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.

The melt flow index (MFI) of seven commercial poly(lactic acid) (PLA) grades is investigated in view of 3D printing quality. A threshold value of 10 g (10 min)⁻¹ (2.16 kg; ISO 1133) is put forward for a successful printing (190–220°C), enabling a fast and practical screening of PLA materials. It is however shown that a sole focus on MFI is insufficient, as the plasticiser type and crystallinity also play a role after the polymer melt deposition. The latter is supported by scanning electron micromorphology and differential scanning calorimetry measurements. In particular, blending with poly(hydroxyl butyrate) (PHB; 20 m%) allows to control both MFI and crystallinity without the need for annealing.

Polypropylene (PP) parts produced by means of extrusion-based additive manufacturing, also known as fused filament fabrication, are prone to detaching from the build platform due to their strong tendency to shrink and warp. Apart from incorporating high volume fractions of fillers, one approach to mitigate this issue is to improve the adhesion between the first deposited layer and the build platform. However, a major challenge for PP is the lack of adhesion on standard platform materials, as well as a high risk of welding on PP-based platform materials. This study reports the material selection of build platform alternatives based on contact angle measurements. The adhesion forces, investigated by shear-off measurements, between PP-based filaments and the most promising platform material, an ultra-high-molecular-weight polyethylene (UHMW-PE), were optimised by a thorough parametric study. Higher adhesion forces were measured by increasing the platform and extrusion temperatures, increasing the flow rate and decreasing the thickness of the first layer. Apart from changes in printer settings, an increased surface roughness of the UHMW-PE platform led to a sufficient, weld-free adhesion for large-area parts of PP-based filaments, due to improved wetting, mechanical interlockings, and an increased surface area between the two materials in contact.

Within this research the effect of injection molding temperature on polypropylene (PP)/poly(ethylene terephthalate) (PET) blends and microfibrillar composites was investigated. Injection molding blends (IMBs) and microfibrillar composites (MFCs) of PP/PET have been prepared in a weight ratio 70/30. The samples were processed at three different injection molding temperatures (T_im) (210, 230, 280 °C) and subjected to extensive characterization. The observations from the fracture surfaces of MFCs showed that PET fibers can be achieved by three step processing. The results indicated that T_im has a big influence on morphology of IMBs and MFCs. With increasing the T_im, distinctive variations in particle and fiber diameters were noticed. The differences in mechanical performances were obtained by flexural and impact tests. Establishing relationships between the processing parameters, properties, and morphology of composites is of key importance for the valorization of MFC polymers.

Recent development in the field of additive manufacturing, also known as three-dimensional (3D) printing, has allowed for the incorporation of continuous fiber reinforcement into 3D-printed polymer parts. These fiber reinforcements allow for the improvement of the mechanical properties, but compared to traditionally produced composite materials, the fiber volume fraction often remains low. This study aims to evaluate the in-nozzle impregnation of continuous aramid fiber reinforcement with glycol-modified polyethylene terephthalate (PETG) using a modified, low-cost, tabletop 3D printer. We analyze how dimensional printing parameters such as layer height and line width affect the fiber volume fraction and fiber dispersion in printed composites. By varying these parameters, unidirectional specimens are printed that have an inner structure going from an array-like to a continuous layered-like structure with fiber loading between 20 and 45 vol%. The inner structure was analyzed by optical microscopy and Computed Tomography (µCT), achieving new insights into the structural composition of printed composites. The printed composites show good fiber alignment and the tensile modulus in the fiber direction increased from 2.2 GPa (non-reinforced) to 33 GPa (45 vol%), while the flexural modulus in the fiber direction increased from 1.6 GPa (non-reinforced) to 27 GPa (45 vol%). The continuous 3D reinforced specimens have quality and properties in the range of traditional composite materials produced by hand lay-up techniques, far exceeding the performance of typical bulk 3D-printed polymers. Hence, this technique has potential for the low-cost additive manufacturing of small, intricate parts with substantial mechanical performance, or parts of which only a small number is needed.