A step to microplastic formation: Microcracking and associated surface transformations of recycled LDPE, LLDPE, HDPE, and PP plastics exposed to UV radiation

Plastics when exposed to UV radiation start to degrade via photooxidative aging including free radical formation, oxidation, chain scission and/or crosslinking reactions. These chemical changes can cause loss in mechanical strength, surface embrittlement, and eventually surface erosion. The eroded particles are microplastics (MPs), which have been identified as a potentially serious threat to the environment and its inhabitants. In general, photodegradation of virgin plastics has been studied extensively, but there is not much literature on the degradation of recycled plastics. The goal of the study was to investigate the changes caused by photodegradation in recycled plastics and assess the potential risks of MPs formation. And eventually, knowing the chemical and physical transformations occurring on the surface understand the mechanism behind surface microcracking, which is the first step of MPs formation. Pellets of five industrially recycled plastics (low-density polyethylene (rLDPE), linear low-density polyethylene (rLLDPE), high-density polyethylene (rHDPE), and two polypropylenes (rPP)) from different waste sources were analysed. UV irradiation was performed in an accelerated weathering chamber for milled (< 400 µm) plastic powder to ensure homogeneous changes throughout the sample. The properties were investigated by ATR-FTIR, HT-SEC, XPS and DSC. Formation of microcracks was studied on plastic pellets by SEM. The results showed that the degradation significantly differed between the recycled plastics, and the waste source was more important than the plastic type. rLDPE and one of the rPP samples showed a significant increase in carbonyl index as well as decrease in molar mass during the first 500 h of UV exposure. The other rPP and rHDPE samples showed first considerable signs of degradation only after 1000 h of UV exposure. Minor changes were observed for the rLLDPE sample during the whole test. The SEM revealed microcracking on the surface of all samples, which also had noticeable degradation identified by other methods. These recycled plastics can be considered the ones with the highest potential of MPs formation. From the chemical and physical transformations identified on the surface, the mechanism leading to microcracking, which is the first step in the formation of MPs, is proposed.