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Differing effects of particle size and shape in the infrared and Raman spectra of kaolinite

Published online by Cambridge University Press:  09 July 2018

V. C. Farmer*
Affiliation:
Soil Science Group, Macaulay Land Use Research Institute, Craigiebuckler, Aberdeen AB15 8QH, UK

Abstract

Infrared (IR) spectra of well-ordered kaolinites generally show four OH-stretching frequencies, near 3697, 3670, 3652 and 3620 cm-1. Raman spectra of the same kaolinites mostly show an additional band near 3686 cm-1, which, in the coarsely crystalline Keokuk kaolinite, largely replaces the 3695 cm-1 band. It is shown that the 3686 cm-1 band can be ascribed to a transverse optical crystal vibration involving the in-phase stretching vibration of the three inner-surface hydroxyl groups in the unit-cell. Raman exciting radiation, commonly of wavelength near 500 nm, can excite this crystal vibration in crystals of comparable and greater thickness.

Infrared studies are usually made on clay-size (<2 μm) particles, which have mean thicknesses of 30-150 nm. Infrared radiation of wavelength near 2.7 <m can only excite whole crystal vibrations perpendicular to the plates. The in-phase vibration of inner-surface OH groups in the whole-crystal mode lies at 3697 cm-1, which is the same frequency as that of the longitudinal optical mode in macroscopic crystals.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1998

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References

Bish, D.L. (1993) Rietveld refinement of the kaolinite structure at 1.5 K. Clays Clay Miner. 41, 738744.CrossRefGoogle Scholar
Farmer, V.C. (1974) The layer silicates. Pp. 331-363 in: The lnJrared Spectra of Minerals (Farmer, V.C., editor). Mineralogical Society, London.CrossRefGoogle Scholar
Farmer, V.C. & Russell, J.D. (1964) The infrared spectra of layer silicates. Spectrochim. Acta, 20, 11491173.CrossRefGoogle Scholar
Farmer, V.C. & Russell, J.D. (1966) Effects of particle size and structure on the vibrational frequencies of layer silicates. Spectrochim. Acta, 22, 389-398.Google Scholar
Frost, R.L. (1995) Fourier transform Raman spectroscopy of kaolinite, dickite and halioysite. Clays Clay Miner. 43, 191195.CrossRefGoogle Scholar
Frost, R.L. & Van der Gaast, S.J. (1997) Kaolinite hydroxyls–a Raman microscopic study. Clay Miner. 32, 471484.CrossRefGoogle Scholar
Frost, R.L., Fredericks, P.M. & Schurvell H,F. (1996) Raman microscopy of some kaolinite clay minerals. Can. J. AppL Spectrosc. 41, 1014.Google Scholar
Gilson, T.R. & Hendra, P.J. (1970) Laser Raman Spectroscopy. Wiley-Interscience, London.Google Scholar
Hadni, A. (1974) The interaction of infrared radiation with crystals. Pp, 27-67 in: The lnJkared Spectra of Minerals (Farmer, V.C., editor). Mineralogical Society, London.Google Scholar
Johnston, C.T. & Stone, D.A. (1990) Influence of hydrazine on the vibrational modes of kaolinite. Clays Clay Miner. 38, 121128.CrossRefGoogle Scholar
Johnston, C.T., Sposito, G. & Birge, R.R. (1985) Raman spectroscopic study of kaolinite in aqueous suspension. Clays Clay Miner. 33, 483489.CrossRefGoogle Scholar
Lombardi, G., Russell, J.D. & Keller, W.D. (1987) Compositional and structural variations in the size fractions of a sedimentary and a hydrothermal kaolin. Clays Clay Miner. 35, 321335.CrossRefGoogle Scholar
Michaelian, K.H. (1986) The Raman spectrum of kaolinite #9 at 21°. Can. J. Chem, 64, 285289.CrossRefGoogle Scholar
Nadeau, P.H. (1987) Relationships between the mean area, volume and thickness for dispersed particles of kaolinites and micaceous clays. Clay Miner. 22, 351356.CrossRefGoogle Scholar
Pajcini, V. & Dhamelincourt, P. (1994) Raman study of OH-stretching vibrations in kaolinite at low temperature. AppL Spectrosc. 48, 638641.CrossRefGoogle Scholar
Rouxhet, P.G., Samudacheata, N., Jacobs, H. & Anton, O. (1977) Attribution of the OH stretching bands of kaolinite. Clay Miner. 12, 171179CrossRefGoogle Scholar
Russell, J.D. & Fraser, A.R. (1994) Infrared methods. Pp. 11 –67 in: Clay Mineralogy: Spectroscopic and Chemical Determinative Methods (Wilson, M.J., editor). Chapman & Hall, London.Google Scholar
Russell, J.D., McHardy, W.J. & Fraser, A.R. (1969) Imogolite: a unique aluminosilicate. Clay Miner. 8, 8799.CrossRefGoogle Scholar
Shoval, S., Boudeulle, M. & Panczer, G. (1995) Raman micro-spectrometry and infrared spectroscopy study of the alteration products of trachyte sills and dykes in Makhtesh Raman area, Israel. Pp. 325–327 in: Physics and Chemistry of Dykes (Baer, G. & Heimann, A., editors). Balkema, Rotterdam.Google Scholar
Wiewiora, A., Wieckowski, T. & Sokolowska, A. (1979) The Raman spectra of kaolinite sub-group minerals and of pyrophyllite. Arch, Mineral. 35, 5–14.Google Scholar