This article reports an evaluation study of the thermal degradation mechanisms of electrically insulating and conducting epoxy/Sn composites by using solid-state kinetic approaches and structural characterizations.Comparison of the thermoanalytical data of epoxy/Sn composites with pure epoxy shows that the addition of tin in epoxy catalyzes the thermal degradation of epoxy and the catalytic ability of tin depends upon its contents in epoxy. Kinetic modeling of the phenomena elaborates the thermal behaviors of epoxy/Sn composites in terms of the comparison of their activation parameters and reaction models. Friedman's differential and ArshadMaaroufi's generalized linear integral isoconversional methods are used to obtain the variation in activation energies with the advancement of reaction. Advanced reaction model determination methodology is effectively employed to evaluate the reaction mechanisms of epoxy/Sn composites. Kinetic analysis suggests that tin increases the thermal degradation rate of epoxy by lowering the activation energy barrier of reaction. It is worth noticing that the parameters of the probable reaction model, i.e., Sest ak Berggren have been found nearly the same for pure epoxy and epoxy/Sn composites, revealing weak epoxy-tin interactions in the composites. The mechanistic information obtained by kinetic analysis fairly agrees with the scanning electron microscopy and X-ray diffraction results.
Dynamic percolation differs from static percolation in polymer composites owing to its occurrence at a particular filler fraction under thermal activation. Mechanistic insights into dynamic percolation might lead to develop polymer composites with controlled electrical properties at lower filler fractions and improved temperature coefficient of resistance phase transitions. Although attempts have been made to kinetically describe the dynamic percolation in polymer composites, a generalized mechanism-based approach has not yet been reported. In this article, a systematic and generalized theoretical approach to kinetically model the dynamic percolation in polymer/carbon composites has been put forward. Based on the proposed approach, a kinetic expression to predict the quasi-thermodynamic equilibrium state in a polymer/ carbon composite at constant temperature is derived. The soundness of the proposed approach is justified by its effective applications on poly(vinylidene fluoride)/multiwalled carbon nanotube (PVDF/MWNT), poly(vinylidene fluoride)/carboxyl-functionalized MWNT (PVDF/MWNT), high-density polyethylene/carbon black, and poly(methyl methacrylate)/carbon black composites. Certain mechanistic complexities of dynamic percolation are also pointed out and discussed. POLYM. ENG. SCI., 60:423-433, 2020.
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