Beryllium

Beryllium is a chemical element with the symbol Be and atomic number 4. 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. It is a divalent element which occurs naturally only in combination with other elements in minerals. Notable gemstones which contain beryllium include beryl (aquamarine, emerald) and chrysoberyl. As a free element it is a steel-gray, strong, lightweight and brittle alkaline earth metal.

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. The high thermal conductivities of beryllium and beryllium oxide have led to their use in thermal management applications. When added as an alloying element to aluminium, copper (notably the alloy beryllium copper), iron or nickel beryllium improves many physical properties. Tools made of beryllium copper alloys are strong and hard and do not create sparks when they strike a steel surface. Beryllium does not form oxides until it reaches very high temperatures.

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.

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. Louis-Nicolas Vauquelin discovered beryllium

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

Early precursors of the word beryllium can be traced to many languages, including Latin beryllus; French béry; Ancient Greek βήρυλλος, bērullos, ‘beryl’; Prakrit वॆरुलिय‌ (veruliya); Pāli वेलुरिय (veḷuriya), भेलिरु (veḷiru) or भिलर् (viḷar) – “to become pale”, in reference to the pale semiprecious gemstone beryl. The original source is probably the Sanskrit word वैडूर्य (vaidurya), which is of South Indian origin and could be related to the name of the modern city of Belur. Until c. 1900, beryllium was also known as glucinum or glucinium (with the accompanying chemical symbol “Gl”, or “G”), the name coming from the Ancient Greek word for sweet: γλυκύς, due to the sweet taste of beryllium salts.

Natural occurence

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 Be 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 being 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.

Economic use

Radiation windows

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 the 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 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 will have 18 hexagonal beryllium sections for its mirrors. 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 fuel bundle to pressure tube contact, 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.

Safety

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.

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 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).