Hostname: page-component-cd9895bd7-gxg78 Total loading time: 0 Render date: 2024-12-27T06:01:24.823Z Has data issue: false hasContentIssue false
  • English
  • Français

Thermal Evolution of Fluorine From Smectite and Kaolinite

Published online by Cambridge University Press:  01 January 2024

Steve J. Chipera  and
David L. Bish
Steve J. Chipera*
Affiliation:
Earth and Environmental Sciences Division, Los Alamos National Laboratory, Mail Stop D469, Los Alamos, New Mexico 87545, USA
David L. Bish
Affiliation:
Earth and Environmental Sciences Division, Los Alamos National Laboratory, Mail Stop D469, Los Alamos, New Mexico 87545, USA
*
*E-mail address of corresponding author: Chipera@lanl.gov
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 fluoride ion is crystal chemically very similar to the hydroxyl ion, substituting for hydroxyl in many minerals in which hydrogen bonding is not important. Fluoride substitutions are particularly common in 2:1 layer silicates, such as micas, illites and smectites. The brick and tile industries, which use naturally occurring clays as their primary raw materials, have devoted considerable effort to understanding fluorine evolution during firing of the raw materials due to increasingly stringent fluorine emission regulations. In order to understand fluorine evolution from ceramic raw materials, we have studied a number of phyllosilicate materials used in making bricks. X-ray powder diffraction and fluorine analyses were combined with heating experiments and thermogravimetric analysis to evaluate the chemical and structural changes taking place on heating. Fluorine remained in 2:1 layer silicates to higher temperatures than did hydroxyl, but it behaved identically to hydroxyl in the kaolinite studied. In all cases, fluorine evolution coincided with structural breakdown of the clay host. These results show that fluorine evolution will consistently occur during firing of clay raw materials, and the problems of fluorine emission cannot be readily solved by simple variations of firing temperatures or times.

Keywords

BrickFiringFluorineKaoliniteSmectiteTGAThermogravimetric AnalysisX-ray Diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 50 , Issue 1 , February 2002 , pp. 38 - 46
Copyright
Copyright © 2002, The Clay Minerals Society

References

Bassett, W.A., (1960) Role of hydroxyl orientation in mica alteration Bulletin of the Geological Society of America 71 449–456 10.1130/0016-7606(1960)71[449:ROHOIM]2.0.CO;2.Google Scholar
Bish, D.L., Vaniman, D.T. and Chipera, S.J. (1999) Effects of particle size and trace-mineral content on kaolin trace element chemistry. Proceedings of the 36th Annual Clay Minerals Society Meeting, p. 15.Google Scholar
Chipera, S.J. and Bish, D.L. (1989) The nature of fluorine in a partially ordered I/S clay. Proceedings of the 25th Annual Clay Minerals Society meeting, p. 23.Google Scholar
Chipera, S.J. Guthrie, G.D. Jr Bish, D.L., Guthrie, G.D. and Mossman, B.T., (1993) Preparation and Purification of Mineral Dusts Health Effects of Mineral Dusts Washington, D.C. Mineralogical Society of America 235–249 10.1515/9781501509711-009 Reviews in Mineralogy, 28 .Google Scholar
Chung, F.H., (1974) Quantitative interpretation of X-ray diffraction patterns of mixtures. II: Adiabatic principle of X-ray diffraction analysis of mixtures Journal of Applied Crystallography 7 526–531 10.1107/S0021889874010387.Google Scholar
Clarke, F.W. and Washington, H.S. (1924) The composition of the earth’s crust. U.S. Geological Survey Professional Paper 125, as referenced in Robinson and Edgington (1946).Google Scholar
Eagers, R.Y., (1969) Toxic Properties of Inorganic Fluorine Compounds New York Elsevier 152 pp.Google Scholar
Giese, R.F. Jr, (1975) The effect of F/OH substitution on some layer-silicate minerals Zeitschrift für Kristallographie 141 138–144 10.1524/zkri.1975.141.1-2.138.Google Scholar
Giese, R.F., (1978) The electrostatic interlayer forces of layer structure minerals Clays and Clay Minerals 26 51–57 10.1346/CCMN.1978.0260106.Google Scholar
Giese, R.F. Jr, (1982) Theoretical studies of the kaolin minerals. Electrostatic calculations Bulletin de Mineralogie 105 417 424.Google Scholar
Hauck, D. and Hilker, E., (1986) Possibilities for the reduction of fluorine emission in the firing of bricks and tiles Ziegelindustrie International 7–8/86 373 385.Google Scholar
Hazen, R.M. and Burnham, C.W., (1973) The crystal structures of one-layer phlogopite and annite American Mineralogist 58 889 900.Google Scholar
Ingram, B.L., (1970) Determination of fluoride in silicate rocks without separation of aluminum using a specific ion electrode Analytical Chemistry 42 1825–1827 10.1021/ac50160a067.Google Scholar
Joswig, W. (1972) Neutronenbeugungsmessungen an einem 1M-phlogopit. Neues Jahrbuch für Mineralogie-Monatshefte, 1–11.Google Scholar
Keller, W.D., (1986) Compositions of condensates from heated clay minerals and shales American Mineralogist 71 1420 1425.Google Scholar
Kerr, P.F. and Kulp, J.L. (1949) Reference Clay Localities — United States. American Petroleum Institute Project 49 (Clay Minerals Standards), Preliminary Report 2, 101 pp.Google Scholar
Kolkmeier, H., (1986) Emission control in the brick and tile industry Ziegelindustrie International 10 86 516 530.Google Scholar
Labouriau, A. Kim, Y.-W. Chipera, S.J. Bish, D.L. and Earl, W.L., (1995) A 19F nuclear magnetic resonance study of natural clays Clays and Clay Minerals 43 697–704 10.1346/CCMN.1995.0430606.Google Scholar
Mumenthaler, T. Schmitt, H.W. Peters, T. Ramseyer, K. and Zweili, F., (1995) Tracing the reaction processes during firing of carbonate-containing brick mixes with the help of cathodoluminescence Ziegelindustrie International 5/95 307 318.Google Scholar
Ohashi, Y. and Burnham, C.W., (1972) Electrostatic and repulsive energies of the M1 and M2 cation sites in pyroxenes Journal of Geophysical Research 77 5761–5766 10.1029/JB077i029p05761.Google Scholar
Reynolds, R.C. Jr and Reynolds, R.C. III, (1987) Description of program NEWMOD for the calculation of the one-dimensional X-ray diffraction patterns of mixed-layered clays Hanover, New Hampshire Department of Earth Sciences, Dartmouth College.Google Scholar
Robinson, W.O. and Edgington, G., (1946) Fluorine in soils Soil Science 61 341–353 10.1097/00010694-194605000-00001.Google Scholar
Romo, L.A. and Roy, R., (1957) Studies of the substitution of OH− by F− in various hydroxylic minerals American Mineralogist 42 165 177.Google Scholar
Rothbauer, R. (1971) Untersuchung eines 2M1-muskovits mit neutronenstrahlen. Neues Jahrbuch für Mineralogie-Monatshefte, 143–154.Google Scholar
Sedej, B., (1988) The emission of volatile fluorides during the process in the ceramic industry Ziegelindustrie International 7–8 88 372 376.Google Scholar
Steinkoenig, L.A., (1919) The relation of fluorine in soils, plants, and animals Journal of Industrial and Engineering Chemistry 11 463 10.1021/ie50113a027 as referenced in Robinson and Edgington (1946).Google Scholar
Storer-Folt, J.A. Cooper, D.J. and Boeck, E., (1992) Fluorine release in a brick tunnel kiln Ceramic Bulletin 71 636 638.Google Scholar
Strohmenger, W., (1983) Problems associated with fluorine Ziegelindustrie International 2 83 67 72.Google Scholar
Sugiyama, H. Ōya, A. and Ōtani, S., (1988) Syntheses and thermal degradation behaviours of saponite-α-naphthylamine complexes: Effects of substitution of OH in saponite by fluorine Journal of Materials Science 23 1764–1768 10.1007/BF01115720.Google Scholar
Thomas, J Jr Glass, H.D. White, W.A. and Trandel, R.M., (1977) Fluorine content of clay minerals and argillaceous earth materials Clays and Clay Minerals 25 278–284 10.1346/CCMN.1977.0250405.Google Scholar
Troll, G. Farzaneh, A. and Cammann, K., (1977) Rapid determination of fluoride in mineral and rock samples using an ion-selective electrode Chemical Geology 20 295–305 10.1016/0009-2541(77)90054-7.Google Scholar
Wilson, H.H. and Johnson, L.D., (1975) Characterization of air pollutants emitted from brick plant kilns Ceramic Bulletin 54 990 993.Google Scholar
Wolfe, R.W. and Giese, R.F. Jr, (1978) The stability of fluorine analogues of kaolinite Clays and Clay Minerals 26 76–78 10.1346/CCMN.1978.0260110.Google Scholar