Low Solids Emulsion Gels Based on Nanocellulose for 3D-Printing.

Abstract

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 nonpolar or organic phase (0 to 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 rewetting, the combination of the hydrophilicity imparted by CNF and alginate together with the highly porous structure of the 3D material and the internal microchannels 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.