The planar disorder of Ca-montmorillonite (Fuller’s earth) has been investigated using structural simulations of X-ray powder patterns. A standard sample was fully characterized using chemical, microscopic, and diffraction methods. Earlier models of disorder taken from the literature and newly formulated combined models were used to generate simulated powder patterns to be compared with the experimental spectrum. A new model of disorder with random shifts of −a/3 and ±b/3, with a total density of defects of 75%, gives the best fit to the observed data. Thus, the sample cannot be classified as a turbostratic structure (fully disordered) and consequently turbostratic disorder does not invariably apply to all smectite samples. These findings open a debate on the nature and application of turbostratic disorder: is it possible for smectite samples to have intermediate degrees of disorder between a fully disordered stacking (turbostratic) and a highly faulted but well-defined stacking or is the result obtained for the Ca-montmorillonite just an exception? This model of disorder is useful for the quantitative phase analysis by X-ray powder diffraction based on the Rietveld method, which can now benefit from a more reliable initial structure model for Ca-montmorillonite and which will improve the accuracy of the weight-fraction estimates.

This study clarifies the crystal structure variations and relationships in the zeolites erionite and offretite. The crystal structure analyses used Rietveld analysis of X-ray powder diffraction data, obtained both by synchrotron radiation and conventional X-ray sources, and on diffraction patterns obtained by transmission electron microscopy. The framework Al atoms in erionite are preferentially located in the single six-membered ring of tetrahedra (T2 site), whereas the Si-Al distribution is essentially disordered on the tetrahedral framework sites in offretite. In both zeolites, the center of the cancrinite cage is always occupied by K cations in similar amounts in both minerals. The erionite cage in erionite is occupied by Ca and Na atoms distributed on four distinct cation sites. Mg ions can be present up to 0.8 atoms per cell and are located between the Ca1 and Ca3 sites and very close to the Ca2 site on the symmetry axis. In offretite, the Mg site is located on the trigonal axis of the gmelinite cage and the Mg atoms are bonded to a variable number (five or six) of H ₂ O molecules, depending on the site population. The structural data and TEM analysis clearly show that the crystal chemistry of the extraframework cations, Mg in particular, is a major factor controlling whether erionite or offretite crystallizes, the Si-A1 distribution in the framework, and the possible stacking intergrowths of the two minerals.