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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

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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

References

Alcover, J.F. Gatineau, L. and Mering, J., (1973) Exchangeable cation distribution in nickel- and magnesium-vermiculites Clays and Clay Minerals 21 131–136 10.1346/CCMN.1973.0210209.CrossRefGoogle Scholar
Favre, H. and Lagaly, G., (1991) Organo-bentonites with quaternary alkylammonium ions Clay Minerals 26 19–32 10.1180/claymin.1991.026.1.03.CrossRefGoogle Scholar
Henry, N.F.M. and Lonsdale, K., (1969) editors () International Tables for X-ray Crystallography. vol. 1, p. 19. Kynoch Press, Birmingham, UK.Google Scholar
Lagaly, G., (1981) Characterization of clays by organic compounds Clay Minerals 16 1–21 10.1180/claymin.1981.016.1.01.CrossRefGoogle Scholar
Lee, S.Y. and Kim, S.J., (2002) Expansion of smectite by hexadecyltrimethylammonium Clays and Clay Minerals 50 435–445 10.1346/000986002320514163.CrossRefGoogle Scholar
Norrish, K. (1973) Factors in the weathering of mica to vermiculite. Proceedings of the 1972 International Clay Conference, Madrid, pp. 83–101.Google Scholar
Ogawa, M. and Kuroda, K., (1995) Photo-functions of intercalation compounds Chemical Review 95 399–438 10.1021/cr00034a005.CrossRefGoogle Scholar
Raupach, M. Slade, P.G. Janik, L. and Radoslovich, E.W., (1975) A polarized infrared and X-ray study of lysine-vermiculite Clays and Clay Minerals 23 181–186 10.1346/CCMN.1975.0230303.CrossRefGoogle Scholar
Slade, P.G. and Gates, W.P., (2004) Influence of layer charge on the interlayer structures of HDTMA smectites Applied Clay Science 25 93–101 10.1016/j.clay.2003.07.007.CrossRefGoogle Scholar
Slade, P.G. and Raupach, M., (1982) Structural model for benzidine-vermiculite Clays and Clay Minerals 30 297–305 10.1346/CCMN.1982.0300408.CrossRefGoogle Scholar
Slade, P.G. and Stone, P.A., (1983) Structure of a vermiculite-aniline intercalate Clays and Clay Minerals 31 200–206 10.1346/CCMN.1983.0310305.CrossRefGoogle Scholar
Slade, P.G. and Stone, P.A., (1984) Three-dimensional order and the structure of aniline-vermiculite Clays and Clay Minerals 32 233–226 10.1346/CCMN.1984.0320310.CrossRefGoogle Scholar
Slade, P.G. Raupach, M. and Emerson, W.W., (1978) The ordering of cetylpyridinium bromide on vermiculite Clays and Clay Minerals 26 125–134 10.1346/CCMN.1978.0260207.CrossRefGoogle Scholar
Slade, P.G. Self, P.G. and Quirk, J.P., (1998) The interlayer structure of La-vermiculite Clays and Clay Minerals 46 629–635 10.1346/CCMN.1998.0460603.CrossRefGoogle Scholar
Theng, B.K.G., (1974) The Chemistry of Clay-Organic Reactions London Adam Hilger.Google Scholar
Xu, S. and Boyd, S.A., (1995) Cationic surfactant adsorption of swelling and nonswelling layer silicates Langmuir 11 2508–2514 10.1021/la00007a033.CrossRefGoogle Scholar