Hostname: page-component-cd9895bd7-dzt6s Total loading time: 0 Render date: 2024-12-26T08:53:56.522Z Has data issue: false hasContentIssue false

X-ray photoelectron spectroscopic analysis of halloysites with different composition and particle morphology

Published online by Cambridge University Press:  09 July 2018

M. Soma
Affiliation:
National Institute for Environmental Studies, Tsukuba, Ibaraki 305, Japan
G. J. Churchman
Affiliation:
CSIRO Division of Soils, Glen Osmond, SA 5064, Australia
B. K. G. Theng
Affiliation:
DSIR Land Resources, Lower Hutt, New Zealand

Abstract

The surface composition of some halloysites with different particle morphology has been investigated by X-ray photoelectron spectroscopy (XPS) before and after removal of external Fe. The Fe(III) 2p3/2 binding energy of external Fe is appreciably smaller than that of structural Fe. Particle morphology is influenced by structural Fe content. The long-tubular halloysite has very little surface Fe, and its concentration tends to increase with the proportion of non-tubular particles in the samples. The spheroidal sample contains the most structural Fe which, however, does not appear to influence particle shape directly. Study by XPS indicates that Fe substitutes for Al in octahedral positions in approximately 1 : 2 proportion. As a result, an increase in octahedral vacancies and cation exchange capacity would be predicted. Further, halloysite layers within a crystal are generally inhomogeneous in composition. Built up like “onion skins”, the surface layers would either be enriched or depleted in Fe depending on the chemical environment in which crystal growth occurs.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1992

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

Askenasy, P.E., Dixon, J.B. & McKee, T.R. (1973) Spheroidal halloysite in a Guatemalan soil. Soil Sci. Soc. Am. Proc., 37, 799–803.Google Scholar
Bailey, S.W. (1990) Halloysite—a critical assessment. Proc. 9th Int. Clay Conf., Strasbourg, 89–;98.Google Scholar
Bates, T.F., Hildebrand, F.A. & Swineford, A. (1950) Morphology and structure of endellite and halloysite. Am. Miner., 35, 463–;484.Google Scholar
Carson, C.D. & Kunze, G.W. (1970) New occurrences of tabular halloysite. Soil Sci. Soc. Am. Proc., 34, 538–540.Google Scholar
Churchman, G.J. & Theng, B.K.G. (1984) Interactions of halloysites with amides: morphological factors affecting complex formation. Clay Miner., 19, 161–175.Google Scholar
Dixon, J.B. & McKee, T.R. (1974) Internal and external morphology of tubular and spheroidal halloysite particles. Clays Clay Miner., 22, 127–137.Google Scholar
Evans, S. & Raftery, E. (1982) Determination of the oxidation state of manganese in lepidolite by X-ray photoelectron spectroscopy. Clay Miner., 17, 477–481.Google Scholar
Johnson, S.L., Guggenheim, S. & Roster van Groos, A.F. (1990) Thermal stability of halloysite by high-pressure differential thermal analysis. Clays Clay Miner, 38, 477–484.Google Scholar
Kirkman, J.H. (1977) Possible structure of halloysite disks and cylinders observed in some New Zealand rhyolitic tephras. Clay Miner 12, 199–;216.CrossRefGoogle Scholar
Kohyama, N., Fukushima, K. & Fukami, A. (1982) Interlayer hydrates and complexes of day minerals observed by electron mciroscopy using an environmental cell. Proc. Int. Clay Conf. Bologna-Pavia,, 373–;384.Google Scholar
Kunze, G.W. & Bradley, W.F. (1964) Occurrence of a tabular halloysite in a Texas soil. Clays Clay Miner.12, 523–;527.Google Scholar
Mehra, O.P. & Jackson, M. L.(1960) Iron oxide removal from soils and clays by a dithionite-citrate system buffered with sodium bicarbonate. Clays Clay Miner., 7, 317–327.Google Scholar
Noko, H. (1986) Hexagonal platy halloysite in an altered tuff bed, Komaki City, Aichi Prefecture, central Japan. Clay Miner. 21, 401–;415.Google Scholar
Parfht, R.L., Saigusa, M. & Cowie J,D. (1984) Allophane and halloysite formation in a volcanic ash bed under different moisture conditions. Soil Sci. 138, 360–;364.Google Scholar
Radoslovjch, E.W. (1963) The cell dimensions and symmetry of Jayer-Iattice silicates. VI. Serpentine and kaolin morphology. Am. Miner. 48, 368–;378.Google Scholar
Seyama, H. & Soma, M. (1984) X-ray photoelectron spectroscopic study of montmorillonite containing exchangeable divalent cations. J. Chem. Soc., Faraday Trans. 1,, 80, 237–248.Google Scholar
Seyama, H. & Soma, M. (1985) Bonding-state characterization of the constituent elements of silicate minerals by X-ray photoelectron spectroscopy. J. Chem. Soc., Faraday Trans. 1, 81, 485–;495.Google Scholar
Seyama, H. & Soma, M. (1987) Fe 2p spectra of silicate minerals. J. Electron Spectrosc. Relat. Phenom. 42, 97–;101.Google Scholar
Soma, M., Tanaka, A., Seyama, H., Hayasi, S. & Hayamizu, K. (1990) Bonding states of sodium in tetrasilicic sodium fluor mica. Clay Sci., 8, 1–8.Google Scholar
Stucki, J.W., Roth, C.B. & Baitinger, W.E. (1976) Analysis of iron-bearing day minerals by electron spectroscopy for chemical analysis (ESCA). Clays Clay Miner., 24, 289–292.Google Scholar
Tazaki, K. (1979) Micromorphology of halloysite produced by weathering of plagioclase in volcanic ash. Proc. Int. Clay Conf. Oxford,, 415–;422.Google Scholar
Tazaki, K. (1982) Analytical electron microscopic studies of halloysite formation processes—morphology and composition of halloysite. Proc. Int. Clay Conf. Bologna-Pavia,, 573–;584.Google Scholar
Theng, B.K.G., Russell, M., Churchman, G J. & Parfitt, R.L. (1982) Surface properties of allophane, halloysite, and imogolite. Clays Clay Miner., 30, 143–149.Google Scholar
Wada, K. (1980) Mineralogical characteristics of Andisols. Pp. 87-107 in: Soils with Variable Charge(Theng, B.K.G., editor). NZ Soc. Soil Sci. Lower Hutt.Google Scholar
Whitton, J.S. & Churchman, G.J. (1987) Standard methods for mineral analysis of soil survey samples for characterisation and classification in NZ Soil Bureau. NZ Soil Bureau Scientific Report, 79, 8–10.Google Scholar