Hostname: page-component-848d4c4894-wzw2p Total loading time: 0 Render date: 2024-06-09T16:23:37.763Z Has data issue: false hasContentIssue false

Interactions of halloysites with amides: mineralogical factors affecting complex formation

Published online by Cambridge University Press:  09 July 2018

G. J. Churchman
Affiliation:
NZ Soil Bureau, Department of Scientific and Industrial Research, Private Bag, Lower Hutt, New Zealand
B. K. G. Theng
Affiliation:
NZ Soil Bureau, Department of Scientific and Industrial Research, Private Bag, Lower Hutt, New Zealand

Abstract

Complex formation between halloysites, from soil and geological sources, and a series of amides has been investigated. All the amides used can be intercalated to give single-layer complexes with basal spacings between 10·4 Å (for formamide) and 12·4 Å (for N,N-dimethylacetamide). When the interlayer space of halloysite has already been expanded by water, as is the case with fully hydrated samples, the rate and extent of intercalation depend more on the properties of the organic species than on the mineralogy of the clay. With partially and completely dehydrated halloysite, however, complex formation is influenced by the particle size, crystallinity, and iron content of the mineral. A large particle size, a high degree of crystallinity, and a low iron content are all conducive to complex formation. The iron content of halloysite also appears to affect particle shape. Low structural iron contents are associated with long tubular particles, intermediate contents with short and/or wide tubes, and high contents with spheroidal and other non-tubular forms. Halloysites containing high amounts of extractable (non-structural) iron generally show a low intercalating ability.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1984

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

Adams, J.M. (1978) Unifying features relating to the 3D structures of some intercalates of kaolinite. Clays Clay Miner. 26, 291295.Google Scholar
Adams, J.M. & Jefferson, D.A. (1976) The crystal structure or a dickiterformamide intercalate (Al2Si2O5(OH)4.HCONH2). Acta Cryst. B32, 11801183.CrossRefGoogle Scholar
Aylmore, L.A.G. & Quirk, J.P. (1960) Domain or turbostratic structure of clays. Nature 187, 10461048.CrossRefGoogle Scholar
Blakemore, L.C., Searle, P.L. & Daly, B.K. (1981) Methods for chemical analysis of soils. Pp. A8.7A8.9 in: N.Z. Soil Bureau Scientific Report I0A. Google Scholar
Bramao, L., Cady, J.G., Hendricks, S.B. & Swerdlow, W. (1952) Criteria for the characterization of kaolinite, halloysite and a related mineral in clays and soils. Soil Sci. 73, 273287.Google Scholar
Caillere, S., Glaeser, R., Esquevin, J. & Henin, S. (1950) Preparation d'halloysite à 14 Å et à 17 Å. C.R. Acad. Sci. Paris 230, 308310.Google Scholar
Carr, R.M. & Chih, Hwa (1971) Complexes of halloysite with organic compounds. Clay Miner. 9, 153166.Google Scholar
Carson, C.D. & Kunze, G.W. (1970) New occurrence of tabular halloysite. Soil Sci. Soc. Am. Proc. 34, 538540.CrossRefGoogle Scholar
Churchman, G.J. (1970) Interlayer water in halloysite. PhD thesis, Univ. Otago, New Zealand.Google Scholar
Churchman, G.J., Aldridge, L.P. & Carr, R.M. (1972) The relationship between the hydrated and dehydrated states of an halloysite. Clays Clay Miner. 20, 241246.CrossRefGoogle Scholar
Dixon, J.B. (1977) Kaolinite and serpentine group minerals. Pp. 357403 in: Minerals in Soil Environments (Dixon, J. B. & Weed, S. B., editors). Soil Science Society of America, Madison, Wisconsin, USA.Google Scholar
Hughes, I.R. (1966) Mineral changes of halloysite on drying. N.Z. J. Sci. 9, 103113.Google Scholar
Hughes, J.C. & Brown, G. (1979) A crystallinity index for soil kaolins and its relation to parent rock, climate and soil maturity. J. Soil Sci. 30, 557563.Google Scholar
Kirkman, J.H. (1977) Possible structure of halloysite disks and cylinders observed in some New Zealand rhyolitic tephras. Clay Miner. 8, 199216.CrossRefGoogle Scholar
Kunze, G.W. & Bradley, W.F. (1964) Occurrence of a tabular halloysite in a Texas soil. Clays Clay Miner. 12, 523527.Google Scholar
Ledoux, R.L. & White, J.L. (1966) Infrared studies of hydrogen bonding interaction between kaolinite surfaces and intercalated potassium acetate, hydrazine, formamide and urea. J. Colloid Interface Sci. 21, 127152.Google Scholar
MacEwan, D.M.C. (1946) Halloysite-organic complexes. Nature 157, 159160.Google Scholar
MacEwan, D.M.C. (1948) Complexes of clays with organic compounds. 1. Complex formation between montmorillonite and halloysite and certain organic liquids. Trans. Faraday Soc. 44, 349367.Google Scholar
Marsters, S. (1978) Report upon the extraction and industrial uses of halloysite. Proc. Ann. Conf. Aust. Inst. Mining Metallurgy, Whangarei, N.Z. 91100.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, 317327.Google Scholar
Nagasawa, K. (1969) Kaolin minerals in Cenozoic sediments of Central Japan. Proc. Int. Clay Conf. Tokyo 1, 1530.Google Scholar
New Zealand Soil Bureau (1968) Soils of New Zealand, Part 3. Google Scholar
Norrish, K. & Hutton, J.T. (1969) An accurate X-ray spectrographic method for the analysis of a wide range of geological samples. Geochim. Cosmochim. Acta 33, 431453.Google Scholar
Olejnik, S., Aylmore, L.A.G., Posner, A.M. & Quirk, J.P. (1968) Infrared spectra of kaolin mineral-dimethyl sulfoxide complexes. J. Phys. Chem. 72, 241249.Google Scholar
Olejnik, S., Posner, A.M. & Quirk, J.P. (1970) The intercalation of polar organic compounds into kaolinite. Clay Miner. 8, 421434.CrossRefGoogle Scholar
Parker, T.W. (1969) A classification of kaolinites by infrared spectroscopy. Clay Miner. 8, 135141.Google Scholar
Range, K.J., Range, A. & Weiss, A. (1969) Fire-clay type kaolinite or fire-clay mineral? Experimental classification of kaolinite-halloysite minerals. Proc. Int. Clay Conf. Tokyo 1, 313.Google Scholar
Smykatz-Kloss, W. (1974) The determination of the degree of (dis-)order of kaolinites by means of differential thermal analysis. Chem. Erde 33, 358364.Google Scholar
Tazaki, K.(1982) Analytical electron microscopic studies of halloysite formation processes—morphology and composition of halloysite. Pp. 573584 in: International Clay Conference 1981, Developments in Sedimentology 35 (van Olphen, H. & Veniale, F., editors). Elsevier, Amsterdam.Google Scholar
Theng, B.K.G. (1974) The Chemistry of Clay-Organic Reactions, pp. 239260. Adam Hilger, London.Google Scholar
Theng, B.K.G., Greenland, D.J. & Quirk, J.P. (1967) The swelling in water of complexes of montmoriUonite with polyvinyl alcohol. Aust. J. Soil Res. 5, 6975.CrossRefGoogle 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, 143149.CrossRefGoogle Scholar
Tonkin, P.J. (1970) Contorted stratification with clay lobes in volcanic ash beds, Raglan-Hamilton region, New Zealand. Earth Sci. J. 4, 129140.Google Scholar
Wada, S.I. & Mizota, C. (1982) Morphology of iron-rich halloysite. Clays Clay Miner. 30, 315317.Google Scholar
Weaver, C.E. & Pollard, L.D. (1973) The Chemistry of Clay Minerals, pp. 149154. Developments in Sedimentology 15, Elsevier, Amsterdam.Google Scholar
Weiss, A., Thielepape, W., Göring, G., Ritter, W. & Schäfer, H. (1963) Kaolinit-Einlagerungs- Verbindungen. Proc. Int. Clay Conf. Stockholm 1, 287305.Google Scholar
Weiss, A., Thielepape, W. & Orth, H. (1966) Neue Kaolinit-Einlagerungsverbindungen. Proc. Int. Clay Conf. Jerusalem 1, 277293.Google Scholar