Robust and self-healable nanocomposite physical hydrogel facilitated by the synergy of ternary crosslinking points in...

Acrylamide (AM) and a small amount of stearyl methacrylate (C18) hydrophobic monomer copolymerize to graft on the surface of vinyl hybrid silica nanoparticles (VSNPs), forming nanobrush gelators, thereby constructing ternarily crosslinked nanocomposite physical hydrogels (TC-NCP gels). The TC-NCP gel is composed of a single network ternarily crosslinked by hydrogen bonds and hydrophobic interactions among the grafting polymer chains as physical cross-linking points and thus the polymer grafted VSNPs as analogous covalent crosslinking points. Under stretching, the physical crosslinking points successively break to gradually dissipate energy and then recombine to homogenize the network. During the stretching process, the polymer chains grafted VSNPs can homogenize the stress distribution as transferring centers. The synergy of the ternary crosslinking points leads the TC-NCP gels to dissipate more energy and redistribute the stress more effectively when compared with hydrogels dually crosslinked by both hydrogen bonds and VSNPs as analogous covalent crosslinking points (without hydrophobic interactions) and by both hydrogen bonds and hydrophobic interactions (without VSNPs). As a result, the TC-NCP gels demonstrate remarkably improved mechanical properties, including tensile strength of 256 kPa, stretch ratio at break of 28.23 and toughness of 1.92 MJ m^-3 at a water content of 90%. Pure shear test shows that the TC-NCP gel is able to resist notch propagation by micro-crack development from the notch tip to the whole gel network and has a high tearing energy of 1.21 × 10⁴ J m^-2. The dynamic nature of the network endows the TC-NCP gels with excellent self-healing ability. The results evidently indicate that constructing a single gel network with hierarchical crosslinking points is a versatile method to fabricate robust hydrogels.