Ultrastiff and Tough Supramolecular Hydrogels with a Dense and Robust Hydrogen Bond Network

Design of tough hydrogels has made great progress in the past two decades. However, the synthetic tough gels are usually much softer than some biotissues (e.g., skins with modulus up to 100 MPa). Here we report a new class of ultrastiff and tough supramolecular hydrogels facilely prepared by copolymerization of methacrylic acid and methacrylamide. The gels with water content of approximately 50–70 wt % possessed remarkable mechanical properties, with Young’s modulus of 2.3–217.3 MPa, tensile breaking stress of 1.2–8.3 MPa, breaking strain of 200–620%, and tearing fracture energy of 2.9–23.5 kJ/m2, superior to most existing hydrogels, especially in terms of modulus. Typical yielding and crazing were observed in the gel under tensile loading, indicating the forced elastic deformation of these hydrogels in a glassy state, as confirmed by dynamic mechanical analysis. The ultrahigh stiffness was attributed to the dense cross-linking and reduced segmental mobility caused by the robust intra- and interchain hydrogen bonds. Because of the dynamic nature of noncovalent bonds, these supramolecular gels also showed rate-dependent mechanical performances along with good shape memory and recyclability. This strategy should be applicable for other systems toward robust mechanical properties, versatile functionalities, and promising applications of hydrogel materials as structural elements.