Biodegradable polymers and their blends have been advised as an eco-sustainable solution; however, the generation of microplastics (MPs) from their degradation in aquatic environments is still not fully grasped. In this study, we investigated the formation of bio-microplastics (BMPs) and the changes in the physicochemical properties of blown packaging films based on polylactic acid (PLA), polybutylene succinate (PBS) and a PBS/PLA 70/30 wt% blend after degradation in different aquatic media. The tests were carried out in two temperature/light conditions to simulate degradation in either warm water, under sunlight exposure (named Warm and Light—W&L), and cold deep water (named Cold and Dark—C&D). The pH changes in the aqueous environments were evaluated, while the formed BMPs were analyzed for their size and shape alongside with variations in polymer crystallinity, surface and mechanical properties. In W&L conditions, for all the films, the hydrolytic degradation led to the reorganization of the polymer crystalline phases, strong embrittlement and an increase in hydrophilicity. The PBS/PLA 70/30 blend exhibited increased resistance to degradation with respect to the neat PLA and PBS films. In C&D conditions, no microparticles were observed up to 12 weeks of degradation.
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