Hierarchical Supramolecular Cross-Linking of Polymers for Biomimetic Fracture Energy Dissipating Sacrificial Bonds and Defect Tolerance under Mechanical Loading

Biological structural materials offer fascinating models how to synergistically increase the solid-state defect tolerance, toughness, and strength using nanocomposite structures by incorporating different levels of supramolecular sacrificial bonds to dissipate fracture energy. Inspired thereof, we show how to turn a commodity acrylate polymer, characteristically showing a brittle solid state fracture, to become defect tolerant manifesting noncatastrophic crack propagation by incorporation of different levels of fracture energy dissipating supramolecular interactions. Therein, poly­(2-hydroxyethyl methacrylate) (pHEMA) is a feasible model polymer showing brittle solid state fracture in spite of a high maximum strain and clear yielding, where the weak hydroxyl group mediated hydrogen bonds do not suffice to dissipate fracture energy. We provide the next level stronger supramolecular interactions toward solid-state networks by postfunctionalizing a minor part of the HEMA repeat units using 2-ureido-4­[1<i>H</i>]-pyrimidinone (UPy), capable of forming four strong parallel hydrogen bonds. Interestingly, such a polymer, denoted here as p­(HEMA-<i>co</i>-UPyMA), shows toughening by suppressed catastrophic crack propagation, even if the strength and stiffness are synergistically increased. At the still higher hierarchical level, colloidal level cross-linking using oxidized carbon nanotubes with hydrogen bonding surface decorations, including UPy, COOH, and OH groups, leads to further increased stiffness and ultimate strength, still leading to suppressed catastrophic crack propagation. The findings suggest to incorporate a hierarchy of supramolecular groups of different interactions strengths upon pursuing toward biomimetic toughening.