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Etude d'une nacrite intercalée par du dimethylsulfoxide et n-methylacetamide

Published online by Cambridge University Press:  09 July 2018

A. Ben Haj Amara
Affiliation:
Laboratoire de physique des matériaux, Ecole Normale Superieure de Bizerte, 7021 Zarzouna, Tunisie
J. Ben Brahim
Affiliation:
Laboratoire de physique des matériaux, Ecole Normale Superieure de Bizerte, 7021 Zarzouna, Tunisie
G. Besson
Affiliation:
CRMD Université d'Õrléans, 45067 Orléans cedex 2, France
C.H. Pons
Affiliation:
CRMD Université d'Õrléans, 45067 Orléans cedex 2, France

Resume

Une nacrite est intercalée par deux composés organiques polaires: le diméthylsulfoxide (DMSO) et le n-méthylacétamide (NMA). Les deux solvants ont des moments dipolaires très voisins (4 debyes) mais des constantes diélectriques différentes (49 pour le DMSO et 179 pour le NMA). L'intercalation du NMA est plus rapide que celle du DMSO. Les deux complexes homogènes obtenus sont étudiés par diffraction des rayons X, spectroscopie infrarouge et ATD. L'étude par spectroscopie IR a montré que la nacrite expansée par du DMSO se comporte comme la kaolinite expansée par le même solvant. Dans le cas de la nacrite intercalée par du NMA, trois nouvelles bandes d'absorption dues aux vibrations de valence des OH liés par pont hydrogène avec le groupement C=O et situées respectivement à 3500, 3543 et 3589 cm−1 apparaissent. La fréquence v(N-H) du NMA est intermédiaire entre celles du liquide et d'une solution diluée, indiquant une liaison par pont hydrogène probablement avec les oxygènes de la couche tétraédrique du silicate. La diffraction des rayons X sur des échantillons orientés nous a permis d'obtenir 13 réflexions 00l pour chaque complexe. Une étude quantitative, par transformée de Fourier monodimensionnelle dans la direction perpendiculaire au plan du feuillet, a permis de déterminer le nombre de molécules organiques intercalées (une molécule par Si2Al2O5(OH)4) et leur orientation dans l'espace interlamellaire. L'ATD a montré par ailleurs que le complexe Nac.DMSO est plus stable que le complexe Nac.NMA.

Abstract

Abstract

Nacrite was intercalated with two polar organic compounds: Dimethylsulphoxide (DMSO) and n-methylacetamide (NMA), which have similar dipolar moments (4 debyes) but different dielectric constants (49 for the DMSO and 179 for the NMA). The rate of the intercalation has been measured and found to increase in order NMA>DMSO. The interlamellar homogeneous nacrite complexes have been studied by XRD, IR and DTA. The IR nacrite-DMSO spectrum shows that interaction between the nacrite layer and DMSO is similar to that obtained in the kaolinite-DMSO complexes. The IR spectrum of the nacrite-NMA complex shows three absorption bands at 3500, 3543 and 3589 cm−1. The v(N-H) frequencies of the NMA in the complex are intermediate between those of dilute non-polar solution and the liquid. This could arise from a degree of association between N-H and O-Si. By XRD, 13 basal reflections were obtained for each complex. The direct method involving a monodimensional electron density projection on the z-axis for each homogeneous complex enabled us to find the amount of organic compound per unit-cell (one molecule per Si2Al2O5(OH)4) and their orientation in the interlamellar space. The DTA showed that the Nac.DMSO complex is more stable than the Nac.NMA complex.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1995

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