Kinetics Study of PVA Polymer by Model-Free and Model-Fitting Methods Using TGA

Thermogravimetric Analysis (TGA) serves a pivotal technique for evaluating the thermal behavior of Polyvinyl alcohol (PVA), a polymer extensively utilized in the production of fibers, films, and membranes. This paper targets the kinetics of PVA thermal degradation using high three heating rate range 20, 30, and 40 K min⁻¹. The kinetic study was performed using six model-free methods: Freidman (FR), Flynn-Wall-Qzawa (FWO), Kissinger-Akahira-Sunose (KAS), Starink (STK), Kissinger (K), and Vyazovkin (VY) for the determination of the activation energy (E_a). TGA showed two reaction stages: the main one at 550–750 K and the second with 700–810 K. But only the first step has been considered in calculating E_a. The average activation energy values for the conversion range (0.1–0.7) are between minimum 104 kJ mol⁻¹ by VY to maximum 199 kJ mol⁻¹ by FR. Model-fitting has been applied by combing Coats–Redfern (CR) with the master plot (Criado’s) to identify the most convenient reaction mechanism. E_a values gained by the above six models were very similar with the average value of (126 kJ mol⁻¹) by CR. The reaction order models-Second order (F2) was recommended as the best mechanism reaction for PVA pyrolysis. Mechanisms were confirmed by the compensation effect. Finally, (∆H, ∆G, and ∆S) parameters were presented and proved that the reaction is endothermic.