Mechano-responsive hydrogen-bonding array of thermoplastic polyurethane elastomer captures both strength and self-healing

Self-repairable materials strive to emulate curable and resilient biological tissue; however, their performance is currently insufficient for commercialization purposes because mending and toughening are mutually exclusive. Here, we report a carbonate-type thermoplastic polyurethane elastomer that self-heals at 35 °C and is as strong as footwear elastomers. This elastomer exhibits the highest tensile strength to date (43 MPa). Distinctively, it has abundant carbonyl groups in soft-segments and is fully amorphous with negligible phase separation due to poor hard-segment stacking. It operates in dual mechano-responsive mode through a reversible disorder-to-order transition of its hydrogen-bonding array; it heals when static and toughens when dynamic. In static mode, non-crystalline hard segments promote dynamic exchange of disordered carbonyl hydrogen-bonds for self-healing. The amorphous phase forms stiff crystals when stretched through a transition that orders inter-chain hydrogen bonding. The phase and strain fully return to the pre-stressed state after release to repeat healing process.