Hostname: page-component-78c5997874-fbnjt Total loading time: 0 Render date: 2024-11-08T05:03:04.852Z Has data issue: false hasContentIssue false

TEM study of mineral transformations in fired carbonated clays: relevance to brick making

Published online by Cambridge University Press:  09 July 2018

B. Bauluz*
Affiliation:
Cristalografía y Mineralogía, Departamento de Ciencias de la Tierra, Universidad de Zaragoza, Pedro Cerbuna 12, 50.009 Zaragoza, Spain
M. J. Mayayo
Affiliation:
Cristalografía y Mineralogía, Departamento de Ciencias de la Tierra, Universidad de Zaragoza, Pedro Cerbuna 12, 50.009 Zaragoza, Spain
A. Yuste
Affiliation:
Cristalografía y Mineralogía, Departamento de Ciencias de la Tierra, Universidad de Zaragoza, Pedro Cerbuna 12, 50.009 Zaragoza, Spain
C. Fernandez-Nieto
Affiliation:
Cristalografía y Mineralogía, Departamento de Ciencias de la Tierra, Universidad de Zaragoza, Pedro Cerbuna 12, 50.009 Zaragoza, Spain
J. M. Gonzalez Lopez
Affiliation:
Cristalografía y Mineralogía, Departamento de Ciencias de la Tierra, Universidad de Zaragoza, Pedro Cerbuna 12, 50.009 Zaragoza, Spain
*

Abstract

This study uses transmission electron microscopy (TEM) and analytical electron microscopy (AEM) supported by X-ray diffraction (XRD) and scanning electron microscopy (SEM) to investigate the mineralogical and textural changes produced in carbonated clays by firing. Sample bars were prepared using raw clays composed of quartz, illite and carbonates with minor amounts of smectite, chlorite, feldspars and Fe oxides. The raw samples were then fired at temperatures of between 800 and 1050°C. The XRD data show that increases in firing temperature result in dehydroxylation of clay minerals, carbonate decomposition and the formation of Ca-bearing silicates (e.g. gehlenite, wollastonite, pyroxenes and anorthite). The sizes of the Ca-silicate crystals make the use of the SEM inappropriate since they lie below the resolution threshold. However, TEM/AEM do provide the required textural and compositional characterization, revealing that there is a broad range of pyroxene compositions, some of which resemble fassaite, and that Ca/Mg ratios increase with temperature. The TEM also shows significant dehydroxylation and vitrification of the clay-rich matrix at T of ~800°C. Observed mineralogical and textural changes probably occurred in a system with a local disequilibrium much like small-scale, high-temperature metamorphic reactions (i.e. pyrometamorphism). The importance of these results is that they enable the selection of more appropriate raw clay composition and firing dynamics (temperature, firing duration and cooling rate) for both the brickmaking industry and brick conservation in the field of cultural heritage.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2004

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.)

References

Biscaye, P.E. (1965) Mineralogy and sedimentation of recent deep-sea clay in the Atlantic ocean and adjacent seas and ocean. Geological Society of America Bulletin, 76, 803–832.Google Scholar
Boynton, R.S. (1980) Chemistry and Technology of Lime and Limestone, 2nd edition. Wiley, New York.Google Scholar
Brearley, A.J. (1986) An electron optical study of muscovite breakdown in pelitic xenoliths during pyrometamorphism. Mineralogical Magazine, 50, 385–397.Google Scholar
Brearley, A.J. & Rubie, D.C. (1990) Effects of H2O on the disequilibrium breakdown of muscovite+quartz. Journal of Petrology, 31, 925–956.Google Scholar
Clark, B.H. & Peacor, D.R. (1992) Pyrometamorphism and partial melting of shales during combustion metamorphism: mineralogical, textural and chemical effects. Contribution to Mineralogy and Petrology, 112, 558–568.CrossRefGoogle Scholar
Cliff, G. & Lorimer, G.W. (1975) The quantitative analysis of thin specimens. Journal of Microscopy, 103, 203–207.CrossRefGoogle Scholar
Cultrone, G., Rodriguez-Navarro C, Sebastian, E., Cazalla, O. & De la Torre, M.J. (2001) Carbonate and silicate phase reactions during ceramic firing. European Journal of Mineralogy, 13, 621–634.Google Scholar
Dondi, M., Ercolani G, Fabbri, B. & Marsigli, M. (1998) An approach to the chemistry of pyroxenes formed during the firing of Ca-rich silicate ceramics. Clay Minerals, 33, 443–452.Google Scholar
Evans, J.L. & White, J. (1958) Further studies of the thermal decomposition of clays. Transactions of the British Ceramic Society, 57, 298.Google Scholar
Everthart, J.O. (1957) Use of auxiliary fluxes to improve structural clay bodies. American Ceramic Society Bulletin, 36, 268–271.Google Scholar
Freestone, I.C. & Middleton, A.P. (1987) Mineralogical application of the analytical SEM in archaeology. Mineralogical Magazine, 51, 21–31.Google Scholar
Goldsmith, J.R. (1953) A ‘simplexity principle’ and its relation to ‘ease’ of crystallization. Bulletin of the Geological Society of America, 64, 439–451.Google Scholar
Grapes, R.H. (1986) Melting and thermal reconstitutions of pelitic xenoliths, Wehr volcano, East Eiffel, Germany. Journal of Petrology, 27, 243–396.Google Scholar
Guggenheim, S., Chang, Y. & Koster van Groos, A.F. (1987) Muscovite dehydroxylation: high-temperature studies. American Mineralogist, 72, 537–550.Google Scholar
Huebner, J.S. & Turnock, A.C. (1980) The melting relations at 1 bar of pyroxenes composed largely of Ca-, Mg- and Fe-bearing components. American Mineralogist, 65, 225–271.Google Scholar
Maggetti, M. (1982) Phase analysis and its significance for technology and origin. Pp. 121–133 in: Archaeological Ceramics (Olin, J.S., editor). Smithsonian Institution Press, Boston.Google Scholar
Mata, M.P., Peacor, D.R. & Gallart-Martí, M.D. (2002) Transmission electron microscopy (TEM) applied to ancient pottery. Archaeometry, 44, 155–176.CrossRefGoogle Scholar
Mazzucato, E., Artioli G & Gualtieri, A. (1999) High temperature dehydroxylation of muscovite-2M1: a kinetic study by in situ XRPD. Physics and Chemistry of Minerals, 26, 375–381.Google Scholar
Minguzzi, V., Morandi, N., Nannetti C, Pirani R & Poppi, L. (1976) Mineralogy and geochemistry of the contact minerals in the Predazzo-Monzoni area - Part I: The fassaite. Mineralogica et Petrografica Acta, 21, 119–136.Google Scholar
Minguzzi, V., Morandi, N., Nannetti C, Pirani R & Poppi, L. (1977) Mineralogy and geochemistry of the contact minerals in the Predazzo-Monzoni area - Part II: The Predazzo fassaite and revision of the fassaite crystal-chemistry. Mineralogica et Petrografica Acta, 21, 189–219.Google Scholar
Morimoto, N. (1988) Nomenclature of pyroxenes. Mineralogical Magazine, 52, 367, 535–550.Google Scholar
Nuñez, R., Delgado, A. & Delgado R (1992) The sintering of calcareous illitic ceramics. Application in archaeological research. Pp. 795–796 in: Electron Microscopy EUREM 92 (Galindo, A., editor). University of Granada, Spain.Google Scholar
Riccardi, M.P., Messiga, B. & Duminuco, P. (1999) An approach to the dynamics of clay firing. Applied Clay Science, 15, 393–409.Google Scholar
Rodriguez-Navarro, C, Cultrone, G., Sánchez-Navas, A. & Sebastian, E. (2003) TEM study of mullite growth after muscovite breakdown. American Mineralogist, 88, 713–724.CrossRefGoogle Scholar
Schmücker, M., Schneider, J., Poorterman, M., Cambier, F. & Meinlhold R (1995) Constitution of mullite glasses produced by ultra-rapid quenching of plasma-sprayed melts. Journal of the European Ceramic Society, 15, 1201–1205.Google Scholar
Schultz, L.G. (1964) Quantitative interpretation of mineralogical composition from X-ray and chemical data for Pierre shale. US Geological Survey Professional Paper, 391-c, 31 pp.Google Scholar
Segnit, E.R. & Anderson, C.A. (1972) Scanning electron microscopy of fired illite. Transactions of the British Ceramic Society, 71, 85–88.Google Scholar
Sundius, N. & Bystroms, A.M. (1953) Decomposition products of muscovite at temperatures between 1000°C and 1260°C. Transactions of the British Ceramic Society, 52, 632–642.Google Scholar
Tite, M.S. & Maniatis, Y. (1975) Examination of ancient pottery using the scanning electron microscope. Nature, 257, 122–123.Google Scholar
Veniale, F. (1990) Modern techniques of analysis applied to ancient ceramics. Pp. 1–45 in: Advanced Workshop on Analytical Methodologies for the Investigation of Damaged Stones (Veniale, F. and Zezza, U., editors). University of Pavia, Italy.Google Scholar
Worden, R.H., Champness, P.E. and Droop, G.T.R. (1987) Transmission electron microscopy of pyrometamorphic breakdown of phengite and chlorite. Mineralogical Magazine, 51, 107–121.Google Scholar