Modifying the structure and flow behaviour of aqueous montmorillonite suspensions with surfactant

Colloidal suspensions of plate-like particles undergo a variety of phase transitions. The predicted isotropic/nematic transition is often pre-empted by a sol/gel transition, especially in suspensions of the most commonly used natural swelling clay montmorillonite (MMT). A number of factors, including charge interactions, flexibility and salt concentration, may contribute to this competition. In this study, the effect of surfactant adsorption on suspensions of MMT was studied using rheology, small-angle X-ray scattering, static light scattering and optical microscopy. The addition of a polyetheramine surfactant reduced the moduli of the system and shifted the sol/gel transition to a much higher clay concentration, compared with suspensions of bare clay particles. Yet, scattering data revealed no change in suspension structure on length scales up to around a micrometre. Primary aggregates remain at this length scale and no nematic phase is formed. There is, however, a change in structure at large length scales (of order 20 μm) where light scattering indicates the presence of string-like aggregates that disappear on addition of surfactant. Microscope images of dried suspensions also revealed a string-like structure. The dried strings show strong birefringence and may consist of concentric cylinders, self-assembled from clay sheets.