Revealing Strong Nanocomposite Hydrogels Reinforced by Cellulose Nanocrystals: Insight into Morphologies and Interactions

Understanding the reinforcement mechanism by dispersing nanoscale particles into a polymer matrix is a critical challenge toward refining control of the composite properties. In this paper, the morphologies and interactions of cellulose nanocrystal/poly(acrylic acid) (CNC/PAA) nanocomposite hydrogels are demystified based on a facile synthetic platform. Two sources of CNCs with different aspect ratios are applied to model the reinforcement process, and the uniaxial tensile measurements indicate that the CNC aspect ratio and the nanocomposite mechanical behaviors are coupled, where the values of aspect ratios and nonpermanent interactions between the fillers and matrix dominate the reinforcement. Dynamic mechanical analysis is performed to examine the nature of the constrained polymer as the semicrystalline fractions, and the results indicate that polymer chain mobility in the vicinity of CNC surfaces is significantly reduced, providing new insight into the origin of the reinforcement mechanism. Rheological analysis and transmission electron microscopy observations show that both stepwise dissociation and polymer chain rearrangements contribute to the viscoelastic behaviors of the nanocomposite hydrogels. The increased modulus of the hydrogels is correlated to the volume of the constrained polymer, where the CNCs impart significant enhancement to the entanglement network. This study of the structure-property relationship deepens the understanding of the filler reinforcement mechanism and provides valuable knowledge for designing high performance nanocomposite hydrogels from cellulose as a raw material.