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Swelling behavior of Na- and Ca-montmorillonite up to 150°C by in situ X-Ray diffraction experiments

Published online by Cambridge University Press:  01 January 2024

Shoji Morodome
Affiliation:
Department of Earth and Planetary Science, Tokyo Institute of Technology, Ookayama 2-12-1-12, Meguro-ku, Tokyo 152-8551, Japan
Katsuyuki Kawamura*
Affiliation:
Department of Earth and Planetary Science, Tokyo Institute of Technology, Ookayama 2-12-1-12, Meguro-ku, Tokyo 152-8551, Japan
*
* E-mail address of corresponding author: kawamura.k.ah@m.titech.ac.jp

Abstract

The effects of temperature on the swelling properties of smectites are important for a variety of different geological conditions, but studies on this topic have been rather limited. The purpose of this study was to investigate the swelling behavior of Na- and Ca-montmorillonite at various temperatures greater than room temperature, up to 150°C, using in situ X-ray diffraction (XRD) analysis. A sample chamber was designed, the temperature and humidity of which were controlled precisely, for environmental in situ measurements. The XRD measurements were performed at small relative humidity (RH) intervals for precise observation of the swelling behavior.

The swelling behavior of Na-montmorillonite showed distinct zero-, one-, and two-layer hydration states. The basal spacings of Na-montmorillonite changed continuously with RH for various temperatures in the transition region between the zero- and one-layer hydration states, and the swelling curves of the transition region moved to greater degrees of RH with increasing temperature. The basal spacings jumped from the one- to two-layer hydration states for all temperatures at almost the same RH.

The basal spacings of Ca-montmorillonite changed continuously from the zero- to the two-layer hydration states at all temperatures. This behavior is remarkably different from that of Na-montmorillonite. At low-RH conditions, the d001 value of Ca-montmorillonite decreased with increasing temperature. The swelling curves of Ca-montmorillonite did not show a plateau at any temperature for the one-layer hydration state. The swelling curves of Ca-montmorillonite moved to greater RH with temperature, similar to the transformation region between the zero- and one-layer hydration states in Na-montmorillonite. These differences between Na- and Ca-montmorillonite are related to the hydration powers of exchangeable cations.

Type
Article
Copyright
Copyright © The Clay Minerals Society 2009

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References

Ben Brahim, J. Armagan, N. Besson, G. and Tchoubar, C., 1983 X-ray diffraction studies on the arrangement of water molecules in a smectite. I. Homogeneous two-water-layer Na-beidellite Journal of Applied Crystallography 16 264269 10.1107/S0021889883010353.CrossRefGoogle Scholar
Bradley, W.F. Grim, R.E. and Clark, G.F., 1937 A study of the behavior of montmorillonite upon wetting Zeitschrift für Kristallographie 97 216222.Google 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. Part I. Montmorillonite hydration properties American Mineralogist 90 13581374 10.2138/am.2005.1776.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Malikova, N. Plançon, A. Sakharov, B.A. and Drits, V.A., 2005 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 34993512 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 17311743 10.2138/am.2007.2273.CrossRefGoogle Scholar
Hendricks, S.B. Nelson, R.A. and Alexander, L.T., 1940 Hydration mechanism of the clay mineral montmorillonite saturated with various cations Journal of the American Chemical Society 62 14571464 10.1021/ja01863a037.CrossRefGoogle Scholar
Ito, M., Okamoto, M., Shibata, M., Sasaki, Y., Danbara, T., Suzuki, K., and Watanabe, T. (1993) Mineral composition analysis of bentonite. PNC TN8430 93-003, Japan Atomic Energy Agency (in Japanese).Google Scholar
Iwasaki, T. and Watanabe, T., 1988 Distribution of Ca and Na ions in dioctahedral smectites and interstratified dioctahedral mica/smectites Clays and Clay Minerals 36 7382 10.1346/CCMN.1988.0360110.CrossRefGoogle Scholar
Kakinoki, J. and Komura, Y., 1952 Intensity of X-ray diffraction by one-dimensionally disordered crystals. I. General derivation in cases of the ‘Reichweite’ S=0 and 1 Journal of Physical Society of Japan 7 3035 10.1143/JPSJ.7.30.CrossRefGoogle Scholar
Kawamura, K. Ichikawa, Y. Nakano, M. Kitayama, K. and Kawamura, H., 1999 Swelling properties of smectite up to 90°C: In situ X-ray diffraction experimental and molecular dynamics simulation Engineering Geology 54 7579 10.1016/S0013-7952(99)00063-0.CrossRefGoogle Scholar
MacEwan, D.M.C., 1958 Fourier transform methods for studying X-ray scattering from lamellar systems. II. The calculation of X-ray diffraction effects for various types of interstratification Kolloidzeitschrift 156 6167.Google Scholar
Mooney, R.W. Keenan, A.G. and Wood, L.A., 1952 Adsorption of water vapor by montmorillonite. II. Effect of exchangeable ions and lattice swelling as measured by X-ray diffraction Journal of the American Chemical Society 74 13711374 10.1021/ja01126a002.CrossRefGoogle Scholar
Moore, D.M. and Hower, J., 1986 Ordered interstratification of dehydrated and hydrated Na-smectite Clays and Clay Minerals 34 379384 10.1346/CCMN.1986.0340404.CrossRefGoogle Scholar
Nagelschmidt, G., 1936 On the lattice shrinkage and structure of montmorillonite Zeitschrift für Kristallographie 93 481487.CrossRefGoogle Scholar
Nakazawa, H. Yamada, H. and Fujita, T., 1992 Crystal synthesis of smectite applying very high pressure and temperature Applied Clay Science 6 395401 10.1016/0169-1317(92)90006-9.CrossRefGoogle Scholar
Prost, R., 1975 Étude de l’hydratation des argiles: Interactions eau-minéral et mécanisme de la rétention de l’eau. II. — Étude d’une smectite (hectorite) Annales Agronomique 26 463535.Google Scholar
Reynolds, R.C. and Hower, J., 1970 The nature of interlayering in mixed-layer illite-montmorillonites Clays and Clay Minerals 18 2536 10.1346/CCMN.1970.0180104.CrossRefGoogle 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 103113 10.1346/CCMN.1992.0400111.CrossRefGoogle Scholar
Suquet, H. De La Calle, C. and Pezerat, H., 1975 Swelling and structural organization of saponite Clays and Clay Minerals 34 379384.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 400404 10.1346/CCMN.2000.0480311.CrossRefGoogle Scholar
Watanabe, T., 1988 The structural model of illite/smectite interstratified mineral and the diagram for its identification Clay Science 7 97114.Google Scholar
Watanabe, T. and Sato, T., 1988 Expansion characteristics of montmorillonite and saponite under various relative humidity conditions Clay Science 7 129138.Google Scholar
Yamada, H. Nakazawa, H. Hashizume, H. Shimomura, S. and Watanabe, T., 1994 Hydration behavior of Na-smectite crystals synthesized at high pressure and high temperature Clays and Clay Minerals 42 7780 10.1346/CCMN.1994.0420110.CrossRefGoogle Scholar