Hostname: page-component-77c89778f8-vsgnj Total loading time: 0 Render date: 2024-07-23T15:10:19.093Z Has data issue: false hasContentIssue false

The viscosity of organic liquid suspensions of trimethyldococylammonium-montmorillonite complexes

Published online by Cambridge University Press:  01 January 2024

Makoto Minase*
Affiliation:
Laboratory of Applied Clay Technology (LACT), Hojun Co. Ltd., 1433-1 Haraichi, Annaka, Gunma 379-0133, Japan Department of Earth and Planetary Sciences, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan
Mitsuji Kondo
Affiliation:
Laboratory of Applied Clay Technology (LACT), Hojun Co. Ltd., 1433-1 Haraichi, Annaka, Gunma 379-0133, Japan
Masanobu Onikata
Affiliation:
Laboratory of Applied Clay Technology (LACT), Hojun Co. Ltd., 1433-1 Haraichi, Annaka, Gunma 379-0133, Japan
Katsuyuki Kawamura
Affiliation:
Department of Earth and Planetary Sciences, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan
*
* E-mail address of corresponding author: minase@hojun.co.jp

Abstract

An organophilic bentonite was prepared by means of a reaction of natural Na-montmorillonite with trimethyldococylammonium which has an especially long n-alkyl chain. The addition of trimethyldococylammonium to montmorillonite was in the range 0.25–3.0 times the cation exchange capacity (CEC) of the clay (i.e. 0.23–2.82 mmol/g clay). The particle morphology in organic liquid suspensions of organoclay complexes was studied by measuring the viscosity based on Eyring’s rate process and Robinson’s relative sediment volume. In toluene, montmorillonite with 1.17 mmol/g clay trimethyldococylammonium (1.25 times the CEC) had the largest specific gel volume, relative sediment volume, and K-factor. The results of the stoichiometry for trimethyldococylammonium-montmorillonite show that practically all of the quaternary ammonium was adsorbed to montmorillonite. Maximum half widths of 001 reflections from X-ray diffraction patterns were obtained in the range 0.74–1.17 mmol/g clay, indicating a disordered arrangement of the organic cation molecules intercalated between the layers. Appreciable shifts to lower-frequency regions in the Fourier transform infrared absorption spectra as a result of CH2-stretching vibrations were observed with increasing amounts of the organic cation. When increasing the amount of organic cation added to the clay from 0.94 to 1.41 mmol/g clay, a large shift occurred to the lower-frequency side, approaching the frequency of the organic cation alone. This indicates that the interaction between adjacent hydrocarbon chains becomes progressively stronger, due to van der Waals attraction, with increases in the amount of organic cation. Interactions of the alkyl chains in trimethyldococylammonium-montmorillonite complexes with irregularly distributed and randomly arranged alkyl chains between the silicate layers were weak, and, as a result, solvation with external organic liquids occurred and gel formation developed through macroscopic swelling of the organoclay.

Type
Research Article
Copyright
Copyright © 2008, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bingham, E., 1922 Fluidity & Plasticity UK McGraw-Hill Co. Berkshire 440 pp.Google Scholar
Bish, D.L. Duffy, C.J., Stucki, J.W. Bish, D.L. and Mumpton, F.A., 1990 Thermogravimetric analysis of minerals Thermal Analysis in Clay Science Boulder, Colorado The Clay Minerals Society 127129.Google Scholar
Bonczek, J.L. Harris, W.G. and Nkedi-Kizza, P., 2002 Monolayer to bilayer transitional arrangements of hexadecyltrimethylammonium cations on Na-montmorillonite Clays and Clay Minerals 50 1117 10.1346/000986002761002612.CrossRefGoogle Scholar
Brindley, G.W. Lemaitre, J. and Newman, A.C.D., 1987 Thermal, oxidation and reduction reactions of clay minerals Chemistry of Clays and Clay Minerals London Mineralogical Society 321.Google Scholar
Brown, G., 1961 The X-ray Identification and Crystal Structure of Clay Minerals London Mineralogical Society 181.Google Scholar
Egashira, K., 1977 Viscosities of allophane and imogolite clay suspensions Clay Science 5 8795.Google Scholar
Einstein, A., 1906 Eine neue Bestimmung der Molekuldimension Annalen der Physik 19 289306 10.1002/andp.19063240204.CrossRefGoogle Scholar
El-Akkada, T.M. Flex, N.S. Guindy, N.M. El-Massry, S.R. and Nashed, S., 1982 Thermal analyses of mono- and divalent montmorillonite cationic derivatives Thermochimica Acta 59 917 10.1016/0040-6031(82)87087-1.CrossRefGoogle Scholar
Gabrysh, W.F. Eyring, H. Lin-Sen, P. and Gabrysh, A.F., 1963 Rheological factors for bentonite suspensions Journal of the American Ceramic Society 46 523529 10.1111/j.1151-2916.1963.tb14603.x.CrossRefGoogle Scholar
Gates, W.P., 2004 Crystalline swelling of organo-modified clays in ethanol-water solutions Applied Clay Science 27 112 10.1016/j.clay.2003.12.001.CrossRefGoogle Scholar
Green, H., 1949 Industrial Rheology and Rheological Structures New York J. Wiley & Sons 127.Google Scholar
Grim, R.E., 1962 Applied Clay Mineralogy New York McGraw-Hill 205216.Google Scholar
Grim, R.E., 1968 Clay Mineralogy New York McGraw-Hill 313328.Google Scholar
Güven, N., Güven, N. and Pollastro, R.M., 1992 Rheological aspects of aqueous smectite suspensions Clay-Water Interface and its Rheological Implications Boulder, Colorado The Clay Minerals Society 8288.Google Scholar
Güven, N., Güven, N. and Pollastro, R.M., 1992 Rheological aspects of aqueous smectite suspensions Clay-Water Interface and its Rheological Implications Boulder, Colorado The Clay Minerals Society 9092.Google Scholar
Hauser, E.A. (1950) Modified gel-forming clay and process of producing same. U.S. Patent, 2,531,427, Nov. 28 (1950).Google Scholar
He, H. Frost, R.L. Deng, F. Zhu, J. Wen, X. and Yuan, P., 2004 Conformation of surfactant molecules in the inter-layer of montmorillonite studied by 13C MAS NMR Clays and Clay Minerals 52 350356 10.1346/CCMN.2004.0520310.CrossRefGoogle Scholar
Huang, P.M. and Brindley, G.W., 1970 Methylene blue absorption by clay minerals. Determination of surface areas and cation exchange capacities (clay-organic studies XVIII) Clays and Clay Minerals 18 203212 10.1346/CCMN.1970.0180404.CrossRefGoogle Scholar
Jordan, J.W., 1949 Organophilic bentonites. I. Swelling in organic liquids Journal of Physical and Colloid Chemistry 53 294306 10.1021/j150467a009.CrossRefGoogle Scholar
Jordan, J.W., 1961 Organophilic clay-base thickeners Proceedings of the Tenth National Conference on Clays and Clay Minerals 299308.CrossRefGoogle Scholar
Jordan, J.W. Hook, B.J. and Finlayson, C.M., 1950 Organophilic bentonites. II. Organic liquid gels Journal of Physical and Colloid Chemistry 54 11961208 10.1021/j150482a012.CrossRefGoogle Scholar
Kuhn, W. and Kuhn, H., 1945 Die abhangigkeit der viskositat vom stromungsgefalle bei hoch verdunnten Suspensionen und lösungen Helvetica Chimica Acta 28 97127 10.1002/hlca.19450280111.CrossRefGoogle Scholar
Lagaly, G. and Weiss, A., 1969 Determination of the layer charge in mica-type silicates 1 6180.Google Scholar
Lagaly, G. and Weiss, A., 1970 Inhomogeneous charge distributions in mica-type layer silicates Proceedings of ‘Reunion Hispano-Belga Minerales de la Arecilla’ Madrid Consejo Superior de Investigaciones Cientificos 179187.Google Scholar
Lagaly, G. Fernandez Gonzalez, M. and Weiss, A., 1976 Problems in layer-charge determination of montmorillonites Clay Minerals 11 173187 10.1180/claymin.1976.011.3.01.CrossRefGoogle Scholar
Lee, S.Y. and Kim, S.J., 2002 Expansion of smectite by hexadecyltrimethylammonium Clays and Clay Minerals 50 435445 10.1346/000986002320514163.CrossRefGoogle Scholar
Li, Y. and Ishida, H., 2003 Concentration-dependent conformation of alkyl tail in the nanoconfined space: Hexadecylamine in the silicate galleries Langmuir 19 24792484 10.1021/la026481c.CrossRefGoogle Scholar
Low, P.F., Güven, N. and Pollastro, R.M., 1992 Interparticle forces in clay suspensions: flocculation, viscous flow and swelling Clay-Water Interface and its Rheological Implications Boulder, Colorado The Clay Minerals Society 163171.Google Scholar
Mitchell, J.K. and Soga, K., 2005 Fundamentals of Soil Behavior New Jersey, USA John Wiley & Sons 9597.Google Scholar
Minase, M., Kondo, M., Onikata, M., and Kawamura, K. (2006) The viscosity of suspensions of bentonite. Clay Science, 12, Supplement 2, 125130. ICC 2005: Clay sphere — Past, present and future. Proceedings of the 13thInternational Clay Conference Tokyo, Japan.Google Scholar
Mori, Y. and Ototake, N., 1956 On the viscosity of suspensions Chemical Engineering, Japanese 9 488494.Google Scholar
Onikata, M. and Kondo, M., 1995 Rheological properties of the partially hydrophobic montmorillonite treated with alkyltrialkoxysilane Clay Science 9 299310.Google Scholar
Park, K. Ree, T. and Eyring, H., 1971 Effect of electrolytes on flow properties of aqueous bentonite suspension Journal of the Korean Chemical Society 15 303312.Google Scholar
Powell, R.E. and Eyring, H., 1944 Mechanisms for the relaxation theory of viscosity Nature 154 427428 10.1038/154427a0.CrossRefGoogle Scholar
Robinson, J.V., 1949 The viscosity of suspensions of spheres Journal of Physical and Colloid Chemistry 53 10421056 10.1021/j150472a007.CrossRefGoogle Scholar
Slade, P.G. and Gates, W.P., 2004 The swelling of HDTMA smectites as influenced by their preparation and layer charges Applied Clay Science 25 93101 10.1016/j.clay.2003.07.007.CrossRefGoogle Scholar
Slade, P.G. and Gates, W.P., 2004 The ordering of HDTMA in the interlayers of vermiculite and the influence of solvents Clays and Clay Minerals 52 204210 10.1346/CCMN.2004.0520206.CrossRefGoogle Scholar
Suito, E. Arakawa, M. and Kondo, M., 1966 Adsorbed state of organic compounds in organo-bentonite I. Infrared study The Bulletin of the Institute for Chemical Research, Kyoto University 44 316324.Google Scholar
Suito, E. Arakawa, M. and Yoshida, T., 1966 Adsorbed state of organic compounds in organo-bentonite II. Differential thermal analysis The Bulletin of the Institute for Chemical Research, Kyoto University 44 325334.Google Scholar
Suito, E. Arakawa, M. and Yoshida, T., 1969 Electron microscopic observation of the layer of organo-montmorillonite Jerusalem Israel Universities Press 757763 1.Google Scholar
Suito, E. and Yoshida, T., 1971 Interstratified layer structure of the organo-montmorillonites as revealed by the electron microscopy Abstracts U.S.-Japan Seminar on Clay-Organic Complexes 5362.Google Scholar
Vaia, R.A. Teukolsky, R.K. and Giannelis, E.P., 1994 Interlayer structure and molecular environment of alkylammonium layered silicates Chemistry of Materials 6 10171022 10.1021/cm00043a025.CrossRefGoogle Scholar
Van Olphen, H., 1977 An Introduction to Clay Colloid Chemistry New York J. Wiley & Sons 254256.Google Scholar