The Temperature Interval of the Liquid–Glass Transition of Amorphous Polymers and Low Molecular Weight Amorphous Substances

Abstract

We present calculation results of the temperature interval δTg characterizing the liquid–glass transition in amorphous materials obtained on the basis of available data of the empirical parameters C1 and C2 in the Williams–Landel–Ferry (WLF) viscosity equation. We consider the unambiguous dependence of the relative transition temperature interval δTg/Tg on the fraction of the fluctuation volume fg frozen at the glass transition temperature Tg utilizing Sanditov’s model of delocalized atoms. The parameter f = ΔVe/V, which determines the molecular mobility characteristic of delocalized atoms in the liquid–glass transition region, is weakly dependent on the nature of most vitreous substances and can be found as fg = 1/C1. We show that the temperature interval δTg is less than 1% of the Tg for most amorphous substances. This result conforms with Simon’s classical idea of a small temperature range in which the structure freezes. The structural relaxation time τg at Tg of polymers and chalcogenide glasses is also calculated.

Keywords

• kinetic criterion for glass transition
• amorphous polymers
• viscosity in the glass transition region
• Williams–Landel–Ferry equation
• fluctuation volume fraction
• vitrification