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Corundum

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Not to be confused with Carborundum or Conundrum.

Corundum
General
CategoryOxide mineral – Hematite group
Formula
(repeating unit)		Al2O3
IMA symbolCrn[1]
Strunz classification4.CB.05
Dana classification4.3.1.1
Crystal systemTrigonal
Crystal classHexagonal scalenohedral (3m)
H-M symbol: (3 2/m)
Space groupR3c (No. 167)
Unit cella = 4.75 Å, c = 12.982 Å; Z = 6
Identification
ColorColorless, gray, golden-brown, brown; purple, pink to red, orange, yellow, green, blue, violet; may be color zoned, asteriated mainly grey and brown
Crystal habitSteep bipyramidal, tabular, prismatic, rhombohedral crystals, massive or granular
TwinningPolysynthetic twinning common
CleavageNone – parting in 3 directions
FractureConchoidal to uneven
TenacityBrittle
Mohs scale hardness9 (defining mineral)[2]
LusterAdamantine to vitreous
StreakColorless
DiaphaneityTransparent, translucent to opaque
Specific gravity3.95–4.10
Optical propertiesUniaxial (−)
Refractive indexnω = 1.767–1.772
nε = 1.759–1.763
PleochroismNone
Melting point2,044 °C (3,711 °F)
FusibilityInfusible
SolubilityInsoluble
Alters toMay alter to mica on surfaces causing a decrease in hardness
Other characteristicsMay fluoresce or phosphoresce under UV light
References[3][4][5][6]
Major varieties
SapphireAny color except red
RubyRed
EmeryBlack granular corundum intimately mixed with magnetite, hematite, or hercynite

Corundum is a crystalline form of aluminium oxide (Al2O3) typically containing traces of iron, titanium, vanadium, and chromium.[3][4] It is a rock-forming mineral. It is a naturally transparent material, but can have different colors depending on the presence of transition metal impurities in its crystalline structure.[7] Corundum has two primary gem varieties: ruby and sapphire. Rubies are red due to the presence of chromium, and sapphires exhibit a range of colors depending on what transition metal is present.[7] A rare type of sapphire, padparadscha sapphire, is pink-orange.

The name "corundum" is derived from the Tamil-Dravidian word kurundam (ruby-sapphire) (appearing in Sanskrit as kuruvinda).[8][9]

Because of corundum's hardness (pure corundum is defined to have 9.0 on the Mohs scale), it can scratch almost all other minerals. It is commonly used as an abrasive on sandpaper and on large tools used in machining metals, plastics, and wood. Emery, a variety of corundum with no value as a gemstone, is commonly used as an abrasive. It is a black granular form of corundum, in which the mineral is intimately mixed with magnetite, hematite, or hercynite.[6]

In addition to its hardness, corundum has a density of 4.02 g/cm3 (251 lb/cu ft), which is unusually high for a transparent mineral composed of the low-atomic mass elements aluminium and oxygen.[10]

Geology and occurrence

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Corundum from Brazil, size about 2 cm × 3 cm (0.8 in × 1 in)

Corundum occurs as a mineral in mica schist, gneiss, and some marbles in metamorphic terranes. It also occurs in low-silica igneous syenite and nepheline syenite intrusives. Other occurrences are as masses adjacent to ultramafic intrusives, associated with lamprophyre dikes and as large crystals in pegmatites.[6] It commonly occurs as a detrital mineral in stream and beach sands because of its hardness and resistance to weathering.[6] The largest documented single crystal of corundum measured about 65 cm × 40 cm × 40 cm (26 in × 16 in × 16 in), and weighed 152 kg (335 lb).[11] The record has since been surpassed by certain synthetic boules.[12]

Corundum for abrasives is mined in Zimbabwe, Pakistan, Afghanistan, Russia, Sri Lanka, and India. Historically it was mined from deposits associated with dunites in North Carolina, US, and from a nepheline syenite in Craigmont, Ontario.[6] Emery-grade corundum is found on the Greek island of Naxos and near Peekskill, New York, US. Abrasive corundum is synthetically manufactured from bauxite.[6]

Four corundum axes dating to 2500 BC from the Liangzhu culture and Sanxingcun culture (the latter of which is located in Jintan District) have been discovered in China.[13][14]

Synthetic corundum

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The Verneuil process allows the production of flawless single-crystal sapphire and ruby gems of much larger size than normally found in nature. It is also possible to grow gem-quality synthetic corundum by flux-growth and hydrothermal synthesis. Because of the simplicity of the methods involved in corundum synthesis, large quantities of these crystals have become available on the market at a fraction of the cost of natural stones.[17]

Synthetic corundum has a lower environmental impact than natural corundum by avoiding destructive mining and conserving resources.[18][19] However, its production is energy-intensive, contributing to carbon emissions if fossil fuels are used, and involves chemicals that can pose risks.[20]

Apart from ornamental uses, synthetic corundum is also used to produce mechanical parts (tubes, rods, bearings, and other machined parts), scratch-resistant optics, scratch-resistant watch crystals, instrument windows for satellites and spacecraft (because of its transparency in the ultraviolet to infrared range), and laser components. For example, the KAGRA gravitational wave detector's main mirrors are 23 kg (50 lb) sapphires,[21] and Advanced LIGO considered 40 kg (88 lb) sapphire mirrors.[22] Corundum has also found use in the development of ceramic armour thanks to its high hardiness.[23]

Structure and physical properties

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Crystal structure of corundum
Molar volume vs. pressure at room temperature

Corundum crystallizes with trigonal symmetry in the space group R3c and has the lattice parameters a = 4.75 Å and c = 12.982 Å at standard conditions. The unit cell contains six formula units.[4][24]

The toughness of corundum is sensitive to surface roughness[25][26] and crystallographic orientation.[27] It may be 6–7 MPa·m1/2 for synthetic crystals,[27] and around 4 MPa·m1/2 for natural.[28]

In the lattice of corundum, the oxygen atoms form a slightly distorted hexagonal close packing, in which two-thirds of the octahedral sites between the oxygen ions are occupied by aluminium ions.[29] The absence of aluminium ions from one of the three sites breaks the symmetry of the hexagonal close packing, reducing the space group symmetry to R3c and the crystal class to trigonal.[30] The structure of corundum is sometimes described as a pseudohexagonal structure.[31]

The Young's modulus of corundum (sapphire) has been reported by many different sources with values varying between 300 and 500 GPa, but a commonly cited value used for calculations is 345 GPa.[32] The Young's modulus is temperature dependent, and has been reported in the [0001] direction as 435 GPa at 323 K and 386 GPa at 1,273 K.[32] The shear modulus of corundum is 145 GPa,[33] and the bulk modulus is 240 GPa.[33]

Single crystal corundum fibers have potential applications in high temperature composites, and the Young's modulus is highly dependent on the crystallographic orientation along the fiber axis. The fiber exhibits a max modulus of 461 GPa when the crystallographic c-axis [0001] is aligned with the fiber axis, and minimum moduli ~373 GPa when a direction 45° away from the c-axis is aligned with the fiber axis.[34]

The hardness of corundum measured by indentation at low loads of 1-2 N has been reported as 22-23 GPa[35] in major crystallographic planes: (0001) (basal plane), (1010) (rhombohedral plane), (1120) (prismatic plane), and (1012). The hardness can drop significantly under high indentation loads. The drop with respect to load varies with the crystallographic plane due to the difference in crack resistance and propagation between directions. One extreme case is seen in the (0001) plane, where the hardness under high load (~1 kN) is nearly half the value under low load (1-2 N).[35]

Polycrystalline corundum formed through sintering and treated with a hot isostatic press process can achieve grain sizes in the range of 0.55-0.7 μm, and has been measured to have four-point bending strength between 600 and 700 MPa and three-point bending strength between 750 and 900 MPa.[36]

Structure type

[edit]
Main article: Corundum (structure)

Because of its prevalence, corundum has also become the name of a major structure type (corundum type) found in various binary and ternary compounds.[37]

See also

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Wikimedia Commons has media related to Corundum.

References

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  1. ^ Warr, L.N. (2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine. 85 (3): 291–320. Bibcode:2021MinM...85..291W. doi:10.1180/mgm.2021.43. S2CID 235729616.
  2. ^ "Mohs' scale of hardness". Collector's corner. Mineralogical Society of America. Retrieved 10 January 2014.
  3. ^ a b Anthony, John W.; Bideaux, Richard A.; Bladh, Kenneth W.; Nichols, Monte C., eds. (1997). "Corundum". Handbook of Mineralogy (PDF). Vol. III Halides, Hydroxides, Oxides. Chantilly, VA, US: Mineralogical Society of America. ISBN 0962209724. Archived (PDF) from the original on 5 September 2006.
  4. ^ a b c "Corundum". Mindat.org.
  5. ^ "Corundum". Webmineral.com. Archived from the original on 25 November 2006.
  6. ^ a b c d e f Hurlbut, Cornelius S.; Klein, Cornelis (1985). Manual of Mineralogy (20th ed.). Wiley. pp. 300–302. ISBN 0-471-80580-7.
  7. ^ a b Giuliani, Gaston; Ohnenstetter, Daniel; Fallick, Anthony E.; Groat, Lee; Fagan; Andrew J. (2014). "The Geology and Genesis of Gem Corundum Deposits". Gem Corundum. Research Gate: Mineralogical Association of Canada. pp. 37–38. ISBN 978-0-921294-54-2.
  8. ^ Harper, Douglas. "corundum". Online Etymology Dictionary.
  9. ^ Jeršek, Miha; Jovanovski, Gligor; Boev, Blažo; Makreski, Petre (2021). "Intriguing minerals: corundum in the world of rubies and sapphires with special attention to Macedonian rubies". ChemTexts. 7 (3): 19. doi:10.1007/s40828-021-00143-0. ISSN 2199-3793. S2CID 233435945.
  10. ^ "The Mineral Corundum". galleries.com.
  11. ^ Rickwood, P. C. (1981). "The largest crystals" (PDF). American Mineralogist. 66: 885–907. Archived (PDF) from the original on 20 June 2009.
  12. ^ "Rubicon Technology grows 200 kg "super boule"". LED Inside. 21 April 2009.
  13. ^ "Chinese made first use of diamond". BBC News. BBC. May 2005.
  14. ^ Alexandra, Goho (16 February 2005). "In the Buff: Stone Age tools may have derived luster from diamond". Science News.
  15. ^ Duroc-Danner, J. M. (2011). "Untreated yellowish orange sapphire exhibiting its natural colour" (PDF). Journal of Gemmology. 32 (5): 175–178. doi:10.15506/jog.2011.32.5.174. Archived from the original (PDF) on 16 May 2013.
  16. ^ Bahadur (1943). "A Handbook of Precious Stones". Retrieved 19 August 2007.
  17. ^ Walsh, Andrew (February 2010). "The commodification of fetishes: Telling the difference between natural and synthetic sapphires". American Ethnologist. 37 (1): 98–114. doi:10.1111/j.1548-1425.2010.01244.x.
  18. ^ "Comparing Alumina and Corundum: From Raw Form to Crystal Clarity". Advanced Ceramic Materials. 1 March 2024. Retrieved 7 October 2024.
  19. ^ Walsh, Andrew (2010). "The commodification of fetishes: Telling the difference between natural and synthetic sapphires". American Ethnologist. 37 (1): 98–114. doi:10.1111/j.1548-1425.2010.01244.x.
  20. ^ Sudiro, Maria; Bertucco, Alberto (2007). "Synthetic Fuels by a Limited CO2 Emission Process Which Uses Both Fossil and Solar Energy". Energy Fuels. 21 (6): 3668–3675. doi:10.1021/ef7003255.
  21. ^ Hirose, Eiichi; et al. (2014). "Sapphire mirror for the KAGRA gravitational wave detector" (PDF). Physical Review D. 89 (6): 062003. Bibcode:2014PhRvD..89f2003H. doi:10.1103/PhysRevD.89.062003. Archived (PDF) from the original on 24 July 2018.
  22. ^ Billingsley, GariLynn (2004). "Advanced Ligo Core Optics Components – Downselect". LIGO Laboratory. Retrieved 6 February 2020.
  23. ^ Defense World.Net, Russia’s Armored Steel-Comparable Ceramic Plate Clears Tests, 5 September 2020, Retrieved 29 December 2020
  24. ^ Newnham, R. E.; de Haan, Y. M. (August 1962). "Refinement of the α Al2O3, Ti2O3, V2O3 and Cr2O3 structures*". Zeitschrift für Kristallographie. 117 (2–3): 235–237. Bibcode:1962ZK....117..235N. doi:10.1524/zkri.1962.117.2-3.235.
  25. ^ Farzin-Nia, Farrokh; Sterrett, Terry; Sirney, Ron (1990). "Effect of machining on fracture toughness of corundum". Journal of Materials Science. 25 (5): 2527–2531. Bibcode:1990JMatS..25.2527F. doi:10.1007/bf00638054. S2CID 137548763.
  26. ^ Becker, Paul F. (1976). "Fracture-Strength Anisotropy of Sapphire". Journal of the American Ceramic Society. 59 (1–2): 59–61. doi:10.1111/j.1151-2916.1976.tb09390.x.
  27. ^ a b Wiederhorn, S. M. (1969). "Fracture of Sapphire". Journal of the American Ceramic Society. 52 (9): 485–491. doi:10.1111/j.1151-2916.1969.tb09199.x.
  28. ^ "Corundum, Aluminum Oxide, Alumina, 99.9%, Al2O3". www.matweb.com.
  29. ^ Nesse, William D. (2000). Introduction to mineralogy. New York: Oxford University Press. pp. 363–364. ISBN 9780195106916.
  30. ^ Borchardt-Ott, Walter; Kaiser, E. T. (1995). Crystallography (2nd ed.). Berlin: Springer. p. 230. ISBN 3540594787.
  31. ^ Gea, Laurence A.; Boatner, L. A.; Rankin, Janet; Budai, J. D. (1995). "The Formation Al 2 O 3 /V 2 O 3 Multilayer Structures by High-Dose Ion Implantation". MRS Proceedings. 382: 107. doi:10.1557/PROC-382-107.
  32. ^ a b Dobrovinskaya, Elena R.; Lytvynov, Leonid A.; Pishchik, Valerian (2009), Pishchik, Valerian; Lytvynov, Leonid A.; Dobrovinskaya, Elena R. (eds.), "Properties of Sapphire", Sapphire: Material, Manufacturing, Applications, Boston, MA: Springer US, pp. 55–176, doi:10.1007/978-0-387-85695-7_2, ISBN 978-0-387-85695-7, retrieved 12 May 2024
  33. ^ a b Ramdas, Roshan L. Aggarwal, Anant K. (3 May 2019). Physical Properties of Diamond and Sapphire. Boca Raton: CRC Press. doi:10.1201/9780429283260. ISBN 978-0-429-28326-0.{{cite book}}: CS1 maint: multiple names: authors list (link)
  34. ^ Wadley, Haydn N. G.; Lu, Yichi; Goldman, Jeffrey A. (1 March 1995). "Ultrasonic determination of single crystal sapphire fiber modulus". Journal of Nondestructive Evaluation. 14 (1): 31–38. doi:10.1007/BF00735669. ISSN 1573-4862.
  35. ^ a b Sinani, A. B.; Dynkin, N. K.; Lytvinov, L. A.; Konevsky, P. V.; Andreev, E. P. (1 October 2009). "Sapphire hardness in different crystallographic directions". Bulletin of the Russian Academy of Sciences: Physics. 73 (10): 1380–1382. doi:10.3103/S1062873809100177. ISSN 1934-9432.
  36. ^ Krell, Andreas; Blank, Paul; Ma, Hongwei; Hutzler, Thomas; van Bruggen, Michel P. B.; Apetz, Rolf (2003). "Transparent Sintered Corundum with High Hardness and Strength". Journal of the American Ceramic Society. 86 (1): 12–18. doi:10.1111/j.1151-2916.2003.tb03270.x. ISSN 0002-7820.
  37. ^ Muller, Olaf; Roy, Rustum (1974). The major ternary structural families. New York: Springer-Verlag. ISBN 0-387-06430-3. OCLC 1056558.
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