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The Ordering of HDTMA in the Interlayers of Vermiculite and the Influence of Solvents

Published online by Cambridge University Press:  01 January 2024

Phil G. Slade  and
Will P. Gates
Phil G. Slade
Affiliation:
CSIRO Land and Water, Mail Bag No. 2, Glen Osmond, SA 5064, Australia
Will P. Gates*
Affiliation:
CSIRO Land and Water, Mail Bag No. 2, Glen Osmond, SA 5064, Australia
*
*E-mail address of corresponding author: will.gates@csiro.au
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Abstract

X-ray basal reflections of several HDTMA-vermiculites show that when these contain co-adsorbed molecules of HDTMA-Br, their interlayer spacings are ∼29.5 Å. After HDTMA-Br has been leached out with ethanol, spacings decrease to ∼26 Å, but when exposed to toluene vapor the spacings increase to ∼36 Å, and to ∼45 Å in toluene liquid. Transmission X-ray diffraction photographs of HDTMA-vermiculites, both with and without co-adsorbed HDTMA-Br, indicate that they have highly ordered interlayer structures. The structure of HDTMA-Br-free vermiculite flakes is more open with the interlayer cations arranged in a 3a × b superstructure. In the HDTMA-Br containing HDTMA vermiculite flakes, HDTMA-Br molecules occupy interstitial positions between the HDTMA cations. Swelling in toluene vapor does not disorder the 2-dimensional arrangement of interlayer cations, but disorder does occur in toluene liquid. In toluene vapor, the aliphatic chains of the cations remain partially interdigitated, but in toluene liquid the interdigitation disappears. In response to the layer-charge density, the organization of the interlayer HDTMA units is caused by the self-assembly process responsible for hydrocarbon close packing.

Keywords

2-dimensional OrderingHDTMA-Br Salt MoleculesHDTMA-vermiculitesInterlayer StructureSelf AssemblySwellingToluene
Type
Research Article
Information
Clays and Clay Minerals , Volume 52 , Issue 2 , April 2004 , pp. 204 - 210
Copyright
Copyright © 2004, The Clay Minerals Society

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