A comparative study of ECNC and CNC suspensions: effect of salt on rheological properties

This paper addresses the effect of monovalent (Na⁺) and divalent (Ca²⁺) ions on the shear viscosity and viscoelastic properties of two different aqueous suspensions of nanoparticles, cellulose nanocrystals (CNCs), and electrosterically stabilized nanocrystals of cellulose (ECNCs). ECNC is similar as CNC, but with carboxylated cellulose chains protruding from both endcaps. The different suspensions were studied in the semi-dilute regime, which corresponded to concentrations ranging from 0.5 to 8 wt% for CNCs and from 0.6 to 9 wt% for ECNCs. As the charges on CNCs are presumably distributed all along the crystal domains and the CNC have a twist in their backbone structure, their suspensions shifted to a cholesteric state as the volume fraction increased while ECNC suspensions did not. This is because the charges on ECNCs are mainly distributed at the endcaps of the particles and the protruding chains expel each other. On the one hand, it was demonstrated that at moderate ionic strength (I = 20 mM), CNC suspensions formed gels even at really low concentrations due to agglomeration. Calcium chloride (CaCl₂) had a greater effect than sodium chloride (NaCl) on both shear and viscoelastic properties due to stronger network formation. On the other hand, ECNCs could withstand much higher ionic strengths than CNCs. NaCl had no effect other than making the ECNC particles precipitate above a concentration of 200 mM, while CaCl₂ made ECNC suspensions turn into gels due to a bridging effect with their carboxylic acid groups at a concentration of [Ca2+] ≈ [COOH]/2.