Hostname: page-component-78c5997874-fbnjt Total loading time: 0 Render date: 2024-11-19T05:59:29.822Z Has data issue: false hasContentIssue false
  • English
  • Français

XRD and NMR characterization of synthetic hectorites and the corresponding surfactant-exchanged clays

Published online by Cambridge University Press:  09 July 2018

A. Gerstmans ,
L. Urbanczyk ,
R. Jérôme ,
J.- L. Robert  and
J. Grandjean
A. Gerstmans
Affiliation:
COSM, University of Liège, Institute of Chemistry B6a, Sart-Tilman, B-4000-Liège, Belgium
L. Urbanczyk
Affiliation:
CERM, University of Liège, Institute of Chemistry B6a, Sart-Tilman, B-4000-Liège, Belgium
R. Jérôme
Affiliation:
CERM, University of Liège, Institute of Chemistry B6a, Sart-Tilman, B-4000-Liège, Belgium
J.- L. Robert
Affiliation:
IMPMC Campus Boucicaut, 140ru e de Lourmel, F-75015 Paris, France
J. Grandjean*
Affiliation:
COSM, University of Liège, Institute of Chemistry B6a, Sart-Tilman, B-4000-Liège, Belgium
*
*E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

Synthetic hectorites and the corresponding surfactant-exchanged clays have been characterized by X-ray diffraction and 1H, 7Li, 13C, 23Na and 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy. The low-charge clays retain water more efficiently, forming aggregates without extensive drying. The hydroxylated hectorite exhibits two 1H NMR signals near 0 ppm whereas the fluorohectorites are characterized by a single peak in the same region. The 23Na 2D 3Q magic angle spinning (MAS) spectra of the low-charge hectorites show a single peak. The 29Si NMR shift depends on the interlayer charge. Tactoids formed by the low-charge hectorites reduce the rate of surfactant incorporation. The population of the all-trans conformer of the hydrocarbon chain, determined by 13C MASNMR, varies with the surfactant content. 13C NMR relaxation data show an increase in mobility with the surfactant loading and along the long alkyl chain, from the polar head to the terminal group. Complexity of the motional behaviour precludes any detailed analysis. These modified clays are not useful in preparing poly(ε-caprolactone) nanocomposites by in situ polymerization.

Keywords

MAS NMRXRDhectorite
Type
Research Article
Information
Clay Minerals , Volume 43 , Issue 2 , June 2008 , pp. 205 - 212
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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

Alba, M.D., Becerro, A.I., Castro, M.A. & Perdigón, A.C. (2000) High resolution 1H MAS NMR spectra of 2:1 phyllosilicates. Chemical Communications, 37-38.Google Scholar
Amoureux, J.-P., Fernandez, C. & Steuernagel, S. (1996) Z-filtering in MQMAS NMR. Journal of Magnetic Resonance, A123, 116–118.Google Scholar
Borsacchi, S., Geppi, M., Ricci, L., Ruggeri, G. & Veracini, C.A. (2007) Interactions at the surface of organophilic-modified laponites: a multinuclear solid-state NMR study. Langmuir, 23, 3953–3960.Google Scholar
d’Espinose de la Caillerie, J.-B., Aimeur, M.R., El Kortobi, Y. & Legrand, A.P. (1997) Water adsorption on pyrogenic silica followed by 1H MAS NMR. Journal of Colloid and Interface Science, 194, 434–439.CrossRefGoogle Scholar
Delevoye, L., Robert, J.-L. & Grandjean, J. (2003) 23Na 2D 3QMAS NMR and 29Si, 27Al MAS NMR investigation of Laponite and synthetic saponites of variable interlayer charge. Clay Minerals, 38, 63–69.Google Scholar
Grandjean, J. (2006) Solid-state NMR study of modified clays and polymer/clay nanocomposites. Clay Minerals, 41, 567–586.Google Scholar
Hamilton, D.L. & Henderson, C.M.B. (1968) Preparation of silicate compositions by a gelling method. Mineralogical Magazine, 36, 832–838.Google Scholar
He, H., Frost, R.L., Deng, F., Zhu, J., Wen, X. & Yuan, P. (2004) Conformation of surfactant molecules in the interlayer of montmorillonite, studied by 13C MAS NMR. Clays and Clay Minerals, 52, 350–356.Google Scholar
Heinz, H., Vaia, R.A., Krishnamoorti, R. & Farmer, B.L. (2007) Self-assembly of alkylammonium chains on montmorillonite: effect of chain length, head group structure and cation exchange capacity. Chemistry of Materials, 19, 59–68.Google Scholar
Hrobarikova, J., Robert, J.-L., Calberg, C., Jerome, R. & Grandjean, J. (2004) Solid-state NMR study of intercalated species in poly(ε-caprolactone)/clay nanocomposites. Langmuir, 20, 9828–9833.Google Scholar
Kubies, D., Jérôme, R. & Grandjean, J. (2002) Surfactant molecules intercalated in laponite as studied by C and 29Si MAS NMR. Langmuir, 18, 6159–6163.Google Scholar
Lagaly, G. (1986) Interaction of alkylamines with different types of layered compounds. Solid State Ionics, 22, 43–51.Google Scholar
Li, Y. & Ishida, H. (2003) Characterization-dependent conformation of alkyl tail in the nanoconfined space: hexadecyl in the silicates galleries. Langmuir, 19, 2479–2484.Google Scholar
Mirau, P.A., Vaia, R.A. & Garber, J. (2005) NMR characterization of the structure and dynamics of polymer interfaces in clay nanocomposites. Polymer Preprints, 46, 440–441.Google Scholar
Müller, R., Hrobarikova, J., Calberg, C., Jérôme, R. & Grandjean, J. (2004) Structure and dynamics of cationic surfactants intercalated in synthetic clays. Langmuir, 20, 2982–2985.CrossRefGoogle ScholarPubMed
Osman, M.A., Ploetze, M. & Skrabal, P. (2004) Structure and properties of alkylammonium monolayers self-assembled on montmorillonite platelets. Journal of Physical Chemistry, B108, 2580–2588.Google Scholar
Rocha, J., Morais, C.M. & Fernandez, C. (2003) Novel nuclear magnetic resonance techniques for the study of quadrupolar nuclei in clays and other layered materials. Clay Minerals, 38, 259–278.Google Scholar
Sanz, J., Robert, J.-L., Diaz, M. & Sobrados, I. (2006) Influence of charge location on 29Si NMR chemical shift of 2:1 phyllosilicates. American Mineralogist, 91, 544–550.Google Scholar
Urbanczyk, L., Hrobarikova, J., Robert, J.-L., Calberg, C., Jérôme, R. & Grandjean, J. (2006) Motional heterogeneity of intercalated species in modified clays and poly(caprolactone)/clay nanocomposites. Langmuir, 22, 4818–4824.Google Scholar
Vaia, R.A., Teukolsky, R.K. & Giannelis, E.P. (1994) Interlayer structure and molecular environment of alkylammonium layered silicates. Chemistry of Materials, 6, 1017–1022.Google Scholar
Wen, X., He, H., Zhu, J., Jun, Y., Ye, C. & Deng, F. (2006) Arrangement, conformation, and mobility of surfactant molecules intercalated in montmorillonite prepared at different pillaring reagent concentrations as studied by solid-state NMR spectroscopy. Journal of Colloid and Interface Science, 299, 754–760.Google Scholar