4D Printable Tough and Thermoresponsive Hydrogels.

Hydrogels with attractive stimuli-responsive volume changing abilities are seeing emerging applications as soft actuators and robots. However, many hydrogels are intrinsically soft and fragile for tolerating mechanical damage in real world applications and could not deliver high actuation force because of the mechanical weakness of the porous polymer network. Conventional tough hydrogels, fabricated by forming double networks, dual cross-linking, and compositing, could not satisfy both high toughness and high stimuli responsiveness. Herein, we present a material design of combining responsive and tough components in a single hydrogel network, which enables the synergistic realization of high toughness and actuation performance. We showcased this material design in an exemplary tough and thermally responsive hydrogel based on PVA/(PVA-MA)-g-PNIPAM, which achieved 100 times higher toughness (∼10 MJ/m3) and 20 times higher actuation stress (∼10 kPa) compared to conventional PNIPAM hydrogels, and a contraction ratio of up to 50% simultaneously. The effects of salt concentration, polymer ratio, and structural design on the mechanical and actuation properties have been systematically investigated. Utilizing 4D printing, actuators of various geometries were fabricated, as well as lattice-architected hydrogels with macro-voids, presenting 4 times faster actuation speed compared to bulk hydrogel, in addition to the high toughness, actuation force, and contraction ratio.