Kinetic analysis of high-resolution TGA variable heating rate data

Isothermal and constant heating rate thermogravimetric analysis (TGA) experiments have been performed for examining decomposition of polymers and composites. In practice, low heating rates are necessary to obtain good resolution under nonisothermal conditions thus increasing the time required for experiments. A novel TGA mode, high-resolution TGA (Hi-Res^TM TGA), provides a means to remarkably increase the resolution while often decreasing the time required for experiments. In this variable heating rate mode of Hi-Res^TMTGA, the heating rate is continuously and dynamically varied to maximize resolution. Thus, traditional methods cannot be directly utilized to determine kinetic parameters. Accordingly, in this work, variable heating rate experiments were run on ethylene-vinylacetate (EVA) copolymer, poly(ether ether ketone) (PEEK), and carbon-fiber-reinforced bismaleimide (BMI), whose kinetics have been quantitatively described with traditional isothermal and nonisothermal experiments. Comparison of the different techniques led to the development of a simplified method by which the activation energy, preexponential factor, and reaction order can be extracted from variable heating rate TGA experiments. The technique, based on the principle that maximum weight loss rate is observed at minimum heating rate, gave kinetic results that were in excellent agreement with values that have been determined by traditional isothermal and dynamic experiments. © 1993 John Wiley & Sons, Inc.