Perovskite

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This article is about the mineral; for synthetic compounds see perovskite structure.
Perovskite
Perovskite mineral.jpg
General
Category Oxide minerals
Formula
(repeating unit)
CaTiO3
Strunz classification 04.CC.30
Identification
Formula mass 135.96
Color Black, reddish brown, pale yellow, yellowish orange
Crystal habit Pseudo cubic – crystals show a cubic outline
Crystal system Orthorhombic (2/m 2/m 2/m) space group: Pnma
Twinning complex penetration twins
Cleavage [100] good, [010] good, [001] good
Fracture Conchoidal
Mohs scale hardness 5–5.5
Luster Adamantine to metallic; may be dull
Streak grayish white
Diaphaneity Transparent to opaque
Specific gravity 3.98–4.26
Optical properties Biaxial (+)
Refractive index nα=2.3, nβ=2.34, nγ=2.38
Other characteristics non-radioactive, non-magnetic
References [1][2][3][4][5][6][7][8]

Perovskite (pronunciation: pe'ɹovskaɪt) is a calcium titanium oxide mineral species composed of calcium titanate, with the chemical formula CaTiO3. The mineral was discovered in the Ural Mountains of Russia by Gustav Rose in 1839 and is named after Russian mineralogist Lev Perovski (1792–1856).[1]

It lends its name to the class of compounds which have the same type of crystal structure as CaTiO3 (XIIA2+VIB4+X2–3) known as the perovskite structure.[9] The perovskite crystal structure was first described by Victor Goldschmidt in 1926, in his work on tolerance factors.[10] The crystal structure was later published in 1945 from X-ray diffraction data on barium titanate by the Irish crystallographer Helen Dick Megaw.[11]

Occurrence[edit]

Perovskite is found in contact carbonate skarns at Magnet Cove, Arkansas. It occurs in altered blocks of limestone ejected from Mount Vesuvius. It occurs in chlorite and talc schist in the Urals and Switzerland.[12] It is also found as an accessory mineral in alkaline and mafic igneous rocks, nepheline syenite, melilitite, kimberlites and rare carbonatites. Perovskite is a common mineral in the Ca-Al-rich inclusions found in some chondritic meteorites.[2]

A rare earth-bearing variety, knopite, (Ca,Ce,Na)(Ti,Fe)O3) is found in alkali intrusive rocks in the Kola Peninsula and near Alnö, Sweden. A niobium-bearing variety, dysanalyte, occurs in carbonatite near Schelingen, Kaiserstuhl, Germany.[12][13][14][15]

Special characteristics[edit]

The stability of perovskite in igneous rocks is limited by its reaction relation with sphene. In volcanic rocks perovskite and sphene are not found together, the only exception being in an atindite from Cameroon.[4]

Physical properties[edit]

Perovskites have a cubic structure with general formula of ABO3. In this structure, an A-site ion, on the corners of the lattice, is usually an alkaline earth or rare earth element. B site ions, on the center of the lattice, could be 3d, 4d, and 5d transitional metal elements. A large number of metallic elements are stable in the perovskite structure, if the tolerance factor “t” is in the range of 0.75 – 1.0.[16]

t=(RA+RO)/(√2 (RB+RO))

where RA, RB and RO are the ionic radii of A and B site elements and oxygen, respectively.

The sub-metallic to metallic luster, colorless streak, cube like structure along with imperfect cleavage and brittle tenacity are physical properties of perovskite. Colors range from black, brown, gray, orange to yellow. Crystals of perovskite appear as cubes, but are pseudocubic and crystallize in the orthorhombic system. Perovskite crystals have been mistaken for galena; however, galena has a better metallic luster, greater density, perfect cleavage and true cubic symmetry.[5]

Layered perovskites[edit]

Perovskites may be structured in layers, with the above ABO3 structure separated by thin sheets of intrusive material. Different forms of intrusions, based on the chemical makeup of the intrusion, are defined as:[17]

  • Aurivillius phase: the intruding layer is composed of a [Bi2O2]2+ ion, occurring every n ABO3 layers, leading to an overall chemical formula of {Bi2O2}-{A(n-1)B2O7}. Their oxide ion-conducting properties were first discovered in the 1970s by Takahashi et al., and they have been used for this purpose ever since.[18]
  • Dion-Jacobson phase: the intruding layer is composed of an alkali metal (M) every n ABO3 layers, giving the overall formula as M+1A(n-1)BnO(3n+1)
  • Ruddlesden-Popper phase: the simplest of the phases, the intruding layer occurs between every one (n = 1) or two (n = 2) layers of the ABO3 lattice.

Geologic occurrence[edit]

Found in the Earth’s mantle, the perovskite’s occurrence at Khibina Massif is restricted to the under saturated ultramafic rocks and foidolites, due to the instability in a paragenesis with feldspar. The complexity is made by an extended series of rocks from early alkaline ultramafic members to late carbonatites that comprise alkaline and mafic igneous rocks such as nepheline syenite, melilitite, kimberlite and rare carbonatites in ultramafites. Perovskite occurs as small anhedral to subhedral crystals filling interstices between the rock-forming silicates.[7]

Discovery and name[edit]

Perovskite was first described in 1839 from an occurrence in the Achmatovsk Mine in the Nazyamskie Mountains, Chelyabinsk Oblast, Southern Urals, Russia. The new mineral was named by Gustav Rose for Russian mineralogist, Lev Perovski (1792–1856).[2][19]

See also[edit]

References[edit]

  1. ^ a b Perovskite. Webmineral
  2. ^ a b c Anthony, John W.; Bideaux, Richard A.; Bladh, Kenneth W. and Nichols, Monte C. (Eds.) Perovskite. Handbook of Mineralogy. Mineralogical Society of America, Chantilly, VA
  3. ^ Naoki Inoue and Yanhui Zou Physical properties of perovskite-type lithium ionic conductor.Ch. 8 in Takashi Sakuma and Haruyuki Takahashi (Eds.) Physics of Solid State Ionics (2006) pp. 247–269 ISBN 81-308-0070-5
  4. ^ a b Veksler, I.V.; Teptelev, M.P. (1990). "Conditions for crystallization and concentration of perovskite-type minerals in alkaline magmas". Lithos 26: 177. Bibcode:1990Litho..26..177V. doi:10.1016/0024-4937(90)90047-5. 
  5. ^ a b Luxová, Jana; Šulcová, Petra; Trojan, M. (2008). "Study of Perovskite". Journal of Thermal Analysis and Calorimetry 93 (3): 823. doi:10.1007/s10973-008-9329-z. 
  6. ^ Lufaso, Michael W.; Woodward, Patrick M. (2004). "Jahn–Teller distortions, cation ordering and octahedral tilting in perovskites". Acta Crystallographica Section B Structural Science 60: 10. doi:10.1107/S0108768103026661. 
  7. ^ a b Chakhmouradian, Anton R. and Mitchell, Roger H. (1998). "Compositional variation of perovskite-group minerals from the Khibina Complex, Kola Peninsula, Russia". The Canadian Mineralogist 36: 953–969. 
  8. ^ Lemanov, V; Sotnikov, A.V.; Smirnova, E.P.; Weihnacht, M.; Kunze, R. (1999). "Perovskite CaTiO3 as an incipient ferroelectric". Solid State Communications 110 (11): 611. Bibcode:1999SSCom.110..611L. doi:10.1016/S0038-1098(99)00153-2. 
  9. ^ Wenk, Hans-Rudolf; Bulakh, Andrei (2004). Minerals: Their Constitution and Origin. New York, NY: Cambridge University Press. p. 413. ISBN 978-0-521-52958-7. 
  10. ^ Golschmidt, V M (1926). "Die Gesetze der Krystallochemie". Die Naturwissenschaften 21 (21): 477. Bibcode:1926NW.....14..477G. doi:10.1007/BF01507527. 
  11. ^ Megaw, Helen (1945). "Crystal Structure of Barium Titanate". Nature 155 (3938): 484. Bibcode:1945Natur.155..484.. doi:10.1038/155484b0. 
  12. ^ a b Palache, Charles, Harry Berman and Clifford Frondel, 1944, Dana's System of Mineralogy Vol. 1, Wiley, 7th ed. p. 733
  13. ^ Deer, William Alexander; Howie, Robert Andrew and Zussman, Jack (1966) An Introduction to the Rock Forming Minerals Longman , ISBN 0-582-44210-9
  14. ^ Knopite. Mindat
  15. ^ Dysanalyte. Mindat
  16. ^ Peña, M. A.; Fierro, J. L. (2001). "Chemical structures and performance of perovskite oxides". Chemical reviews 101 (7): 1981–2017. doi:10.1021/cr980129f. PMID 11710238.  edit
  17. ^ Cava, Robert J. "Cava Lab: Perovskites". Princeton University. Retrieved 13 November 2013. 
  18. ^ Kendall, K. R.; Navas, C.; Thomas, J. K.; Zur Loye, H. C. (1996). "Recent Developments in Oxide Ion Conductors: Aurivillius Phases". Chemistry of Materials 8 (3): 642. doi:10.1021/cm9503083.  edit
  19. ^ Perovskite. Mindat