Solvent triggered shape morphism of 4D printed hydrogels

4D printing of smart materials is a viable field of research for fabricating dynamic structures for various biomedical applications. 4D printing of hydrogel structures is challenging due to poor printability of hydrogels and poor shape fidelity of printed patterns when direct-ink writing-based 3D printers are used. In this study, chitosan (CS) hydrogel ink cross-linked with citric acid (CA) was made printable, exhibiting a shape-morphing behaviour when exposed to solvent as an external trigger. As one side of a printed structure is exposed to solvent, the solvent diffuses in and a concentration gradient is developed across the section. This concentration gradient results in displacement field, which finally leads to out-of-plane bending of the structure. This actuation is irreversible in nature since the concentration gradient is maintained between hydrophilic chitosan and hydrophobic silane layers. The reversibility of the morphed structures was achieved by dipping them in ethanol, which takes up solvent over time and thus diminishes the concentration gradient.The optimized CS/CA ink exhibited excellent rheological properties, with good extrudability and shape fidelity of printed structures. The chitosan ink was printed into various complex 3D architectures and was modified by hydrophobic coating of trimethyl silane (TMS). These hydrophobic patterns were coated on printed structures with varied interspacing, angles, and hinges to generate programmable designs. A printed soft gripper was demonstrated as an application that could lift an object seven times its weight. The shape morphing CS/CA hydrogel with excellent printability exhibits potential for 4D printing that has wide applications in soft robots, actuators, grippers, and sensors.