Mechanically Viscoelastic Properties of Cellulose Nanocrystals Skeleton Reinforced Hierarchical Composite Hydrogels

With inspiration from the concept of natural dynamic materials, binary-component composite hydrogels with excellent mechanical properties and recovery capability were prepared from the cellulose nanocrystal (CNC) skeleton reinforced covalently cross-linked polyacrylamide (PAAm) networks. The hierarchical skeleton obtained by freeze-drying of CNC aqueous suspension was directly impregnated into acrylamide (AAm) monomer solution, and in situ polymerization occurred in the presence of hydrophilic cross-linker PEGDA575. Under stress, hydrogen bonds at the interface between CNC and PAAm as well as inside the CNC skeleton acted as sacrificial bonds to dissipate energy, while the covalently cross-linked PAAm chains bind the network together by providing adhesion to CNC and thereby suppress the catastrophic craze propagation. The above synergistic effects of the CNC skeleton and the elastic PAAm network enabled the composite hydrogels to withstand up to 181 kPa of tensile stress, 1.01 MPa of compressive strength, and 1392% elongation at break with the fracture energy as high as 2.82 kJ/m(2). Moreover, the hydrogels recovered more than 70% elasticity after eight loading-unloading cycles, revealing excellent fatigue resistance. The depth-sensing instrumentation by indentation test corroborated that the CNC skeleton contributed simultaneous improvements in hardness and elasticity by as much as 500% in comparison with the properties of the pristine PAAm hydrogels. This elegant strategy by using the CNC skeleton as a reinforcing template offers a new perspective for the fabrication of robust hydrogels with exceptional mechanical properties that may be important for biomedical applications where high strength is required, such as scaffolds for tissue engineering.