Hostname: page-component-848d4c4894-4rdrl Total loading time: 0 Render date: 2024-07-02T07:20:47.222Z Has data issue: false hasContentIssue false
  • English
  • Français

Determination of the phase composition of partially dehydroxylated kaolinites by modelling their X-ray diffraction patterns

Published online by Cambridge University Press:  01 August 2019

Victor A. Drits ,
Boris A. Sakharov ,
Olga V. Dorzhieva ,
Bella B. Zviagina  and
Holger Lindgreen
Victor A. Drits*
Affiliation:
Geological Institute, Russian Academy of Science, 119017, Moscow, Russia
Boris A. Sakharov
Affiliation:
Geological Institute, Russian Academy of Science, 119017, Moscow, Russia
Olga V. Dorzhieva
Affiliation:
Geological Institute, Russian Academy of Science, 119017, Moscow, Russia Institute of Ore Geology, Petrography, Mineralogy and Geochemistry, Russian Academy of Science, 119017, Moscow, Russia
Bella B. Zviagina
Affiliation:
Geological Institute, Russian Academy of Science, 119017, Moscow, Russia
Holger Lindgreen
Affiliation:
Geological Survey of Denmark and Greenland, DK-1350, Copenhagen K, Denmark
*
*E-mail: victor.drits@mail.ru
Get access Rights & Permissions [Opens in a new window]

Abstract

Modelling of experimental X-ray diffraction (XRD) patterns is used to determine the phase composition of partially dehydroxylated kaolinite samples. To identify unambiguously the presence of two or three phases in the heated kaolinite samples, the full range of their XRD patterns has to be analysed. Two different kaolinites, from Imerys (UK) and from Georgia (USA; KGa-21), were studied. The heating temperatures were selected to cover the entire range of dehydroxylation for both kaolinites (400–550°C for Imerys and 400–495°C for KGa-21). Two different dehydroxylation pathways were observed. At each stage of partial dehydroxylation, the kaolinite from Imerys consisted of the original, non-dehydroxylated kaolinite and of a fully dehydroxylated phase, metakaolinite. During partial dehydroxylation of kaolinite KGa-21, each product formed at a given heating temperature consisted of three phases: the original kaolinite; a dehydroxylated phase, metakaolinite; and a phase with diffraction features corresponding to a defective kaolinite-like structure. To determine the content of metakaolinite in a partially dehydroxylated specimen, its experimental XRD pattern was reproduced by the optimal summation of the diffraction patterns of the initial kaolinite and metakaolinite. A procedure that reveals the basic diffraction features of the third phase is suggested. The XRD patterns and thus the structures of the metakaolinites formed after dehydroxylation of the Imerys and KGa-21 samples differ substantially. The conventional determination of the initial kaolinite and metakaolinite contents in partially dehydroxylated kaolinite based on the analysis of basal reflections and weight losses may lead to overlooking the formation of the intermediate phases.

Keywords

intermediate phaseskaolinitemetakaolinitepartially dehydroxylated kaoliniteXRD pattern modelling
Type
Article
Information
Clay Minerals , Volume 54 , Issue 3 , September 2019 , pp. 309 - 322
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2019 

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.)

Footnotes

Editor: George E. Christidis

References

Bailey, S.W. (1988) Polytypism of 1:1 layer silicates. Pp. 9–27 in: Hydrous Phyllosilicates. Exclusive of Micas (Bailey, S.W., editor). Reviews in Mineralogy. Mineralogical Society of America, Chantilly, VA, USA.Google Scholar
Bergaya, F., Dion, P., Alcover, J.-F., Clinard, C. & Tchoubar, D. (1996) TEM study of kaolinite thermal decomposition by controlled-rate thermal analysis. Journal of Materials Science, 31, 5069–5075.Google Scholar
Bish, D.L. & von Dreele, R.B. (1989) Rietveld refinement of non-hydrogen atomic positions in kaolinite. Clays and Clay Minerals, 37, 289–296.Google Scholar
Bookin, A.S., Drits, V.A., Plançon, A. & Tchoubar, C. (1989) Stacking faults in kaolin-group minerals in the light of real structural features. Clays and Clay Minerals, 37, 297–307.Google Scholar
Brindley, G.W. & Nakahira, M. (1956) A kinetic study of the dehydroxylation of kaolinite. Clays and Clay Minerals, 5, 266–278.Google Scholar
Brindley, G.W. & Nakahira, M. (1957) Kinetics of dehydroxylation of kaolinite and halloysite. Journal of the American Ceramic Society, 40, 346–350.Google Scholar
Brindley, G.W. & Nakahira, M. (1958) A new concept of the transformation sequence of kaolinite to mullite. Nature, 181, 1333–1334.Google Scholar
Brindley, G.W. & Nakahira, M. (1959) The kaolinite–mullite reaction. Series: II, metakaolin. Journal of the American Ceramic Society, 42, 314–318.Google Scholar
Brindley, G.W. & Robinson, K. (1946) The structure of kaolinite. Mineralogical Magazine, 27, 242–253.Google Scholar
Brindley, G.W., Kao, C.C., Harrison, J.L., Lipsicas, M. & Raythatha, R. (1986) Relation between structural disorder and other characteristics of kaolinites and dickites. Clays and Clay Minerals, 34, 239–249.Google Scholar
Dion, P., Alcover, J.F., Bergaya, F., Ortega, A., Llewellyn, P.L. & Rouquerol, F. (1998) Kinetic study by CRTA of the dehydroxylation of kaolinite. Clay Minerals, 33, 269–276.Google 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
Drits, V.A. & Derkowski, A. (2015) Kinetic behavior of partially dehydroxylated kaolinite. American Mineralogist, 100, 883–896.Google Scholar
Drits, V.A. & Tchoubar, C. (1990) X-Ray Diffraction by Disordered Lamellar Structures. Springer-Verlag, Berlin, Germany.Google Scholar
Drits, V.A., Kameneva, M.Y., Sakharov, B.A., Daynyak, L.G., Tsipurski, S.I., Smolyar, B.B., Bookin, A.S. & Salyn, A.L. (1993) The Actual Structure of Glauconites and Related Mica-like Minerals (in Russian). Nauka, Novosibirsk, Russia.Google Scholar
Drits, V.A., Środoń, J. & Eberl, D.D. (1997) XRD measurements of mean crystallite thickness of illite and illite/smectite: reappraisal of the Kubler index and the Scherrer equation. Clays and Clay Minerals, 45, 461–475.Google Scholar
Drits, V.A., Lindgreen, H., Sakharov, B.A., Jakobsen, H.J., Salyn, A.L. & Dainyak, L.G. (2002a) Tobelitization of smectite during oil generation in oil-source shales. Application to North Sea illite-tobelite-smectite-vermiculite. Clays and Clay Minerals, 50, 82–98.Google Scholar
Drits, V.A., Sakharov, B.A., Dainyak, L.G., Salyn, A.L. & Lindgreen, H. (2002b) Structural and chemical heterogeneity of illite-smectites from Upper Jurassic mudstones of East Greenland related to volcanic and weathered parent rocks. American Mineralogist, 87, 1590–1607.Google Scholar
Drits, V.A., Lindgreen, H., Sakharov, B.A., Jakobsen, H.J. & Zviagina, B.B. (2004) The detailed structure and origin of clay minerals at the Cretaceous/Tertiary boundary, Stevns Klint (Denmark). Clay Minerals, 39, 367–390.Google Scholar
Drits, V.A., Derkowski, A. & McCarty, D.K. (2011a) Kinetics of thermal transformation of partially dehydroxylated pyrophyllite. American Mineralogist, 96, 1054–1069.Google Scholar
Drits, V.A., Derkowski, A. & McCarty, D.K. (2011b) New insight into the structural transformation of partially dehydroxylated pyrophyllite. American Mineralogist, 96, 153–171.Google Scholar
Drits, V.A., Derkowski, A. & McCarty, D.K. (2012a) Kinetics of partial dehydroxylation in dioctahedral 2:1 layer clay minerals. American Mineralogist, 97, 930–950.Google Scholar
Drits, V.A., McCarty, D.K. & Derkowski, A. (2012b) Mixed-layered structure formation during trans-vacant Al-rich illite partial dehydroxylation. American Mineralogist, 97, 1922–1938.Google Scholar
Drits, V.A., Derkowski, A., Sakharov, B.A. & Zviagina, B.B. (2016) Experimental evidence of the formation of intermediate phases during transition of kaolinite into metakaolinite. American Mineralogist, 101, 2331–2354.Google Scholar
Ferrage, E., Lanson, B., Sakharov, B.A., Geoffroy, N., Jacquot, E. & Drits, V.A. (2007) Investigation of dioctahedral smectite hydration properties by modeling of X-ray diffraction profiles: influence of layer charge and charge location. American Mineralogist, 92, 1731–1743.Google Scholar
Frost, R.L. & Vassallo, A.M. (1996) The dehydroxylation of the kaolinite clay minerals using infrared emission spectroscopy. Clays and Clay Minerals, 44, 635–651.Google Scholar
Frost, R.L., Finnie, K., Collins, B. & Vassallo, A.M. (1995) Infrared emission spectroscopy of clay minerals and their thermal transformations. Pp. 219–224 in: Proceedings of the 10th International Clay Conference (Fitzpatrik, R.W., Churchman, G.J. & Eggleton, T., editors). CSIRO Publications, Adelaide, Australia.Google Scholar
Guggenheim, S. & van Groos, A.F.K. (1992) High-pressure differential thermal analysis (HR DTA). 1. Dehydroxylation reaction at elevated pressure in phyllosilicates. Journal of Thermal Analysis and Calorimetry, 38, 1701–1728.Google Scholar
He, H.P., Guo, J.G., Zhu, J.X. & Hu, C. (2003) 29Si and 27Al MAS NMR study of the thermal transformations of kaolinite from North China. Clay Minerals, 38, 551–559.Google Scholar
Kogure, T. & Inoue, A. (2005) Determination of defect structures in kaolin minerals by high-resolution transmission electron microscopy (HRTEM). American Mineralogist, 90, 85–89.Google Scholar
Kogure, T., Johnston, C.T., Kogel, J.E. & Bish, D.L. (2010) Stacking disorder in a sedimentary kaolinite. Clays and Clay Minerals, 58, 63–72.Google Scholar
Lanson, B., Sakharov, B.A., Claret, F. & Drits, V.A. (2009) Diagenetic smectite-to-illite transition in clay-rich sediments: a reappraisal of X-ray diffraction results using the multi-specimen method. American Journal of Science, 309, 476–516.Google 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
Lee, S., Kim, Y.J. & Moon, H.-S. (2003) Energy-filtering transmission electron microscopy (EF-TEM) study of a modulated structure in metakaolinite, represented by a 14 Å modulation. Journal of the American Ceramic Society, 86, 174–176.Google Scholar
Lindgreen, H., Drits, V.A., Sakharov, B.A., Jakobsen, H.J., Salyn, A.L., Dainyak, L.G. & Krøyer, H. (2002) The structure and diagenetic transformation of illite-smectite and chlorite-smectite from North Sea Cretaceous–Tertiary chalk. Clay Minerals, 37, 429–450.Google Scholar
MacKenzie, K.J.D., Brown, L.W.M., Meinhold, R.H. & Bowden, E. (1985) Outstanding problems in kaolinite-mullite reaction sequence investigated by 29Si and 27Al solid-state nuclear magnetic resonance: I, metakaolinite. Journal of the American Ceramic Society, 68, 293–302.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
McCarty, D.K., Sakharov, B.A. & Drits, V.A. (2009) New insights into smectite illitization: a zoned K-bentonite revisited. American Mineralogist, 94, 1653–1671.Google Scholar
Murray, H.H. (1954) Structural variation of some kaolinites in relation to dehydroxylated halloysite. American Mineralogist, 39, 97–108.Google Scholar
Ortega, A., Macías, M. & Gotor, F.J. (2010) The multistep nature of the kaolinite dehydroxylation: kinetics and mechanism. Journal of the American Ceramic Society, 93, 197–203.Google Scholar
Plançon, A. & Tchoubar, C. (1977) Determination of structural defects in phyllosilicates by X-ray powder diffraction. II. Nature and proportion of defects in natural kaolinites. Clays and Clay Minerals, 25, 436–450.Google Scholar
Plançon, A., Giese, R.F., Snyder, R., Drits, V.A. & Bookin, A.S. (1989) Stacking faults in the kaolin-group mineral-defect structures of kaolinite. Clays and Clay Minerals, 37, 203–210.Google Scholar
Ptaček, P., Šoukal, P., Opravil, T., Havilica, J. & Brandštetr, J. (2011) The kinetic analysis of the thermal decomposition of kaolinite by DTG technique. Powder Technology, 204, 20–25.Google Scholar
Ptaček, P., Opravil, T., Šoukal, P., Wesserbauer, J., Mosilko, J. & Baraček, J. (2013) The influence of structural order on the kinetics of dehydroxylation of kaolinite. Journal of the European Ceramic Society, 33, 2793–2799.Google Scholar
Reynolds, R.C. Jr (1985) NEWMOD©, a Computer Program for the Calculation of One-Dimensional Diffraction Patterns of Mixed-Layered Clays. Hanover, NH, USA.Google Scholar
Reynolds, R.C. Jr (1986) The Lorentz-polarization factor and preferred orientation in oriented clay aggregates. Clays and Clay Minerals, 34, 359–367.Google Scholar
Reynolds, R.C. Jr & Bish, D.L. (2002) The effects of grinding on the structure of a low-defect kaolinite. American Mineralogist, 87, 1626–1630.Google Scholar
Rocha, J. (1999) Single- and triple-quantum 27Al MAS NMR study of the thermal transformation of kaolinite. Journal of Physical Chemistry B, 103, 9801–9804.Google Scholar
Rocha, J. & Klinowski, J. (1990) 29Si and 27Al magic-angle-spinning NMR studies of the thermal transformation of kaolinite. Physics and Chemistry of Minerals, 17, 179–186.Google Scholar
Sakharov, B.A. & Lanson, B. (2013) X-ray identification of mixed-layer structures. Modeling of diffraction effects. Pp. 51–135 in: Handbook of Clay Society. 2nd Edition. Part B. Techniques and Applications (Bergaya, F. & Lagaly, G., editors). Elsevier, Amsterdam, The Netherlands.Google Scholar
Sakharov, B.A., Lindgreen, H., Salyn, A.L. & Drits, V.A. (1999) Determination of illite-smectite structures using multispecimen X-ray diffraction profile fitting. Clays and Clay Minerals, 47, 555–566.Google Scholar
Sakharov, B.A., Drits, V.A., McCarty, D.K. & Walker, G.M. (2016) Modeling powder X-ray diffraction patterns of the clay minerals society kaolinite standards: KGa-1, KGa-1b, and KGa-2. Clays and Clay Minerals, 64, 324–333.Google Scholar
Sperinck, S., Raiteri, P., Marks, N. & Wright, K. (2011) Dehydroxylation of kaolinite to metakaolin – a molecular dynamics study. Journal of Materials Chemistry, 21, 2118–2125.Google Scholar
Suitch, P.R. (1986) Mechanism for dehydroxylation of kaolinite, and nacrite from room temperature to 455°C. Journal of the American Ceramic Society, 69, 61–65.Google Scholar
White, C.E., Provis, J.L., Riley, D.P., Kearley, G.J. & van Deventer, J.S.J. (2009) What is the structure of kaolinite? Reconciling theory and experiment. Journal of Physical Chemistry A, 113, 6756–6765.Google Scholar
White, C.E., Provis, J.L., Proffen, T., Riley, D.P. & van Deventer, J.S.J. (2010a) Combining density functional theory (DFT) and pair distribution function (PDF) analysis to solve the structure of metastable materials: the case of metakaolinite. Physical Chemistry Chemical Physics, 12, 3239–3245.Google Scholar
White, C.E., Provis, J.L., Proffen, T., Riley, D.P. & van Deventer, J.S.J. (2010b) Density functional modeling of the local structure of kaolinite subjected to thermal dehydroxylation. Journal of Physical Chemistry A, 114, 4988–4996.Google Scholar
Yeskin, D., van Gross, A.F.K. & Guggenheim, S. (1985) The dehydroxylation of kaolinite. American Mineralogist, 70, 159–164.Google Scholar