Hostname: page-component-76fb5796d-5g6vh Total loading time: 0 Render date: 2024-04-29T23:46:01.174Z Has data issue: false hasContentIssue false
  • English
  • Français

Dehydration of Synthetic Hydrated Kaolinites: A Model for the Dehydration of Halloysite(10Å)

Published online by Cambridge University Press:  02 April 2024

P. M. Costanzo  and
R. F. Giese Jr.
P. M. Costanzo
Affiliation:
Department of Geological Sciences, State University of New York, 4240 Ridge Lea Road, Amherst, New York 14226
R. F. Giese Jr.
Affiliation:
Department of Geological Sciences, State University of New York, 4240 Ridge Lea Road, Amherst, New York 14226
Get access Rights & Permissions [Opens in a new window]

Abstract

Several hydrates can be synthesized from well-crystallized kaolinites; of importance to the present work are a 10-Å hydrate (called the QS-10 hydrate), an 8.6-Å hydrate, and two kinds of partially dehydrated mixed-layer hydrates. One kind is a series of unstable materials with d(001) varying continuously between 10 and 8.6 Å, and the other kind is stable with d(001) approximately centered at 7.9 Å. The 10- and 7.9-Å phases have been observed in halloysites by many workers using X-ray powder diffraction, and the 8.6-Å phase has been seen by others in selected area electron diffraction photographs. Infrared spectra reveal additional similarities between the synthetic hydrates and both halloysite(10Å) and partially dehydrated halloysites. Because of these similarities, the synthetic hydrates can be used to develop a model for the dehydration of halloysite(10Å).

Previous work on the 10- and 8.6-Å hydrates identified two structural environments for the interlayer water. In one, the water is keyed into the ditrigonal holes of the silicate layer (hole water), and in the other, the water is more mobile (associated water). Both types are found in the QS-10 hydrate and halloysite(10Å), whereas only hole water occurs in the 8.6-Å hydrate. In the QS-10 hydrate, stronger hydrogen bonding between hole water and the clay makes the hole water more stable than the associated water. This difference in stability is responsible for a two-step dehydration process. The first step is the loss of associated water which results in a material with d(001) = 8.6 Å. This stable hydrate must be heated to temperatures near 200°C to drive off the remaining hole water. The less perfect structure of halloysite and its common curvilinear morphology reduce the difference in stability between hole and associated water molecules, so that when halloysite(10Å) dehydrates, loss of hole water and associated water overlaps, and the d-spacing goes directly to 7.2–7.9 Å.

Keywords

DehydrationHalloysiteHydriteKaoliniteWater
Type
Research Article
Information
Clays and Clay Minerals , Volume 33 , Issue 5 , October 1985 , pp. 415 - 423
Copyright
Copyright © 1985, The Clay Minerals Society

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

Blount, A. M., Threadgold, I. M. and Bailey, S. W., 1969 Refinement of the crystal structure of nacrite Clays & Clay Minerals 17 185–194.CrossRefGoogle Scholar
Brindley, G. W. and Goodyear, J., 1948 X-ray studies of halloysite and metahalloysite. Part II. The transition of halloysite to metahalloysite in relation to relative humidity Mineral. Mag. 28 407–422.Google Scholar
Churchman, G. J., 1970 Interlayer water in halloysite New Zealand University of Otago, Dunedin.Google Scholar
Churchman, G. J., Aldridge, L. P. and Carr, R. M., 1972 The relationship between the hydrated and dehydrated states of an halloysite Clays & Clay Minerals 20 241–246.CrossRefGoogle Scholar
Churchman, G. J. and Carr, R. M., 1973 Dehydration of the washed potassium acetate complex of halloysite Clays & Clay Minerals 21 423–424.CrossRefGoogle Scholar
Costanzo, P. M., 1984 Synthesis and characterization of hydrated kaolinites and the chemical and physical properties of the interlayer water New York State University of New York at Buffalo, Buffalo.Google Scholar
Costanzo, P. M., Clemency, C. V. and Giese, R. F., 1980 Low-temperature synthesis of a 10-Å hydrate of kaolinite using dimethylsulfoxide and ammonium fluoride Clays & Clay Minerals 28 155–156.CrossRefGoogle Scholar
Costanzo, P. M., Giese, R. F. and Clemency, C. V., 1984 Synthesis of a 10-Å hydrated kaolinite Clays & Clay Minerals 32 29–35.CrossRefGoogle Scholar
Costanzo, P. M., Giese, R. F. and Lipsicas, M., 1984 Static and dynamic structure of water in hydrated kaolinites: I. The static structure Clays & Clay Minerals 32 419–428.CrossRefGoogle Scholar
Costanzo, P. M., Giese, R. F., Lipsicas, M. and Straley, C., 1982 Synthesis of a quasi-stable kaolinite and heat capacity of interlayer water Nature 296 549–551.CrossRefGoogle Scholar
Cowley, E.M., 1961 Diffraction intensities from bent crystals Acta Crystallogr. 14 920–927.CrossRefGoogle Scholar
Deeds, C. T. v., Olphen, H., Bradley, W. F., Heller, L. and Weiss, A., 1966 Intersalation and interlayer hydration of minerals of the kaolinite group Proc. Int. Clay Conf. 1966, Jerusalem, Vol. 1 Jerusalem Israel Prog. Sci. Transl. 183–199.Google Scholar
Fijał, J. and Tokarz, M., 1975 Studies on the fluoroderivatives of silicate minerals with layered structure I. Some aspects of the reaction of kaolinite with fluoride solutions Mineral. Polonica 6 59–69.Google Scholar
Harrison, J. L. and Greenberg, S. S., 1962 Dehydration of fully hydrated halloysite from Lawrence County, Indiana Clay Miner. 9 374–377.CrossRefGoogle Scholar
Hughes, I. R., 1966 Mineral changes of halloysite on drying N.Z. J. Sci. 9 103–113.Google Scholar
Kohyama, N., Fukushima, K. and Fukami, A., 1978 Observation of the hydrated form of tubular halloysite by an electron microscope equipped with an environmental cell Clays & Clay Minerals 26 25–40.CrossRefGoogle Scholar
Lipsicas, M., Straley, C., Costanzo, P. M. and Giese, R. F., 1985 Static and dynamic structure of water in hydrated kaolinites: Part II. The dynamic structure J. Coll. Interface Sci. .CrossRefGoogle Scholar
MacEwan, D. M. C., 1946 Halloysite-organic complexes Nature 157 159–160.CrossRefGoogle Scholar
MacEwan, D. M. C., 1947 The nomenclature of the halloysite minerals Mineral. Mag. 28 36–44.Google Scholar
McKee, T. R., Dixon, J. B., Whitehouse, U. G. and Harling, D. F., 1973 Study of Te Puke halloysite by a high resolution electron microscope Abstr. 31st Ann. Electron Microscopy Soc. of America Meeting, New Orleans, 1973 200–201.CrossRefGoogle Scholar
Range, K.-J., Range, A., Weiss, A. and Heller, L., 1969 Fire-clay type kaolinite or fireclay minerals? Experimental classification of kaolinite-halloysite minerals Proc. Int. Clay Conf, Tokyo, 1969, Vol. 1 Jerusalem Israel Univ. Press 3–13.Google Scholar
Suitch, P. R. and Young, R. A., 1983 Atom positions in highly ordered kaolinite Clays & Clay Minerals 31 357–366.CrossRefGoogle Scholar
Tarasevich, Y. I. and Gribina, I. A., 1972 Infrared spectroscopic study of the state of water in halloysite Kolloidnyi Zh. 34 405–411.Google Scholar
van Olphen, H., Deeds, C.T., Rosenqvist, I. Th. and Graff-Petersen, P., 1963 Short contributions Proc. Int. Clay Conf., Stochkholm, 1963, Vol. 1 Oxford Pergamon Press 380–381.Google Scholar
Wada, K., 1965 Intercalation of water in kaolin minerals Amer. Mineral. 50 924–941.Google Scholar
Wada, K. and Yamada, H., 1968 Hydrazine intercalation-intersalation for differentiation of kaolin minerals from chlorites Amer. Mineral. 53 334–339.Google Scholar
Weiss, A., Thielpape, W., Goring, G., Ritter, W., Schafer, H., Rosenqvist, I. Th. and Graff-Petersen, P., 1963 Kaolinit-Einlagerungs-Verbindungen Proc. Int. Clay Conf. Stockholm, 1963, Vol. 1 Oxford Pergamon Press 287–305.Google Scholar