Hostname: page-component-cd9895bd7-lnqnp Total loading time: 0 Render date: 2024-12-23T15:02:31.588Z Has data issue: false hasContentIssue false

Hydroxyl-Stretching Bands in Polarized Micro-Raman Spectra of Oriented Single-Crystal Keokuk Kaolinite

Published online by Cambridge University Press:  01 January 2024

S. Shoval*
Affiliation:
Geology Group, Department of Natural Sciences, The Open University of Israel, 16 Klausner Street, 61392 Tel Aviv, Israel
S. Yariv
Affiliation:
Department of Inorganic and Analytical Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel
K. H. Michaelian
Affiliation:
Natural Resources Canada, CANMET Western Research Centre, Devon Alberta, Canada, T9G 1A8
M. Boudeulle
Affiliation:
LPCML, UMR 5620 CNRS, Claude Bernard University - Lyon 1, 43 Bd 11 November 1918, 69622 Villeurbanne Cedex, France
G. Panczer
Affiliation:
LPCML, UMR 5620 CNRS, Claude Bernard University - Lyon 1, 43 Bd 11 November 1918, 69622 Villeurbanne Cedex, France
*
*E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

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.

Type
Research Article
Copyright
Copyright © 2002, The Clay Minerals Society

References

Bish, D.L., (1993) Rietveld refinement of the kaolinite structure at 1.5 K Clays and Clay Minerals 41 738744 10.1346/CCMN.1993.0410613.Google Scholar
Bish, D.L. and Johnston, C.T., (1993) Rietveld refinement and Fourier transform infrared spectroscopic study of the dickite structure at low temperature Clays and Clay Minerals 41 297304 10.1346/CCMN.1993.0410304.Google Scholar
Farmer, V.C., (1998) Differing effects of particle size and shape in the infrared and Raman spectra of kaolinite Clay Minerals 33 601604 10.1180/claymin.1998.033.4.07.Google Scholar
Farmer, V.C., (2000) Transverse and longitudinal crystal modes associated with OH stretching vibrations in single crystals of kaolinite and dickite Spectrochimica Acta A 56 927930 10.1016/S1386-1425(99)00182-1.Google Scholar
Frost, R.L., (1995) Fourier transform Raman spectroscopy of kaolinite, dickite and halloysite Clays and Clay Minerals 43 191195 10.1346/CCMN.1995.0430206.Google Scholar
Frost, R.L. Fredericks, P.M. and Shurvell, H.F., (1996) Raman microscopy of some kaolinite clay minerals Canadian Journal of Applied Spectroscopy 41 10 14.Google Scholar
Hayes, J.B., (1963) Kaolinite from Warsaw geodes, Keokuk region, Iowa Iowa Academy of Sciences 70 261 272.Google Scholar
Johnston, C.T. Sposito, G. and Birge, R.R., (1985) Raman spectroscopic study of kaolinite in aqueous suspension Clays and Clay Minerals 33 483489 10.1346/CCMN.1985.0330602.Google Scholar
Johnston, C.T. Agnew, S.F. and Bish, D.L., (1990) Polarized single-crystal Fourier-transform infrared microscopy of Ouray dickite and Keokuk kaolinite Clays and Clay Minerals 38 573583 10.1346/CCMN.1990.0380602.Google Scholar
Johnston, C.T. Helsen, J. Schoonheydt, R.A. Bish, D.L. and Agnew, S.F., (1998) Single-crystal Raman spectroscopic study of dickite American Mineralogist 83 7584 10.2138/am-1998-1-208.Google Scholar
Keller, W.D. Pickett, E.E. Reesman, A.L., Heller, L. and Weiss, A., (1966) Elevated dehydroxylation temperature of the Keokuk geode kaolinite — a possible reference mineral Proceedings of the International Clay Conference, Jerusalem, Vol. 1 Jerusalem Israel Program for Scientific Translations 75 85.Google Scholar
Michaelian, K.H., (1986) The Raman spectrum of kaolinite #9 at 210°C Canadian Journal of Chemistry 64 285289 10.1139/v86-048.Google Scholar
Michaelian, K.H., (1990) Step-scan phtoacoustic infrared spectra of kaolinite Infrared Physics 30 181186 10.1016/0020-0891(90)90029-U.Google Scholar
Michaelian, K.H. Yariv, S. and Nasser, A., (1991) Study of the interactions between cesium bromide and kaolinite, by photoacoustic and diffuse reflectance infrared spectroscopy Canadian Journal of Chemistry 69 749754 10.1139/v91-110.Google Scholar
Michaelian, K.H. Friesen, W.I. Yariv, S. and Nasser, A., (1991) Diffuse reflectance infrared spectra of kaolinite and kaolinite/alkali halide mixtures. Curve-fitting of the OH stretching region Canadian Journal of Chemistry 69 17861790 10.1139/v91-262.Google Scholar
Miller, J.G. and Oulton, J.D., (1970) Prototropy in kaolinite during percussive grinding Clays and Clay Minerals 18 313323 10.1346/CCMN.1970.0180603.Google Scholar
Shoval, S. Boudeulle, M. Panczer, G. Yariv, S., Baer, G. and Heimann, A., (1995) Raman micro-spectrometry and infrared spectroscopy study of the alteration products of trachyte sills and dykes in Makhtesh Ramon area, Israel Physics and Chemistry of Dykes Rotterdam, The Netherlands Balkema 325 337.Google Scholar
Shoval, S. Yariv, S. Michaelian, K.H. Lapides, I. Boudeulle, M. and Panczer, G., (1999) A fifth OH-stretching band in IR spectra of kaolinites Journal of Colloid and Interface Science 212 523529 10.1006/jcis.1998.6055.Google Scholar
Shoval, S. Yariv, S. Michaelian, K.H. Boudeulle, M. and Panczer, G., (1999) Hydroxyl-stretching bands ‘A’ and ‘Z’ in Raman and infrared spectra of kaolinites Clay Minerals 34 551563 10.1180/000985599546442.Google Scholar
Swanson, B.I., (1973) General notation for polarized Raman scattering from gases, liquids, and single crystals Applied Spectroscopy 27 382385 10.1366/000370273774333245.Google Scholar
Wiewióra, A. Wieckowski, T. and Sokolowska, A., (1979) The Raman spectra of kaolinite subgroup minerals and of pyrophyllite Archiwum Mineralogiczne 35 5 14.Google Scholar
Yariv, S., (1975) Some effect of grinding kaolinite with potassium bromide Clays and Clay Minerals 23 8082 10.1346/CCMN.1975.0230113.Google Scholar
Yariv, S., (1975) Infrared study of grinding kaolinite with alkali metal chlorides Powder Technology 12 131138 10.1016/0032-5910(75)80005-2.Google Scholar