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“Dealumination” and Aluminum Intercalation of Vermiculite

Published online by Cambridge University Press:  02 April 2024

Jean-Baptiste D'Espinose de la Caillerie
Affiliation:
Department of Chemistry and Laboratory for Surface Studies, University of Wisconsin-Milwaukee, P.O. Box 413, Milwaukee, Wisconsin 53201
José J. Fripiat
Affiliation:
Department of Chemistry and Laboratory for Surface Studies, University of Wisconsin-Milwaukee, P.O. Box 413, Milwaukee, Wisconsin 53201

Abstract

Dealumination of vermiculite was carried out using (NH4)2SiF6 solutions. The dealuminated products were studied by high-resolution solid state 29Si and 27Al nuclear magnetic resonance. A decrease in the cation-exchange capacity (CEC) resulted from the partial removal of Al from the tetrahedral layer, which decreased the framework negative charge, and from the partial replacement of Mg by Al in the octahedral layer, which increased its positive charge contribution. The lowest CEC was obtained by swelling the structure with butyl-ammonium prior to the reaction with (NH4)2SiF6. Thus, CECs in the range observed for beidellite were measured; however, the lowest (Al/Si)IV ratio was still more than twice as high as in beidellite. In addition, the dealumination reaction yielded noncrystalline silica as a by-product.

In contact with a solution of Al hydroxypolymer (Al13), the dealuminated vermiculite showed no 18-Å reflection characteristic of Al13-intercalated smectite; instead it showed an ill-defined interstratification. For some samples, however, a significant increase in the specific surface area (as much as 230 m2/g) was observed, suggesting that an intercalation of Al moieties did occur. The 27Al resonance spectra of the intercalated structure showed at least two components in octahedral coordination. On thermal activation, a resonance line attributable to pentacoordinated Al was observed.

Type
Research Article
Copyright
Copyright © 1991, The Clay Minerals Society

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