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.

An important polymer processing technique is additive manufacturing (AM), which enables shape-free design of complex final parts with limited waste during the development change, at least if the impact of molecular degradation reactions is minimized. In the present work, polystyrene (PS) and acrylonitrile butadiene styrene (ABS) polymer have been processed via: (i) fused filament fabrication (FFF), separately accounting for the prior single screw extrusion (SSE) filament production; and (ii) pellet-based additive manufacturing (PBAM), which are two important AM techniques. The influence of printing temperature, layer thickness, printing velocity, and printing technique on the degradation of both polymeric materials is studied by means of thermogravimetric analysis (TGA), size exclusion chromatography (SEC), small amplitude oscillatory shearing tests (SAOS), Fourier-transform infrared spectroscopy (FTIR), and yellowness index (YI) measurements. For ABS, SSE-FF leads to more fission (higher mechanical loading) whereas PBAM results in more cross-linking (more thermal loading). For PS, fission is always dominant and this more evident under FFF conditions. ABS also exhibits yellowing upon processing, indicating thermo-oxidative degradation although below the FTIR sensitivity limit. The selected PBAM conditions with PS are already delivering printed specimens with good mechanical properties and lower degradation. For ABS, a further PBAM optimization is still desired compared to the FFF countercase, taking into account layer-by-layer adhesion.

To improve the product quality of polymeric parts realized through extrusion-based additive manufacturing (EAM) utilizing pellets, a good control of the melting is required. In the present work, we demonstrate the strength of a previously developed melt removal using a drag framework to support such improvement. This model, downscaled from conventional extrusion, is successfully validated for pellet-based EAM—hence, micro-extrusion—employing three material types with different measured rheological behavior, i.e., acrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA) and styrene-ethylene-butylene-styrene polymer (SEBS). The model’s validation is made possible by conducting for the first time dedicated EAM screw-freezing experiments combined with appropriate image/data analysis and inputting rheological data. It is showcased that the (overall) processing temperature is crucial to enable similar melting efficiencies. The melting mechanism can vary with the material type. For ABS, an initially large contribution of viscous heat dissipation is observed, while for PLA and SEBS thermal conduction is always more relevant. It is highlighted based on scanning electron microscopy (SEM) analysis that upon properly tuning the finalization of the melting point within the envisaged melting zone, better final material properties are achieved. The model can be further used to find an optimal balance between processing time (e.g., by variation of the screw frequency) and material product performance (e.g., strength of the printed polymeric part).