Hostname: page-component-848d4c4894-m9kch Total loading time: 0 Render date: 2024-06-11T21:33:54.324Z Has data issue: false hasContentIssue false
  • English
  • Français

Correlations among the mineralogical and physical properties of halloysite nanotubes (HNTs)

Published online by Cambridge University Press:  02 January 2018

Stephen Hillier ,
Rik Brydson ,
Evelyne Delbos ,
Tony Fraser ,
Nia Gray ,
Helen Pendlowski ,
Ian Phillips ,
Jean Robertson  and
Ian Wilson
Stephen Hillier*
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK Department of Soil and Environment, Swedish University of Agricultural Sciences (SLU), Uppsala SE-75007, Sweden
Rik Brydson
Affiliation:
Institute for Materials Research, SCaPE, University of Leeds, Leeds LS2 9JT, UK
Evelyne Delbos
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK
Tony Fraser
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK
Nia Gray
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK
Helen Pendlowski
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK
Ian Phillips
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK
Jean Robertson
Affiliation:
The James Hutton Institute, Craigiebuckler, Aberdeen AB15 8QH, UK
Ian Wilson
Affiliation:
Withielgoose Farmhouse, Withiel, Bodmin, Cornwall PL30 5NW, UK
*
*E-mail: stephen.hillier@hutton.ac.uk
Get access Rights & Permissions [Opens in a new window]

Abstract

Twenty one samples of relatively pure tubular halloysites (HNTs) from localities in Australia, China, New Zealand, Scotland, Turkey and the USA have been investigated by X-ray diffraction (XRD), infrared spectroscopy (IR) and electron microscopy. The halloysites occur in cylindrical tubular forms with circular or elliptical cross sections and curved layers and also as prismatic tubular forms with polygonal cross sections and flat faces. Measurements of particle size indicate a range from 40 to 12,700 nm for tube lengths and from 20 to 600 nm for diameters. Size distributions are positively skewed with mean lengths ranging from 170 to 950 nm and mean diameters from 50 to 160 nm. Cylindrical tubes are systematically smaller than prismatic ones. Features related to order/ disorder in XRD patterns e.g. as measured by a ‘cylindrical/prismatic’ (CP) index and IR spectra as measured by an ‘OH-stretching band ratio’ are related to the proportions of cylindrical vs. prismatic tubes and correlated with other physical measurements such as specific surface area and cation exchange capacity. The relationships of size to geometric form, along with evidence for the existence of the prismatic form in the hydrated state and the same 2M1 stacking sequence irrespective of hydration state (i.e. 10 vs. 7 Å) or form, suggests that prismatic halloysites are the result of continued growth of cylindrical forms.

Keywords

halloysitenanotubesHNTscylindricalprismaticpolygonallengthdiameterspecific surface area
Type
Research Article
Information
Clay Minerals , Volume 51 , Issue 3 , June 2016 , pp. 325 - 350
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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

Bailey, S.W. (1980) Summary of recommendations of AIPEA nomenclature committee. Clay Minerals, 15, 85–93.10.1180/claymin.1980.015.1.07CrossRefGoogle Scholar
Bailey, S.W. (1990) Halloysite: a critical assessment. Pp. 89–98 in: Proceedings of the 9th International Clay Conference 1989 (V.C. Farmer & Y. Tardy, editors). Sciences Géologiques, Mémoire 86, Strasbourg, France.Google Scholar
Bailey, S.W. (1993) Review of the structural relationships of the kaolin minerals. Pp. 25–42 in: Kaolin Genesis and Utilization (H.H. Murray, W.M. Bundy & C.C. Harvey, editors). The Clay Minerals Society, Boulder, CO, USA.Google Scholar
Baronnet, A. & Devouard, B. (1996) Topology and crystal growth of natural chrysotile and polygonal serpentine. Journal of Crystal Growth, 166, 952–960.10.1016/0022-0248(96)00042-5CrossRefGoogle Scholar
Bates, T.F. (1971) The kaolin minerals. Pp. 109–157 in: The Electron Optical Investigation of Clays (J.A. Gard, editor). Monograph 3, Mineralogical Society, London.CrossRefGoogle Scholar
Bates, T.F. & Comer, J.J. (1957) Further observations on the morphology of chrysotile and halloysite. Clays and Clay Minerals, 6, 237–248.Google Scholar
Bates, T.F., Hildebrand, F.A. & Swineford, A. (1950) Morphology and structure of endellite and halloysite. American Mineralogist, 35, 463–84.Google Scholar
Brindley, G.W. (1984) Order-disorder in clay mineral structures. Pp. 125–196 in: Crystal Structures of Clay Minerals and their X-ray Identification (G.W. Brindley & G. Brown, editors). Monograph 5, Mineralogical Society, London, UK.Google Scholar
Brindley, G.W. & Robinson, K. (1948) X-ray studies of halloysite and metahalloysite. Mineralogical Magazine, 28, 393–406.10.1180/minmag.1948.028.203.01Google Scholar
Brindley, G.W., de Souza Santos, P. & de Souza Santos, H. (1963) Mineralogical studies of kaolinite-halloysite clays: Part I. Identification problems. American Mineralogist, 48, 897–910.Google Scholar
Chukhrov, F.V. & Zvyagin, B.B. (1966) Halloysite, a crystallochemically and mineralogically distinct species. Pp. 11–25 in: Proceedings of the International Clay Conference Jerusalem, Israel (L. Heller & A. Weiss, editors). Israel Program for Scientific Translation, Jerusalem, Israel.Google Scholar
Churchman, G.J. (2015) The identification and nomenclature of halloysite (a historical perspective). Pp. 51–67 in: Natural Mineral Nanotubes (P. Pasbakhsh & G.J. Churchman, editors). Apple Academic Press, Oakville, Canada.10.1201/b18107-5Google Scholar
Churchman, G.J. & Carr, R.M. (1975) The definition and nomenclature of halloysites. Clays and Clay Minerals, 23, 382–388.10.1346/CCMN.1975.0230510CrossRefGoogle Scholar
Churchman, G.J., Whitton, J.S., Claridge, G.G.C. & Theng, B.K.G. (1984) Intercalation method using formamide for differentiating halloysite from kaolinite. Clays and Clay Minerals, 32, 241–248.10.1346/CCMN.1984.0320401Google Scholar
Churchman, G.J., Davy, T.J., Aylmore, L.A.G., Gilkes, R.J. & Self, P.G. (1995) Characteristics of fine pores in some halloysites. Clay Minerals, 30, 89–98.CrossRefGoogle Scholar
Costanzo, P.M., Giese, R.F. & Lipsicas, M. (1984) Static and dynamic structure of water in hydrated kaolinites; I. The static structure. Clays and Clay Minerals, 32, 419–128.10.1346/CCMN.1984.0320511CrossRefGoogle Scholar
de Souza Santos, P., Brindley, G.W. & de Souza Santos, H. (1965) Mineralogical studies of kaolinite-halloysite clays: part III. A fibrous kaolin mineral from Piedade, Säo Paulo, Brazil. American Mineralogist, 50, 619–628.Google Scholar
Dixon, J.B. (1989) Kaolin and serpentine group minerals. Pp. 467–525 in: Minerals in Soil Environments (J.B. Dixon & S.B. Weed, editors). Soil Science Society of America, Madison, Wisconsin, USA.Google Scholar
Dixon, J.B. & McKee, T.R. (1974) Internal and external morphology of tubular and spheroidal halloysite particles. Clays and Clay Minerals, 22, 127–137.10.1346/CCMN.1974.0220118Google Scholar
Ece, Ö.I. & Schroeder, P.A. (2007) Hydrothermal alteration of Oligocene volcanic rocks and genesis of hallyosite-alunite-kaolinite deposits in the Turplu area, Balikesir, Turkey. Clays and Clay Minerals, 55, 18–36.10.1346/CCMN.2007.0550102CrossRefGoogle Scholar
Farmer, V.C. (1974) The layer silicates. Pp. 331–363 in: The Infrared Spectra of Minerals. IR spectra (V.C. Farmer, editor). Monograph 4, Mineralogical Society, London, UK.10.1180/mono-4.15Google Scholar
Giese, R.F. Jr (1988) Kaolin minerals structures and stabilities. Pp. 29–66 in: Hydrous Phyllosilicates (Exclusive of Micas) (S.W Bailey, editor). Reviews in Mineralogy, 19, Mineralogical Society of America, Washington, D.C. 10.1515/9781501508998-008Google Scholar
Gray, N., Lumsdon, D.G. & Hillier, S. (2016) Effect of pH on the cation exchange capacity of some tubular halloysites (HNTs). Clay Minerals, 51, 373–383.10.1180/claymin.2016.051.3.04CrossRefGoogle Scholar
Heddle, M. (1882) Minerals new to Britain. Mineralogical Magazine. 5, 1–2.10.1180/minmag.1882.005.22.01Google Scholar
Hillier, S. (1999) Use of an air brush to spray dry samples for X-ray powder diffraction. Clay Minerals, 34, 127–135.10.1180/000985599545984Google Scholar
Hillier, S. & Ryan, P.C. (2002) Identification of halloysite (7 angstrom) by ethylene glycol solvation: the ‘MacEwan effect'. Clay Minerals, 37, 487–96.Google Scholar
Hoffman, U., Morcos, S. & Schembra, F.W. (1962) Das sonderbarste Tonmineral, der halloysite. Berichte der Deutschen Keramischen Gesellschaft, 39, 474–482.Google Scholar
Honjo, G., Kitamura, N. & Mihama, K. (1954) A study of clay minerals by means of single-crystal electron diffraction diagrams - the structure of tubular kaolin. Clay Minerals Bulletin, 4, 133–141.10.1180/claymin.1954.002.12.03Google Scholar
Joussein, E., Petit, S., Churchman, J., Theng, B., Righi, D. & Delvaux, B. (2005) Halloysite clay minerals — a review. Clay Minerals, 40, 383–26.10.1180/0009855054040180CrossRefGoogle Scholar
Keeling, J., Pasbakhsh, P. & Churchman, G.J. (2011) Halloysite from the Eucla Basin, South Australia -comparison of physical properties for potential new uses. Pp. 351–359 in: 10th International Congress for Applied Mineralogy (ICAM) (M. Broekmans, editor). Trondheim, Norway.CrossRefGoogle Scholar
Kogure, T., Mori, K., Drits, Y.A. & Takai, Y. (2013) Structure of prismatic halloysite. American Mineralogist, 98, 1008–1016.10.2138/am.2013.4385CrossRefGoogle Scholar
Kohyama, N., Fukushima, K. & Fukami, A. (1978) Observation of the hydrated form of tubular halloysite by an electron microscope equipped with an environmental cell. Clays and Clay Minerals, 26, 25–0.10.1346/CCMN.1978.0260103Google Scholar
Limpert, E., Stahel, W. & Abbt, M. (2001) Log-normal distributions across the sciences: keys and clues. BioScience, 51, 341–352.10.1641/0006-3568(2001)051[0341:LNDATS]2.0.CO;2Google Scholar
Norrish, K. (1995) An unusual fibrous halloysite. Pp. 275–284 in: Clays Controlling the Environment. Proceedings of the 10th International Clay Conference, Adelaide 1993 (G.J. Churchman, R.W. Fitzpatrick & R.A. Eggleton, editors). CSIRO Publishing, Melbourne, Australia.Google Scholar
Omotoso, O., McCarty, D.K., Hillier, S. & Kleeberg, R. (2006) Some successful approaches to quantitative mineral analysis as revealed by the 3rd Reynolds Cup Contest. Clays and Clay Minerals, 54, 748–760.10.1346/CCMN.2006.0540609Google Scholar
Pasbakhsh, P., Churchman, G.J. & Keeling, J.L. (2013) Characterisation of properties of various halloysites relevant to their use as nanotubes and microfibre fillers. Applied Clay Science, 74, 47–57.10.1016/j.clay.2012.06.014Google Scholar
Rasband, W.S. (1997-2015) ImageJ, U. S. National Institutes of Health, Bethesda, Maryland, USA, http://imagej.nih.gov/ij/. Google Scholar
Singh, B. (1996) Why does halloysite roll? - A new model. Clays and Clay Minerals, 44, 191–196.10.1346/CCMN.1996.0440204CrossRefGoogle Scholar
Ünal-Ercan, H., Ece, Ö.I., Schroeder, P.A. & Karacik, Z. (2016) Differentiating styles of alteration within kaolin-alunite hydrothermal deposits of Çanakkale, Turkey. Clays and Clay Minerals, 64, 245–274.CrossRefGoogle Scholar
Wilson, I.R. (2004) Kaolin and halloysite deposits of China. Clay Minerals, 39, 1–15.10.1180/0009855043910116Google Scholar
Wilson, I.R. & Keeling, J.L. (2016) Global occurrence and geology of halloysite. Clay Minerals, 51, 309–324.10.1180/claymin.2016.051.3.12CrossRefGoogle Scholar