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Charge Heterogeneity and Nanostructure of 2:1 Layer Silicates by High-Resolution Transmission Electron Microscopy

Published online by Cambridge University Press:  28 February 2024

P. B. Malla ,
M. Robert ,
L. A. Douglas ,
D. Tessier  and
S. Komarneni
P. B. Malla
Affiliation:
Research & Development, Thiele Kaolin Company, P.O. Box 1056, Sandersville, Georgia 31082
M. Robert
Affiliation:
Station de Science du Sol, INRA, 78000 Versailles, France
L. A. Douglas
Affiliation:
Department of Environmental Sciences, Rutgers University, New Brunswick, New Jersey 08903
D. Tessier
Affiliation:
Station de Science du Sol, INRA, 78000 Versailles, France
S. Komarneni
Affiliation:
Materials Research Laboratory, Pennsylvania State University, University Park, Pennsylvania 16802
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Abstract

Several soil and reference smectites and vermiculites and one reference illite were examined by high-resolution transmission electron microscopy (HRTEM) to decipher the nanostructure and layer charge heterogeneity in these minerals. HRTEM results were compared with those obtained from powder X-ray diffraction (XRD) analysis. Samples were either exchanged with Na+ ions followed by equilibration with a very dilute solution of NaCl in a pressure membrane apparatus at 316 hPa (pF = 2.5) to see the effect of hydration and applied pressure on layer organization, or exchanged with dodecylammonium ions to see the expansion behavior. Oriented samples were embedded in a low viscosity resin and cut approximately 500 Å thick perpendicular to d(001) using an ultramicrotome fitted with a diamond knife. In general, Na-saturated soil clays possessed crystallites that were thinner (c-direction) and shorter (ab-direction) as compared with reference clays. In all cases, samples treated with dodecylammonium chloride exhibited nanostructures that were more disintegrated as compared with Na-saturated samples. In a soil vermiculite, dodecylammonium ion exchange showed frayed edges indicating the initiation of mica transformation to vermiculite from edge toward core. In a reference vermiculite (Transvaal) treated with dodecylammonium ions, in addition to completely expanded crystallites, a regular interstratification between expanded vermiculite and mica (phlogopite) layers was clearly observed in some crystallites. Such nanostructural details were not detected by XRD. HRTEM of the Na-treated illite showed thick crystallites having 10 Å layer separations, whereas the dodecylammonium-exchanged illite showed three types of layers with different degrees of expansion indicating charge heterogeneity in illite: 1) unexpanded (10 Å, highest charge) crystallites; 2) expanded high-charge vermiculite-like (24 Å) crystallites; and 3) occasionally expanded high-charge vermiculite-like (24 Å) layers interspersed in the matrix of 10Å crystallites.

Keywords

Charge heterogeneityClaysHigh-resolution transmission electron microscopyIlliteMontmorilloniteNanostructureSmectiteVermiculite
Type
Research Article
Information
Clays and Clay Minerals , Volume 41 , Issue 4 , August 1993 , pp. 412 - 422
Copyright
Copyright © 1993, The Clay Minerals Society

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References

Ahn, J. H. and Peacor, D. R., 1986 Transmission and analytical electron microscopy of the smectite-to-illite transition Clays & Clay Minerals 34 165 – 179 10.1346/CCMN.1986.0340207.Google Scholar
Ahn, J. H. and Peacor, D. R., 1987 Illite/smectite from Gulf Coast shales: A reappraisal of transmission electron microscope images Clays & Clay Minerals 37 542 – 546.Google Scholar
Bailey, S. W., 1980 Summary of recommendation of AI-PEA nomenclature committee Clays & Clay Minerals 28 73 – 78 10.1346/CCMN.1980.0280114.Google Scholar
Banfield, J. F. and Eggleton, R. A., 1988 Transmission electron microscopy study of biotite weathering Clays & Clay Minerals 36 47 – 60 10.1346/CCMN.1988.0360107.CrossRefGoogle Scholar
Bell, T. E., 1986 Microstructure in mixed-layer illite/smectite and its relationship to the reaction of smectite to illite Clays & Clay Minerals 34 146 – 154 10.1346/CCMN.1986.0340205.CrossRefGoogle Scholar
Ben Rhaiem, H., Pons, C. H., Tessier, D., Schultz, L. G., van Olphen, H. and Mumpton, F. A., 1987 Factors affecting the microstructure of smectites: Role of cation and history of applied stresses Proc. Intern. Clay Conf., Denver, 1985 Bloomington, Indiana The Clay Minerals Society 292 – 297.Google Scholar
Brindley, G., 1966 Ethylene glycol and glycerol complexes of smectites and vermiculites Clays & Clay Minerals 6 237 – 260 10.1180/claymin.1966.006.4.01.CrossRefGoogle Scholar
Eggleton, R. A. and Banfield, J. F., 1985 The alteration of granitic biotite to chlorite Amer. Mineral. 70 902 – 910.Google Scholar
Ghabru, S. K., Mermut, A. R. and Arnaud, R. J. S., 1989 Layer-charge and cation-exchange characteristics of ver-miculite (weathered biotite) isolated from a gray luvisol in northeastern Saskatchewan Clays & Clay Minerals 37 164 – 172 10.1346/CCMN.1989.0370208.CrossRefGoogle Scholar
Hower, J. and Mowatt, T. C., 1966 The mineralogy of illites and mixed-layer illite/montmorillonite A mer. Mineral. 51 825 – 854.Google Scholar
Hsu, P. H., 1968 Heterogeneity of montmorillonite surface and its effect on the nature of hydroxy-aluminum interlay-ers Clays & Clay Minerals 16 303 – 311 10.1346/CCMN.1968.0160407.CrossRefGoogle Scholar
Iijima, S. and Allpress, J. G., 1974 Structural studies by high resolution electron microscopy: Tetragonal tungsten bronze-type structures in the system Nb205-WO3 Acta. Cryst. A30 22 – 29 10.1107/S0567739474000039.CrossRefGoogle Scholar
Jackson, M. L., 1969 Soil Chemical Analysis—Advanced Course 2 Madison, Wisconsin Department Soil Science, University of Wisconsin.Google Scholar
Jackson, M. L., Hseung, Y., Corey, R. B., Evans, E. J. and Vanden Heuvel, R. C., 1952 Weathering sequence of clay-size minerals in soils and sediments: II. Chemical weathering and layer silicates Soils Sci. Soc. Am. Proc. 16 3 – 6 10.2136/sssaj1952.03615995001600010002x.CrossRefGoogle Scholar
Lagaly, G., 1982 Layer charge heterogeneity in vermiculites Clays & Clay Minerals 30 215 – 222 10.1346/CCMN.1982.0300308.CrossRefGoogle Scholar
Lagaly, G., Weiss, A. and Heller, L., 1969 Determination of the layer charge in mica-type layer silicates Proc. Intern. Clay Conf., Tokyo, 1969, Vol. 1 Jerusalem Israel University Press 61 – 80.Google Scholar
Lagaly, G., and Weiss, A., (1970) Inhomogenous charge distribution in mica-type layer silicates: in Reunion Hispano-Belgade Minerals de la Arcilla, Serratosa, J. M., ed., Consejo Superior de Investigaciones Científicas, Madrid, 179–187.Google Scholar
Laird, D. A., Scott, A. D. and Fenton, T. E., 1987 Interpretation of alkylammonium characterization of soil clays Soil Sci. Soc. Am. J. 51 1659 – 1663 10.2136/sssaj1987.03615995005100060046x.CrossRefGoogle Scholar
Laird, D. A., Thompson, M. L. and Scott, A. D., 1989 Technique for transmission electron microscopy and X-ray powder diffraction analyses of the same clay mineral specimen Clays & Clay Minerals 37 280 – 282 10.1346/CCMN.1989.0370313.CrossRefGoogle Scholar
MacEwan, D. C. M., 1944 Identification of the montmorillonite group of minerals by X-rays Nature 154 577 – 578 10.1038/154577b0.CrossRefGoogle Scholar
Malla, P. B., (1987) Characterization of layer charge, expansion behavior, and weathering of 2:1 layer silicate clays: Ph.D. dissertation, Rutgers University, New Brunswick, New Jersey, 205 pp.Google Scholar
Malla, P. B., Douglas, L. A., Schultz, L. G., van Olphen, H. and Mumpton, F. A., 1987a Identification of expanding layer silicates: Layer charge vs expansion properties Proc. Intern. Clay Conf., Denver, 1985 Bloomington, Indiana The Clay Minerals Society 277 – 283.Google Scholar
Malla, P. B. and Douglas, L. A., 1987b Layer charge properties of smectites and vermiculites: Tetrahedral vs octahedral Soil Sci. Soc. Am. J. 51 1362 – 1366 10.2136/sssaj1987.03615995005100050048x.CrossRefGoogle Scholar
Malla, P. B., Douglas, L. A., Robert, M. and Balasubramaniam, K. S., 1989 Weathering and layer charge dynamics in 2:1 layer silicate clays Weathering: Its Products and Deposits, Vol. 1 Athens, Greece Theophrastus Publications 231 – 256.Google Scholar
Malla, P. B. and Komarneni, S., 1990 High resolution transmission electron microscopy (HRTEM) in the study of soils and clays Adv. Soil Sci. 12 159 – 186 10.1007/978-1-4612-3316-9_4.CrossRefGoogle Scholar
Olives Banos, J. and Amouric, M., 1984 Biotite chloriti-zation by interlayer bricitization as seen by HRTEM A mer. Mineral. 69 869 – 871.Google Scholar
Page, R. and Wenk, H. R., 1979 Phyllosilicate alteration of plagioclase studied by transmission electron microscopy Geology 7 393 – 397 10.1130/0091-7613(1979)7<393:PAOPSB>2.0.CO;2.2.0.CO;2>CrossRefGoogle Scholar
Reynolds, R. C. and Hower, J., 1970 The nature of inter-layering in mixed-layer illite/montmorillonite Clays & Clay Minerals 18 25 – 36 10.1346/CCMN.1970.0180104.CrossRefGoogle Scholar
Robert, M., Hardy, M. and Elsass, F., 1991 Crystallo-chemistry, properties and organization of soil clays derived from major sedimentary rocks in France Clay Miner. 26 409 – 420 10.1180/claymin.1991.026.3.09.CrossRefGoogle Scholar
Ruehlicke, G. and Niederbudde, E. A., 1985 Determination of layer charge density of expandable 2:1 clay minerals in soils and loess sediment using alkylammonium method Clay Miner. 20 291 – 300 10.1180/claymin.1985.020.3.02.CrossRefGoogle Scholar
Sawhney, B. L., 1967 Interstratification in vermiculite Clays & Clay Minerals 15 75 – 84 10.1346/CCMN.1967.0150109.CrossRefGoogle Scholar
Scott, D. A. and Smith, S. J., 1967 Visible changes in macroscopic particles that occur with potassium depletion Clays & Clay Minerals 15 357 – 373 10.1346/CCMN.1967.0150138.CrossRefGoogle Scholar
Srodoń, J., Andreoli, C., Elsass, F. and Robert, M., 1990 Direct high-resolution transmission electron microscopic measurement of expandability of mixed-layer illite/smectite in bentonite rock Clays & Clay Minerals 38 373 – 379 10.1346/CCMN.1990.0380406.CrossRefGoogle Scholar
Tessier, D., (1984) Etude expérimentale de l’organisation des matériaux argileux: Docteur es sciences thesis, INR A, Paris, 361 pp.Google Scholar
Tessier, D. and Berner, J., 1979 Utilisation de la micros-copie électronique a balayage dans l’étude des sols. Observation de sols humides soumis a defferents pF Science du Sol 1 67 – 82.Google Scholar
Vali, H. and Roster, H. M., 1986 Expanding behavior, structural disorder, regular and random irregular interstratification of 2:1 layer silicates studied by high-resolution images of transmission electron microscope Clay Miner. 2 827 – 859 10.1180/claymin.1986.021.5.01.CrossRefGoogle Scholar
Veblen, D. R. and Ferry, J. M., 1983 A TEM study of the biotite-chlorite reaction and comparison with petrologic observations Amer. Mineral. 68 1160 – 1168.Google Scholar