Part A

Aluminium and Its Alloys

It was the chemist Louis Guyton de Morveau (1'/36-1816), a co-worker of Antoine
Laurent Lavoisier (1743-1794), who coined the word "alumine" for one of the sulphates
contained in alum. "Alumine" is derived from the Latin word alumen, which is said to have
been used for potassium alum KAl(SO4)2-12HeO during Roman period. Aluminium
compounds were used in large quantities in antique pottery, as dyestuff and as an astringent
in medicine [ 1].
It is not the word "alumine" which has come to designate aluminium ore, but the word
"bauxite". This is because in 1821 Pierre Berthier (1782-1867), a mining engineer,
discovered that the red soil of the village Les-Baux-de-Provence contained 4 0 - 5 0 %
alumina, the rest being comprised essentially of iron oxide, Fe304 (the source of its red
colour), and silica, SiOe.
Even though it is widely distributed in the earth's crust, aluminium did not become an
industrial metal before the end of the 19th century. Alumina is one of the most stable of all
oxides, with an enthalpy AG of - 1 5 8 2 kJ.mol -~ (the enthalpy of iron oxide is
- 1015 kJ.mol-1). It is very difficult to reduce this oxide [2].
The discovery of metallic aluminium is attributed to Sir Humphrey Davy (1778-1829).
He referred to it using the term "aluminium" in 1809. By electrolysis of molten aluminium
salts, he obtained an alloy of aluminium with iron, because he had used an iron cathode [3].
The chemist Hans Christian (Ersted (1777-1851) and later Friedrich W6hler (1800-
1882) chose to reduce aluminium chloride with potassium. The chloride had been prepared
by chlorination of bauxite in the presence of carbon.
It was W6hler who, in 1827, succeeded in producing a sufficiently pure metal to
determine some of its properties, most notably its low density.
In 1854, Henri Sainte-Claire Deville (1817-1881) improved W6hler' s process. He
replaced potassium with sodium, for two reasons: the reduction of 1 mol of A1 uses 3 mol
of Na (sodium), totalling 60 g, instead of 3 mol of K (potassium) amounting to 117 g. At
that time, sodium was less expensive than potassium. He also replaced aluminium
chloride, which is rather volatile, with a sodium aluminium chloride.
The first plant was created in Paris, in 1856, in the La Glaci~re area, but soon it was shut
down: "The small plant of La Glaci~re, located in an inner suburb of Paris, amidst houses
and market gardens, releasing into the atmosphere smoke laden with soda and chlorine,
was forced to cease its aluminium production after numerous complaints [4]".
In the spring of 1857, Sainte-Claire Deville moved the plant to Nanterre, far away from
residential areas. In 1859, production reached 500 kg. That same year, when Louis Le
4 Corrosion of Aluminium

Chatelier had patented a reduction process of alumina with sodium carbonate, a plant was
built in Salindres, close to Al~s in the Gard country, not far from the bauxite supply and the
salt fields of La Camargue. The production in Salindres has varied between 505 kg, when
the plant was started in 1860, and 2959 kg in 1880, when this process was discontinued.
The first kilograms of aluminium manufactured in 1856 were sold at a price slightly
higher than silver, around 300 Germinal Francs, corresponding to about F15 000 in 1998.
During the 1880s, the metal from the Salindres plant was sold at a price of F 6 0 - 7 0 per kg.
Aluminium, which Sainte-Claire Deville liked to compare to silver, was mainly used for
silverware and jewellery. Charles Cristofle (1805-1863), the celebrated Parisian
silversmith, produced cast artwork made of aluminium alloyed with 2% copper. In
1858, the son of Napoleon III was offered a rattle made of aluminium.
In 1871, Z6nobe Gramme (1826-1901) invented the first revolving machine called a
"dynamo". The use of powerful sources of direct current made it possible to envision
production methods based on electrolysis. Sainte-Claire Deville had tried unsuccessfully
to electrolyse molten aluminium chloride.
The manufacturing process of aluminium by electrolysis of molten alumina was
developed in France by Paul Louis Toussaint H6roult (1863-1914), who filed a patent on
April 23, 1886, and in the United States by Charles Martin Hall (1863 - 1914), who filed his
patent on July 9, 1886. Both had succeeded in dissolving alumina (melting point 2030 ~
in cryolithe A1F3 9 3NaF, which melts at 977 ~ the industrial melt contained about 2 or 3%
alumina.
In 1887, Bayer filed a patent for a method to extract alumina from bauxite based on the
attack of bauxite by hot caustic soda. H~roult went to Switzerland, to Neuhausen, in order
to set up his process; the year after, he came back to France and in 1888 created the Froges
plant near Grenoble. In 1889, 1100 kg were produced in Froges, and sold at F50 per kg

Table A1. World production of primary aluminium

Annual world
Year production (kt)

1900 6
1910 44
1920 125
1930 270
1940 780
1950 1500
1960 4540
1970 10 300
1980 16 080
1990 19 830
 Aluminium and Its Alloys 5

(kt)
20 000

16 000

12 000

8 000

4 000

1950 1960 1970 1980 1990

Figure A1. World production of primary aluminium.

(corresponding to F2500 in 1998). And in 1893, the production reached 86 300 kg, while
the selling prices dropped to F5 per kg (F250 in 1998) [5].
Several plants were set up in France, Switzerland and the United States. Six thousand
metric tons were produced in 1900, and the sales price of aluminium stabilised around F3
per kg (F15 in 1998). This was the start of the industrial adventure of aluminium. The
world production of the so-called primary aluminium amounted to 6000 tonnes in 1900
(see Table A1) and has steadily increased (see Figure A1), especially since 1950.

REFERENCES

[1] Rey A., (dir.), Dictionnaire historique de la languefrangaise, Le Robert, Paris, 1993.
[2] Talbot J., Les ~ldments chimiques et les hommes, SIRPE, 1995.
[3] Pascal P., Nouveau trait~ de chimie min~rale, Masson et Cie, Paris, 1961.
[4] Sainte-Claire Deville H., De l'aluminium, Ses properidt~s, sa fabrication, et ses applications,
Mallet-Bachelier, Paris, 1859, p. 8.
[5] Bocquentin J., La fabrication de l'aluminium par ~lectrolyse, Histoire technique de la
production de l'aluminium, PUG, Grenoble, 1992.