Hostname: page-component-586b7cd67f-2plfb Total loading time: 0 Render date: 2024-11-24T11:59:28.791Z Has data issue: false hasContentIssue false
  • English
  • Français

Crystal Structures of Biotite at High Temperatures and of Heat-Treated Biotite using Neutron Powder Diffraction

Published online by Cambridge University Press:  01 January 2024

Chul-Min Chon ,
Shin Ae Kim  and
Hi-Soo Moon
Chul-Min Chon
Affiliation:
Department of Earth System Sciences, Yonsei University, Seoul 120-749, Korea
Shin Ae Kim
Affiliation:
Korea Atomic Energy Research Institute, Daejeon 305-600, Korea
Hi-Soo Moon*
Affiliation:
Department of Earth System Sciences, Yonsei University, Seoul 120-749, Korea
*
*E-mail address of corresponding author: [email protected]
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 crystal structure of biotite-1 M from Bancroft, Ontario, with the formula: (K1.96Na0.13Ca0.01)(Mg3.15Fe2.592+Ti0.17Mn0.09)(Si5.98Al1.92Ti0.10)O20[(OH)1.47F1.98], was determined by Rietveld refinement using high-resolution neutron powder diffraction at in situ temperatures ranging from 20 to 900°C. The room-temperature structure of the samples heated to between 400 and 900°C using an electric furnace in air was also refined. The crystal structures were refined to an RP of 2.98 — 5.06% and Rwp of 3.84–6.77%. For the in situ heating experiments in a vacuum, the unit-cell dimensions increased linearly to 600°C. The linear expansion coefficient for the c axis was 1.65 × 10−5°C−1, while those for the a and b dimensions were 4.44 × 10−6°C−1 and 5.21 × 10−6°C−1, respectively. Accordingly, the increase in the unit-cell volume up to 600 C occurred mainly along the c axis, resulting from the expansion in the K coordination sphere along that direction. Results for all K−O bonds were analyzed in terms of the lattice component and an inner component of the structural strain. The ditrigonal distortion decreased (3.76 at 20°C to 1.95 at 600°C) with temperature, because the shorter bonds expanded and the longer bonds contracted. The increase in the interlayer separation and the decrease in the interlayer octahedral flattening angle confirmed that the c-dominated expansion occurred in the interlayer region. In the case of the ex situ-heated samples, the cell dimensions decreased sharply at temperatures over 400 C. The octahedral sheet thickness and mean <M−O> distance decreased linearly due to oxidation of octahedral Fe. However, the interlayer separation and mean <K−O> distance decreased at temperatures over 400°C. At 400°C, dehydroxylation began to increase and interlayer regions became more constricted. The overall cell parameters decreased rapidly with increasing temperatures due to dehydroxylation. The large inner strain components in the K−O bonds also resulted in an increase in the considerable ditrigonal distortion (3.57° at 400°C to 6.15° at 900°C).

Keywords

BiotiteCrystal StructureIron OxidationLattice and Inner StrainNeutron Powder Diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 51 , Issue 5 , October 2003 , pp. 519 - 528
Copyright
Copyright © 2003, The Clay Minerals Society

References

Akiba, E. Hayakawa, H. Hayashi, S. Miyawaki, R. and Tomura, S., (1997) Structure refinement of synthetic deuterated kaolinite by Rietveld analysis using time-offlight neutron powder diffraction data Clays and Clay Minerals 45 781–788 10.1346/CCMN.1997.0450602.Google Scholar
Bigi, S. and Brigatti, M.F., (1994) Crystal chemistry and micro structures of plutonic biotite American Mineralogist 79 63 72.Google Scholar
Bish, D.L., (1993) Rietveld refinement of the kaolinite structure at 1.5 K Clays and Clay Minerals 41 738–744 10.1346/CCMN.1993.0410613.Google Scholar
Bohlen, S.R. Peacor, D.R. and Essene, E.J., (1980) Crystal chemistry of a metamorphic biotite and its significance in water barometry American Mineralogist 65 55 62.Google Scholar
Born, M. and Huang, K., (1954) Dynamical Theory of Crystal Lattices Oxford, UK Clarendon Press.Google Scholar
Brigatti, M.F. and Davoli, P., (1990) Crystal-structure refinements of 1M plutonic biotites American Mineralogist 75 305 313.Google Scholar
Cagliotti, G. Paoletti, A. and Ricci, F., (1958) Choice of collimators for a crystal spectrometer for neutron diffraction Nuclear Instruments 3 223–228 10.1016/0369-643X(58)90029-X.Google Scholar
Catti, M., (1989) Calculation of elasticity and inner strain: a computational model Acta Crystallographica A45 494 500.Google Scholar
Catti, M. Ferraris, G. and Ivaldi, G., (1989) Thermal strain analysis in the crystal structure of muscovite at 700°C European Journal of Mineralogy 1 625–632 10.1127/ejm/1/5/0625.Google Scholar
Catti, M. Ferraris, G. Hull, S. and Pavese, A., (1994) Powder neutron diffraction study of 2M 1 muscovite at room pressure and at 2 GPa European Journal of Mineralogy 6 171–178 10.1127/ejm/6/2/0171.Google Scholar
Dollase, W.A., (1986) Correction of intensities for preferred orientation in powder diffractometry: Application of the march model Journal of Applied Crystallography 19 267–272 10.1107/S0021889886089458.Google Scholar
Guggenheim, S. Chang, Y.-H. and Van Koster Groos, A.F., (1987) Muscovite dehydroxylation: High-temperature studies American Mineralogist 72 537 550.Google Scholar
Hazen, R.M. and Burnham, C.W., (1973) The crystal structure of one-layer phlogopite and annite American Mineralogist 58 889 900.Google Scholar
Hogg, C.S. and Meads, R.E., (1975) A Mössbauer study of thermal decomposition of biotites Mineralogical Magazine 40 79–88 10.1180/minmag.1975.040.309.11.CrossRefGoogle Scholar
Joswig, W. (1972) Neutronenbeugungsmessungen an einem 1 M-Phlogopit. Neues Jahrbuch fur Mineralogie Mo natshefte, Niemcy, 1–11.Google Scholar
Joswig, W. Fuess, H. and Rothbauer, R., (1980) A neutron diffraction study of a one-layer triclinic chlorite (penninite) American Mineralogist 65 349 352.Google Scholar
Liang, J.J. and Hawthorne, F.C., (1998) Triclinic muscovite: X-ray diffraction, neutron diffraction and photo-acoustic FTIR spectroscopy The Canadian Mineralogist 37 1017 1027.Google Scholar
Mookerjee, M. and Redfern, S.A.T., (2002) A high-temperature Fourier transform infrared study of the interlayer and Si-O-stretching region in phengite-2M 1 Clay Minerals 37 323–336 10.1180/0009855023720036.Google Scholar
Mookerjee, M. Redfern, S.A.T. and Zhang, M., (2001) Thermal response of structure and hydroxyl ion of phengite-2M 1: an in situ neutron diffraction and FTIR study European Journal ofMineralogy 13 545–555 10.1127/0935-1221/2001/0013-0545.Google Scholar
Ohta, T. Takeda, H. and Takéuchi, Y., (1982) Mica polytypism: similarities in the crystal structures of 1 M and 2M1 oxybiotite American Mineralogist 67 298 310.Google Scholar
Pavese, A. Ferraris, G. Prencipe, M. and Ibberson, R., (1997) Cation site ordering in phengite 3T from the Dora-maira massif (Western Alps): A variable-temperature neutron powder diffraction study European Journal of Mineralogy 9 1183–1190 10.1127/ejm/9/6/1183.Google Scholar
Pavese, A. Ferraris, G. Pischedda, V. and Ibberson, R., (1999) Tetrahedral order in thermodynamic consequences European Journal of Mineralogy 11 309–320 10.1127/ejm/11/2/0309.Google Scholar
Pavese, A. Ferraris, G. Pischedda, V. and Radaelli, P., (2000) Further study of the cation ordering in phengite 3T by neutron powder diffraction Mineralogical Magazine 64 11–18 10.1180/002646100549085.Google Scholar
Pavese, A. Ferraris, G. Pischedda, V. and Fauth, F., (2001) M1 -site occupancy in 3T and 2M(1) phengites by low temperature neutron powder diffraction: Reality or artifact? European Journal ofMineralogy 13 1071–1078 10.1127/0935-1221/2001/0013-1071.Google Scholar
Rancourt, D.G. Christie, I.A.D. Lamarche, G. Swainson, I. and Flandrois, S., (1994) Magnetism of synthetic and natural annite mica: ground state and nature of excitations in an exchange-wise two-dimensional easy-plane ferromagnet with disorder Journal of Magnetism and Magnetic Materials 138 31–44 10.1016/0304-8853(94)90396-4.CrossRefGoogle Scholar
Rancourt, D.G. Mercier, P.H.J. Cherniak, D.J. Desgreniers, S. Kodama, H. and Robert, J.L., (2001) Mechanisms and crystal chemistry of oxidation in annite: Resolving the hydrogen-loss and vacancy reactions Clays and Clay Minerals 49 455–491 10.1346/CCMN.2001.0490601.Google Scholar
Rayner, J.H., (1974) The crystal structure of phlogopite by neutron diffraction Mineralogical Magazine 39 850–856 10.1180/minmag.1974.039.308.04.Google Scholar
Rietveld, H.M., (1969) A profile refinement method for nuclear and magnetic structures Journal of Applied Crystallography 2 65–71 10.1107/S0021889869006558.Google Scholar
Rodriguez-Carvajal, J. (1998) FullProf: Rietveld profile matching and integrated intensity refinement of X-ray and neutron data (PC-version). Version 3.5d.Google Scholar
Russell, R.L. and Guggenheim, S., (1999) Crystal structures of near-end-member phlogopite at high temperatures and heat-treated Fe-rich phlogopite: The influence of the O, OH, F site The Canadian Mineralogist 37 711 729.Google Scholar
Takeda, H. and Donnay, J.D.H., (1966) Trioctahedral one-layer micas. III. Crystal structure of a synthetic lithium fluormica Acta Crystallographica 20 638–646 10.1107/S0365110X66001543.Google Scholar
Takeda, H. and Morosin, B., (1975) Comparison of observed and predicted structural parameters of mica at high temperature Acta Crystallographica B31 2444–2452 10.1107/S0567740875007777.Google Scholar
Takeda, H. and Ross, M., (1975) Mica polytypism: dissimilarities in the crystal structures of coexisting 1 M and 2M1 biotite American Mineralogist 60 1030 1040.Google Scholar
Tripathi, R.P. Chandra, U. Chandra, R. and Lokanathan, S., (1978) A Mössbauer study of the effect of heating biotite, phlogopite and vermiculite Journal of Inorganic Nuclear Chemistry 40 1293–1298 10.1016/0022-1902(78)80037-2.Google Scholar
Virgo, D. and Popp, R.K., (2000) Hydrogen deficiency in mantle-derived phlogopites American Mineralogist 85 753–759 10.2138/am-2000-5-614.Google Scholar
Wiles, D.B. and Young, R.A., (1981) A new computer program for Rietveld analysis of X-ray powder diffraction patterns Journal of Applied Crystallography 14 149–151 10.1107/S0021889881008996.Google Scholar
Young, R.A., (1993) The Rietveld Method Oxford, UK International Union of Crystallography, Oxford University Press 298 pp.Google Scholar