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Kaolinite hydroxyls – a Raman microscopy study

Published online by Cambridge University Press:  09 July 2018

R. L. Frost  and
S. J. van der Gaast
R. L. Frost
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane Q 4001, Australia
S. J. van der Gaast
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane Q 4001, Australia
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Abstract

Raman microscopy of the kaolinite polymorphs was used to study single crystals and bundles of aligned crystals of kaolinite. The spectra of the hydroxyl stretching region were both sample and orientation dependent. Kaolinites can be classified into two groups according to the ratio of the intensities of the 3685 and 3695 cm−1 bands. No relationship was found between the d-spacing and the crystal domain size measurement from the 001 reflection and the Raman spectral intensities indicating the Raman spectra are independent of d-spacing and crystallinity. However, a relationship of the crystallinity in the a-b direction and intensities of the 3685 and 3695 cm−1 bands indicate that the relative position of one layer to the other determines the position of the inner surface hydroxyl groups and the hydrogen bonding with the oxygen of the opposite layer. A new hypothesis based on symmetric and non-symmetric hydrogen bonding of the inner surface hydroxyl groups is proposed to explain the two inner surface hydroxyl bands centred at 3685 and 3695 cm−1. The bands at 3670 and 3650 cm−1 are described in terms of the out-of-phase vibrations of the in-phase vibrations at 3695 and 3685 cm−1.

Type
Research Article
Information
Clay Minerals , Volume 32 , Issue 3 , September 1997 , pp. 471 - 484
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1997

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References

Brindley, G.W., Chih-Chun Kao, Harrison, J.L., Lipsiscas, M. & Raythatha, R. (1986) Relation between the structural disorder and other characteristics of kaolinites and dickites. Clay Clay Miner. 34, 233–249.CrossRefGoogle Scholar
Collins, D.R. & Catlow, C.R.A. (1991) Energy minimised hydrogen atom positions of kaolinite. Acta Cryst. B47, 678–682.CrossRefGoogle Scholar
Dhalemincourt, P., Beny, J.M., Dubessy, J. & Poty, B. (1979) Analysis of fluid inclusions with the MOLE Raman microprobe. Bull. Mineral. 102, 600–610.Google Scholar
Dubessy, J., Audeoud, D., Wilkins, R. & Kostolyani, C. (1982) The use of the Raman microprobe MOLE in the determination of the electrolytes dissolved in the aqueous phase of fluid inclusions. Chem Geol. 37, 137–150.CrossRefGoogle Scholar
Farmer, V.C. (1974) The layer silicates. Pp. 331-363 in: Infrared Spectra of Minerals. (Farmer, V.C., editor) Mineralogical Society, London.CrossRefGoogle Scholar
Farmer, V.C. & Russell, J.D. (1964). The IR spectra of layered silicates. Spectrochim. Acta, 20, 1149–1173.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D. (1967) IR absorption spectroscopy in clay minerals. Proc. 15th Conf. Clays Clay Minerals, 27–29.Google Scholar
Friesen, W.I. & Michaelian, K.H. 1986. Fourier deconvolution of photoacoustic FTIR spectra. IR Physics, 26, 235–239.Google Scholar
Frost, R.L. (1995) Fourier Transform Raman spectroscopy of kaolinite, dickite and halloysite. Clays Clay Miner. 43, 191–195.Google Scholar
Frost, R.L. (1997) The structure of the kaolinite clay minerals – an FT Raman study. Clay Miner. 32, 73–85.Google Scholar
Frost, R.L. & James, D.W. (1982) Ion solvent interactions in solution, part 3: Aqueous solutions of sodium nitrate. J. Chem. Soc. Faraday 1, 78, 3223–3233.CrossRefGoogle Scholar
Frost, R.L. & James, D.W. (1982) Ion solvent interactions in solution, part 4: Raman spectra of aqueous solutions of nitrates with monovalent cations. J. Chem. Soc. Faraday 1, 78, 3233–3248.Google Scholar
Frost, R.L. & James, D.W. (1982) Ion solvent interactions in solution part 5: influence of added halide, change in temperature, and solvent deuteration on ion association in aqueous solutions of nitrate salts. J. Chem Soc. Faraday 1, 78, 3249–3261.CrossRefGoogle Scholar
Frost, R.L., Appleby, R., Carrick, M.T. & James, D.W. (1982) Using Fourier transformations and Raman band shape analysis to study ion solvent interactions in aqueous solutions. Can. J. Spectros. 27, 82–87.Google Scholar
Frost, R.L., Carrick, M.T. & James, D.W. (1982) Structure of aqueous solutions: Fourier Transformation and band component analysis. J. Raman Spect. 13, 115–119.Google Scholar
Frost, R.L., Fredericks, P.M. & Bartlett, J.R. (1993) FT Raman spectroscopy of the kandite clay minerals. Spectrochim. Acta, 20, 667–674 Google Scholar
Frost, R.L., Tran, T.H. & Kristof, J. (1997b) The structure of an intercalated ordered kaolinite – a Raman microscopy study. Clay Miner. (in press).Google Scholar
Giese, R.F. (1982) Theoretical studies of the kaolin minerals: Electrostatic calculations. Bull. Mineral. 105, 417–424.Google Scholar
Giese, R.F. (1988) Kaolin minerals: structures and stabilities. Chapter 3 in: Reviews in Mineralogy Volume 19 Hydrous Phyllosilicates. (Bailey, S.W., editor), Mineralogical Society of America, Washington, D.C. Google Scholar
Hess, C.A. & Saunders, V.R. (1992) Periodic ab initio Hartree-Fock calculations of the low symmetry mineral kaolinite. J. Phys. Chem. 96, 4367–4374.Google Scholar
James, D.W. & Frost, R.L. (1978a) Raman line shapes and solute and solvent interactions. Can. J. Spectros. 23, 1–7.Google Scholar
James, D.W. & Frost, R.L. (1978b) Relaxation processes in aqueous solution: a Raman spectral study of Hydrogen bonded interactions. Disc. Faraday Soc. 64, 48–84.CrossRefGoogle Scholar
Johnston, C.T., Sposito, G. & Birge, R.R. (1985) Raman spectroscopic study of kaolinite in aqueous suspension. Clays Clay Miner. 33, 483–489.Google Scholar
Johnston, C.T., Agnew, S.F. & Bish, D.L., (1990) Polarised single-crystal Fourier Transform IR Microscopy of Ouray dickite and Keokuk kaolinite. Clays Clay Miner. 38, 573–583.Google Scholar
Ledoux, R.L. & White, J.L. (1964) IR study of selective deuteration of kaolinite and halloysite at room temperature. Science, 145, 47–49.Google Scholar
Michaelian, K.H. (1986) The Raman spectrum of kaolinite #9 at 21° Can. J. Chem., 64 285-289.Google Scholar
Newman, A.C.D. (1987) Editor, Chemistry of Clays and Clay Minerals, Pp. 49–53. Mineralogical Society Monograph No. 6, Longman Scientific and Technical, London.Google Scholar
Pajcini, V. & Dhamelincourt, P. (1994) Raman study of the OH-stretching vibrations in kaolinite at low temperature. Appl. Spectros. 48, 638–641.CrossRefGoogle Scholar
Prost, R., Damene, A.S., Huard, E., Driard, J. & Leydecker, J.P. (1989) IR study of structural OH in kaolinite, dickite and nacrite and poorly crystalline kaolinite at 5 to 600 K. Clays Clay Miner. 37, 464–468.Google Scholar
Rouxhet, P.G., Samudacheata, N., Jacobs, H. & Anton, O. (1977) Attribution of the OH stretching bands of kaolinite. Clay Miner. 12, 171–178.CrossRefGoogle Scholar
Russell, J.D. (1987) IR Methods. Pp. 133-173, in: A Handbook of Determinative Methods in Clay Mineralogy. (Wilson, M.J., editor). Blackie, Glasgow.Google Scholar
Wada, K. (1967) A study of hydroxyl groups in kaolin minerals utilising selective deuteration and IR spectroscopy. Clay Miner. 7, 51–61.Google Scholar
White, J.L., Laycock, A. & Cruz, M. (1970) IR studies of proton delocalisation in kaolinite. Bull. Gr. Franc. Argiles, 22, 157–165.Google Scholar
Wiewiora, A., Wieckowski, T. & Sokolowska, A. (1979) The Raman spectra of kaolinite subgroup minerals and of pyrophyllite. Arch. Mineral. 135, 5–14.Google Scholar