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29Si and 27Al MAS NMR study of the thermal transformations of kaolinite from North China

Published online by Cambridge University Press:  09 July 2018

H. P. He ,
J . G. Guo ,
J . X. Zhu  and
C. Hu
H. P. He*
Affiliation:
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou510640
J . G. Guo
Affiliation:
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou510640
J . X. Zhu
Affiliation:
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou510640
C. Hu
Affiliation:
National Laboratory of Solid State Microstructural Physics, Nanjing University, Nanjing 210093, China
*
*E-mail: [email protected]
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Abstract

The thermal transformations of kaolinite have been studied using 27Al and 29Si magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetric analysis (TG). The experimental results show that this sample is a pure kaolinite which contains ∼3% carbonaceous material as impurity. 27Al and 29Si MAS NMR spectra show that the microstructural evolution of the thermal transformation of kaolinite at 450 –1050ºC is similar to that of the kaolinite– mullite reaction series previously published by many authors. 29Si MAS NMR spectra of mullite at 1190 and 1250ºC display two resonances at ∼ – 87 and –92 ppm, corresponding to sillimanite-type geometry around Si and the typical Si environment of mullite, respectively. At 1350ºC, the splitting of (hk0) and (kh0) of mullite occurs, indicating that the primary mullite transforms into orthorhombic mullite. Simultaneously, the resonance at ∼ – 92 ppm splits into two signals at ∼ –90 and –94 ppm. 27Al MAS NMR spectra of the mullite consist of three signals centred at ∼ –4, 45 and 60 ppm, corresponding to octahedral, distorted tetrahedral and tetrahedral Al sites, respectively.

Keywords

kaolinitemullitethermal transformation27Al and 29Si MAS NMRChina
Type
Research Article
Information
Clay Minerals , Volume 38 , Issue 4 , December 2003 , pp. 551 - 559
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2003

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References

Bergaya, F., Dion, P., Alcover, J.F., Clinard, C. and Tchoubar, D. (1996) TEM study of kaolinite thermal decomposition by CRTA. Journal of Materials Science, 31, 5069– 5075.Google Scholar
Bi, C.P. & Luo, X.J. (2001) Market prospect and present situation for calcined tonstein in China. Non-Metallic Mines, 24(5), 5–7.Google Scholar
Blinc, R. (1981) Magnetic resonance and relaxation in structural incommensurate systems. Physics Reports, 79, 331–398.Google Scholar
Brindley, G.W. & Nakahira, M. (1959) The kaolinitemullite reaction series. Journal of the American Ceramic Society, 42, 311– 314.Google Scholar
Brown, W.M., Mackenzie, K.J.D., Bowden, M.E. & Meinhold, R.H. (1985) Outstanding problems in the kaolinite-mullite reaction sequence investigated by 29Si and 27Al solid-state nuclear magnetic resonance: II. High-temperature transformations of metakaolinite. Journal of the American Ceramic Society, 68, 298–301.Google Scholar
Dan, Z., Liu, C.Q. & Haigh, M.J. (2002) Mobility of heavy metals associated with the natural weathering of coal mine spoils. Environmental Pollution, 118, 419–426.Google Scholar
Dion, P., Alcover, J.F., Bergaya, F., Ortega, A., Llewellyn, P.L. and Rouquerol, F. (1998) Kinetic study by CRTA of the dehydroxylation of kaolinite. Clay Minerals, 33, 269–276.CrossRefGoogle Scholar
Djemai, A., Balan, E., Morin, G., Hernandez, G., Labbe, J.C. & Muller, J.P. (2001) Behaviour of paramagnetic iron during the thermal transformations of kaolinite. Journal of the American Ceramic Society, 84, 1017–1024.Google Scholar
Guo, J.G., He, H.P., Wang, F.Y., Zhang, H.F. & Hu, C. (1996) The structural state of aluminum atoms and its influence on some properties of metakaolinite. Pp. 221–227 in. Progress in Geochemistry (Tu Guangzhi and Zhao Zhenghua, editors). Zhongshan University Press, Guangzhou, China.Google Scholar
He, H.P., Hu, C., Guo, J.G., Wang, F.Y. & Zhang, H.F. (1995) 29Si and 27Al Magic-Angle-Spinning Nuclear Magnetic Resonance Studies of kaolinite and its thermal products. Chinese Journal of Geochemistry, 74, 78–82.Google Scholar
Hinckley, D.N. (1963) Variability in crystallinity values among the kaolin deposits of the coastal plain of Georgia and South Carolina. Clays and Clay Minerals, 11, 229–235.Google Scholar
Lambert, J.F., Millman, W.S. & Fripiat, J.J. (1989) Revisiting kaolinite dehydroxylation: A 29Si and 27Al MAS NMR study. Journal of the American Ceramic Society, 111, 3517–3522.CrossRefGoogle Scholar
Lee, S., Kim, Y.J. & Moon, H.S. (1999) Phase transformation sequence from kaolinite to mullite investigated by an energy-filtering transmission electron microscope. Journal of the American Ceramic Society, 82, 2841– 2848.Google Scholar
Liu, Q.P. & Zhang, P.F. (1997) Compositions and Forming Mechanism of Kaolinite within Late Palaeozoic Coal beds in North China, pp. 4 – 22. Ocean Press, Beijing.Google Scholar
Loughnan, F.C. (1978) Flint clays, tonsteins and the kaolinite clayrock facies. Clay Minerals, 13, 387– 400.Google Scholar
Mackenzie, K.J.D. (1972) Infrared frequency calculation for ideal mullite (3Al2O3.2SiO2). Journal of the American Ceramic Society, 55, 68– 71.Google Scholar
Mackenzie, K.J.D., Brown, I.W.M., Meinhold, R.H. & Bowden, M.E. (1985) Outstanding problems in the kaolinite-mullite reaction sequence investigated by 29Si and 27Al solid-state nuclear magnetic resonance: I. Metakaolinite. Journal of the American Ceramic Society, 68, 293– 297.Google Scholar
Massiot, D., Dion, P., Alcover, J.F. & Bergaya, F. (1995) 27Al and 29Si MAS NMR study of kaolinite thermal decomposition by controlled rate thermal analysis. Journal of the American Ceramic Society, 78, 2940–2944.Google Scholar
Meinhold, R.H., Mackenzie, K.J.D. & Brown, I.W.M. (1985) Thermal reactions of kaolinite studied by solid state 27-Al and 29-Si NMR. Journal of Materials Science Letters, 4, 163–166.Google Scholar
Merwin, L.H., Sebald, A., Rager, H. & Schneider, H. (1991) 29Si and 27Al MAS NMR spectroscopy of mullite. Physics and Chemistry of Minerals, 18, 47–52.Google Scholar
Percival, H.J., Duncan, J.F. & Foster, P.K. (1974) Interpretation of the kaolinite-mullite reaction sequence from infrared absorption spectra. Journal of the American Ceramic Society, 59, 57–61.Google Scholar
Rocha, J. & Klinowski, J. (1990a) 29Si and 27Al magicangle-spinning N.R. studies of the thermal transformation of kaolinite. Physics and Chemistry of Minerals, 17, 179– 186.Google Scholar
Rocha, J. and Klinwoski, J. (1990b) Solid-state NMR studies of the structure and reactivity of metakaolinite. Angewandte Chemie-International Edition, 29, 553– 554.Google Scholar
Rocha, J., Klinwoski, J. & Adams, J.M. (1991) Solid-state NMR elucidation of the role of mineralizers in the thermal stability and phase transformations of kaolinit e. Journal of Material s Science, 26, 3009–3018.CrossRefGoogle Scholar
Sanz, J., Madani, A. & Serratosa, J.M. (1988) Aluminum- 27 and silicon-29 magic-angle-spinning nuclear magnetic resonance study of the kaolinite-mullite transformation. Journal of the American Ceramic Society, 71, c418–c421.Google Scholar
Sherriff, B.L. & Grundy, H.D. (1988) Calculations of 29Si MAS NMR chemical shift from silicate mineral structure. Nature, 332, 819–822.Google Scholar
Smith, J.V. & Blackwell, C.S. (1983) Nuclear magnetic resonance of silica polymorphs. Nature, 303, 223–225.CrossRefGoogle Scholar
Sonuparlak, B., Sarikaya, M. & Aksay, I. (1987) Spinel phase formation during the 980ºC exothermic reaction in kaolinite-to-mull ite reaction series. Journal of the American Ceramic Society, 70, 837–842.CrossRefGoogle Scholar
Watanabe, T., Shimizu, H.J., Nagasawa, K., Masuda, A. & Saito, H. (1987) 29Si- and 27Al- MAS/NMR study of the thermal transformations of kaolinite. Clay Minerals, 22, 37–48.Google Scholar
Zielinski, R.P. (1985) Element mobility during alteration of silicic ash to kaolinite – a study of tonstein. Sedimentology, 32, 567–579.Google Scholar