Microstructural and Swelling Properties of Ca and Na Montmorillonite: (In Situ) Observations with Cryo-TEM and SAXS

Aqueous dispersions of pure sodium and calcium smectite clays with platelet sizes on the order of a few hundred nanometers were characterized using a combination of cryo-transmission electron microscopy (cryo-TEM) and small-angle X-ray scattering (SAXS). With monovalent sodium counterions the clay is dispersed as individual platelets, as seen by cryo-TEM, that order into a nematic phase. From SAXS a one-dimensional swelling of the day in water is observed with the characteristic spacing h(s) = delta/phi(c), where h(s) is the separation between the platelets, delta = 1 nm is the effective platelet thickness, and phi(c) is the clay volume fraction in the sample. In calcium montmorillonite, on the other hand, cryo-TEM images dearly show the presence of tactoids, where the platelets have aggregated into stacks with a periodic spacing of 2 nm. From imaging a large number of tactoids the distribution function f(N) far the number of platelets per tactoid was estimated, and the average number (N) approximate to 10. The characteristic 2 nm spacing as well as the small number of platelets per tactoid was also confirmed by SAXS. The present study demonstrates that cryo-TEM, with carefully prepared specimen, is a very useful technique to characterize clay dispersions, particularly in aggregated systems.