Hostname: page-component-cd9895bd7-fscjk Total loading time: 0 Render date: 2024-12-26T16:19:34.020Z Has data issue: false hasContentIssue false
  • English
  • Français

Hydroxyl Deformation in Kaolins

Published online by Cambridge University Press:  28 February 2024

Ray L. Frost
Ray L. Frost*
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane Qld. 4001, Australia
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.

The hydroxyl deformation modes of kaolins have been studied by Fourier transform (FT) Raman spectroscopy. Kaolinites showed well-resolved bands at 959, 938 and 915 cm−1 and an additional band at 923 cm−1. For dickites, well-resolved bands were observed at 955, 936.5, 915 and 903 cm−1. Halloysites showed less-resolved Raman bands at 950, 938, 923, 913 and 895 cm−1. The first 3 bands were assigned to the librational modes of the 3 inner-surface hydroxyl groups, and the 915-cm−1 band was assigned to the libration of the inner hydroxyl group. The band in the 905 to 895 cm−1 range was attributed to “free― or non-hydrogen-bonded inner-surface hydroxyl groups. The 915-cm−1 band contributed ~65% of the total spectral profile and was a sharp band with a bandwidth of 11.8 cm−1 for dickite, 14.0 cm−1 for kaolinites and 17.6 cm−1 for halloysites. Such small bandwidths suggest that the rotation of the inner hydroxyl group is severely restricted. For the inner-surface hydroxyl groups, it is proposed that the hydroxyl deformation modes are not coupled and that the 3 inner-surface deformation modes are attributable to the three OH2-4 hydroxyls of the kaolinite structure. For intercalates of kaolinite and halloysite with urea, a new intense band at ~903 cm−1 was observed with concomitant loss in intensity of the bands at 959, 938 and 923 cm−1 bands. This band was assigned to the non-hydrogen-bonded hydroxyl libration of the kaolinite-urea intercalate. Infrared reflectance (IR) spectroscopy confirms these band assignments.

Keywords

Deformation ModeDickiteFT RamanHalloysiteHydroxylInfraredIntercalationKaoliniteLibrationReflectance
Type
Research Article
Information
Clays and Clay Minerals , Volume 46 , Issue 3 , June 1998 , pp. 280 - 289
Copyright
Copyright © 1998, The Clay Minerals Society

References

Barrios, J. Plancon, A. Cruz, M.I. and Tchoubar, C., 1977 Qualitative and quantitative study of the stacking faults in a hydrazine treated kaolinite. Relationship with the infrared spectra Clays Clay Miner 25 422–429 10.1346/CCMN.1977.0250608.CrossRefGoogle Scholar
Brindley, G.W. Kao, C.-C. Harrison, J.L. Lipsiscas, M. and Raythatha, R., 1986 Relation between the structural disorder and other characteristics of kaolinites and dickites Clays Clay Miner 34 233–249 10.1346/CCMN.1986.0340303.CrossRefGoogle Scholar
Farmer, V.C. and Farmer, V.C., 1974 The layer silicates The infrared spectra of minerals London Mineral Soc 331–363 10.1180/mono-4.15.CrossRefGoogle Scholar
Fanner, V.C. and Russell, J.D., 1964 The infrared spectra of layered silicates Spectrochimica Acta 20 1149–1173 10.1016/0371-1951(64)80165-X.Google Scholar
Frost, R.L., 1995 Fourier transform Raman spectroscopy of kaolinite, dickite and halloysite Clays Clay Miner 43 191–195 10.1346/CCMN.1995.0430206.CrossRefGoogle Scholar
Frost, R.L., 1997 The structure of the kaolin clay minerals — An FT Raman study Clay Miner 32 73–85.Google Scholar
Frost, R.L. Fredericks, P.M. and Bartlett, J.R., 1993 Fourier transform Raman spectroscopy of kandite clays Spectrochimica Acta 20 667–674 10.1016/0584-8539(93)80088-R.CrossRefGoogle Scholar
Frost, R.L. and Shurvell, H.F., 1997 Raman microprobe spectroscopy of halloysite Clays Clay Miner 45 68–72 10.1346/CCMN.1997.0450107.CrossRefGoogle Scholar
Frost, R.L. Tran, T.H. and Kristof, J., 1997 Ft Raman spectroscopy of the lattice region of kaolinite and its intercalates Vibrational Spectroscopy 13 175–186 10.1016/S0924-2031(96)00049-5.CrossRefGoogle Scholar
Giese, R.F., 1988 Kaolin minerals: Structures and stabilities. Rev Mineral Hydrous phyl-losilicates. Mineral Soc Am 19 29–66.CrossRefGoogle Scholar
Hess, C.A. and Saunders, V.R., 1992 Periodic ab initio Hartree-Fock calculations of the low symmetry mineral kaolinite J Phys Chem 96 4367–4374 10.1021/j100190a047.CrossRefGoogle Scholar
Johnston, C.T. Agnew, S.F. and Bish, D.L., 1990 Polarised single crystal Fourier-transform infrared microscopy of Ouray Dickite and Keokuk kaolinite Clays Clay Miner 38 573–583 10.1346/CCMN.1990.0380602.CrossRefGoogle Scholar
Johnston, C.T. and Stone, D.A., 1990 Influence of hydrazine on the vibrational modes of kaolinite Clays Clay Miner 38 121–128 10.1346/CCMN.1990.0380202.CrossRefGoogle Scholar
Ledoux, R.L. and White, J.L., 1964 Infrared study of selective deu-teration of kaolinite and halloysite at room temperature Science 145 47–49 10.1126/science.145.3627.47.CrossRefGoogle ScholarPubMed
Ledoux, R.L. and White, J.L., 1966 Infrared studies of hydrogen bonding interaction between kaolinite surfaces and intercalated potassium acetate, hydrazine, formamide and urea J Colloid Interface Sci 21 127–152 10.1016/0095-8522(66)90029-8.CrossRefGoogle Scholar
Michaelian, K.H., 1986 The Raman spectrum of kaolinite #9 at 21°C Can J Chem 64 285–289 10.1139/v86-048.CrossRefGoogle Scholar
Rouxhet, P.G. Samudacheata, N. Jacobs, H. and Anton, O., 1977 Attribution of the OH stretching bands of kaolinite Clay Miner 12 171–178 10.1180/claymin.1977.012.02.07.CrossRefGoogle Scholar
Wada, K., 1967 A study of hydroxyl groups in kaolin minerals utilising selective deuteration and infrared spectroscopy Clay Miner 7 51–61 10.1180/claymin.1967.007.1.05.CrossRefGoogle Scholar
White, J.L. Laycock, A. and Cruz, M., 1970 Infrared studies of proton delocalisation in kaolinite Bull Groupe Franc Argiles 22 157–165 10.3406/argil.1970.1130.CrossRefGoogle Scholar
Wieckowski, T. and Wiewióra, A., 1976 New approach to the problem of interlayer bonding in kaolinite Clays Clay Miner 24 219–223 10.1346/CCMN.1976.0240502.CrossRefGoogle Scholar
Young, R.A. and Hewatt, A.W., 1988 Verification of the triclinic crytal structure of kaolinite Clays Clay Miner 36 225–232 10.1346/CCMN.1988.0360303.CrossRefGoogle Scholar