3D Printable Hybrid Gel Made of Polymer Surface-Modified Cellulose Nanofibrils Prepared by Surface-Initiated Controlled Radical Polymerization (SI-SET-LRP) and Upconversion Luminescent Nanoparticles.

A cellulose nanofibril-based hybrid gel material was developed by grafting the polymerized stearyl acrylate (PSA) and upconversion nanoparticles (UCNPs) onto cellulose nanofibrils (CNFs) via Cu0-mediated radical polymerization (SET-LRP) to create a highly cross-linked CNF system. A two-step strategy was exploited to surface-exchange the ligand of the UCNPs from a hydrophobic ligand (oleic acid) to a hydrophilic small-molecule ligand (2-acrylamido-2-methyl-1-propanesulfonic acid, AMPS) and therefore be suitable for SET-LRP. The characteristics and properties of the hybrid material (UCNP-PSA-CNF) were monitored by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), rheology, X-ray diffraction (XRD), and microscopic analysis. Those characterization techniques prove the efficient modification of the CNF, with the presence of 1.8% UCNPs. The luminescence measurement was carried out using a homebuilt confocal microscope with a 980 nm laser source. The nanostructure of UCNPs and their incorporated CNF species were measured by small-angle X-ray scattering (SAXS). In addition, this CNF-based hybrid gel has decisive rheological properties, such as good viscoelasticity (loss tangent was below 0.35 for the UCNP-PSA-CNF gel, while the PSA-CNF gel reached the highest value of 0.42), shear-thinning behavior, and shape retention, and was successfully applied to three-dimensional (3D) gel printing throughout various 3D print models.

3D printing of a bio-based ink made of cross-linked cellulose nanofibrils with various metal cations.

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.