Development of Thermoinks for 4D Direct Printing of Temperature‐Induced Self‐Rolling Hydrogel Actuators

Abstract 4D printing has emerged as an important technique for fabricating 3D objects from programmable materials capable of time‐dependent reshaping. In the present investigation, novel 4D thermoinks composed of laponite (LAP), an interpenetrating network of poly( N ‐isopropylacrylamide) (PNIPAAm), and alginate (ALG) are developed for direct printing of shape‐morphing structures. This approach consists of the design and fabrication of 3D honeycomb‐patterned hydrogel discs self‐rolling into tubular constructs under the stimulus of temperature. The shape morphing behavior of hydrogels is due to shear‐induced anisotropy generated via 3D printing. The compositionally tunable hydrogel discs can be programmed to exhibit different actuation behaviors at different temperatures. Upon immersion in 12 °C water, singly crosslinked sheets roll up into a tubular construct. When transferred to 42 °C water, the tubes first rapidly unfold and then slightly curve up in the opposite direction. Through a dual photocrosslinking of PNIPAAm, it is possible to inverse temperature‐dependent shape morphing and induce self‐folding at higher and unrolling at lower temperatures. The extensive self‐assembling motion is essential to developing thermal actuators with broad applications in, e.g., soft robotics and active implantology, whereas controllable self‐rolling of planar hydrogels is of the highest interest to biomedical engineering as it allows for effective fabrication of hollow tubes.