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A comprehensive characterization of dioctahedral smectites

Published online by Cambridge University Press:  01 January 2024

Felicitas Wolters ,
Gerhard Lagaly ,
Guenter Kahr ,
Rolf Nueesch  and
Katja Emmerich
Felicitas Wolters*
Affiliation:
Institute for Technical Chemistry, Water and Geotechnology Division, Forschungszentrum Karlsruhe GmbH, P.O. Box 3640, 76021 Karlsruhe, Germany
Gerhard Lagaly
Affiliation:
Institute of Inorganic Chemistry, University of Kiel, D-24098 Kiel, Germany
Guenter Kahr
Affiliation:
ETH Zurich, Institute for Geotechnical Engineering, Schafmattstr. 6, 8093 Zürich, Switzerland
Katja Emmerich
Affiliation:
Institute for Technical Chemistry, Water and Geotechnology Division, Forschungszentrum Karlsruhe GmbH, P.O. Box 3640, 76021 Karlsruhe, Germany Competence Center for Material Moisture, University of Karlsruhe, c/o Forschungszentrum Karlsruhe, ITC-WGT, P.O. Box 3640, 76021, Karlsruhe, Germany
*
‡Present address: Bergstraße 47, 58300 Wetter, (Ruhr), Germany
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Abstract

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The term ‘montmorillonite’ encompasses a wide range of chemical compositions and structures. Comprehensive and reliable characterization is essential for unambiguous classification. Twenty eight purified, Na-exchanged smectites (<0.2 µm) were characterized by layer-charge measurement using the alkylammonium method, by cation exchange capacity (CEC) measurement with Cu-triethylenetetramine, by determination of the chemical composition using X-ray fluorescence analysis, by calculation of the structural formula following determination of the octahedral structure (trans-vacant vs. cis-vacant) by simultaneous thermal analysis, and by X-ray diffraction analysis. Mössbauer spectroscopy was applied to determine the oxidation state and coordination of Fe and changes thereof during purification of the source materials.

The charge derived from chemical composition was considerably greater (by up to 30%) than the measured layer charge. The independently measured layer charge was used to calculate the structural formula. The measured CEC values, comprising the permanent charges and the pH-dependent edge charges, were consistent with measured layer charge but not with layer charge derived from the chemical composition. Therefore, the structural formula of smectites should be calculated using the measured layer charge.

The dehydroxylation temperature, which conveys information about the structure of the octahedral sheet, was correlated to the amount of Mg and Fe3+ and the location of charges. No relationship was found among the dehydroxylation temperature and the mean layer charge or the Mg content. In contrast, a clear relationship was observed between the Fe content and the dehydroxylation temperature. Montmorillonites with an Fe content <0.3/f.u. are cis-vacant and those containing Fe3+ > 0.3 mol/f.u. are trans-vacant, mostly with additional cis-vacancies. Tetrahedral substitution also appeared to be a function of the number of trans-vacancies.

The parameters analyzed provide the basis for a new descriptive classification system.

Keywords

CECChemical CompositionCis-vacantDehydroxylationFe contentLayer ChargeMontmorilloniteOctahedral ChargeSimultaneous Thermal AnalysisStructural FormulaTetrahedral ChargeTrans-vacant
Type
Article
Information
Clays and Clay Minerals , Volume 57 , Issue 1 , February 2009 , pp. 115 - 133
Copyright
Copyright © The Clay Minerals Society 2009

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