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Etude comparee des complexes hectorite- et vermiculite-decylammonium a l'aide des spectrometries infrarouge et raman

Published online by Cambridge University Press:  09 July 2018

A. Vimond-Laboudigue  and
R. Prost
A. Vimond-Laboudigue
Affiliation:
Station de Science du Sol, INRA, Route de Saint Cyr, F-78026, Versailles, France
R. Prost
Affiliation:
Station de Science du Sol, INRA, Route de Saint Cyr, F-78026, Versailles, France
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Resume

L'arrangement des cations décylammonium échangés entre les feuillets de la vermiculite et de l'hectorite a été précisé à l'aide des spectrométries infrarouge (IR) et Raman. Les expériences de deutération et de dichroïsme faites par spectrométrie IR montrent que l'axe C3 du groupe NH3+ est confondu avec l'axe de la cavité hexagonale sous-jacente, dans le cas de la vermiculite comme dans celui de l'hectorite, et que dans la vermiculite, les groupes NH sont engagés dans des liaisons hydrogène avec les atomes d'oxygène des tétraèdres substitués. La spectrométrie Raman permet de comparer l'arrangement des chaînes alkyles dans les deux phyllosilicates. En effet, cette technique donne accès à des modes de vibration très sensibles à la conformation des chaînes carbonées, en particulier grâce à la décomposition des bandes de vibration de valence des groupements CH2 et CH3. Ainsi, dans la vermiculite, on montre que les chaînes sont linéaires, et que leur arrangement interdigité est proche de celui du chlorure de décylammonium cristallisé. Les spectres Raman obtenus pour l'hectorite mettent en évidence l'existence de conformations gauches dans les chaînes alkyles, qui caractérisent une rotation de la chaîne autour de la liaison C-C voisine du groupe NH3+ terminal. Les résultats obtenus en Raman montrent par ailleurs que les interactions entre les chaînes alkyles sont beaucoup plus faibles que dans le cas de la vermiculite et confortent le modèle proposé ici pour le complexe hectorite-décylammonium, pour lequel les chaînes sont parallèle aux surfaces des feuillets.

Abstract

Abstract

Hectorite- and vermiculite-decylammonium complexes were studied by means of infrared (IR) and Raman spectroscopies in order to compare the distribution of alkylammonium for two clays which have different charges. In each complex, a perpendicular arrangement of terminal NH+3 groups to the silicate plane was deduced on IR spectra from deuteration and dichroïsm experiments. It was shown from IR results that for vermiculite-decylammonium, NH groups are involved in hydrogen bonds with oxygen atoms of the silica sheet linked to Si/Al substituted tetrahedra. Raman spectroscopy was particularly useful for comparing the arrangement of decylammonium cations in the interlayer spaces of both phyllosilicates; decomposition of complex stretching bands showed vibration modes which are very sensitive to intra and inter-molecular conformations of hydrocarbon chains. For vermiculite, the arrangement of linear chains in interdigitated bilayers is close to that of crystallized decylammonium chloride. For hectorite, specific modes on Raman spectra were characteristic of a kink conformation of hydrocarbon chains next to the polar end. It could be deduced from these spectra that interchain interactions are much weaker in hectorite than in vermiculite, in relation to a flat disposition of the alkyl chains relative to the layers in hectorite-decylammonium.

Type
Research Article
Information
Clay Minerals , Volume 30 , Issue 4 , December 1995 , pp. 337 - 352
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1995

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