Mikhail Melikhov

Бор is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the boron group it has three valence electrons for forming covalent bonds, resulting in many compounds such as boric acid, the mineral sodium borate, and the ultra-hard crystal boron carbide.

Borax crystals

Boron is synthesized entirely by cosmic ray spallation and supernovae and not by stellar nucleosynthesis, so it is a low-abundance element in the Solar System and in the Earth's crust. It constitutes about 0.001 percent by weight of Earth's crust. It is concentrated on Earth by the water-solubility of its more common naturally occurring compounds, the borate minerals. These are mined industrially as evaporites, such as borax and kernite. The largest known deposits are in Turkey, the largest producer of boron minerals.

Elemental boron is a metalloid that is found in small amounts in meteoroids but chemically uncombined boron is not otherwise found naturally on Earth. Industrially, the very pure element is produced with difficulty because of contamination by carbon or other elements that resist removal.Several allotropes exist: amorphous boron is a brown powder; crystalline boron is silvery to black, extremely hard (about 9.5 on the Mohs scale), and a poor electrical conductor at room temperature. The primary use of the element itself is as boron filaments with applications similar to carbon fibers in some high-strength materials.

Boron is primarily used in chemical compounds. About half of all production consumed globally is an additive in fiberglass for insulation and structural materials. The next leading use is in polymers and ceramics in high-strength, lightweight structural and heat-resistant materials. Borosilicate glass is desired for its greater strength and thermal shock resistance than ordinary soda lime glass. As sodium perborate, it is used as a bleach. A small amount is used as a dopant in semiconductors, and reagent intermediates in the synthesis of organic fine chemicals. A few boron-containing organic pharmaceuticals are used or are in study. Natural boron is composed of two stable isotopes, one of which (boron-10) has a number of uses as a neutron-capturing agent.

The intersection of boron with biology is very small. Consensus on it as essential for mammalian life is lacking. Borates have low toxicity in mammals (similar to table salt) but are more toxic to arthropods and are occasionally used as insecticides. Boron-containing organic antibiotics are known. Although only traces are required, it is an essential plant nutrient.

Sassolite

History

The word boron was coined from borax, the mineral from which it was isolated, by analogy with carbon, which boron resembles chemically. Borax in its mineral form (then known as tincal) first saw use as a glaze, beginning in China circa 300 AD. Some crude borax traveled westward, and was apparently mentioned by the alchemist Jabir ibn Hayyan around 700 AD. Marco Polo brought some glazes back to Italy in the 13th century. Georgius Agricola, in around 1600 AD, reported the use of borax as a flux in metallurgy. In 1777, boric acid was recognized in the hot springs (soffioni) near Florence, Italy, at which point it became known as sal sedativum, with ostensible medical benefits. The mineral was named sassolite, after Sasso Pisano in Italy. Sasso was the main source of European borax from 1827 to 1872, when American sources replaced it. Boron compounds were relatively rarely used until the late 1800s when Francis Marion Smith's Pacific Coast Borax Company first popularized and produced them in volume at low cost.

Boron was not recognized as an element until it was isolated by Sir Humphry Davy and by Joseph Louis Gay-Lussac and Louis Jacques Thénard. In 1808 Davy observed that electric current sent through a solution of borates produced a brown precipitate on one of the electrodes. In his subsequent experiments, he used potassium to reduce boric acid instead of electrolysis. He produced enough boron to confirm a new element and named it boracium. Gay-Lussac and Thénard used iron to reduce boric acid at high temperatures. By oxidizing boron with air, they showed that boric acid is its oxidation product. Jöns Jacob Berzelius identified it as an element in 1824. Pure boron was arguably first produced by the American chemist Ezekiel Weintraub in 1909.

Preparation of elemental boron in the laboratory

The earliest routes to elemental boron involved the reduction of boric oxide with metals such as magnesium or aluminium. However, the product is almost always contaminated with borides of those metals.[citation needed] Pure boron can be prepared by reducing volatile boron halides with hydrogen at high temperatures. Ultrapure boron for use in the semiconductor industry is produced by the decomposition of diborane at high temperatures and then further purified by the zone melting or Czochralski processes.

The production of boron compounds does not involve the formation of elemental boron, but exploits the convenient availability of borates.

Borosilicate glassware. Displayed are two beakers and a test tube

Characteristics

Boron is similar to carbon in its capability to form stable covalently bonded molecular networks. Even nominally disordered (amorphous) boron contains regular boron icosahedra which are bonded randomly to each other without long-range order. Crystalline boron is a very hard, black material with a melting point of above 2000 °C. It forms four major allotropes: α-rhombohedral and β-rhombohedral (α-R and β-R), γ-orthorhombic (γ) and β-tetragonal (β-T). All four phases are stable at ambient conditions, and β-rhombohedral is the most common and stable. An α-tetragonal phase also exists (α-T), but is very difficult to produce without significant contamination. Most of the phases are based on B12 icosahedra, but the γ phase can be described as a rocksalt-type arrangement of the icosahedra and B2 atomic pairs. It can be produced by compressing other boron phases to 12–20 GPa and heating to 1500–1800 °C; it remains stable after releasing the temperature and pressure. The β-T phase is produced at similar pressures, but higher temperatures of 1800–2200 °C. The α-T and β-T phases might coexist at ambient conditions, with the β-T phase being the more stable. Compressing boron above 160 GPa produces a boron phase with an as yet unknown structure, and this phase is a superconductor at temperatures below 6–12 K. Borospherene (fullerene-like B40 molecules) and borophene.

Chemistry of the element

Elemental boron is rare and poorly studied because the pure material is extremely difficult to prepare. Most studies of "boron" involve samples that contain small amounts of carbon. The chemical behavior of boron resembles that of silicon more than aluminium. Crystalline boron is chemically inert and resistant to attack by boiling hydrofluoric or hydrochloric acid. When finely divided, it is attacked slowly by hot concentrated hydrogen peroxide, hot concentrated nitric acid, hot sulfuric acid or hot mixture of sulfuric and chromic acids.

The rate of oxidation of boron depends on the crystallinity, particle size, purity and temperature. Boron does not react with air at room temperature, but at higher temperatures it burns to form boron trioxide.

4 B + 3 O2 → 2 B2O3

Boron undergoes halogenation to give trihalides; for example,

2 B + 3 Br2 → 2 BBr3

The trichloride in practice is usually made from the oxide.

Atomic structure

Boron is the lightest element having an electron in a p-orbital in its ground state. But, unlike most other p-elements, it rarely obeys the octet rule and usually places only six electrons (in three molecular orbitals) onto its valence shell. Boron is the prototype for the boron group (the IUPAC group 13), although the other members of this group are metals and more typical p-elements (only aluminium to some extent shares boron's aversion to the octet rule).

Chemical compounds

In the most familiar compounds, boron has the formal oxidation state III. These include oxides, sulfides, nitrides, and halides.

The trihalides adopt a planar trigonal structure. These compounds are Lewis acids in that they readily form adducts with electron-pair donors, which are called Lewis bases. For example, fluoride (F−) and boron trifluoride (BF3) combined to give the tetrafluoroborate anion, BF4−. Boron trifluoride is used in the petrochemical industry as a catalyst. The halides react with water to form boric acid.

It is found in nature on Earth almost entirely as various oxides of B(III), often associated with other elements. More than one hundred borate minerals contain boron in oxidation state +3. These minerals resemble silicates in some respect, although it is often found not only in a tetrahedral coordination with oxygen, but also in a trigonal planar configuration. Unlike silicates, boron minerals never contain it with coordination number greater than four. A typical motif is exemplified by the tetraborate anions of the common mineral borax, shown at left. The formal negative charge of the tetrahedral borate center is balanced by metal cations in the minerals, such as the sodium (Na+) in borax. The tourmaline group of borate-silicates is also a very important boron-bearing mineral group, and a number of borosilicates are also known to exist naturally.

Boranes are chemical compounds of boron and hydrogen, with the generic formula of BxHy. These compounds do not occur in nature. Many of the boranes readily oxidise on contact with air, some violently. The parent member BH3 is called borane, but it is known only in the gaseous state, and dimerises to form diborane, B2H6. The larger boranes all consist of boron clusters that are polyhedral, some of which exist as isomers. For example, isomers of B20H26 are based on the fusion of two 10-atom clusters.

The most important boranes are diborane B2H6 and two of its pyrolysis products, pentaborane B5H9 and decaborane B10H14. A large number of anionic boron hydrides are known, e.g. [B12H12]2−.

The formal oxidation number in boranes is positive, and is based on the assumption that hydrogen is counted as −1 as in active metal hydrides. The mean oxidation number for the borons is then simply the ratio of hydrogen to boron in the molecule. For example, in diborane B2H6, the boron oxidation state is +3, but in decaborane B10H14, it is 7/5 or +1.4. In these compounds the oxidation state of boron is often not a whole number.

Main article: Boron nitride

The boron nitrides are notable for the variety of structures that they adopt. They exhibit structures analogous to various allotropes of carbon, including graphite, diamond, and nanotubes. In the diamond-like structure, called cubic boron nitride (tradename Borazon), boron atoms exist in the tetrahedral structure of carbon atoms in diamond, but one in every four B-N bonds can be viewed as a coordinate covalent bond, wherein two electrons are donated by the nitrogen atom which acts as the Lewis base to a bond to the Lewis acidic boron(III) centre. Cubic boron nitride, among other applications, is used as an abrasive, as it has a hardness comparable with diamond (the two substances are able to produce scratches on each other). In the BN compound analogue of graphite, hexagonal boron nitride (h-BN), the positively charged boron and negatively charged nitrogen atoms in each plane lie adjacent to the oppositely charged atom in the next plane. Consequently, graphite and h-BN have very different properties, although both are lubricants, as these planes slip past each other easily. However, h-BN is a relatively poor electrical and thermal conductor in the planar directions.

Organoboron chemistry

A large number of organoboron compounds are known and many are useful in organic synthesis. Many are produced from hydroboration, which employs diborane, B2H6, a simple borane chemical. Organoboron(III) compounds are usually tetrahedral or trigonal planar, for example, tetraphenylborate, [B(C6H5)4]− vs. triphenylborane, B(C6H5)3. However, multiple boron atoms reacting with each other have a tendency to form novel dodecahedral (12-sided) and icosahedral (20-sided) structures composed complete

ly of boron atoms, or with varying numbers of carbon heteroatoms.

Organoboron chemicals have been employed in uses as diverse as boron carbide (see below), a complex very hard ceramic composed of boron-carbon cluster anions and cations, to carboranes, carbon-boron cluster chemistry compounds that can be halogenated to form reactive structures including carborane acid, a superacid. As one example, carboranes form useful molecular moieties that add considerable amounts of boron to other biochemicals in order to synthesize boron-containing compounds for boron neutron capture therapy for cancer.

Compounds of B(I) and B

(II)

As anticipated by its hydride clusters, boron forms a variety of stable compounds with formal oxidation state less than three. B2F4 and B4Cl4 are well characterized.Binary metal-boron compounds, the metal borides, contain boron in negative oxidation states. Illustrative is magnesium diboride (MgB2). Each boron atom has a formal −1 charge and magnesium is assigned a formal charge of +2. In this material, the boron centers are trigonal planar with an extra double bond for each boron, forming sheets akin to the carbon in graphite. However, unlike hexagonal boron nitride, which lacks electrons in the plane of the covalent atoms, the delocalized electrons in magnesium diboride allow it to conduct electricity similar to isoelectronic graphite. In 2001, this material was found to be a high-temperature superconductor. It is a superconductor under active development. A project at CERN to make MgB2 cables has resulted in superconducting test cables able to carry 20,000 amperes for extremely high current distribution applications, such as the contemplated high luminosity version of the large hadron collider.

Certain other metal borides find specialized applications as hard materials for cutting tools. Often the boron in borides has fractional oxidation states, such as −1/3 in calcium hexaboride (CaB6).

From the structural perspective, the most distinctive chemical compounds of boron are the hydrides. Included in this series are the cluster compounds dodecaborate (B

12H2−

12), decaborane (B10H14), and the carboranes such as C2B10H12. Characteristically such compounds contain boron with coordination numbers greater than four. Isotopes

Main article: Isotopes of boron

Boron has two naturally occurring and stable isotopes, 11B (80.1%) and 10B (19.9%). The mass difference results in a wide range of δ11B values, which are defined as a fractional difference between the 11B and 10B and traditionally expressed in parts per thousand, in natural waters ranging from −16 to +59. There are 13 known isotopes of boron, the shortest-lived isotope is 7B which decays through proton emission and alpha decay. It has a half-life of 3.5×10−22 s. Isotopic fractionation of boron is controlled by the exchange reactions of the boron species B(OH)3 and [B(OH)4]−. Boron isotopes are also fractionated during mineral crystallization, during H2O phase changes in hydrothermal systems, and during hydrothermal alteration of rock. The latter effect results in preferential removal of the [10B(OH)4]− ion onto clays. It results in solutions enriched in 11B(OH)3 and therefore may be responsible for the large 11B enrichment in seawater relative to both oceanic crust and continental crust; this difference may act as an isotopic signature.

The exotic 17B exhibits a nuclear halo, i.e. its radius is appreciably larger than that predicted by the liquid drop model.

The 10B isotope is useful for capturing thermal neutrons (see neutron cross section#Typical cross sections). The nuclear industry enriches natural boron to nearly pure 10B. The less-valuable by-product, depleted boron, is nearly pure 11B.

Commercial isotope enrichment

Because of its high neutron cross-section, boron-10 is often used to control fission in nuclear reactors as a neutron-capturing substance. Several industrial-scale enrichment processes have been developed; however, only the fractionated vacuum distillation of the dimethyl ether adduct of boron trifluoride (DME-BF3) and column chromatography of borates are being used.

Enriched boron (boron-10)

Enriched boron or 10B is used in both radiation shielding and is the primary nuclide used in neutron capture therapy of cancer. In the latter ("boron neutron capture therapy" or BNCT), a compound containing 10B is incorporated into a pharmaceutical which is selectively taken up by a malignant tumor and tissues near it. The patient is then treated with a beam of low energy neutrons at a relatively low neutron radiation dose. The neutrons, however, trigger energetic and short-range secondary alpha particle and lithium-7 heavy ion radiation that are products of the boron + neutron nuclear reaction, and this ion radiation additionally bombards the tumor, especially from inside the tumor cells.

In nuclear reactors, 10B is used for reactivity control and in emergency shutdown systems. It can serve either function in the form of borosilicate control rods or as boric acid. In pressurized water reactors, 10B boric acid is added to the reactor coolant when the plant is shut down for refueling. It is then slowly filtered out over many months as fissile material is used up and the fuel becomes less reactive.

In future manned interplanetary spacecraft, 10B has a theoretical role as structural material (as boron fibers or BN nanotube material) which would also serve a special role in the radiation shield. One of the difficulties in dealing with cosmic rays, which are mostly high energy protons, is that some secondary radiation from interaction of cosmic rays and spacecraft materials is high energy spallation neutrons. Such neutrons can be moderated by materials high in light elements, such as polyethylene, but the moderated neutrons continue to be a radiation hazard unless actively absorbed in the shielding. Among light elements that absorb thermal neutrons, 6Li and 10B appear as potential spacecraft structural materials which serve both for mechanical reinforcement and radiation protection.

Depleted boron (boron-11)

Radiation-hardened semiconductors

Cosmic radiation will produce secondary neutrons if it hits spacecraft structures. Those neutrons will be captured in 10B, if it is present in the spacecraft's semiconductors, producing a gamma ray, an alpha particle, and a lithium ion. Those resultant decay products may then irradiate nearby semiconductor "chip" structures, causing data loss (bit flipping, or single event upset). In radiation-hardened semiconductor designs, one countermeasure is to use depleted boron, which is greatly enriched in 11B and contains almost no 10B. This is useful because 11B is largely immune to radiation damage. Depleted boron is a byproduct of the nuclear industry (see above).

Proton-boron fusion

11B is also a candidate as a fuel for aneutronic fusion. When struck by a proton with energy of about 500 keV, it produces three alpha particles and 8.7 MeV of energy. Most other fusion reactions involving hydrogen and helium produce penetrating neutron radiation, which weakens reactor structures and induces long-term radioactivity, thereby endangering operating personnel. However, the alpha particles from 11B fusion can be turned directly into electric power, and all radiation stops as soon as the reactor is turned off.

NMR spectroscopy

Both 10B and 11B possess nuclear spin. The nuclear spin of 10B is 3 and that of 11B is

3

/

2

. These isotopes are, therefore, of use in nuclear magnetic resonance spectroscopy; and spectrometers specially adapted to detecting the boron-11 nuclei are available commercially. The 10B and 11B nuclei also cause splitting in the resonances of attached nuclei.

Occurrence Boron is rare in the Universe and solar system due to trace formation in the Big Bang and in stars. It is formed in minor amounts in cosmic ray spallation nucleosynthesis and may be found uncombined in cosmic dust and meteoroid materials.

In the high oxygen environment of Earth, boron is always found fully oxidized to borate. Boron does not appear on Earth in elemental form. Extremely small traces of elemental boron were detected in Lunar regolith.

Although boron is a relatively rare element in the Earth's crust, representing only 0.001% of the crust mass, it can be highly concentrated by the action of water, in which many borates are soluble. It is found naturally combined in compounds such as borax and boric acid (sometimes found in volcanic spring waters). About a hundred borate minerals are known.

On 5 September 2017, scientists reported that the Curiosity rover detected boron, an essential ingredient for life on Earth, on the planet Mars. Such a finding, along with previous discoveries that water may have been present on ancient Mars, further supports the possible early habitability of Gale Crater on Mars.

Production

Economically important sources of boron are the minerals colemanite, rasorite (kernite), ulexite and tincal. Together these constitute 90% of mined boron-containing ore. The largest global borax deposits known, many still untapped, are in Central and Western Turkey, including the provinces of Eskişehir, Kütahya and Balıkesir. Global proven boron mineral mining reserves exceed one billion metric tonnes, against a yearly production of about four million tonnes.

Turkey and the United States are the largest producers of boron products. Turkey produces about half of the global yearly demand, through Eti Mine Works (Turkish: Eti Maden İşletmeleri) a Turkish state-owned mining and chemicals company focusing on boron products. It holds a government monopoly on the mining of borate minerals in Turkey, which possesses 72% of the world's known deposits. In 2012, it held a 47% share of production of global borate minerals, ahead of its main competitor, Rio Tinto Group.

Almost a quarter (23%) of global boron production comes from the single Rio Tinto Borax Mine (also known as the U.S. Borax Boron Mine) 35°2′34.447″N 117°40′45.412″W near Boron, California.

Market trend

The average cost of crystalline boron is $5/g.Free boron is chiefly used in making boron fibers, where it is deposited by chemical vapor deposition on a tungsten core (see below). Boron fibers are used in lightweight composite applications, such as high strength tapes. This use is a very small fraction of total boron use. Boron is introduced into semiconductors as boron compounds, by ion implantation.

Estimated global consumption of boron (almost entirely as boron compounds) was about 4 million tonnes of B2O3 in 2012. Boron mining and refining capacities are considered to be adequate to meet expected levels of growth through the next decade.

The form in which boron is consumed has changed in recent years. The use of ores like colemanite has declined following concerns over arsenic content. Consumers have moved toward the use of refined borates and boric acid that have a lower pollutant content.

Increasing demand for boric acid has led a number of producers to invest in additional capacity. Turkey's state-owned Eti Mine Works opened a new boric acid plant with the production capacity of 100,000 tonnes per year at Emet in 2003. Rio Tinto Group increased the capacity of its boron plant from 260,000 tonnes per year in 2003 to 310,000 tonnes per year by May 2005, with plans to grow this to 366,000 tonnes per year in 2006. Chinese boron producers have been unable to meet rapidly growing demand for high quality borates. This has led to imports of sodium tetraborate (borax) growing by a hundredfold between 2000 and 2005 and boric acid imports increasing by 28% per year over the same period.

The rise in global demand has been driven by high growth rates in glass fiber, fiberglass and borosilicate glassware production. A rapid increase in the manufacture of reinforcement-grade boron-containing fiberglass in Asia, has offset the development of boron-free reinforcement-grade fiberglass in Europe and the US. The recent rises in energy prices may lead to greater use of insulation-grade fiberglass, with consequent growth in the boron consumption. Roskill Consulting Group forecasts that world demand for boron will grow by 3.4% per year to reach 21 million tonnes by 2010. The highest growth in demand is expected to be in Asia where demand could rise by an average 5.7% per year.

Applications

See also: Boron deficiency (plant disorder) and Boron deficiency (medicine)

Nearly all boron ore extracted from the Earth is destined for refinement into boric acid and sodium tetraborate pentahydrate. In the United States, 70% of the boron is used for the production of glass and ceramics.The major global industrial-scale use of boron compounds (about 46% of end-use) is in production of glass fiber for boron-containing insulating and structural fiberglasses, especially in Asia. Boron is added to the glass as borax pentahydrate or boron oxide, to influence the strength or fluxing qualities of the glass fibers. Another 10% of global boron production is for borosilicate glass as used in high strength glassware. About 15% of global boron is used in boron ceramics, including super-hard materials discussed below. Agriculture consumes 11% of global boron production, and bleaches and detergents about 6%.

Elemental boron fiber

Boron fibers (boron filaments) are high-strength, lightweight materials that are used chiefly for advanced aerospace structures as a component of composite materials, as well as limited production consumer and sporting goods such as golf clubs and fishing rods. The fibers can be produced by chemical vapor deposition of boron on a tungsten filament.

Boron fibers and sub-millimeter sized crystalline boron springs are produced by laser-assisted chemical vapor deposition. Translation of the focused laser beam allows production of even complex helical structures. Such structures show good mechanical properties (elastic modulus 450 GPa, fracture strain 3.7%, fracture stress 17 GPa) and can be applied as reinforcement of ceramics or in micromechanical systems.

Boronated fiberglass

Fiberglass is a fiber reinforced polymer made of plastic reinforced by glass fibers, commonly woven into a mat. The glass fibers used in the material are made of various types of glass depending upon the fiberglass use. These glasses all contain silica or silicate, with varying amounts of oxides of calcium, magnesium, and sometimes boron. The boron is present as borosilicate, borax, or boron oxide, and is added to increase the strength of the glass, or as a fluxing agent to decrease the melting temperature of silica, which is too high to be easily worked in its pure form to make glass fibers.

The highly boronated glasses used in fiberglass are E-glass (named for "Electrical" use, but now the most common fiberglass for general use). E-glass is alumino-borosilicate glass with less than 1% w/w alkali oxides, mainly used for glass-reinforced plastics. Other common high-boron glasses include C-glass, an alkali-lime glass with high boron oxide content, used for glass staple fibers and insulation, and D-glass, a borosilicate glass, named for its low dielectric constant).

Not all fiberglasses contain boron, but on a global scale, most of the fiberglass used does contain it. Because the ubiquitous use of fiberglass in construction and insulation, boron-containing fiberglasses consume half the global production of boron, and are the single largest commercial boron market.

Borosilicate glass

Borosilicate glass, which is typically 12–15% B2O3, 80% SiO2, and 2% Al2O3, has a low coefficient of thermal expansion, giving it a good resistance to thermal shock. Schott AG's "Duran" and Owens-Corning's trademarked Pyrex are two major brand names for this glass, used both in laboratory glassware and in consumer cookware and bakeware, chiefly for this resistance.

Boron carbide ceramic

Several boron compounds are known for their extreme hardness and toughness. Boron carbide is a ceramic material which is obtained by decomposing B2O3 with carbon in an electric furnace:

2 B2O3 + 7 C → B4C + 6 CO

Boron carbide's structure is only approximately B4C, and it shows a clear depletion of carbon from this suggested stoichiometric ratio. This is due to its very complex structure. The substance can be seen with empirical formula B12C3 (i.e., with B12 dodecahedra being a motif), but with less carbon, as the suggested C3 units are replaced with C-B-C chains, and some smaller (B6) octahedra are present as well (see the boron carbide article for structural analysis). The repeating polymer plus semi-crystalline structure of boron carbide gives it great structural strength per weight. It is used in tank armor, bulletproof vests, and numerous other structural applications.

Boron carbide's ability to absorb neutrons without forming long-lived radionuclides (especially when doped with extra boron-10) makes the material attractive as an absorbent for neutron radiation arising in nuclear power plants. Nuclear applications of boron carbide include shielding, control rods and shut-down pellets. Within control rods, boron carbide is often powdered, to increase its surface area.

High-hardness and abrasive compounds

Boron carbide and cubic boron nitride powders are widely used as abrasives. Boron nitride is a material isoelectronic to carbon. Similar to carbon, it has both hexagonal (soft graphite-like h-BN) and cubic (hard, diamond-like c-BN) forms. h-BN is used as a high temperature component and lubricant. c-BN, also known under commercial name borazon,[94] is a superior abrasive. Its hardness is only slightly smaller than, but its chemical stability is superior, to that of diamond. Heterodiamond (also called BCN) is another diamond-like boron compound.

Metallurgy

Main articles: Boron steel and Boriding

Boron is added to boron steels at the level of a few parts per million to increase hardenability. Higher percentages are added to steels used in the nuclear industry due to boron's neutron absorption ability.

Boron can also increase the surface hardness of steels and alloys through boriding. Additionally metal borides are used for coating tools through chemical vapor deposition or physical vapor deposition. Implantation of boron ions into metals and alloys, through ion implantation or ion beam deposition, results in a spectacular increase in surface resistance and microhardness. Laser alloying has also been successfully used for the same purpose. These borides are an alternative to diamond coated tools, and their (treated) surfaces have similar properties to those of the bulk boride.

For example, rhenium diboride can be produced at ambient pressures, but is rather expensive because of rhenium. The hardness of ReB2 exhibits considerable anisotropy because of its hexagonal layered structure. Its value is comparable to that of tungsten carbide, silicon carbide, titanium diboride or zirconium diboride.Similarly, AlMgB14 + TiB2 composites possess high hardness and wear resistance and are used in either bulk form or as coatings for components exposed to high temperatures and wear loads.

Detergent formulations and bleaching agents

Borax is used in various household laundry and cleaning products, including the "20 Mule Team Borax" laundry booster and "Boraxo" powdered hand soap. It is also present in some tooth bleaching formulas.

Sodium perborate serves as a source of active oxygen in many detergents, laundry detergents, cleaning products, and laundry bleaches. However, despite its name, "Borateem" laundry bleach no longer contains any boron compounds, using sodium percarbonate instead as a bleaching agent.

Insecticides

Boric acid is used as an insecticide, notably against ants, fleas, and cockroaches.

Semiconductors

Boron is a useful dopant for such semiconductors as silicon, germanium, and silicon carbide. Having one fewer valence electron than the host atom, it donates a hole resulting in p-type conductivity. Traditional method of introducing boron into semiconductors is via its atomic diffusion at high temperatures. This process uses either solid (B2O3), liquid (BBr3), or gaseous boron sources (B2H6 or BF3). However, after the 1970s, it was mostly replaced by ion implantation, which relies mostly on BF3 as a boron source.Boron trichloride gas is also an important chemical in semiconductor industry, however, not for doping but rather for plasma etching of metals and their oxides. Triethylborane is also injected into vapor deposition reactors as a boron source.[citation needed] Examples are the plasma deposition of boron-containing hard carbon films, silicon nitride–boron nitride films, and for doping of diamond film with boron.

Magnets

Boron is a component of neodymium magnets (Nd2Fe14B), which are among the strongest type of permanent magnet. These magnets are found in a variety of electromechanical and electronic devices, such as magnetic resonance imaging (MRI) medical imaging systems, in compact and relatively small motors and actuators. As examples, computer HDDs (hard disk drives), CD (compact disk) and DVD (digital versatile disk) players rely on neodymium magnet motors to deliver intense rotary power in a remarkably compact package. In mobile phones 'Neo' magnets provide the magnetic field which allows tiny speakers to deliver appreciable audio power.

Shielding and neutron absorber in nuclear reactors

Boron shielding is used as a control for nuclear reactors, taking advantage of its high cross-section for neutron capture.

In pressurized water reactors a variable concentration of boronic acid in the cooling water is used as a neutron poison to compensate the variable reactivity of the fuel. When new rods are inserted the concentration of boronic acid is maximal, and is reduced during the lifetime.

Other nonmedical uses

Because of its distinctive green flame, amorphous boron is used in pyrotechnic flares.

Starch and casein-based adhesives contain sodium tetraborate decahydrate (Na2B4O7·10 H2O)

Some anti-corrosion systems contain borax.

Sodium borates are used as a flux for soldering silver and gold and with ammonium chloride for welding ferrous metals. They are also fire retarding additives to plastics and rubber articles.

Boric acid (also known as orthoboric acid) H3BO3 is used in the production of textile fiberglass and flat panel displays and in many PVAc- and PVOH-based adhesives.

Triethylborane is a substance which ignites the JP-7 fuel of the Pratt & Whitney J58 turbojet/ramjet engines powering the Lockheed SR-71 Blackbird. It was also used to ignite the F-1 Engines on the Saturn V Rocket utilized by NASA's Apollo and Skylab programs from 1967 until 1973. Today SpaceX uses it to ignite the engines on their Falcon 9 rocket. Triethylborane is suitable for this because of its pyrophoric properties, especially the fact that it burns with a very high temperature. Triethylborane is an industrial initiator in radical reactions, where it is effective even at low temperatures.

Borates are used as environmentally benign wood preservatives.

Pharmaceutical and biological applications

Boric acid has antiseptic, antifungal, and antiviral properties and for these reasons is applied as a water clarifier in swimming pool water treatment. Mild solutions of boric acid have been used as eye antiseptics.

Bortezomib (marketed as Velcade and Cytomib). Boron appears as an active element in the organic pharmaceutical bortezomib, a new class of drug called the proteasome inhibitor, for the treatment of myeloma and one form of lymphoma (it is in currently in experimental trials against other types of lymphoma). The boron atom in bortezomib binds the catalytic site of the 26S proteasome with high affinity and specificity.

A number of potential boronated pharmaceuticals using boron-10, have been prepared for use in boron neutron capture therapy (BNCT).

Some boron compounds show promise in treating arthritis, though none have as yet been generally approved for the purpose.

Tavaborole (marketed as Kerydin) is an Aminoacyl tRNA synthetase inhibitor which is used to treat toenail fungus. It gained FDA approval in July 2014.

Dioxaborolane chemistry enables radioactive fluoride (18F) labeling of antibodies or red blood cells, which allows for positron emission tomography (PET) imaging of cancer and hemorrhages, respectively. A Human-Derived, Genetic, Positron-emitting and Fluorescent (HD-GPF) reporter system uses a human protein, PSMA and non-immunogenic, and a small molecule that is positron-emitting (boron bound 18F) and fluorescence for dual modality PET and fluorescent imaging of genome modified cells, e.g. cancer, CRISPR/Cas9, or CAR T-cells, in an entire mouse.The dual-modality small molecule targeting PSMA was tested in humans and found the location of primary and metastatic prostate cancer, fluorescence-guided removal of cancer, and detects single cancer cells in tissue margins.

Research areas

Magnesium diboride is an important superconducting material with the transition temperature of 39 K. MgB2 wires are produced with the powder-in-tube process and applied in superconducting magnets.

Amorphous boron is used as a melting point depressant in nickel-chromium braze alloys.

Hexagonal boron nitride forms atomically thin layers, which have been used to enhance the electron mobility in graphene devices. It also forms nanotubular structures (BNNTs), which have high strength, high chemical stability, and high thermal conductivity, among its list of desirable properties.

Biological role

Boron is an essential plant nutrient, required primarily for maintaining the integrity of cell walls. However, high soil concentrations of greater than 1.0 ppm lead to marginal and tip necrosis in leaves as well as poor overall growth performance. Levels as low as 0.8 ppm produce these same symptoms in plants that are particularly sensitive to boron in the soil. Nearly all plants, even those somewhat tolerant of soil boron, will show at least some symptoms of boron toxicity when soil boron content is greater than 1.8 ppm. When this content exceeds 2.0 ppm, few plants will perform well and some may not survive.

It is thought that boron plays several essential roles in animals, including humans, but the exact physiological role is poorly understood. A small human trial published in 1987 reported on postmenopausal women first made boron deficient and then repleted with 3 mg/day. Boron supplementation markedly reduced urinary calcium excretion and elevated the serum concentrations of 17 beta-estradiol and testosterone.

The U.S. Institute of Medicine has not confirmed that boron is an essential nutrient for humans, so neither a Recommended Dietary Allowance (RDA) nor an Adequate Intake have been established. Adult dietary intake is estimated at 0.9 to 1.4 mg/day, with about 90% absorbed. What is absorbed is mostly excreted in urine. The Tolerable Upper Intake Level for adults is 20 mg/day.

In 2013, a hypothesis suggested it was possible that boron and molybdenum catalyzed the production of RNA on Mars with life being transported to Earth via a meteorite around 3 billion years ago.

There exist several known boron-containing natural antibiotics. The first one found was boromycin, isolated from streptomyces.

Congenital endothelial dystrophy type 2, a rare form of corneal dystrophy, is linked to mutations in SLC4A11 gene that encodes a transporter reportedly regulating the intracellular concentration of boron.

Analytical quantification

For determination of boron content in food or materials, the colorimetric curcumin method is used. Boron is converted to boric acid or borates and on reaction with curcumin in acidic solution, a red colored boron-chelate complex, rosocyanine, is formed.

Health issues and toxicity

Elemental boron, boron oxide, boric acid, borates, and many organoboron compounds are relatively nontoxic to humans and animals (with toxicity similar to that of table salt). The LD50 (dose at which there is 50% mortality) for animals is about 6 g per kg of body weight. Substances with LD50 above 2 g are considered nontoxic. An intake of 4 g/day of boric acid was reported without incident, but more than this is considered toxic in more than a few doses. Intakes of more than 0.5 grams per day for 50 days cause minor digestive and other problems suggestive of toxicity. Dietary supplementation of boron may be helpful for bone growth, wound healing, and antioxidant activity, and insufficient amount of boron in diet may result in boron deficiency.

Single medical doses of 20 g of boric acid for neutron capture therapy have been used without undue toxicity.

Boric acid is more toxic to insects than to mammals, and is routinely used as an insecticide.

The boranes (boron hydrogen compounds) and similar gaseous compounds are quite poisonous. As usual, boron is not an element that is intrinsically poisonous, but the toxicity of these compounds depends on structure (for another example of this phenomenon, see phosphine). The boranes are also highly flammable and require special care when handling. Sodium borohydride presents a fire hazard owing to its reducing nature and the liberation of hydrogen on contact with acid. Boron halides are corrosive. Boron is necessary for plant growth, but an excess of boron is toxic to plants, and occurs particularly in acidic soil. It presents as a yellowing from the tip inwards of the oldest leaves and black spots in barley leaves, but it can be confused with other stresses such as magnesium deficiency in other plants.

Beryllium is a chemical element with the symbol Be and atomic number 4. It is a steel-gray, strong, lightweight and brittle alkaline earth metal. It is a divalent element that occurs naturally only in combination with other elements to form minerals. Notable gemstones high in beryllium include beryl (aquamarine, emerald) and chrysoberyl. It is a relatively rare element in the universe, usually occurring as a product of the spallation of larger atomic nuclei that have collided with cosmic rays. Within the cores of stars, beryllium is depleted as it is fused into heavier elements. Beryllium constitutes about 0.0004 percent by mass of Earth's crust. The world's annual beryllium production of 220 tons is usually manufactured by extraction from the mineral beryl, a difficult process because beryllium bonds strongly to oxygen.

In structural applications, the combination of high flexural rigidity, thermal stability, thermal conductivity and low density (1.85 times that of water) make beryllium metal a desirable aerospace material for aircraft components, missiles, spacecraft, and satellites. Because of its low density and atomic mass, beryllium is relatively transparent to X-rays and other forms of ionizing radiation; therefore, it is the most common window material for X-ray equipment and components of particle detectors.[6] When added as an alloying element to aluminium, copper (notably the alloy beryllium copper), iron, or nickel, beryllium improves many physical properties. For example, tools and components made of beryllium copper alloys are strong and hard and do not create sparks when they strike a steel surface. In air, the surface of beryllium oxidizes readily at room temperature to form a passivation layer 1–10 nm thick that protects it from further oxidation and corrosion. The metal oxidizes in bulk (beyond the passivation layer) when heated above 500 °C (932 °F), and burns brilliantly when heated to about 2,500 °C (4,530 °F).

The commercial use of beryllium requires the use of appropriate dust control equipment and industrial controls at all times because of the toxicity of inhaled beryllium-containing dusts that can cause a chronic life-threatening allergic disease in some people called berylliosis. Berylliosis causes pneumonia and other associated respiratory illness.

Characteristics

1.1 Physical properties

Beryllium is a steel gray and hard metal that is brittle at room temperature and has a close-packed hexagonal crystal structure. It has exceptional stiffness (Young's modulus 287 GPa) and a melting point of 1287 °C. The modulus of elasticity of beryllium is approximately 50% greater than that of steel. The combination of this modulus and a relatively low density results in an unusually fast sound conduction speed in beryllium – about 12.9 km/s at ambient conditions. Other significant properties are high specific heat (1925 J·kg−1·K−1) and thermal conductivity (216 W·m−1·K−1), which make beryllium the metal with the best heat dissipation characteristics per unit weight. In combination with the relatively low coefficient of linear thermal expansion (11.4×10−6 K−1), these characteristics result in a unique stability under conditions of thermal loading.

Nuclear properties

Naturally occurring beryllium, save for slight contamination by the cosmogenic radioisotopes, is isotopically pure beryllium-9, which has a nuclear spin of

3

/

2

. Beryllium has a large scattering cross section for high-energy neutrons, about 6 barns for energies above approximately 10 keV. Therefore, it works as a neutron reflector and neutron moderator, effectively slowing the neutrons to the thermal energy range of below 0.03 eV, where the total cross section is at least an order of magnitude lower; the exact value strongly depends on the purity and size of the crystallites in the material.

The single primordial beryllium isotope 9Be also undergoes a (n,2n) neutron reaction with neutron energies over about 1.9 MeV, to produce 8Be, which almost immediately breaks into two alpha particles. Thus, for high-energy neutrons, beryllium is a neutron multiplier, releasing more neutrons than it absorbs. This nuclear reaction is:

94Be+ n → 2 42He+ 2 n

Neutrons are liberated when beryllium nuclei are struck by energetic alpha particles producing the nuclear reaction

94Be+ 42He→ 126C+ n

where 4

2He is an alpha particle and 126C

is a carbon-12 nucleus. Beryllium also releases neutrons under bombardment by gamma rays. Thus, natural beryllium bombarded either by alphas or gammas from a suitable radioisotope is a key component of most radioisotope-powered nuclear reaction neutron sources for the laboratory production of free neutrons.

Small amounts of tritium are liberated when 9

4Be

nuclei absorb low energy neutrons in the three-step nuclear reaction

94Be+ n → 42He+ 62He, 62He→ 63Li+ β−, 63Li+ n → 42He+ 31H

Note that 6

2Hehas a half-life of only 0.8 seconds, β− is an electron, and 63Li

has a high neutron absorption cross section. Tritium is a radioisotope of concern in nuclear reactor waste streams.

Optical properties

As a metal, beryllium is transparent or translucent to most wavelengths of X-rays and gamma rays, making it useful for the output windows of X-ray tubes and other such apparatus.

Isotopes and nucleosynthesis

Main article: Isotopes of beryllium

Both stable and unstable isotopes of beryllium are created in stars, but the radioisotopes do not last long. It is believed that most of the stable beryllium in the universe was originally created in the interstellar medium when cosmic rays induced fission in heavier elements found in interstellar gas and dust. Primordial beryllium contains only one stable isotope, 9Be, and therefore beryllium is a monoisotopic and mononuclidic element.

Radioactive cosmogenic 10Be is produced in the atmosphere of the Earth by the cosmic ray spallation of oxygen. 10Be accumulates at the soil surface, where its relatively long half-life (1.36 million years) permits a long residence time before decaying to boron-10. Thus, 10Be and its daughter products are used to examine natural soil erosion, soil formation and the development of lateritic soils, and as a proxy for measurement of the variations in solar activity and the age of ice cores. The production of 10Be is inversely proportional to solar activity, because increased solar wind during periods of high solar activity decreases the flux of galactic cosmic rays that reach the Earth. Nuclear explosions also form 10Be by the reaction of fast neutrons with 13C in the carbon dioxide in air. This is one of the indicators of past activity at nuclear weapon test sites. The isotope 7Be (half-life 53 days) is also cosmogenic, and shows an atmospheric abundance linked to sunspots, much like 10Be.

8Be has a very short half-life of about 8×10−17 s that contributes to its significant cosmological role, as elements heavier than beryllium could not have been produced by nuclear fusion in the Big Bang. This is due to the lack of sufficient time during the Big Bang's nucleosynthesis phase to produce carbon by the fusion of 4He nuclei and the very low concentrations of available beryllium-8. British astronomer Sir Fred Hoyle first showed that the energy levels of 8Be and 12C allow carbon production by the so-called triple-alpha process in helium-fueled stars where more nucleosynthesis time is available. This process allows carbon to be produced in stars, but not in the Big Bang. Star-created carbon (the basis of carbon-based life) is thus a component in the elements in the gas and dust ejected by AGB stars and supernovae (see also Big Bang nucleosynthesis), as well as the creation of all other elements with atomic numbers larger than that of carbon.

The 2s electrons of beryllium may contribute to chemical bonding. Therefore, when 7Be decays by L-electron capture, it does so by taking electrons from its atomic orbitals that may be participating in bonding. This makes its decay rate dependent to a measurable degree upon its chemical surroundings – a rare occurrence in nuclear decay

The shortest-lived known isotope of beryllium is 16Be, which decays through neutron emission with a half-life of 6.5×10−22 s. The exotic isotopes 11Be and 14Be are known to exhibit a nuclear halo. This phenomenon can be understood as the nuclei of 11Be and 14Be have, respectively, 1 and 4 neutrons orbiting substantially outside the classical Fermi 'waterdrop' model of the nucleus.

Occurrence

The Sun has a concentration of 0.1 parts per billion (ppb) of beryllium. Beryllium has a concentration of 2 to 6 parts per million (ppm) in the Earth's crust.It is most concentrated in the soils, 6 ppm. Trace amounts of 9Be are found in the Earth's atmosphere . The concentration of beryllium in sea water is 0.2–0.6 parts per trillion.In stream water, however, beryllium is more abundant with a concentration of 0.1 ppb.

Beryllium is found in over 100 minerals, but most are uncommon to rare. The more common beryllium containing minerals include: bertrandite (Be4Si2O7(OH)2), beryl (Al2Be3Si6O18), chrysoberyl (Al2BeO4) and phenakite (Be2SiO4). Precious forms of beryl are aquamarine, red beryl and emerald. The green color in gem-quality forms of beryl comes from varying amounts of chromium (about 2% for emerald).

The two main ores of beryllium, beryl and bertrandite, are found in Argentina, Brazil, India, Madagascar, Russia and the United States. Total world reserves of beryllium ore are greater than 400,000 tonnes.

Production The extraction of beryllium from its compounds is a difficult process due to its high affinity for oxygen at elevated temperatures, and its ability to reduce water when its oxide film is removed. Currently the United States, China and Kazakhstan are the only three countries involved in the industrial-scale extraction of beryllium. Kazakhstan produces beryllium from a concentrate stockpiled before the breakup of the Soviet Union around 1991. This resource has become nearly depleted by mid-2010s.

Production of beryllium in Russia was halted in 1997, and is planned to be resumed in the 2020s.

Beryllium is most commonly extracted from the mineral beryl, which is either sintered using an extraction agent or melted into a soluble mixture. The sintering process involves mixing beryl with sodium fluorosilicate and soda at 770 °C (1,420 °F) to form sodium fluoroberyllate, aluminium oxide and silicon dioxide. Beryllium hydroxide is precipitated from a solution of sodium fluoroberyllate and sodium hydroxide in water. Extraction of beryllium using the melt method involves grinding beryl into a powder and heating it to 1,650 °C (3,000 °F). The melt is quickly cooled with water and then reheated 250 to 300 °C (482 to 572 °F) in concentrated sulfuric acid, mostly yielding beryllium sulfate and aluminium sulfate. Aqueous ammonia is then used to remove the aluminium and sulfur, leaving beryllium hydroxide.

Beryllium hydroxide created using either the sinter or melt method is then converted into beryllium fluoride or beryllium chloride. To form the fluoride, aqueous ammonium hydrogen fluoride is added to beryllium hydroxide to yield a precipitate of ammonium tetrafluoroberyllate, which is heated to 1,000 °C (1,830 °F) to form beryllium fluoride. Heating the fluoride to 900 °C (1,650 °F) with magnesium forms finely divided beryllium, and additional heating to 1,300 °C (2,370 °F) creates the compact metal. Heating beryllium hydroxide forms the oxide, which becomes beryllium chloride when combined with carbon and chlorine. Electrolysis of molten beryllium chloride is then used to obtain the metal.

Chemical properties A beryllium atom has the electronic configuration 2s2. The predominant oxidation state of beryllium is +2; the beryllium atom has lost both of its valence electrons. Lower oxidation states have been found in, for example, bis(carbene) compounds. Beryllium's chemical behavior is largely a result of its small atomic and ionic radii. It thus has very high ionization potentials and strong polarization while bonded to other atoms, which is why all of its compounds are covalent. Its chemistry has similarities with the chemistry of aluminium, an example of a diagonal relationship.

At room temperature, the surface of beryllium forms a 1−10 nm-thick oxide passivation layer that prevents further reactions with air, except for gradual thickening of the oxide up to about 25 nm. When heated above about 500 °C, oxidation into the bulk metal progresses along grain boundaries. Once the metal is ignited in air by heating above the oxide melting point around 2500 °C, beryllium burns brilliantly, forming a mixture of beryllium oxide and beryllium nitride. Beryllium dissolves readily in non-oxidizing acids, such as HCl and diluted H2SO4, but not in nitric acid or water as this forms the oxide. This behavior is similar to that of aluminium metal. Beryllium also dissolves in alkali solutions.

Binary compounds of beryllium(II) are polymeric in the solid state. BeF2 has a silica-like structure with corner-shared BeF4 tetrahedra. BeCl2 and BeBr2 have chain structures with edge-shared tetrahedra. Beryllium oxide, BeO, is a white refractory solid, which has the wurtzite crystal structure and a thermal conductivity as high as some metals. BeO is amphoteric. Beryllium sulfide, selenide and telluride are known, all having the zincblende structure. Beryllium nitride, Be3N2 is a high-melting-point compound which is readily hydrolyzed. Beryllium azide, BeN6 is known and beryllium phosphide, Be3P2 has a similar structure to Be3N2. A number of beryllium borides are known, such as Be5B, Be4B, Be2B, BeB2, BeB6 and BeB12. Beryllium carbide, Be2C, is a refractory brick-red compound that reacts with water to give methane. No beryllium silicide has been identified.

The halides BeX2 (X = F, Cl, Br, I) have a linear monomeric molecular structure in the gas phase. Complexes of the halides are formed with one or more ligands donating at total of two pairs of electrons. Such compounds obey the octet rule. Other 4-coordinate complexes such as the aqua-ion [Be(H2O)4]2+ also obey the octet rule.

Solutions of beryllium salts, such as beryllium sulfate and beryllium nitrate, are acidic because of hydrolysis of the [Be(H2O)4]2+ ion. The concentration of the first hydrolysis product, [Be(H2O)3(OH)]+, is less than 1% of the beryllium concentration. The most stable hydrolysis product is the trimeric ion [Be3(OH)3(H2O)6]3+. Beryllium hydroxide, Be(OH)2, is insoluble in water at pH 5 or more. Consequently, beryllium compounds are generally insoluble at biological pH. Because of this, inhalation of beryllium metal dust by people leads to the development of the fatal condition of berylliosis. Be(OH)2 dissolves in strongly alkaline solutions. In basic beryllium acetate the central oxygen atom is surrounded by a tetrahedron of beryllium atoms. Beryllium difluoride, unlike the other alkaline earth difluorides, is very soluble in water. Aqueous solutions of this salt contain ions such as [Be(H2O)3F]+. Beryllium hydroxide reacts with ammonium bifluoride to form the ammonium salt of the tetrafluoroberyllate complex.

Organic chemistry

Organoberyllium chemistry is limited to academic research due to the cost and toxicity of beryllium, beryllium derivatives and reagents required for the introduction of beryllium, such as beryllium chloride. Organometallic beryllium compounds are known to be highly reactive Examples of known organoberyllium compounds are dineopentylberyllium,beryllocene (Cp2Be), diallylberyllium (by exchange reaction of diethyl beryllium with triallyl boron), bis(1,3-trimethylsilylallyl)berylliumand Be(mes)2. Ligands can also be aryls and alkynyls.

History The mineral beryl, which contains beryllium, has been used at least since the Ptolemaic dynasty of Egypt. In the first century CE, Roman naturalist Pliny the Elder mentioned in his encyclopedia Natural History that beryl and emerald ("smaragdus") were similar. The Papyrus Graecus Holmiensis, written in the third or fourth century CE, contains notes on how to prepare artificial emerald and beryl. Early analyses of emeralds and beryls by Martin Heinrich Klaproth, Torbern Olof Bergman, Franz Karl Achard, and Johann Jakob Bindheim always yielded similar elements, leading to the fallacious conclusion that both substances are aluminium silicates.Mineralogist René Just Haüy discovered that both crystals are geometrically identical, and he asked chemist Louis-Nicolas Vauquelin for a chemical analysis.

In a 1798 paper read before the Institut de France, Vauquelin reported that he found a new "earth" by dissolving aluminium hydroxide from emerald and beryl in an additional alkali.The editors of the journal Annales de Chimie et de Physique named the new earth "glucine" for the sweet taste of some of its compounds. Klaproth preferred the name "beryllina" due to the fact that yttria also formed sweet salts.The name "beryllium" was first used by Wöhler in 1828. Friedrich Wöhler and Antoine Bussy independently isolated beryllium in 1828 by the chemical reaction of metallic potassium with beryllium chloride, as follows:

BeCl2 + 2 K → 2 KCl + Be

Using an alcohol lamp, Wöhler heated alternating layers of beryllium chloride and potassium in a wired-shut platinum crucible. The above reaction immediately took place and caused the crucible to become white hot. Upon cooling and washing the resulting gray-black powder he saw that it was made of fine particles with a dark metallic luster. The highly reactive potassium had been produced by the electrolysis of its compounds, a process discovered 21 years before. The chemical method using potassium yielded only small grains of beryllium from which no ingot of metal could be cast or hammered.

The direct electrolysis of a molten mixture of beryllium fluoride and sodium fluoride by Paul Lebeau in 1898 resulted in the first pure (99.5 to 99.8%) samples of beryllium. However, industrial production started only after the First World War. The original industrial involvement included subsidiaries and scientists related to the Union Carbide and Carbon Corporation in Cleveland OH and Siemens & Halske AG in Berlin. In the US, the process was ruled by Hugh S. Cooper, director of The Kemet Laboratories Company. In Germany, the first commercially successful process for producing beryllium was developed in 1921 by Alfred Stock and Hans Goldschmidt.

A sample of beryllium was bombarded with alpha rays from the decay of radium in a 1932 experiment by James Chadwick that uncovered the existence of the neutron. This same method is used in one class of radioisotope-based laboratory neutron sources that produce 30 neutrons for every million α particles.

Beryllium production saw a rapid increase during World War II, due to the rising demand for hard beryllium-copper alloys and phosphors for fluorescent lights. Most early fluorescent lamps used zinc orthosilicate with varying content of beryllium to emit greenish light. Small additions of magnesium tungstate improved the blue part of the spectrum to yield an acceptable white light. Halophosphate-based phosphors replaced beryllium-based phosphors after beryllium was found to be toxic.

Electrolysis of a mixture of beryllium fluoride and sodium fluoride was used to isolate beryllium during the 19th century. The metal's high melting point makes this process more energy-consuming than corresponding processes used for the alkali metals. Early in the 20th century, the production of beryllium by the thermal decomposition of beryllium iodide was investigated following the success of a similar process for the production of zirconium, but this process proved to be uneconomical for volume production.

Pure beryllium metal did not become readily available until 1957, even though it had been used as an alloying metal to harden and toughen copper much earlier. Beryllium could be produced by reducing beryllium compounds such as beryllium chloride with metallic potassium or sodium. Currently, most beryllium is produced by reducing beryllium fluoride with magnesium. The price on the American market for vacuum-cast beryllium ingots was about $338 per pound ($745 per kilogram) in 2001.

Between 1998 and 2008, the world's production of beryllium had decreased from 343 to about 200 tonnes. It then increased to 230 tonnes by 2018, of which 170 tonnes came from the United States.

Etymology

Named after beryl, a semiprecious mineral, from which it was first isolated.

Applications Because of its low atomic number and very low absorption for X-rays, the oldest and still one of the most important applications of beryllium is in radiation windows for X-ray tubes. Extreme demands are placed on purity and cleanliness of beryllium to avoid artifacts in the X-ray images. Thin beryllium foils are used as radiation windows for X-ray detectors, and the extremely low absorption minimizes the heating effects caused by high intensity, low energy X-rays typical of synchrotron radiation. Vacuum-tight windows and beam-tubes for radiation experiments on synchrotrons are manufactured exclusively from beryllium. In scientific setups for various X-ray emission studies (e.g., energy-dispersive X-ray spectroscopy) the sample holder is usually made of beryllium because its emitted X-rays have much lower energies (≈100 eV) than X-rays from most studied materials.

Low atomic number also makes beryllium relatively transparent to energetic particles. Therefore, it is used to build the beam pipe around the collision region in particle physics setups, such as all four main detector experiments at the Large Hadron Collider (ALICE, ATLAS, CMS, LHCb), the Tevatron and at SLAC. The low density of beryllium allows collision products to reach the surrounding detectors without significant interaction, its stiffness allows a powerful vacuum to be produced within the pipe to minimize interaction with gases, its thermal stability allows it to function correctly at temperatures of only a few degrees above absolute zero, and its diamagnetic nature keeps it from interfering with the complex multipole magnet systems used to steer and focus the particle beams.

Mechanical applications

Because of its stiffness, light weight and dimensional stability over a wide temperature range, beryllium metal is used for lightweight structural components in the defense and aerospace industries in high-speed aircraft, guided missiles, spacecraft, and satellites, including the James Webb Space Telescope. Several liquid-fuel rockets have used rocket nozzles made of pure beryllium. Beryllium powder was itself studied as a rocket fuel, but this use has never materialized.A small number of extreme high-end bicycle frames have been built with beryllium. From 1998 to 2000, the McLaren Formula One team used Mercedes-Benz engines with beryllium-aluminium-alloy pistons. The use of beryllium engine components was banned following a protest by Scuderia Ferrari.

Mixing about 2.0% beryllium into copper forms an alloy called beryllium copper that is six times stronger than copper alone. Beryllium alloys are used in many applications because of their combination of elasticity, high electrical conductivity and thermal conductivity, high strength and hardness, nonmagnetic properties, as well as good corrosion and fatigue resistance. These applications include non-sparking tools that are used near flammable gases (beryllium nickel), in springs and membranes (beryllium nickel and beryllium iron) used in surgical instruments and high temperature devices. As little as 50 parts per million of beryllium alloyed with liquid magnesium leads to a significant increase in oxidation resistance and decrease in flammability.

The high elastic stiffness of beryllium has led to its extensive use in precision instrumentation, e.g. in inertial guidance systems and in the support mechanisms for optical systems. Beryllium-copper alloys were also applied as a hardening agent in "Jason pistols", which were used to strip the paint from the hulls of ships.

Beryllium was also used for cantilevers in high performance phonograph cartridge styli, where its extreme stiffness and low density allowed for tracking weights to be reduced to 1 gram, yet still track high frequency passages with minimal distortion.

An earlier major application of beryllium was in brakes for military airplanes because of its hardness, high melting point, and exceptional ability to dissipate heat. Environmental considerations have led to substitution by other materials.

To reduce costs, beryllium can be alloyed with significant amounts of aluminium, resulting in the AlBeMet alloy (a trade name). This blend is cheaper than pure beryllium, while still retaining many desirable properties.

Mirrors

Beryllium mirrors are of particular interest. Large-area mirrors, frequently with a honeycomb support structure, are used, for example, in meteorological satellites where low weight and long-term dimensional stability are critical. Smaller beryllium mirrors are used in optical guidance systems and in fire-control systems, e.g. in the German-made Leopard 1 and Leopard 2 main battle tanks. In these systems, very rapid movement of the mirror is required which again dictates low mass and high rigidity. Usually the beryllium mirror is coated with hard electroless nickel plating which can be more easily polished to a finer optical finish than beryllium. In some applications, though, the beryllium blank is polished without any coating. This is particularly applicable to cryogenic operation where thermal expansion mismatch can cause the coating to buckle.

The James Webb Space Telescope has 18 hexagonal beryllium sections for its mirrors, each plated with a thin layer of gold. Because JWST will face a temperature of 33 K, the mirror is made of gold-plated beryllium, capable of handling extreme cold better than glass. Beryllium contracts and deforms less than glass – and remains more uniform – in such temperatures. For the same reason, the optics of the Spitzer Space Telescope are entirely built of beryllium metal.

Magnetic applications Beryllium is non-magnetic. Therefore, tools fabricated out of beryllium-based materials are used by naval or military explosive ordnance disposal teams for work on or near naval mines, since these mines commonly have magnetic fuzes. They are also found in maintenance and construction materials near magnetic resonance imaging (MRI) machines because of the high magnetic fields generated. In the fields of radio communications and powerful (usually military) radars, hand tools made of beryllium are used to tune the highly magnetic klystrons, magnetrons, traveling wave tubes, etc., that are used for generating high levels of microwave power in the transmitters.

Nuclear applications

Thin plates or foils of beryllium are sometimes used in nuclear weapon designs as the very outer layer of the plutonium pits in the primary stages of thermonuclear bombs, placed to surround the fissile material. These layers of beryllium are good "pushers" for the implosion of the plutonium-239, and they are good neutron reflectors, just as in beryllium-moderated nuclear reactors.

Beryllium is also commonly used in some neutron sources in laboratory devices in which relatively few neutrons are needed (rather than having to use a nuclear reactor, or a particle accelerator-powered neutron generator). For this purpose, a target of beryllium-9 is bombarded with energetic alpha particles from a radioisotope such as polonium-210, radium-226, plutonium-238, or americium-241. In the nuclear reaction that occurs, a beryllium nucleus is transmuted into carbon-12, and one free neutron is emitted, traveling in about the same direction as the alpha particle was heading. Such alpha decay driven beryllium neutron sources, named "urchin" neutron initiators, were used in some early atomic bombs. Neutron sources in which beryllium is bombarded with gamma rays from a gamma decay radioisotope, are also used to produce laboratory neutrons. Beryllium is also used in fuel fabrication for CANDU reactors. The fuel elements have small appendages that are resistance brazed to the fuel cladding using an induction brazing process with Be as the braze filler material. Bearing pads are brazed in place to prevent contact between the fuel bundle and the pressure tube containing it, and inter-element spacer pads are brazed on to prevent element to element contact.

Beryllium is also used at the Joint European Torus nuclear-fusion research laboratory, and it will be used in the more advanced ITER to condition the components which face the plasma. Beryllium has also been proposed as a cladding material for nuclear fuel rods, because of its good combination of mechanical, chemical, and nuclear properties.Beryllium fluoride is one of the constituent salts of the eutectic salt mixture FLiBe, which is used as a solvent, moderator and coolant in many hypothetical molten salt reactor designs, including the liquid fluoride thorium reactor (LFTR).

Acoustics

The low weight and high rigidity of beryllium make it useful as a material for high-frequency speaker drivers. Because beryllium is expensive (many times more than titanium), hard to shape due to its brittleness, and toxic if mishandled, beryllium tweeters are limited to high-end home, pro audio, and public address applications. Some high-fidelity products have been fraudulently claimed to be made of the material.

Some high-end phonograph cartridges used beryllium cantilevers to improve tracking by reducing mass.

Electronic

Beryllium is a p-type dopant in III-V compound semiconductors. It is widely used in materials such as GaAs, AlGaAs, InGaAs and InAlAs grown by molecular beam epitaxy (MBE).Cross-rolled beryllium sheet is an excellent structural support for printed circuit boards in surface-mount technology. In critical electronic applications, beryllium is both a structural support and heat sink. The application also requires a coefficient of thermal expansion that is well matched to the alumina and polyimide-glass substrates. The beryllium-beryllium oxide composite "E-Materials" have been specially designed for these electronic applications and have the additional advantage that the thermal expansion coefficient can be tailored to match diverse substrate materials.

Beryllium oxide is useful for many applications that require the combined properties of an electrical insulator and an excellent heat conductor, with high strength and hardness, and a very high melting point. Beryllium oxide is frequently used as an insulator base plate in high-power transistors in radio frequency transmitters for telecommunications. Beryllium oxide is also being studied for use in increasing the thermal conductivity of uranium dioxide nuclear fuel pellets. Beryllium compounds were used in fluorescent lighting tubes, but this use was discontinued because of the disease berylliosis which developed in the workers who were making the tubes.

Healthcare

Beryllium is a component of several dental alloys.

Occupational safety and health

Beryllium is a health and safety issue for workers. Exposure to beryllium in the workplace can lead to a sensitization immune response and can over time develop chronic beryllium disease (CBD). The National Institute for Occupational Safety and Health (NIOSH) in the United States researches these effects in collaboration with a major manufacturer of beryllium products. The goal of this research is to prevent sensitization and CBD by developing a better understanding of the work processes and exposures that may present a potential risk for workers, and to develop effective interventions that will reduce the risk for adverse health effects. NIOSH also conducts genetic research on sensitization and CBD, independently of this collaboration.The NIOSH Manual of Analytical Methods contains methods for measuring occupational exposures to beryllium.

Precautions Approximately 35 micrograms of beryllium is found in the average human body, an amount not considered harmful. Beryllium is chemically similar to magnesium and therefore can displace it from enzymes, which causes them to malfunction. Because Be2+ is a highly charged and small ion, it can easily get into many tissues and cells, where it specifically targets cell nuclei, inhibiting many enzymes, including those used for synthesizing DNA. Its toxicity is exacerbated by the fact that the body has no means to control beryllium levels, and once inside the body the beryllium cannot be removed. Chronic berylliosis is a pulmonary and systemic granulomatous disease caused by inhalation of dust or fumes contaminated with beryllium; either large amounts over a short time or small amounts over a long time can lead to this ailment. Symptoms of the disease can take up to five years to develop; about a third of patients with it die and the survivors are left disabled.The International Agency for Research on Cancer (IARC) lists beryllium and beryllium compounds as Category 1 carcinogens. In the US, the Occupational Safety and Health Administration (OSHA) has designated a permissible exposure limit (PEL) in the workplace with a time-weighted average (TWA) 2 µg/m3 and a constant exposure limit of 5 µg/m3 over 30 minutes, with a maximum peak limit of 25 µg/m3. The National Institute for Occupational Safety and Health (NIOSH) has set a recommended exposure limit (REL) of constant 500 ng/m3. The IDLH (immediately dangerous to life and health) value is 4 mg/m3. The toxicity of beryllium is on par with other toxic metals, such as arsenic and mercury.

The toxicity of finely divided beryllium (dust or powder, mainly encountered in industrial settings where beryllium is produced or machined) is very well-documented. Solid beryllium metal does not carry the same hazards as airborne inhaled dust, but any hazard associated with physical contact is poorly documented. Workers handling finished beryllium pieces are routinely advised to handle them with gloves, both as a precaution and because many if not most applications of beryllium cannot tolerate residue of skin contact such as fingerprints.

Acute beryllium disease in the form of chemical pneumonitis was first reported in Europe in 1933 and in the United States in 1943. A survey found that about 5% of workers in plants manufacturing fluorescent lamps in 1949 in the United States had beryllium-related lung diseases. Chronic berylliosis resembles sarcoidosis in many respects, and the differential diagnosis is often difficult. It killed some early workers in nuclear weapons design, such as Herbert L. Anderson.

Beryllium may be found in coal slag. When the slag is formulated into an abrasive agent for blasting paint and rust from hard surfaces, the beryllium can become airborne and become a source of exposure.

Early researchers tasted beryllium and its various compounds for sweetness in order to verify its presence. Modern diagnostic equipment no longer necessitates this highly risky procedure and no attempt should be made to ingest this highly toxic substance. Beryllium and its compounds should be handled with great care and special precautions must be taken when carrying out any activity which could result in the release of beryllium dust (lung cancer is a possible result of prolonged exposure to beryllium-laden dust). Although the use of beryllium compounds in fluorescent lighting tubes was discontinued in 1949, potential for exposure to beryllium exists in the nuclear and aerospace industries and in the refining of beryllium metal and melting of beryllium-containing alloys, the manufacturing of electronic devices, and the handling of other beryllium-containing material.

A successful test for beryllium in air and on surfaces has been recently developed and published as an international voluntary consensus standard ASTM D7202. The procedure uses dilute ammonium bifluoride for dissolution and fluorescence detection with beryllium bound to sulfonated hydroxybenzoquinoline, allowing up to 100 times more sensitive detection than the recommended limit for beryllium concentration in the workplace. Fluorescence increases with increasing beryllium concentration. The new procedure has been successfully tested on a variety of surfaces and is effective for the dissolution and ultratrace detection of refractory beryllium oxide and siliceous beryllium (ASTM D7458).

Lithium (from Greek: λίθος, romanized: lithos, lit. 'stone') is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid element. Like all alkali metals, lithium is highly reactive and flammable, and must be stored in vacuum, inert atmosphere .

r inert liquid such as purified kerosene or mineral oil. When cut, it exhibits a metallic luster, but moist air corrodes it quickly to a dull silvery gray, then black tarnish. It never occurs freely in nature, but only in (usually ionic) compounds, such as pegmatitic minerals, which were once the main source of lithium. Due to its solubility as an ion, it is present in ocean water and is commonly obtained from brines. Lithium metal is isolated electrolytically from a mixture of lithium chloride and potassium chloride.

The nucleus of the lithium atom verges on instability, since the two stable lithium isotopes found in nature have among the lowest binding energies per nucleon of all stable nuclides. Because of its relative nuclear instability, lithium is less common in the solar system than 25 of the first 32 chemical elements even though its nuclei are very light: it is an exception to the trend that heavier nuclei are less common. For related reasons, lithium has important uses in nuclear physics. The transmutation of lithium atoms to helium in 1932 was the first fully man-made nuclear reaction, and lithium deuteride serves as a fusion fuel in staged thermonuclear weapons.

Lithium and its compounds have several industrial applications, including heat-resistant glass and ceramics, lithium grease lubricants, flux additives for iron, steel and aluminium production, lithium batteries, and lithium-ion batteries. These uses consume more than three-quarters of lithium production.

Lithium is present in biological systems in trace amounts; its functions are uncertain. Lithium salts have proven to be useful as a mood stabilizer and antidepressant in the treatment of mental illness such as bipolar disorder.

Properties

The alkali metals are also called the lithium family, after its leading element. Like the other alkali metals (which are sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr)), lithium has a single valence electron that is easily given up to form a cation. Because of this, lithium is a good conductor of heat and electricity as well as a highly reactive element, though it is the least reactive of the alkali metals. Lithium's low reactivity is due to the proximity of its valence electron to its nucleus (the remaining two electrons are in the 1s orbital, much lower in energy, and do not participate in chemical bonds). Molten lithium is significantly more reactive than its solid form.

Lithium metal is soft enough to be cut with a knife. When cut, it possesses a silvery-white color that quickly changes to gray as it oxidizes to lithium oxide. Its melting point of 180.50 °C (453.65 K; 356.90 °F) and its boiling point of 1,342 °C (1,615 K; 2,448 °F) are each the highest of all the alkali metals while its density of 0.534

g

/

cm3

is the lowest.

Lithium has a very low density (0.534 g/cm3), comparable with pine wood. It is the least dense of all elements that are solids at room temperature; the next lightest solid element (potassium, at 0.862 g/cm3) is more than 60% denser. Apart from helium and hydrogen, as a solid it is less dense than any other element as a liquid, being only two-thirds as dense as liquid nitrogen (0.808 g/cm3). Lithium can float on the lightest hydrocarbon oils and is one of only three metals that can float on water, the other two being sodium and potassium.

Lithium floating in oil

Lithium's coefficient of thermal expansion is twice that of aluminium and almost four times that of iron.Lithium is superconductive below 400 μK at standard pressure and at higher temperatures (more than 9 K) at very high pressures (>20 GPa). At temperatures below 70 K, lithium, like sodium, undergoes diffusionless phase change transformations. At 4.2 K it has a rhombohedral crystal system (with a nine-layer repeat spacing); at higher temperatures it transforms to face-centered cubic and then body-centered cubic. At liquid-helium temperatures (4 K) the rhombohedral structure is prevalent.Multiple allotropic forms have been identified for lithium at high pressures.

Lithium has a mass specific heat capacity of 3.58 kilojoules per kilogram-kelvin, the highest of all solids.Because of this, lithium metal is often used in coolants for heat transfer applications.

Isotopes

Main article: Isotopes of lithium

Naturally occurring lithium is composed of two stable isotopes, 6Li and 7Li, the latter being the more abundant (92.5% natural abundance). Both natural isotopes have anomalously low nuclear binding energy per nucleon (compared to the neighboring elements on the periodic table, helium and beryllium); lithium is the only low numbered element that can produce net energy through nuclear fission. The two lithium nuclei have lower binding energies per nucleon than any other stable nuclides other than deuterium and helium-3. As a result of this, though very light in atomic weight, lithium is less common in the Solar System than 25 of the first 32 chemical elements.Seven radioisotopes have been characterized, the most stable being 8Li with a half-life of 838 ms and 9Li with a half-life of 178 ms. All of the remaining radioactive isotopes have half-lives that are shorter than 8.6 ms. The shortest-lived isotope of lithium is 4Li, which decays through proton emission and has a half-life of 7.6 × 10−23 s. The 6Li isotope is one of only five stable nuclides to have both an odd number of protons and an odd number of neutrons, the other four stable odd-odd nuclides being hydrogen-2, boron-10, nitrogen-14, and tantalum-180m.

7Li is one of the primordial elements (or, more properly, primordial nuclides) produced in Big Bang nucleosynthesis. A small amount of both 6Li and 7Li are produced in stars during stellar nucleosynthesis, but it is further "burned" as fast as produced. 7Li can also be generated in carbon stars. Additional small amounts of both 6Li and 7Li may be generated from solar wind, cosmic rays hitting heavier atoms, and from early solar system 7Be and 10Be radioactive decay.

Lithium isotopes fractionate substantially during a wide variety of natural processes, including mineral formation (chemical precipitation), metabolism, and ion exchange. Lithium ions substitute for magnesium and iron in octahedral sites in clay minerals, where 6Li is preferred to 7Li, resulting in enrichment of the light isotope in processes of hyperfiltration and rock alteration. The exotic 11Li is known to exhibit a neutron halo, with 2 neutrons orbiting around its nucleus of 3 protons and 6 neutrons. The process known as laser isotope separation can be used to separate lithium isotopes, in particular 7Li from 6Li.

Nuclear weapons manufacture and other nuclear physics applications are a major source of artificial lithium fractionation, with the light isotope 6Li being retained by industry and military stockpiles to such an extent that it has caused slight but measurable change in the 6Li to 7Li ratios in natural sources, such as rivers. This has led to unusual uncertainty in the standardized atomic weight of lithium, since this quantity depends on the natural abundance ratios of these naturally-occurring stable lithium isotopes, as they are available in commercial lithium mineral sources.

Both stable isotopes of lithium can be laser cooled and were used to produce the first quantum degenerate Bose-Fermi mixture.

Occurrence

Astronomical

Main articles: Nucleosynthesis, Stellar nucleosynthesis, and Lithium burning

Although it was synthesized in the Big Bang, lithium (together with beryllium and boron) is markedly less abundant in the universe than other elements. This is a result of the comparatively low stellar temperatures necessary to destroy lithium, along with a lack of common processes to produce it.

According to modern cosmological theory, lithium—in both stable isotopes (lithium-6 and lithium-7)—was one of the three elements synthesized in the Big Bang. Though the amount of lithium generated in Big Bang nucleosynthesis is dependent upon the number of photons per baryon, for accepted values the lithium abundance can be calculated, and there is a "cosmological lithium discrepancy" in the universe: older stars seem to have less lithium than they should, and some younger stars have much more. The lack of lithium in older stars is apparently caused by the "mixing" of lithium into the interior of stars, where it is destroyed,while lithium is produced in younger stars. Although it transmutes into two atoms of helium due to collision with a proton at temperatures above 2.4 million degrees Celsius (most stars easily attain this temperature in their interiors), lithium is more abundant than computations would predict in later-generation stars.

Astronomical

Main articles: Nucleosynthesis, Stellar nucleosynthesis, and Lithium burning

Although it was synthesized in the Big Bang, lithium (together with beryllium and boron) is markedly less abundant in the universe than other elements. This is a result of the comparatively low stellar temperatures necessary to destroy lithium, along with a lack of common processes to produce it.

According to modern cosmological theory, lithium—in both stable isotopes (lithium-6 and lithium-7)—was one of the three elements synthesized in the Big Bang. Though the amount of lithium generated in Big Bang nucleosynthesis is dependent upon the number of photons per baryon, for accepted values the lithium abundance can be calculated, and there is a "cosmological lithium discrepancy" in the universe: older stars seem to have less lithium than they should, and some younger stars have much more. The lack of lithium in older stars is apparently caused by the "mixing" of lithium into the interior of stars, where it is destroyed, while lithium is produced in younger stars. Although it transmutes into two atoms of helium due to collision with a proton at temperatures above 2.4 million degrees Celsius (most stars easily attain this temperature in their interiors), lithium is more abundant than computations would predict in later-generation stars.

Terrestrial

Although lithium is widely distributed on Earth, it does not naturally occur in elemental form due to its high reactivity. The total lithium content of seawater is very large and is estimated as 230 billion tonnes, where the element exists at a relatively constant concentration of 0.14 to 0.25 parts per million (ppm), or 25 micromolar; higher concentrations approaching 7 ppm are found near hydrothermal vents.

Estimates for the Earth's crustal content range from 20 to 70 ppm by weight. Lithium constitutes about 0.002 percent of Earth's crust. In keeping with its name, lithium forms a minor part of igneous rocks, with the largest concentrations in granites. Granitic pegmatites also provide the greatest abundance of lithium-containing minerals, with spodumene and petalite being the most commercially viable sources. Another significant mineral of lithium is lepidolite which is now an obsolete name for a series formed by polylithionite and trilithionite. A newer source for lithium is hectorite clay, the only active development of which is through the Western Lithium Corporation in the United States. At 20 mg lithium per kg of Earth's crust, lithium is the 25th most abundant element.

According to the Handbook of Lithium and Natural Calcium, "Lithium is a comparatively rare element, although it is found in many rocks and some brines, but always in very low concentrations. There are a fairly large number of both lithium mineral and brine deposits but only comparatively few of them are of actual or potential commercial value. Many are very small, others are too low in grade."

Chile is estimated (2020) to have the largest reserves by far (9.2 million tonnes), and Australia the highest annual production (40,000 tonnes). One of the largest reserve basesof lithium is in the Salar de Uyuni area of Bolivia, which has 5.4 million tonnes. Other major suppliers include Australia, Argentina and China. As of 2015, the Czech Geological Survey considered the entire Ore Mountains in the Czech Republic as lithium province. Five deposits are registered, one near Cínovec is considered as a potentially economical deposit, with 160 000 tonnes of lithium. In December 2019, Finnish mining company Keliber Oy reported its Rapasaari lithium deposit has estimated proven and probable ore reserves of 5.280 million tonnes.

In June 2010, The New York Times reported that American geologists were conducting ground surveys on dry salt lakes in western Afghanistan believing that large deposits of lithium are located there. These estimates are "based principally on old data, which was gathered mainly by the Soviets during their occupation of Afghanistan from 1979–1989". The Department of Defense estimated the lithium reserves in Afghanistan to amount to the ones in Bolivia and dubbed it as a potential "Saudi-Arabia of lithium". In Cornwall, England, the presence of brine rich in lithium was well known due to the region's historic mining industry, and private investors have conducted tests to investigate potential lithium extraction in this area.

Biological

ithium is found in trace amount in numerous plants, plankton, and invertebrates, at concentrations of 69 to 5,760 parts per billion (ppb). In vertebrates the concentration is slightly lower, and nearly all vertebrate tissue and body fluids contain lithium ranging from 21 to 763 ppb. Marine organisms tend to bioaccumulate lithium more than terrestrial organisms. Whether lithium has a physiological role in any of these organisms is unknown.

Studies of lithium concentrations in mineral-rich soil give ranges between around 0.1 and 50−100 ppm, with some concentrations as high as 100−400 ppm, although it is unlikely that all of it is available for uptake by plants. Lithium concentration in plant tissue is typically around 1 ppm, with some plant families bioaccumulating more lithium than others; lithium accumulation does not appear to affect the essential nutrient composition of plants. Tolerance to lithium varies by plant species and typically parallels sodium tolerance; maize and Rhodes grass, for example, are highly tolerant to lithium injury while avocado and soybean are very sensitive. Similarly, lithium at concentrations of 5 ppm reduces seed germination in some species (e.g. Asian rice and chickpea) but not in others (e.g. barley and wheat). Many of lithium's major biological effects can be explained by its competition with other ions. The monovalent lithium ion Li+

competes with other ions such as sodium (immediately below lithium on the periodic table), which like lithium is also a monovalent alkali metal. Lithium also competes with bivalent magnesium ions, whose ionic radius (86 pm) is approximately that of the lithium ion (90 pm). Mechanisms that transport sodium across cellular membranes also transport lithium. For instance, sodium channels (both voltage-gated and epithelial) are particularly major pathways of entry for lithium. Lithium ions can also permeate through ligand-gated ion channels as well as cross both nuclear and mitochondrial membranes. Like sodium, lithium can enter and partially block (although not permeate) potassium channels and calcium channels. The biological effects of lithium are many and varied but its mechanisms of action are only partially understood. For instance, studies of lithium-treated patients with bipolar disorder show that, among many other effects, lithium partially reverses telomere shortening in these patients and also increases mitochondrial function, although how lithium produces these pharmacological effects is not understood. Even the exact mechanisms involved in lithium toxicity are not fully understood.

History. Petalite (LiAlSi4O10) was discovered in 1800 by the Brazilian chemist and statesman José Bonifácio de Andrada e Silva in a mine on the island of Utö, Sweden. However, it was not until 1817 that Johan August Arfwedson, then working in the laboratory of the chemist Jöns Jakob Berzelius, detected the presence of a new element while analyzing petalite ore. This element formed compounds similar to those of sodium and potassium, though its carbonate and hydroxide were less soluble in water and less alkaline.Berzelius gave the alkaline material the name "lithion/lithina", from the Greek word λιθoς (transliterated as lithos, meaning "stone"), to reflect its discovery in a solid mineral, as opposed to potassium, which had been discovered in plant ashes, and sodium, which was known partly for its high abundance in animal blood. He named the metal inside the material "lithium".

Arfwedson later showed that this same element was present in the minerals spodumene and lepidolite. In 1818, Christian Gmelin was the first to observe that lithium salts give a bright red color to flame. However, both Arfwedson and Gmelin tried and failed to isolate the pure element from its salts. It was not isolated until 1821, when William Thomas Brande obtained it by electrolysis of lithium oxide, a process that had previously been employed by the chemist Sir Humphry Davy to isolate the alkali metals potassium and sodium. Brande also described some pure salts of lithium, such as the chloride, and, estimating that lithia (lithium oxide) contained about 55% metal, estimated the atomic weight of lithium to be around 9.8 g/mol (modern value ~6.94 g/mol). In 1855, larger quantities of lithium were produced through the electrolysis of lithium chloride by Robert Bunsen and Augustus Matthiessen. The discovery of this procedure led to commercial production of lithium in 1923 by the German company Metallgesellschaft AG, which performed an electrolysis of a liquid mixture of lithium chloride and potassium chloride.

Australian psychiatrist John Cade is credited with reintroducing and popularizing the use of lithium to treat mania in 1949. Shortly after, throughout the mid 20th century, lithium's mood stabilizing applicability for mania and depression took off in Europe and the United States.

The production and use of lithium underwent several drastic changes in history. The first major application of lithium was in high-temperature lithium greases for aircraft engines and similar applications in World War II and shortly after. This use was supported by the fact that lithium-based soaps have a higher melting point than other alkali soaps, and are less corrosive than calcium based soaps. The small demand for lithium soaps and lubricating greases was supported by several small mining operations, mostly in the US.

The demand for lithium increased dramatically during the Cold War with the production of nuclear fusion weapons. Both lithium-6 and lithium-7 produce tritium when irradiated by neutrons, and are thus useful for the production of tritium by itself, as well as a form of solid fusion fuel used inside hydrogen bombs in the form of lithium deuteride. The US became the prime producer of lithium between the late 1950s and the mid 1980s. At the end, the stockpile of lithium was roughly 42,000 tonnes of lithium hydroxide. The stockpiled lithium was depleted in lithium-6 by 75%, which was enough to affect the measured atomic weight of lithium in many standardized chemicals, and even the atomic weight of lithium in some "natural sources" of lithium ion which had been "contaminated" by lithium salts discharged from isotope separation facilities, which had found its way into ground water

Lithium is used to decrease the melting temperature of glass and to improve the melting behavior of aluminium oxide in the Hall-Héroult process. These two uses dominated the market until the middle of the 1990s. After the end of the nuclear arms race, the demand for lithium decreased and the sale of department of energy stockpiles on the open market further reduced prices. In the mid 1990s, several companies started to isolate lithium from brine which proved to be a less expensive option than underground or open-pit mining. Most of the mines closed or shifted their focus to other materials because only the ore from zoned pegmatites could be mined for a competitive price. For example, the US mines near Kings Mountain, North Carolina closed before the beginning of the 21st century.

The development of lithium ion batteries increased the demand for lithium and became the dominant use in 2007. With the surge of lithium demand in batteries in the 2000s, new companies have expanded brine isolation efforts to meet the rising demand.

It has been argued that lithium will be one of the main objects of geopolitical competition in a world running on renewable energy and dependent on batteries, but this perspective has also been criticised for underestimating the power of economic incentives for expanded production.

Chemistry Of lithium metal

Lithium reacts with water easily, but with noticeably less vigor than other alkali metals. The reaction forms hydrogen gas and lithium hydroxide. When placed over a flame, lithium compounds give off a striking crimson color, but when the metal burns strongly, the flame becomes a brilliant silver. Lithium will ignite and burn in oxygen when exposed to water or water vapor. In moist air, lithium rapidly tarnishes to form a black coating of lithium hydroxide (LiOH and LiOH·H2O), lithium nitride (Li3N) and lithium carbonate (Li2CO3, the result of a secondary reaction between LiOH and CO2). Lithium is one of the few metals that react with nitrogen gas.

Because of its reactivity with water, and especially nitrogen, lithium metal is usually stored in a hydrocarbon sealant, often petroleum jelly. Although the heavier alkali metals can be stored under mineral oil, lithium is not dense enough to fully submerge itself in these liquids.

Lithium has a diagonal relationship with magnesium, an element of similar atomic and ionic radius. Chemical resemblances between the two metals include the formation of a nitride by reaction with N2, the formation of an oxide (Li2O) and peroxide (Li2O2) when burnt in O2, salts with similar solubilities, and thermal instability of the carbonates and nitrides. The metal reacts with hydrogen gas at high temperatures to produce lithium hydride (LiH).

Lithium forms a variety of binary and ternary materials by direct reaction with the main group elements. These Zintl phases, although highly covalent, can be viewed as salts of polyatomic anions such as Si44-, P73-, and Te52-. With graphite, lithium forms a variety of intercalation compounds.

It dissolves in ammonia (and amines) to give [Li(NH3)4]+ and the solvated electron.

Inorganic compounds Lithium forms salt-like derivatives with all halides and pseudohalides. Some examples include the halides LiF, LiCl, LiBr, LiI, as well as the pseudohalides and related anions. Lithium carbonate has been described as the most important compound of lithium. This white solid is the principal product of beneficiation of lithium ores. It is a precursor to other salts including ceramics and materials for lithium batteries.

The compounds LiBH

4 and LiAlH

4 are useful reagents. These salts and many other lithium salts exhibit distinctively high solubility in ethers, in contrast with salts of heavier alkali metals.

In aqueous solution, the coordination complex [Li(H2O)4]+ predominates for many lithium salts. Related complexes are known with amines and ethers.

Organic chemistry Organolithium compounds are numerous and useful. They are defined by the presence of a bond between carbon and lithium. They serve as metal-stabilized carbanions, although their solution and solid-state structures are more complex than this simplistic view. Thus, these are extremely powerful bases and nucleophiles. They have also been applied in asymmetric synthesis in the pharmaceutical industry. For laboratory organic synthesis, many organolithium reagents are commercially available in solution form. These reagents are highly reactive, and are sometimes pyrophoric.

Like its inorganic compounds, almost all organic compounds of lithium formally follow the duet rule (e.g., BuLi, MeLi). However, it is important to note that in the absence of coordinating solvents or ligands, organolithium compounds form dimeric, tetrameric, and hexameric clusters (e.g., BuLi is actually [BuLi]6 and MeLi is actually [MeLi]4) which feature multi-center bonding and increase the coordination number around lithium. These clusters are broken down into smaller or monomeric units in the presence of solvents like dimethoxyethane (DME) or ligands like tetramethylethylenediamine (TMEDA). As an exception to the duet rule, a two-coordinate lithate complex with four electrons around lithium, [Li(thf)4]+[((Me3Si)3C)2Li]–, has been characterized crystallographically.

Production Lithium production has greatly increased since the end of World War II. The main sources of lithium are brines and ores.

Lithium metal is produced through electrolysis from a mixture of fused 55% lithium chloride and 45% potassium chloride at about 450 °C.

Reserves and occurrence Worldwide identified reserves in 2020 and 2021 were estimated by the US Geological Survey (USGS) to be 17 million and 21 million tonnes, respectively. An accurate estimate of world lithium reserves is difficult. One reason for this is that most lithium classification schemes are developed for solid ore deposits, whereas brine is a fluid that is problematic to treat with the same classification scheme due to varying concentrations and pumping effects.

Following a hike in lithium price in 2015 and concern for insufficiency of lithium resource for the growing battery industry, a peer-reviewed analysis of USGS data in 2017 predicted that there will be no shortage of lithium and the current estimates of the reserves will be subject to increase along with the demand. Worldwide lithium resources identified by USGS started to increase in 2017 owing to continuing exploration. Identified resources in 2016, 2017, 2018, 2019 and 2020 were 41, 47, 54, 62 and 80 million tonnes, respectively.

The world in 2013 was estimated to contain about 15 million tonnes of lithium reserves, while 65 million tonnes of known resources were reasonable. A total of 75% of everything could typically be found in the ten largest deposits of the world. Another study noted that 83% of the geological resources of lithium are located in six brine, two pegmatite, and two sedimentary deposits.

In the US, lithium is recovered from brine pools in Nevada. A deposit discovered in 2013 in Wyoming's Rock Springs Uplift is estimated to contain 228,000 tons. Additional deposits in the same formation were estimated to be as much as 18 million tons. Similarly in Nevada, the McDermitt Caldera hosts lithium-bearing volcanic muds that consist of the largest known deposits of lithium within the United States.

Lithium triangle

The world's top four lithium-producing countries from 2019, as reported by the US Geological Survey are Australia, Chile, China and Argentina. The intersection of Chile, Bolivia, and Argentina make up the region known as the Lithium Triangle. The Lithium Triangle is known for its high quality salt flats including Bolivia's Salar de Uyuni, Chile's Salar de Atacama, and Argentina's Salar de Arizaro. The Lithium Triangle is believed to contain over 75% of existing known lithium reserves. Deposits are found in South America throughout the Andes mountain chain. Chile is the leading producer, followed by Argentina. Both countries recover lithium from brine pools. According to USGS, Bolivia's Uyuni Desert has 5.4 million tonnes of lithium. Half the world's known reserves are located in Bolivia along the central eastern slope of the Andes. Since 2009 the Bolivian government was looking for investors for developing the Salar de Uyuni mine among which were Japanese, French, and Korean firms. In 2019 Bolivian state-run company YLB has signed a contract with Germany's ACI Systems estimated to be $1.2 billion worth to build a lithium hydroxide and lithium-ion batteries plants but quickly scrapped the deal.

Since 2018 the Democratic Republic of Congo is known to have the largest lithium spodumene hard rock deposit in the world. The total resource of the deposit located in Manono, central DRC, has the potential to be in the magnitude of 1.5 billion tons of lithium spodumene hard-rock. The two largest pegmatites (known as the Carriere de l'Este Pegmatite and the Roche Dure Pegmatite) are each of similar size or larger than the famous Greenbushes Pegmatite in Western Australia. In the near future by 2023, the Democratic Republic of Congo is expected to be a significant supplier of lithium to the world with its high grade and low impurities.

According to a later 2011 study by Lawrence Berkeley National Laboratory and the University of California, Berkeley, the then estimated reserve base of lithium should not be a limiting factor for large-scale battery production for electric vehicles because an estimated 1 billion 40 kWh Li-based batteries could be built with those reserves - about 10 kg of lithium per car. Another 2011 study at the University of Michigan and Ford Motor Company found enough resources to support global demand until 2100, including the lithium required for the potential widespread transportation use. The study estimated global reserves at 39 million tons, and total demand for lithium during the 90-year period annualized at 12–20 million tons, depending on the scenarios regarding economic growth and recycling rates.

In 2014, The Financialist stated that demand for lithium was growing at more than 12% a year. According to Credit Suisse, this rate exceeded projected availability by 25%. The publication compared the 2014 lithium situation with oil, whereby "higher oil prices spurred investment in expensive deepwater and oil sands production techniques"; that is, the price of lithium would continue to rise until more expensive production methods that could boost total output would receive the attention of investors.

On 16 July 2018 2.5 million tonnes of high-grade lithium resources and 124 million pounds of uranium resources were found in the Falchani hard rock deposit in the region Puno, Peru.

In 2019, world production of lithium from spodumene was around 80,000t per annum, primarily from the Greenbushes pegmatite and from some Chinese and Chilean sources. The Talison mine in Greenbushes is reported to be the largest and to have the highest grade of ore at 2.4% Li2O (2012 figures).

Oceans are estimated to contain 230 billion tons of lithium, but the concentration is 0.1-0.2ppm, making it more expensive to isolate with 2020 technology than from land based brine and rock.

Sources

Another potential source of lithium as of 2012 was identified as the leachates of geothermal wells, which are carried to the surface. Recovery of this type of lithium has been demonstrated in the field; the lithium is separated by simple filtration. Reserves are more limited than those of brine reservoirs and hard rock.

Pricing

In 1998, the price of lithium metal was about 95 USD/kg (or US$43/lb). After the 2007 financial crisis, major suppliers, such as Sociedad Química y Minera (SQM), dropped lithium carbonate pricing by 20%. Prices rose in 2012. A 2012 Business Week article outlined an oligopoly in the lithium space: "SQM, controlled by billionaire Julio Ponce, is the second-largest, followed by Rockwood, which is backed by Henry Kravis’s KKR & Co., and Philadelphia-based FMC", with Talison mentioned as the biggest producer. Global consumption may jump to 300,000 metric tons a year by 2020[failed verification] from about 150,000 tons in 2012, to match the demand for lithium batteries that has been growing at about 25% a year, outpacing the 4% to 5% overall gain in lithium production.

Extraction Lithium and its compounds were historically isolated and extracted from hard rock but by the 1990s mineral springs, brine pools, and brine deposits had become the dominant source. Most of these were in Chile, Argentina and Bolivia. Large lithium-clay deposits under development in the McDermitt caldera (Nevada, USA) require concentrated sulfuric acid to leach lithium from the clay ore.

By early 2021, much of the lithium mined globally comes from either "spodumene, the mineral contained in hard rocks found in places such as Australia and North Carolina" or from the salty brine pumped directly out of the ground, as it is in locations in Chile.

Low-cobalt cathodes for lithium batteries are expected to require lithium hydroxide rather than lithium carbonate as a feedstock, and this trend favours rock as a source.

In one method of making lithium intermediates from brine, the brine is first pumped up from underground pools and concentrated by solar evaporation. When the lithium concentration is sufficient, lithium carbonate and lithium hydroxide are precipitated by addition of sodium carbonate and calcium hydroxide respectively. Each batch takes from 18 to 24 months.

The use of electrodialysis and electrochemical intercalation has been proposed to extract lithium compounds from seawater (which contains lithium at 0.2 parts per million), but it is not yet commercially viable. Environmental issues

The manufacturing processes of lithium, including the solvent and mining waste, presents significant environmental and health hazards. Lithium extraction can be fatal to aquatic life due to water pollution. It is known to cause surface water contamination, drinking water contamination, respiratory problems, ecosystem degradation and landscape damage. It also leads to unsustainable water consumption in arid regions (1.9 million liters per ton of lithium). Massive byproduct generation of lithium extraction also presents unsolved problems, such as large amounts of magnesium and lime waste.

In the United States, there is active competition between environmentally catastrophic open-pit mining, mountaintop removal mining and less damaging brine extraction mining in an effort to drastically expand domestic lithium mining capacity. Environmental concerns include wildlife habitat degradation, potable water pollution including arsenic and antimony contamination, unsustainable water table reduction, and massive mining waste, including radioactive uranium byproduct and sulfuric acid discharge.

Human rights issues

A study of relationships between lithium extraction companies and indigenous peoples in Argentina indicated that the state may not have protected indigenous peoples' right to free prior and informed consent, and that extraction companies generally controlled community access to information and set the terms for discussion of the projects and benefit sharing.

Development of the Thacker Pass lithium mine in Nevada, USA has met with protests and lawsuits from several indigenous tribes who have said they were not provided free prior and informed consent and that the project threatens cultural and sacred sites. They have also expressed concerns that development of the project will create risks to indigenous women, because resource extraction is linked to missing and murdered indigenous women. Protestors have been occupying the site of the proposed mine since January, 2021.

Investment A number of options are available in the marketplace to invest in the metal. While buying physical stock of lithium is hardly possible, investors can buy shares of companies engaged in lithium mining and producing. Also, investors can purchase a dedicated lithium ETF offering exposure to a group of commodity producers.

With substantial demand growth for lithium occurring in the 2020s, lithium mining and production companies are growing and some are experiencing marked increases in market valuation. Lithium Americas, Piedmont Lithium, AVZ Minerals and MP Materials stock prices have increased substantially as a result of the increased importance of lithium to the global economy. In 2021, AVZ Minerals, an Australian company, is developing the Manono Lithium and Tin project in Manono, Democratic Republic of the Congo, the resource has high grade low impurities at 1.65% Li2O (Lithium oxide) spodumene hard-rock based on studies and drilling of Roche Dure, one of several pegmatites in the deposit. There is a push globally by the EU and major car manufacturers (OEM) for all lithium to be produced and sourced sustainably with ESG initiatives and zero to low carbon footprint. The AVZ Minerals Manono project has completed a GHG greenhouse study in 2021 into its future carbon footprint. This has become more commonplace now for batteries supply chain companies to comply with Environmental, social, and governance (ESG), sustainable practices, compliance with government environmental regulations, EIA and low carbon footprint performance, in order to be considered for financing/Investment activities and funds portfolios. Responsible investments is critical to help meet the Paris Agreement and the UN SDGs. The study shows the AVZ Minerals DRC Manono project to likely have one of the lowest carbon footprint of all the spodumene hard rock producers by 30% to 40% and some brine producers throughout the world. AVZ Minerals signed a long-term offtake partnership with major Ganfeng Lithium, China's largest lithium compounds producer. Importantly, the partnership makes provisions for both parties to focus on environmental, social and governance (ESG) development.

Johan August Arfwedson is credited with the discovery of lithium in 1817

As of early 2021, Piedmont Lithium Ltd—an Australian company founded in 2016—is exploring 2,300 acres (930 ha) of land it owns or has mineral rights to in Gaston County, North Carolina. "The modern lithium-mining industry started in this North Carolina region in the 1950s, when the metal was used to make components for nuclear bombs. One of the world’s biggest lithium miners by production, Albemarle Corp, is based in nearby Charlotte. Nearly all of its lithium, however, is extracted in Australia and Chile, which have large, accessible deposits of the metal." As of 2021, just one percent of global lithium supply is both mined and processed in the United States (3,150 t (6,940,000 lb)), while 233,550 t (514,890,000 lb) is produced in Australia and Chile.

It is expected that lithium will be recycled from end-of-life lithium-ion batteries in the future but as of 2020, batteries are not designed for recycling, the technology is not well developed, and recycling rates are 5% or lower.In any case, the most valuable component is likely to remain the NCM cathode material, and the recovery of this material is expected to be the driver.

Applications

Estimates of global lithium uses in 2011 (picture) and 2019 (numbers below)

Ceramics and glass (18%)

Batteries (65%)

Lubricating greases (5%)

Continuous casting (3%)

Air treatment (1%)

Polymers

Primary aluminum production

Pharmaceuticals

Other (5%)

Ceramics and glass

Lithium oxide is widely used as a flux for processing silica, reducing the melting point and viscosity of the material and leading to glazes with improved physical properties including low coefficients of thermal expansion. Worldwide, this is one of the largest use for lithium compounds. Glazes containing lithium oxides are used for ovenware. Lithium carbonate (Li2CO3) is generally used in this application because it converts to the oxide upon heating.

Late in the 20th century, lithium became an important component of battery electrolytes and electrodes, because of its high electrode potential. Because of its low atomic mass, it has a high charge- and power-to-weight ratio. A typical lithium-ion battery can generate approximately 3 volts per cell, compared with 2.1 volts for lead-acid and 1.5 volts for zinc-carbon. Lithium-ion batteries, which are rechargeable and have a high energy density, differ from lithium batteries, which are disposable (primary) batteriesanode. Other rechargeable batteries that use lithium include the lithium-ion polymer battery, lithium iron phosphate battery, and the nanowire battery.

Over the years opinions have been differing about potential growth. A 2008 study concluded that "realistically achievable lithium carbonate production would be sufficient for only a small fraction of future PHEV and EV global market requirements", that "demand from the portable electronics sector will absorb much of the planned production increases in the next decade", and that "mass production of lithium carbonate is not environmentally sound, it will cause irreparable ecological damage to ecosystems that should be protected and that LiIon propulsion is incompatible with the notion of the 'Green Car'".

Lubricating greases

Main article: Lithium grease

The third most common use of lithium is in greases. Lithium hydroxide is a strong base and, when heated with a fat, produces a soap made of lithium stearate. Lithium soap has the ability to thicken oils, and it is used to manufacture all-purpose, high-temperature lubricating greases.

Lithium floating in oil

Metallurgy

Lithium (e.g. as lithium carbonate) is used as an additive to continuous casting mould flux slags where it increases fluidity, a use which accounts for 5% of global lithium use (2011). Lithium compounds are also used as additives (fluxes) to foundry sand for iron casting to reduce veining.

Lithium (as lithium fluoride) is used as an additive to aluminium smelters (Hall–Héroult process), reducing melting temperature and increasing electrical resistance, a use which accounts for 3% of production (2011).

When used as a flux for welding or soldering, metallic lithium promotes the fusing of metals during the process and eliminates the forming of oxides by absorbing impurities. Alloys of the metal with aluminium, cadmium, copper and manganese are used to make high-performance, low density aircraft parts (see also Lithium-aluminium alloys).

Silicon nano-welding

Lithium has been found effective in assisting the perfection of silicon nano-welds in electronic components for electric batteries and other devices.

Pyrotechnics

Lithium compounds are used as pyrotechnic colorants and oxidizers in red fireworks and flares.

Air purification

Lithium chloride and lithium bromide are hygroscopic and are used as desiccants for gas streams. Lithium hydroxide and lithium peroxide are the salts most used in confined areas, such as aboard spacecraft and submarines, for carbon dioxide removal and air purification. Lithium hydroxide absorbs carbon dioxide from the air by forming lithium carbonate, and is preferred over other alkaline hydroxides for its low weight.

Lithium peroxide (Li2O2) in presence of moisture not only reacts with carbon dioxide to form lithium carbonate, but also releases oxygen. The reaction is as follows:

2 Li2O2 + 2 CO2 → 2 Li2CO3 + O2.

Some of the aforementioned compounds, as well as lithium perchlorate, are used in oxygen candles that supply submarines with oxygen. These can also include small amounts of boron, magnesium, aluminum, silicon, titanium, manganese, and iron.

Optics

Lithium fluoride, artificially grown as crystal, is clear and transparent and often used in specialist optics for IR, UV and VUV (vacuum UV) applications. It has one of the lowest refractive indexes and the furthest transmission range in the deep UV of most common materials. Finely divided lithium fluoride powder has been used for thermoluminescent radiation dosimetry (TLD): when a sample of such is exposed to radiation, it accumulates crystal defects which, when heated, resolve via a release of bluish light whose intensity is proportional to the absorbed dose, thus allowing this to be quantified. Lithium fluoride is sometimes used in focal lenses of telescopes.

The high non-linearity of lithium niobate also makes it useful in non-linear optics applications. It is used extensively in telecommunication products such as mobile phones and optical modulators, for such components as resonant crystals. Lithium applications are used in more than 60% of mobile phones.

Satellite images of the Salar del Hombre Muerto, Argentina

Organic and polymer chemistry

Organolithium compounds are widely used in the production of polymer and fine-chemicals. In the polymer industry, which is the dominant consumer of these reagents, alkyl lithium compounds are catalysts/initiators. in anionic polymerization of unfunctionalized olefins. For the production of fine chemicals, organolithium compounds function as strong bases and as reagents for the formation of carbon-carbon bonds. Organolithium compounds are prepared from lithium metal and alkyl halides.

Many other lithium compounds are used as reagents to prepare organic compounds. Some popular compounds include lithium aluminium hydride (LiAlH4), lithium triethylborohydride, n-butyllithium and tert-butyllithium.

Military

Metallic lithium and its complex hydrides, such as Li[AlH4], are used as high-energy additives to rocket propellants. Lithium aluminum hydride can also be used by itself as a solid fuel.

The Mark 50 torpedo stored chemical energy propulsion system (SCEPS) uses a small tank of sulfur hexafluoride, which is sprayed over a block of solid lithium. The reaction generates heat, creating steam to propel the torpedo in a closed Rankine cycle.

Lithium hydride containing lithium-6 is used in thermonuclear weapons, where it serves as fuel for the fusion stage of the bomb.

Nuclear Lithium-6 is valued as a source material for tritium production and as a neutron absorber in nuclear fusion. Natural lithium contains about 7.5% lithium-6 from which large amounts of lithium-6 have been produced by isotope separation for use in nuclear weapons.Lithium-7 gained interest for use in nuclear reactor coolants.

Lithium deuteride was the fusion fuel of choice in early versions of the hydrogen bomb. When bombarded by neutrons, both 6Li and 7Li produce tritium — this reaction, which was not fully understood when hydrogen bombs were first tested, was responsible for the runaway yield of the Castle Bravo nuclear test. Tritium fuses with deuterium in a fusion reaction that is relatively easy to achieve. Although details remain secret, lithium-6 deuteride apparently still plays a role in modern nuclear weapons as a fusion material.

Lithium fluoride, when highly enriched in the lithium-7 isotope, forms the basic constituent of the fluoride salt mixture LiF-BeF2 used in liquid fluoride nuclear reactors. Lithium fluoride is exceptionally chemically stable and LiF-BeF2 mixtures have low melting points. In addition, 7Li, Be, and F are among the few nuclides with low enough thermal neutron capture cross-sections not to poison the fission reactions inside a nuclear fission reactor.

In conceptualized (hypothetical) nuclear fusion power plants, lithium will be used to produce tritium in magnetically confined reactors using deuterium and tritium as the fuel. Naturally occurring tritium is extremely rare, and must be synthetically produced by surrounding the reacting plasma with a 'blanket' containing lithium where neutrons from the deuterium-tritium reaction in the plasma will fission the lithium to produce more tritium:

6Li + n → 4He + 3H.

Lithium is also used as a source for alpha particles, or helium nuclei. When 7Li is bombarded by accelerated protons 8Be is formed, which almost immediately undergoes fission to form two alpha particles. This feat, called "splitting the atom" at the time, was the first fully man-made nuclear reaction. It was produced by Cockroft and Walton in 1932.

In 2013, the US Government Accountability Office said a shortage of lithium-7 critical to the operation of 65 out of 100 American nuclear reactors "places their ability to continue to provide electricity at some risk". Castle Bravo first used lithium-7, in the Shrimp, its first device, which weighed only 10 tons, and generated massive nuclear atmospheric contamination of Bikini Atoll. This perhaps accounts for the decline of US nuclear infrastructure. The equipment needed to separate lithium-6 from lithium-7 is mostly a cold war leftover. The US shut down most of this machinery in 1963, when it had a huge surplus of separated lithium, mostly consumed during the twentieth century. The report said it would take five years and $10 million to $12 million to reestablish the ability to separate lithium-6 from lithium-7.

Reactors that use lithium-7 heat water under high pressure and transfer heat through heat exchangers that are prone to corrosion. The reactors use lithium to counteract the corrosive effects of boric acid, which is added to the water to absorb excess neutrons.

Lithium deuteride was used as fuel in the Castle Bravo nuclear device.

Medicine

Main article: Lithium (medication)

Lithium is useful in the treatment of bipolar disorder. Lithium salts may also be helpful for related diagnoses, such as schizoaffective disorder and cyclic major depression. The active part of these salts is the lithium ion Li+. They may increase the risk of developing Ebstein's cardiac anomaly in infants born to women who take lithium during the first trimester of pregnancy.

Lithium has also been researched as a possible treatment for cluster headaches.