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. C