Structure-property relations in rheology of cellulose nanofibrils-based hydrogels

Hydrogels prepared from self-assembled cellulose nanofibrils (CNFs) are widely used in biomedicine, electronics and environmental technology. Their ability to serve as inks for extrusion-based 3D printing is conventionally evaluated by means of rheological tests. A model is developed that describes the response of CNF gels in small- and large-amplitude oscillatory tests in a unified manner. The model involves a reasonably small number of material parameters, ensures good agreement between results of simulation and observations in oscillatory tests and correctly predicts the stress-strain Lissajous curves, experimental data in hysteresis loop tests, and measurements of the steady-state viscosity. The model is applied to analyze how composition and preparation conditions for CNF gels affect transition from shear thinning to weak strain overshoot in large-amplitude shear oscillatory tests. Based on the model, simple relations are derived for the fractal dimension of CNF clusters and the storage modulus of gels prepared in aqueous solutions of multivalent salts. The validity of these equations is confirmed by comparison of their predictions with observations in independent tests.