4.

2 • Alkaline Earth Metals

361 4

.. Table 4.21 World beryllium metal producers

Producer Address

Materion (formerly Brush Wellman Inc., 14710 W. Portage River Road South, Elmore, OH 43416, USA
Beryllium Metals Products Division) Tel.: +1-419-8624173
Fax: +1-419-8624174
URL: ▶ http://www.brushwellman.com

NGK Metals Corporation 917 US Highway 11 South, Sweetwater, TN 37874, USA

Tel.: +1-909-3400190
Fax: +1-877-6452328
E-mail: marketing@ngkmetals.com
URL: ▶ http://www.ngkmetals.com/

same form for electrical components. Approximately 13% is used as an alloy, oxide, or metal
in aerospace and defense applications, while the balance is used as an alloy, metal, or oxide for
other purposes.

4.2.1.7 Major Beryllium Metal Producers

The two major beryllium producers are listed in . Table 4.21.

4.2.1.8 Further Reading

Grew, E.S. (ed.) (2002) Beryllium: Mineralogy, Petrology and Geochemistry. Reviews in Miner-
alogy and Geochemistry Vol. 50, Mineralogical Society of America, Chantilly, VA.
Kjellgren, B.R.F (1954) Beryllium. In: Hampel, C.A. (ed.) Rare Metals Handbook. Reinhold,
New York.
Pinto, N.P.; Greenspan, J. (1968) Beryllium. In: Gonser, B.W. (ed.) Modern Materials, Vol. 6.
Academic, New York.
Stonehouse, A.J.; Marder, J.M. (1995) Beryllium. In: ASM Metals Handbook, 10th. ed. Vol. 2.
Properties and Selection: Nonferrous Alloys and Special-Purpose Materials. ASM, Materials
Park, OH, pp. 683–687.

4.2.2 Magnesium and Magnesium Alloys

4.2.2.1 Description and General Properties

Magnesium [CAS RN 7439-95-4], chemical symbol Mg, atomic number 12, and relative atomic
mass 24.3050, is the second element of the alkaline earth metals; that is, group IIA (2) of the
periodic table. It is a silvery-white metal quite similar in appearance to bright aluminum but
with a lower density of only 1738 kg · m−3. Hence, it is the lightest structural metal known.
It has a hexagonal close packed crystalline structure; therefore, like most metals having this
crystal lattice structure, it lacks ductility when worked at low temperatures. In addition, in its
pure form, it lacks sufficient strength for most structural applications. However, the addition of
alloying elements greatly improves these properties to such an extent that both cast and wrought
magnesium alloys are widely used, particularly where strength-to-weight ratio is an important
requirement. Magnesium derives its name from magnesite, a magnesium-carbonate mineral
(MgCO3, rhombohedral), and this mineral in turn is said to owe its name to magnesite deposits
found in Magnesia, a district in the ancient region of Thessaly (Greece). Magnesium is strongly
 362 Chapter 4 • Less Common Nonferrous Metals

reactive with oxygen at high temperatures; above its ignition temperature of 645 °C in dry air, it
burns with a dazzling bright white light and generates intense heat. For this reason, magnesium
powders were used in the first generation of photograph flash bulbs, but today this property is
only used in pyrotechnics. Owing to its more negative standard electrode potential (−2.356 V
vs SHE), magnesium is an active element, and as a general rule most magnesium alloys are at
or near the top of the galvanic or electrochemical series. At room temperature, magnesium and
magnesium alloys may be sufficiently resistant to atmospheric corrosion because a protective
anodic film of water-insoluble magnesium hydroxide, Mg(OH)2, forms in a process similar to
4 the formation of passivating film in the active metal aluminum. When corrosion does occur, it
is only the result of the breakdown of this protective layer. Being a strong reducing agent that
forms stable compounds with chlorine, oxygen, and sulfur, magnesium has several pyrometal-
lurgical applications, such as in the production of titanium or zirconium from metallothermic
reduction of their tetrachlorides and in the desulfurization of blast-furnace iron. Its chemical
reactivity is also evident in the magnesium compounds that have wide application in industry,
medicine, and agriculture. Chemical reactions of magnesium metal are reported in . Table 4.22.

Prices (2016) Pure magnesium metal (i.e., 99.8 wt% Mg) is sold as ingots and is priced at
US$ 2.00 per kilogram (i.e., US$ 0.91 per pound).

4.2.2.2 History
The British chemist Sir Humphry Davy is said to have produced an amalgam of magnesium in
1808 by electrolyzing moist magnesium sulfate using a liquid-mercury cathode. The first me-
tallic magnesium, however, was produced 20 years later in 1828 by the French scientist A.A.B.
Bussy. He achieved the reduction of molten magnesium chloride by metallic potassium. In 1833,
the British scientist Sir Michael Faraday was the first to produce magnesium by the electrolysis
of molten magnesium chloride (MgCl2). His experiments were successfully repeated by the
German chemist Robert Bunsen. The first successful industrial production began in Germany
in 1886 by Aluminium und Magnesiumfabrik Hemelingen GmbH based on the electrolysis
of molten carnallite. Aluminium und Magnesiumfabrik Hemelingen later became part of the
industrial complex IG Farben Industrie, which during the 1920s and 1930s developed a pro-
cess for producing large quantities of molten and essentially water-free magnesium chloride,
now known as the IG Farben process, as well as the technology for electrolyzing this product
to magnesium metal and chlorine. Other contributions by IG Farben were the development of
numerous cast and malleable alloys, refining and protective fluxes, wrought magnesium prod-
ucts, and a large number of aircraft and automobile applications. During World War II, Dow
Chemical Company of the USA and Magnesium Elektron of the UK began the electrolytic re-
duction of magnesium from seawater pumped from Galveston Bay at Freeport, Texas, USA and
the North Sea at Hartlepool, UK. At the same time, in Ontario, Canada, L.M. Pidgeon’s process
of thermally reducing magnesium oxide with silicon in externally fired retorts was introduced.
Following the war, military applications lost prominence. Dow Chemical broadened civilian
markets by developing wrought products, photoengraving technology, and surface treatment
systems. Extraction remained based on electrolysis and thermal reduction. Refinements were
made to these processes such as the internal heating of retorts (the Magnetherm process, intro-
duced in France in 1961), extraction from dehydrated magnesium chloride prills introduced by
the Norwegian company Norsk Hydro in 1974, and improvements in electrolytic cell technology
from about 1970. Magnesium is the lightest of all machinable metals. Its casting characteristics
4.2 • Alkaline Earth Metals
363 4

.. Table 4.22 Reactions of magnesium metal with acids and bases

Acid Solution Chemical reaction scheme Notes

Acetic acid Dilute Mg0 + 2CH3COOH → Mg2+ + 2CH3COO− + H2(g) Dissolves rapidly
(CH3COOH) with strong
effervescence

Hydrochloric Dilute Mg0 + 2HCl → Mg2+ + 2Cl− + H2(g) Dissolves rapidly

acid (HCl) with strong
effervescence

Sulfuric acid Dilute Mg0 + H2SO4 → Mg2+ + SO2−

4 + H2(g)
Dissolves rapidly
(H2SO4) with strong
effervescence

Concentrated Mg0 + 2H2SO4 → Mg2+ + SO2−

4 + SO2(g) + 2H2O
Dissolves
rapidly

Nitric acid Very dilute 4Mg0 + 10HNO3 → 4Mg2+ + NH+4 + 9NO−3 + 3H2O Dissolves
(HNO3) 0 2+
Dilute 3Mg + 8HNO3 → 3Mg + 6NO−3 + 2NO(g) + 4H2O Dissolves
0 2+
Concentrated Mg + 4HNO3 → Mg + 2NO−3 + 2NO2(g) + 2H2O Dissolves

Sodium hydrox- Dilute None Does not

ide (NaOH) dissolve

The major insoluble magnesium compounds are magnesium ammonium phosphate [Mg(NH4)PO4], mag-
nesium arsenate [Mg3(AsO4)2], magnesium carbonate (MgCO3), magnesium fluoride (MgF2), magnesium
hydroxide [Mg(OH)2], magnesium oxalate (MgC2O4), and magnesium phosphate [Mg3(PO4)2]

are excellent, since the molten metal has a low heat content and low viscosity. Magnesium alloys
have limited cold-forming capabilities, owing to the hexagonal crystalline structure of magne-
sium, but they are readily hot worked at temperatures ranging from 150 to 400 °C.

4.2.2.3 Natural Occurrence, Minerals, and Ores

Magnesium is the eighth most abundant element in Earth’s crust and constitutes 2.5 wt% of
the lithosphere and an average of 1.3 kg/m3 of ocean water, with a maximum of 35 kg/m3 for
certain seas. Owing to its strong chemical reactivity, it does not occur in the native state but
rather is found in a wide variety of compounds in seawater, brines, and rocks. Among the ore
minerals, the most common are the carbonates such as dolomite [(Mg, Ca)(CO3)2, rhombohe-
dral] and magnesite (MgCO3, rhombohedral). Less common are the hydroxide mineral brucite
[Mg(OH)2], the sulfates kiesserite (MgSO4·H2O), kainite (MgSO4·KCl·3H2O), and langbeinite
(2MgSO4·H2O), and the halide mineral carnallite (MgCl2 KCl·6H2O). Magnesium chloride is
recoverable from naturally occurring brines such as the Great Salt Lake (typically containing
1.1 wt% Mg) and the Dead Sea (3.4 wt% Mg), but by far the largest source is the oceans of the
world. Although seawater contains only approximately 0.13 wt% Mg, it represents an almost
inexhaustible source. Both dolomite and magnesite are mined and concentrated by conventional
methods. Carnallite is dug as ore or separated from other salt compounds that are brought to the
surface by solution mining. Naturally occurring magnesium-containing brines are concentrated
in large ponds by solar evaporation. Magnesium is produced profitably in such places as the
USA, Canada, western Europe, South America, and Asia.
 364 Chapter 4 • Less Common Nonferrous Metals

4.2.2.4 Processing and Industrial Preparation

Owing to its strong chemical reactivity, magnesium combines with oxygen and chlorine to form
stable compounds. This means that the extraction of the metal from raw materials is always an
energy-intensive process requiring both low-cost electricity and well-tuned technologies. All
commercial producers of magnesium metal use either the electrolytic reduction of molten an-
hydrous (e.g., Norsk Hydro process) or hydrated (e.g., Dow Chemical process) magnesium chlo-
ride or the nonelectrolytic processes, which consist mainly in the thermochemical reduction
of either calcined magnesite (i.e., magnesia, MgO) or dolomite (i.e., a mixture of magnesium
4 and calcium oxides, called dolime). These nonelectrolytic processes can be sorted according to
the reducing agent: ferrosilicon in the silicothermic process (e.g., the Pidgeon and Magnetherm
processes), carbon in the carbothermic process, or aluminum powder in the aluminothermic
process. Where power costs are low, electrolysis is the cheaper method, and it accounts for
approximately 75–80% of world magnesium production, while the nonelectrolytic processes
account for the balance. Hence, the chief raw materials for magnesium metal preparation are
dolomite [CaMg(CO3)2], magnesia (MgO), carnallite [KMgCl3·6H2O], seawater, and brines.

Electrolytic reduction processes The electrolytic processes comprise two steps: the preparation
of a feedstock containing anhydrous (essentially water-free) magnesium chloride – that is,
MgCl2, (e.g., Norsk Hydro process) – or partially dehydrated magnesium chloride – that is,
MgCl2·H2O (e.g., Dow Chemical process) – or sometimes anhydrous carnallite (e.g., Russian
processes), and the dissociation of this compound into magnesium metal and chlorine gas in
an electrolytic cell. To avoid impurities present in carnallite ores, dehydrated artificial carnal-
lite is produced by controlled crystallization from heated magnesium- and potassium-contain-
ing solutions. Partly dehydrated magnesium chloride can be obtained by the Dow Chemical
process, in which seawater is mixed in a flocculator with lightly burned reactive dolomite (i.e.,
dolime). An insoluble magnesium hydroxide precipitates at the bottom of a settling tank, from
where it is pumped as a slurry, filtered, converted to magnesium chloride by reaction with
hydrochloric acid, and dried in a series of evaporation steps to 25 wt% water content. Final
dehydration occurs during smelting. Finally, anhydrous magnesium chloride is produced
either by dehydration of magnesium chloride brines or by direct chlorination of magnesium
oxide with HCl. In the latter method, exemplified by the IG Farben process, lightly burned
dolomite is mixed with seawater in a flocculator, where magnesium hydroxide is precipitated
out, filtered, and calcined in a kiln to dry magnesium oxide. This is mixed with charcoal,
formed into globules with the addition of magnesium chloride solution, and dried. The glob-
ules are fed into a chlorinator, a brick-lined shaft furnace, where they are heated by carbon
electrodes to approximately 1000–1200 °C. Chlorine gas introduced through portholes in
the furnace reacts with the magnesium oxide to produce molten magnesium chloride, which
is tapped at intervals and sent to the electrolytic cells. Dehydration of magnesium brines is
conducted in stages. In the Norsk Hydro process, impurities are first removed by precipitation
and filtering. The purified brine, which contains approximately 8.5 wt% Mg, is concentrated
by evaporation to 14 wt% and converted to particulates in a prilling tower. This product is
further dried to water-free particles and conveyed to the electrolytic cells. In the Norsk Hydro
(or Dow Chemical) process, electrolytic cells form a refractory semiwall separator (or no wall)
and are essentially refractory brick-lined (or carbon steel) vessels equipped with multiple cast
mild steel cathodes and graphite anodes. These are mounted vertically through the cell hood
and partially submerged in a molten-salt electrolyte composed of a mixture of alkali chlorides
(e.g., 20 wt% MgCl2, 20 wt% CaCl2, and 60 wt% NaCl) to which the anhydrous (or hydrous)
4.2 • Alkaline Earth Metals
365 4
magnesium chloride produced in the processes described earlier is added in concentrations
of 18 wt% (or 6 wt%). The cell is internally (or externally) heated by the Joule effect, with an
operating temperature of 750 °C (or 700 °C), and the specific energy consumption is 18 kWh
(or 12 kWh) per kilogram of magnesium metal produced. In the two electrolytic processes,
chlorine is generated at the graphite anodes, leading to a certain consumption of the anode
material, due to the formation of chlorinated hydrocarbons. Molten magnesium metal forms
into droplets that coalesce, and, because of buoyancy, rise to the surface of the fused salt
bath, forming a liquid metal pool, from which it is collected. The chlorine can be reused in
the dehydration process.

Thermochemical reduction processes These metallothermic reductions are commonly achieved

on either calcined magnesite (i.e., magnesia, MgO) or calcined dolomite (i.e., mixture of mag-
nesium and calcium oxides, called dolime). In the silicothermic reduction (i.e., the Pidgeon
process), a mixture of ground and briquetted dolime, ferrosilicon (i.e., reducing agent, con-
taining 75 wt% Si),25 and fluorspar (i.e., fluxing agent) is fed into a horizontally tubular stainless
steel retort. Because the reaction is endothermic, heat must be supplied to initiate and sustain
the reduction; hence, retorts are externally heated by an oil- or gas-fired furnace. Moreover,
because magnesium reaches a vapor pressure of 1 atm at only 1100 °C, the heat requirements
can be quite high, and to lower reaction temperatures, the process operates under a primary
vacuum (13 Pa) at 1200 °C. After the reduction is complete, magnesium crystals (called crowns)
are removed from the condensers (i.e., cold walls), and the silicate slag (i.e., CaSiO3) with iron
particles is removed as a spent solid, and the retort is recharged. In the Bolzano process, do-
lime–ferrosilicon briquettes are stacked onto a special electrically conductive charge support
system, allowing heat to be provided to the charge by Joule heating. A complete reaction takes
24 h at 1200 °C under a pressure of 400 Pa. In the aluminothermic reduction, the thermal
reduction of dolime is performed with aluminum as the reducing agent and alumina as the
fluxing agent. By addition of alumina (i.e., aluminum oxide, Al2O3) to the charge, the melting
point can be reduced to 1550–1600 °C. This technique has the advantage that the liquid slag can
be heated directly by electric current through a water-cooled copper electrode. The reduction
reaction occurs at 1600 °C and 400–670 Pa. Vaporized magnesium is condensed in a separate
system attached to the reactor, and molten slag and depleted ferrosilicon (20 wt% Si) are tapped
at intervals.

Refining After extraction by the different processes described earlier, crude magnesium metal
is transported to cast shops for removal of impurities, addition of alloying elements, and trans-
formation into ingots, billets, and slabs. During melting and handling, molten magnesium metal
and alloys are protected from burning by a layer of flux or a gas such as sulfur hexafluoride or
sulfur dioxide. For shipping and handling under severe climatic conditions, suitable ventilated
plastic or paper wrappings are required to prevent corrosion. Primary magnesium is available
in grades of 99.90, 99.95, and 99.98 wt%, but in practice grades of 99.95 wt% and 99.98 wt%
have only limited use in the uranium and nuclear industries. For bulk use, commercial grades
of 99.90 wt% and 99.80 wt% are supplied.
Today the world production capacity is around 940,000 tonnes per year. Major magnesium
metal producers are listed in . Table 4.23, which shows that with more than 100 plants operat-
ing the thermal process, Chinese companies are now by far the dominant producers.

25 Ferrosilicon is usually prepared by direct melting of quartzite and iron scrap in an arc melting furnace.
 4
366

.. Table 4.23 Major magnesium metal producers worldwide

Region Country Plant location Owner Annual capacity (tonnes) Process Technology Feedstock

Europe Norway Porsgrunn Norsk Hydro 55,000 Electrolytic IG Farben Anhydrous MgCl2 by-product
(closed December 2001) from Mg-rich brines from
potash production

France Marignac Péchiney 18,000 Thermal Magnetherm Dolime from calcined dolomite
(closed August 2001) reduction

Serbia Bela sterna Thermal Pidgeon Dolime from calcined dolomite

reduction

Russia Berezniki Avisma 35,000 Electrolysis UTI/VAMI Synthetic carnallite

Solikamsk 20,000 Electrolysis UTI/VAMI Synthetic carnallite

Middle East Israel Sdom Dead Sea 27,500 Electrolysis UTI/VAMI Synthetic carnallite
Chapter 4 • Less Common Nonferrous Metals

Magnesium

North Canada Bécancourt, Quebec Norsk Hydro 42,000 Electrolysis IG Farben Magnesite
America
Asbestos, Quebec Noranda 63,000 (closed February Electrolysis Alcan multipolar Serpentine tailings
(Magnola) 2002) cell design

Haley Station, Timminco 7000 Thermal Pidgeon Dolime from calcined dolomite
Ontario reduction

USA Rowley, Uhah Magcorp 38,000 (Chap. 11 Electrolysis Magcorp Natural brines
bankruptcy in 2002)

Freeport, Texas Dow Chemical 65,000 (closed 1998) Electrolysis Dow MgCl2 from seawater

Addy, Washington Northwest Alloys 45,000 (closed June 2001) Thermal Magnetherm Dolime from calcined dolomite
(Alcoa) reduction
.. Table 4.23 (continued)

Region Country Plant location Owner Annual capacity (tonnes) Process Technology Feedstock

Asia China 100+ producers 226,000 Thermal Pidgeon Dolomite

reduction

India Bangalore 1000

4.2 • Alkaline Earth Metals

Hyderabad 1000

Kazakhstan Ust-Kamenogorsk Ust-Kamenogorsk 45,000 Electrolysis UTI/VAMI Synthetic carnallite

Titanium and
Magnesium Plant

Ukraine Kalush 18,000 Electrolysis UTI/VAMI Synthetic carnallite

Zaparozhye 23,000 Electrolysis UTI/VAMI Synthetic carnallite

South Brazil Bocauina Rima Thermal Pidgeon Dolime from calcined dolomite
America reduction

Oceania Australia Weeroona SAMAG 52,000

Port Pirie AMC 90,000 Electrolysis Alcan cell

4 367
 368 Chapter 4 • Less Common Nonferrous Metals

4.2.2.5 Properties of Magnesium Alloys

See . Table 4.25.

4.2.2.6 Industrial Applications and Uses

The applications of magnesium stem from its low weight, high strength and damping capacity,
close dimensional tolerance, and the ease of fabrication of its alloys. Its chief uses and appli-
cations are listed in . Table 4.26. ASTM standard for designating Magnesium alloys are listed
in . Table 4.24.
4
4.2.2.7 Recycling of Magnesium Scrap and Drosses
At present, recycling of magnesium consists in simply remelting the scrap in the presence of
a molten-salt mixture of magnesium, calcium, sodium, and potassium chlorides as a fluxing
agent in an inert and protective atmosphere, usually argon. Several types of magnesium scrap
must be considered; in decreasing order of quality they are:
1. Clean, compact scrap with known composition
2. Scrap castings, painted
3. Dirty scrap mainly contaminated with oil and sand (e.g., turnings)
4. Drosses skimmed from melt surface

4.2.2.8 Major Magnesium Metal Producers

Major magnesium metal producers are listed in . Table 4.27.

4.2.2.9 Further Reading

Avedesian, M.; Baker, H. (eds.) (1998) ASM Specialty Handbook: Magnesium and Magnesium
Alloys. ASM, Materials Park, OH.
Beck, A. (ed.) (2001) Magnesium und seine Legierungen. Springer, Berlin Heidelberg New York.
Friedrich, H.E.; Mordike, B.L. (eds.) (2006) Magnesium Technology. Metallurgy, Design Data,
Applications. Springer, Berlin Heidelberg New York.
Kainer, K.U. (ed.) (2003) Magnesium Alloys and Technologies. Wiley, Weinheim.
Kipouros, G.J.; Sadoway, D.R. (1987) The Chemistry and Electrochemistry of Magnesium Pro-
duction. In: Mammantov, G; Mamantov, C.B.; Braunstein, J. (eds.) Advances in Molten
Salts, Vol. 6. Elsevier, Amsterdam, pp. 127–209.
Mordike, B.L.; Kainer, K.U. (eds.) (1998) Magnesium Alloys and Their Applications. Wiley,
Weinheim.
Rokhlin, L.L. (2002) Magnesium Alloys Containing Rare-Earth Metals: Structure and Properties.
CRC Press, Boca Raton, FL.
Roskill (2004) The Economics of Magnesium Metal. Roskill Information Services, London.
Strelets, K.L. (1998) Electrolytic Production of Magnesium. International Magnesium Asso-
ciation, McLean, VA.

4.2.3 Calcium

4.2.3.1 Description and General Properties

Calcium [CAS RN 7440-70-2], chemical symbol Ca, atomic number 20, and relative atomic mass
(i.e., atomic weight) 40.078(4), is the third element of the alkaline earth metals; that is, group
IIA (2) of the periodic table. The name is derived from the Latin word calx, calcis, meaning