Thermal Physics and Thermal Analysis pp 213-236 | Cite as

# Imperfections of Kissinger Evaluation Method and the Explanation of Crystallization Kinetics of Glasses and Melts

## Abstract

The famous Kissinger’s kinetic evaluation method (see Anal. Chem. 1957) is examined with respect to both the relation between the DTA signal *θ*(*t*) and the reaction rate *r*(*t*) ≡ d*α*/d*t*, the requirements on reaction mechanism model *f*(*α*), and the relation of starting kinetic equation to the equilibrium behavior of sample under study. Distorting effect of heat inertia and difference between the temperature *T* _{ p } of extreme DTA deviation and the temperature *T* _{ m } at which the reaction rate is maximal are revealed. DTA equation of Borchard and Daniels is criticized regarding the neglection of heat inertia correction. The kinetic equations respecting the influence of equilibrium temperature *T* _{ eq }, especially fusion/melting temperature *T* _{ f }, are tested as bases for a modified Kissinger-like evaluation of kinetics. Crystallization kinetics on melt solidification is examined under integration of undercooling and needed Gibbs approximations are explored. This chapter provides a new insight into the routine practice of nonisothermal kinetics showing forward-looking outlook and encompasses hundreds of references.

## Keywords

Kissinger Method Maximum Reaction Rate Kissinger Equation Kissinger Plot Heat Inertia## Notes

### Acknowledgements

The present work was developed at the Join Research Laboratory of the Institute of Physics CAS and the New Technologies Centre of the University of West Bohemia in Pilsen (the CENTEM project, reg. no. CZ.1.05/2.1.00/03.0088 that is co-funded from the ERDF as a part of the MEYS—Ministry of Education, Youth and Sports OP RDI Program and, in the follow-up sustainability stage supported through the CENTEM PLUS LO 1402). The abandoned support by the Grant Agency of ČR for the projected grant ‘Thermal inertia and its significance for the analysis of DTA measurements’ (No 17-21840S-2016) is worth mentioning as an example of fatal misunderstanding of current needs of thermal science. Deep thanks are due to long-lasting collaboration activity by J.J. Mareš, P. Hubík (Institute of Physics), J. Málek (University of Pardubice), N. Koga (Hiroshima University in Japan) and P. Šimon (The President of the Slovak Chemical Society, with Technical University in Bratislava).

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