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) ≡ dα/dt, 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.