Impact of Glycerol and Heating Rate on the Thermal Decomposition of PVA Films

This study analyzes the thermal degradation of PVA and PVA/glycerol films in air under varying heating rates. Thermogravimetric analysis (TGA) of pure PVA in both air and inert atmospheres confirmed that oxidative conditions significantly influence degradation, particularly at lower heating rates. For PVA/glycerol films in air, deconvolution of the differential thermogravimetry (DTG) curves during the main degradation stage revealed distinct peaks attributable to the degradation of glycerol, PVA/glycerol complexes, and PVA itself. Isoconversional methods showed that, for pure PVA in air, the apparent activation energy (Ea) increased with conversion, suggesting the simultaneous occurrence of multiple degradation mechanisms, including oxidative reactions, whose contribution changes over the course of the degradation process. In contrast, under an inert atmosphere, Ea remained nearly constant, consistent with degradation proceeding through a single dominant mechanism, or through multiple steps with similar kinetic parameters. For glycerol-plasticized films in air, Ea exhibited reduced dependence on conversion compared with that of pure PVA in air, with values similar to those of pure PVA under inert conditions. These results indicate that glycerol influences the oxidative degradation pathways in PVA films. These findings are relevant to high-temperature processing of PVA-based materials and to the design of thermal treatments—such as sterilization or pyrolysis—where control over degradation mechanisms is essential.