Kissinger equation versus glass transition phenomenology

• Published in: Journal of thermal analysis and calorimetry 2013-10, Vol.114 (1), p.285-293
• Main Authors: Svoboda, Roman, Čičmanec, Pavel, Málek, Jiří
• Format: Article
• Language: English
• Subjects: Activation analysis; Analytical Chemistry; Applied sciences; Building materials. Ceramics. Glasses; Chemical industry and chemicals; Chemistry; Chemistry and Materials Science; Exact sciences and technology; Glasses; Inorganic Chemistry; Measurement Science and Instrumentation; Physical Chemistry; Polymer Sciences
• ISSN: 1388-6150; 1588-2926; 1572-8943
• DOI: 10.1007/s10973-012-2892-3

The applicability of the Kissinger equation for the evaluation of apparent activation energy corresponding to glass transition kinetics is examined. Theoretically simulated data based on the generally accepted Tool–Narayanaswamy–Moynihan model were used to represent relevant cases of structural relaxation behavior. The values of the apparent activation energy determined by the Kissinger equation were, despite the linearity of the dependencies, in major disagreement with the original values of ∆ h * used for the simulation of the source data. Furthermore, a large dependence of the ∆ h Kis * evaluation (performed using the Kissinger equation) on the thermal history of the glass was found. The latter represents an unacceptable systematic error in the methodology, implying the incorrectness of the Kissinger equation usage for the evaluation of “glass transition activation energy”. This study addresses the currently widespread (incorrect) usage of the Kissinger equation for the above-mentioned purpose.