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In situ X-ray Diffraction Study of the Swelling of Montmorillonite as Affected by Exchangeable Cations and Temperature

Published online by Cambridge University Press:  01 January 2024

Shoji Morodome  and
Katsuyuki Kawamura
Shoji Morodome*
Affiliation:
Department of Earth and Planetary Science, Tokyo Institute of Technology, Ookayama 2-12-1, Megro-ku, Tokyo 152-8551, Japan
Katsuyuki Kawamura*
Affiliation:
Department of Earth and Planetary Science, Tokyo Institute of Technology, Ookayama 2-12-1, Megro-ku, Tokyo 152-8551, Japan
*
†Present addresse: Research Laboratories, Kunimine Industries Co. Ltd., Nabekake 1085-454, 325-0013, Nasushiobara, Tochigi, Japan
‡Present addresse: Graduate School of Environmental Science, Okayama University, 3-1-1, Tsushimanaka, Kita-Ku, 700-8530, Okayama, Okayama, Japan
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Abstract

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The swelling property of smectite is dominated by the hydration of exchangeable cations in the interlayer spacing (‘interlayer hydration’). By investigating systematically the swelling behavior of various exchangeable cations with different valences and ionic radii, the interlayer hydration of smectite was explored. The swelling behavior of Li+-, K+-, Rb+-, Cs+-, Mg2+-, Sr2+-, Ba2+-, and La3+- montmorillonites in undersaturated conditions was measured precisely over the range 50–150°C by in situ X-ray diffraction (XRD) analyses. The systematic swelling behavior of ten homocationic montmorillonites, the aforementioned eight homoionic montmorillonites, plus Na+ and Ca2+ from a previous study, and the cation hydration energies were analysed by studying the changes occurring in the basal spacing and the 001 peak width. With decreasing cation hydration energy, swelling curves (i.e. plots of basal spacing vs. relative humidity (RH)) change from continuous (Mg2+, La3+, and Ca2+) to stepwise (Sr2+, Li+, Ba2+, and Na+) to one-layer only (K+, Rb+, and Cs+). For the first two groups, the RH at the midpoint between the one- and two-layer hydration states increased as the cation hydration energy decreased. Under low RH, with increasing temperature, the basal spacings of Mg-, La-, Ca-, Sr-, Li-, and Ba-montmorillonites decreased continuously to the zero-layer hydration state, whereas Na-, K-, Rb-, and Cs-montmorillonites swelled from the zero-layer hydration state even at the lowest temperature (50°C). A decrease in the basal spacing at the same RH but at different temperatures suggests the existence of metastable states or that the layer-stacking structure changes with temperature. The systematics of the swelling behavior of various homocationic montmorillonites as functions of RH and temperature (<150°C) at 1 atmare reported here.

Keywords

Basal SpacingHydrationInterlayer Exchangeable CationMontmorilloniteRelative HumiditySmectiteSwellingVapor PressureX-ray Diffraction
Type
Article
Information
Clays and Clay Minerals , Volume 59 , Issue 2 , April 2011 , pp. 165 - 175
Copyright
Copyright © The Clay Minerals Society 2011

References

Berend, I. Cases, J.M. Francois, M. Uriot, J.P. Michot, L. Maison, A. and Thomas, F., 1995 Mechanism of adsorption and desorption of water vapor by homoionic montmorillonites: 2. the Li+, Na+, K+, Rb+ and Cs+-exchanged forms. Clays and Clay Minerals 43 324–336 10.1346/CCMN.1995.0430307.CrossRefGoogle Scholar
Cases, J.M. Berend, I. Francois, M. Uriot, J.P. Michot, L.J. and Thomas, F., 1997 Mechanism of adsorption and desorption of water vapor by homoionic montmorillonites: 3. the Mg2+, Ca2+, Sr2+ and Ba2+-exchanged forms Clays and Clay Minerals 45 8–22 10.1346/CCMN.1997.0450102.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Sakharov, B.A. and Drits, V.A., 2005 Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns American Mineralogist 90 1358–1374 10.2138/am.2005.1776.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Malikova, N. Plançon, A. Sakharov, B.A. and Drits, V.A., 2005b New insights on the distribution of interlayer water in bi-hydrated smectite from X-ray diffraction profile modeling of 00l reflections Chemistry of Materials 17 3499–3512 10.1021/cm047995v.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Sakharov, B.A. Geoffroy, N. Jacquot, E. and Drits, V.A., 2007 Investigation of dioctahedral smectite hydration properties by modeling of X-ray diffraction profiles: Influence of layer charge and charge location American Mineralogist 92 1731–1743 10.2138/am.2007.2273.CrossRefGoogle Scholar
Ito, M. Okamoto, M. Shibata, M. Sasaki, Y. Danbara, T. Suzuki, K. and Watanabe, T., 1993 Mineral composition analysis of bentonite Japan Atomic Energy Agency .Google Scholar
Mooney, R.W. Keenan, A.G. and Wood, L.A., 1952 Adsorption of water vapor by montmorilllonite. II. Effect of exchangeableions and lattice swelling as measured by X-ray diffraction Journal of the American Chemical Society 74 1371–1374 10.1021/ja01126a002.CrossRefGoogle Scholar
Morodome, S. and Kawamura, K., 2009 Swelling behavior of Na- and Ca-montmorillonite up to 150°C by in situ X-ray diffraction experiments Clays and Clay Minerals 57 150–160 10.1346/CCMN.2009.0570202.CrossRefGoogle Scholar
Nakazawa, H. Yamada, H. and Fujita, T., 1992 Crystal synthesis of smectite applying very high pressure and temperature Applied Clay Science 6 395–401 10.1016/0169-1317(92)90006-9.CrossRefGoogle Scholar
Prost, R., 1975 Étude de l’hydratation des argiles: Interactions eau-miné ral et mécanism e de la ré tention de l’eau. II. Étude d’une smectite (hectorite) Annales Agronomiques 26 463–535.Google Scholar
Sato, T. Watanabe, T. and Otsuka, R., 1992 Effects of layer charge, charge location, and energy change on expansion properties of dioctahedral smectites Clays and Clay Minerals 40 103–113 10.1346/CCMN.1992.0400111.CrossRefGoogle Scholar
Shannon, R.D., 1976 Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Acta Crystallographica Section A 32 751–767 10.1107/S0567739476001551.CrossRefGoogle Scholar
Suquet, H D L C ^C and Pezerat, H., 1975 Swelling and structural organization of saponite Clays and Clay Minerals 34 379–384.Google Scholar
Tamura, K. Yamada, H. and Nakazawa, H., 2000 Stepwise hydration of high-quality synthetic smectite with various cations Clays and Clay Minerals 48 400–404 10.1346/CCMN.2000.0480311.CrossRefGoogle Scholar
Watanabe, T. and Sato, T., 1988 Expansion characteristics of montmorillonite and saponite under various relative humidity conditions Clay Science 7 129–138.Google Scholar