Boron

Boron is a chemical element with the symbol B and atomic number 5. Produced entirely by cosmic ray spallation and supernovae and not by stellar nucleosynthesis, it is a low-abundance element in the Solar system and in the Earth’s crust. Boron 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 boron 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, very pure boron is produced with difficulty because of refractory contamination by carbon or other elements. Several allotropes of boron 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 elemental boron 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 boron 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 refractory materials. Borosilicate glass is desired for its greater strength and thermal shock resistance than ordinary soda lime glass. Boron as sodium perborate is used as a bleach. A small amount of boron 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.

In biology, borates have low toxicity in mammals (similar to table salt), but are more toxic to arthropods and are used as insecticides. Boric acid is mildly antimicrobial, and several natural boron-containing organic antibiotics are known. Boron is an essential plant nutrient and boron compounds such as borax and boric acid are used as fertilizers in agriculture, although it’s only required in small amounts, with excess being toxic. Boron compounds play a strengthening role in the cell walls of all plants. There is no consensus on whether boron is an essential nutrient for mammals, including humans, although there is some evidence it supports bone health.

History

The word boron was coined from borax, the mineral from which it was isolated, by analogy with carbon, which boron resembles chemically.

Borax, its mineral form then known as tincal, glazes were used in China from AD 300, and some crude borax reached the West, where the Perso-Arab alchemist Jābir ibn Hayyān apparently mentioned it in AD 700. Marco Polo brought some glazes back to Italy in the 13th century. Agricola, around 1600, reports the use of borax as a flux in metallurgy. In 1777, boric acid was recognized in the hot springs (soffioni) near Florence, Italy, and became known as sal sedativum, with primarily medical uses. The rare mineral is called sassolite, which is found at Sasso, 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 the element 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 an oxidation product of boron. Jöns Jacob Berzelius identified boron as an element in 1824. Pure boron was arguably first produced by the American chemist Ezekiel Weintraub in 1909.

Natural occurence

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 September 5, 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.

Economic use

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.

Metallurgy

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. 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 its first-approved organic pharmaceutical in the pharmaceutical bortezomib, a new class of drug called the proteasome inhibitors, which are active in 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 fluorescent for dual modality PET and fluorescence imaging of genome modified cells, e.g. cancer, CRISPR/Cas9, or CAR T-cells, in an entire mouse.

Biology

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.

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, it is not an element that is intrinsically poisonous, but their toxicity depends on structure. 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.