Hostname: page-component-76fb5796d-45l2p Total loading time: 0 Render date: 2024-04-28T22:39:05.671Z Has data issue: false hasContentIssue false
  • English
  • Français

The Dehydroxylation of the Kaolinite Clay Minerals using Infrared Emission Spectroscopy

Published online by Cambridge University Press:  28 February 2024

Ray L. Frost  and
Anthony M. Vassallo
Ray L. Frost
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane Queensland 4001, Australia
Anthony M. Vassallo
Affiliation:
CSIRO Division of Coal and Energy Technology, PO Box 136, North Ryde NSW 2113, Australia
Get access Rights & Permissions [Opens in a new window]

Abstract

The dehydroxylation of a series of the kaolinite clay minerals, kaolinite, halloysite and dickite, has been investigated by Fourier transform in situ infrared emission spectroscopy over a temperature range of 100 to 800°C at both 50 and 5° intervals. Excellent correspondence was obtained between the high temperature emission spectra and FTIR absorption spectra of the quenched clay mineral phases. The major advantage of the technique lies in the ability to obtain vibrational spectroscopic information in situ at the elevated temperature. Dehydroxylation at a number of temperatures was determined by the loss of intensity of hydroxyl bands as indicated by intensity changes of the 3550 cm−1 to 3750 cm−1 emission spectra. As with all clay minerals, kaolinite clay mineral dehydroxylation is structure dependent. No clay phase changes occur until after dehydroxylation takes place. The kaolinite clay mineral loses the inner sheet and inner hydroxyl groups simultaneously, whereas dickite and halloysites are shown to lose the outer hydroxyls, as evidenced by the intensity loss of the ~3684 cm−1 peak, before the inner hydroxyl groups as determined by the intensity loss of the 3620 cm−1 peak. Evidence for a high temperature stable hydroxyl band at 3730 cm−1 for dickite and halloysite was obtained. This band is attributed to the formation of a silanol group formed during the dehydroxylation process. It is proposed that the dehydroxylation process for kaolinite takes place homogenously and involves 2 mechanisms. The dehydroxylation of dickite and halloysite takes place in steps, with the first hydroxyl loss taking place homogenously and the second inhomogenously.

Keywords

DehydroxylationDickiteEmissionHalloysiteHydroxylInfraredKanditeKaoliniteMechanism of dehydroxylation
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 5 , October 1996 , pp. 635 - 651
Copyright
Copyright © 1996, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Axelson, D.E.. 1987. 27Al and 29Si solid state nuclear magnetic resonance of coal and heavy oil-derived mineral matter. Fuel Sci Technol Int 5: 561–92.CrossRefGoogle Scholar
Ball, M.C. and Taylor, H.F.W.. 1961. Dehydration of Brucite. Mineral Mag 32: 754–766.Google Scholar
Bish, D.L. and Johnston, C.T.. 1993. Reitfeld refinement and Fourier Transform Infrared Spectroscopic Study of the Dickite Structure at Low Temperatures. Clays Clay Miner 41: 297–304.CrossRefGoogle Scholar
Brindley, G.W.. 1961. Role of crystal structure in the dehydration reactions of some layer-type minerals. J Miner Soc Japan 5: 217–237.Google Scholar
Brindley, G.W.. 1963. Crystallographic aspects of some decomposition and recrystallisation reactions. Prog Ceram Sci 3: 3–55.Google Scholar
Brindley, G.W.. 1976. Aspects of layer stacking order in clays and layer silicates. Seventh Conference on clay mineralogy and petrology, Karlovy Vary. p 13–24.Google Scholar
Brindley, G.W., Chin-Chun, K., 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.CrossRefGoogle Scholar
Brindley, G.W. and Lemaitre, J.. 1987. Thermal, oxidation and reduction of clay minerals. In: Newman, A.C.D., editor. Chemistry of clay and clay minerals. Essex, England: Longman Scientific and Technical. 319–370.Google Scholar
Brindley, G.W. and Porter, A.R.D.. 1978. Occurrence of Dickite in Jamaica: Ordered and disordered varieties. Am Miner 63: 554–562.Google Scholar
Brindley, G.W., Sharp, J.H., Patterson, J.H., Achar, B.N. and Narahari, . 1967. Kinetics and mechanism of dehydroxylation processes. I. Temperature and vapour pressure dependence of dehydroxylation of kaolinite. Am Mineral 52: 201–211.Google Scholar
Brindley, G.W., Suzuki, T. and Thiry, M.. 1983. Interstratified kaolinite/smectite from the Paris Basin: Correlations of layer proportions, chemical compositions and other data. Bull Mineral 106: 403–410.Google Scholar
Brindley, G.W. and Wan, H.. 1978. The 14 Å phase developed in heated dickites. Clay Miner 13: 17–24.CrossRefGoogle Scholar
Chakraborty, and Akshoy, K.. 1992. Resolution of thermal peaks of kaolinite in thermomechanical analysis and differential thermal analysis studies. J Am Ceram Soc 75: 2013–2016.CrossRefGoogle Scholar
Collins, D.R., Fitch, A.N., Catlow, C. and Richard, A.. 1991. Time-resolved powder neutron diffraction study of thermal reactions in clay minerals. J Mater Chem 1: 965–970.CrossRefGoogle Scholar
Criado, J.M., Ortega, A., Real, C. and Torres de Torres, E.. 1986. Effect of experimental conditions and particle size on the thermal dehydroxylation of kaolinite in a linear heating program. Bol Soc Esp Ceram Vidrio 25: 299–305.Google Scholar
Davies, T.W. and Hooper, R.M.. 1985. Structural changes in kaolinite caused by rapid dehydroxylation. J Mater Sci Lett 4: 39–42.CrossRefGoogle Scholar
Farmer, V.C.. 1974. The layer silicates (Ch 15). In: Farmer, V.C., editor. The infrared spectra of minerals. London: Mineralogical Society. p 331–363.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D.. 1964. The infrared spectra of layered silicates. Spectrochimica Acta 20: 1149–1173.CrossRefGoogle Scholar
Friesen, W.I. and Michaelian, K.H.. 1986. Fourier Deconvolution of photoacoustic FTIR spectra. Infrared Phys 26: 235–239.CrossRefGoogle Scholar
Fripiat, J.J. and Toussaint, F.. 1960. Predehydroxylation state of kaolinite. Nature 186: 627–628.CrossRefGoogle Scholar
Fripiat, J.J. and Toussaint, F.. 1963. Dehydroxylation of kaolinite II conductometric measurements and infrared spectroscopy. J Phys Chem 67: 30–36.CrossRefGoogle Scholar
Frost, R.L.. 1995. Fourier Transform Raman Spectroscopy of kaolinite, dickite and halloysite. Clays Clay Miner 43: 191–195.CrossRefGoogle Scholar
Frost, R.L., Bartlett, J.R. and Fredericks, P.M.. 1993. Fourier Transform Raman spectra of kandite clays. Spectrochim Acta 49A: 667–674.CrossRefGoogle Scholar
Frost, R.L., Finnie, K., Collins, B. and Vassallo, M.J.. 1995. Infrared emission spectroscopy of clay minerals and their thermal transformations. In: Fitzpatrick, R.W., Churchman, G.J., Eggleton, T., editors. The Proceedings of the 10th Intertnational Clay Conference. Adelaide, Australia: CSIRO Publications. p 219–224.Google Scholar
Guggenheim, S. and van Groos, A.F.K.. 1992. High-pressure differential thermal analysis (HP-DTA). II. Dehydroxylation reactions at elevated pressures phyllosilicates. J Therm Anal 38: 2529–2548.CrossRefGoogle Scholar
Han, X. and Chen, K.. 1982. Infrared absorption spectra of minerals of the kaolinite-halloysite series. Dizhi Kexue 1: 71–79.Google Scholar
Holdridge, D.A. and Vaughan, F.. 1957. The kaolin minerals (Ch 4). In: Mackenzie, R.C., editor. The differential thermal investigation of clays. London: The Mineralogical Society. p 123–125.Google Scholar
Horvath, I.. 1985. Kinetics and compensation effect in kaolinite dehydroxylation. Thermochim Acta 85: 193–8.CrossRefGoogle Scholar
Jalajakumari, B., Warrier, K.G.K. and Satyanarayana, K.G.. 1989. Thermal dehydroxylation in surface modified kaolinite. J Mater Sci 24: 2653–9.CrossRefGoogle Scholar
Johnson, S.L., Guggenheim, S. and van Groos, A.F.K.. 1990. Thermal stability of halloysite by high-pressure differential thermal analysis. Clays Clay Miner 38: 477–84.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.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.CrossRefGoogle Scholar
Kristof, J., Mink, J., Horvath, E. and Gabor, M.. 1993. Intercalation study of clay minerals by Fourier transform infrared spectrometry. Vib Spectros 5: 61–73.CrossRefGoogle Scholar
Lambert, J.F., Millman, W.S. and Fripiat, J.J.. 1989. Revisiting kaolinite dehydroxylation: A silicon-29 and aluminium-27 MAS NMR study. J Am Chem Soc 111: 3517–22.CrossRefGoogle Scholar
La Iglesia, A.. 1993. Pressure-induced disorder in kaolinite. Clay Miner 28: 311–9.CrossRefGoogle Scholar
Lazarev, A.N.. 1972. Vibrational spectra and structure of silicates. New York: Plenum Press. p 178–182.Google Scholar
Ledoux, R.L. and White, J.L.. 1964. Infrared study of selective deuteration of kaolinite and halloysite at room temperature. Science 145: 47–49.CrossRefGoogle ScholarPubMed
Levy, J.H. and Hurst, H.J.. 1993. Kinetics of dehydroxylation, in nitrogen and water vapor, of kaolinite and smectite from Australian Tertiary oil shales. Fuel 72: 873–877.CrossRefGoogle Scholar
Levy, J.H.. 1990. Effect of water vapor pressure on the dehydration and dehydroxylation of kaolinite and smectite isolated from Australian tertiary oil shales. Energy Fuels 4: 146–151.CrossRefGoogle Scholar
Mackenzie, K.J.D.. 1973. Simple high-temperature infrared cell and its application to the dehydroxylation of kaolinite. J Appl Chem Biotechnol 23: 903–908.CrossRefGoogle Scholar
Maiti, G.C. and Freund, F.. 1981. Dehydration-related proton conductivity in kaolinite. Clay Miner 16: 395–413.CrossRefGoogle Scholar
Meinhold, R.H., Atakul, H., Davies, T.W. and Slade, R.C.T.. 1992. Flash calcination of kaolinite studied by DSC, TG and MAS NMR. J Therm Anal 38: 2053–65.CrossRefGoogle Scholar
Meinhold, R.H., Slade, R.C.T. and Davies, T.W.. 1993. High-field aluminium-27 MAS NMR studies of the formation of metakaolinite by flash calcination of kaolinite. Appl Magn Reson 4: 141–55.CrossRefGoogle Scholar
Michaelian, K.H., Bukka, K. and Permann, D.N.S.. 1987. Photoacoustic infrared spectra (250-10,000 cm–1) of partially deuterated kaolinite. Can J Chem 65: 1420–1423.CrossRefGoogle Scholar
Murat, M., Chbihi, M.E.M. and Mathurin, D.. 1976. Heat of solution of different kaolinites and metakaolinites in hydrofluoric acid. Effect of crystal-chemical characteristics. Ind Ceram (Paris) 822: 799–801.Google Scholar
Murata, M., Mathurin, D., Driouche, M. and Bachiorrini, A.. 1990. Investigations on some structural and physico-chemical properties of metakaolinite. Sci Geol Bull 43: 213–223.CrossRefGoogle Scholar
Ogloza, A.A. and Malhotra, V.M.. 1989. Dehydroxylation induced structural transformations in montmorillonite: An isothermal FTIR study. Phys Chem Miner 16: 379–385.CrossRefGoogle Scholar
Ohta, K. and Venkatesan, M.I.. 1992. Pyrolysis of wood specimens with and without minerals: Implications to lignin diagenesis. Energy Fuels 6: 271–277.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.CrossRefGoogle Scholar
Pampuch, R.. 1971. Le Mechanisme de la deshydroxylation des hydroxides et des silicates phylliteux. Bull Groupe Fr Argiles 23: 107–118.CrossRefGoogle Scholar
Pampuch, R.. 1973. Applying IR spectroscopy to thermal decomposition of hydroxides and phyllosilicates. In: Boldyrev, V., Meyer, K., editors. Festkoerperchemie. Leipzig, East Germany Verlag Grundstoffind. p179-93.Google Scholar
Patterson, J.H., Hurst, H.J., Levy, J.H. and Killingley, J.S.. 1990. Mineral reactions in the processing of Australian Tertiary oil shales. Fuel 69: 1119–1123.CrossRefGoogle Scholar
Petzold, D., Poppe, B. and Trager, T.. 1985. Calorimetric determination of the dehydroxylation enthalpy of kaolinite. Silikattechnik 36: 352–4.Google Scholar
Prost, R., Damene, A.S., Huard, E., Driard, J. and Leydecker, J.P.. 1989. Infrared study of structural OH in kaolinite, dickite and nacrite and poorly crystalline kaolinite at 5 to 600K. Clays Clay Miner 37: 464–468.CrossRefGoogle Scholar
Prost, R., Damene, A., Huard, E. and Driard, J.. 1987. Infrared study of structural OH in kaolinite, dickite and nacrite at 300 to 5K. In: Schutz, L.G., van Olphen, H., Mumpton, F.A., editors. Proceedings of the International Clay Conference, Denver. p 17–23.Google Scholar
Qiu, X. and Zhang, Q.. 1992. Measurement of mechanochemical changes of kaolin during dry fine grinding. Huanan Ligong Daxue Xuebao, Ziran Kexueban 20: 145–52.Google Scholar
Redfern, S.A.T.. 1987. The kinetics of dehydroxylation of kaolinite. Clay Miner 22: 447–56.CrossRefGoogle Scholar
Rocha, J., Adams, J.M. and Klinowski, J.. 1990. The rehydration of metakaolinite to kaolinite: Evidence from solid state NMR and cognate techniques. J Sol State Chem 89: 260–274.CrossRefGoogle Scholar
Rocha, J. and Klinowski, J.. 1990. Silicon-29 and aluminium-27 magic-angle-spinning NMR studies of the thermal transformation of kaolinite. Phys Chem Miner 17: 179—86.CrossRefGoogle Scholar
Rocha, J., Klinowski, J. and Adams, J.M.. 1991. Solid-state NMR elucidation of the role of mineralizers in the thermal stability and phase transformations of kaolinite. J Mater Sci 26: 3009–18.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.CrossRefGoogle Scholar
Roy, R. and Brindley, G.W.. 1956. Hydrothermal reconstruction of the kaolin clay minerals. Clays Clay Miner 4: 125–132.CrossRefGoogle Scholar
Rue, J.W. and Ott, W.R.. 1974. Scanning electron microscopic interpretation of the thermal analysis of kaolinite. J Therm Anal 6: 513–519.CrossRefGoogle Scholar
Slade, R.C.T., Davies, T.W. and Atakul, H.. 1991. Flash calcination of kaolinite mechanistic information from thermogravimetry. J Mater Chem 1: 751–756.CrossRefGoogle Scholar
Slade, R.C.T. and Davies, T.W.. 1989. The mechanism of kaolinite dehydroxylation followed by high resolution aluminium-27 and silicon-29 NMR. Coll Surf 36: 119–25.CrossRefGoogle Scholar
Stoch, L. and Waclawska, I.. 1981a. Dehydroxylation of kaolinite group minerals. I. Kinetics of dehydroxylation of kaolinite and halloysite. J Therm Anal 20: 291–304.CrossRefGoogle Scholar
Stoch, L. and Waclawska, I.. 1981b. Dehydroxylation of kaolinite group minerals. II. Kinetics of dickite dehydroxylation. J Therm Anal 20: 305–310.CrossRefGoogle Scholar
Stoch, L.. 1964. Thermal dehydroxylation of minerals of the kaolinite group. Bull Acad Polonaise Sci 12: 173–180.Google Scholar
Stubican, V. and Roy, R.. 1961. Proton retention in heated 1: 1 clays studied by infrared spectroscopy, weight loss and deuterium uptake. J Phys Chem 65: 1348–1351.CrossRefGoogle Scholar
Taranukhina, L.D., Paukstis, E. and Goncharuk, V.V.. 1991. Quantitative study of the proton acidity of natural aluminosilicates by IR spectroscopic method. Z Prikl Khim (St.-Petersburg) 64: 2633–6.Google Scholar
Tarasevich, Y.I. and Gribina, I.A.. 1985. State of structural hydroxyl groups in minerals of the kaolinite group according to IR spectroscopy data. Teor Eksp Khim 21: 73–81.Google Scholar
Toussaint, F., Fripiat, J.J. and Gastuche, M.C.. 1963. Dehydroxylation of kaolinite I. Kinetics. J Phys Chem 67: 26–29.CrossRefGoogle Scholar
Van der Marel, H.W. and Krohmer, P.. 1976. Beitr Mineral Petrol 22: 73–82.CrossRefGoogle Scholar
Vassallo, A.M., Cole-Clarke, P.A., Pang, L.S.K. and Palmisano, A.. 1992. Infrared Emission spectroscopy of coal minerals and their thermal transformations. J Appl Spectrosc 46: 73–78.CrossRefGoogle Scholar
Wada, K.. 1967. A study of hydroxyl groups in kaolin minerals utilising selective deuteration and infrared spectroscopy. Clay Miner 7: 51–61.CrossRefGoogle Scholar
White, J.L., Laycock, A. and Cruz, M.. 1970. Infrared studies of proton delocalization in kaolinite. Bull Groupe Fr Argiles 22: 157–165.CrossRefGoogle Scholar
Yeskis, D., van Groos, A.F.K. and Guggenheim, S.. 1985. The dehydroxylation of kaolinite. Am Mineral 70: 159–64.Google Scholar
Zhang, Z. and Yuan, R.. 1993. Dehydroxylation process of kaolinite and its structural change. Guisuanyan Tongbao 12: 37–41.Google Scholar