Zirconium
Zirconium is a chemical element with symbol Zr and atomic number 40.
The name zirconium is taken from the name of the mineral zircon, the
most important source of zirconium. The word zircon comes from the
Persian word zargun زرگون, meaning "gold-colored".[5] It is a
lustrous, grey-white, strong transition metal that resembles hafnium
and, to a lesser extent, titanium.
Zirconium
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
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
Zirconium compounds have no
known biological role.
Contents
1 Characteristics
1.1 Isotopes
1.2 Occurrence
2 Production
2.1 Separation of zirconium and hafnium
3 Compounds
3.1 Oxides, nitrides and carbides
3.2 Halides and pseudohalides
3.3 Organic derivatives
4 History
5 Applications
5.1 Compounds
5.2 Metal
5.2.1 Nuclear applications
5.2.2 Space and aeronautic industries
5.3
Positron emission
Positron emission tomography cameras
5.4 Biomedical applications
5.5 Defunct applications
6 Safety
7 See also
8 References
9 External links
Characteristics[edit]
Zirconium
Zirconium rod
Zirconium
Zirconium is a lustrous, greyish-white, soft, ductile and 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
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]
The melting point of zirconium is 1855 °C (3371 °F), and
the boiling point is 4371 °C (7900 °F).[8]
Zirconium
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]
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
Zirconium exists in the
β-phase until the melting point.[11]
Isotopes[edit]
Main article: Isotopes of zirconium
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]
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]
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[edit]
See also: Category:
Zirconium
Zirconium minerals.
World production trend of zirconium mineral concentrates
Zirconium
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
Zircon resources exceed 60 million tonnes worldwide[15]
and annual worldwide zirconium production is approximately 900,000
tonnes.[13]
Zirconium
Zirconium also occurs in more than 140 other minerals,
including the commercially useful ores baddeleyite and kosnarite.[16]
Zirconium
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[edit]
Zirconium
Zirconium output in 2005
Zirconium
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
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[edit]
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
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
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[edit]
See also: the categories
Zirconium
Zirconium compounds and
Zirconium
Zirconium minerals.
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[edit]
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
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
Zirconium tungstate has the unusual property of shrinking in all
dimensions when heated, whereas most other substances expand when
heated.[8]
Zirconyl chloride
.jpg/440px-ZrOCl2_(octahydrate).jpg)
Zirconyl chloride is a rare water-soluble zirconium complex
with the relatively complicated formula [Zr4(OH)12(H2O)16]Cl8.
Zirconium carbide
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
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[edit]
All four common halides are known, ZrF4, ZrCl4, ZrBr4, 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[edit]
Zirconocene dichloride, a representative organozirconium compound
Organozirconium chemistry
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
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[edit]
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
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[edit]
Approximately 900,000 tonnes of Zr ores were mined in 1995, mostly as
zircon.[18]
Compounds[edit]
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
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
Zircon (ZrSiO4) and the cubic zirconia
(ZrO2) are cut into gemstones for use in jewelry.
Zirconia
Zirconia is a component in some abrasives, such as grinding wheels and
sandpaper.[30]
Metal[edit]
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 nano-particles as pyrophoric material in explosive
weapons such as the BLU-97/B Combined Effects Bomb.
Nuclear applications[edit]
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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.[33] 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 recombinator is installed that converts hydrogen and
oxygen into water at room temperature before the hazard
arises.[citation needed]
Space and aeronautic industries[edit]
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.[34]
Positron emission
Positron emission tomography cameras[edit]
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.[35][36][37] 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,[38] 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.[39]
Biomedical applications[edit]
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.[40]
Zirconium
Zirconium binds urea, a property that has been utilized extensively to
the benefit of patients with chronic kidney disease.[40] 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.[41] 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
Sodium zirconium cyclosilicate is under investigation for oral therapy
in the treatment of hyperkalemia. It is a highly selective oral
sorbent designed specifically to trap potassium ions in preference to
other ions throughout the gastrointestinal tract.[42]
Defunct applications[edit]
Zirconium
Zirconium carbonate (3ZrO2·CO2·H2O) was used in lotions to treat
poison ivy but was discontinued because it occasionally caused skin
reactions.[6]
Safety[edit]
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.[43]
Zirconium
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.[44] 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).[40]
Short-term exposure to zirconium powder can cause irritation, but only
contact with the eyes requires medical attention.[45] 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.[46] The U.S.
Occupational Safety and Health Administration
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.[47] However, zirconium is not considered an industrial
health hazard.[40] Furthermore, reports of zirconium-related adverse
reactions are rare and, in general, rigorous cause-and-effect
relationships have not been established.[40] No evidence has been
validated that zirconium is carcinogenic or genotoxic.[48]
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[edit]
Chemistry portal
Zirconium
Zirconium alloys
Zirconia
Zirconia light
Books
View or order collections of articles
Zirconium
Period 5 elements
Group 4 elements
Chemical elements (sorted alphabetically)
Chemical elements (sorted by number)
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immuno-PET". The Journal of Nuclear Medicine. 52 (10): 1608–15.
doi:10.2967/jnumed.111.092098. PMC 3537833 .
PMID 21908391.
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v
t
e
Periodic table
Periodic table (Large cells)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
1
H
He
2
Li
Be
B
C
N
O
F
Ne
3
Na
Mg
Al
Si
P
S
Cl
Ar
4
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
5
Rb
Sr
Y
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
I
Xe
6
Cs
Ba
La
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Hg
Tl
Pb
Bi
Po
At
Rn
7
Fr
Ra
Ac
Th
Pa
U
Np
Pu
Am
Cm
Bk
Cf
Es
Fm
Md
No
Lr
Rf
Db
Sg
Bh
Hs
Mt
Ds
Rg
Cn
Nh
Fl
Mc
Lv
Ts
Og
Alkali metal
Alkaline earth metal
Lanthanide
Actinide
Transition metal
Post-transition metal
Metalloid
Polyatomic nonmetal
Diatomic nonmetal
Noble gas
Unknown
chemical
properties
v
t
e
Zirconium
Zirconium compounds
Zr(II)
ZrB2
ZrH2
ZrSi2
Zr(III)
ZrN
ZrCl3
Zr(IV)
ZrBr4
ZrC
ZrCl4
ZrF4
ZrI4
Zr(NO3)4
ZrOCl2
Zr(OH)4
ZrO2
ZrS2
Zr(SO4)2
ZrSiO4
Zr(WO4)2
Organozirconium(IV)
Zr(acac)4
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