In this work, we present an approach to cross-link cellulose nanofibrils (CNFs) with various metallic cations (Fe³⁺, Al³⁺, Ca²⁺, and Mg²⁺) to produce inks suitable for three-dimensional (3D) printing application. The printability of each hydrogel ink was evaluated, and several parameters such as the optimal ratio of Mⁿ⁺:TOCNF:H₂O were discussed. CNF suspensions were produced by mechanical disintegration of cellulose pulp with a microfluidizer and then oxidized with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). Finally, metal cations were introduced to the deprotonated TEMPO-oxidized CNF (TOCNF) suspension to cross-link the nanofibrils and form the corresponding hydrogels. The performances of each gel-ink were evaluated by rheological measurements and 3D printing. Only the gels incorporated with divalent cations Ca²⁺ and Mg²⁺ were suitable for 3D printing. The 3D printed structures were freeze-dried and characterized with Fourier transform infrared spectroscopy (FT-IR) and Scanning Electron Microscopy (SEM). The better interaction of the TOCNFs with the divalent metallic cations in terms of printability, the viscoelastic properties of the inks, and the variation trends owing to various metal cations and ratios are discussed.

This work aims to produce a 3D-printable bio-based filament composed of high-density polyethylene (HDPE) and chemically modified cellulose nanofibrils. Printing using HDPE as a raw material is challenging due to its massive shrinkage and warping problems. This paper presents a new method to overcome those difficulties by enhancing the mechanical properties and achieving better print quality. This was achieved using modified cellulose nanofibrils (CNFs) as fillers. Firstly, CNF was converted to a CNF-based macroinitiator through an esterification reaction, followed by a surface-initiated single-electron transfer living radical polymerization (SI-SET-LRP) of the hydrophobic monomer stearyl acrylate. Poly stearyl acrylate-grafted cellulose nanofibrils, CNF-PSAs, were synthesized, purified and characterized with ATR-FTIR, ¹³C CP-MAS NMR, FE-SEM and water contact angle measurements. A composite was successfully produced using a twin-screw extruder with a CNF-PSA content of 10 wt.%. Mechanical tests were carried out with tensile testing. An increase in the mechanical properties, up to 23% for the Young’s modulus, was observed. A morphologic analysis also revealed the good matrix/CNF compatibility, as no CNF aggregates could be observed. A reduction in the warping behavior for the composite filament compared to HDPE was assessed using a circular arc method. The 3D printing of complex objects using the CNF-PSA/HDPE filament resulted in better print quality when compared to the object printed with neat HDPE. Therefore, it could be concluded that CNF-PSA was a suitable filler for the reinforcement of HDPE, thus, rendering it suitable for 3D printing.

The growing interest in gel-based additive manufacturing, also known as three-dimensional (3D) gel-printing technology, for research underscores the crucial need to develop robust biobased materials with excellent printing quality and reproducibility. The main focus of this study is to prepare and characterize some composite gels obtained with a low-molecular-weight gelling (LMWG) peptide called Fmoc-diphenylalanine (Fmoc-FF) and two types of cellulose nanofibrils (CNFs). The so-called Fmoc-FF peptide has the ability to self-assemble into a nanowire shape and therefore create an organized network that induces the formation of a gel. Despite their ease of preparation and potential use in biological systems, unfortunately, those Fmoc-FF nanowire gel systems cannot be 3D printed due to the high stiffness of the gel. For this reason, this study focuses on composite materials made of cellulose nanofibrils and Fmoc-FF nanowires, with the main objective being that the composite gels will be suitable for 3D printing applications. Two types of cellulose nanofibrils are employed in this study: (1) unmodified pristine cellulose nanofibrils (uCNF) and (2) chemically modified cellulose nanofibrils, which ones have been grafted with polymers containing the Fmoc unit on their backbone (CNF-g-Fmoc). The obtained products were characterized through solid-state cross-polarization magic angle-spinning ¹H NMR and confocal laser scanning microscopy. Within these two CNF structures, two composite gels were produced: uCNF/Fmoc-FF and CNF-g-Fmoc/Fmoc-FF. The mechanical properties and printability of the composites are assessed using rheology and challenging 3D object printing. With the addition of water, different properties of the gels were observed. In this instance, CNF-g-Fmoc/Fmoc-FF (c = 5.1%) was selected as the most suitable option within this product range. For the composite bearing uCNF, exceptional print quality and mechanical properties are achieved with the CNF/Fmoc-FF gel (c = 5.1%). The structures are characterized by using field emission scanning electron microscopy (FESEM) and small-angle X-ray scattering (SAXS) measurements.