Aggregation of Halloysite Nanotubes in the Presence of Multivalent Ions and Ionic Liquids

Colloidal stability was investigated in two types of particle systems, namely, with bare (h-HNT) and polyimidazolium-functionalized (h-HNT-IP-2) alkali-treated halloysite nanotubes in solutions of metal salts and ionic liquids (ILs). The valence of the metal ions and the number of carbon atoms in the hydrocarbon chain of the IL cations (1-methylimidazolium (MIM⁺), 1-ethyl-3-methylimidazolium (EMIM⁺), 1-butyl-3-methylimidazolium (BMIM⁺), and 1-hexyl-3-methylimidazolium (HMIM⁺)) were altered in the measurements. For the bare h-HNT with a negative surface charge, multivalent counterions destabilized the dispersions at low values of critical coagulation concentration (CCC) in line with the Schulze-Hardy rule. In the presence of ILs, significant adsorption of HMIM⁺ took place on the h-HNT surface, leading to charge neutralization and overcharging at appropriate concentrations. A weaker affinity was observed for MIM⁺, EMIM⁺, and BMIM⁺, while they adsorbed on the particles to different extents. The order HMIM⁺ < BMIM⁺ < EMIM⁺ < MIM⁺ was obtained for the CCCs of h-HNT, indicating that HMIM⁺ was the most effective in the destabilization of the colloids. For h-HNT-IP-2 with a positive surface charge, no specific interaction was observed between the salt and the IL constituent cations and the particles, i.e., the determined charge and aggregation parameters were the same within experimental error, irrespective of the type of co-ions. These results clearly indicate the relevance of ion adsorption in the colloidal stability of the nanotubes and thus provide useful information for further design of processable h-HNT dispersions.