Thermodynamic Study of Ion-Driven Aggregation of Cellulose Nanocrystals.

The thermodynamics of interactions between cations of the second group of the periodic table and differently negatively charged cellulose nanocrystals was investigated using isothermal titration calorimetry (ITC). The interaction of cations with the negatively charged CNCs was found to be endothermic and driven by an increase in entropy upon adsorption of the ions, due to an increase in degrees of freedom gained by the surface bound water upon ion adsorption. The effect was pH-dependent, showing an increase in enthalpy for cellulose suspensions at near-neutral pH (6.5) when compared to acidic pH (2). Sulfated cellulose nanoparticles were found to readily interact with divalent ions at both pH levels. The adsorption on carboxylate nanocrystals was found to be pH dependent, showing that the carboxylic group needs to be in the deprotonated form to interact with divalent ions. For the combined system (sulfate and carboxylate present at the same time), at neutral pH, the adsorption enthalpy was higher than the value obtained from cellulose nanocrystals containing a single functional group, while the association constant was higher due to an increased favorable entropic contribution. The higher entropic contribution indicates a more restricted surface-bound water layer when multiple functionalities are present. The stoichiometric number was nearly constant for all systems, showing that the adsorption depends almost completely on the ion valency and on the amount of ionic groups on the CNC surface, independent of the type of functional group on the CNC surface as long as it is deprotonated. In addition, we showed that the reduction in Gibbs free energy drives the ionotropic gelation of nanocellulose suspensions, and we show that ITC is able to detect gel formation at the same time as determining the critical association concentration.