Tungsten

Physical properties In its raw form, tungsten is a hard steel-grey metal that is often brittle and hard to work. Purified, monocrystalline tungsten retains its hardness (which exceeds that of many steels), and becomes malleable enough that it can be worked easily. Although carbon remains solid at higher temperatures than tungsten, carbon sublimes at atmospheric pressure instead of melting, so it has no melting point. Moreover, tungsten's most stable crystal phase does not exhibit any high-pressure-induced structural transformations for pressures up to at least 364 gigapascals. 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. 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. on average, this yields about two alpha decays of 180W per gram of natural tungsten per year. This rate is equivalent to a specific activity of roughly 63 micro-becquerel per kilogram. This rate of decay is orders of magnitude lower than that observed in carbon or potassium as found on earth, which likewise contain small amounts of long-lived radioactive isotopes. Bismuth was long thought to be non-radioactive, but (its longest lived isotope) actually decays with a half-life of years or about a factor 10 slower than . However, due to naturally occurring bismuth being 100% , its specific activity is actually higher than that of natural tungsten at 3 milli-becquerel per kilogram. The other naturally occurring isotopes of tungsten have not been observed to decay, constraining their half-lives to be at least . Another 34 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. Tungsten typically combines with oxygen to form the yellow tungstic oxide, WO3, which dissolves in aqueous alkaline solutions to form tungstate ions, . 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). Further acidification produces the very soluble metatungstate anion, , 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. In gaseous form, tungsten forms the diatomic species W2. These molecules feature a sextuple bond between tungsten atoms — the highest known bond order among stable atoms. ==History==

In 1781, Carl Wilhelm Scheele discovered that a new acid, tungstic acid, could be made from scheelite (at the time called tungsten). Scheele and Torbern Bergman suggested that it might be possible to obtain a new metal by reducing this acid. 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. Now tungsten is used in many more applications such as aircraft and motorsport ballast weights, darts, anti-vibration tooling, and sporting equipment. Tungsten is unique amongst the elements in that it has been the subject of patent proceedings. In 1928, a US court rejected General Electric's attempt to patent it, overturning granted in 1913 to William D. Coolidge. It is suggested that remnants of wolfram have been found in what may have been the garden of the astronomer and alchemist Tycho Brahe. Etymology The name tungsten (which means in Swedish and was the old Swedish name for the mineral scheelite and other minerals of similar density) is used in English, French, and many other languages as the name of the element, but wolfram (or volfram) is used in most European (especially Germanic 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 (), the name given to tungsten by Johan Gottschalk Wallerius in 1747. This, in turn, derives from Latin , the name Georg Agricola used for the mineral in 1546, which translates into English as and is a reference to the large amounts of tin consumed by the mineral during its extraction, as though the mineral devoured it like a wolf. This naming follows a tradition of colorful names miners from the Ore Mountains would give various minerals, out of a superstition that certain ones that looked as if they contained then-known valuable metals but when extracted were somehow "hexed". Cobalt (cf. Kobold), pitchblende (cf. German for ) and nickel (cf. "Old Nick") derive their names from the same miners' idiom. ==Occurrence==

Tungsten has thus far not been found in nature in its pure form. Instead, tungsten is found mainly in the minerals wolframite and scheelite. ==Chemical compounds==

Tungsten forms chemical compounds in oxidation states from −2 to +6. 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). 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 its 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 and octahedral . ==Production==

forms an important part of the country's economy. Reserves 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 to 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. 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. Within the EU, the Austrian Felbertal scheelite deposit is one of the few producing tungsten mines. Portugal is one of Europe's main tungsten producers, with 121 kt of contained tungsten in mineral concentrates from 1910 to 2020, accounting for roughly 3.3% of the global production. Tungsten is considered to be a conflict mineral due to the unethical mining practices observed in the Democratic Republic of the Congo. South Korea's Sangdong mine, one of the world's largest tungsten mines with 7,890,000 tonnes of high-grade tungsten reportedly buried, was closed in 1994 due to low profitability but has since re-registered mining rights and is scheduled to resume activities in 2024. Extraction 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 or pyrolytic decomposition: The prices are usually quoted for tungsten concentrate or WO3. ==Applications==

jewelry 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 is a form of 3D printing and allows creating complex three-dimensional shapes. Industrial Tungsten is mainly used in the production of hard materials based on tungsten carbide (WC), one of the hardest carbides. 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, dies, milling and turning tools used by the metalworking, woodworking, mining, petroleum and construction industries. 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 heat resistance of tungsten can contribute to useful 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 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. 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. Permanent magnets 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 it is present in steel in these proportions, it stabilizes the martensite phase, which has greater ferromagnetism than the ferrite (iron) phase due to its greater resistance to magnetic domain wall motion. Military Tungsten, usually alloyed with nickel, 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 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, caused in part by the Wolfram Crisis, limited their use. 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 containing catalysts are promising for epoxidation, oxidation, and hydrogenolysis reactions. Tungsten heteropoly acids are key component of multifunctional catalysts. Tungstates can be used as photocatalyst, while the tungsten sulfide as electrocatalyst. Niche uses Applications requiring its high density include weights, counterweights, ballast keels for yachts, tail ballast for commercial aircraft, rotor weights for civil and military helicopters, and as ballast in race cars for NASCAR and Formula One. Being slightly less than twice the density, tungsten is seen as an alternative (albeit more expensive) to lead fishing sinkers. 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 artificial flies (tungsten beads allow the fly to sink rapidly). Tungsten is also used as a heavy bolt to lower the rate of fire of the SWD M11/9 sub-machine gun from 1300 RPM to 700 RPM. Some string instrument strings incorporates tungsten. Tungsten is used as an absorber on the electron telescope on the Cosmic Ray System of the two Voyager spacecraft. 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. 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 incandescent light bulb, cathode-ray tube, and vacuum tube filaments, heating elements, and rocket engine nozzles. torch 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. Tungsten is used in producing vibration motors, also known as mobile vibrators. These motors are integral components that provide tactile feedback to users, alerting them to incoming calls, messages, and notifications. Tungsten's high density, hardness, and wear resistance property helps to endure the high-speed rotational vibrations these motors generate. 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. Fusion power Due to its high melting point and good erosion resistance, tungsten is a lead candidate for the most exposed sections of the plasma-facing inner wall of nuclear fusion reactors. Tungsten, as a plasma-facing component material, features exceptionally low tritium retention through co-deposition and implantation, which enhances safety by minimizing radioactive inventory, improves fuel efficiency by making more fuel available for fusion reactions, and supports operational continuity by reducing the need for frequent fuel removal from surfaces. It will be used as the plasma-facing material of the divertor in the ITER reactor, and is currently in use in the JET test reactor. ==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 molybdopterin-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 salts may be used as biological copper chelation chemicals, similar to the tetrathiomolybdates.