Spinning of cellulose nanofibrils (CNF) offers promising opportunities to develop renewable fibers and filaments with strong, aligned structure. This review introduces recent findings on the relationship between the properties of CNF hydrogels, the spinning conditions and the performance of filaments obtained by dry- and wet-spinning. For example, the filament Young’s modulus correlates with CNF structural factors, such as slenderness and crystallinity. Furthermore, high shear rates and extensional flow strengthen the filament, mainly by improving structural uniformity and partly by effectively orienting the fibrils. However, other less obvious factors, such as those associated with coagulation and drying, play critical roles in filament performance. These and other details related to this timely application of CNF are presented here for the benefit of researchers and users of fibers and filaments for composites, textiles and others.

Multiphase (emulsion) gels with internal phase fractions between 0.1 and 0.5 were formulated at low loadings of cellulose nanofibrils (CNF), alginate and polylactide (PLA). Their properties (rheology and morphology) fitted those of inks used for direct ink writing (DIW). The effect of formulation and composition variables were elucidated after printing cubic scaffolds and other solid designs. The distinctive microstructures that were developed allowed high printing fidelity and displayed limited shrinkage after room temperature and freeze drying (0 and 5% shrinkage in the out-of-plane and in-plane directions upon freeze drying, respectively). The CNF added in the continuous phase was shown to be critical to achieve rheology control, as an effective interfacial stabilizer and to ensure the printability of the ink toward high structural reliability.We found that the extent of shape retention of the dried scaffolds resulted from the tightly locked internal structure. The PLA that was initially added in the non-polar or organic phase (0 to 2 12%), was randomly embedded in the entire scaffold, providing a strong resistance to shrinkage during the slow water evaporation at ambient temperature. No surface collapse or lateral deformation of the dried scaffolds occurred, indicating that the incorporation of PLA limited drying-induced shape failure. It also reduced compression strain by providing better CNF skeletal support, improving the mechanical strength.Upon re-wetting, the combination of the hydrophilicity imparted by CNF and alginate together with the highly porous structure of the 3D material and the internal micro-channels contributed to high water absorption via capillary and other phenomena (swelling % between ~400 and 900 %). However, no shape changes occurred compared to the initial 3D-printed shape. The swelling of the scaffolds correlated inversely with the PLA content in the precursor emulsion gel, providing a means to regulate the interaction with water given its low surface energy.Overall, the results demonstrate that by compatibilization of the CNF-based hydrophilic and the PLA-based hydrophobic components, it is possible to achieve shape control and retention upon 3D printing, opening the possibility of adopting low-solids inks for DIW into dry objects. The dryable CNF-based 3D structural materials absorb water while being able to support load (high elastic modulus) and maintain the shape upon hydration.

A continuous and scalable method for the wet spinning of cellulose nanofibrils (CNFs) is introduced in a core/shell configuration. Control on the interfacial interactions was possible by the choice of the shell material and coagulant, as demonstrated here with guar gum (GG) and cellulose acetate (CA). Upon coagulation in acetone, ethanol, or water, GG and CA formed supporting polymer shells that interacted to different degrees with the CNF core. Coagulation rate was shown to markedly influence the CNF orientation in the filament and, as a result, its mechanical strength. The fastest coagulation noted for the CNF/GG core/shell system in acetone led to an orientation index of ∼0.55 (Herman’s orientation parameter of 0.40), Young’s modulus of ∼2.1 GPa, a tensile strength of ∼70 MPa, and a tenacity of ∼8 cN/tex. The system that underwent the slowest coagulation rate (CNF/GG in ethanol) displayed a limited CNF orientation but achieved an intermediate level of mechanical resistance, owing to the strong core/shell interfacial affinity. By using CA as the supporting shell, it was possible to spin CNF into filaments with high water absorption capacity (43 g water/g dry filament). This was explained by the fact that water (used as the coagulant for CA) limited the densification of the CNF core structure, yielding filaments with high accessible area and pore density.

The aim of the present study was to investigate the additive manufacturing process for high consistency nanocellulose. Unlike thermoformable plastics, wood derived nanocelluloses are typically processed as aqueous dispersions because they are not melt-processable on their own. The ability to use nanocellulose directly in additive manufacturing broadens the possibilities regarding usable raw materials and achievable properties thereof. Modern additive manufacturing systems are capable of depositing nanocellulose with micrometer precision, which enables the printing of accurate three-dimensional wet structures. Typically, these wet structures are produced from dilute aqueous fibrillar dispersions. As a consequence of the high water content, the structures deform and shrink during drying unless the constructs are freeze-dried. While freeze-drying preserves the geometry, it results in high porosity which manifests as poor mechanical and barrier properties. Herein, we study an additive manufacturing process for high consistency enzymatically fibrillated cellulose nanofibers in terms of printability, shape retention, structure, and mechanical properties. Particular emphasis is placed on quantitative shape analysis based on 3D scanning, point cloud analysis, and x-ray microtomography. Despite substantial volumetric as well as anisotropic deformation, we demonstrate repeatability of the printed construct and its properties.

Three-dimensional (3D) printing of biomaterials has the potential to become an ecologically advantageous alternative compared with conventional manufacturing based on oil-derived polymer materials. In this study, a novel 3D printing technology is applied that combines ultraviolet (UV) curing with paste extrusion. This hybrid manufacturing technique enables the fabrication of complex geometries from high filler-ratio pastes. The developed biocomposite aims for suitable mechanical properties in terms of tensile and compressive strength. It is composed of acrylic acid, cellulose acetate, a-cellulose, and fumed silica with a cellulose ratio of more than 25 vol-%. The material is extruded with an in-house-developed 3D printer equipped with a 12 W UV light curing source, which enables concurrent curing and extrusion. Two different UV-curing strategies were tested: postcuring without concurrent curing and postcuring with concurrent curing. The total UV-curing duration was kept constant with all samples. Tensile testing in accordance with ASTM standard D638-14 Type 4, compression testing according to ASTM D695-15, and overhang tests were conducted. As a result, samples without notable shrinkage, suitable tensile strength (up to 17.72 MPa), competitive compression testing parameters (up to 19.73 MPa), and an enhanced overhang angle (increase of more than 25°) were produced, leading to new applications and more freedom in design due to higher possible unsupported overhangs when using UV-curing during the print. Overall, constant UV light radiation during the print leads to improved mechanical properties due to the possibility of bypassing the UV-penetration depth constraint. It should be considered when extruding photopolymer-based composites, especially for large and complex components with a low degree of translucency.