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Dehydration of Hydroxy-Interlayered Vermiculite as a Function of Time and Temperature

Published online by Cambridge University Press:  28 February 2024

W. G. Harris ,
K. A. Hollien ,
S. R. Bates  and
W. A. Acree
W. G. Harris
Affiliation:
Soil Science Department, University of Florida, Gainesville, Florida 32611
K. A. Hollien
Affiliation:
Soil Science Department, University of Florida, Gainesville, Florida 32611
S. R. Bates
Affiliation:
Materials Engineering Department, University of Florida, Gainesville, Florida 32611
W. A. Acree
Affiliation:
Materials Engineering Department, University of Florida, Gainesville, Florida 32611
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Abstract

Nonexchangeable polymers in interlayers of expansible phyllosilicates influence thermal dehydration in ways not completely understood. Thermal dehydration of hydroxy-interlayered vermiculite (HIV) from Florida soils, for example, results in irreversible d001 shifts. This study was conducted to characterize HIV dehydration as a function of time (t) and temperature (T), and to determine how reversibility of dehydration is affected by elevated T. Clay-sized HIV from 3 soils was heated incrementally and d-spacing shifts (Δd) were monitored by X-ray diffraction (XRD) at low relative humidity (RH). Samples were then mounted on a metal heating strip in the XRD focal plane and scanned repeatedly at constant T levels to monitor Δd with t. Finally, Δd in response to RH shifts from <5% to >85% was determined at 25°C and at elevated temperatures. Incremental heating revealed a Δd plateau roughly corresponding to the z dimension of hexameric octahedrally coordinated Al. The initial slope of Δd-vs-t curves increased with T. The same maximum Δd reached at 200°C was reached at 160°C, but more slowly. All samples exhibited reversible and irreversible dehydration, the former being attributable to sites in equilibrium with external vapor and the latter to sites requiring heat for desorption. Reversible sites were not perturbed by moderate heating, but were apparently eliminated by polymer dehydroxytation. The dehydration behavior of HIV could be explained by steric resistance of water vapor diffusion within a tortuous interlayer polymeric network. Alternatively, new polymer/oxygen-surface bonds exceeding the hydration energy of interlayer components could form via heat-induced re-articulation of polymer/oxygen-surface bonds at smaller basal spacings.

Keywords

DehydroxylationHydrationX-ray diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 40 , Issue 3 , June 1992 , pp. 335 - 340
Copyright
Copyright © 1992, The Clay Minerals Society

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