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(20 B.C. to 14 A.D.) by heating a mixture of
powdered calamine, charcoal and granules of copper.
Roman writers observed that coins made from orichalcum
were undistinguished from gold.
Zinc in India
The production of metallic zinc was described
in the Hindu book Rasarnava which was written
around 1200 A.D. The fourteenth century Hindu
work Rasaratnassamuchchaya describes how 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. By 1374,
the Hindus had recognized that zinc was a new
metal, the eighth known to man at that time, and
a limited amount of commercial zinc production
was underway.
At Zawar, in Rajasthan, great heaps of small
retorts bear testimony to extensive zinc production
from the twelfth to the sixteenth centuries. The
tubular retorts are about 25 cm long and 15 cm
in diameter with walls about 1 cm thick. A small
diameter tube was sealed onto the open end and
the zinc vapors likely condensed in this. The
retorts were closely spaced in a furnace which
was probably heated with charcoal fanned by bellows.
Both zinc metal and zinc oxide were produced.
Zinc was used to make brass whereas the oxide
was used medicinally. Over 130,000 tons of residues
remain at Zawar and this represents the extraction
of the equivalent of 1,000,000 tons of metallic
zinc and zinc oxide.
Zinc in China
From India, zinc manufacture moved to China where
it developed as an industry to supply the needs
of brass manufacture. The Chinese apparently learned
about zinc production sometime around 1600 A.D.
An encyclopedia issued in the latter half of the
sixteenth century makes no mention of zinc, but
the book Tien-kong-kai-ou published early in the
17th century related a procedure for zinc manufacture.
Calamine ore, mixed with powdered charcoal, was
placed in clay jars and heated to evolve zinc
vapor. The crucibles are piled up in a pyramid
with lump coal between them, and, after being
brought to redness, are cooled and broken. The
metal is found in the center in the form of a
round regulus. Zinc production expanded and metal
began to be exported.
Zinc in Europe
Albertus Magnus (ca. 1248) described how either
calamine or furnace tutty might be used to color
copper gold. He suggested that a more golden luster
might be obtained by sprinkling crushed glass
on top of the mixture in the crucible to form
a slag which would help prevent the escape of
the zinc vapor; in other words, increase the zinc
content of the brass.
Biringuccio (ca. 1540) has the next most complete
description of brass making. He described how
either calamine or furnace tutty could be mixed
with broken up pieces of copper and sprinkled
with a layer of powdered glass, then heated in
a closed crucible for 24 hours.
Agricola in 1546 reported that a white metal
was condensed and scraped off the walls of the
furnace when Rammelsberg ore was smelted in the
Harz Mountains to obtain lead and silver to which
he gave the name "contrefey" because
it was used to imitate gold. This often consisted
to metallic zinc, although he did not recognize
it as such. He observed, furthermore, that a similar
metal called "zincum" was being produced
under similar circumstances in Silesia by the
local people. Paracelsus (1493-1541) was the first
European to state clearly that "zincum"
was a new metal and that it had properties distinct
from other known metals.
Thus, by about 1600, European scientists were
aware of the existence of zinc. All the metal
they had examined, however, had likely been imported
from the East by Portuguese, Dutch and Arab traders.
However, there was a profusion of names quite
unrelated to the local names for zinc ores. These
included tutenag (derived from the Persian tutiya,
calamine, which became the English tutty, zinc
oxide) and spelter (likely from the similar colored
lead-tin alloy, pewter, or the Dutch equivalent,
spiauter or Indian tin which the British scientist
Robert Boyle latinised to speltrum in 1690 from
which originates spelter, the commercial term
for zinc. The word tutia, an old name for zinc
oxide, is derived from a Persian word that means
smoke and refers to the fact that zinc oxide is
evolved as white smoke when zinc ores are roasted
with charcoal.
In an extensive research "On the method
of extracting zinc from its true mineral, calamine",
Andreas Marggraf in 1746 reduced calamine from
Poland, England, Breslau and Hungary with carbon
in closed retorts and obtained metallic zinc from
all of them. He described his method in detail,
thereby establishing the basic theory of zinc
production. Marggraf also showed that the lead
ores from Rammelsberg contained zinc and that
zinc can be prepared from sphalerite. Marggraf
was probably unaware that in 1742, the Swedish
chemist Anton von Swab (1703-1768) had distilled
zinc from calamine and that, two years later,
he had even prepared it from blende. Since the
vapors rose to the top of the alembic before passing
into the receiver, this process was called distillation
per ascendum. In 1752 Swab and another Swedish
chemist Axel Fredrik Cronstedt (1722-1765) developed
at government expense the use of Swedish zinc
ores for the manufacture of brass, to avoid the
necessity of importing calamine.
The knowledge of deliberate zinc smelting in
a retort was acquired by an Englishman on a visit
to China just prior to 1740. A vertical retort
procedure was developed by William Champion (1709-1789)
and by 1743 a zinc smelter had been established
at Bristol in the United Kingdom. A charge of
calamine and carbon was sealed into a clay crucible
having a hole in the bottom. This was luted onto
an iron tube extending below the crucible furnace
into a cool chamber below. The closed end of the
iron tube sat in a tub of water and it was here
that the metallic zinc was collected (Figure 7).
The distillation took a total of about 70 hours
to yield 400 kg of metal from all 6 crucibles
positioned in the furnace. An annual production
rate of 200 tons has been suggested for the works
at that time.
This type of apparatus continued to be employed
until 1851 although it was fuel inefficient, consuming
24 tons of coal for every ton of spelter produced.
In 1758, William's brother, John, patented the
calcination of zinc sulfide to oxide for use in
the retort process, thereby laying the foundation
for the commercial zinc practice which continued
well into the twentieth century. The English zinc
industry was concentrated in Bristol and Swansea.
The excellent resistance of zinc towards atmospheric
corrosion soon led to its use in sheet production.
The possibility of rolling zinc was discovered
as early as 1805 and the first rolling mill was
built in Belgium in 1812. More such mills were
built in Silesia from 1821 onwards. Hot-dip galvanizing,
the oldest anticorrosion process, was introduced
in 1836 in France. This became possible on an
industrial scale only after the development of
effective processes for cleaning iron and steel
surfaces. At first, only small workpieces were
zinc coated. Continuous hot-dip galvanizing of
semi-finished products and wire came later. In
the United States, the rich ore deposits led to
rapid growth in zinc production in 1840, so that
by 1907, Germany, which had for long been the
world's leading producer of zinc, was left behind.
Zinc was produced for about 500 years from its
oxide ores which are far less abundant than the
sulfides, before the sulfides became the major
source of supply. The technology of zinc production
changed gradually during the centuries towards
a more pyrometallurgical route. However, this
tendency underwent a radical change during World
War I when the roasting-leaching-electrowinning
process was introduced and in the 1980's, when
pressure leaching-electrowinning offered another
practical route to zinc production.
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