Hostname: page-component-78c5997874-4rdpn Total loading time: 0 Render date: 2024-11-05T06:50:05.278Z Has data issue: false hasContentIssue false
  • English
  • Français

Intercalation of Halloysite: A Raman Spectroscopic Study

Published online by Cambridge University Press:  28 February 2024

Ray L. Frost  and
Janos Kristof
Ray L. Frost
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane Queensland 4001, Australia
Janos Kristof
Affiliation:
Department of Analytical Chemistry, University of Veszprem, H8201 Veszprem, PO Box 158, Hungary
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.

Intercalates from an ordered halloysite with urea and potassium acetate were studied using Raman microscopy. The urea intercalate showed new Raman bands at 3387, 3410, 3497 and 3598 cm−1 which were attributed to the formation of a urea-Si2O5 complex. New Raman bands were observed at 3585 and 3602 cm−1 for the potassium acetate intercalate with concomitant loss of intensity of the bands at 3635, 3655, 3675 and 3696 cm−1. These new bands were attributed to the hydrogen bonds formed between the acetate and the inner surface hydroxyl groups. Remarkable changes in intensity in the lattice region of the halloysite were observed, the foremost being the reduction of the intensity of the bands at 243, 271 and 336 cm−1. Pronounced changes in the bands at 913 and 143 cm−1 attributed to the Al-OH librations were also observed.

It is proposed that 2 distinct types of intercalation were present, as exemplified by: 1) urea intercalate, where the intercalating molecule hydrogen bonds to the Si-O of the halloysite layers and 2) potassium acetate intercalate, where the molecule is hydrogen-bonded to the inner surface hydroxyls of the halloysite layer and interacts with the tetrahedral sheet of the next adjacent halloysite layer. The Raman spectra of the intercalated halloysite strongly resembled that of an intercalated kaolinite.

Keywords

HalloysiteIntercalationKaoliniteRamanRaman MicroprobeX-ray Diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 4 , August 1997 , pp. 551 - 563
Copyright
Copyright © 1997, The Clay Minerals Society

References

Brindley, G.W. Kao, 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
Churchman, G.J. Whitton, J.S. Claridge, G.G.C. and Theng, B.K.G., 1984 Intercalation method using formamide for differentiating halloysite from kaolinite Clays Clay Miner 32 241–248 10.1346/CCMN.1984.0320401.CrossRefGoogle Scholar
Collins, D.R. and Catlow, C.R.A., 1991 Energy minimised hydrogen atom positions of kaolinite Acta Crystallogr Sect B47 678–682 10.1107/S010876819100561X.CrossRefGoogle Scholar
Dhalemincourt, P. Beny, J.M. Dubessy, J. and 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. and 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 10.1016/0009-2541(82)90073-0.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D., 1964 The infrared spectra of layered silicates Spectrochim Acta 20 1149–1173 10.1016/0371-1951(64)80165-X.CrossRefGoogle Scholar
Farmer, V.C. and Farmer, V.C., 1974 The layer silicates Infrared spectra of minerals London Mineral Soc 331–363 10.1180/mono-4.15.CrossRefGoogle Scholar
Friesen, W.I. and Michaelian, K.H., 1986 Fourier deconvolution of photoacoustic FTIR spectra Infrared Physics 26 235–239 10.1016/0020-0891(86)90075-8.CrossRefGoogle 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 kaolinite 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 Spectrochim Acta 20 1149 152.Google Scholar
Frost, R.L. Fredericks, P.M. and Shurvell, H.E., 1996 Raman microscopy of some Kaolinite clay minerals Can J Appl Spectrosc 41 1 10–14.Google Scholar
Frost, R.L. and Shurvell, H.E., 1997 Raman microprobe spectroscopy of halloysite Clays Clay Miner 45 68–72 10.1346/CCMN.1997.0450107.CrossRefGoogle Scholar
Hess, A.C. 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
Janik, L.J. and Keeling, J.L., 1993 FT-IR partial least-squares analysis of tubular halloysite in kaolin samples from the Mount Hope kaolin deposit Clay Miner 28 365–378 10.1180/claymin.1993.028.3.03.CrossRefGoogle 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 Clay Miner 38 573–583 10.1346/CCMN.1990.0380602.CrossRefGoogle Scholar
Johnston, C.T. Sposito, G. and Birge, R.R., 1985 Raman spectroscopic study of kaolinite in aqueous suspension Clays Clay Miner 33 483–489 10.1346/CCMN.1985.0330602.CrossRefGoogle Scholar
Kaklhana, M. Kotaka, M. and Okamoto, M., 1983 Vibrational analysis of the acetate ion molecules and estimation of equilibrium constants for their hydrogen isotope exchange reactions J Phys Chem 87 2526–2535 10.1021/j100237a016.CrossRefGoogle Scholar
Lagaly, G., 1984 Clay organic reactions Phil Trans R Soc Lond A311 315–332 10.1098/rsta.1984.0031.Google Scholar
Ledoux, R.L. and White, J.L., 1964 Infrared study of selective deu-teration of kaolinite and halloy site at room temperature Science 145 47–49 10.1126/science.145.3627.47.CrossRefGoogle Scholar
Ledoux, R.L. and White, J.L., 1967 Infrared study of intercalation complexes of kaolinite Silicates Ind 32 269–273.Google 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
Olejnik, S. Aylmore, L.A.G. Posner, A.M. and Quirk, J.P., 1968 Infrared spectra of kaolin mineral-dimethyl sulfoxide complexes J Phys Chem 72 241–249 10.1021/j100847a045.CrossRefGoogle Scholar
Pajcini, V. and Dhamelincourt, P., 1994 Raman study of the OH-stretching vibrations in kaolinite at low temperature Appl Spectrosc 48 638–641 10.1366/0003702944924844.CrossRefGoogle Scholar
Prost, R. Damene, A.S. Huard, E. Driard, J. and Leydecker, J.P., 1989 Infrared study of structural OH in kaolinite, dickite nacrite and poorly crystalline kaolinite at 5 to 600K Clays Clay Miner 37 464–468 10.1346/CCMN.1989.0370511.CrossRefGoogle Scholar
Raupach, M. Barron, P.F. and Thompson, J.G., 1987 Nuclear magnetic resonance, infrared, and X-ray powder diffraction study of dimethylsulfoxide and dimethylselenoxide intercalates with kaolinite Clays Clay Miner 35 208–219 10.1346/CCMN.1987.0350307.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
Singh, B., 1996 Why does halloysite roll?—A new model Clays Clay Miner 44 191–196 10.1346/CCMN.1996.0440204.CrossRefGoogle Scholar
Theng, B.K.G. Churchman, G.J. Whitton, J.S. and Claridge, G.G., 1984 Comparison of intercalation methods for differentiating halloysite from kaolinite Clays Clay Miner 32 249–258 10.1346/CCMN.1984.0320402.CrossRefGoogle Scholar
Thompson, J.G. and Cuff, C., 1985 Crystal structure of kaolinite: Dimethyl sulfoxide intercalate Clays Clay Miner 33 490–500 10.1346/CCMN.1985.0330603.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
Weiss, A. Thielepape, W. Orth, H., Heller, L. and Weiss, A., 1966 Intercalation into kaolinite minerals Proc Int Clay Conf Jerusalem Israel Univ Pr 277–293.Google Scholar
Weiss, A. Thielepape, W. Ritter, W. Schafer, H. and Goring, G., 1963 Zur Kenntnis von hydrazin-kaolinit Anorg Allg Chem 320 183–204 10.1002/zaac.19633200122.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
Wiewióra, A. Wieckowski, T. and Sokolowska, A., 1979 The Raman spectra of kaolinite subgroup minerals and of pyro-phyllite Arch Mineral 135 5–14.Google Scholar