Hostname: page-component-586b7cd67f-vdxz6 Total loading time: 0 Render date: 2024-11-26T15:11:22.451Z Has data issue: false hasContentIssue false
  • English
  • Français

An Improved Model for Structural Transformations of Heat-Treated Aluminous Dioctahedral 2:1 Layer Silicates

Published online by Cambridge University Press:  28 February 2024

V. A. Drits ,
G. Besson  and
F. Muller
V. A. Drits
Affiliation:
Geological Institute of the Russian Acad. of Sciences, Pyjzhevsky Street 7, 109017 Moscow, Russia
G. Besson
Affiliation:
C.R.M.D., Université-C.N.R.S., B.P. 6759, 45067 ORLEANS Cédex 2, France
F. Muller
Affiliation:
C.R.M.D., Université-C.N.R.S., B.P. 6759, 45067 ORLEANS Cédex 2, France
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.

An improved model for the interpretation of thermal effects during dehydroxylation in aluminous dioctahedral 2:1 layer phyllosilicates considers trans-vacant (tv) and cis-vacant (cv) 2:1 layers and leads to very different temperatures of dehydroxylation for these tv and cv vacant modifications. In particular, smectites and illites consisting of cv 2:1 layers are characterized by dehydroxylated temperatures which are higher by 150°C to 200°C than those for the same minerals consisting of the tv 2:1 layers. A considerable lengthening of the OH-OH edges in cv 2:1 layers in comparison with the OH-OH edges in the tv 2:1 layers is postulated as the reason for the higher dehydroxylation.

Dehydroxylation in aluminous cv 2:1 layer silicates should occur in two stages. Initially, each two adjacent OH groups are replaced by a residual oxygen atom and the Al cations, which originally occupied cis -and trans-sites, become 5- and 6-coordinated, respectively. The structure of 2:1 layers corresponding to this stage of the dehydroxylation is unstable. Thus the Al cations migrate from the former trans-sites to vacant pentagonal prisms. The resulting dehydroxylated structure of the original cv 2:1 layers is similar to that of the former tv 2:1 layers.

Diffraction and structural features of the cv dehydroxylates predicted by the model are in agreement with X-ray diffraction effects observed for cv illite, illite-smectite and montmorillonite samples heated to different temperatures. In particular, the diffusion of Al cations to empty five-fold prisms during dehydroxylation of the tv 2:1 layers explains why dehydroxylation of reheated cv montmorillonites occurs at temperatures lower by 150°C to 200°C than samples that were not recycled.

Keywords

BeidelitesCis-vacant octahedraDehydroxylationIllitesMontmorillonitesTrans-vacant octahedra
Type
Research Article
Information
Clays and Clay Minerals , Volume 43 , Issue 6 , December 1995 , pp. 718 - 731
Copyright
Copyright © 1995, The Clay Minerals Society

References

Bailey, S. W., 1984. Crystal chemistry of the true mica. In Micas, Reviews in Mineralogy. Bailey, S. W., ed. Blacksburg, VA: Mineralogical Society of America, 13–60.Google Scholar
Bartoli, C., 1993. Determination cristallochimique de smectites naturelles. Report of DEA stage, University of Orléans, France (in French).Google Scholar
Brindley, G. W., 1976. Thermal transformations of clays and layer silicates. Proc. Internat. Clay Conf. 1975. Wilmette, Illinois: Applied Publishing Ltd., 119–129.Google Scholar
Cole, W. F., and Hasking, J. S. 1957. Clay minerals mixtures and interstratified minerals. In The Differential Thermal Investigation of Clays. Mackenzie, R. C., ed. London: Mineralogical Society, 248–274.Google Scholar
Drits, V. A., Plançon, A., Sakharov, B. A., Besson, G., Tsipursky, S. I., and Tchoubar, C. 1984. Diffraction effects calculated for structural models of K-saturated montmorillonite containing different types of defects. Clay Miner. 19: 541–562.Google Scholar
Drits, V. A., 1987. Mixed-layer minerals: Diffraction methods and structural features. Proc. Internat. Clay Conf. Schultz, L. G., Olphen, H., and Mumpton, F. A., eds. Bloomington, Ind.: The Clay Mineral Society, 33–45.Google Scholar
Drits, V. A., Weber, F., Salyn, A. I., and Tsipursky, S. I. 1993a. X-ray identification of one-layer illite varieties: application to the study of illites around uranium deposits of Canada. Clays & Clay Miner. 41: 389–398.Google Scholar
Drits, V. A., Kameneva, M. Yu., Sacharov, B. A., Daynyac, L. G., Tsipursky, S. I., Smoliar, B. B., Bookin, A. S., and Salyn, A. L. 1993b. The Problems of the Determination of Actual Structures of Glauconites and Related Minerals. Novosibirsk, Nanka, 200 pp.Google Scholar
Drits, V. A., Besson, G., and Tsipursky, S. 1994. Crystal-chemistry of dioctahedral smectites; part 2: A generalized structural model of dehydroxylation in dioctahedral phyl-losilicates. In 31st Annual Meeting of Clay Miner. Soc., Meeting program and Abstract, University of Saskatchewan, 20.Google Scholar
Green-Kelly, R., 1955. Dehydratation of the montmorillonite minerals. Mineral. Mag. 30: 604–615.Google Scholar
Green-Kelly, R., 1957. The montmorillonite minerals (smectites). In The Differential Thermal Investigation of Clays. Mackenzie, R. C., ed. London: Mineralogical Society, 139–164.Google Scholar
Grim, R. E., Bray, R. H., and Bradley, W. F. 1937. Mica in argillaceous sediments. Amer. Miner. 22: 813–829.Google Scholar
Grim, R. E., Bradley, W. F., and Brown, G. 1951. X-ray Identification and Crystal Structures of Clay Minerals. Brindley, G. W., ed. London: Mineralogical Society, 138–172.Google Scholar
Grim, R. E., 1968. Clay Mineralogy: International Series in the Earth and Planetary Sciences. Press, F., ed. New York: McGraw-Hill Book Company, 596 pp.Google Scholar
Guggenheim, S., 1990. The dynamics of thermal decomposition in aluminous dioctahedral 2: 1 layer silicates: A crystal chemical model. Proc. 9th Internat. Clay Conf, Vol. 2: Surface chemistry structure and mixed layering of clays. Farmer, V. C., and Tardy, Y., eds. Strasbourg, France, 99–107.Google Scholar
Guggenheim, S., Chang, H. Y., and Koster van Groos, A. F. 1987. Muscovite dehydroxylation: High-temperature studies. Amer. Mineral. 72: 537–550.Google Scholar
Guggenheim, S., and Koster van Groos, A. F. 1992. High-pressure differential thermal analysis (HP-DTA). II. Dehydroxylation reactions at elevated pressures in phyllosilicates. Journal Thermal Analysis 38: 2529–2548.Google Scholar
Heller-Kallai, L., Farmer, V. C., Mackenzie, R. C., Mitchell, B. D., and Taylor, H. F. W. 1962. The dehydroxylation and rehydroxylation of triphormic dioctahedral clay minerals. Clay Minerals Bull. 5: 56–72.Google Scholar
Heller-Kallai, L., and Rozenson, I. 1980. Dehydroxylation of dioctahedral phyllosilicates. Clays & Clay Miner. 28: 355–368.Google Scholar
Koster van Groos, A. F., and Guggenheim, S. 1987. High-pressure differential thermal analysis (HP-DTA) of the dehydroxylation of Na-rich montmorillonite and K-exchanged montmorillonite. Amer. Mineral. 72: 1170–1175.Google Scholar
Koster van Groos, A. F., and Guggenheim, S. 1990. Dehydroxylation of Ca- and Mg-exchanged montmorillonite. Amer. Mineral. 74: 627–636.Google Scholar
McCarty, D., and Reynolds, R. C. 1995. Rotationally disordered illite-smectites in Palozoic K-bentonites. Clays & Clay Miner. 43: 271–284.Google Scholar
Mackenzie, R. C., Walker, G. F., and Hart, R. 1949. Illite from Ballaker. Mineral. Mag. 28: 704–713.Google Scholar
Mackenzie, R. C., 1957. The Differential Thermal Investigation of Clays. London: Mineralogical Society, 456 pp.Google Scholar
Mackenzie, R. C., 1982. Down-to-earth thermal analysis. Thermal Analysis. Miller, B., ed. Chischester, Great Brit: Wiley Heyden Ltd., 25–36.Google Scholar
Moore, D. M., and Reynolds, R. C. 1989. X-ray Diffraction and the Identification and Analysis of Clays Minerals. Oxford N.Y.: Oxford University Press, 332 pp.Google Scholar
Reynolds, R. C., 1993. Three-dimensional X-ray powder diffraction from disordered illite: simulation and interpretation of the diffraction patterns. In Computer Applications to X-ray Powder Diffraction Analysis of Clay Minerals. Reynolds, R. C., and Walker, J. R., eds. Clay Mineral Society of America, 5: 44–78.Google Scholar
Reynolds, R. C., and Thompson, C. H. 1993. Illite from the Postdam Sandstone of New York, a probable noncentrosymmetric mica structure. Clays & Clay Miner. 41: 66–72.Google Scholar
Sakharov, B. A., Besson, G., Drits, V. A., Kameneva, M. Y., Salyn, A. L., and Smolyar, B. B. 1990. X-ray study of the nature of stacking faults in the structure of glauconites. Clay Miner. 25: 419–435.Google Scholar
Sokolova, T. N., Drits, V. A., Sokolava, A. L., and Stepanova, K. A. 1976. Structural and mineralogical characteristics and formation conditions of leucophillite from a salt deposits. Litologiya i poleznie iscopaemie 26: 80-95 (in Russian).Google Scholar
Sucha, V., Kraus, I., Mosser, C., Hroncova, Z., Soboleva, K. A., and Siranova, V. 1992. Mixed-layer illite/smectite from the Dolna'Ves hydrothermal deposit, the western Carpathians Kremnica Mts. Geologica Carphathia, series clays, 1: 13–19.Google Scholar
Tsipursky, S. I., and Drits, V. A. 1984. The distribution of octahedral cations in the 2: 1 layers of dioctahedral smectites studied by oblique texture electron diffraction. Clay Miner. 19: 177–192.Google Scholar
Tsipursky, S. I., Kameneva, M. Y., and Drits, V. A. 1985. Structural transformation of Fe3+-containing 2: 1 dioctahedral phyllosilicates in the course of dehydration. 5th of the European Clay Groups J. Konta, ed. Prague, 569–577.Google Scholar
Udagawa, S., Urabe, K., and Hasu, H. 1974. The crystal structure of muscovite dehydroxylate. Japan. Assoc. Minerl. Petrol. Econom. Geol. 69: 381–389.Google Scholar
Wardle, R., and Brindley, G. W. 1972. The crystal structures of pyrophyllite-1Tc and of its dehydroxylate. Amer. Mineral. 57: 732–750.Google Scholar
Zvyagin, B. B., Rabotnov, V. T., Sidorenko, O. V., and Kotelnikov, D. D. 1985. Unique mica from noncentrosym-metric layers. Izvestiya Akad. Nauk SSSR. Ser. Geol. 35: 121-124 (in Russian).Google Scholar