Additive manufacturing, especially material extrusion (MEX), has received a lot of attention recently. The reasons for this are the numerous advantages compared to conventional manufacturing processes, which result in various new possibilities for product development and -design. By applying material layer by layer, parts with complex, load-path optimized geometries can be manufactured at neutral costs. To expand the application fields of MEX, high-strength and simultaneously lightweight materials are required which fulfill the requirements of highly resilient technical parts. For instance, the embedding of continuous carbon and flax fibers in a polymer matrix offers great potential for this. To achieve the highest possible variability with regard to the material combinations while ensuring simple and economical production, the fiber–matrix bonding should be carried out in one process step together with the actual parts manufacture. This paper deals with the adaptation and improvement of the 3D printer on the one hand and the characterization of 3D printed test specimens based on carbon and flax fibers on the other hand. For this purpose, the print head development for in-situ processing of contin uous fiber-reinforced parts with improved mechanical properties is described. It was determined that compared to neat polylactic acid (PLA), the continuous fiber-reinforced test specimens achieve up to 430% higher tensile strength and 890% higher tensile modulus for the carbon fiber reinforcement and an increase of up to 325% in tensile strength and 570% in tensile modulus for the flax fibers. Similar improvements in performance were achieved in the bending tests.

Sugar beet residues (SBR) were converted into thermomechanical pulp (sugar beet pulp, SBP) and compounded with either polylactic acid (PLA) or high‐density polyethylene (HDPE) as matrix. Pressed, thin sheets made with the compounds were placed on soil for 16 weeks outdoors and changes in material properties, including weight losses, monitored. Chloroform extraction showed that proportionally more SBP than PLA was degraded after biodegradation. A reduction in molecular weight of the PLA in composites during processing was determined, which was attributed to moisture in SBP and led to PLA hydrolysis. No further significant reduction in molecular weight of the PLA in composites occurred during outdoor exposure. In case of the HDPE‐SBP composites, results of acid hydrolysis indicated that primarily, the SBP component was degraded. Tensile strength tests, microscopy, FT‐IR spectroscopy and thermal analyses were also performed with the composites. Under the conditions of this study, it was shown that PLA composites with 70% (wt.) of SBP were completely disintegrated before completion of 12 weeks exposure. The addition of SBP to PLA accelerates biodegradation significantly which is an asset for agricultural (mulch films), forestry, horticulture and packaging applications. Highlights: Degradation of composites based on SBP with PLA or HDPE matrix was evaluated on soil Addition of SBP increased weight loss, irrespective of the matrix type during the degradation tests Differences in material composition over exposure time were analyzed Combination of SBP with PLA enhances biodegradability of composites SBP offers huge potential as filler in biodegradable polymer composites

Oil-in-water emulsions stabilized using cellulose nanofibrils (CNF) form extremely stable and high-volume creaming layers which do not coalesce over extended periods of time. The stability is a result of the synergistic action of Pickering stabilization and the formation of a CNF percolation network in the continuous phase. The use of methyl cellulose (MC) as a co-emulsifier together with CNF further increases the viscosity of the system and is known to affect the droplet size distribution of the formed emulsion. Here, we utilize these highly stable creaming layer systems for in situ polymerization of styrene with the aim to prepare an emulsion-based dope for additive manufacturing. We show that the approach exploiting the creaming layer enables the effortless water removal yielding a paste-like material consisting of polystyrene beads decorated with CNF and MC. Further, we report comprehensive characterization that reveals the properties and the performance of the creaming layer. Solid-state NMR measurements confirmed the successful polymerization taking place inside the nanocellulosic network, and size exclusion chromatography revealed average molecular weight (M_w) of polystyrene as approximately 700,000 Da. Moreover, the amount of the leftover monomer was found to be less than 1% as detected by gas chromatography. The dry solids content of the paste was ∼20% which is a significant increase compared to the solids content of the original CNF dispersion (1.7 wt%). The shrinkage of the CNF, MC and polystyrene structures upon drying—an often-faced challenge—was found to be acceptable for this composite containing highly hygroscopic biobased materials. At best, the two dimensional shrinkage was no more than ca. 20% which is significantly lower than the shrinkage of pure CNF being as high as 50%. The paste, which is a composite of biobased materials and a synthetic polymer, was demonstrated in direct-ink-writing to print small objects. With further optimization of the formulation, we find the emulsion templating approach as a promising route to prepare composite materials.

The effectiveness of maleated polypropylene (MAPP) in emulsified form for the pre-treatment of thermo-mechanical pulp (TMP) before extrusion with polypropylene fibres was evaluated. MAPP in pellet form, which was applied during the compounding step, served as a benchmark. In addition, commercial softwood flour was included as a reference. The influence of the temperature during the defibration process and the presence or absence of the coupling agent on composite performance were evaluated. Composites were processed with a high wood content of 70 wt.%, which is common for extruded profiles. It was found that TMP based on Robinia (Robinia pseudoacacia L.) conferred higher strength properties to the composites compared to TMP based on Scots pine (Pinus sylvestris L.), which was attributed to the higher length/diameter ratio of fibres in Robinia. However, under the conditions of this study, strength properties were superior and water uptake and swelling were reduced when wood flour was used instead of TMP. On the other hand, in many formulations, larger improvements in flexural and tensile strength due to MAPP were found for the TMP-based composites compared to the wood flour-based composites. This could be due to the larger surface/volume ratio for TMP compared to wood flour and more efficient stress transfer from fibres to the matrix. Results from X-ray photoelectron spectroscopy (XPS) showed that TMP surfaces were more hydrophobic than wood flour due to coverage with lignin, which reduced the effectiveness of MAPP. Esterification between the emulsified MAPP and fibre surfaces was determined using Fourier-Transform Infrared (FTIR) spectroscopy, but some non-activated maleic anhydride remained. Under the conditions of this study, MAPP added during compounding provided better performance compared to MAPP which included a non-ionic emulsifier and which was added during the refining process. Lower temperature (150 °C) during defibration was shown to be beneficial for the strength properties of composites compared to high temperature (180 °C) when MAPP was included in the formulations.