Authors:N. Sbirrazzuoli, L. Vincent, J. Bouillard, and L. Elégant
In the case of a complex mechanism of two parallel independent reactions, peak maximum evolution methods and model-fitting
methods give only a mean value of the kinetic parameters, while isoconversional methods are useful to describe the complexity
of the mechanism. Isothermal and non-isothermal isoconversional methods can be used to elucidate the kinetics of the process.
Nevertheless, isothermal isoconversional methods can be limited by restrictions on the temperature regions experimentally
available because of duration times or detection limits.
Authors:S. Du, G. Zhang, H. Li, P. Wang, and X. Wang
The free-radical bulk polymerization of 2,2-dinitro-1-butyl-acrylate (DNBA) in the presence of 2,2′-azobisisobutyronitrile
(AIBN) as the initiator was investigated by DSC in the non-isothermal mode. Kissinger and Ozawa methods were applied to determine
the activation energy (Ea) and the reaction order of free-radical polymerization. The results showed that the temperature of exothermic polymerization
peaks increased with increasing the heating rate. The reaction order of non-isothermal polymerization of DNBA in the presence
of AIBN is approximately 1. The average activation energy (92.91±1.88 kJ mol −1) obtained was smaller slightly than the value of Ea=96.82 kJ mol−1 found with the Barrett method.
A near-linear representation of the linear heating rate is presented which converts the exponential integral into an integrable form and allows a simple determination of the activation energy to high accuracy.