Evaluation of the Activation Energy for Pyrolytic Degradation of Poly‐L‐Lactide (<scp>PLA</scp>) During Artificially Accelerated Aging

In the course of this study, the pyrolytic degradation characteristics of three poly(lactic acid) (PLA) types were investigated under inert conditions using dynamic thermogravimetric analysis (TGA) across the temperature range of 23°C-600°C with four heating rates. Specifically, the activation energy and its implications were determined at different stages of degradation. For this purpose, a comparative analysis of various isoconversional methods, including Kissinger, Flynn-Wall-Ozawa (FWO), Friedman, and Kissinger-Akahira-Sunnose (KAS) was undertaken to evaluate the reliability of each. The results indicate a decrease in thermal stability, indicated by a shift of the derived mass loss curves to lower temperatures, as confirmed by an increased water content and decreased crystallinity of the test specimen during aging. The study also highlights that if crystallinity and moisture content increase moderately, the thermal degradation curves remain unchanged. Additionally, kinetic analyses using mentioned models indicate a multi-step degradation process of PLA. The activation energy fluctuates with the conversion rate, suggesting complex underlying kinetics. These findings emphasize the need for dynamic adjustment of predictive models for material lifespan. The three PLA types were characterized by Differential Scanning Calorimetry (DSC), moisture absorption measurement and Gel permeation chromatography (GPC).