Beryllium


Contents

  1. Introduction
  2. Mineralogy
  3. Nuclear Properties
  4. Metallurgy
  5. Properties and Uses
  6. References

Introduction

Beryllium is not a metal that is often encountered everyday. Although more abundant in the earth's crust than silver, it is more expensive and difficult to produce. The metal itself is very rarely seen, a grey metal formed mainly by powder metallurgy when used as a metal, but more commonly appears as a minor constituent in alloys. Its name comes from the common mineral beryl, which as emerald and aquamarine is an important gemstone, and its chemical symbol is Be. It is also called glucinium, symbol Gl. Glycium and glycinium have been variant spellings.

The oxide was first identified as containing a new element by Haüy (of crystal fame) and Vauquelin in 1797 or 1798 by decomposing beryl. The metal itself was isolated independently by Wöhler and Bussy in 1818, through the reduction of BeCl2 by potassium metal. It was merely a laboratory curiosity until the excellent properties of its alloys with copper were recognized in the 1930's. It was considered a strategic material in World War II because of these alloys.

Mineralogy

Beryllium is a constituent of about 30 identified minerals, but most are rare. The most common beryllium mineral by far is beryl, 3BeO·Al2O3·6SiO2. This is a hard (Mohs 7.5-8.0), relatively light (spgr 2.75-2.80) found in granitic rocks, pegmatites, mica schists and similar environments, occasionally in huge crystals. One crystal was 9 m in length, and weighed 25 tons. Beryl is typically full of inclusions, milky but translucent, and of a greenish color. Clear crystals, which are much smaller but can still be of considerable size, are valuable gemstones. Pure beryl is clear and transparent, but small amounts of impurities color it very attractively. Aquamarine is a fine, pale green-blue, while emerald is deep green due to Cr+++ ion. Because of its color, emerald is the most expensive gemstone, sometimes more costly than diamond. Since the index of refraction of beryl is only 1.580, not much different from that of glass, it does not have the fire or brilliance of diamond and similar gems. However, it is very hard (only corundum, 9, and diamond, 10) are harder. Morganite, a pink to rose beryl, and Golden Beryl, a golden-yellow gem, are less costly than emerald and aquamarine. Usually, the crystals are hand-picked to separate them from the gangue. In ancient times, precious green gems were called smaragdos. This term was applied not only to emerald, but also to malachite.

Currently, most beryllium (93% of world output in 2000) comes from a bertrandite deposit in Juab County, Utah, in Spor Mountain. Bertrandite is Be4Si2O7(OH)2, an alteration product of beryl. It forms clear or white orthorhombic crystals with one plane of good cleavage, is hard (6-7) and of moderate weight (sp.gr. 3.3-3.5; one source says 2.6). The concentrate is sent to Ohio for processing.

Perhaps the most important beryllium mineral after beryl and bertrandite is chrysoberyl, Be(AlO2)2, which at 8.5 is nearly as hard as corundum. Its crystals are orthorhombic, often occurring in pseudo-hexagonal clusters. When of gem quality, chrysoberyl provides alexandrite, with its amazing dichroism, that makes it red when seen from one direction, green from another, and also cat's eye, with inclusions of rutile (TiO2). Another rare beryllium mineral is euclase, named after its perfect cleavage. Its formula is BeAlSiO4(OH). It is a phyllosilicate (layered, like mica; beryl is a 3D tectosilicate), found in granite pegmatites, often with topaz. Due to its hardness (7.5) and durability, it is also found in placers. It may be clear, green or blue.

Nuclear Properties

The atomic number of Be is only 4, and the only naturally occurring isotope has mass number 9, so the nucleus contains 4 protons and 5 neutrons. The atomic weight is 9.012. The isotope with mass number 8, which might be expected to be quite stable with paired-off protons and neutrons, actually splits with a half-life of less than 4 x 10-16 seconds into two alpha particles, which are even more stable. The decay energy is only 90 keV, however. Be8 is the only light nuclide to undergo alpha decay, but it is a very unusual sort of alpha-decay, that is also fission at the same time. Be7 captures an orbital electron (K-capture) to become Li7, half-life 53 days. Be10 is nearly stable, since its half-life is 2 x 106 years against beta-decay to stable B10. These are the only four beryllium nuclides.

Beryllium played an important role in the discovery of the neutron. The nuclear reactions that occurred when fast alpha-particles collided with light nuclei were extensively studied. The (α,p) [alpha in, proton out] reaction was an example, as in N14(α,p)O17. The reaction with Be9 produced a very penetrating radiation, very unlike a fast proton, that was initially believed to be a gamma ray (photon). However, in 1932 Chadwick showed that it was an uncharged massive particle that could eject protons by collision, which a gamma could never do. The reaction was, in fact, Be9(α,n)C12. This solved the outstanding problem of the constitution of the nucleus, since everything was consistent with an assembly of Z protons and A - Z neutrons, all with half-integral spin.

The thermal neutron absorption cross section of Be9 is only 10 mbarns, a rather small value, so beryllium makes a good neutron moderator in fission reactors. It is lighter than C (9 vs. 12), so a neutron can lose more energy in one collision with beryllium that with carbon. Neutron absorption reactions are Be9(n,α)He6 (winding up as Li6), and Be9(n,2n)Be8 (winding up as 2α). Beryllium is not only a moderator, but also a source of neutrons. Beryllium was considered a promising material for high-temperature nuclear reactors (carbon, of course, cannot be used). Beryllium was used as a neutron reflector to reduce the size of reactor cores. It is used in nuclear weapons for the same purpose.

Metallurgy

Beryllium ores contain no more than 5% Be, because it is so light. The first step is to decompose the beryl, and separate the beryllium. This can be done with hydrofluoric acid or fluorides, producing a soluble fluoberyllate such as BeF2·2KF. Sulphates or chlorides can also be formed. Beryllium can then be precipitated as the hydroxide Be(OH)2, which on heating gives BeO. BeO, beryllia, is a very useful ceramic with a melting point of 2570°C and great resistance to thermal shock.

The metal can be produced by electrolysis at temperatures just below its melting point, or about 1300°C. Unlike most metallic halides, BeCl2 is poorly conducting when fused, so it is usually mixed with NaCl. Barium and sodium fluorides, in which BeO or BeF2 are dissolved, can also be electrolyzed. The metal is obtained in fine flakes or globules, and considerable processing is necessary to remove the slag. BeO can be reduced by carbon, but the product is the carbide, Be2C. Currently, the preferred method is reducing BeF2 by magnesium metal. In general, the metallurgy of beryllium is very difficult.

Beryllium and beryllium oxide in any forms are quite expensive, and this fact limits their use. The current price (2004) for the powder metal is $375 per pound, and for copper master alloy, $160 per pound of Be content.

Properties and Uses

Beryllium crystallizes in the hexagonal close packed structure. It is definitely a metal, but a hard and brittle one. Its electron configuration is 1s22s2, so its compounds can be expected to be electron-poor and somewhat exotic. It is a rather small ion, of radius 0.31Å. Its ionic valence is clearly +2, and this is shown in numerous compounds. The first ionizing potential is 9.28V, greater even than that of magnesium. In the halides, the electron transfer is not by any means complete, and these compounds do not ionize easily. The compounds of beryllium are colorless. Aside from these properties, beryllium behaves similarly to aluminium. It is not much like magnesium, calcium or barium, the other elements called the alkaline earths, except in valence. In fact, it is not very alkaline at all, and its oxide and hydroxide are not even soluble. It is not mentioned in qualtitative analysis texts, since it is encountered very rarely. It probably is separated with the aluminium and must then be distinguished from it by the precipitation of a basic carbonate by adding ammonium carbonate. An excess of reagent dissolves the precipitate. Like aluminum, it forms a protective oxide layer on exposure to air, which makes the surface very hard. Beryllium resists atmospheric corrosion at high temperatures better than titanium or zirconium. Above 600°C, the oxide is first formed, and then the nitride, Be3N2 at 1000°C. Metallic beryllium should not be used at temperatures over 600°C.

The specific gravity is 1.85, only slightly greater than that of magnesium (1.74) and considerably less than that of aluminium (2.7). Its hardness is 6.5, melting point 1285°C, boiling point 2780°C. It would be an exellent light, strong structural material for high temperatures if it were not for its brittleness and extreme difficulty of working. Its electrical resistivity is 18.5 μΩ-cm, a relatively low value, making it useful for electrical leads. The thermal expansion coefficient is 12.3 x 10-6 °C-1, heat capacity 0.425 cal/g/°C and heat conductivity 0.3847 cal/s/cm2/°C/cm. The latent heat of fusion is 341 cal/g.

As a sintered powder (1000°C, 500 psi), the ultimate strength is 45,000 psi, yield point 25,000 psi, Young's modulus 44 x 106 psi, and Poisson's ratio 0.024 (? this seems a very small value). The high Young's modulus and low density make the speed of sound in beryllium quite large (12,500 m/s). The elongation of a tensile specimen on fracture is only around 2%, so the ductility is low. Impact strength is also low. Hot-pressed beryllium can be succesfully machined and drilled. Beryllium can also be vacuum cast, but it is very difficult to machine the castings. Beryllium can be forged hot if encased in steel, and it can be welded, but must be protected from the air.

The alloy 97.75 Cu, 2.25 Be has six times the strength of copper. It is nonsparking (chips do not oxidize readily in air), nonmagnetic, and does not exhibit fatigue failure. Similar alloys may have from 2% to 3% beryllium. This material makes excellent springs, and is a good electrical conductor, since the resistivity of the copper is not raised excessively by the beryllium. Beryllium for alloying is supplied as a 4% alloy with copper, called "master alloy." Since little beryllium is used, its high cost is a minor factor. Be-Al alloys, with up to 65% Be, are also being studied. Phosphor bronze is a substitute for beryllium copper, but is not as serviceable. The Chemical Society's internet periodic table says beryllium is used "to increase the ability to conduct electricity" in copper and nickel, but this is erroneous. Beryllium improves the mechanical properties of the metals, but does not increase the resistivity as much as other alloying elements.

Beryllium and its compounds are very poisonous, especially as dusts. When inhaled, they can produce beryllosis, which is like silicosis, and destroys the lungs. Although some people are little affected, others can develop a sensititivity to beryllium called chronic beryllium disease that scars the lungs. Carcinoma can also result from beryllium poisoning. It is chilling to think that glucinium was named because of the sweet taste of its compounds; its poisonous nature was probably verified at the same time. BeO was used as a phosphor in fluorescent lamps, which made broken discarded fluorescent lamps a great hazard. I understand that BeO phosphor is no longer used. This is much more of a hazard than mercury in refuse. Atomic weapons workers are also subject to beryllium poisoning, although great care has been taken to eliminate the hazard. It is easy to blame beryllium for any lung problems that occur with these workers whatever the cause, to the great delight of lawyers. Beryllium copper and similar uses of the metal, or of beryllia, are not hazardous. There is very little beryllium in the environment, and no evidence that trace amounts are dangerous. The EPA limit is 0.01 μg/m3

in air, the OSHA limit 2 μg/m3 for an 8-hour shift. Beryllium dust from burning coal is a negligible hazard, because of the very small amounts involved.

Because of its low atomic number, beryllium is nearly transparent to X-rays and can be used as windows for X-ray tubes. Currently, the greatest demand for beryllium comes from the telecommunications equipment industry.

References

F. X. M. Zippe, Geschichte der Metalle (Wien: Wilhelm Braumüller, 1857). pp. 358-360.

J. L. Bray, Non-Ferrous Production Metallurgy, 2nd ed. (New York: John Wiley & Sons, 1947). pp. 89-93.

C. H. Hurlbut, Jr., Dana's Manual of Mineralogy, 16th ed. (New York: John Wiley & Sons, 1952). pp. 238, 376, 378

W. N. Jones, Jr., Inorganic Chemistry (Philadelphia: Blakiston, 1949). pp. 607-609.

S. Glasstone and A. Sesonske, Nuclear Reactor Engineering (New York: Van Nostrand Reinhold Co., 1967). pp. 442-445.

For the latest data on beryllium, see Roskill. For toxicity information, see ATSDR.


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Composed by J. B. Calvert
Created 4 March 2004
Last revised 30 June 2004