Corundum Explained

Corundum
Category:Oxide mineral – Hematite group
Formula:Al2O3
Imasymbol:Crn[1]
Strunz:4.CB.05
Dana:4.3.1.1
System:Trigonal
Class:Hexagonal scalenohedral (m)
H-M symbol: (2/m)
Symmetry: (No. 167)
Unit Cell:, ;
Color:Colorless, gray, golden-brown, brown; purple, pink to red, orange, yellow, green, blue, violet; may be color zoned, asteriated mainly grey and brown
Habit:Steep bipyramidal, tabular, prismatic, rhombohedral crystals, massive or granular
Twinning:Polysynthetic twinning common
Cleavage:None – parting in 3 directions
Tenacity:Brittle
Fracture:Conchoidal to uneven
Mohs:9 (defining mineral)[2]
Luster:Adamantine to vitreous
Refractive:
Opticalprop:Uniaxial (-)
Pleochroism:None
Streak:Colorless
Diaphaneity:Transparent, translucent to opaque
Gravity:3.95–4.10
Fusibility:Infusible
Solubility:Insoluble
Other:May fluoresce or phosphoresce under UV light
Alteration:May alter to mica on surfaces causing a decrease in hardness
References:[3] [4] [5] [6]
Var1:Sapphire
Var1text:Any color except red
Var2text:Red
Var3text:Black granular corundum intimately mixed with magnetite, hematite, or hercynite

Corundum is a crystalline form of aluminium oxide 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]

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, which is unusually high for a transparent mineral composed of the low-atomic mass elements aluminium and oxygen.[9]

Geology and occurrence

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×, and weighed 152kg (335lb).[10] The record has since been surpassed by certain synthetic boules.[11]

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.[12] [13]

Synthetic corundum

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.[16]

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 sapphires,[17] and Advanced LIGO considered sapphire mirrors.[18] Corundum has also found use in the development of ceramic armour thanks to its high hardiness.[19]

Structure and physical properties

Corundum crystallizes with trigonal symmetry in the space group and has the lattice parameters and at standard conditions. The unit cell contains six formula units.[20]

The toughness of corundum is sensitive to surface roughness[21] [22] and crystallographic orientation.[23] It may be 6–7 MPa·m for synthetic crystals,[23] and around 4 MPa·m for natural.[24]

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.[25] 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 and the crystal class to trigonal.[26] The structure of corundum is sometimes described as a pseudohexagonal structure.[27]

The Young’s modulus of corundum (sapphire) has been reported by many different sources with values varying between 300-500 GPa, but a commonly cited value used for calculations is 345 GPa. 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. The shear modulus of corundum is 145 GPa,[28] and the bulk modulus is 240 GPa.

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.[29]

The hardness of corundum measured by indentation at low loads of 1-2 N has been reported as 22-23 GPa[30] in major crystallographic planes: (0001) (basal plane), (100) (rhombohedral plane), (110) (prismatic plane), and (102). 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 (~1kN) is nearly half the value under low load (1-2 N).

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 600-700 MPa and three-point bending strength between 750-900 Mpa.[31]

Generalization

See 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.[32]

See also

Notes and References

  1. Warr. L.N.. 2021. IMA–CNMNC approved mineral symbols. Mineralogical Magazine. 85. 3. 291–320. 10.1180/mgm.2021.43. 2021MinM...85..291W. 235729616. free.
  2. Web site: Mohs' scale of hardness . Collector's corner . Mineralogical Society of America . 10 January 2014.
  3. Book: Anthony, John W. . Bideaux, Richard A. . Bladh, Kenneth W. . Nichols, Monte C. . Handbook of Mineralogy . 1997 . Mineralogical Society of America . Chantilly, VA, US . https://web.archive.org/web/20060905204655/http://rruff.geo.arizona.edu/doclib/hom/corundum.pdf . 2006-09-05 . live . Corundum . 0962209724 . III Halides, Hydroxides, Oxides.
  4. Web site: Corundum . Mindat.org.
  5. Web site: Corundum . Webmineral.com . https://web.archive.org/web/20061125202622/http://webmineral.com/data/Corundum.shtml . 2006-11-25 . dmy-all.
  6. Book: Hurlbut, Cornelius S. . Klein, Cornelis . 1985 . Manual of Mineralogy . registration . 20th . Wiley . 300–302 . 0-471-80580-7.
  7. Book: Gem Corundum . Giuliani . Gaston . Ohnenstetter . Daniel . Fallick . Anthony E. . Groat . Lee . Fagan . Andrew J. . Mineralogical Association of Canada . 2014 . 978-0-921294-54-2 . Research Gate . 37–38 . The Geology and Genesis of Gem Corundum Deposits.
  8. 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 . en . 7 . 3 . 19 . 10.1007/s40828-021-00143-0 . 233435945 . 2199-3793.
  9. Web site: The Mineral Corundum . galleries.com.
  10. Rickwood, P. C. . 1981 . The largest crystals . American Mineralogist . 66 . 885–907 . https://web.archive.org/web/20090620081033/http://www.minsocam.org/ammin/AM66/AM66_885.pdf . 2009-06-20 . live.
  11. Web site: Rubicon Technology grows 200 kg "super boule" . LED Inside . April 21, 2009 . dmy-all.
  12. Web site: Chinese made first use of diamond . BBC . May 2005 . BBC News.
  13. Web site: Alexandra . Goho . In the Buff: Stone Age tools may have derived luster from diamond . Science News . 16 February 2005 .
  14. Untreated yellowish orange sapphire exhibiting its natural colour . Journal of Gemmology . 32 . 175–178 . 2011 . Duroc-Danner, J. M. . 5 . 10.15506/jog.2011.32.5.174 . dead . https://web.archive.org/web/20130516231326/http://www.gem-a.com/media/94808/duroc%20danner%20website.pdf . 2013-05-16 . dmy-all.
  15. Web site: A Handbook of Precious Stones . Bahadur . 1943 . 2007-08-19 . dmy-all.
  16. Walsh . Andrew . The commodification of fetishes: Telling the difference between natural and synthetic sapphires . American Ethnologist . February 2010 . 37 . 1 . 98–114 . 10.1111/j.1548-1425.2010.01244.x.
  17. Eiichi . Hirose . etal . 2014 . Sapphire mirror for the KAGRA gravitational wave detector . Physical Review D . 89 . 6 . 062003 . 10.1103/PhysRevD.89.062003 . 2014PhRvD..89f2003H . https://web.archive.org/web/20180724161640/https://authors.library.caltech.edu/45938/1/PhysRevD.89.062003.pdf . 2018-07-24 . live.
  18. Web site: GariLynn . Billingsley . Advanced Ligo Core Optics Components – Downselect . LIGO Laboratory . 2004 . 2020-02-06 . dmy-all.
  19. Defense World.Net, Russia’s Armored Steel-Comparable Ceramic Plate Clears Tests, 5 September 2020, Retrieved 29 December 2020
  20. Newnham . R. E. . de Haan . Y. M. . Refinement of the α Al2O3, Ti2O3, V2O3 and Cr2O3 structures* . Zeitschrift für Kristallographie . August 1962 . 117 . 2–3 . 235–237 . 10.1524/zkri.1962.117.2-3.235. 1962ZK....117..235N .
  21. Effect of machining on fracture toughness of corundum . Farrokh . Farzin-Nia . Terry . Sterrett . Ron . Sirney . Journal of Materials Science . 1990 . 25 . 5 . 2527–2531 . 10.1007/bf00638054. 1990JMatS..25.2527F . 137548763 .
  22. 10.1111/j.1151-2916.1976.tb09390.x . 59 . Fracture-Strength Anisotropy of Sapphire . Journal of the American Ceramic Society . 1976 . 59–61. Becker . Paul F. . 1–2 .
  23. 10.1111/j.1151-2916.1969.tb09199.x . 52 . Fracture of Sapphire . Journal of the American Ceramic Society . 1969 . 485–491. Wiederhorn . S. M. . 9 .
  24. Web site: Corundum, Aluminum Oxide, Alumina, 99.9%, Al2O3 . www.matweb.com .
  25. Book: Nesse . William D. . Introduction to mineralogy . 2000 . Oxford University Press . New York . 9780195106916 . 363–364.
  26. Book: Borchardt-Ott . Walter . Kaiser . E. T. . Crystallography . 1995 . Springer . Berlin . 3540594787 . 230 . 2nd.
  27. Gea . Laurence A. . Boatner . L. A. . Rankin . Janet . Budai . J. D. . The Formation Al 2 O 3 /V 2 O 3 Multilayer Structures by High-Dose Ion Implantation . MRS Proceedings . 1995 . 382 . 107 . 10.1557/PROC-382-107.
  28. Book: Ramdas, Roshan L. Aggarwal, Anant K. . Physical Properties of Diamond and Sapphire . 2019-05-03 . CRC Press . 978-0-429-28326-0 . Boca Raton . 10.1201/9780429283260.
  29. Wadley . Haydn N. G. . Lu . Yichi . Goldman . Jeffrey A. . 1995-03-01 . Ultrasonic determination of single crystal sapphire fiber modulus . Journal of Nondestructive Evaluation . en . 14 . 1 . 31–38 . 10.1007/BF00735669 . 1573-4862.
  30. Sinani . A. B. . Dynkin . N. K. . Lytvinov . L. A. . Konevsky . P. V. . Andreev . E. P. . 2009-10-01 . Sapphire hardness in different crystallographic directions . Bulletin of the Russian Academy of Sciences: Physics . en . 73 . 10 . 1380–1382 . 10.3103/S1062873809100177 . 1934-9432.
  31. 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 . en . 86 . 1 . 12–18 . 10.1111/j.1151-2916.2003.tb03270.x . 0002-7820.
  32. Book: Muller . Olaf . Roy . Rustum . The major ternary structural families . 1974 . Springer-Verlag . 0-387-06430-3 . New York . 1056558.