Calcium Ion-Induced Structural Changes in Carboxymethylcellulose Solutions and Their Effects on Adsorption on...

The adsorption of carboxymethylcellulose (CMC) on cellulose surfaces is one of the most studied examples of the adsorption of an anionic polyelectrolyte on a like-charged surface. It has been suggested that divalent ions can act as a bridge between CMC chains and the surface of cellulose and enhance the CMC adsorption: they can, however, also alter the structure of CMCs in the solution. In previous investigations, the influence of cations on solution properties has been largely overlooked. This study investigates the effect of Ca²⁺ ions on the properties of CMC solutions as well as the influence on cellulose nanofibers (CNFs), which was studied by dynamic light scattering and correlated with the adsorption of CMC on a cellulose surface probed using QCM-D. The presence of Ca²⁺ facilitated the multichain association of CMC chains and increased the hydrodynamic diameter. This suggests that the adsorption of CMCs at high concentrations of CaCl₂ is governed mainly by changes in solution properties rather than by changes in the cellulose surface. Furthermore, an entropy-driven mechanism has been suggested for the adsorption of CMC on cellulose. By comparing the adsorption of CMC from H₂O and D₂O, it was found that the release of water from the cellulose surface is driving the adsorption of CMC.