film samples were prepared by thermal evaporation techniques in vacuum. It is shown that for both bulk and film forms of a–Se, within experimental errors, log(r/T²_gm) vs 1/T_gm plot where T_gm is the peak glass transformation temperature, and log(r) vs 1/T_gh plot, where T_gh is the glass transition onset temperature from DSC heating scans, are parallel to the log(q) vs 1/T_gc plot where T_gc is the glass transition temperature from cooling scans. Within the Hutchinson and Kovacs formulation of the glass transformation phenomenon, the results imply that the structural contribution to the mean retardation time, τ, is negligible in comparison with the temperature dependent part. The mean structural relaxation time for both bulk and film forms was found to exhibit a typical Vogel-Tammann-Fulcher type of temperature dependence. Furthermore, the structural relaxation rate was observed to be inversely proportional to the viscosity, η(T), implying that the mean structural retardation time is proportional to the viscosity, τ ∼ η. The results also confirm that the earlier studies of glass transformation kinetics in a–Se utilizing only DSC heating scans remain meaningful.