Strong, Fast-Response Printable Lignin/PNIPAM Thermo-Responsive Hydrogel via Hierarchical Phase Separation

Stimuli-responsive hydrogels have gained significant attention as one of the most attractive materials for soft robots. Herein, a facile, printable thermo-responsive hydrogel (NL hydrogel) with rapid volume change capability and excellent mechanical properties was developed through the self-assembly of poly(N-isopropylacrylamide) (PNIPAM) and hydrophobic lignin. The lignin and PNIPAM self-assembled into a hierarchical phase-separated structure consisting of lignin-rich dense regions with a bicontinuous morphology and PNIPAM-rich, chain-sparse regions. This unique architecture results in multiscale water channels, enabling an ultrafast dehydration response (expelling 90% of its water within 10 s) and an ultrahigh volume shrinkage of up to 96.4% above its lower critical solution temperature (LCST). The phase separation structure also endows the NL hydrogels with outstanding mechanical properties, achieving tensile stress and strain values exceeding 1 MPa and 500% below the LCST, and approximately 5 MPa and 1500% above the LCST. The responsive speed and mechanical properties of the NL hydrogels surpass those of most reported thermo-responsive hydrogels. The NL hydrogels can be readily printed via direct ink writing into various geometries. The printed NL hydrogels demonstrate thermo-triggered shape morphing, functioning as temperature-controlled actuators with adjustable curvature and as manipulators for capture, wrapping, encapsulation, and switching. Furthermore, the photothermal effect of lignin enables light-controlled actuation of the NL hydrogel.