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Density Functional Theory (DFT) Study of the Hydration Steps of Na+/Mg2+/Ca2+/Sr2+/Ba2+-Exchanged Montmorillonites

Published online by Cambridge University Press:  01 January 2024

Abid Berghout ,
Daniel Tunega  and
Ali Zaoui
Abid Berghout
Affiliation:
Laboratoire de Génie Civil et géo-Environment (EA 4515) Lille Nord de France, Ecole Polytechnique de Lille, Université des Sciences et Technologie de Lille, Cité Scientifique, Avenue Paul Langevin, 59655 Villeneuve d’Ascq Cedex, France
Daniel Tunega
Affiliation:
Institute for Theoretical Chemistry, University of Vienna, Währinger Straße 17, A-1090 Vienna, Austria Institute of Soil Research, University of Natural Resources and Applied Life Sciences Vienna, Peter-Jordan-Straße 82, A-1190 Vienna, Austria
Ali Zaoui*
Affiliation:
Laboratoire de Génie Civil et géo-Environment (EA 4515) Lille Nord de France, Ecole Polytechnique de Lille, Université des Sciences et Technologie de Lille, Cité Scientifique, Avenue Paul Langevin, 59655 Villeneuve d’Ascq Cedex, France
*
* E-mail address of corresponding author: azaoui@polytech-lille.fr
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Abstract

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Theoretical models of the mechanical properties of hydrated smectites, saturated with a variety of cations, are of much value in determining the potential for their use in various applications, including clay-polymer nanocomposites, but the development of such models is still in its infancy. The purpose of this study was to calculate the effects of divalent cations on the structural and mechanical elasticity of montmorillonite under different degrees of hydration. A theoretical study of the swelling and hydration behavior of montmorillonite was, therefore, undertaken using density functional theory (DFT) to investigate the basal spacing behavior of the homoionic montmorillonite with varying amounts of water in the interlayer space. The effect of the degree of the hydration of divalent interlayer cations (Mg2+/Ca2+/ Sr2+/Ba2+) on the structure expansion of the interlayer space was analyzed. In addition, the results obtained were compared to calculations performed on the montmorillonite model with a monovalent cation (Na+). The basal spacing (d001) is governed by the size and the degree of hydration of the countercations. The structures containing divalent cations are more compact than structures with monovalent cations. Ba-exchanged montmorillonite was found to have the largest d001 value for any degree of hydration (‘dry,’ one water layer, or two layers). The basal spacings of ‘dry’ montmorillonite exchanged with small cations, Mg2+ and Ca2+, are very similar. In hydrated models, the d001 expansion correlates with the ionic radius of the interlayer cation. The dependence of the total electronic energy on the volume expansion was calculated. From the energetic curves, bulk modulus (B0) was obtained by fitting in order to show how the compliance of the material depends on the type of interlayer cation and on the degree of hydration. With increasing water content in the interlayer space, the bulk modulus decreased, suggesting that the c-axial compression becomes easier with increasing hydration of the clay mineral. The values of the bulk modulus in hydrated systems are less sensitive to the type of the interlayer cation.

Keywords

HydrationDensity Functional TheoryInterlayer CationMontmorillonite
Type
Article
Information
Clays and Clay Minerals , Volume 58 , Issue 2 , April 2010 , pp. 174 - 187
Copyright
Copyright © Clays and Clay Minerals 2010

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