Enhance Fracture Toughness and Fatigue Resistance of Hydrogels by Reversible Alignment of Nanofibers

Biological tissues, such as heart valve, tendon, etc., possess excellent mechanical properties, which arises from their inherent anisotropic arrangement of soft and hard phases. Inspired by the anisotropic structures, many methods have been developed to synthesize hydrogels that can achieve mechanical properties comparable to biological tissues. Here, we describe a new method to enhance fracture toughness and fatigue resistance of hydrogels by introducing nanofibers which can reversibly align with elastic deformation to form an anisotropic structure. As a demonstration, we introduce stiff, rod-like cellulose nanocrystals (CNCs) into a polyacrylamide (PAAm) network. CNCs aggregate into clusters to form hard phases and entangle with the PAAm network. The CNC/PAAm composite hydrogel is initially isotropic, becomes anisotropic upon loading, and recovers to be isotropic upon unloading. During the deformation, the aligned CNC clusters at the crack tip can transmit the stress over the size of the cluster, effectively resisting crack growth. We use photoelasticity and small-angle X-ray scattering (SAXS) tests to observe the change of microstructures associated with deformation. The fracture toughness of CNC/PAAm hydrogels with different sizes of CNCs can reach 1000 J/m². The fatigue threshold is about 100 J/m², an order of magnitude higher than that of PAAm hydrogel. This work provides a simple and general method to strengthen hydrogels under both monotonic and cyclic loads.