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Interlayer conformations of intercalated dodecyltrimethylammonium in rectorite as determined by FTIR, XRD, and TG analyses

Published online by Cambridge University Press:  01 January 2024

Zhaohui Li  and
Wei-Teh Jiang
Zhaohui Li*
Affiliation:
Geosciences Department, University of Wisconsin - Parkside, Kenosha, WI 53141-2000, USA Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan
Wei-Teh Jiang
Affiliation:
Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan
*
* E-mail address of corresponding author: [email protected]
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Abstract

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Intercalation of a wide variety of alkylammonium cations into the interlayer spaces of swelling clay minerals leads to many different applications, ranging from surface-charge measurements to rendering the clay compatible for the preparation of clay nanocomposites, but knowledge of the exact conformation of the intercalated organic species is still incomplete, thus preventing a full understanding of this process. The purpose of this study was to investigate the interlayer conformation of dodecyltrimethylammonium (DDTMA) bromide in rectorite as affected by the amounts of DDTMA intercalated, using a battery of physical and spectroscopic methods. The capacity of rectorite to intercalate DDTMA was equivalent to 1.67 times the cation exchange capacity (1.67 CEC) of the mineral even though the initial input was as much as 5.00 CEC. When the DDTMA intercalated was <0.50 CEC of the mineral, minimal counterion sorption was associated with DDTMA intercalation. Derivative thermogravimetric (DTG) analyses revealed a single-peak decomposition temperature (Tpeak) at 430°C. X-ray diffraction (XRD) analyses indicated a flat-lying monolayer of the intercalated molecules, while shifts in Fourier Transform infrared (FTIR) bands confirmed gauche conformation. These results suggested that cation exchange was the dominant mechanism. At the maximum intercalation, the DDTMA adopted a horizontal trilayer arrangement with mainly gauche conformation as determined by FTIR and XRD. Meanwhile a second Tpeak appeared at 255°C, similar to the Tpeak of solid DDTMA. Counterion bromide sorption accompanying DDTMA intercalation reached a capacity of 310 mmol/kg. The results indicated that van der Waals interaction was responsible for the DDTMA uptake at the amount beyond 0.50 CEC. When the amount of DDTMA intercalated was between 0.5 and 1.67 CEC, the XRD patterns showed non-integrality, i.e. the 002 reflection was split into two non-integral peaks with 2 × d002 < d001 and 3 × d003 > d001. They became integral at 1.67 CEC. The results suggest that the mineral might be composed of mixed layers of a monolayer intercalated rectorite and a trilayer intercalated rectorite, without a bilayer as intermediate, when the amount of DDTMA intercalated was between 0.5 and 1.67 CEC.

Keywords

DDTMAFTIRIntercalationOrgano-clayTGXRD
Type
Article
Information
Clays and Clay Minerals , Volume 57 , Issue 2 , April 2009 , pp. 194 - 204
Copyright
Copyright © The Clay Minerals Society 2009

References

Casal, H.L. Mantsch, H.H. Cameron, D.G. and Snyder, R.G., 1982 Interchain vibrational coupling in phase II (hexagonal) n-alkanes Journal of Chemical Physics 77 2825–2830 10.1063/1.444173.CrossRefGoogle Scholar
He, H.P. Frost, R.L. and Zhu, J., 2004 Infrared study of HDTMA+ intercalated montmorillonite Spectrochimica Acta A 60 2853–2859 10.1016/S1386-1425(03)00337-8.Google Scholar
He, H.P. Frost, R.L. Bostrom, T. Yuan, P. Duong, L. Yang, D. Xi, Y. and Kloprogge, T., 2006 Changes in the morphology of organoclays with HDTMA+ surfactant loading Applied Clay Science 31 262–271 10.1016/j.clay.2005.10.011.CrossRefGoogle Scholar
Hedley, C.B. Yuan, G. and Theng, B.K.G., 2007 Thermal analysis of montmorillonites modified with quaternary phosphonium and ammonium surfactants Applied Clay Science 35 180–188 10.1016/j.clay.2006.09.005.CrossRefGoogle Scholar
Hong, H.L. Jiang, W.-T. Zhang, X. Tie, L. and Li, Z., 2008 Adsorption of Cr(VI) on STAC-modified rectorite Applied Clay Science 42 292–299 10.1016/j.clay.2008.01.015.CrossRefGoogle Scholar
Kloprogge, J.T. Frost, R.L. and Hickey, L., 1999 Infrared absorption and emission study of synthetic mica-montmorillonite in comparison to rectorite, beidellite and paragonite Journal of Materials Science Letters 18 1921–1923 10.1023/A:1006672913161.CrossRefGoogle Scholar
Kooli, F. and Magusin, P.C.M.M., 2005 Adsorption of cetyltrimethylammonium ions on an acid- activated smectite and their thermal stability Clay Minerals 40 233–243 10.1180/0009855054020169.CrossRefGoogle Scholar
Kung, K. and Hayes, K.F., 1993 Fourier transform infrared spectroscopic study of the adsorption of cetyltrimethylammonium bromide and cetylpyridinium chloride on silica Langmuir 9 263–267 10.1021/la00025a050.CrossRefGoogle Scholar
Lagaly, G. Gonzalez, M.F. and Weiss, A., 1976 Problems in layer charge determination of montmorillonites Clay Minerals 11 173–187 10.1180/claymin.1976.011.3.01.CrossRefGoogle Scholar
Lee, S.Y. and Kim, S.J., 2003 Study on the exchange reaction of HDTMA with the inorganic cations in reference montmorillonites Geosciences Journal 7 203–208 10.1007/BF02910286.CrossRefGoogle Scholar
Lee, S.Y. Cho, W.J. Hahn, P.S. Lee, M. Lee, Y.B. and Kim, K.J., 2005 Microstructural changes of reference montmorillonites by cationic surfactants Applied Clay Science 30 174–180 10.1016/j.clay.2005.03.009.CrossRefGoogle Scholar
Li, Z. and Gallus, L., 2005 Surface configuration of sorbed hexadecyltrimethylammonium on kaolinite as indicated by surfactant and counterion sorption, cation desorption, and FTIR Colloids and Surfaces A: Physicochemical and Engineering Aspects 264 61–67 10.1016/j.colsurfa.2005.05.016.CrossRefGoogle Scholar
Li, Z. Jiang, W.-T. and Hong, H., 2008 An FTIR investigation of hexadecyltrimethylammonium intercalation into rectorite Spectrochimica Acta A 71 1525–1534 10.1016/j.saa.2008.05.015.CrossRefGoogle ScholarPubMed
Mermut, A.R. and Lagaly, G., 2001 Baseline studies of the Clay Minerals Society Source Clays: layer-charge determination and characteristics of those minerals containing 2:1 layers Clay and Clay Minerals 49 393–397 10.1346/CCMN.2001.0490506.CrossRefGoogle Scholar
Ruehlicke, G. and Kohler, E.E., 1981 A simplified procedure for determining layer charge by the y-alkylammonium method Clay Minerals 16 305–307 10.1180/claymin.1981.016.3.08.CrossRefGoogle 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 1017–1022 10.1021/cm00043a025.CrossRefGoogle Scholar
Venkataraman, N.V. and Vasudevan, S., 2001 Conformation of methylene chains in an intercalated surfactant bilayer Journal of Physical Chemistry B 105 1805–1812 10.1021/jp002505h.CrossRefGoogle Scholar
Weers, J.G. Scheuing, D.R. and Scheuing, D.R., 1990 Micellar sphere to rod transitions Fourier Transform Infrared Spectroscopy in Colloidal and Interface Science Washington DC American Chemical Society 87–122 10.1021/bk-1990-0447.ch006.CrossRefGoogle Scholar
Xi, Y. Ding, Z. He, H. and Frost, R.L., 2004 Structure of organoclays — an X-ray diffraction and thermogravimetric analysis study Journal of Colloid and Interface Science 277 116–120 10.1016/j.jcis.2004.04.053.CrossRefGoogle ScholarPubMed
Xi, Y. Martens, W. He, H. and Frost, R.L., 2005 Thermogravimetric analysis of organoclays intercalated with the surfactant octadecyltrimethylammonium bromide Journal of Thermal Analysis and Calorimetry 81 91–97 10.1007/s10973-005-0750-2.CrossRefGoogle Scholar
Xie, W. Gao, Z. Liu, K. Pan, W.-P. Vaia, R. Hunter, D. and Singh, A., 2001 Thermal characterization of organically modified montmorillonite Thermochimica Acta 367–368 339–350 10.1016/S0040-6031(00)00690-0.CrossRefGoogle Scholar
Xu, S. and Boyd, S.A., 1995 Cationic surfactant adsorption by swelling and nonswelling layer silicates Langmuir 11 2508–2514 10.1021/la00007a033.CrossRefGoogle Scholar
Xue, H. He, H. Zhu, J. and Yuan, P., 2007 FTIR investigation of CTAB-A1-montmorillonite complexes Spectrochimica Acta A 67 1030–1036 10.1016/j.saa.2006.09.024.CrossRefGoogle ScholarPubMed
Zhou, Q. Frost, R.L. He, H. and Xi, Y., 2007 Changes in the surfaces of adsorbed para-nitrophenol on HDTMA organo-clay — the XRD and TG study Journal of Colloid and Interface Science 307 50–55 10.1016/j.jcis.2006.11.016.CrossRefGoogle Scholar