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Formation and Restacking of Disordered Smectite Osmotic Hydrates

Published online by Cambridge University Press:  01 January 2024

Benjamin Gilbert
Affiliation:
Energy Geoscience Division, Lawrence Berkeley National Laboratory, Berkeley, USA
Luis R. Comolli
Affiliation:
Life Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA
Ruth M. Tinnacher
Affiliation:
Energy Geoscience Division, Lawrence Berkeley National Laboratory, Berkeley, USA
Martin Kunz
Affiliation:
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, USA
Jillian F. Banfield*
Affiliation:
Energy Geoscience Division, Lawrence Berkeley National Laboratory, Berkeley, USA Earth and Planetary Sciences, University of California — Berkeley, Berkeley, USA
*
*E-mail address of corresponding author: jbanfield@berkeley.edu

Abstract

Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutions was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. No evidence was found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. Drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.

Type
Article
Copyright
Copyright © The Clay Minerals Society 2015

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Footnotes

Equal co-authors

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