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Luminescence and ESR studies of relationships between O−-centres and structural iron in natural and synthetically hydrated kaolinites

Published online by Cambridge University Press:  09 July 2018

Lelia M. Coyne ,
Patricia M. Costanzo  and
B. K. G. Theng
Lelia M. Coyne
Affiliation:
Department of Chemistry, San Jose State University, Mail Stop 239-4, NASA-Ames Research Center, Moffett Field, CA 94035
Patricia M. Costanzo
Affiliation:
Department of Geology, University at Buffalo, State University of New York, 4240 Ridge Lea Road, Buffalo, NY 14226, USA
B. K. G. Theng
Affiliation:
NZ Soil Bureau, DSIR, Private Bag, Lower Hutt, New Zealand
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Abstract

Luminescence, induced by dehydration and by wetting with hydrazine and unsymmetrically substituted hydrazine, and related ESR spectra have been observed from several kaolinites, synthetically hydrated kaolinites, and metahalloysites. The amine-wetting luminescence results suggest that intercalation, not a chemiluminescence reaction, is the luminescence trigger. Correlation between dehydration-induced luminescence and g = 2 ESR signals associated with O−-centres in several natural halloysites, and concurrent diminution of the intensity of both these signal types as a function of aging in two 8.4 Å synthetically hydrated kaolinites, confirm a previously-reported relationship between the luminescence induced by dehydration and in the presence of O−-centres (holes, i.e., electron vacancies) in the tetrahedral sheet. Furthermore, the ESR spectra of the 8.4 Å hydrate showed a concurrent change in the line shape of the g = 4 signal from a shape usually associated with structural Fe in an ordered kaolinite, to a simpler one typically observed in more disordered kaolinite, halloysite, and montmorillonite. Either structural Fe centres and the O−-centres interact, or both are subject to factors previously associated with degree of order. The results question the long-term stability of the 8.4 Å hydrate, although XRD does not indicate interlayer collapse over this period. Complex inter-relationships are shown between intercalation, stored energy, structural Fe, and the degree of hydration which may be reflected in catalytic as well as spectroscopic properties of the clays.

Type
Research Article
Information
Clay Minerals , Volume 24 , Issue 4 , December 1989 , pp. 671 - 693
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1989

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