Structure analysis of montmorillonite crystallites by convergent-beam electron diffraction

The small particle size and the random stacking of layers has previously hindered systematic structure investigations of montmorillonite. By applying the convergent-beam electron diffraction mode (CBED) of a transmission electron microscope (TEM) with a beam spot of similar to 800 angstrom we were able to examine undisturbed areas of montmorillonite crystallites. Because montmorillonite crystallites are mostly thin particles, kinematic theory can be applied and the CBED patterns can be interpreted directly, provided that the particle thickness remains below the critical value of 350 angstrom. An average thickness of similar to 90 angstrom was calculated here for montmorillonite of bulk samples from X-ray diffraction analysis and lattice-fringe images. However, satisfactory diffraction intensity patterns for quantitative evaluation were obtained only from crystallites with a thickness above the average, which yielded a sufficient scattering volume. These patterns could be described in terms of the kinematic theory and therefore these crystallites were < 350 angstrom thick. Yet, crystallites of adequate thickness were extremely rare in the three samples investigated (Clay Spur, Rock River and Upton, all in Wyoming, USA). The diffraction intensities from the ab plane of single montmorillonite crystallites of the various origins fit the three structural models for a trans-vacancy distribution, a cis-vacancy distribution or a random-cation distribution within the octahedral sheets. The configuration of the diffraction patterns also shows a 1M symmetry of the layer. Due to the limited data set of CBED patterns, a refinement of the structure could not be achieved. However, energy dispersive X-ray spectroscopy data and computation of the cation-anion distances and valences using the 'distance valence least square' program permitted a refinement of the models.