Cellulose Nanofibrils vs Nanocrystals: Rheology of Suspensions and Hydrogels

Plant-derived nanocellulose particles, such as cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs), are becoming increasingly popular for a wide range of applications. In particular, when they are employed as rheology modifiers and/or fillers, a choice between CNFs and CNCs is often not obvious. Here, we present the results of a comparative study on the rheological properties of suspensions and gels of carboxymethylated CNFs and CNCs with the same surface chemistry, surface density of charged groups, and thickness. We demonstrate that, at the same weight concentration, CNF suspensions have much higher viscosity and storage modulus, which is due to their longer length providing many entanglements. However, when comparing at the same nanoparticle concentration relative to C*, the situation is reversed: viscosity and storage modulus of CNCs appear to be much higher. This may be due in particular to the higher rigidity and intrinsic strength of highly crystalline CNCs. The gel points for CNF and CNC suspensions (without crosslinker) were compared for the first time. It was found that in the case of CNFs, the gel point occurs at a 3.5-fold lower concentration compared to that of CNCs. Hydrogels were also obtained by crosslinking negatively charged nanocellulose particles of both types by divalent calcium cations. For the first time, the thermodynamic parameters of the crosslinking of carboxymethylated CNFs by calcium ions were determined. Isothermal titration calorimetry data revealed that, for both CNFs and CNCs, crosslinking is endothermic and driven by increasing entropy, which is most likely due to the release of water molecules surrounding the interacting nanoparticles and Ca²⁺ ions. The addition of CaCl₂ to suspensions of nanocellulose particles leads to an increase in the storage modulus; the increase being much more significant for CNCs. Physically crosslinked hydrogels of both CNFs and CNCs can be reversibly destroyed by increasing the shear rate and then quickly recover up to 85% of their original viscosity when the shear rate decreases. The recovery time for CFC networks is only 6 s, which is much shorter than that of CNC networks. This property is promising for various applications, where nanocellulose suspensions are subjected to high shear forces (e.g., mixing, stirring, extrusion, injection, coating) and then need to regain their original properties when at rest.