Effects of different salt ions on the structure and rheological behavior of sulfated cellulose nanocrystal hydrogel

Cellulose nanocrystal (CNC) hydrogels are increasingly used in various applications. Here, CNC hydrogels were formed by adding four salt ions (NaCl, KCl, MgCl2, and CaCl2) to sulfated CNC suspensions. NaCl and KCl are monovalent salt ions and MgCl2 and CaCl2 are divalent salt ions; each pair has similar cation charges but different cation radii. This study compared the effects of four salt ions on the structure and rheological behavior of CNC hydrogels. At the same ion concentration, compared with NaCl and KCl, the addition of MgCl2 and CaCl2 significantly reduced the distance between the CNC particles, forming pronounced aggregates and denser network structures. Furthermore, the G′ and G″ of the CNC hydrogels with salt ions followed the order NaCl < KCl < MgCl2 < CaCl2 in the small-amplitude oscillatory shear (SAOS) test, and more viscoelastic hydrogels exhibited relatively lower deformability in the creep-recovery test. Under large-amplitude oscillatory shear (LAOS) conditions, the CNC hydrogels with salt ions exhibited LAOS type III behavior, and the change in yield stress followed the same order as the SAOS results. Among them, CNC hydrogel with CaCl2 exhibited stronger nonlinear response and enhanced strain-stiffening behavior (higher I3/I1 and e3/e1) to resist deformation before 20% strain, as well as an enhanced softening effect (higher |v3/v1|) as the structure was destroyed and rearranged at strains ranging from 20% to 100%. Such CNC hydrogels with different salt ions, which can regulate structural and rheological properties, provide basis for designing hydrogels and meet potential requirements in food and biomedicine fields.