Direct-ink-writable nanocellulose ternary hydrogels via one-pot gelation with alginate and calcium montmorillonite

Nanocellulose hydrogels are promising to replace synthetic ones for direct ink writing (DIW)-based 3D printing biobased applications. However, less gelation strength and low solid content of the hydrogels limit the printability and subsequent fidelity of the dried object. Herein, a biobased, ternary DIW hydrogel ink is developed by one-pot gelation of cellulose nanofibrils (CNF), sodium alginate (SA), and Ca-montmorillonite (Ca-MMT) via in situ ionic crosslinking. The addition of Ca-MMT into CNF/SA formulation simultaneously increases the solid content and gelation strength of the hydrogel. The resultant hydrogels exhibit shape recovery after compression. The optimal CNF concentration in the hydrogel is 1.2 wt%, enabling the highest compressive mechanical performance of the scaffolds. A series of complex, customized shapes with different curvatures and three-dimensional structures (e.g., high-curvature letters, pyramids, human ears, etc.) can be printed with high fidelity before and after drying. This study opens an avenue on preparing nanocellulose-based DIW hydrogel inks using one-pot gelation of the components, which offers a solution to combine DIW-based 3D printing with biobased hydrogel inks, towards diverse biobased applications.