Zirconium

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Zirconium,  40Zr
Zirconium crystal bar and 1cm3 cube.jpg
Zirconium
Pronunciation /zərˈkniəm/ (zər-KOH-nee-əm)
Appearancesilvery white
Standard atomic weight Ar, std(Zr)91.224(2) [1]
Zirconium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Ti

Zr

Hf
yttriumzirconiumniobium
Atomic number (Z)40
Group group 4
Period period 5
Block d-block
Element category   Transition metal
Electron configuration [ Kr ] 4d2 5s2
Electrons per shell
2, 8, 18, 10, 2
Physical properties
Phase at  STP solid
Melting point 2128  K (1855 °C,3371 °F)
Boiling point 4650 K(4377 °C,7911 °F)
Density (near r.t.)6.52 g/cm3
when liquid (at m.p.)5.8 g/cm3
Heat of fusion 14  kJ/mol
Heat of vaporization 591 kJ/mol
Molar heat capacity 25.36 J/(mol·K)
Vapor pressure
P (Pa)1101001 k10 k100 k
at T (K)263928913197357540534678
Atomic properties
Oxidation states −2, +1, [2] +2, +3, +4 (an  amphoteric oxide)
Electronegativity Pauling scale: 1.33
Ionization energies
  • 1st: 640.1 kJ/mol
  • 2nd: 1270 kJ/mol
  • 3rd: 2218 kJ/mol
Atomic radius empirical:160  pm
Covalent radius 175±7 pm
Color lines in a spectral range Zirconium spectrum visible.png
Color lines in a spectral range
Spectral lines of zirconium
Other properties
Natural occurrence primordial
Crystal structure hexagonal close-packed (hcp)
Hexagonal close packed.svg
Speed of sound thin rod3800 m/s(at 20 °C)
Thermal expansion 5.7 µm/(m·K)(at 25 °C)
Thermal conductivity 22.6 W/(m·K)
Electrical resistivity 421 nΩ·m(at 20 °C)
Magnetic ordering paramagnetic [3]
Young's modulus 88 GPa
Shear modulus 33 GPa
Bulk modulus 91.1 GPa
Poisson ratio 0.34
Mohs hardness 5.0
Vickers hardness 820–1800 MPa
Brinell hardness 638–1880 MPa
CAS Number 7440-67-7
History
Namingafter zircon, zargun زرگون meaning "gold-colored".
Discovery Martin Heinrich Klaproth (1789)
First isolation Jöns Jakob Berzelius (1824)
Main isotopes of zirconium
Iso­tope Abun­dance Half-life (t1/2) Decay mode Pro­duct
88Zr syn 83.4 d ε 88Y
γ
89Zrsyn78.4 hε 89Y
β+ 89Y
γ
90Zr51.45% stable
91Zr11.22%stable
92Zr17.15%stable
93Zr trace 1.53×106 y β 93Nb
94Zr17.38%stable
96Zr2.80%2.0×1019 y [4] ββ 96Mo
| references

Zirconium is a chemical element with the symbol Zr and atomic number 40. The name zirconium is taken from the name of the mineral zircon (the word is related to Persian zargun (zircon;zar-gun, "gold-like" or "as gold")), the most important source of zirconium. [5] It is a lustrous, grey-white, strong transition metal that closely resembles hafnium and, to a lesser extent, titanium. Zirconium is mainly used as a refractory and opacifier, although small amounts are used as an alloying agent for its strong resistance to corrosion. Zirconium forms a variety of inorganic and organometallic compounds such as zirconium dioxide and zirconocene dichloride, respectively. Five isotopes occur naturally, three of which are stable. Zirconium compounds have no known biological role.

Chemical element a species of atoms having the same number of protons in the atomic nucleus

A chemical element is a species of atom having the same number of protons in their atomic nuclei. For example, the atomic number of oxygen is 8, so the element oxygen consists of all atoms which have 8 protons.

Symbol (chemistry) an arbitrary or conventional sign used in chemical science to represent a chemical element

In chemistry, a symbol is an abbreviation for a chemical element. Symbols for chemical elements normally consist of one or two letters from the Latin alphabet and are written with the first letter capitalised.

Atomic number number of protons found in the nucleus of an atom

The atomic number or proton number of a chemical element is the number of protons found in the nucleus of every atom of that element. The atomic number uniquely identifies a chemical element. It is identical to the charge number of the nucleus. In an uncharged atom, the atomic number is also equal to the number of electrons.

Contents

Characteristics

Zirconium rod Zirconium rod.jpg
Zirconium rod

Zirconium is a lustrous, greyish-white, soft, ductile, malleable metal that is solid at room temperature, though it is hard and brittle at lesser purities. [6] [7] In powder form, zirconium is highly flammable, but the solid form is much less prone to ignition. Zirconium is highly resistant to corrosion by alkalis, acids, salt water and other agents. [8] However, it will dissolve in hydrochloric and sulfuric acid, especially when fluorine is present. [9] Alloys with zinc are magnetic at less than 35 K. [8]

Hydrochloric acid strong mineral acid

Hydrochloric acid or muriatic acid is a colorless inorganic chemical system with the formula H
2
O:HCl
. Hydrochloric acid has a distinctive pungent smell. It is classified as strongly acidic and can attack the skin over a wide composition range, since the hydrogen chloride completely dissociates in aqueous solution.

Sulfuric acid chemical compound

Sulfuric acid (alternative spelling sulphuric acid), also known as vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with molecular formula H2SO4. It is a colorless, odorless, and syrupy liquid that is soluble in water and is synthesized in reactions that are highly exothermic.

Fluorine Chemical element with atomic number 9

Fluorine is a chemical element with the symbol F and atomic number 9. It is the lightest halogen and exists as a highly toxic pale yellow diatomic gas at standard conditions. As the most electronegative element, it is extremely reactive, as it reacts with almost all other elements, except for helium and neon.

The melting point of zirconium is 1855 °C (3371 °F), and the boiling point is 4371 °C (7900 °F). [8] Zirconium has an electronegativity of 1.33 on the Pauling scale. Of the elements within the d-block with known electronegativities, zirconium has the fifth lowest electronegativity after hafnium, yttrium, lanthanum, and actinium. [10]

Melting point temperature at which a solid turns liquid

The melting point of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends on pressure and is usually specified at a standard pressure such as 1 atmosphere or 100 kPa.

Boiling point Temperature at which a substance changes from liquid into vapor

The boiling point of a substance is the temperature at which the vapor pressure of a liquid equals the pressure surrounding the liquid and the liquid changes into a vapor.

Electronegativity, symbol χ, is a chemical property that describes the tendency of an atom to attract a shared pair of electrons towards itself. An atom's electronegativity is affected by both its atomic number and the distance at which its valence electrons reside from the charged nucleus. The higher the associated electronegativity number, the more an atom or a substituent group attracts electrons towards itself.

At room temperature zirconium exhibits a hexagonally close-packed crystal structure, α-Zr, which changes to β-Zr, a body-centered cubic crystal structure, at 863 °C. Zirconium exists in the β-phase until the melting point. [11]

Isotopes

Naturally occurring zirconium is composed of five isotopes. 90Zr, 91Zr, 92Zr and 94Zr are stable, although 94Zr is predicted to undergo double beta decay (not observed experimentally) with a half-life of more than 1.10×1017 years. 96Zr has a half-life of 2.4×1019 years, and is 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. [12]

Double beta decay decay mode

In nuclear physics, double beta decay is a type of radioactive decay in which two neutrons are simultaneously transformed into two protons, or vice versa, inside an atomic nucleus. As in single beta decay, this process allows the atom to move closer to the optimal ratio of protons and neutrons. As a result of this transformation, the nucleus emits two detectable beta particles, which are electrons or positrons.

Half-life is the time required for a quantity to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo, or how long stable atoms survive, radioactive decay. The term is also used more generally to characterize any type of exponential or non-exponential decay. For example, the medical sciences refer to the biological half-life of drugs and other chemicals in the human body. The converse of half-life is doubling time.

Twenty-eight 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 the most radioactive, with an estimated half-life of 30 milliseconds. Radioactive isotopes at or above mass number 93 decay by electron emission, whereas those at or below 89 decay by positron emission. The only exception is 88Zr, which decays by electron capture. [12]

Beta decay decay where electrons (β-, beta minus) or positrons (β+, positron emission) are emitted

In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which a beta particle is emitted from an atomic nucleus, transforming the original nuclide to an isobar. For example, beta decay of a neutron transforms it into a proton by the emission of an electron accompanied by an antineutrino; or, conversely a proton is converted into a neutron by the emission of a positron with a neutrino in so-called positron emission. Neither the beta particle nor its associated (anti-)neutrino exist within the nucleus prior to beta decay, but are created in the decay process. By this process, unstable atoms obtain a more stable ratio of protons to neutrons. The probability of a nuclide decaying due to beta and other forms of decay is determined by its nuclear binding energy. The binding energies of all existing nuclides form what is called the nuclear band or valley of stability. For either electron or positron emission to be energetically possible, the energy release or Q value must be positive.

Electron capture Process in which a proton-rich nuclide absorbs an inner atomic electron

Electron capture is a process in which the proton-rich nucleus of an electrically neutral atom absorbs an inner atomic electron, usually from the K or L electron shell. This process thereby changes a nuclear proton to a neutron and simultaneously causes the emission of an electron neutrino.

Five isotopes of zirconium also exist as 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. [12]

Occurrence

World production trend of zirconium mineral concentrates Zirconium mineral concentrates - world production trend.svg
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. [13] It is not found in nature as a native metal, reflecting its intrinsic instability with respect to water. The principal commercial source of zirconium is zircon (ZrSiO4), a silicate mineral, [6] which is found primarily in Australia, Brazil, India, Russia, South Africa and the United States, as well as in smaller deposits around the world. [7] As of 2013, two-thirds of zircon mining occurs in Australia and South Africa. [14] Zircon resources exceed 60 million tonnes worldwide [15] and annual worldwide zirconium production is approximately 900,000 tonnes. [13] Zirconium also occurs in more than 140 other minerals, including the commercially useful ores baddeleyite and kosnarite. [16]

Zirconium 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 missions to the moon have a high zirconium oxide content relative to terrestrial rocks. [8]

Production

Zirconium output in 2005 2005zirconium.PNG
Zirconium output in 2005

Zirconium 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, while prices for the mineral zircon steadily increased from $360 to $840 per tonne, the price for unwrought zirconium metal decreased from $39,900 to $22,700 per ton. Zirconium metal is much higher priced than zircon because the reduction processes are expensive. [15]

Collected from coastal waters, zircon-bearing sand is purified by spiral concentrators to remove lighter materials, which are then returned to the water because they are natural components of beach sand. Using magnetic separation, the titanium ores ilmenite and rutile are removed.

Most zircon is used directly in commercial applications, but a small percentage is converted to the metal. Most Zr metal is produced by the reduction of the zirconium(IV) chloride with magnesium metal in the Kroll process. [8] The resulting metal is sintered until sufficiently ductile for metalworking. [7]

Separation of zirconium and hafnium

Commercial zirconium metal typically contains 1–3% of hafnium, [18] which is usually not problematic because the chemical properties of hafnium and zirconium are very similar. Their neutron-absorbing properties differ strongly, however, necessitating the separation of hafnium from zirconium for nuclear reactors. [19] Several separation schemes are in use. [18] The liquid-liquid extraction of the thiocyanate-oxide derivatives exploits the fact that the hafnium derivative is slightly more soluble in methyl isobutyl ketone than in water. This method is used mainly in United States.

Zr and Hf can also be separated by fractional crystallization of potassium hexafluorozirconate (K2ZrF6), which is less soluble in water than the analogous hafnium derivative.

Fractional distillation of the tetrachlorides, also called extractive distillation, is used primarily in Europe.

The product of a quadruple VAM (vacuum arc melting) process, combined with hot extruding and different rolling applications is cured using high-pressure, high-temperature gas autoclaving. This produces reactor-grade zirconium that is about 10 times more expensive than the hafnium-contaminated commercial grade.

Hafnium must be removed from zirconium for nuclear applications because hafnium has a neutron absorption cross-section 600 times greater than zirconium. [20] The separated hafnium can be used for reactor control rods. [21]

Compounds

Like other transition metals, zirconium forms a wide range of inorganic compounds and coordination complexes. [22] In general, these compounds are colourless diamagnetic solids wherein zirconium has the oxidation state +4. Far fewer Zr(III) compounds are known, and Zr(II) is very rare.

Oxides, nitrides, and carbides

The most common oxide is zirconium dioxide, ZrO2, also known as zirconia. This clear to white-coloured solid has exceptional fracture toughness and chemical resistance, especially in its cubic form. [23] These properties make zirconia useful as a thermal barrier coating, [24] although it is also a common diamond substitute. [23] Zirconium monoxide, ZrO, is also known and S-type stars are recognised by detection of its emission lines in the visual spectrum. [25]

Zirconium tungstate has the unusual property of shrinking in all dimensions when heated, whereas most other substances expand when heated. [8] Zirconyl chloride is a rare water-soluble zirconium complex with the relatively complicated formula [Zr4(OH)12(H2O)16]Cl8.

Zirconium carbide and zirconium nitride are refractory solids. The carbide is used for drilling tools and cutting edges. Zirconium hydride phases are also known.

Lead zirconate titanate (PZT) is the most commonly used piezoelectric material, with applications such as ultrasonic transducers, hydrophones, common rail injectors, piezoelectric transformers and micro-actuators.

Halides and pseudohalides

All four common halides are known, ZrF4, ZrCl4, ZrBr4, and ZrI4. All have polymeric structures and are far less volatile than the corresponding monomeric titanium tetrahalides. All tend to hydrolyse to give the so-called oxyhalides and dioxides.

The corresponding tetraalkoxides are also known. Unlike the halides, the alkoxides dissolve in nonpolar solvents. Dihydrogen hexafluorozirconate is used in the metal finishing industry as an etching agent to promote paint adhesion. [26]

Organic derivatives

Zirconocene dichloride, a representative organozirconium compound Zirconocene-dichloride-from-xtal-3D-balls.png
Zirconocene dichloride, a representative organozirconium compound

Organozirconium chemistry is the study of compounds containing a carbon-zirconium bond. The first such compound was zirconocene dibromide ((C5H5)2ZrBr2), reported in 1952 by Birmingham and Wilkinson. [27] Schwartz's reagent, prepared in 1970 by P. C. Wailes and H. Weigold, [28] is a metallocene used in organic synthesis for transformations of alkenes and alkynes. [29]

Zirconium is also a component of some Ziegler–Natta catalysts, used to produce polypropylene. This application exploits the ability of zirconium to reversibly form bonds to carbon. Most complexes of Zr(II) are derivatives of zirconocene, one example being (C5Me5)2Zr(CO)2.

History

The zirconium-containing mineral zircon and related minerals (jargoon, hyacinth, jacinth, ligure) were mentioned in biblical writings. [8] [19] The mineral was not known to contain a new element until 1789, [30] when Klaproth analyzed a jargoon from the island of Ceylon (now Sri Lanka). He named the new element Zirkonerde (zirconia). [8] Humphry Davy attempted to isolate this new element in 1808 through electrolysis, but failed. [6] Zirconium metal was first obtained in an impure form in 1824 by Berzelius by heating a mixture of potassium and potassium zirconium fluoride in an iron tube. [8]

The crystal bar process (also known as the 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 metallic zirconium. It involves the formation and subsequent thermal decomposition of zirconium tetraiodide, and was superseded in 1945 by the much cheaper Kroll process developed by William Justin Kroll, in which zirconium tetrachloride is reduced by magnesium: [7] [31]

ZrCl4 + 2 Mg → Zr + 2 MgCl2

Applications

Approximately 900,000 tonnes of zirconium ores were mined in 1995, mostly as zircon. [18]

Compounds

Most zircon is used directly in high-temperature applications. This material is refractory, hard, and resistant to chemical attack. Because of these properties, zircon finds many applications, few of which are highly publicized. Its main use is as an opacifier, conferring a white, opaque appearance to ceramic materials. Because of its chemical resistance, zircon is also used in aggressive environments, such as moulds for molten metals.

Zirconium dioxide (ZrO2) is used in laboratory crucibles, in metallurgical furnaces, and as a refractory material. [8] Because it is mechanically strong and flexible, it can be sintered into ceramic knives and other blades. [32] Zircon (ZrSiO4) and the cubic zirconia (ZrO2) are cut into gemstones for use in jewelry.

Zirconia is a component in some abrasives, such as grinding wheels and sandpaper. [30]

Metal

A small fraction of the zircon is converted to the metal, which finds various niche applications. Because of zirconium's excellent resistance to corrosion, it is often used as an alloying agent in materials that are exposed to aggressive environments, such as surgical appliances, light filaments, and watch cases. The high reactivity of zirconium with oxygen at high temperatures is exploited in some specialised applications such as explosive primers and as getters in vacuum tubes. The same property is (probably) the purpose of including Zr nanoparticles as pyrophoric material in explosive weapons such as the BLU-97/B Combined Effects Bomb. Burning zirconium was used as a light source in some photographic flashbulbs. Zirconium powder with a mesh size from 10 to 80 is occasionally used in pyrotechnic compositions to generate sparks. The high reactivity of zirconium leads to bright white sparks. [33]

Nuclear applications

Cladding for nuclear reactor fuels consumes about 1% of the zirconium supply, [18] mainly in the form of zircaloys. The desired properties of these alloys are a low neutron-capture cross-section and resistance to corrosion under normal service conditions. [7] [8] Efficient methods for removing the hafnium impurities were developed to serve this purpose.

One disadvantage of zirconium alloys is that zirconium reacts with water at high temperatures, producing hydrogen gas and accelerated degradation of the fuel rod cladding:

Zr + 2 H2O → ZrO2 + 2 H2

This exothermic reaction is very slow below 100 °C, but at temperature above 900 °C the reaction is rapid. Most metals undergo similar reactions. The redox reaction is relevant to the instability of fuel assemblies at high temperatures. [34] This reaction was responsible for a small hydrogen explosion first observed inside the reactor building of Three Mile Island nuclear power plant in 1979, but at that time, the containment building was not damaged. The same reaction occurred in the reactors 1, 2 and 3 of the Fukushima I Nuclear Power Plant (Japan) after the reactor cooling was interrupted by the earthquake and tsunami disaster of March 11, 2011, leading to the Fukushima I nuclear accidents. After venting the hydrogen in the maintenance hall of those three reactors, the mixture of hydrogen with atmospheric oxygen exploded, severely damaging the installations and at least one of the containment buildings. To avoid explosion, the direct venting of hydrogen to the open atmosphere would have been a preferred design option. Now, to prevent the risk of explosion in many pressurized water reactor (PWR) containment buildings, a catalyst-based recombiner is installed that converts hydrogen and oxygen into water at room temperature before the hazard arises. [35]

Space and aeronautic industries

Materials fabricated from zirconium metal and ZrO2 are used in space vehicles where resistance to heat is needed. [19]

High temperature parts such as combustors, blades, and vanes in jet engines and stationary gas turbines are increasingly being protected by thin ceramic layers, usually composed of a mixture of zirconia and yttria. [36]

Positron emission tomography cameras

The isotope 89Zr has been applied to the tracking and quantification of molecular antibodies with positron emission tomography (PET) cameras (a method called "immuno-PET"). Immuno-PET has reached a maturity of technical development and is now entering the phase of wide-scale clinical applications. [37] [38] [39] Until recently, radiolabeling with 89Zr was a complicated procedure requiring multiple steps. In 2001–2003 an improved multistep procedure was developed using a succinylated derivative of desferrioxamine B (N-sucDf) as a bifunctional chelate, [40] and a better way of binding 89Zr to mAbs was reported in 2009. The new method is fast, consists of only two steps, and uses two widely available ingredients: 89Zr and the appropriate chelate. [41] On-going developments also include the use of siderophore derivatives to bind 89Zr(IV). [42] [43]

Medication uses

Zirconium-bearing compounds are used in many biomedical applications, including dental implants and crowns, knee and hip replacements, middle-ear ossicular chain reconstruction, and other restorative and prosthetic devices. [44]

Zirconium binds urea, a property that has been utilized extensively to the benefit of patients with chronic kidney disease. [44] For example, zirconium is a primary component of the sorbent column dependent dialysate regeneration and recirculation system known as the REDY system, which was first introduced in 1973. More than 2,000,000 dialysis treatments have been performed using the sorbent column in the REDY system. [45] Although the REDY system was superseded in the 1990s by less expensive alternatives, new sorbent-based dialysis systems are being evaluated and approved by the U.S. Food and Drug Administration (FDA). Renal Solutions developed the DIALISORB technology, a portable, low water dialysis system. Also, developmental versions of a Wearable Artificial Kidney have incorporated sorbent-based technologies.[ citation needed ]

Sodium zirconium cyclosilicate is used by mouth in the treatment of hyperkalemia. It is a selective sorbent designed to trap potassium ions in preference to other ions throughout the gastrointestinal tract. [46]

A mixture of monomeric and polymeric Zr4+ and Al3+ complexes with hydroxide, chloride and glycine, called Aluminium zirconium tetrachlorohydrex gly or AZG, is used in a preparation as an antiperspirant in many deodorant products. It is selected for its ability to obstruct pores in the skin and prevent sweat from leaving the body.

Defunct applications

Zirconium carbonate (3ZrO2·CO2·H2O) was used in lotions to treat poison ivy but was discontinued because it occasionally caused skin reactions. [6]

Safety

Zirconium
Hazards
NFPA 704 (fire diamond)
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilHealth code 0: Exposure under fire conditions would offer no hazard beyond that of ordinary combustible material. E.g. sodium chlorideReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no codeZirconium
1
0
0

Although zirconium has no known biological role, the human body contains, on average, 250 milligrams of zirconium, and daily intake is approximately 4.15 milligrams (3.5 milligrams from food and 0.65 milligrams from water), depending on dietary habits. [47] Zirconium is widely distributed in nature and is found in all biological systems, for example: 2.86 μg/g in whole wheat, 3.09 μg/g in brown rice, 0.55 μg/g in spinach, 1.23 μg/g in eggs, and 0.86 μg/g in ground beef. [47] Further, zirconium is commonly used in commercial products (e.g. deodorant sticks, aerosol antiperspirants) and also in water purification (e.g. control of phosphorus pollution, bacteria- and pyrogen-contaminated water). [44]

Short-term exposure to zirconium powder can cause irritation, but only contact with the eyes requires medical attention. [48] Persistent exposure to zirconium tetrachloride results in increased mortality in rats and guinea pigs and a decrease of blood hemoglobin and red blood cell s in dogs. However, in a study of 20 rats given a standard diet containing ~4% zirconium oxide, there were no adverse effects on growth rate, blood and urine parameters, or mortality. [49] The U.S. Occupational Safety and Health Administration (OSHA) legal limit (permissible exposure limit) for zirconium exposure is 5 mg/m3 over an 8-hour workday. The National Institute for Occupational Safety and Health (NIOSH) recommended exposure limit (REL) is 5 mg/m3 over an 8-hour workday and a short term limit of 10 mg/m3. At levels of 25 mg/m3, zirconium is immediately dangerous to life and health. [50] However, zirconium is not considered an industrial health hazard. [44] Furthermore, reports of zirconium-related adverse reactions are rare and, in general, rigorous cause-and-effect relationships have not been established. [44] No evidence has been validated that zirconium is carcinogenic or genotoxic. [51]

Among the numerous radioactive isotopes of zirconium, 93Zr is among the most common. It is released as a product of 235U, mainly in nuclear plants and during nuclear weapons tests in the 1950s and 1960s. It has a very long half-life (1.53 million years), its decay emits only low energy radiations, and it is not considered as highly hazardous.[ citation needed ]

See also

Related Research Articles

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Group 4 is a group of elements in the periodic table. It contains the elements titanium (Ti), zirconium (Zr), hafnium (Hf) and rutherfordium (Rf). This group lies in the d-block of the periodic table. The group itself has not acquired a trivial name; it belongs to the broader grouping of the transition metals.

Thorium dioxide Chemical compound

Thorium dioxide (ThO2), also called thorium(IV) oxide, is a crystalline solid, often white or yellow in color. Also known as thoria, it is produced mainly as a by-product of lanthanide and uranium production. Thorianite is the name of the mineralogical form of thorium dioxide. It is moderately rare and crystallizes in an isometric system. The melting point of thorium oxide is 3300 °C – the highest of all known oxides. Only a few elements (including tungsten and carbon) and a few compounds (including tantalum carbide) have higher melting points. All thorium compounds are radioactive because there are no stable isotopes of thorium.

Neutron capture Atomic nuclear process

Neutron capture is a nuclear reaction in which an atomic nucleus and one or more neutrons collide and merge to form a heavier nucleus. Since neutrons have no electric charge, they can enter a nucleus more easily than positively charged protons, which are repelled electrostatically.

Naturally occurring zirconium (40Zr) is composed of four stable isotopes (of which one may in the future be found radioactive), and one very long-lived radioisotope (96Zr), a primordial nuclide that decays via double beta decay with an observed half-life of 2.0×1019 years; it can also undergo single beta decay, which is not yet observed, but the theoretically predicted value of t1/2 is 2.4×1020 years. The second most stable radioisotope is 93Zr, which has a half-life of 1.53 million years. Twenty-seven other radioisotopes have been observed. All have half-lives less than a day except for 95Zr (64.02 days), 88Zr (83.4 days), and 89Zr (78.41 hours). The primary decay mode is electron capture for isotopes lighter than 92Zr, and the primary mode for heavier isotopes is beta decay.

Hafnium tetrachloride chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Zirconium alloys are solid solutions of zirconium or other metals, a common subgroup having the trade mark Zircaloy. Zirconium has very low absorption cross-section of thermal neutrons, high hardness, ductility and corrosion resistance. One of the main uses of zirconium alloys is in nuclear technology, as cladding of fuel rods in nuclear reactors, especially water reactors. A typical composition of nuclear-grade zirconium alloys is more than 95 weight percent zirconium and less than 2% of tin, niobium, iron, chromium, nickel and other metals, which are added to improve mechanical properties and corrosion resistance.

Zirconium hydride

Zirconium hydride describes an alloy made by combining zirconium and hydrogen. Hydrogen acts as a hardening agent, preventing dislocations in the zirconium atom crystal lattice from sliding past one another. Varying the amount of hydrogen and the form of its presence in the zirconium hydride controls qualities such as the hardness, ductility, and tensile strength of the resulting zirconium hydride. Zirconium hydride with increased hydrogen content can be made harder and stronger than zirconium, but such zirconium hydride is also less ductile than zirconium.

Zirconium carbide chemical compound

Zirconium carbide (ZrC) is an extremely hard refractory ceramic material, commercially used in tool bits for cutting tools. It is usually processed by sintering.

Zirconium(IV) chloride chemical compound

Zirconium(IV) chloride, also known as zirconium tetrachloride, (ZrCl4) is an inorganic compound frequently used as a precursor to other compounds of zirconium. This white high-melting solid hydrolyzes rapidly in humid air.

Zirconium silicate, also zirconium orthosilicate, ZrSiO4, is a chemical compound, a silicate of zirconium. It occurs in nature as zircon, a silicate mineral. Powdered zirconium silicate is also known as zircon flour.

Zirconium tetrafluoride chemical compound

Zirconium(IV) fluoride (ZrF4) is an inorganic chemical compound. It is a component of ZBLAN fluoride glass. It is insoluble in water. It is the main component of fluorozirconate glasses.

This page describes how uranium dioxide nuclear fuel behaves during both normal nuclear reactor operation and under reactor accident conditions, such as overheating. Work in this area is often very expensive to conduct, and so has often been performed on a collaborative basis between groups of countries, usually under the aegis of the Organisation for Economic Co-operation and Development's Committee on the Safety of Nuclear Installations (CSNI).

Organozirconium chemistry

Organozirconium compounds are organometallic compounds containing a carbon to zirconium chemical bond. Organozirconium chemistry is the corresponding science exploring properties, structure and reactivity of these compounds. Organozirconium compounds have been widely studied, in part because they are useful catalysts in Ziegler-Natta polymerization.

Ultra-high-temperature ceramics (UHTCs) are a class of refractory ceramics that offer excellent stability at temperatures exceeding 2000 °C being investigated as possible thermal protection system (TPS) materials, coatings for materials subjected to high temperatures, and bulk materials for heating elements. Broadly speaking, UHTCs are borides, carbides, nitrides, and oxides of early transition metals. Current efforts have focused on heavy, early transition metal borides such as hafnium diboride (HfB2) and zirconium diboride (ZrB2); additional UHTCs under investigation for TPS applications include hafnium nitride (HfN), zirconium nitride (ZrN), titanium carbide (TiC), titanium nitride (TiN), thorium dioxide (ThO2), tantalum carbide (TaC) and their associated composites.

Zirconium nitrate chemical compound

Zirconium nitrate is a volatile anhydrous transition metal nitrate of zirconium with formula Zr(NO3)4. It has alternate names of zirconium tetranitrate, or zirconium(IV) nitrate.

Titanium in zircon geothermometry

Titanium in zircon geothermometry is a form of a geothermometry technique by which the crystallization temperature of a zircon crystal can be estimated by the amount of titanium atoms which can only be found in the crystal lattice. In zircon crystals, titanium is commonly incorporated, replacing similarly charged zirconium and silicon atoms. This process is relatively unaffected by pressure and highly temperature dependent, with the amount of titanium incorporated rising exponentially with temperature, making this an accurate geothermometry method. This measurement of titanium in zircons can be used to estimate the cooling temperatures of the crystal and infer conditions during which it crystallized. Compositional changes in the crystals growth rings can be used to estimate the thermodynamic history of the entire crystal. This method is useful as it can be combined with radiometric dating techniques that are commonly used with zircon crystals, to correlate quantitative temperature measurements with specific absolute ages. This technique can be used to estimate early Earth conditions, determine metamorphic facies, or to determine the source of detrital zircons, among other uses.

References

  1. Meija, Juris; et al. (2016). "Atomic weights of the elements 2013 (IUPAC Technical Report)". Pure and Applied Chemistry . 88 (3): 265–91. doi: 10.1515/pac-2015-0305 .
  2. "Zirconium: zirconium(I) fluoride compound data". OpenMOPAC.net. Retrieved 2007-12-10.
  3. Lide, D. R., ed. (2005). "Magnetic susceptibility of the elements and inorganic compounds". CRC Handbook of Chemistry and Physics (PDF) (86th ed.). Boca Raton (FL): CRC Press. ISBN   0-8493-0486-5.
  4. Pritychenko, Boris; Tretyak, V. "Adopted Double Beta Decay Data". National Nuclear Data Center. Retrieved 2008-02-11.
  5. Harper, Douglas. "zircon". Online Etymology Dictionary .
  6. 1 2 3 4 Emsley, John (2001). Nature's Building Blocks. Oxford: Oxford University Press. pp. 506–510. ISBN   978-0-19-850341-5.
  7. 1 2 3 4 5 "Zirconium". How Products Are Made. Advameg Inc. 2007. Retrieved 2008-03-26.
  8. 1 2 3 4 5 6 7 8 9 10 11 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.
  9. Considine, Glenn D., ed. (2005). "Zirconium". Van Nostrand's Encyclopedia of Chemistry. New York: Wylie-Interscience. pp. 1778–1779. ISBN   978-0-471-61525-5.
  10. Winter, Mark (2007). "Electronegativity (Pauling)". University of Sheffield. Retrieved 2008-03-05.
  11. Schnell I & Albers RC (January 2006). "Zirconium under pressure: phase transitions and thermodynamics". Journal of Physics: Condensed Matter. 18 (5): 16. Bibcode:2006JPCM...18.1483S. doi:10.1088/0953-8984/18/5/001.
  12. 1 2 3 Audi, Georges; Bersillon, Olivier; Blachot, Jean; Wapstra, Aaldert Hendrik (2003), "The NUBASE evaluation of nuclear and decay properties", Nuclear Physics A, 729: 3–128, Bibcode:2003NuPhA.729....3A, doi:10.1016/j.nuclphysa.2003.11.001
  13. 1 2 Peterson, John; MacDonell, Margaret (2007). "Zirconium". Radiological and Chemical Fact Sheets to Support Health Risk Analyses for Contaminated Areas (PDF). Argonne National Laboratory. pp. 64–65. Archived from the original (PDF) on 2008-05-28. Retrieved 2008-02-26.
  14. "Zirconium and Hafnium - Mineral resources" (PDF). 2014.
  15. 1 2 "Zirconium and Hafnium" (PDF). Mineral Commodity Summaries: 192–193. January 2008. Retrieved 2008-02-24.
  16. Ralph, Jolyon & Ralph, Ida (2008). "Minerals that include Zr". Mindat.org. Retrieved 2008-02-23.
  17. Callaghan, R. (2008-02-21). "Zirconium and Hafnium Statistics and Information". US Geological Survey. Retrieved 2008-02-24.
  18. 1 2 3 4 Nielsen, Ralph (2005) "Zirconium and Zirconium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a28_543
  19. 1 2 3 Stwertka, Albert (1996). A Guide to the Elements. Oxford University Press. pp. 117–119. ISBN   978-0-19-508083-4.
  20. Brady, George Stuart; Clauser, Henry R. & Vaccari, John A. (24 July 2002). Materials handbook: an encyclopedia for managers, technical professionals, purchasing and production managers, technicians, and supervisors. McGraw-Hill Professional. pp. 1063–. ISBN   978-0-07-136076-0 . Retrieved 2011-03-18.
  21. Zardiackas, Lyle D.; Kraay, Matthew J. & Freese, Howard L. (1 January 2006). Titanium, niobium, zirconium and tantalum for medical and surgical applications. ASTM International. pp. 21–. ISBN   978-0-8031-3497-3 . Retrieved 2011-03-18.
  22. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  23. 1 2 "Zirconia". AZoM.com. 2008. Retrieved 2008-03-17.
  24. Gauthier, V.; Dettenwanger, F.; Schütze, M. (2002-04-10). "Oxidation behavior of γ-TiAl coated with zirconia thermal barriers". Intermetallics. 10 (7): 667–674. doi:10.1016/S0966-9795(02)00036-5.
  25. Keenan, P. C. (1954). "Classification of the S-Type Stars". Astrophysical Journal . 120: 484–505. Bibcode:1954ApJ...120..484K. doi:10.1086/145937.
  26. MSDS sheet for Duratec 400, DuBois Chemicals, Inc.
  27. Wilkinson, G.; Birmingham, J. M. (1954). "Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta". J. Am. Chem. Soc. 76 (17): 4281–4284. doi:10.1021/ja01646a008.Rouhi, A. Maureen (2004-04-19). "Organozirconium Chemistry Arrives". Science & Technology. 82 (16): 36–39. doi:10.1021/cen-v082n015.p035. ISSN   0009-2347 . Retrieved 2008-03-17.
  28. Wailes, P. C. & Weigold, H. (1970). "Hydrido complexes of zirconium I. Preparation". Journal of Organometallic Chemistry . 24 (2): 405–411. doi:10.1016/S0022-328X(00)80281-8.
  29. Hart, D. W. & 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.
  30. 1 2 Krebs, Robert E. (1998). The History and Use of our Earth's Chemical Elements . Westport, Connecticut: Greenwood Press. pp. 98–100. ISBN   978-0-313-30123-0.
  31. Hedrick, James B. (1998). "Zirconium". Metal Prices in the United States through 1998 (PDF). US Geological Survey. pp. 175–178. Retrieved 2008-02-26.
  32. "Fine ceramics - zirconia". Kyocera Inc.
  33. Kosanke, Kenneth L.; Kosanke, Bonnie J. (1999), "Pyrotechnic Spark Generation", Journal of Pyrotechnics: 49–62, ISBN   978-1-889526-12-6
  34. Gillon, Luc (1979). Le nucléaire en question, Gembloux Duculot, French edition.
  35. Arnould, F.; Bachellerie, E.; Auglaire, M.; Boeck, D.; Braillard, O.; Eckardt, B.; Ferroni, F.; Moffett, R.; Van Goethem, G. (2001). "State of the art on hydrogen passive autocatalytic recombiner" (PDF). 9th International Conference on Nuclear Engineering, Nice, France, 8–12 April 2001. Retrieved 4 March 2018.
  36. 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.
  37. Heuveling, Derek A.; Visser, Gerard W. M.; Baclayon, Marian; Roos, Wouter H.; Wuite, Gijs J. L.; Hoekstra, Otto S.; Leemans, C. René; de Bree, Remco; van Dongen, Guus A. M. S. (2011). "89Zr-Nanocolloidal Albumin–Based PET/CT Lymphoscintigraphy for Sentinel Node Detection in Head and Neck Cancer: Preclinical Results" (PDF). The Journal of Nuclear Medicine. 52 (10): 1580–1584. doi:10.2967/jnumed.111.089557. PMID   21890880.
  38. van Rij, Catharina M.; Sharkey, Robert M.; Goldenberg, David M.; Frielink, Cathelijne; Molkenboer, Janneke D. M.; Franssen, Gerben M.; van Weerden, Wietske M.; Oyen, Wim J. G.; Boerman, Otto C. (2011). "Imaging of Prostate Cancer with Immuno-PET and Immuno-SPECT Using a Radiolabeled Anti-EGP-1 Monoclonal Antibody". The Journal of Nuclear Medicine. 52 (10): 1601–1607. doi:10.2967/jnumed.110.086520. PMID   21865288.
  39. Ruggiero, A.; Holland, J. P.; Hudolin, T.; Shenker, L.; Koulova, A.; Bander, N. H.; Lewis, J. S.; Grimm, J. (2011). "Targeting the internal epitope of prostate-specific membrane antigen with 89Zr-7E11 immuno-PET". The Journal of Nuclear Medicine. 52 (10): 1608–15. doi:10.2967/jnumed.111.092098. PMC   3537833 . PMID   21908391.
  40. Verel, I.; Visser, G. W.; Boellaard, R.; Stigter-Van Walsum, M.; Snow, G. B.; Van Dongen, G. A. (2003). "89Zr immuno-PET: Comprehensive procedures for the production of 89Zr-labeled monoclonal antibodies" (PDF). J Nucl Med. 44 (8): 1271–81. PMID   12902418.
  41. Perk, L, "The Future of Immuno-PET in Drug Development Zirconium-89 and Iodine-124 as Key Factors in Molecular Imaging" Archived April 25, 2012, at the Wayback Machine , Amsterdam, Cyclotron, 2009.
  42. Deri, Melissa A.; Ponnala, Shashikanth; Zeglis, Brian M.; Pohl, Gabor; Dannenberg, J. J.; Lewis, Jason S.; Francesconi, Lynn C. (2014-06-12). "Alternative Chelator for 89Zr Radiopharmaceuticals: Radiolabeling and Evaluation of 3,4,3-(LI-1,2-HOPO)". Journal of Medicinal Chemistry. 57 (11): 4849–4860. doi:10.1021/jm500389b. ISSN   0022-2623. PMC   4059252 . PMID   24814511.
  43. Captain, Ilya; Deblonde, Gauthier J.-P.; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Rostan, Emeline; Ralston, Corie Y.; Strong, Roland K.; Abergel, Rebecca J. (2016-11-21). "Engineered Recognition of Tetravalent Zirconium and Thorium by Chelator–Protein Systems: Toward Flexible Radiotherapy and Imaging Platforms". Inorganic Chemistry. 55 (22): 11930–11936. doi:10.1021/acs.inorgchem.6b02041. ISSN   0020-1669. PMID   27802058.
  44. 1 2 3 4 5 Lee DBN, Roberts M, Bluchel CG, Odell RA. (2010) Zirconium: Biomedical and nephrological applications. ASAIO J 56(6):550-556.
  45. Ash SR. Sorbents in treatment of uremia: A short history and a great future. 2009 Semin Dial 22: 615-622
  46. Ingelfinger, Julie R. (2015). "A New Era for the Treatment of Hyperkalemia?". New England Journal of Medicine. 372 (3): 275–7. doi:10.1056/NEJMe1414112. PMID   25415806.
  47. 1 2 Schroeder, Henry A.; Balassa, Joseph J. (May 1966). "Abnormal trace metals in man: zirconium". Journal of Chronic Diseases. 19 (5): 573–586. doi:10.1016/0021-9681(66)90095-6. PMID   5338082.
  48. "Zirconium". International Chemical Safety Cards. International Labour Organization. October 2004. Retrieved 2008-03-30.
  49. Zirconium and its compounds 1999. The MAK Collection for Occupational Health and Safety. 224–236
  50. "CDC - NIOSH Pocket Guide to Chemical Hazards - Zirconium compounds (as Zr)". www.cdc.gov. Retrieved 2015-11-27.
  51. toxnet.nlm.nih.gov/cgi-bin/sis/search/f?./temp/~EHRbeW:2