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Clays and Clay Minerals; February 2002; v. 50; no. 1; p. 56-62
© 2002 Clay Minerals Society
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HYDROXYL-STRETCHING BANDS IN POLARIZED MICRO-RAMAN SPECTRA OF ORIENTED SINGLE-CRYSTAL KEOKUK KAOLINITE

S. Shoval1,*, S. Yariv2, K. H. Michaelian3, M. Boudeulle4 and G. Panczer4

1 Geology Group, Department of Natural Sciences, The Open University of Israel, 16 Klausner Street, 61392 Tel Aviv, Israel
2 Department of Inorganic and Analytical Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
3 Natural Resources Canada, CANMET Western Research Centre, Devon Alberta, Canada, T9G 1A8k
4 LPCML, UMR 5620 CNRS, Claude Bernard University - Lyon 1, 43 Bd 11 November 1918, 69622 Villeurbanne Cedex, France

* E-mail address of corresponding author: shoval{at}oumail.openu.ac.il

Polarized micro-Raman spectra of a single large crystal of Keokuk kaolinite were recorded in the OH-stretching region with the laser beam directed along the different crystal axes. The Raman spectra are characterized by five OH-stretching bands at 3694, 3683, 3668, 3650 and 3620 cm–1 labeled A, Z, B, C and D, respectively. The relative intensities of these five bands depend on the orientation of the crystal and the scattering geometry. The spectra agree with the assertion that bands A and Z arise from out-of-plane vibrations, whereas band D corresponds to an in-plane vibration. The area ratios of the various bands were calculated from fitted curves of spectra recorded with the electric vector of the laser beam parallel to different crystallographic planes. The increments in the relative areas of bands B and C were parallel to those of bands A and Z and it appears that out-of-plane vibrations made considerable contributions to these bands also. From the change of area ratios with the change in the direction of the electric vector of the laser beam, bands A and Z were attributed to LO and TO frequencies of one inner-surface hydroxyl vibration. Bands A + Z, B, C and D were attributed to the vibrations of the hydroxyls assigned by Bish (1993) as OH(3), OH(4), OH(2) and OH(1), respectively. These observations were supported by photoacoustic and transmission IR spectra.

Key Words: Hydroxyl Groups • IR Spectra • Kaolinite • Raman Spectra • SEM Micrographs




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