Molecular Pathways for Polymer Degradation during Conventional Processing, Additive Manufacturing, and Mechanical Recycling

The assessment of the extent of degradation of polymer molecules during processing via conventional (e.g., extrusion and injection molding) and emerging (e.g., additive manufacturing; AM) techniques is important for both the final polymer material performance with respect to technical specifications and the material circularity. In this contribution, the most relevant (thermal, thermo-mechanical, thermal-oxidative, hydrolysis) degradation mechanisms of polymer materials during processing are discussed, addressing conventional extrusion-based manufacturing, including mechanical recycling, and AM. An overview is given of the most important experimental characterization techniques, and it is explained how these can be connected with modeling tools. Case studies are incorporated, dealing with polyesters, styrene-based materials, and polyolefins, as well as the typical AM polymers. Guidelines are formulated in view of a better molecular scale driven degradation control.