Hostname: page-component-cd9895bd7-dk4vv Total loading time: 0 Render date: 2024-12-26T14:16:17.878Z Has data issue: false hasContentIssue false
  • English
  • Français

Native Morphology of Hydrated Spheroidal Halloysite Observed by Environmental Transmission Electron Microscopy

Published online by Cambridge University Press:  01 January 2024

Jeremie Berthonneau ,
Olivier Grauby ,
Charlotte Jeannin ,
Damien Chaudanson ,
Emmanuel Joussein  and
Alain Baronnet
Jeremie Berthonneau*
Affiliation:
Aix Marseille Université, CNRS, CINaM UMR 7325, 13288, Marseille, France , the CNRS-MIT Joint Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA
Olivier Grauby
Affiliation:
Aix Marseille Université, CNRS, CINaM UMR 7325, 13288, Marseille, France
Charlotte Jeannin
Affiliation:
Aix Marseille Université, CNRS, CINaM UMR 7325, 13288, Marseille, France
Damien Chaudanson
Affiliation:
Aix Marseille Université, CNRS, CINaM UMR 7325, 13288, Marseille, France
Emmanuel Joussein
Affiliation:
Université de Limoges, FST, GRESE, 123 avenue Albert Thomas, 87060, Limoges, France
Alain Baronnet
Affiliation:
Aix Marseille Université, CNRS, CINaM UMR 7325, 13288, Marseille, France
*
*E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Natural mineral materials such as tabular and spheroidal halloysites have recently been suggested as candidates for intercalating metal ions or organic molecules. Their potential use as nanoadsorbents is related to their porous structure and water content. Although the two morphologies can coexist in natural deposits, spheroidal halloysites remain poorly characterized whereas much literature exists on tubular halloysites. The present study investigates the native morphology, internal porous structure, and behavior upon dehydration of spheroidal halloysite from Opotiki (New Zealand). This mineral was characterized in its natural hydrated state using a transmission electron microscope equipped with an environmental cell (EC-TEM). The sample was placed in a sealed block in which water vapor-saturated air circulated at a pressure of 30 Torr. The observed particles consisted of almost complete spheroids displaying polyhedral external surfaces. 1:1 layers stack concentrically as a pore-free, onion-like structure. The dynamic processes of dehydration created by slow depressurization of the cell resulted in a decrease in the layer-to-layer distance (d001) from ~10 Å to ~7 Å due to the loss of interlayer water molecules. Irreversible formation of spurious ‘internal pores’ was recorded during this process. These pores were not indigenous to the hydrated 10 Å halloysite and resulted from the collapse of the native layers. They cannot account for the physical chemical properties of spheroidal halloysite. Spheroidal halloysites would have a lower propensity for intercalating ions or molecules than tubular halloysites. Isolated facets were also observed in high-resolution-TEM and displayed a pseudo-hexagonal morphology. The three-dimensional microstructure of the spheroid appeared bent along the three pseudo equivalent yi directions of the kaolinite-like single layers. An analogy with polyhedral serpentine has allowed the proposal of a formation process of hydrated spheroidal halloysite triggered by enrichment in divalent ions in the growth system.

Keywords

Crystal GrowthDehydration BehaviorNano-adsorbentNative HalloysiteTransmission Electron Microscopy
Type
Article
Information
Clays and Clay Minerals , Volume 63 , Issue 5 , October 2015 , pp. 368 - 377
Copyright
Copyright © The Clay Minerals Society 2015

References

Alexander, L.T. Faust, G.T. Hendricks, S.B. Insley, H. and McMurdie, H.F., 1943 Relationship of the clay minerals halloysite and endellite American Mineralogist 28 1–18.Google Scholar
Andreani, M. Grauby, O. Baronnet, A. and Munoz, M., 2008 Occurrence, composition and growth of polyhedral serpentine European Journal of Mineralogy 20 159–171.CrossRefGoogle Scholar
Askenasy, P.E. Dixon, J.B. and McKee, T.R., 1973 Spheroidal halloysite in a Guatemalan soil Soil Science Society of America Journal 37 799–803.CrossRefGoogle Scholar
Bailey, S.W. (1990) Halloysite — A critical assessment. Pp. 89–98 in: Surface Chemistry Structure and Mixed Layering of Clays, Proceedings of the 9th International Clay Conference, Strasbourg, 1989, Volume II (Farmer, V.C. and Tardy, Y., editors). Sciences Géologiques Memoire 86.Google Scholar
Baronnet, A. Andreani, M. Grauby, O. Devouard, B. Nitsche, S. and Chaudanson, D., 2007 Onion morphology and microstructure of polyhedral serpentine American Mineralogist 92 687–690.CrossRefGoogle Scholar
Bates, T.F. Hildebrand, F.A. and Swineford, A., 1950 Morphology and structure of endellite and halloysite American Mineralogist 6 237–248.Google Scholar
Chisholm, J.E., 1992 The number of sectors in polygonal serpentine The Canadian Mineralogist 30 355–365.Google Scholar
Churchman, G.J. and Carr, R.M., 1975 The definition and nomenclature of halloysites Clays and Clay Minerals 23 382–388.CrossRefGoogle Scholar
Churchman, G.J. and Theng, B.K.G., 1984 Interactions of halloysites with amides: mineralogical factors affecting complex formation Clay Minerals 19 161–175.CrossRefGoogle Scholar
Churchman, G.J. Davy, T.J. Aylmore, L.A.G. Gilkes, R.J. and Self, P.G., 1995 Characteristics of fine pores in some halloysites Clay Minerals 30 89–98.CrossRefGoogle Scholar
Churchman, G.J., Sumner, M.E., 2000 The alteration and formation of soil minerals by weathering Handbook of Soil Science Boca Raton, Florida, USA CRC Press.Google Scholar
Costanzo, P.M. and Giese, R.F., 1985 Dehydration of synthetic hydrated kaolinites: a model for the dehydration of halloysite (10 Å) Clays and Clay Minerals 33 415–423.CrossRefGoogle Scholar
Delvaux, B. Herbillon, A.J. and Vielvoye, L., 1990 Surface properties and clay mineralogy of hydrated halloysitic soil clays. I. Existence of interlayer K+ specific sites Clay Minerals 25 129–139.CrossRefGoogle Scholar
Giese, R.F., Bailey, S.W., 1991 Kaolin minerals: structures and stabilities Hydrous Phyllosilicates (Exclusive of Micas) Washington, D.C. Mineralogical Society of America.Google Scholar
Grauby, O. and Baronnet, A. (2009) Synthesis of polyhedral serpentine. XIV International Clay Conference, Italy, Abstract vol. 2, p. 466.Google Scholar
Guggenheim, S., Brady, J. Mogk, D. and Perkins, D., 1977 Introduction to the properties of clay minerals Teaching Mineralogy Washington, D.C. Mineralogical Society of America.Google Scholar
Joussein, E. Petit, S. Churchman, J. Theng, B. Righi, D. and Delvaux, B., 2005 Halloysite clay minerals — a review Clay Minerals 40 383–426.CrossRefGoogle Scholar
Joussein, E. Petit, S. Fialips, C.-I. Vieillard, P. and Righi, D., 2006 Differences in the dehydration-rehydration behavior of halloysites: new evidence and interpretations Clays and Clay Minerals 54 473–484.CrossRefGoogle Scholar
Joussein, E. Petit, S. and Delvaux, B., 2007 Behavior of halloysite clay under formamide treatment Applied Clay Science 35 17–24.CrossRefGoogle Scholar
Kiani, G., 2014 High removal capacity of silver ions from aqueous solution onto halloysite nanotubes Applied Clay Science 90 159–164.CrossRefGoogle Scholar
Kirkman, J.H., 1977 Possible structure of halloysite disks and cylinders observed in some New Zealand tephras Clay Minerals 12 199–215.CrossRefGoogle 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 and Clay Minerals 26 25–40.CrossRefGoogle Scholar
Kohyama, N. Fukushima, K. Fukami, A., van Olphen, F.V.H., 1982 Interlayer hydrates and complexes of clay minerals observed by electron microscopy using an environmental cell Proceedings of the 7th International Clay Conference (1981) Bologna, Italy Amsterdam Elsevier.Google Scholar
MacEwan, D.M.C., 1948 Complexes of clay with organic compounds. I. Complex formation between montmorillonite and halloysite and certain organic liquids Journal of the Chemical Society Faraday Transactions 44 349–367.CrossRefGoogle Scholar
Parham, W.E. (1970) Halloysite-rich tropical weathering products of Hong-Kong. Pp. 403–416 in: Proceeding of the International Clay Conference, Tokyo, Japan, 1969.Google Scholar
Petit, S. Decarreau, A. Mosser, C. Ehret, G. and Grauby, O., 1995 Hydrothermal synthesis (250°C) of copper-substituted kaolinites Clays and Clay Minerals 43 482–494.CrossRefGoogle Scholar
Radoslovich, E.W., 1963 The cell dimensions and symmetry of layer-lattice silicate. VI. Serpentine and kaolin morphology American Mineralogist 48 368–378.Google Scholar
Sand, L.B., 1956 On the genesis of residual kaolin American Mineralogist 41 28–40.Google Scholar
Tarasevich, Y.I. and Gribina, I.A., 1972 Infrared spectroscopy study of the state of water in halloysite Kolloidnyi Zhurnal 34 405–411.Google Scholar
Tan, D. Yuan, P. Annabi-Bergaya, F. Liu, D. Wang, L. Liu, H. and He, H., 2014 Loading and in vitro release of ibuprofen in tubular halloysite Applied Clay Science 96 50–55.CrossRefGoogle Scholar
Theng, B.K.G., 1974 The Chemistry of Clay-Organic Reactions London Adam Hilger.Google Scholar
Tomura, S. Shibasaki, Y. Mizuta, H. and Kitamura, M., 1985 Growth conditions and genesis of spherical and platy kaolinite Clays and Clay Minerals 33 200–206.CrossRefGoogle Scholar
Zega, T.J. Garvie, L.A.J. Dodony, I. Friedrich, H. Stroud, R.M. and Buseck, P.R., 2006 Polyhedral serpentine grains in CM chondrites Meteoritics and Planetary Science 41 681–690.CrossRefGoogle Scholar