Thermokinetic Description of the Heat Capacity Change at the Glass Transition: 1. Can Glass Transition Kinetics Be Adequately Described by a Single Activation Energy? 2. Can the Glass Transition Temperature Be Predicted from Basic Physical Parameters? 3. What is the Role of Heat Capacity in the Vogel-Fulcher-Tammann Equation Describing Primary Relaxation in Glasses?

12 December 2025, Version 1
This content is an early or alternative research output and has not been peer-reviewed by Cambridge University Press at the time of posting.

Abstract

By coupling non-equilibrium thermodynamics with solid-state kinetics, a description of the heat capacity (cP) evolution as a function of the temperature (T) is derived that can be used to supplant commonly used empirical models. In addition to accurately describing the characteristic sigmoidal shape in the vicinity of the glass transition temperature (Tg), the proposed equation predicts a relaxation enthalpy peak to arise when either the enthalpy change of system relaxation is large or when the relaxation rate is fast. Such thermal events are often detected for amorphous compounds that have been annealed or stored for extended times. The activation energy of relaxation (E) is readily determined using different heating rates. Lastly, simple relationships are put forth to demonstrate the utility of cP in predicting both Tg and the empirical parameter, B, in the Vogel-Fulcher-Tammann (VFT) equation widely used to describe primary relaxation in glasses.

Keywords

heat capacity
glass transition temperature
prediction
amorphous
non-equilibrium thermodynamics
thermokinetic equation

Supplementary materials

Title
Description
Actions
Title
Supporting Information
Description
Derivation of Eq. 1 and Eq. 5 in the text.
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting and Discussion Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.