Entropy‐Mediated Polymer–Cluster Interactions Enable Dramatic Thermal Stiffening Hydrogels for Mechanoadaptive Smart Fabrics

Thermal stiffening materials that are naturally soft but adaptively self-strengthen upon heat are intriguing for load-bearing and self-protection applications at elevated temperatures. However, to simultaneously achieve high modulus change amplitude and high mechanical strength at the stiffened state remains challenging. Herein, entropy-mediated polymer-mineral cluster interactions are exploited to afford thermal stiffening hydrogels with a record-high storage modulus enhancement of 13 000 times covering a super wide regime from 1.3 kPa to 17 MPa. Such a dramatic thermal stiffening effect is ascribed to the transition from liquid-liquid to solid-liquid phase separations, and at the molecular level, driven by enhanced polymer-cluster interactions. The hydrogel is further processed into sheath-core fibers and smart fabrics, which demonstrate self-strengthening and self-powered sensing properties by co-weaving another liquid metal fiber as both the joule heater and triboelectric layer.