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Effects of Layer Charge, Charge Location, and Energy Change on Expansion Properties of Dioctahedral Smectites

Published online by Cambridge University Press:  28 February 2024

Tsutomu Sato
Affiliation:
Department of Mineral Resources Engineering, School of Science and Engineering, Waseda University Okubo, Shinjuku-ku, Tokyo 169, Japan
Takashi Watanabe
Affiliation:
Department of Geoscience, Joetsu University of Education Yamayashiki, Joetsu, Niigata, 943 Japan
Ryohei Otsuka
Affiliation:
Department of Mineral Resources Engineering, School of Science and Engineering, Waseda University Okubo, Shinjuku-ku, Tokyo 169, Japan

Abstract

Expansion properties often homoionic smectites that differed in amount and location of layer charge were examined by X-ray powder diffraction analysis at various relative humidities, or after glycerol or ethylene glycol solvations. Except for K-samples with glycerol solvation, and Na- and Ca-samples with ethylene glycol, differences in the basal spacings are observed in samples having similar layer charge. These results show that the basal spacings are larger when the layer charge is located in octahedral sites than when it is in tetrahedral sites. This suggests that expansion is due to the combined effects of the charge location and amount.

The effects of layer charge magnitude and location on expansion were represented by an energy change (expansion energy: ΔEr) during the hydration and solvation processes. Plots of basal spacings versus ΔEr show a reasonable relationship; the spacings generally decrease stepwise as the value of ΔEr increases. The basal spacings of K-samples with glycerol solvation, Na-saturated and K-saturated samples at 100% RH are apt to contract stepwise with increasing value of ΔEr. For these samples, the figures showing the relationship between each expanded phase and the charge characteristics are obtained from the isoquants of ΔEr, given the boundary of the expanded phases. A behavior test using these figures may be combined with the Greene-Kelly test to estimate the amount and the location of the layer charge of common smectites.

Type
Research Article
Copyright
Copyright © 1992, The Clay Minerals Society

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References

Aoki, S., Kohyama, N. and Sudo, T., An iron-rich montmorillonite in sediment core from the northeastern Pacific Deep-Sea Res 1974 21 865875.Google Scholar
Brindley, G. W., Ethylene glycol and glycerol complexes of smectites and vermiculites Clay Miner 1966 6 237259 10.1180/claymin.1966.006.4.01.CrossRefGoogle Scholar
Brown, G. and Farrow, R., Introduction of glycerol into flake aggregates by vapor pressure Clay Miner. Bull 1956 3 4445 10.1180/claymin.1956.003.15.13.CrossRefGoogle Scholar
Brunton, G., Vapor glycolation Amer. Mineral 1955 40 124126.Google Scholar
Farmer, V. C. and Russell, J. D., Interlayer complexes in layer silicates Trans. Faraday Soc 1971 67 27372749 10.1039/tf9716702737.CrossRefGoogle Scholar
Glaeser, R. and Mering, J., Homogeneous hydration domains of the smectites C.R. Acad. Sci., Paris 1968 46 436466.Google Scholar
Greene-Kelly, R., Irreversible dehydration in mont-morillonite. Part II Clay Miner. Bull 1953 2 5256 10.1180/claymin.1953.002.9.09.CrossRefGoogle Scholar
Greene-Kelly, R., The identification of montmorillonoids in clays J. Soil Sci 1953 4 233237 10.1111/j.1365-2389.1953.tb00657.x.CrossRefGoogle Scholar
Greene-Kelly, R., Dehydration of montmorillonite minerals Miner. Mag 1955 30 604615.Google Scholar
Harward, M. E. and Brindley, G. W., Swelling prop-erties of synthetic smectite in relation to lattice substitu-tions Clays & Clay Minerals 1965 13 209222 10.1346/CCMN.1964.0130121.CrossRefGoogle Scholar
Harward, M. E., Carstea, D. D. and Sayegh, A. H., Properties of vermiculites and smectites: Expansion and collapse Clays & Clay Minerals 1969 16 437447 10.1346/CCMN.1969.0160605.CrossRefGoogle Scholar
Hawel, B. F. and Licastro, P. H., Dielectric behavior of rocks and minerals Amer. Mineral 1961 46 269288.Google Scholar
Horváth, I., Novák, I. and Bailey, S. W., Potassium fixation and the charge of montmorillonite layers Proc. Int. Clay Conf., Mexico City, 1975 1976 Illinois Applied Publishing, Wilmette 185189.Google Scholar
Iwasaki, T., Relationship between X-ray basal reflections and interlayer cations of montmorillonite: On the distribution of Ca and Na ions J. Miner. Soc. Japan, Spec. Issue 1979 14 7889.Google Scholar
Iwasaki, T. and Watanabe, T., Distribution of Ca and Na ions in dioctahedral smectites and interstratified dioctahedral mica/smectites Clays & Clay Minerals 1988 36 7382 10.1346/CCMN.1988.0360110.CrossRefGoogle Scholar
Jaynes, W. F. and Bigham, J. M., Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites Clays & Clay Minerals 1987 35 440448 10.1346/CCMN.1987.0350604.CrossRefGoogle Scholar
Jenkins, H D B and Hartman, P., A new approach to electrostatic energy relations in minerals: The dioctahedral and trioctahedral micas Phil. Trans. Roy. Soc 1979 A293 169208 10.1098/rsta.1979.0088.Google Scholar
Jenkins, H D B and Hartman, P., A new approach to electrostatic calculations for complex silicate structures and their application to vermiculites containing a single layer of water molecules Proc. Int. Clay Conf., Bologna, Pavia, 1981, H. van Olphen and F. Veniale, Elsevier, Amsterdam 1982 8795.Google Scholar
Keren, R. and Shainberg, I., Water vapor isotherms and heat of immersion of Na/Ca-montmorillonite systems—I: Homoionic clay Clays & Clay Minerals 1975 23 193200 10.1346/CCMN.1975.0230305.CrossRefGoogle Scholar
Kodama, H., Ross, G. J., Iiyama, J. T. and Robert, J. L., Effect of layer charge location on potassium exchange and hydration of micas Amer. Mineral 1974 59 491495.Google Scholar
Machajdik, D. and Cicel, B., Potassium and ammonium-treated montmorillonites. II. Calculation of characteristic layer charge Clays & Clay Minerals 1981 29 4751 10.1346/CCMN.1981.0290107.CrossRefGoogle Scholar
Malla, P. B. and Douglas, L. A., Layer charge properties of smectites and vermiculites: Tetrahedral vs. octahedral Soil Sci. Soc. Amer. J 1987 51 13621366 10.2136/sssaj1987.03615995005100050048x.CrossRefGoogle Scholar
Matsuda, T., Beidellite from the Sano mine, Nagano Prefecture, Japan Clay Sci 1988 7 151159.Google Scholar
Mooney, R. W., Keenan, A. G. and Wood, L. A., Adsorption of water vapor by montmorillonite. II. Effect of exchangeable ions and lattice swelling as measured by X-ray diffraction J. Amer. Chem. Soc 1952 74 13311374 10.1021/ja01125a058.CrossRefGoogle Scholar
Moore, D. M. and Hower, J., Ordered interstratification of dehydrated and hydrated Na-smectite Clays & Clay Minerals 1975 34 379384 10.1346/CCMN.1986.0340404.CrossRefGoogle Scholar
Nadeau, P. H., Farmer, V. C., McHardy, W. J. and Bain, D. C., Compositional variations of the Unterrupsroth beidellite A mer. Mineral 1985 70 10041010.Google Scholar
Nagasawa, K., Study on a behavior of water in heating of clay minerals Report of grant-aid for science research 1988.Google Scholar
Schultz, L. G., Lithium and potassium adsorption; Dehydroxylation and structural water content of aluminous smectites Clays & Clay Minerals 1969 17 115149 10.1346/CCMN.1969.0170302.CrossRefGoogle Scholar
Suquet, H., De la Calle, C. and Pezerat, H., Swelling and structural organization of saponite Clays & Clay Minerals 1975 23 19 10.1346/CCMN.1975.0230101.CrossRefGoogle Scholar
Suquet, H., Iiyama, J. T., Kodama, H. and Pezerat, H., Synthesis and swelling properties of saponites with increasing layer charge Clays & Clay Minerals 1977 25 231242 10.1346/CCMN.1977.0250310.CrossRefGoogle Scholar
Walker, G. F., The mechanism of dehydration of Mg-vermiculite Clays & Clay Minerals 1956 4 101115 10.1346/CCMN.1955.0040115.CrossRefGoogle Scholar
Walker, G. F., Reactions of expanding-lattice clay minerals with glycerol and ethylene glycol Clay Miner. Bull 1958 3 302313 10.1180/claymin.1958.003.20.05.CrossRefGoogle Scholar
Watanabe, T., Identification of illite/montmorillonite interstratification by X-ray powder diffraction J. Miner. Soc. Japan, Spec. Issue 1981 15 3241.Google Scholar
Watanabe, T. and Sato, T., Expansion characteristics of montmorillonite and saponite under various relative humidity conditions Clay Sci 1988 7 129138.Google Scholar
Weaver, C. E., The distribution and identification of mixed layer clays in sedimentary rocks Amer. Mineral 1956 41 202221.Google Scholar