Zirconium

Zirconium (pronounced /zərˈkoʊniəm/ zər-KOH-ni-əm) is a chemical element with the symbol Zr and atomic number 40. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium. Zirconium is used as an alloying agent for its strong resistance to corrosion. It is never found as a native metal; it is obtained mainly from the mineral zircon, which can be purified with chlorine. Zirconium was first isolated in an impure form in 1824 by Jöns Jakob Berzelius.

Zirconium has no known biological role. Zirconium forms both inorganic and organometallic compounds such as zirconium dioxide and zirconocene dichloride, respectively. There are five naturally-occurring isotopes, three of which are stable. Short-term exposure to zirconium powder causes minor irritation, and inhalation of zirconium compounds can cause skin and lung granulomas.

Characteristics

Zirconium is a lustrous, grayish-white, soft, ductile, and malleable metal which is solid at room temperature, though it becomes hard and brittle at lower purities.[4][5] In powder form, zirconium is highly flammable, but the solid form is far less prone to ignition. Zirconium is highly resistant to corrosion by alkalis, acids, salt water, and other agents.[6] However, it will dissolve in hydrochloric and sulfuric acid, especially when fluorine is present.[7] Alloys with zinc become magnetic below 35 K.[6]

Zirconium's melting point is at 1855°C, and its boiling point 4409°C.[6] Zirconium has an electronegativity of 1.33 on the Pauling scale. Of the elements within d-block, zirconium has the fourth lowest electronegativity after yttrium, lutetium, and hafnium.[8]

Applications

Because of zirconium's excellent resistance to corrosion, it is often used as an alloying agent in materials that are exposed to corrosive agents, such as surgical appliances, explosive primers, vacuum tube getters and filaments. Zirconium dioxide (ZrO2) is used in laboratory crucibles, metallurgical furnaces, as a refractory material,[6] and it can be sintered into a ceramic knife. Zircon (ZrSiO4) is cut into gemstones for use in jewelry. Zirconium carbonate (3ZrO2·CO2·H2O) was used in lotions to treat poison ivy, but this was discontinued because it occasionally caused bad skin reactions.[4]

Ninety percent of all zirconium produced is used in nuclear reactors (in the form of zircaloys) because of its low neutron-capture cross-section and resistance to corrosion.[5][6] Zirconium alloys are used in space vehicle parts for their resistance to heat, an important quality given the extreme heat associated with atmospheric reentry.[9] Zirconium is also a component in some abrasives, such as grinding wheels and sandpaper.[10] Zirconium is used in weapons such as the BLU-97/B Combined Effects Bomb for incendiary effect.

High temperature parts such as combustors, blades and vanes in modern jet engines and stationary gas turbines are to an ever increasing extent being protected by thin ceramic layers which reduce the metal temperatures below and keep them from undergoing (too) extensive deformation which could possibly result in early failure. They are absolutely necessary for the most modern gas turbines which are driven to ever higher firing temperatures to produce more electricity at less CO2. These ceramic layers are usually composed by a mixture of zirconium and yttrium oxide.[11]

Refining

Upon being collected from coastal waters, the solid mineral zircon is purified by spiral concentrators to remove excess sand and gravel and by magnetic separators to remove ilmenite and rutile. The byproducts can then be dumped back into the water safely, as they are all natural components of beach sand. The refined zircon is then purified into pure zirconium by chlorine or other agents, then sintered until sufficiently ductile for metalworking.[5] Zirconium and hafnium are both contained in zircon and they are quite difficult to separate due to their similar chemical properties.[9]

History
Zirconium crystal bar, 99.97%, made by the crystal bar process

The zirconium-containing mineral zircon, or its variations (jargoon, hyacinth, jacinth, ligure), were mentioned in biblical writings.[6][9] The mineral was not known to contain a new element until 1789,[10] when Klaproth analyzed a jargoon from the island of Sri Lanka in the Indian Ocean. He named the new element Zirkonerde (zirconia).[6] Humphry Davy attempted to isolate this new element in 1808 through electrolysis, but failed.[4] Zirconium (from Syriac ܙܐܪܓܥܢܥ zargono,[12] Arabic zarkûn ئشقنعى from Persian zargûn زرگون meaning "gold like")[9] was first isolated in an impure form in 1824 by Berzelius by heating a mixture of potassium and potassium-zirconium fluoride in a small decomposition process conducted in an iron tube.[6] These words were adapted into German Zirkon which became the source of the English words: Zircon and Zirconium. [13]

The crystal bar process (or Iodide process), discovered by Anton Eduard van Arkel and Jan Hendrik de Boer in 1925, was the first industrial process for the commercial production of pure metallic zirconium. The process involved thermally decomposing zirconium tetraiodide. It was superseded in 1945 by the much cheaper Kroll process developed by William Justin Kroll, in which zirconium tetrachloride is broken down by magnesium.[5][14]

Occurrence

Geological
Zirconium output in 2005
See also: Category:Zirconium minerals
World production trend of zirconium mineral concentrates

Zirconium has a concentration of about 130 mg/kg within the earth's crust and about 0.026 μg/L in sea water,[15] though it is never found in nature as a native metal. The principal commercial source of zirconium is the zirconium silicate mineral, zircon (ZrSiO4),[4] which is found primarily in Australia, Brazil, India, Russia, South Africa, and the United States, as well as in smaller deposits around the world.[5] 80% of zircon mining occurs in Australia and South Africa.[4] Zircon resources exceed 60 million metric tons worldwide[16] and annual worldwide zirconium production is approximately 900,000 metric tons.[15]

Zircon is a by-product of the mining and processing of the titanium minerals ilmenite and rutile, as well as tin mining.[17] From 2003 to 2007, zircon prices have steadily increased from $360 to $840 per metric ton.[16] Zirconium also occurs in more than 140 other recognized mineral species including baddeleyite and kosnarite.[18] This metal is commercially produced mostly by the reduction of the zirconium(IV) chloride with magnesium metal in the Kroll process.[6] Commercial-quality zirconium for most uses still has a content of 1% to 3% hafnium.[4]

This element is relatively-abundant in S-type stars, and it has been detected in the sun and in meteorites. Lunar rock samples brought back from several Apollo program missions to the moon have a quite high zirconium oxide content relative to terrestrial rocks.[6]

Biological

Zirconium has no known biological role, though zirconium salts are of low toxicity. The human body contains, on average, only 1 milligram of zirconium, and daily intake is approximately 50 μg per day. Zirconium content in human blood is as low as 10 parts per billion. Aquatic plants readily take up soluble zirconium, but it is rare in land plants. 70% of plants have no zirconium content at all, and those that do have as little as 5 parts per billion.[4]

Compounds
See also: Category: Zirconium compounds

As a transition metal, zirconium forms various inorganic compounds, such as zirconium dioxide (ZrO2). This compound, also referred to as zirconia, has exceptional fracture toughness and chemical resistance, especially in its cubic form.[19] These properties make zirconia useful as a thermal barrier coating,[20] though it is also a common diamond substitute.[19] Zirconium tungstate is an unusual substance in that it shrinks in all directions when heated, whereas most other substances expand when heated.[6] ZrZn2 is one of only two substances to exhibit superconductivity and ferromagnetism simultaneously, with the other being UGe2.[21] Other inorganic zirconium compounds include zirconium(II) hydride, zirconium nitride, and zirconium tetrachloride (ZrCl4), which is used in the Friedel-Crafts reaction.[22]

Organozirconium chemistry is the study of compounds containing a carbon-zirconium bond. These organozirconium compounds are often employed as polymerization catalysts. The first such compound was zirconocene dibromide, prepared in 1952 by John M. Birmingham at Harvard University.[23] Schwartz's reagent, prepared in 1970 by P. C. Wailes and H. Weigold,[24] is a metallocene used in organic synthesis for transformations of alkenes and alkynes.[25]

Isotopes
A zirconium rod
Main article: Isotopes of zirconium

Naturally-occurring zirconium is composed of five isotopes. 90Zr, 91Zr, and 92Zr are stable. 94Zr has a half-life of 1.10×1017 years. 96Zr has a half-life of 2.4×1019 years, making it the longest-lived radioisotope of zirconium. Of these natural isotopes, 90Zr is the most common, making up 51.45% of all zirconium. 96Zr is the least common, comprising only 2.80% of zirconium.[26]

28 artificial isotopes of zirconium have been synthesized, ranging in atomic mass from 78 to 110. 93Zr is the longest-lived artificial isotope, with a half-life of 1.53×106 years. 110Zr, the heaviest isotope of zirconium, is also the shortest-lived, with an estimated half-life of only 30 milliseconds. Radioactive isotopes at or above mass number 93 decay by β−, whereas those at or below 89 decay by β+. The only exception is 88Zr, which decays by ε.[26]

Zirconium also has six metastable isomers: 83mZr, 85mZr, 89mZr, 90m1Zr, 90m2Zr, and 91mZr. Of these, 90m2Zr has the shortest half-life at 131 nanoseconds. 89mZr is the longest lived with a half-life of 4.161 minutes.[26]

Toxicity

Short-term exposure to zirconium powder can cause irritation, but only contact with the eyes requires medical attention.[27] Inhalation of zirconium compounds can cause skin and lung granulomas. Zirconium aerosols can cause pulmonary granulomas. Persistent exposure to zirconium tetrachloride resulted in increased mortality in rats and guinea pigs and a decrease of blood hemoglobin and red blood cells in dogs. OSHA recommends a 5 mg/m3 time weighted average limit and a 10 mg/m3 short-term exposure limit.[28]

Chemical thermodynamics of zirconium, Paul L. Brown, OECD Nuclear Energy Agency

See also

* Zirconium compounds
* Zirconium minerals

Notes

1. ^ "Zirconium: zirconium(I) fluoride compound data". OpenMOPAC.net. http://openmopac.net/data_normal/zirconium(i)%20fluoride_jmol.html. Retrieved 2007-12-10.
2. ^ Magnetic susceptibility of the elements and inorganic compounds, in Handbook of Chemistry and Physics 81st edition, CRC press.
3. ^ Pritychenko, Boris; V. Tretyak. "Adopted Double Beta Decay Data". National Nuclear Data Center. http://www.nndc.bnl.gov/bbdecay/list.html. Retrieved 2008-02-11.
4. ^ a b c d e f g Emsley, John (2001). Nature's Building Blocks. Oxford: Oxford University Press. pp. 506–510. ISBN 0-19-850341-5.
5. ^ a b c d e "Zirconium". How Products Are Made. Advameg Inc.. 2007. http://www.madehow.com/Volume-1/Zirconium.html. Retrieved 2008-03-26.
6. ^ a b c d e f g h i j k Lide, David R., ed (2007–2008). "Zirconium". CRC Handbook of Chemistry and Physics. 4. New York: CRC Press. p. 42. ISBN 978-0-8493-0488-0.
7. ^ Considine, Glenn D., ed (2005). "Zirconium". Van Nostrand's Encyclopedia of Chemistry. New York: Wylie-Interscience. pp. 1778–1779. ISBN 0-471-61525-0.
8. ^ Winter, Mark (2007). "Electronegativity (Pauling)". University of Sheffield. http://www.webelements.com/webelements/properties/text/image-flash/electroneg-pauling.html. Retrieved 2008-03-05.
9. ^ a b c d Stwertka, Albert (1996). A Guide to the Elements. Oxford University Press. pp. 117–119. ISBN 0-19-508083-1.
10. ^ a b Krebs, Robert E. (1998). The History and Use of our Earth's Chemical Elements. Westport, Connecticut: Greenwood Press. pp. 98–100. ISBN 0-313-30123-9.
11. ^ Meier, S. M.; Gupta, D. K. (1994). "The Evolution of Thermal Barrier Coatings in Gas Turbine Engine Applications". Journal of Engineering for Gas Turbines and Power 116: 250. doi:10.1115/1.2906801.
12. ^ Pearse, Roger (2002-09-16). "Syriac Literature". http://www.tertullian.org/rpearse/oriental/syriac.htm. Retrieved 2008-02-11.
13. ^ http://www.etymonline.com/index.php?term=zircon
14. ^ Hedrick, James B. (1998). "Zirconium" (PDF). Metal Prices in the United States through 1998. US Geological Survey. pp. 175–178. http://minerals.usgs.gov/minerals/pubs/metal_prices/metal_prices1998.pdf. Retrieved 2008-02-26.
15. ^ a b Peterson, John; MacDonell, Margaret (2007). "Zirconium" (PDF). Radiological and Chemical Fact Sheets to Support Health Risk Analyses for Contaminated Areas. Argonne National Laboratory. pp. 64–65. http://www.evs.anl.gov/pub/doc/ANL_ContaminantFactSheets_All_070418.pdf. Retrieved 2008-02-26.
16. ^ a b "Zirconium and Hafnium" (PDF). Mineral Commodity Summaries (US Geological Survey): 192–193. January 2008. http://minerals.usgs.gov/minerals/pubs/commodity/zirconium/mcs-2008-zirco.pdf. Retrieved 2008-02-24.
17. ^ Callaghan, R. (2008-02-21). "Zirconium and Hafnium Statistics and Information". US Geological Survey. http://minerals.usgs.gov/minerals/pubs/commodity/zirconium/. Retrieved 2008-02-24.
18. ^ Ralph, Jolyon; Ida Ralph (2008). "Minerals that include Zr". Mindat.org. http://www.mindat.org/chemsearch.php?inc=Zr%2C&exc=&sub=Search+for+Minerals. Retrieved 2008-02-23.
19. ^ a b "Zirconia". AZoM.com. 2008. http://www.azom.com/details.asp?ArticleID=133#_Key_Properties. Retrieved 2008-03-17.
20. ^ Gauthier, V.; Dettenwanger, F.; Schütze, M. (2002-04-10). "Oxidation behavior of γ-TiAl coated with zirconia thermal barriers". Intermetallics (Frankfurt, Germany: Karl Winnacker Institut der Dechema) 10 (7): 667–674. doi:10.1016/S0966-9795(02)00036-5.
21. ^ Day, Charles (September 2001). "Second Material Found that Superconducts in a Ferromagnetic State". Physics Today (American Institute of Physics) 54 (9): 16. doi:10.1063/1.1420499.
22. ^ Bora U. (2003). "Zirconium Tetrachloride". Synlett: 1073–1074. doi:10.1055/s-2003-39323.
23. ^ Rouhi, A. Maureen (2004-04-19). "Organozirconium Chemistry Arrives". Science & Technology (Chemical & Engineering News) 82 (16): 36–39. ISSN 0009-2347. http://pubs.acs.org/cen/nlw/8216sci1.html. Retrieved 2008-03-17.
24. ^ Wailes, P. C. and Weigold, H. (1970). "Hydrido complexes of zirconium I. Preparation". Journal of Organometallic Chemistry 24: 405–411. doi:10.1016/S0022-328X(00)80281-8.
25. ^ Hart, D. W. and Schwartz,J. (1974). "Hydrozirconation. Organic Synthesis via Organozirconium Intermediates. Synthesis and Rearrangement of Alkylzirconium(IV) Complexes and Their Reaction with Electrophiles". J. Am. Chem. Soc. 96 (26): 8115–8116. doi:10.1021/ja00833a048.
26. ^ a b c Audi, G (2003). "Nubase2003 Evaluation of Nuclear and Decay Properties". Nuclear Physics A (Atomic Mass Data Center) 729: 3–128. doi:10.1016/j.nuclphysa.2003.11.001.
27. ^ "Zirconium". International Chemical Safety Cards. International Labour Organization. October 2004. http://www.oit.org/public/english/protection/safework/cis/products/icsc/dtasht/_icsc14/icsc1405.htm. Retrieved 2008-03-30.
28. ^ "Zirconium Compounds". National Institute for Occupational Health and Safety. 2007-12-17. http://www.cdc.gov/niosh/pel88/7440-67.html. Retrieved 2008-02-17.

External links

* WebElements.com: Zirconium
* Chemistry in its element podcast (MP3) from the Royal Society of Chemistry's Chemistry World: Zirconium