Chemistry:Halloysite

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Short description: Aluminosilicate clay mineral
Halloysite
Halloysite variety Indianaite Hydrous Aluminum silicate Bedford, Lawrence County, Indiana 2770.jpg
General
CategoryPhyllosilicates
Kaolinite-serpentine group
Formula
(repeating unit)		Al2Si2O5(OH)4
Strunz classification9.ED.10
Crystal systemMonoclinic
Crystal classDomatic (m)
(same H-M symbol)
Space groupCc
Unit cella = 5.14, b = 8.9,
c = 7.214 [Å]; β = 99.7°; Z = 1
Identification
ColorWhite; grey, green, blue, yellow, red from included impurities.
Crystal habitSpherical clusters, massive
CleavageProbable on {001}
FractureConchoidal
Mohs scale hardness2–2.5
|re|er}}Pearly, waxy, or dull
DiaphaneitySemitransparent
Specific gravity2–2.65
Optical propertiesBiaxial
Refractive indexnα = 1.553–1.565
nβ = 1.559–1.569
nγ = 1.560–1.570
Birefringenceδ = 0.007
References[1][2][3]

Halloysite is an aluminosilicate clay mineral with the empirical formula Al2Si2O5(OH)4. Its main constituents are oxygen (55.78%), silicon (21.76%), aluminium (20.90%), and hydrogen (1.56%). It is a member of the kaolinite group. Halloysite typically forms by hydrothermal alteration of alumino-silicate minerals.[4] It can occur intermixed with dickite, kaolinite, montmorillonite and other clay minerals. X-ray diffraction studies are required for positive identification. It was first described in 1826, and subsequently named after, the Belgian geologist Omalius d'Halloy.

Structure

Halloysite naturally occurs as small cylinders (nanotubes) that have a wall thickness of 10–15 atomic aluminosilicate sheets, an outer diameter of 50–60 nm, an inner diameter of 12–15 nm, and a length of 0.5–10 μm.[5] Their outer surface is mostly composed of SiO2 and the inner surface of Al2O3, and hence those surfaces are oppositely charged.[6][7] Two common forms are found. When hydrated, the clay exhibits a 1 nm spacing of the layers, and when dehydrated (meta-halloysite), the spacing is 0.7 nm. The cation exchange capacity depends on the amount of hydration, as 2H2O has 5–10 meq/100 g, while 4H2O has 40–50 meq/100g.[8] Endellite is the alternative name for the Al2Si2O5(OH)4·2(H2O) structure.[8][9]

Owing to the layered structure of the halloysite, it has a large specific surface area, which can reach 117 m2/g.[10]

Formation

Electron micrograph of halloysite nanotubes[6]
Halloysite nanotubes intercalated with ruthenium catalytic nanoparticles[6]

The formation of halloysite is due to hydrothermal alteration, and it is often found near carbonate rocks. For example, halloysite samples found in Wagon Wheel Gap, Colorado, United States are suspected to be the weathering product of rhyolite by downward moving waters.[4] In general the formation of clay minerals is highly favoured in tropical and sub-tropical climates due to the immense amounts of water flow. Halloysite has also been found overlaying basaltic rock, showing no gradual changes from rock to mineral formation.[11] Halloysite occurs primarily in recently exposed volcanic-derived soils, but it also forms from primary minerals in tropical soils or pre-glacially weathered materials.[12] Igneous rocks, especially glassy basaltic rocks are more susceptible to weathering and alteration forming halloysite.

Often as is the case with halloysite found in Juab County, Utah, United States the clay is found in close association with goethite and limonite and often interspersed with alunite. Feldspars are also subject to decomposition by water saturated with carbon dioxide. When feldspar occurs near the surface of lava flows, the CO2 concentration is high, and reaction rates are rapid. With increasing depth, the leaching solutions become saturated with silica, aluminium, sodium, and calcium. Once the solutions are depleted of CO2 they precipitate as secondary minerals. The decomposition is dependent on the flow of water. In the case that halloysite is formed from plagioclase it will not pass through intermediate stages.[4]

Locations

A highly refined halloysite is mined, then processed, from a rhyolite occurrence in Matauri Bay, New Zealand.[13][14][15][16] Annual output of this mine is up to 20,000 tonnes per annum.[17]

One of the largest halloysite deposits in the world is Dunino, near Legnica in Poland.[18] It has reserves estimated at 10 million tons of material. This halloysite is characterized by layered-tubular and platy structure.[19]

The Dragon mine, located in the Tintic district, Eureka, Utah, US deposit contains catalytic quality halloysite. The Dragon Mine Deposit is one of the largest in the United States. The total production throughout 1931–1962 resulted in nearly 750,000 metric tons of extracted halloysite. Pure halloysite classified at 10a and 7a are present.[20]

Applications

Commercial

Uses of the halloysite produced at the Matauri Bay deposit in New Zealand include porcelain and bone china by manufacturers in various countries, particularly in Asia.[13][14][15][16]

Laboratory studies

  • Halloysite is an efficient adsorbent both for cations and anions. It has also been used as a petroleum cracking catalyst, and Exxon has developed a cracking catalyst based on synthetic halloysite in the 1970s.[21] Owing to its structure, halloysite can be used as filler in either natural or modified forms in nanocomposites. Halloysite nanotube can be intercalated with catalytic metal nanoparticles made of silver, ruthenium, rhodium, platinum or cobalt, thereby serving as a catalyst support.[6]
  • Due to its nanostructure, halloysite is used as the main nanostructured filler in multifunctional mixed matrix membranes (MMMs), opening up new possibilities in the separation of gaseous and liquid mixtures [24] and water purification.[25]
  • Besides supporting nanoparticles, halloysite nanotubes can also be used as a template to produce round well-dispersed nanoparticles (NPs). For example, bismuth and bismuth subcarbonate NPs with controlled size (~7 nm) were synthesized in water. Importantly, when halloysite was not used, large nanoplates instead of round spheres are obtained.[26]
  • Halloysite is also used to purify water, e.g. from two azo dyes were removed from aq. solutions. by adsorption on a Polish halloysite from Dunino deposit.[27]
  • Halloysite have many advantages and reported as a nanocontainer.[28][29]
  • Halloysite can also be used to produce porous silicon nanotubes as anode materials for Li-ion batteries through the selective etching of aluminium oxide and thermal reduction.[30]
  • As a nanofiller in nanocomposite e.g. thermoplastic polyurethane acting on the mechanical, physicochemical and biological properties.[31]

Chemistry and mineralogy

Typical chemical and mineralogical analyses of two commercial grades of halloysite are:[32]

Product name Premium Yunnan
Country New Zealand China
Area Northland Yunnan
SiO2, % 49.5 42.7
Al2O3, % 35.5 37.0
Fe2O3, % 0.29 0.10
TiO2, % 0.09 <0.05
CaO, % - -
MgO, % - -
K2O, % - <0.05
Na2O, % - <0.05
LOI, % 13.8 19.8
Halloysite, % 92 99.1
Cristobalite, % 4 -
Quartz, % 1 0.1

References

  1. ↑ "Halloysite". Handbook of Mineralogy. II, 2003 Silica, Silicates. Chantilly, VA, US: Mineralogical Society of America. 1995. ISBN 978-0962209710. http://rruff.info/doclib/hom/halloysite.pdf. 
  2. ↑ "Halloysite: Halloysite mineral information and data.". mindat.org. http://www.mindat.org/show.php?id=1808&ld=1&pho=. 
  3. ↑ Barthelmy, Dave. "Halloysite Mineral Data". webmineral.com. http://webmineral.com/data/Halloysite.shtml. 
  4. ↑ 4.0 4.1 4.2 Kerr, Paul F. (1952). "Formation and occurrence of clay minerals". Clays and Clay Minerals 1 (1): 19–32. doi:10.1346/CCMN.1952.0010104. Bibcode: 1952CCM.....1...19K. 
  5. ↑ Saharudin, Mohd Shahneel; Hasbi, Syafawati; Nazri, Muhammad Naguib Ahmad; Inam, Fawad (2020). "A Review of Recent Developments in Mechanical Properties of Polymer–Clay Nanocomposites". in Emamian, Seyed Sattar; Awang, Mokhtar; Yusof, Farazila (in en). Advances in Manufacturing Engineering. Lecture Notes in Mechanical Engineering. Singapore: Springer. pp. 107–129. doi:10.1007/978-981-15-5753-8_11. ISBN 978-981-15-5753-8. https://link.springer.com/chapter/10.1007/978-981-15-5753-8_11. 
  6. ↑ 6.0 6.1 6.2 6.3 Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.; Ivanov, Evgenii V.; Shrestha, Lok Kumar; Ariga, Katsuhiko; Darrat, Yusuf A.; Lvov, Yuri M. (2017). "Formation of metal clusters in halloysite clay nanotubes". Science and Technology of Advanced Materials 18 (1): 147–151. doi:10.1080/14686996.2016.1278352. PMID 28458738. Bibcode: 2017STAdM..18..147V. 
  7. ↑ Brindley, George W. (1952). "Structural mineralogy of clays". Clays and Clay Minerals 1 (1): 33–43. doi:10.1346/CCMN.1952.0010105. Bibcode: 1952CCM.....1...33B. 
  8. ↑ 8.0 8.1 Carroll, Dorothy (1959). "Ion exchange in clays and other minerals". Geological Society of America Bulletin 70 (6): 749‐780. doi:10.1130/0016-7606(1959)70[749:IEICAO2.0.CO;2]. Bibcode: 1959GSAB...70..749C. 
  9. ↑ Endellite. Webminerals
  10. ↑ Yang, Y. Zhang; J. Ouyang (2016). "Physicochemical Properties of Halloysite". Nanosized Tubular Clay Minerals - Halloysite and Imogolite. Developments in Clay Science. 7. pp. 67–91. doi:10.1016/B978-0-08-100293-3.00004-2. ISBN 9780081002933. 
  11. ↑ Papke, Keith G. (1971). "Halloysite Deposits in the terraced Hills Washoe County, Nevada". Clays and Clay Minerals 19 (2): 71–74. doi:10.1346/CCMN.1971.0190202. Bibcode: 1971CCM....19...71P. 
  12. ↑ Wilson M. J. (1999). "The Origin and Formation of Clay Minerals in Soils: Past Present and Future Perspectives". Clay Minerals 34 (1): 7–25. doi:10.1180/000985599545957. Bibcode: 1999ClMin..34....7W. 
  13. ↑ 13.0 13.1 CASE STUDY: Halloysite Clay. minerals.co.nz
  14. ↑ 14.0 14.1 Murray, H. H.; Harvey, C.; Smith, J. M. (1 February 1977). "Mineralogy and geology of the Maungaparerua halloysite deposit in New Zealand". Clays and Clay Minerals 25 (1): 1–5. doi:10.1346/CCMN.1977.0250101. Bibcode: 1977CCM....25....1M. http://ccm.geoscienceworld.org/content/25/1/1. 
  15. ↑ 15.0 15.1 "Common molecules sample 50642". Reciprocal Net. http://www.reciprocalnet.org/recipnet/showsampledetailed.jsp?sampleHistoryId=21742&sampleId=27344589. 
  16. ↑ 16.0 16.1 Lyday, Travis Q. (2002) The Mineral Industry of New Zealand. minerals.usgs.gov
  17. ↑ 'Global Occurrence, Geology And Characteristics Of Tubular Halloysite Deposits.' I. Wilson and J. Keeling. Clay Minerals, Vol 51, 2016. pg 309-324.
  18. ↑ Lutyński, Marcin; Sakiewicz, Piotr; Lutyńska, Sylwia (2019-10-31). "Characterization of Diatomaceous Earth and Halloysite Resources of Poland" (in en). Minerals 9 (11): 670. doi:10.3390/min9110670. ISSN 2075-163X. Bibcode: 2019Mine....9..670L. 
  19. ↑ Sakiewicz, P.; Lutynski, M.; Soltys, J.; Pytlinski, A. (2016). "Purification of Halloysite by Magnetic Separation". Physicochemical Problems of Mineral Processing 52 (2): 991–1001. doi:10.5277/ppmp160236. 
  20. ↑ Patterson, S., & Murray, H. (1984). Kaolin, refractory clay, ball clay, and halloysite in North America, Hawaii, and the Caribbean region. Professional Paper, 44-45. doi:10.3133/pp1306
  21. ↑ Robson, Harry E., Exxon Research & Engineering Co. (1976) "Synthetic halloysites as hydrocarbon conversion catalysts" U.S. Patent 4,098,676
  22. ↑ Lutyński, M.; Sakiewicz, P.; Gonzalez, M. a. G. (2014). "Halloysite as Mineral Adsorbent of CO2 – Kinetics and Adsorption Capacity" (in EN). Inżynieria Mineralna R. 15, nr 1. ISSN 1640-4920. http://yadda.icm.edu.pl/baztech/element/bwmeta1.element.baztech-1059065e-3ccb-4293-b319-41fa548227b0. 
  23. ↑ Pajdak, Anna; Skoczylas, Norbert; Szymanek, Arkadiusz; Lutyński, Marcin; Sakiewicz, Piotr (2020-02-19). "Sorption of CO2 and CH4 on Raw and Calcined Halloysite—Structural and Pore Characterization Study" (in en). Materials 13 (4): 917. doi:10.3390/ma13040917. ISSN 1996-1944. PMID 32092961. Bibcode: 2020Mate...13..917P. 
  24. ↑ Piotrowski, Krzysztof; Sakiewicz, Piotr; Gołombek, Klaudiusz (2021). "Halloysite as main nanostructural filler in multifunctional mixed matrix membranes – review of applications and new possibilities". Desalination and Water Treatment 243: 91–106. doi:10.5004/dwt.2021.27873. https://doi.org/10.5004/dwt.2021.27873. 
  25. ↑ Sakiewicz Piotr; Piotrowski Krzysztof; Boryn Dominika; Kruk Milena; Mscichecka Joanna; Korus Irena Barbusinski, Krzysztof (August 2020). "Zastosowanie sorbentu haloizytowego do usuwania syntetycznych barwników azowych Acid Red 27 i Reactive Black 5 z roztworów wodnych". Przemysl Chemiczny 99 (8): 1142–1148. https://sigma-not.pl/publikacja-127557-zastosowanie-sorbentu-haloizytowego-do-usuwania-syntetycznych-barwnik%C3%B3w-azowych-acid-red-27-i-reactive-black-5-z-roztwor%C3%B3w-wodnych-przemysl-chemiczny-2020-8.html. 
  26. ↑ Ortiz-Quiñonez, J.L.; Vega-Verduga, C; Díaz, D; Zumeta-Dubé, I (June 13, 2018). "Transformation of Bismuth and β‑Bi2O3 Nanoparticles into (BiO)2CO3 and (BiO)4(OH)2CO3 by Capturing CO2: The Role of Halloysite Nanotubes and "Sunlight" on the Crystal Shape and Size". Crystal Growth & Design 18 (8): 4334−4346. doi:10.1021/acs.cgd.8b00177. 
  27. ↑ Sakiewicz, Piotr (2020-08-17). "Zastosowanie sorbentu haloizytowego do usuwania syntetycznych barwników azowych Acid Red 27 i Reactive Black 5 z roztworów wodnych" (in en). Przemysł Chemiczny 1 (8): 48–54. doi:10.15199/62.2020.8.5. ISSN 0033-2496. https://sigma-not.pl/publikacja-127557-2020-8.html. 
  28. ↑ Azmi Zahidah, Khairina (2017-09-19). "Benzimidazole-loaded Halloysite Nanotube as a Smart Coating Application" (in en). International Journal of Engineering and Technology Innovation 7 (4): 243–254. ISSN 2226-809X. https://www.researchgate.net/publication/320142351. 
  29. ↑ Azmi Zahidah, Khairina (2017-05-19). "Halloysite Nanotubes as Nanocontainer for Smart Coating Application: A Review" (in en). Progress in Organic Coatings 111 (C): 175–185. doi:10.1016/j.porgcoat.2017.05.018. ISSN 0300-9440. https://www.sciencedirect.com/science/article/pii/S0300944017301030. 
  30. ↑ Yeom, S. J.; Lee, C. M.; Kang, S.; Wi, T.-W.; Lee, C.; Chae, S.; Cho, J.; Shin, D. O. et al. (2019-11-01). "Native void space for maximum volumetric capacity in silicon-based anodes". Nano Letters 19 (12): 8793–8800. doi:10.1021/acs.nanolett.9b03583. PMID 31675476. Bibcode: 2019NanoL..19.8793Y. 
  31. ↑ Mrowka, Maciej; Szymiczek, Malgorzata; Machoczek, Tomasz; Lenza, Joanna; Matusik, Jakub; Sakiewicz, Piotr; Skonieczna, Magdalena (November 2020). "The influence of halloysite on the physicochemical, mechanical and biological properties of polyurethane-based nanocomposites". Polimery 65 (11/12): 784–791. doi:10.14314/polimery.2020.11.5. https://ichp.vot.pl/index.php/p/article/view/92/. 
  32. ↑ 'Positive Outlook For Kaolin In Ceramics' F. Hart, I. Wilson. Industrial Minerals, April 2019. Pg.28

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