New 3D Ink Formulation Comprising a Nanocellulose Aerogel Based on Electrostatic Repulsion and Sol-Gel Transition.

New 3D printing aerogel materials are environmentally friendly and could be used in environmental protection and biomedical fields. There is significant research interest in 3D printing cellulose-based aerogels since cellulose materials are biocompatible and are abundant in nature. The gel-like nature of the cellulose water suspension is suitable for 3D printing; however, the complexity and resolution of the geometry of aerogels are quite limited, mainly due to the inks' low viscosity that fails to maintain the integrity of the shape after printing. To address this limitation, a carefully optimized formulation incorporating three key ingredients, i.e., nanofibrils (TEMPO-CNFs), 2,2,6,6-tetramethyl-1-piperidinyloxy modified cellulose nanocrystals (TEMPO-CNC), and sodium carboxymethyl cellulose (CMC), is utilized to enhance the viscosity and structural stability of the ink. This combination of cellulose derivatives utilizes the electrostatic repulsive forces between the negatively charged components to form a stable and uniformly distributed suspension of cellulose materials. Our ink formulations improve printability and shape retention during 3D printing and are optimal for DIW printing. We print by employing an all cellulose-based composite ink using a modified direct ink writing (DIW) 3D printing method, plus an in situ freezing stage to form a layer-by-layer structure, and then follow a freeze-drying process to obtain the well-aligned aerogels. We have investigated the rheological properties of the ink formulation by varying the concentration of these three cellulose materials. The obtained aerogels exhibit highly ordered microstructures in which the micropores are well-aligned along the freezing direction. This study demonstrates a strategy for overcoming the challenges of 3D printing cellulose-based aerogels by formulating a stable composite ink, optimizing its rheological properties, and employing a modified DIW printing process with in situ freezing, resulting in highly ordered, structurally robust aerogels with aligned microporous architectures.