Rheology of cellulose nanocrystal and nanofibril suspensions

Nanocellulose is a sustainable nanomaterial and a versatile green platform that has attracted increasing attention. Although the wide applications of its aqueous suspensions are closely related to rheology, comprehensive studies of their rheological behavior, especially the yielding behavior, are still limited. Herein, to investigate the relationship between structure and rheological properties, the viscoelasticity, thixotropy and yielding behavior of two commonly used nanocelluloses, rod-shaped cellulose nanocrystals (CNCs) and filamentous cellulose nanofibrils (CNFs), were systematically investigated. The viscosity, viscoelasticity and thixotropic behavior of the suspensions were analyzed by steady-state shear, frequency sweep, creep-recovery, hysteresis loop, and three-interval thixotropic recovery tests. The yielding behaviors were evaluated through creep, steady-state shear, step shear rate, stress ramps, amplitude sweep, and large amplitude oscillatory shear tests. The rheological properties of the two typical suspensions showed a strong dependence on concentration and time. However, compared to CNC suspensions, CNF suspensions exhibited stronger thixotropy and higher yield stress due to the higher aspect ratio of CNF and the stronger structural skeleton of the suspensions as supported by Simha's equation and micromorphology analysis. This work provides a theoretical rheology basis for the practical applications of nanocellulose suspensions in various fields.