Effects of Repeated Thermo-Mechanical Processing on the Degradation Behavior of Bottle-Grade PET Under Controlled Conditions

Mechanical recycling of polyethylene terephthalate (PET) is a key strategy for circular packaging applications; however, repeated thermo-mechanical processing leads to progressive polymer degradation. In this study, the effect of controlled repeated extrusion on the degradation behavior of bottle-grade PET was systematically investigated under laboratory conditions. Mechanical recycling was simulated using a co-rotating twin-screw extruder, where PET was subjected to up to four consecutive processing cycles corresponding to a cumulative residence time of 8 min. Progressive processing resulted in chain scission, reflected by a decrease in intrinsic viscosity from approximately 0.80 to 0.65 dL·g−1 and a corresponding reduction in molecular weight. Melt flow rate increased accordingly, indicating a gradual loss of melt strength. Differential scanning calorimetry revealed that the glass transition and melting temperatures remained nearly unchanged, while the degree of crystallinity increased from approximately 23.0% to 29.5%, accompanied by changes in crystallization behavior. These structural changes led to reduced ductility, with elongation at break decreasing from about 84% to 60%. Optical analysis showed systematic material darkening, and a strong linear correlation between lightness (L*) and intrinsic viscosity was observed. By isolating intrinsic thermo-mechanical degradation effects under controlled processing conditions, this study enables a clearer definition of realistic reuse limits for mechanically recycled bottle-grade PET. The results indicate that bottle-grade PET retains properties compatible with demanding applications only after a limited number of thermo-mechanical processing cycles, whereas further processing restricts its usability to less demanding applications such as fibers, films, and non-food packaging.