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Zirconium
Zirconium is a chemical element with the symbol
Zr and atomic number 40. The name zirconium is Zirconium, 40Zr
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 Zirconium
dioxide and zirconocene dichloride, respectively. Five Pronunciation /zərˈkoʊniəm/
isotopes occur naturally, three of which are stable. (zər-KOH-nee-əm)
Zirconium compounds have no known biological role.
Appearance silvery white
Standard atomic 91.224(2)[1]
weight Ar, std(Zr)
Contents
Zirconium in the periodic table
Characteristics
Isotopes H H Ti
LB BCNOFN ↑
Occurrence SM
PCS
ASPSCA Zr
TVCMIrCNCZGGASBK ↓
RSY ZNMTRRPSCInTATIoX
Production CBLCPNPSEGTDHETYLHTTROIrPGMTLBPAR Hf
FRATPUNPACBCEFMNLRDSBHMDRCNFMLTO
Separation of zirconium and hafnium yttrium ← zirconium → niobium

Compounds Atomic number (Z) 40

Oxides, nitrides, and carbides Group group 4
Halides and pseudohalides Period period 5
Organic derivatives
Block d-block
History Element category Transition metal
Applications
Electron [Kr] 4d2 5s2
Compounds
configuration
Metal
Nuclear applications Electrons per shell 2, 8, 18, 10, 2

Space and aeronautic industries Physical properties

Positron emission tomography cameras Phase at STP solid
Medication uses Melting point 2128 K (1855 °C, 3371 °F)
Defunct applications Boiling point 4650 K (4377 °C, 7911 °F)
Safety Density (near r.t.) 6.52 g/cm3
See also when liquid (at m.p.) 5.8 g/cm3
References Heat of fusion 14 kJ/mol
External links
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Heat of 591 kJ/mol

vaporization
Characteristics Molar heat capacity 25.36 J/(mol·K)
Vapor pressure
Zirconium is a lustrous, greyish-
white, soft, ductile, malleable P (Pa) 1 10 100 1k 10 k 100 k
metal that is solid at room
at T (K) 2639 2891 3197 3575 4053 4678
temperature, though it is hard and
Zirconium rod brittle at lesser purities.[6][7] In Atomic properties
powder form, zirconium is highly
flammable, but the solid form is Oxidation states −2, +1,[2] +2, +3, +4
much less prone to ignition. Zirconium is highly (an amphoteric oxide)
resistant to corrosion by alkalis, acids, salt water and Electronegativity Pauling scale: 1.33
other agents.[8] However, it will dissolve in
Ionization energies 1st: 640.1 kJ/mol
hydrochloric and sulfuric acid, especially when
fluorine is present.[9] Alloys with zinc are magnetic at 2nd: 1270 kJ/mol
less than 35 K.[8] 3rd: 2218 kJ/mol

The melting point of zirconium is 1855 °C (3371 °F), Atomic radius empirical: 160 pm
and the boiling point is 4371 °C (7900 °F).[8] Covalent radius 175±7 pm
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, Spectral lines of zirconium
lanthanum, and actinium.[10] Other properties

At room temperature zirconium exhibits a Natural occurrence primordial

hexagonally close-packed crystal structure, α-Zr, Crystal structure hexagonal close-packed (hcp)
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]
Speed of sound 3800 m/s (at 20 °C)
thin rod
Isotopes
Thermal expansion 5.7 µm/(m·K) (at 25 °C)
Naturally occurring zirconium is composed of five Thermal 22.6 W/(m·K)
isotopes. 90Zr, 91Zr, 92Zr and 94Zr are stable, conductivity
although 94Zr is predicted to undergo double beta Electrical resistivity 421 nΩ·m (at 20 °C)
decay (not observed experimentally) with a half-life
of more than 1.10×1017 years. 96Zr has a half-life of Magnetic ordering paramagnetic[3]
2.4×1019 years, and is the longest-lived radioisotope Young's modulus 88 GPa
of zirconium. Of these natural isotopes, 90Zr is the Shear modulus 33 GPa
most common, making up 51.45% of all zirconium.
96Zr is the least common, comprising only 2.80% of Bulk modulus 91.1 GPa
zirconium.[12] Poisson ratio 0.34
Mohs hardness 5.0
Twenty-eight artificial isotopes of zirconium have
been synthesized, ranging in atomic mass from 78 to Vickers hardness 820–1800 MPa
110. 93Zr is the longest-lived artificial isotope, with a Brinell hardness 638–1880 MPa
half-life of 1.53×106 years. 110Zr, the heaviest isotope CAS Number 7440-67-7
of zirconium, is the most radioactive, with an
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estimated half-life of 30 milliseconds. Radioactive History

isotopes at or above mass number 93 decay by Naming after zircon, zargun ‫زرﮔون‬
electron emission, whereas those at or below 89
meaning "gold-colored".
decay by positron emission. The only exception is
88Zr, which decays by electron capture.[12] Discovery Martin Heinrich Klaproth
(1789)
Five isotopes of zirconium also exist as metastable First isolation Jöns Jakob Berzelius (1824)
isomers: 83mZr, 85mZr, 89mZr, 90m1Zr, 90m2Zr and
91mZr. Of these, 90m2Zr has the shortest half-life at Main isotopes of zirconium
131 nanoseconds. 89mZr is the longest lived with a Iso- Abun- Half-life Decay Pro-
half-life of 4.161 minutes.[12] tope dance (t1/2) mode duct

ε 88Y
Occurrence 88Zr syn 83.4 d
γ –

ε 89Y

89Zr syn 78.4 h β+ 89Y

γ –

90Zr 51.45% stable

91Zr 11.22% stable

92Zr 17.15% stable

World production trend of zirconium
mineral concentrates 93Zr trace 1.53×106 y β− 93Nb

94Zr 17.38% stable

Zirconium has a concentration of about 130 mg/kg
96Zr 2.80% 2.0×1019 y[4] β−β− 96Mo
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]

EPR spectroscopy has been used in investigations of the unusual 3+ valence state of zirconium. The EPR
spectrum of Zr3+, which has been initially observed as a parasitic signal in Fe‐doped single crystals of
ScPO4, was definitively identified by preparing single crystals of ScPO4 doped with isotopically enriched
(94.6%)91Zr. Single crystals of LuPO4 and YPO4 doped with both naturally abundant and isotopically
enriched Zr have also been grown and investigated.[17]

Production
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Zirconium is a by-product of the mining and processing of the

titanium minerals ilmenite and rutile, as well as tin mining.[18] 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 more expensive than zircon because the reduction processes
are costly[15] Zirconium output in 2005

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,[19] 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.[20] Several separation schemes are in use.[19] 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.[21] The separated hafnium can be used for
reactor control rods.[22]

Compounds
Like other transition metals, zirconium forms a wide range of inorganic compounds and coordination
complexes.[23] 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

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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.[24] These
properties make zirconia useful as a thermal barrier coating,[25] although it is also a common diamond
substitute.[24] Zirconium monoxide, ZrO, is also known and S-type stars are recognised by detection of
its emission lines in the visual spectrum.[26]

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.[27]

Organic derivatives

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.[28] Schwartz's reagent, prepared in 1970 by P. C. Wailes and
H. Weigold,[29] is a metallocene used in organic synthesis for
transformations of alkenes and alkynes.[30]

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.
Zirconocene dichloride, a
History representative
organozirconium compound

The zirconium-containing mineral zircon and related minerals (jargoon,

hyacinth, jacinth, ligure) were mentioned in biblical writings.[8][20] The mineral was not known to
contain a new element until 1789,[31] 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

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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][32]

ZrCl4 + 2 Mg → Zr + 2 MgCl2

Applications
Approximately 900,000 tonnes of zirconium ores were mined in 1995, mostly as zircon.[19]

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.[33] 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.[31]

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.[34]

Nuclear applications

Cladding for nuclear reactor fuels consumes about 1% of the zirconium supply,[19] 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.
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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.[35] 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.[36] In some commercial nuclear plants, hydrogen
igniters have been installed to burn the hydrogen as it is generated, before it can reach a concentration
and volume to create a dangerous explosion.[37]

Zirconium is a constituent of the uranium zirconium hydride (UZrH) nuclear fuel used in TRIGA
reactors.

Space and aeronautic industries

Materials fabricated from zirconium metal and ZrO2 are used in space vehicles where resistance to heat
is needed.[20]

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.[38]

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.[39][40][41] 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,[42] 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.[43] On-going developments also include the use
of siderophore derivatives to bind 89Zr(IV).[44][45]

Medication uses

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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.[46]

Zirconium binds urea, a property that has been utilized extensively to the benefit of patients with chronic
kidney disease.[46] 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.[47] 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.

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.[48]

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
Although zirconium has no known biological role, the human body Zirconium
contains, on average, 250 milligrams of zirconium, and daily intake
Hazards
is approximately 4.15 milligrams (3.5 milligrams from food and 0.65
milligrams from water), depending on dietary habits.[49] Zirconium NFPA 704
is widely distributed in nature and is found in all biological systems, (fire diamond)
1
for example: 2.86 μg/g in whole wheat, 3.09 μg/g in brown rice, 0.55
0 0
μg/g in spinach, 1.23 μg/g in eggs, and 0.86 μg/g in ground beef.[49]
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).[46]

Short-term exposure to zirconium powder can cause irritation, but only contact with the eyes requires
medical attention.[50] Persistent exposure to zirconium tetrachloride results in increased mortality in
rats and guinea pigs and a decrease of blood hemoglobin and red blood cells 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.[51] 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

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of 25 mg/m3, zirconium is immediately dangerous to life and health.[52] However, zirconium is not
considered an industrial health hazard.[46] Furthermore, reports of zirconium-related adverse reactions
are rare and, in general, rigorous cause-and-effect relationships have not been established.[46] No
evidence has been validated that zirconium is carcinogenic or genotoxic.[53]

Among the numerous radioactive isotopes of zirconium, 93Zr is among the most common. It is released
as a product of nuclear fission of 235U and 239Pu, mainly in nuclear power 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.[54]

See also
Zirconium alloys
Zirconia light

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External links
Chemistry in its element podcast (http://www.rsc.org/chemistryworld/podcast/element.asp) (MP3)
from the Royal Society of Chemistry's Chemistry World: Zirconium (http://www.rsc.org/images/CIIE_z
irconium_remix2_48k_tcm18-117340.mp3)
Zirconium (http://www.periodicvideos.com/videos/040.htm) at The Periodic Table of Videos
(University of Nottingham)

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