Supramolecular cross-linking affords chitin nanofibril nanocomposites with high strength and water resistance

Polysaccharide nanofibrils of chitins or celluloses are emerging biobased building blocks for sustainable, high-performance bioinspired nanocomposites fusing high stiffness, strength, and other functionalities. Owing to their hygroscopicity, a crucial challenge towards real-life applications of these nanocomposites is to maintain their mechanical performances in the humid or even fully swollen conditions. Here, we report water resistant nanocomposites composed of sustainable chitin nanofibrils (ChNFs) and polyvinyl alcohol (PVA) that are physically cross-linked by tannic acid (TA) to enhance and stabilize wet mechanical properties. We demonstrate that the formation of polymer-coated core/shell nanofibrils at the intermediate stage is crucial for the well-defined nanopaper structures after casting. By infiltrating TA, the formation of hydrogen bonding in the PVA matrix and at the ChNF/PVA interface renders the nanocomposites with extremely high strength and stiffness, even under high humidity and swelling conditions. With the increase in the amount of conjugated TA, the Young's modulus and tensile strength of the swollen nanocomposites reach up to 3.0 GPa and 70 MPa, respectively, which are superior to the existing water-borne nanofibils/polymer nanocomposites. Moreover, the nanocomposite films show excellent gas barrier properties at high relative humidity (90%), as well as UV shielding, antibacterial properties and biodegradability, complementing the multifunctional property profile and allowing a transfer into applications as advanced packaging materials.