Impact of counterion valency on the rheology of sulfonated cellulose nanocrystal hydrogels.

A systematic rheological study on the influence of valency of different counterions on the properties of CNC hydrogels was carried out. Rheo-polarized microscopy was used to prove that preshear of 500 s for 1 min is adequate to completely breakdown agglomerates in the suspension. Furthermore, a rest period of 30 min is sufficient to recover the equilibrium structure of hydrogels. Changing counterions from monovalent (Na, K, Li), to divalent (Mg, Ca) and to trivalent (Al) influenced the network formation. CNC suspensions with monovalent counterions are isotropic at 3 wt%, anisotropic with chiral nematic structures at 5 wt% and form birefringent gels at 7 wt%. Conversely, divalent and trivalent counterions facilitate network formation, leading to gel like behavior at all concentrations. Sonication of CNC samples with monovalent counterions lowers the viscosity by two orders of magnitude while the opposite is true for multivalent counterions due to the formation of strong networks. The varying rheological properties displayed from CNCs with different counter ions may influence the use of CNC as rheological modifiers in fluid-based applications.