Tungsten | |||||||||||||||||||||||||||||||||||||||||
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Pronunciation | /ˈtʌŋstən/ | ||||||||||||||||||||||||||||||||||||||||
Alternative name | wolfram, pronounced: /ˈwʊlfrəm/ (WUUL-frəm) | ||||||||||||||||||||||||||||||||||||||||
Appearance | grayish white, lustrous | ||||||||||||||||||||||||||||||||||||||||
Standard atomic weight Ar, std(W) | 183.84(1) | ||||||||||||||||||||||||||||||||||||||||
Tungsten in the periodic table | |||||||||||||||||||||||||||||||||||||||||
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Atomic number (Z) | 74 | ||||||||||||||||||||||||||||||||||||||||
Group | group 6 | ||||||||||||||||||||||||||||||||||||||||
Period | period 6 | ||||||||||||||||||||||||||||||||||||||||
Block | d-block | ||||||||||||||||||||||||||||||||||||||||
Element category | transition metal | ||||||||||||||||||||||||||||||||||||||||
Electron configuration | [Xe] 4f14 5d4 6s2 | ||||||||||||||||||||||||||||||||||||||||
Electrons per shell
| 2, 8, 18, 32, 12, 2 | ||||||||||||||||||||||||||||||||||||||||
Physical properties | |||||||||||||||||||||||||||||||||||||||||
Phase at STP | solid | ||||||||||||||||||||||||||||||||||||||||
Melting point | 3695 K (3422 °C, 6192 °F) | ||||||||||||||||||||||||||||||||||||||||
Boiling point | 6203 K (5930 °C, 10706 °F) | ||||||||||||||||||||||||||||||||||||||||
Density (near r.t.) | 19.3 g/cm3 | ||||||||||||||||||||||||||||||||||||||||
when liquid (at m.p.) | 17.6 g/cm3 | ||||||||||||||||||||||||||||||||||||||||
Heat of fusion | 52.31 kJ/mol | ||||||||||||||||||||||||||||||||||||||||
Heat of vaporization | 774 kJ/mol | ||||||||||||||||||||||||||||||||||||||||
Molar heat capacity | 24.27 J/(mol·K) | ||||||||||||||||||||||||||||||||||||||||
Vapor pressure
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Atomic properties | |||||||||||||||||||||||||||||||||||||||||
Oxidation states | −4, −2, −1, 0, +1, +2, +3, +4, +5, +6 (a mildly acidic oxide) | ||||||||||||||||||||||||||||||||||||||||
Electronegativity | Pauling scale: 2.36 | ||||||||||||||||||||||||||||||||||||||||
Ionization energies |
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Atomic radius | empirical: 139 pm | ||||||||||||||||||||||||||||||||||||||||
Covalent radius | 162±7 pm | ||||||||||||||||||||||||||||||||||||||||
Spectral lines of tungsten | |||||||||||||||||||||||||||||||||||||||||
Other properties | |||||||||||||||||||||||||||||||||||||||||
Natural occurrence | primordial | ||||||||||||||||||||||||||||||||||||||||
Crystal structure | body-centered cubic (bcc) | ||||||||||||||||||||||||||||||||||||||||
Speed of sound thin rod | 4620 m/s (at r.t.) (annealed) | ||||||||||||||||||||||||||||||||||||||||
Thermal expansion | 4.5 µm/(m·K) (at 25 °C) | ||||||||||||||||||||||||||||||||||||||||
Thermal conductivity | 173 W/(m·K) | ||||||||||||||||||||||||||||||||||||||||
Electrical resistivity | 52.8 nΩ·m (at 20 °C) | ||||||||||||||||||||||||||||||||||||||||
Magnetic ordering | paramagnetic | ||||||||||||||||||||||||||||||||||||||||
Magnetic susceptibility | +59.0·10−6 cm3/mol (298 K) | ||||||||||||||||||||||||||||||||||||||||
Young's modulus | 411 GPa | ||||||||||||||||||||||||||||||||||||||||
Shear modulus | 161 GPa | ||||||||||||||||||||||||||||||||||||||||
Bulk modulus | 310 GPa | ||||||||||||||||||||||||||||||||||||||||
Poisson ratio | 0.28 | ||||||||||||||||||||||||||||||||||||||||
Mohs hardness | 7.5 | ||||||||||||||||||||||||||||||||||||||||
Vickers hardness | 3430–4600 MPa | ||||||||||||||||||||||||||||||||||||||||
Brinell hardness | 2000–4000 MPa | ||||||||||||||||||||||||||||||||||||||||
CAS Number | 7440-33-7 | ||||||||||||||||||||||||||||||||||||||||
History | |||||||||||||||||||||||||||||||||||||||||
Discovery | Carl Wilhelm Scheele (1781) | ||||||||||||||||||||||||||||||||||||||||
First isolation | Juan José Elhuyar and Fausto Elhuyar (1783) | ||||||||||||||||||||||||||||||||||||||||
Named by | Torbern Bergman (1781) | ||||||||||||||||||||||||||||||||||||||||
Main isotopes of tungsten | |||||||||||||||||||||||||||||||||||||||||
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Tungsten, or wolfram, is a chemical element with symbol W and atomic number 74. The name tungsten comes from the former Swedish name for the tungstate mineral scheelite, tung sten or "heavy stone". Tungsten is a rare metal found naturally on Earth almost exclusively combined with other elements in chemical compounds rather than alone. It was identified as a new element in 1781 and first isolated as a metal in 1783. Its important ores include wolframite and scheelite.
The free element is remarkable for its robustness, especially the fact that it has the highest melting point of all the elements discovered, melting at 3422 °C (6192 °F, 3695 K). It also has the highest boiling point, at 5930 °C (10706 °F, 6203 K). Its density is 19.3 times that of water, comparable to that of uranium and gold, and much higher (about 1.7 times) than that of lead. Polycrystalline tungsten is an intrinsically brittle and hard material (under standard conditions, when uncombined), making it difficult to work. However, pure single-crystalline tungsten is more ductile and can be cut with a hard-steel hacksaw.
Tungsten's many alloys have numerous applications, including incandescent light bulb filaments, X-ray tubes (as both the filament and target), electrodes in gas tungsten arc welding, superalloys, and radiation shielding. Tungsten's hardness and high density give it military applications in penetrating projectiles. Tungsten compounds are also often used as industrial catalysts.
Tungsten is the only metal from the third transition series that is known to occur in biomolecules that are found in a few species of bacteria and archaea. It is the heaviest element known to be essential to any living organism. However, tungsten interferes with molybdenum and copper metabolism and is somewhat toxic to more familiar forms of animal life.
Characteristics
Physical properties
In its raw form, tungsten is a hard steel-grey metal that is often brittle and hard to work. If made very pure, tungsten retains its hardness (which exceeds that of many steels), and becomes malleable enough that it can be worked easily. It is worked by forging, drawing, or extruding. Tungsten objects are also commonly formed by sintering.
Of all metals in pure form, tungsten has the highest melting point (3422 °C, 6192 °F), lowest vapor pressure (at temperatures above 1650 °C, 3000 °F), and the highest tensile strength. Although carbon remains solid at higher temperatures than tungsten, carbon sublimes at atmospheric pressure instead of melting, so it has no melting point. Tungsten has the lowest coefficient of thermal expansion of any pure metal. The low thermal expansion and high melting point and tensile strength of tungsten originate from strong covalent bonds formed between tungsten atoms by the 5d electrons.
Alloying small quantities of tungsten with steel greatly increases its toughness.
Tungsten exists in two major crystalline forms: α and β. The former has a body-centered cubic structure and is the more stable form. The structure of the β phase is called A15 cubic; it is metastable,
but can coexist with the α phase at ambient conditions owing to
non-equilibrium synthesis or stabilization by impurities. Contrary to
the α phase which crystallizes in isometric grains, the β form exhibits a
columnar habit. The α phase has one third of the electrical resistivity and a much lower superconducting transition temperature TC relative to the β phase: ca. 0.015 K vs. 1–4 K; mixing the two phases allows obtaining intermediate TC values. The TC value can also be raised by alloying tungsten with another metal (e.g. 7.9 K for W-Tc). Such tungsten alloys are sometimes used in low-temperature superconducting circuits.
Isotopes
Naturally occurring tungsten consists of four stable isotopes (182W, 183W, 184W, and 186W) and one very long-lived radioisotope, 180W. Theoretically, all five can decay into isotopes of element 72 (hafnium) by alpha emission, but only 180W has been observed to do so, with a half-life of (1.8±0.2)×1018 years; on average, this yields about two alpha decays of 180W per gram of natural tungsten per year. The other naturally occurring isotopes have not been observed to decay, constraining their half-lives to be at least 4 × 1021 years.
Another 30 artificial radioisotopes of tungsten have been characterized, the most stable of which are 181W with a half-life of 121.2 days, 185W with a half-life of 75.1 days, 188W with a half-life of 69.4 days, 178W with a half-life of 21.6 days, and 187W with a half-life of 23.72 h. All of the remaining radioactive isotopes have half-lives of less than 3 hours, and most of these have half-lives below 8 minutes. Tungsten also has 11 meta states, with the most stable being 179mW (t1/2 6.4 minutes).
Chemical properties
The most common formal oxidation state of tungsten is +6, but it exhibits all oxidation states from −2 to +6. Tungsten typically combines with oxygen to form the yellow tungstic oxide, WO3, which dissolves in aqueous alkaline solutions to form tungstate ions, WO2−
4.
4.
Tungsten carbides (W2C and WC) are produced by heating powdered tungsten with carbon. W2C is resistant to chemical attack, although it reacts strongly with chlorine to form tungsten hexachloride (WCl6).
In aqueous solution, tungstate gives the heteropoly acids and polyoxometalate anions under neutral and acidic conditions. As tungstate is progressively treated with acid, it first yields the soluble, metastable "paratungstate A" anion, W
7O6–
24, which over time converts to the less soluble "paratungstate B" anion, H
2W
12O10–
42. Further acidification produces the very soluble metatungstate anion, H
2W
12O6–
40, after which equilibrium is reached. The metatungstate ion exists as a symmetric cluster of twelve tungsten-oxygen octahedra known as the Keggin anion. Many other polyoxometalate anions exist as metastable species. The inclusion of a different atom such as phosphorus in place of the two central hydrogens in metatungstate produces a wide variety of heteropoly acids, such as phosphotungstic acid H3PW12O40.
7O6–
24, which over time converts to the less soluble "paratungstate B" anion, H
2W
12O10–
42. Further acidification produces the very soluble metatungstate anion, H
2W
12O6–
40, after which equilibrium is reached. The metatungstate ion exists as a symmetric cluster of twelve tungsten-oxygen octahedra known as the Keggin anion. Many other polyoxometalate anions exist as metastable species. The inclusion of a different atom such as phosphorus in place of the two central hydrogens in metatungstate produces a wide variety of heteropoly acids, such as phosphotungstic acid H3PW12O40.
Tungsten trioxide can form intercalation compounds with alkali metals. These are known as bronzes; an example is sodium tungsten bronze.
History
In 1781, Carl Wilhelm Scheele discovered that a new acid, tungstic acid, could be made from scheelite (at the time named tungsten). Scheele and Torbern Bergman suggested that it might be possible to obtain a new metal by reducing this acid. In 1783, José and Fausto Elhuyar found an acid made from wolframite that was identical to tungstic acid. Later that year, at the Royal Basque Society in the town of Bergara, Spain, the brothers succeeded in isolating tungsten by reduction of this acid with charcoal, and they are credited with the discovery of the element (they called it "wolfram" or "volfram").
The strategic value of tungsten came to notice in the early 20th
century. British authorities acted in 1912 to free the Carrock mine from
the German owned Cumbrian Mining Company and, during World War I, restrict German access elsewhere. In World War II,
tungsten played a more significant role in background political
dealings. Portugal, as the main European source of the element, was put
under pressure from both sides, because of its deposits of wolframite
ore at Panasqueira.
Tungsten's desirable properties such as resistance to high
temperatures, its hardness and density, and its strengthening of alloys
made it an important raw material for the arms industry, both as a constituent of weapons and equipment and employed in production itself, e.g., in tungsten carbide cutting tools for machining steel.
Etymology
The name "tungsten" (from the Swedish tung sten, "heavy stone") is used in English, French, and many other languages as the name of the element, but not in the Nordic countries. "Tungsten" was the old Swedish name for the mineral scheelite.
"Wolfram" (or "volfram") is used in most European (especially Germanic,
Spanish and Slavic) languages and is derived from the mineral wolframite, which is the origin of the chemical symbol W. The name "wolframite" is derived from German "wolf rahm" ("wolf soot" or "wolf cream"), the name given to tungsten by Johan Gottschalk Wallerius in 1747. This, in turn, derives from Latin "lupi spuma", the name Georg Agricola used for the element in 1546, which translates into English as "wolf's froth" and is a reference to the large amounts of tin consumed by the mineral during its extraction.
Occurrence
Tungsten is found mainly in the minerals wolframite (iron–manganese tungstate (Fe,Mn)WO4, which is a solid solution of the two minerals ferberite FeWO4, and hübnerite MnWO4) and scheelite (calcium tungstate (CaWO4). Other tungsten minerals range in their level of abundance from moderate to very rare, and have almost no economical value.
Chemical compounds
Tungsten forms chemical compounds in oxidation states from -II to VI.
Higher oxidation states, always as oxides, are relevant to its
terrestrial occurrence and its biological roles, mid-level oxidation
states are often associated with metal clusters, and very low oxidation states are typically associated with CO complexes. The chemistries of tungsten and molybdenum show strong similarities to each other, as well as contrasts with their lighter congener, chromium.
The relative rarity of tungsten(III), for example, contrasts with the
pervasiveness of the chromium(III) compounds. The highest oxidation
state is seen in tungsten(VI) oxide (WO3). Molybdenum trioxide,
which is volatile at high temperatures, is the precursor to virtually
all other Mo compounds as well as alloys. Tungsten(VI) oxide is soluble
in aqueous base, forming tungstate (WO42−). This oxyanion condenses at lower pH values, forming polyoxotungstates.
The broad range of oxidation states of tungsten is reflected in it various chlorides:
- Tungsten(II) chloride, which exists as the hexamer W6Cl12
- Tungsten(III) chloride, which exists as the hexamer W6Cl18
- Tungsten(IV) chloride, WCl4, a black solid, which adopts a polymeric structure.
- Tungsten(V) chloride WCl5, a black solid which adopts a dimeric structure.
- Tungsten(VI) chloride WCl6, which contrasts with the instability of MoCl6.
Organotungsten compounds are numerous and also span a range of oxidation states. Notable examples include the trigonal prismatic W(CH3)6 and octahedral W(CO)6.
Production
The world's reserves of tungsten are 3,200,000 tonnes; they are mostly located in China (1,800,000 t), Canada (290,000 t),
Russia (160,000 t), Vietnam (95,000 t) and Bolivia. As of 2017, China,
Vietnam and Russia are the leading suppliers with 79,000, 7,200 and
3,100 tonnes, respectively. Canada had ceased production in late 2015
due the closure of its sole tungsten mine. Meanwhile Vietnam had
significantly increased its output in the 2010s, owing to the major
optimization of its domestic refining operations, and overtook Russia
and Bolivia.
China remains the world's leader not only in production, but also
in export and consumption of tungsten products. The tungsten production
gradually increases outside China because of the rising demand.
Meanwhile its supply by China is strictly regulated by the Chinese
Government, which fights illegal mining and excessive pollution
originating from mining and refining processes.
Tungsten is considered to be a conflict mineral due to the unethical mining practices observed in the Democratic Republic of the Congo.
There is a large deposit of tungsten ore on the edge of Dartmoor in the United Kingdom, which was exploited during World War I and World War II as the Hemerdon Mine. Following increases in tungsten prices, this mine was reactivated in 2014, but ceased activities in 2018.
Tungsten is extracted from its ores in several stages. The ore is eventually converted to tungsten(VI) oxide (WO3), which is heated with hydrogen or carbon to produce powdered tungsten. Because of tungsten's high melting point, it is not commercially feasible to cast tungsten ingots. Instead, powdered tungsten is mixed with small amounts of powdered nickel or other metals, and sintered. During the sintering process, the nickel diffuses into the tungsten, producing an alloy.
Tungsten can also be extracted by hydrogen reduction of WF6:
- WF6 + 3 H2 → W + 6 HF
- WF6 → W + 3 F2 (ΔHr = +)
Tungsten is not traded as a futures contract and cannot be tracked on exchanges like the London Metal Exchange. The prices are usually quoted for tungsten concentrate or WO3.
Applications
Approximately half of the tungsten is consumed for the production of hard materials – namely tungsten carbide – with the remaining major use being in alloys and steels. Less than 10% is used in other chemical compounds. Because of the high ductile-brittle transition temperature of tungsten, its products are conventionally manufactured through powder metallurgy, spark plasma sintering, chemical vapor deposition, hot isostatic pressing, and thermoplastic routes. A more flexible manufacturing alternative is selective laser melting, which allows creating complex three-dimensional shapes.
Hard materials
Tungsten is mainly used in the production of hard materials based on tungsten carbide, one of the hardest carbides, with a melting point of 2770 °C. WC is an efficient electrical conductor, but W2C is less so. WC is used to make wear-resistant abrasives, and "carbide" cutting tools such as knives, drills, circular saws, milling and turning tools used by the metalworking, woodworking, mining, petroleum and construction industries. Carbide tooling is actually a ceramic/metal composite, where metallic cobalt acts as a binding (matrix) material to hold the WC particles in place. This type of industrial use accounts for about 60% of current tungsten consumption.
The jewelry industry makes rings of sintered tungsten carbide, tungsten carbide/metal composites, and also metallic tungsten.
WC/metal composite rings use nickel as the metal matrix in place of
cobalt because it takes a higher luster when polished. Sometimes
manufacturers or retailers refer to tungsten carbide as a metal, but it
is a ceramic.
Because of tungsten carbide's hardness, rings made of this material are
extremely abrasion resistant, and will hold a burnished finish longer
than rings made of metallic tungsten. Tungsten carbide rings are
brittle, however, and may crack under a sharp blow.
Alloys
The hardness and density of tungsten are applied in obtaining heavy metal alloys. A good example is high speed steel, which can contain as much as 18% tungsten. Tungsten's high melting point makes tungsten a good material for applications like rocket nozzles, for example in the UGM-27 Polaris submarine-launched ballistic missile.
Tungsten alloys are used in a wide range of different applications,
including the aerospace and automotive industries and radiation
shielding. Superalloys containing tungsten, such as Hastelloy and Stellite, are used in turbine blades and wear-resistant parts and coatings.
Quenched (martensitic) tungsten steel (approx. 5.5% to 7.0% W
with 0.5% to 0.7% C) was used for making hard permanent magnets, due to
its high remanence and coercivity, as noted by John Hopkinson
(1849–1898) as early as 1886. The magnetic properties of a metal or an
alloy are very sensitive to microstructure. For example, while the
element tungsten is not ferromagnetic (but iron is), when present in steel in these proportions, it stabilizes the martensite phase, which has an enhanced ferromagnetism, as compared to the ferrite (iron) phase, due to its greater resistance to magnetic domain wall motion.
Tungsten's heat resistance makes it useful in arc welding
applications when combined with another highly-conductive metal such as
silver or copper. The silver or copper provides the necessary
conductivity and the tungsten allows the welding rod to withstand the
high temperatures of the arc welding environment.
Armaments
Tungsten, usually alloyed with nickel and iron or cobalt to form heavy alloys, is used in kinetic energy penetrators as an alternative to depleted uranium, in applications where uranium's radioactivity is problematic even in depleted form, or where uranium's additional pyrophoric
properties are not desired (for example, in ordinary small arms bullets
designed to penetrate body armor). Similarly, tungsten alloys have also
been used in cannon shells, grenades and missiles,
to create supersonic shrapnel. Germany used tungsten during World War
II to produce shells for anti-tank gun designs using the Gerlich squeeze bore
principle to achieve very high muzzle velocity and enhanced armor
penetration from comparatively small caliber and light weight field
artillery. The weapons were highly effective but a shortage of tungsten
used in the shell core limited that effectiveness.
Tungsten has also been used in Dense Inert Metal Explosives, which use it as dense powder to reduce collateral damage while increasing the lethality of explosives within a small radius.
Chemical applications
Tungsten(IV) sulfide is a high temperature lubricant and is a component of catalysts for hydrodesulfurization. MoS2 is more commonly used for such applications.
Tungsten oxides are used in ceramic glazes and calcium/magnesium tungstates are used widely in fluorescent lighting. Crystal tungstates are used as scintillation detectors in nuclear physics and nuclear medicine. Other salts that contain tungsten are used in the chemical and tanning industries.
Tungsten oxide (WO3) is incorporated into selective catalytic reduction (SCR) catalysts found in coal-fired power plants. These catalysts convert nitrogen oxides (NOx) to nitrogen (N2) and water (H2O) using ammonia (NH3). The tungsten oxide helps with the physical strength of the catalyst and extends catalyst life.
Niche uses
Applications requiring its high density include weights, counterweights, ballast keels for yachts, tail ballast for commercial aircraft, and as ballast in race cars for NASCAR and Formula One. In Formula One nowadays, a much more advanced material is utilized: a tungsten alloy trademarked, Densamet. Depleted uranium
is also used for these purposes, due to similarly high density.
Seventy-five-kg blocks of tungsten were used as "cruise balance mass
devices" on the entry vehicle portion of the 2012 Mars Science Laboratory spacecraft. It is an ideal material to use as a dolly for riveting,
where the mass necessary for good results can be achieved in a compact
bar. High-density alloys of tungsten with nickel, copper or iron are
used in high-quality darts (to allow for a smaller diameter and thus tighter groupings) or for fishing lures (tungsten beads allow the fly to sink rapidly). Tungsten has seen use recently in nozzles for 3D printing; the high wear resistance and thermal conductivity of tungsten carbide improves the printing of abrasive filaments. Some cello
C strings are wound with tungsten. The extra density gives this string
more projection and often cellists will buy just this string and use it
with three strings from a different set. Tungsten is used as an absorber on the electron telescope on the Cosmic Ray System of the two Voyager spacecraft.
Sodium tungstate is used in Folin-Ciocalteu's reagent, a mixture of different chemicals used in the "Lowry Assay" for protein content analysis.
Gold substitution
Its density, similar to that of gold, allows tungsten to be used in jewelry as an alternative to gold or platinum. Metallic tungsten is hypoallergenic, and is harder than gold alloys (though not as hard as tungsten carbide), making it useful for rings that will resist scratching, especially in designs with a brushed finish.
Because the density is so similar to that of gold (tungsten is
only 0.36% less dense), and its price of the order of one-thousandth,
tungsten can also be used in counterfeiting of gold bars, such as by plating a tungsten bar with gold, which has been observed since the 1980s, or taking an existing gold bar, drilling holes, and replacing the removed gold with tungsten rods.
The densities are not exactly the same, and other properties of gold
and tungsten differ, but gold-plated tungsten will pass superficial
tests.
Gold-plated tungsten is available commercially from China (the main source of tungsten), both in jewelry and as bars.
Electronics
Because it retains its strength at high temperatures and has a high melting point, elemental tungsten is used in many high-temperature applications, such as light bulb, cathode-ray tube, and vacuum tube filaments, heating elements, and rocket engine nozzles.
Its high melting point also makes tungsten suitable for aerospace and
high-temperature uses such as electrical, heating, and welding
applications, notably in the gas tungsten arc welding process (also called tungsten inert gas (TIG) welding).
Because of its conductive properties and relative chemical inertness, tungsten is also used in electrodes, and in the emitter tips in electron-beam instruments that use field emission guns, such as electron microscopes. In electronics, tungsten is used as an interconnect material in integrated circuits, between the silicon dioxide dielectric
material and the transistors. It is used in metallic films, which
replace the wiring used in conventional electronics with a coat of
tungsten (or molybdenum) on silicon.
The electronic structure of tungsten makes it one of the main sources for X-ray targets, and also for shielding from high-energy radiations (such as in the radiopharmaceutical industry for shielding radioactive samples of FDG).
It is also used in gamma imaging as a material from which coded
apertures are made, due to its excellent shielding properties. Tungsten
powder is used as a filler material in plastic composites, which are used as a nontoxic substitute for lead in bullets, shot, and radiation shields. Since this element's thermal expansion is similar to borosilicate glass, it is used for making glass-to-metal seals.
In addition to its high melting point, when tungsten is doped with
potassium, it leads to an increased shape stability (compared to
non-doped tungsten). This ensures that the filament does not sag, and no
undesired changes occur.
Nanowires
Through top-down nanofabrication processes, tungsten nanowires have been fabricated and studied since 2002.
Due to a particularly high surface to volume ratio, the formation of a
surface oxide layer and the single crystal nature of such material, the
mechanical properties differ fundamentally from those of bulk tungsten. Such tungsten nanowires have potential applications in nanoelectronics and importantly as pH probes and gas sensors. In similarity to silicon nanowires, tungsten nanowires are frequently produced from a bulk tungsten precursor followed by a thermal oxidation step to control morphology in terms of length and aspect ratio. Using the Deal–Grove model it is possible to predict the oxidation kinetics of nanowires fabricated through such thermal oxidation processing.
Biological role
Tungsten, at atomic number Z = 74, is the heaviest element known to be biologically functional. It is used by some bacteria and archaea, but not in eukaryotes. For example, enzymes called oxidoreductases use tungsten similarly to molybdenum by using it in a tungsten-pterin complex with molybdopterin
(molybdopterin, despite its name, does not contain molybdenum, but may
complex with either molybdenum or tungsten in use by living organisms).
Tungsten-using enzymes typically reduce carboxylic acids to aldehydes. The tungsten oxidoreductases
may also catalyse oxidations. The first tungsten-requiring enzyme to be
discovered also requires selenium, and in this case the
tungsten-selenium pair may function analogously to the molybdenum-sulfur
pairing of some molybdenum cofactor-requiring enzymes. One of the enzymes in the oxidoreductase family which sometimes employ tungsten (bacterial formate dehydrogenase H) is known to use a selenium-molybdenum version of molybdopterin. Acetylene hydratase is an unusual metalloenzyme
in that it catalyzes a hydration reaction. Two reaction mechanisms have
been proposed, in one of which there is a direct interaction between
the tungsten atom and the C≡C triple bond. Although a tungsten-containing xanthine dehydrogenase
from bacteria has been found to contain tungsten-molydopterin and also
non-protein bound selenium, a tungsten-selenium molybdopterin complex
has not been definitively described.
In soil, tungsten metal oxidizes to the tungstate anion. It can be selectively or non-selectively imported by some prokaryotic organisms and may substitute for molybdate in certain enzymes. Its effect on the action of these enzymes is in some cases inhibitory and in others positive. The soil's chemistry determines how the tungsten polymerizes; alkaline soils cause monomeric tungstates; acidic soils cause polymeric tungstates.
Sodium tungstate and lead have been studied for their effect on earthworms.
Lead was found to be lethal at low levels and sodium tungstate was much
less toxic, but the tungstate completely inhibited their reproductive ability.
Tungsten has been studied as a biological copper metabolic antagonist, in a role similar to the action of molybdenum. It has been found that tetrathiotungstates may be used as biological copper chelation chemicals, similar to the tetrathiomolybdates.
In archaea
Tungsten is essential for some archaea. The following tungsten-utilizing enzymes are known:
- Aldehyde ferredoxin oxidoreductase (AOR) in Thermococcus strain ES-1
- Formaldehyde ferredoxin oxidoreductase (FOR) in Thermococcus litoralis
- Glyceraldehyde-3-phosphate ferredoxin oxidoreductase (GAPOR) in Pyrococcus furiosus
A wtp system is known to selectively transport tungsten in archaea:
- WtpA is tungsten-binding protein of ABC family of transporters
- WptB is a permease
- WtpC is ATPase
Health factors
Because tungsten is a rare metal and its compounds are generally inert, the effects of tungsten on the environment are limited.
The abundance of tungsten in the Earth's crust is thought to be about
1.5 parts per million. It is one of the more rare elements.
It was at first believed to be relatively inert and an only
slightly toxic metal, but beginning in the year 2000, the risk presented
by tungsten alloys, its dusts and particulates to induce cancer and
several other adverse effects in animals as well as humans has been
highlighted from in vitro and in vivo experiments.
The median lethal dose LD50 depends strongly on the animal and the method of administration and varies between 59 mg/kg (intravenous, rabbits) and 5000 mg/kg (tungsten metal powder, intraperitoneal, rats).
People can be exposed to tungsten in the workplace by breathing it in, swallowing it, skin contact, and eye contact. The National Institute for Occupational Safety and Health (NIOSH) has set a recommended exposure limit (REL) of 5 mg/m3 over an 8-hour workday and a short term limit of 10 mg/m3.