METALS AND METALLURGY THROUGH THE AGES

Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering
Laval University, Québec City, Canada
[email protected]

ABSTRACT

Seven metals were known to the ancient people: gold, silver, copper, iron, mercury, lead, and tin.
In the Middle Ages the metalloids arsenic, antimony, and bismuth were added. Platinum was later
brought from South America then zinc and boron became known from the East. It was only in the
eighteenth century that mineralogists, travellers, and analysts supplied mineral specimens from
different localities to laboratories where they were analyzed and this resulted in the discovery of
other metals. In the nineteenth century the bulk of metals became known mainly due to Swedish
chemists. In the twentieth century the very rare remaining metals: rhenium and hafnium were
discovered and isolated. In the mean time metals that do not occur in nature or occur only in
infinitesimal quantities became known and were isolated. Metallurgy developed as a result of these
discoveries.

INTRODUCTION

People had inhabited the Earth for hundreds of thousands of years before they began to use metals.
This was the Stone Age in which the only tools available were pieces of wood, bone, flint, or sea
shells. The ancient people used only those metals that were available without mining or chemical
treatment, for example, pieces of native gold, silver, and copper, and rare pieces of meteoric iron.
These were too small in quantity to be of any consequence.

THE SEVEN METALS OF ANTINQUITY

The ancient people knew only seven metals: gold, silver, copper, iron, mercury, lead, and tin. There
are reasons for the early availability of these metals:
 Some of these metals occur in the native state, for example gold and silver.
o
 Oxides of copper, iron, tin, and lead are readily reduced below 800 C. Such temperature can be
attained by burning carbonaceous material.
 Some of these metals have low melting points, for example, lead and tin, while mercury is
already liquid at room temperature, thus they are easy to recover. Impurities in a metal lower the
melting point considerably; for example, iron containing 4% carbon already melts at 1100oC while
the pure metal melts at 1540oC. Metals used by the ancient people were seldom pure. Brass, an
alloy of copper with zinc, was prepared by smelting a copper ore and another ore known as
calamine.

Gold
As civilization progressed, gold became an important metal in Egypt. The pharaohs sent
expeditions of ten of thousands of slaves and soldiers to mine gold in the Eastern Desert. They cast
the metal and produced beautiful artefacts. As early as the Fifth Dynasty (2690-2420 BC) the
ancient Egyptians documented primitive metallurgical operations on wall paintings which show
blow-pipes in use with small furnaces and later they depict the use of bellows so that a high
temperature can be reached when air is blown in the fire by these means (Figure 1). They were
able to hammer gold so that foils can be produced and used for gilding wood and stones.

Figure 1 - Ancient Egyptian wall paintings showing furnaces, manually

operated bellows, melting, and casting of gold

Silver and lead

Silver occurs as native metal or an alloy with gold called electrum. The mines of Laurion near
Athens in ancient Greece supplied most of the silver which was mainly used to mint coins (Figure
2). Lead ores also contain silver and they were sometimes treated for silver. Lead was widely used
in Roman times mainly in making pipes (Figure 3).

Figure 2 - Ancient Greek coin Figure 3 - Typical Roman street with lead
pipe

Copper and tin

Metallic copper was produced by the reduction of its oxide ores in primitive furnaces. Sinai in
Egypt and Cyprus were the main producers. This is believed to be the first metal produced from
oxides by reduction around 4000 BC. An ancient copper ingot is shown in Figure 4. This was,
however, slowly superseded by bronze - - a copper alloy containing about 10% tin, easy to melt
and to cast. Bronze was either produced by mixing tin produced from its oxide by reduction, with
metallic copper, or by reducing a mixture of copper ore with a tin ore; this period of civilization
became known as the Bronze Age. A Roman tin ingot is shown in Figure 5.
 Figure 4 - An Figure 5 - Roman tin ingot
ancient copper [Royal Museum in Truro, Cornwall]
ingot [British
Museum]

Iron
Iron became known much later than copper although iron ores are more abundant than copper ores,
having colorful minerals, and almost as easy to smelt. This may be due to the fact that copper can
be shaped by cold-hammering, whereas iron must be hammered hot. The Iron Age began around
2000 BC and most probably the Hittites in Asia Minor were skilled in this technology. Not many
iron objects resisted corrosion through time except perhaps the Iron Pillar of Delhi which was
made in the fourth century AD (Figure 6).

Figure 6 - Iron Pillar of Delhi [fourth Figure 7 - A gilded bronze statue of

century AD] Marcus Aurelius in Rome

Mercury
Mercury was recovered by heating cinnabar ore which occurred in abundance in Spain and north
of Italy. It was used as a sticking medium to gild copper statues (Figure 7). Gold leaf adheres
firmly on the shiny amalgamated copper surface.
 THE AGE OF ALCHEMY

When an alchemist (Figure 8) dipped a piece of iron into a solution of copper vitriol, i.e., copper
sulfate, the iron was immediately covered by a layer of metallic copper. This apparent
transmutation of iron into copper led the alchemists to be occupied with the transmutation of base
metals into gold. Gold, the most noble of all metals was insoluble in all acids or alkalies known at
that time. The Arab alchemists of the eighth and ninth centuries, e.g., the Jabir Ibn Hayyan (720-
813 AD) thought they could change iron into gold, a process which became known as the
transmutation of metals. He discovered aqua regia, i.e., royal water is a mixture of HCI and HNO3
that dissolves gold; neither of the acids alone has any dissolving action on gold. Nothing
worthwhile in the field of metallurgy took place during the dark ages of magic, superstition, and
alchemy except that many acids and salts were prepared, described, and used for a variety of
purposes.

Figure 8 - An alchemist

The flow of knowledge from the East to the West

The art of making Toledo swords, famous for 200 years thrived under the Arabs in the eighth
century A D. There was cultural contact between the Arabs in Damascus and the Indians, who
excelled in iron making. It was only with the translation of Arabic texts into Latin, and henceforth
the flow of alchemical knowledge to Europe in the tenth century, and the appearance of the
Renaissance in Italy few centuries later, that the art of metal extraction started to take shape.

New metal discoveries

In the 13th and 14th centuries three new metalloids: arsenic, antimony, and bismuth became known
in Europe in the elemental state and were described by the German monk Albertus Magnus (1193-
1280) (Figure 9) and others.
 Figure 9 - Albertus Magnus Figure 10 - Georgius Agricola
(1193-1280) (1494- 1555)

Mining and metallurgical literature

In the sixteenth century two important books on metallurgy appeared. The first “De La
Pirotechnia” appeared in 1540; its author Vannoccio Biringuccio (1480-1538) was working in the
Armoury of Siena in Italy, and had traveled widely through Germany and Italy. The book, written
in Italian, was concerned with ores, assaying, smelting, separating gold from silver, making of
alloys, melting, casting, and fireworks. The second book “De Re Metallica” appeared in 1556; a
year after the death of its author, Georgius Agricola (1494- 1555) (Figure 10) a medical doctor
from Saxony who traveled widely in the mining districts in this area. The title means “Of things
Metallic”; it was the reference book on mining and metallurgy for at least two centuries.

Fire Assaying
Control of the purity of gold and silver, and the prevention of counterfeiting of coins was always
of primary importance to the administrators of the early communities. It is not surprising, therefore,
that methods for analyzing gold and silver were developed. The earliest known procedure which
is still in use today, is known as the fire assaying was documented by Lazarus Ercker (1530-1594).
In summary the material is melted with fluxes, litharge (PbO), and a reducing agent such as flour.
The fluxes contained such ingredients as silica glass, salt, and borax. The gold and silver are
collected in the lead formed by the reduction of litharge. The lead is then removed as oxide under
oxidizing conditions in another step known as “cupellation” by absorption in the material of the
cupel, and there remains a bead of gold and silver, to be weighed. The same principle was applied
on large scale for the recovery of precious metals from lead ores

PLATINA FROM SOUTH AMERICA

For centuries the American Indians in Ecuador in South America collected the silver-like metallic
particles found near the river bed mixed then with gold to make jewellery. They were unable to
melt these particles. After the Spanish Conquest, it was the Spanish naval officer Antonio de Ulloa
(1716-1795) (Figure 11) who brought attention to this metal when he visited this region. The
Spaniards unable to melt these particles, they called them platina a diminutive of silver. It took
nearly a century to identify and isolate the components of platina:
- 1750: Brownrigg and Watson, platinum - 1803 : Walloston : rhodium and palladium
- 1803: Tennant, osmium - 1844 : Klaus, ruthenium
- 1803: Tennant and Des Costils. iridium

Figure 11 - Antonio de Ulloa (1716-1795)

METALS FROM THE EAST

Zinc
The production of metallic zinc was described in a Hindu book written around 1200 AD. The new
“tin-like” metal was made by indirectly heating calamine with organic matter in a covered crucible
fitted with a condenser. Zinc vapor was evolved and the vapor was air cooled in the condenser
located below the refractory crucible (Figure 12). By 1374, the Hindus had recognized that zinc
was a new metal, and a limited amount of commercial zinc production was underway.

Figure 12 - Schematic representation of the Figure 13 - Chinese method for producing zinc
Indian method for producing zinc

From India, zinc manufacture moved to China where it developed as an industry to supply the
needs of brass manufacture (Figure 13). The Chinese apparently learned about zinc production
sometime around 1600 AD., and from China zinc production became known in Europe about a
century and half later. The Chinese also prepared another alloy which looked like silver but did
not contain silver; instead, it contained copper. They called it pai-thung, i.e., white copper. It was
imported to Europe in small quantities in the early 1700s. Much later, it was found out that this
alloy contained a new metal that was called nickel.
Boron
The Arabic word for borax, Al-Buraq, is found in old manuscripts from ancient Persia and Arabia
dating 2000 years ago. Borates were known in ancient times to be useful as a flux for welding gold
and have been found in enamels from China as early as 300 BC. At the end of the 13th century
Marco Polo brought borax from Mongolia to Europe. The same substance was brought later to
Europe from the East Indies by Dutch and Portuguese traders to be used in the fusion of metals
and the preparation of glazes. Boric acid was first prepared in 1702 by Willem Homberg (1652-
1715) a Dutchman born at Batavia on the island of Java. When his father left the service of the
Dutch East India Company, the family settled in Amsterdam. In 1702 he reported to the French
Academy of Sciences in Paris that he had heated borax with a solution of iron vitriol (ferrous
sulfate) and sublimed off with the water vapor a substance which he called “sel volatil narcotique
du vitriol” [boric acid].

Boron was isolated concurrently in 1808 by the French chemist Joseph Louis Gay-Lussac (1778-
1850) and Louis-Jacques Thénard (1778-1857) prepared it through the reduction of boron trioxide
(B2O3) with potassium, and the English chemist Humphry Davy (1778-1829) through the
electrolysis of boric acid. Davy saw similarities between the new element and carbon and found it
logical to use the name boron.

METALS OF THE EIGHTEENTH CENTURY

In the eighteenth century, mineralogists, travellers, and analysts played an important role in the
discovery of new metals. Mineral specimens from different localities were continuously supplied
to laboratories where they were analyzed. It was a hobby of monarchs and wealthy people to collect
minerals (Figure 14). This activity resulted in the discovery of cobalt, nickel, manganese,
molybdenum, chromium, tellurium, and uranium (Table 1). Famous analyst of this period was
Martin Heinrich Klaproth (1743-1817) (Figure 15) who discovered uranium. Beside the blowpipe
which was a useful analytical tool for chemists, new reagents were discovered which were useful
in isolating new metals. Also, the fall of the phlogiston theory contributed to the better
understanding of the smelting process the main metallurgical operation.

Figure 14 - Emperor Franz I (1708-1765) of Figure 15 - Martin Heinrich Klaproth

Austria studies minerals at the Museum of (1743-1817)
Natural History in Vienna
Blowpipe
The blowpipe (Figure 16) was so essential for chemical analysis in the eighteenth century. With
its help the qualitative composition of most minerals was ascertained and the metals were
discovered. The blowpipe is essentially a narrow tube with which air can be blown into the flame.
By mixing suitable fluxes with the sample and using an oxidizing or reducing flame, the mineral
samples were fused and from the color and appearance of the fused material it was possible to
draw conclusions regarding its composition. This useful tool was abandoned only after the
invention of spectral analysis in the middle of the nineteenth century.

Figure 16 - The blowpipe

Table 1 - Metals discovered in the eighteenth century

Year Metal Discoverer Remarks
1735 Cobalt Brandt Discovered in Sweden
1741 Platinum Wood Metal from South America
1745 Boron Bergman Metal from the East. Isolated in 1808 by Gay-Lussac, Thénard, and
Davy
1746 Zinc Marggraff Metal from the East
1751 Nickel Cronstedt Discovered in Sweden
1753 Bismuth Geoffrey Metalloid of the alchemists
1774 Manganese Ghan Discovered in Sweden
1781 Molybdenum Hjelm Discovered in Sweden
1782 Tellurium Müller von Isolated by Müller von Reichenstein but not named. Named in 1798 by
Reichenstein Klaproth
Elhujar Discovered in Spain
1783 Tungsten
brothers
1789 Uranium Klaproth Klaproth believed that he prepared uranium metal when he reduced
U308 with carbon. In fact, he obtained only a lower oxide (UO2). The
metal was isolated by Peligot in 1841 by the reduction of UCl4 with
potassium
1789 Zirconium Klaproth Isolated by Berzelius in 1824 by the reduction of the fluoride with
sodium
1791 Titanium Gregor Isolated by Berzelius in 1824 (impure metal), Nilson and Pettersson in
1887 (95 % pure), and by Hunter in 1910 (99.9 % pure).
1794 Yttrium Gadolin Discovered in Sweden
1797 Beryllium Vauquelin Isolated by Wöhler and Bussy in 1828 by the reduction of the fluoride
with sodium.
1797 Chromium Vauquelin Isolated by Wöhler in 1859 by reducing molten chromium chloride
with zinc

Discovery of hydrogen
Hydrogen discovered by Henry Cavendish (1731-1810) in 1766 was responsible for the isolation
of pure metallic tungsten by the Swedish chemist Jons Jakob Berzelius (1779-1848) (Figure 17)
around 1783. Although hydrogen is a more powerful reducing agent than hot carbon, yet it failed
to liberate the alkali metals, the alkaline earth metals, and aluminum from their oxides.
 Figure 17- Jons Jakob Berzelius (1779-1848)
discovered cerium, selenium, and thorium

Discovery of chlorine
Chlorine discovered by the Swedish chemist Karl Wilhelm Scheele (1742-1786) in 1774 was used
to convert oxides to chlorides from which metals could be obtained by reduction when the oxides
resisted reduction to metals. For example, niobium, zirconium, vanadium were first prepared by
reduction of chlorides when it was not possible to reduce the oxides.

Hydrofluoric acid
Hydrofluoric acid discovered by Scheele in 1771 when he reacted fluorite with sulfuric acid, was
used to prepare fluorides and reduce them to metals when the oxides resisted reduction. Titanium
fluoride was prepared in this way.

Fall of the phlogiston theory

In the seventeenth century, attempts were made to understand the nature of fire and the smelting
process. It was once believed that when coal was burnt, phlogiston which in Greek means flame,
was released and a calx, that is, ash remained. If an ore or an oxide was heated with coal it takes
up the escaping phlogiston in the fire to form the metal:

Ore (oxide) + Phlogiston (from coal) → Metal

It was the French chemist Antoine Laurent Lavoisier (1743-1794) who in 1772 finally directed the
fatal blow to the theory, when a few years earlier oxygen was discovered, and he interpreted the
phenomenon of combustion as an oxidation process.

Foundation of Schools of Mines

The need for schools to train students in the fields of geology, mining, metal extraction and
metallurgy was then realized and this was accomplished by establishing schools in many European
cities as well as in the New World where important mining activities were taking place in the
Spanish colonies. The professors at these schools created the basic literature for the next
generations and also contributed to the discovery of more metals.
 METALS OF THE NINETEENTH CENTURY

In the 19th century the bulk of metals were discovered (Table 2). This was a result of the discovery
of electric current and the development in analytical chemistry and chemical theory.

The discovery of electric current

At the very beginning of the century, the Italian scientist Alessandro Volta (1745-1827) discovered
electric current and this proved to be a very important tool for metallurgists. The newly invented
Volta cell was for the first time used by the British chemist Humphry Davy (1778-1829) (Figure
18) to discover new metals. He joined a large number of these cells in series, and thus was able to
get a large current. He decomposed solid potash just moistened to conduct current; he noticed that
something burned brightly at the cathode. That was potassium metal, which being strongly
reactive, burned in air. In the same way, he electrolyzed soda ash and demonstrated that sodium
metal can be liberated.

Table 2 - Metals discovered and isolated in the nineteenth century

Year Metal Discoverer Remarks

1801 Niobium Hatchett Isolated by Blomstrand in 1864 by reduction of NbCl5 with H2 and
by Moissan in 1901 by carbon reduction of Nb205 in an electric
furnace
1802 Tantalum Ekeberg Discovered in Sweden
1803 Iridium Tennnat Discovered in England
Osmium
Palladium Wollaston Discovered in England
Rhodium
1807 Potassium Davy Discovered in England
Sodium
1808 Boron Gay-Lussac, Thenard, Davy Discovered in France and England
Barium Davy Discovered in England

Calcium Davy Discovered in England

Magnesium Davy Discovered in England
Strontium Davy Discovered in England
1814 Cerium Berzelius Isolated by Hillebrand and Norton in 1895
1817 Lithium Arfwedson Isolated by Davy in minute amounts, but in pure form by Arfwedson
Cadmium Stromeyer Discovered in Germany
Selenium Berzelius Discovered in Sweden
1823 Silicon Berzelius Discovered in Sweden
1827 Aluminum Wöhler Discovered in Germany
1828 Thorium Berzelius Discovered in Sweden
1830 Vanadium Sofstrom Isolated by Roscoe in 1869 by H2 reduction of VCl2. Prepared by
Marden and Rich in 1927 [purity 99.9%] by reduction of the oxide
with Ca
1839 Lanthanum Mosander Discovered in Sweden
1843 Erbium Mosander Discovered in Sweden
Terbium Mosander Discovered in Sweden
1844 Ruthenium Klaus Discovered in Russia
1860 Cesium Bunsen and Kirchhoff Discovered in Prussia

1861 Rubidium Bunsen and Kirchhoff Discovered in Prussia

Thallium Crookes Discovered in England
1863 Indium Reich and Richter
1875 Gallium de Boisbaudran Discovered in France
1878 Ytterbium Marignac Discovered in France
1879 Samarium de Boisbaudran Discovered in France
 Scandium Nilson Discovered in Sweden
Holmium Cleve Discovered in Sweden
Thulium Cleve Discovered in Sweden
1880 Gadolinium Marignac Discovered in France
1885 Praseodymium Auer von Welsbach Discovered in Austria
Neodymuim Auer von Welsbach Discovered in Austria
1886 Dysprosium de Boisbaudran Discovered in France
Germanium Winkler Discovered in Prussia
1896 Europium Demarçay Discovered in France
1898 Polonium Curie Isolated by Mme. Curie and Debierne in 1910

Radium Curie Isolated by Mme. Curie and Debierne in 1910

1899 Actinium Debierne Isolated by Giesel in 1902

Figure 18 - Davy using Volta cells to isolate sodium and potassium

The work of Davy and others opened an entirely new area in metallurgy, though the fact was not
recognized at that time. The intense difficulties to be overcome when removing the oxygen from
such oxides as those of potassium, sodium, barium, calcium, and magnesium clearly suggested
that the alkaline metals themselves might be used to extract the oxygen from other oxides that
prove difficult to split. Aluminum oxide was so resistant to all methods of decomposition that it
was considered at one time to be an element. It was the Danish scientist Christian Oersted (1777-
1851) who in 1852 reacted aluminum chloride with potassium amalgam from which minute
particles of aluminum were recovered by distilling off the mercury. The method was later applied
to other chlorides and to fluorides.

Flame tests
It was Robert Bunsen (1811-1899) (Figure 19) at the University of Heidelberg, who paved the way
for the great discoveries in the nineteenth century with his invention of the burner in 1852 that
carries his name and is found today in most chemical laboratories (Figure 20). This burner
permitted higher temperature to be achieved in the laboratory when conducting a test. Before this
burner the flame of a candle or from alcohol was used. The Bunsen burner flame permitted
performing the flame tests (Figure 21) and later spectroscopic analysis.
 Figure 19 - Robert Bunsen Figure 20- Bunsen burner
(1811-1899)

Figure 21 - Examples of coloured flames in flame tests

The discovery of the spectroscope

In the second half of the nineteenth century the spectroscope (Figure 22) was invented by the
German chemist Bunsen and the physicist Kirchhoff in 1859. This led to the discovery of four new
metals in the period 1860-1853, namely cesium, rubidium, thallium, and indium. The spectroscope
gradually displaced the blowpipe in chemical analysis. An example of emission spectra is shown
in Figure 23.

Figure 22 - A first spectroscope

 Figure 23 - Examples of emission spectra: calcium, strontium, and barium

Foundation of the atomic theory

John Dalton (1766-1844) the English teacher of mathematics and physics at New College in
Manchester showed in his book New System of Chemical Philosophy published in 1810 how his
atomic theory can be used to explain the laws which govern chemical combination

The discovery of the Periodic System

In 1869, the Russian chemist Dimitry Ivanovitch Mendeleev (1834-1907) (Figure 24) arranged the
elements with increasing atomic weight and discovered the Periodic System leaving gaps in this
Table for elements not yet discovered, and was able to predict their properties (Figure 25). This
prediction helped the chemists at that time to search for these elements. Within two decades the
three metals gallium, scandium, and germanium were discovered.

Figure 24 - Dmitry Figure 25 - Mendeleev’s Periodic Table of 1869 in modern form. Shaded
Ivanovitch Mendeleev areas were predicted elements, empty spaces were unknown
(1834-1907)

The great similarity in the chemical properties of the rare earths made their isolation a difficult
task and the success in separating them contributed to the knowledge of a dozen new metals during
this period.

Metallothermic reactions
Chemists of the early nineteenth century used the alkali metals to liberate metals from their
compounds -- a reaction that became known as metallothermic reaction. The Swedish chemist Jöns
Jakob Berzelius (1779-1848) isolated zirconium and titanium in 1824 for the first time by this
method. The method was used in 1850s by the French chemist Henri Saint-Claire Deville (1818-
1881) who produced the first aluminum on industrial scale by heating AlCl3-NaCl with metallic
sodium. Once aluminum became available in large quantities, it was also used to liberate metals
from their compounds.
The industrial production of aluminum
A great technological advance was the invention of the dynamo in the 1870’s that made available
electricity in bulk which encouraged the expansion of electrolytic copper refining to supply the
pure copper needed for the electrical industry. Another important application of electricity was in
the electrolytic production of aluminum. Once aluminum was available inexpensively, it was used
for reducing other oxides to metals. Thus, chromium and manganese were prepared a few years
later by this technique.

Chemical effects of electric current

Shortly after the discovery of the voltaic pile, William Nicholson (1753–1815) in England
demonstrated the chemical effects of the pile. He found that hydrogen and oxygen were evolved
at the surface of gold and platinum wires if they were connected with the terminals of a pile and
dipped in water. From this time on the nature of electricity became an intensive topic of research
simultaneously by physicists and chemists. The physicists examining the passage of electricity in
gases and they discovered the electron. The chemists examined the passage of electric current in
solutions which led to the formulation of the laws of electrochemistry.

X-rays and radioactivity

In 1895 x-rays were discovered by Wilhelm Conrad Roentgen (1845-1923) followed by the
discovery of radioactivity in 1898 by Antoine Henri Becquerel (1852-1908) which was responsible
for the discovery of polonium and radium shortly afterwards by Marie Curie (1867-1934) (Figure
26). A year later, André Debièrne (1874-1949) (Figure 27), a co-worker with Curie discovered and
isolated actinium.

METALS OF THE TWENTIETH CENTURY

Elements discovered in the 20th century are those which are very rare or do not occur in nature
(Table 3). Elements beyond plutonium were discovered at the Lawrence Radiation
Laboratory, University of California from 1944 to 1961 by Seaborg, McMillan, and Ghiorso:

- 1944, americium and curium - 1952, einsteinium

- 1949, berkelium - 1956, nobelium
- 1950, californium - 1961, lawrentium

Figure 26 - Pierre Curie (1859-1906) and

Marie Curie (1867-1934) making a Figure 27 - André Debièrne (1874-1949)
measurement of a radioactive substance
 Table 3 - Metals discovered in the twentieth century

Year Metal Discoverer Remarks

1907 Lutetium Urbain Discovered in France
1917 Protactinium Hahn and Meitner Isolated by von
Grosse in 1934.
1923 Hafnium Coster and Hevesy Isolated by van Arkel and de Boer in 1925
1924 Rhenium Noddack, Tacke, Discovered in Germany
and Berg
1937 Technetium Segre By bombardment of molybdenum with α-particles;
later on found in uranium fission components
1939 Francium Perey Discovered in France
1940-1961 Trans- Seaborg et al. Discovered in USA
uranium
metals
1945 Promethium Glendenin and Discovered in USA
Merinsky

Development of radiochemistry
Radiochemists played an important role in separating the individual radioelements, their
identification, and their arrangement in series. New methods of measurements such as the
Geiger counter and the gamma scintillation counter replaced the gold leaf electroscope. Radiations
from radioactive substances were identified as alpha, beta, and gamma. As a result two very rare
radioactive metals: protactinium and francium were discovered. Protactinium was discovered in
1917-18 by Otto Hahn (1879-1968) and Lise Meitner (1878-1968) (Figure 28) in Germany the
new element was part of the decay chain of uranium-235.

Francium was discovered in 1939 at Curie Institute in Paris, France by Marguerite Perey (1909-
1975) (Figure 29) from which the element takes its name. It was discovered during the purification
of a sample of actinium 227. It is extremely rare, with trace amounts found in uranium and thorium
ores, where the isotope francium-223 continually forms and decays.

Figure 28 - Otto Hahn (1879- Figure 29 - Marguerite Perey Figure 30 - Georges Urbain
1968) and Lise Meitner (1909-1975) (1872-1938)
(1878-1968)

The discovery of lutetium

Lutetium, element 71, was discovered spectroscopically in 1907 by the French chemist Georges
Urbain (1872-1938) (Figure 30) who named it after Lutia the Roman name of the place where
Paris was founded. It was identified by Bohr as a rare earth and not as a member of Group IV.

Quantum theory
The quantum theory by Max Planck (1858-1947) is based on the principle that energy like matter
is also composed of minute quantities called quanta, i.e., energy is not continuous but occurs in
small parcels. This allowed the understanding of the movement of electrons in the atom by Niels
Bohr (1885-1962), the hypothesis of the formation of electron shells, and the explanation of
emission spectra.

Electronic structure of rare earths

In 1922 Bohr elucidated the electronic structure of the rare earths (Table 4). The 14 rare earth
elements were identified as “inner transition metals” and were assigned a special place in the
Periodic Table that became known as “lanthanides”. In this group the two outermost electronic
shells are filled with the same number of electrons, and it is in the third shell that the number of
electrons is increased gradually. This explained the close similarity of the members of this group
in their chemical behaviour. Bohr concluded that element 72 which occurs after lutetium must be
tetra-valent rather than trivalent and must belong to the zirconium family and not the rare earths.
He advised his co-workers in his laboratory to search for this element in zirconium ores.

Table 4 - Electronic structure of lanthanides. At that time

element 61 was not yet discovered

X-ray analysis
X-ray spectrum analysis by Henry Moseley (1887-1915) in 1914 led to the discovery of two
metals: hafnium and rhenium.

□ In 1923, Dirk Coster (1889-1950) (Figure 31) and Georg von Hevesy (1885-1966) (Figure 32)
in Bohr’s Institute in Copenhagen discovered element 72 in a Norwegian zircon and later in all the
zirconium minerals and all the commercial zirconium preparations they investigated. This metal
was named hafnium for the city of Copenhagen.

□ In 1925 Ida Tacke (1896-1978) and Walter Noddack (1893-1962) (Figure 33) of the Physico-
Technical Testing Office in Berlin In June 1925, with the help of Otto Berg, an X-ray specialist at
Siemens-Halske identified in a Norwegian columbite a new element which they called rhenium in
honour of the River Rhein.
 Figure 31 - Dirk Coster Figure 32 - Georg von Hevesy
(1889-1950) (1885-1966)

Figure 33 - Ida Noddack [born Tacke] (1896-1978) and Walter Noddack (1893-1962)

Discovery of the neutron

James Chadwick (1891–1974) in Cambridge in 1932 explained the experiments of Frédéric Joliot
(1900-1958) and Irène Curie (1897-1957) in Paris by supposing that alpha particles were knocking
neutral particles out of the nuclei of the beryllium atom and that these neutral particles were in turn
knocking protons out of the paraffin. In this way the neutron was discovered.

Neutron capture
In 1934, Enrico Fermi (1901-1954) in Rome discovered that neutrons may be captured by
atoms and that the frequency of capture increases when they are slowed down by passing them
through a hydrogen-rich material such as paraffin or water. He was thus able to produce atoms of
higher atomic weights than those bombarded. For example, on bombarding cobalt with neutrons
he was able to produce nickel. When, however, he and his coworkers bombarded uranium with
neutrons, they obtained more than one radioactive product. Following the same line of thought as
in their previous experiments they suggested that one of these products was formed by neutron
capture, i.e., that it was a trans-uranium element or element number 93. Fermi put the new element
under rhenium in the Periodic Table and called it eka-rhenium (Figure 34).
 Figure 34 - Eka-rhenium according to Fermi, 1934

Fermis' paper naturally attracted the attention of Ida Noddack the discoverer of rhenium because
it dealt with another element in the manganese group. Soon afterward, she published a paper which
showed that Fermi's experimental evidence was incomplete. She was critical of his conclusions,
saying that all elements in the Periodic System would have to be eliminated before one could claim
to have found a trans-uranium element. She went further and suggested that: "When heavy nuclei
are bombarded by neutrons, it would be reasonable to conceive that they break down into
numerous large fragments which are isotopes of known elements but are not neighbours of the
bombarded elements [Translation by the writer].

Her argument was as follows: when atoms are bombarded by protons or alpha particles, the nuclear
reactions that take place involve the emission of an electron, a proton, or a helium nucleus and the
mass of the bombarded atom suffers little change. When, however, neutrons are used, new types
of nuclear reaction should take place that are completely different from those previously known.

Discovery of uranium fission

Fermi's experiments were repeated by Otto Hahn (1879-1968) and his coworkers in Berlin. They
confirmed Fermi’s conclusions and published a series of papers on extensive radiochemical
separations of the so-called trans-uranium elements. The results, however, became so
contradictory that after five years of intensive research and extensive publication the concept of
trans-uranium elements had to be abandoned. Hahn then announced in January 1939 the definite
formation of barium during the bombardment of uranium and started speculating about the
mechanism of its formation. Hahn could not accept the new idea that the uranium atom was split
into two fragments. It was Lise Meitner in Sweden who finally explained the results of the work
as fission, a few months after she was forced to leave Germany in 1939.

Cyclotron
The cyclotron was invented by Ernest O. Lawrence (1901-1958) (Figure 35) of the University of
California, Berkeley, where it was first operated in 1932. By its means technetium and the trans-
uranium metals were discovered.
 Figure 35- Ernest O. Lawrence (1901-1958) [right]
standing next to the cyclotron

Technetium
In 1937 the Italian physicists Emilio Segrè (1905-1989) (Figure 37) and his co-worker C. Perrier
announced the detection of the element with atomic number 43 in trace amounts in a molybdenum
target which has been bombarded in the cyclotron for several months with a strong deuteron beam.
They called this new element technetium deriving the name from the Greek word for "artificial".

Figure 37 - Emilio Segrè Figure 38 – Glenn T. Seaborg

(1905-1989) (1912-1999)

Trans-uranium metals
After elucidating the electronic structure of the trans-uranium (Table 5) which resembled that of
the lanthanides, Seaborg (1912-1999) (Figure 38) proposed a second series of inner transition
metals similar to the lanthanides that became known as “actinides”. He changed the Periodic Table
of 1945 (Figure 39). Thus, uranium was removed from Group VI to become a member of this new
group as shown in Figure 40.
 Table 5 - Electronic structure of trans-uranium

Figure 39 - The Periodic Table of 1945

Figure 40 - Periodic Table after 1945incorporating the actinides

Promethium
The existence of a rare earth element between neodymium and samarium was predicted by
Brunauer. This was confirmed in 1914 by Henry Moseley who, having measured the atomic
numbers of all the elements then known, found there was no element with atomic number 61. This
element was discovered by Glendenin (Figure 41), Marinsky (Figure 42), and Coryell (Figure 43)
in 1945 at Oak Ridge National Laboratory in uranium fission products and named “promethium”.
Promethium does not occur in nature.

Figure 41- Jacob A. Marinsky Figure 42- Lawrence E. Figure 43 - Charles D. Coryell
(1918-2005) Glendenin (1918-2008) (1912-1971)
 Metallurgy in the Past Decades

Word War II ended by the use of atomic bomb. The

bomb was the result of Manhattan Project in USA
in 1940s which played an important role in
developing extractive metallurgy for the
production of uranium. It was responsible for
advancing the technology of metallothermic
reactions, introducing new leaching processes, new
precipitation methods, new reagents, ion exchange
technology, and solvent extraction.

For the peaceful uses of atomic energy, uranium and trans-uranium elements were thoroughly
studied, and the chemistry of other metals such as beryllium, boron, cadmium, zirconium, hafnium,
rare earths, etc., became widely known. For the sake of conveniently outlining these developments,
extractive metallurgy is divided into three sectors: pyro-, hydro-, and electrometallurgy. However,
it is not possible to separate the three sectors since in general all three may be involved in the
recovery of a particular metal.

PYROMETALLURGY

Pyrometallurgy is the oldest branch of extractive metallurgy. In the past decades it became one of
the most modern sectors.

Agglomeration and sintering

With the wide spread of flotation process to obtain a powdered concentrate from a low-grade ore,
the iron industry was compelled to agglomerate and sinter this material before charging it to the
blast furnace (Figure 44). This became an important unit operation.
 Figure 44- An agglomerating disc [left] is used to transform powdered iron ore concentrates into regular lumps
which are then heat-treated in a moving grate furnace [right] to become hard enough for handling in a shaft furnace

Fluidized bed
Roasting in a fluidized bed (Figure 45) was adopted from the petroleum industry and first
introduced in the metallurgical industry in 1947 for treating arsenopyrite containing gold then
became wide spread for other industries. It is based on a rapid exothermic reaction between a
sulfide concentrate for example and air. It was applied later for a variety of reactions.

Figure 45 - A fluidized bed system

Flash smelting
The first flash smelting furnace utilizing the heat generated by the rapid oxidation of sulfides to
melt the other components of the charge was built by Outocompu in Finland in 1947 (Figure 46).
Since then it started to gradually replace the reverberatory furnace in the copper industry.

Figure 46 - Flash smelting furnace

 Figure 47- Small scale
metallothermic reactor
Metallothermic reactions
Metals which cannot be produced by reduction of their compounds by carbon or by hydrogen were
produced on a small scale by reduction with more active metals such aluminum or magnesium
(Figure 47). The technology of metallothermic reactions was developed on large scale, for
example, for the production of uranium from its fluoride by magnesium (Figure 48):
UF4 + 2Mg → U + 2MgF2

Figure 48 - Large scale production of uranium by metallothermic reaction

Conversion reaction
The production of copper and lead by blowing air into their molten sulfides was the standard
method for producing these metals. Application to nickel sulfide, Ni3S2, was only possible by the
invention in the 1970s of the top blown rotary convertor by the International Nickel Company
(Figure 49).
High temperature was assured by the use of
oxygen instead or air and the rotation was
necessary to make sure that any oxide formed
reacts with the sulfide to produce the metal:
Ni3S2 + 1/2O2 → 3NiO + 2SO2
4NiO + Ni3S2 → 7Ni + 2SO2
Overall reaction
Ni3S2 +2O2 → 3Ni + 2SO2

Figure 49 - Top rotary converter for nickel

Oxygen in steelmaking
After World War II when much scrap steel was available, oxygen was used in the Linzer
Düsenverfahren to produce steel using such scrap (Figure 50). It was a noisy technology that
produced much smoke. It was realized that bottom blowing would avoid these problems. This
became only possible in the 1980s when oxygen was shrouded by a small amount of natural gas
to prevent the deterioration of the refractories (Figure 51).

Figure 50 - LD process for steelmaking Figure 51 - Bottom-blowing of oxygen for

steelmaking

Continuous flow of molten material

In the Mitsubishi process developed in Japan in the 1970s and introduced in Canada later, the
molten materials move from one furnace to the other by gravity, i.e., there are no laddles, cranes,
or furnace-tilting devices (Figure52). In the first furnace, the melting of the charge is achieved.
The matte and slag formed overflow to the second furnace by means of launders where the matte
is allowed to separate from the slag. Slag from this furnace is discarded, while the matte overflows
to the third furnace where oxygen-enriched air is injected through lances and fluxes added to slag
the iron, then convert the white metal to blister copper.
 Figure 52- Mitsubishi process for continuous production of copper

Continuous casting
Continuous casting was first introduced in the steel industry in the 1960s (Figure 53) was then
applied to other metals. It avoids numerous steps for handling metal as well as adapts to
automation.

Figure 53 - Continuous casting

HYDROMETALLURGY

Heap leaching
To minimize material handling and mineral beneficiation methods new hydrometallurgical
techniques were introduced and old ones were perfected to deal with low grade ores. For example,
in-situ and heap leaching techniques (Figures 54 and 55) were greatly improved in the 1980s including
methods of heap construction. These proved to be so economical for copper, uranium, and gold ores
that they were even applied for high grade deposits. During this period also the role of autotrophic
bacteria became widely known.
 Figure 54- Preparation of heaps

Figure 55- Leaching of heaps

Pressure leaching
Pressure leaching of bauxite for the production of alumina was practiced for many years but it was
in the 1980s that the application of this technology for the treatment of zinc sulfide concentrate
was a breakthrough. Zinc was produced for the first time from its raw material completely by
hydro - electrometallurgical technique without any pyrometallurgical process as previously was
the case (Figure 56). The technology was also applied for treating of refractory gold ores before
cyanidation, for the recovery of nickel from laterites, and for other applications.
 Figure 56- Autoclave for pressure leaching of zinc sulfide concentrates

Ion exchange
Since the Manhattan Project uranium was extracted from solution by ion exchange resins. The
technique was also used for other metals and for the separation of the individual rare earth elements
- - now replaced by solvent extraction (Figure 57).

Figure 57- Ion exchange columns used for separating rare earths

Solvent extraction
Solvent extraction techniques used in the Manhattan Project for the recovery of uranium was
applied in the late 1960s for the extraction of copper (Figure 58). Today about 20% of copper is
recovered by this technology replacing the old method of cementation with scrap iron which
became obsolete.

Figure 58 - Solvent extraction of copper replaced cementation process

Precipitation under pressure

Autoclaves were used since 1950s by Sherritt-Gordon in Canada to precipitate nickel and cobalt
from solution by hydrogen under pressure. For the reaction:

M2+ + H2 → M + 2H+

more metal will be deposited if the hydrogen ions are removed as soon as they are formed. For nickel,
and cobalt, this is conveniently done by operating in ammoniacal medium:

H+ + NH3 → NH4+

Although this technology is competitive with electrowinning, it has the disadvantage of producing
ammonium salts as a by-product which is marketed as a fertilizer.

ELECTROMETALLURGY

Improvement in aluminum technology

Aluminum is now the second metal in production after iron - - it passed copper in the 1960s and
further it became cheaper than copper. Its production has undergone numerous improvements in
the design of cells. These became completely closed so that no pollutant gases could escape during
adding the alumina (Figure 59). Improvement in electrical supply lines resulted in the decrease of
energy supplied through the years (Figure 60).
 Figure 60- Improvement in aluminum reduction
Figure 59- Aluminum reduction cell is cell
fully enclosed

Automation
With the advent of computer systems and physical methods of chemical analysis, it became possible
to improve the quality and to control the composition of metallurgical products. Control room in a
metallurgical plant is now equipped with TV cameras, computers, a flowsheet, and press buttons
for remote control starting or stopping of equipment. Utilizing machines that can do the job of
humans is usually desirable. Formerly a metal deposited on a cathode had to be stripped manually.
Now, machines have been introduced to do that job.

SUMMARY

Figure 61 gives a summary of the discovery of metals. Metalloids known during the Age of
Alchemy, platina from South America, and metals from the East are combined in one period:
Medieval metals. The Figure shows that the metals discovered in the 19th century because of the
discovery of the spectroscope and the Periodic Table:

- Spectroscope: cesium, rubidium, thallium, indium

- Periodic Table: gallium, scandium, and germanium

In the 20th century it was the discovery of X-ray analysis, the new tools in radiochemistry, and the
cyclotron that led to the discovery of the last remaining elements:
- X-ray analysis: hafnium and rhenium
- New tools in radiochemistry: francium and promethium
- Cyclotron: technetium and the trans-uranium elements
 Figure 61 - Summary of the discovery of metals

SUGGESTED READINGS 1

L. Aitcheson, A History of Metals, 2 volumes, Interscience, New York 1960

F. Habashi, A Textbook of Hydrometallurgy, 1993, second edition 1999
F. Habashi, Pollution Problems in the Mineral and Metallurgical Industries, 1996
F. Habashi, editor, Handbook of Extractive Metallurgy, 4 volumes, WILEY-VCH, Weinheim, Germany 1997
F. Habashi, Principles of Extractive Metallurgy, Volume 4. Amalgam & Electrometallurgy, 1998
F. Habashi, Extractive Metallurgy Today. Progress and Problems, 2000
F. Habashi, Textbook of Pyrometallurgy, 2002
F. Habashi, Readings in Historical Metallurgy, Volume 1. Changing Technology in Extractive Metallurgy, 2006
F. Habashi, editor, A History of Metallurgy, 1994
F. Habashi, Readings in Historical Metallurgy, Volume 1 – Changing Technology in Extractive Metallurgy, 2006
M.E. Weeks, Discovery of the Elements, 6th edition, Journal of Chemical Education, Easton, PA 1960

1
Published by Métallurgie Extractive Québec, Québec City, Canada and distributed by Laval University Bookstore.
www.zone.ul.ca unless otherwise stated