Relation Between Crystal-Lattice Configuration and Swelling of Montmorillonites

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Abstract
Prompted by Foster’s observation that free swelling is related to octahedral substitution, the authors determined the free swelling of six Na-montmorillonites with different amounts of octahedral and tetrahedral substitution. They found that the montmorillonites exhibited marked differences in free swelling. These differences were not related to differences in cation exchange capacity. Nor were they related to differences in ζ potential, which is a criterion of cation dissociation. Further, calculations indicated that they could not be accounted for by differences in double-layer repulsion or van der Waals attraction. Therefore, to see if dimensional changes produced by isomorphous substitution were responsible, free swelling was plotted against the b-dimension of the clay structure, which was calculated from its mineralogical composition. The result was a straight line with a negative slope. A similar result was obtained with Foster’s data. In addition, free swelling was plotted against the degree of tetrahedral rotation in the clay structure, which was also calculated from its mineralogical composition. The result was a family of nearly parallel straight lines that were distinguished from each other by the amount of tetrahedral Al3+ in the clays identified with them. These results led to the proposal that the clay surface acts as a template for the structure of the adjacent water and that, as the configuration of the surface changes, the water structure changes accordingly. This causes a change in the free energy of the water and, hence, in the swelling of the clay.