Ink Based on the Tunable Swollen Microsphere for a 3D Printing Hydrogel with Broad-Range Mechanical Properties

The development of the effective 3D printing strategy for diverse functional monomers is still challenging. Moreover, the conventional 3D printing hydrogels are usually soft and fragile due to the lack of an energy dissipation mechanism. Herein, a microsphere mediating ink preparation strategy is developed to provide tailored rheological behavior for various monomer direct ink writings. The chitosan microspheres are used as an exemplary material due to their tunable swelling ratio under the acid-drived electrostatic repulsion of the protonated amino groups. The rheological behaviors of the swollen chitosan microsphere (SCM) are independent on the monomer types, and various functional secondary polymers could be carried at a wide loading ratio by the acid driving. The SCM reinforces the hydrogel as the sacrificial bonds. With the adjustable composition, the 3D printing hydrogel mechanical properties are tunable in wide windows: strength (0.4–1.01 MPa), dissipated energy (0.11–3.25 MJ m^–3), and elongation at break (47–626%). With the excellent printing and mechanical properties, the SCM inks enable multi-functional integration for soft device production, such as 4D printing robots and wearable strain sensors. We anticipate that this microsphere mediating 3D printing strategy can inspire new possibilities for the design of the robust hydrogels with a broad range of functionalities and mechanical performances.