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Characterization of Montmorillonite Surfaces After Modification by Organosilane

Published online by Cambridge University Press:  28 February 2024

Kang Song*
Affiliation:
Chemistry Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439, USA
Giselle Sandí*
Affiliation:
Chemistry Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, Illinois 60439, USA
*
Present address: Novellus Systems, Inc., 4000 N. First Street, M/S 81A, San Jose, California 95134, USA
*E-mail address of corresponding author: gsandi@anl.gov
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Abstract

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X-ray powder diffraction (XRD), thermal gravimetric analysis (TGA), surface area measurements, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy were used to examine the surface properties of organosilane-modified smectite-type aluminosilicate clays. Organic modified clays derived from the reactions of montmorillonite (containing 93–95% montmorillonite from a bentonite, <1% quartz, and 4–6% opal CT) with octadecyltrichlorosilane (C18H37SiCl3) and octadecyltrimethoxysilane [C18H37Si(OMe)3] are highly hydrophobic. Surface loadings of the modified clays depend on the organosilane and the solvent, and they range from 10 to 25 wt. %. The organic species are probably adsorbed to the outer surfaces and bound to the edges of the clay via condensation with edge-OH groups. Encapsulation of montmorillonite with C18H37SiCl3 and C18H37Si(OMe)3 resulted in a hydrophobic coating that acts like a “cage” around the clay particles to limit diffusion. Basal spacings of the organic modified clays remain at ∼15 Å upon heating to 400°C in N2, whereas those of unmodified clays collapse to ∼10 Å. A considerable reduction in surface area (by 75–90%) for organic modified clays is observed, which is consistent with the existence of a surface coating. The solvent used can affect the amount of organic silane coated on the clay particles, whereas the difference between the products prepared using C18H37SiCl3 and C18H37Si(OMe)3 in the same solvent is relatively small. The carbon and oxygen K-edge NEXAFS spectroscopy of the modified montmorillonite surfaces showed that surface coatings on the outside of the clay particles exist. The encapsulating system may allow for economical remediation and storage of hazardous materials.

Type
Research Article
Copyright
Copyright © 2001, The Clay Minerals Society

References

Allara, D.L. and Nuzzo, R.G., 1985 Spontaneously organized molecular assemblies. 1. Formation, dynamics, and physical properties of n-alkanoic acids adsorbed from solution on an oxidized aluminum surface Langmuir 1 4552 10.1021/la00061a007.CrossRefGoogle Scholar
Aznar, A.J. Sanz, J. and Ruiz-Hitzky, E., 1992 Mechanism of the grafting of organosilanes on mineral surfaces. IV. Phenylderivatives of sepiolite and poly(organosiloxanes) Colloid Polymer Science 270 165176 10.1007/BF00652183.CrossRefGoogle Scholar
Berger, G., 1941 Structure of montmorillonite Chem Weekhlat 38 4243.Google Scholar
Boyd, S.A., Mortland, M.M. and Chiou, C.T. (1988) Sorption characteristics of organic compounds on hexadecyltri-methylammonium-smectite. Soil Science Society of America Journal, 52, 652—657.CrossRefGoogle Scholar
Braggs, B. Fornasiero, D. Ralston, J.S. and Smart, R., 1994 The effect of surface modification by an organosilane on the electrochemical properties of kaolinite Clays and Clay Minerals 42 123136 10.1346/CCMN.1994.0420203.CrossRefGoogle Scholar
Brauner, S. Emmett, R.H. and Teller, E., 1938 Adsorption of gases in multimolecular layers Journal of the American Chemical Society 62 17231732 10.1021/ja01864a025.Google Scholar
Carrado, K.A. Hayatsu, R. Botto, R.E. and Winans, R.E., 1990 Reactivity of anisoles on clay and pillared clay surfaces Clays and Clay Minerals 38 250256 10.1346/CCMN.1990.0380303.CrossRefGoogle Scholar
Carson, G.A. and Granick, S., 1990 Self-assembly of octa-decyltrichlorosilane monolayers on mica Journal of Material Research 5 17451751 10.1557/JMR.1990.1745.CrossRefGoogle Scholar
Chen, J.G. Kim, C.M. Frühberger, B. DeVries, B.D. and Touvelle, M.S., 1994 A NEXAFS determination of the oxidation state of vanadium carbide on V(110): Observation of charge transfer from vanadium to carbon Surface Science 321 145155 10.1016/0039-6028(94)90035-3.CrossRefGoogle Scholar
Cowan, C.T., 1963 Adsorption by organo-clay complexes II Clays and Clay Minerals 10 226234 10.1346/CCMN.1961.0100118.CrossRefGoogle Scholar
Deuel, H. Huber, G. and Iberg, R., 1950 Organische deri-vate von tonmineralien Helvetica Chimica Acta 33 12291232 10.1002/hlca.19500330514.CrossRefGoogle Scholar
Fernandez-Hernandez, M.N. and Ruiz-Hitzky, E., 1979 Interaction of isocyanate with sepiolite Clay Minerals 14 295305 10.1180/claymin.1979.014.4.06.CrossRefGoogle Scholar
Giaquinta, D.M. Soderholm, L. Yuchs, S.E. and Wasserman, S.R., 1997 The speciation of uranium in a smectite clay. Evidence for catalyzed uranyl reduction Radiochimica Acta 76 113121 10.1524/ract.1997.76.3.113.CrossRefGoogle Scholar
Gieseking, J.E., 1949 The clay minerals in soils Advances in Agronomy 1 59204.Google Scholar
Hair, M.L., 1977 Effect of surface structure on the reaction of silica surface with hydrogen-sequestering agents Journal of Colloid and Interface Science 60 154161 10.1016/0021-9797(77)90266-1.CrossRefGoogle Scholar
Hair, M.L. and Hertl, W., 1969 Reaction of chlorosilanes with silica surfaces Journal of Physical Chemistry 73 23722378 10.1021/j100727a046.CrossRefGoogle Scholar
Hermosin, M.C. and Cornejo, J., 1993 Organic chemicals in the environment Journal of Environmental Quality 22 325331 10.2134/jeq1993.00472425002200020013x.CrossRefGoogle Scholar
Hermosin, M.C. Cornejo, J. and Perez-Rodriguez, J.L., 1982 Reaction of sepiolite and palygorskite with diazo-methane. I Reunion Iberoamericana de Arcillas (abstracts). .Google Scholar
Kessel, C.R. and Granick, S., 1991 Formation and characterization of a highly ordered and well-anchored alkylsilane monolayers on mica by self-assembly Langmuir 7 532538 10.1021/la00051a020.CrossRefGoogle Scholar
Maoz, R. and Sagiv, J., 1987 Penetration controlled reactions in organized monolayer assemblies. 1. Aqueous permanganate interaction with monolayer and multilayer films of long-chain surfactants Langmuir 3 10341044 10.1021/la00078a027.CrossRefGoogle Scholar
Morris, H.D. Bank, S. and Ellis, P.D., 1990 27A1 NMR spectroscopy of iron-bearing montmorillonite clays Journal of Physical Chemistry 94 31213129 10.1021/j100370a069.CrossRefGoogle Scholar
Mortland, M.M. Shaobai, S. and Boyd, S.A., 1986 Clay-organic complexes as adsorbents for phenol and chloro-phenols Clays and Clay Minerals 34 581585 10.1346/CCMN.1986.0340512.CrossRefGoogle Scholar
Nuzzo, R.G. Fusco, F.A. and Allara, D.L., 1987 Spontaneously organized molecular assemblies. 3. Preparation and properties of solution adsorbed monolayers of organic disulfides on gold surfaces Journal of the American Chemical Society 109 23582368 10.1021/ja00242a020.CrossRefGoogle Scholar
Ogawa, H. Chihara, T. and Taya, K., 1985 Selective monomethyl esterification of dicarboxylic acids by use of mon-ocarboxylate chemisorption on alumina Journal of the American Chemical Society 107 13651369 10.1021/ja00291a042.CrossRefGoogle Scholar
Ogawa, M. Okutomo, S. and Kuroda, K., 1998 Control of interlayer microstructures of a layered silicate by surface modification with organochlorosilanes Journal of the American Chemical Society 120 73617362 10.1021/ja981055s.CrossRefGoogle Scholar
Parker, J.L. Cho, D.L. and Claesson, P.M., 1989 Plasma modification of mica: Forces between fluorocarbon surfaces in water and a nonpolar liquid Journal of Physical Chemistry 93 61216125 10.1021/j100353a034.CrossRefGoogle Scholar
Parker, J.L., Claesson, P.M., Cho, D.L., Ahlberg, A., Tidblad, J. and Blomberg, E. (1990) Plasma modification of mica. Journal of Colloid and Interface Science, 134, 449—458.CrossRefGoogle Scholar
Porter, M.D. Bright, T.B. Allara, D.L. and Chidsey, C.E., 1987 Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry Journal of the American Chemical Society 109 35593568 10.1021/ja00246a011.CrossRefGoogle Scholar
Rausell-Colom, J.A. Serratosa, J.M. and Newman, A.C.D., 1987 Reactions of clays with organic substances. I Chemistry of Clays and Clay Minerals New York Wiley-Interscience 371422.Google Scholar
Roberts, A.L. Street, G.B. and White, D., 1964 The mechanism of phenol adsorption by organo-clay derivatives Journal of Applied Chemistry 14 261265 10.1002/jctb.5010140608.CrossRefGoogle Scholar
Ruiz-Hitzky, E. and Fripiatt, J.J., 1976 Organomineral derivatives obtained by reacting organochlorosilanes with the surface of silicates in organic solvents Clays and Clay Minerals 24 2530 10.1346/CCMN.1976.0240102.CrossRefGoogle Scholar
Rutherford, D. Chiou, C.T. and Eberl, D.D., 1997 Effects of exchanged cation on the microporosity of montmorillon-ite Clays and Clay Minerals 45 534543 10.1346/CCMN.1997.0450405.CrossRefGoogle Scholar
Srinavasan, K.R. and Fogler, H.S., 1990 Use of inorgano-organo-clays in the removal of priority pollutants from industrial wastwaters: Adsorption of beno(a)pyrene and chlorophenols from aqueous solutions Clays and Clay Minerals 38 287293 10.1346/CCMN.1990.0380307.CrossRefGoogle Scholar
Stöhr, J., 1992 NEXAFS Spectroscopy. New York Springer-Verlag 10.1007/978-3-662-02853-7.CrossRefGoogle Scholar
Thomas, J.M., Whittingham, M.S. and Jacobson, A.J., 1982 Sheet silicate intercalates: New agents for unusual chemical conversions. I Intercalation Chemistry New York Academic Press 55100 10.1016/B978-0-12-747380-2.50008-0.CrossRefGoogle Scholar
Wasserman, S.R. Soderholm, L. and Staub, U., 1998 Effect of surface modification on the interlayer chemistry of iron in a smectite clay Chemistry of Materials 10 559566 10.1021/cm9705597.CrossRefGoogle Scholar
Wasserman, S.R. Tao, Y.T. and Whitesides, G.M., 1989 Structure and reactivity of alkylsiloxane monolayers formed by reaction of alkyltrichlorosilanes on silicon substrates Langmuir 5 10741087 10.1021/la00088a035.CrossRefGoogle Scholar
Wood, J. and Sharma, R., 1994 Preparation of a robust hydrophobic monolayer on mica Langmuir 10 23072310 10.1021/la00019a047.CrossRefGoogle Scholar