The origins of extraction metallurgy go back into pre-history.

The first discoveries

must have been made accidentally in camp fires and hearths where stones of easily
reducible metallic ores would have been converted to metal by the heat and
reducing flames. Copper, lead and tin were amongst the first metals to be made by
such a smelting process, over 5000 years ago.
At a very early age the alloy bronze, usually about 10 parts of copper to one of tin,
was made by smelting mixed ores of the two metals together and was much prized
because of its great hardness and because, when melted, it could be cast easily into
intricate shapes by letting it solidify in shaped holes in clay or sand moulds. Early
brasses were similarly made by smelting mixed copper and zinc ores. The modern
method of making alloys by mixing metals was developed later.
Iron ores are also easily reduced but the high melting point of the metal prevented
iron from being produced in a liquid form. Instead, a pasty porous mass of sponge
iron mixed up with slag (a crude glass containing unreduced oxides and silicates),
was produced and this had to be compacted, while hot and soft, by beating or
forging it down with hammers, so making something rather like wrought iron. The
need for higher temperatures to achieve greater outputs led to the gradual
evolution of the early iron-making hearth into the blast furnace, with an air blast
directed into the hot zone above the hearth and a tall enclosed stack above, down
which the ore and charcoal fuel travelled.
A great advance occurred in the fourteenth century. Temperatures became high
enough to produce liquid iron. The blast furnace could then be operated
continuously, being periodically 'tapped' to run out the pool of molten iron at the
bottom, and this greatly increased its output. The liquid pig iron produced in this
way contained about 4 wt per cent dissolved carbon, picked up from the furnace
fuel. This carbon greatly lowered the melting point and so made the metal easy to
re-melt and cast into moulds. This cast iron was, however, brittle due to the carbon,
which forms a brittle iron carbide, and other impurities, and so could not be used for
the same purposes as forged sponge iron. The problem of converting pig iron to a
ductile form by refining away the carbon was solved by Cort in the eighteenth
century with his puddling process for making wrought iron. These two forms of iron,
wrought and cast, remained the staple ferrous constructional materials until the
later part of the nineteenth century.
The delicate carbon control required to make mild steel (about 025 wt per cent
carbon) was beyond the scope of the metallurgy of those days.
Admittedly, a type of tool steel for swords and cutting tools, which contained about
1 wt per cent carbon and which could be hardened by quenching, red-hot, into cold
water, was made from very early times by the cementation process in which forged
sponge iron was heated in charcoal; and in 1740
Huntsman made tool steel by melting irons of different carbon contents in a
crucible, which was the foundation of the Sheffield cutlery industry. But the
discovery that cheap low-carbon steel could be made on a large scale for
constructional uses did not come until the mid-nineteenth century, when Bessemer
invented his converter process. This was followed a few years later by the openhearth steelmaking process and the modern age of steel was then begun.
Electricity plays a large part in many modern extraction processes. The decisive
step was the Hall-Herault process for the commercial production of aluminium,
announced in 1886. Many other metals such as magnesium, sodium and calcium are
also produced electrically, and these metals in turn are now used to produce the
modern' metals such as titanium, zirconium, uranium and niobium.
The science of extraction metallurgy has developed rapidly in recent years, with the
application of thermodynamics and the theory of reaction kinetics to its problems.
The thermodynamics of metallurgical reactions is now well established but there are
many opportunities for further advances, both scientific and technological, in the
study and control of reaction rates.
Many of the newest extraction processes, such as oxygen steel-making, flash
roasting, spray refining and the zinc blast furnace process, depend critically on
reaction kinetics.
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