History
The first signs of use of iron come from the Sumerians and the Egyptians, where around 4000 BC, small items, such as the tips of spears and ornaments, were being fashioned from iron recovered from meteorites.
By 3000 BC to 2000 BC, increasing numbers of smelted iron objects (distinguishable from meteoric iron by the lack of nickel in the product) appear in Mesopotamia, Anatolia, and Egypt. However, their use appears to be ceremonial, and iron was an expensive metal, more expensive than gold. Some resources (see the reference What Caused the Iron Age? below) suggest that iron was being created then as a by-product of copper refining, as sponge iron, and was not reproducible by the metallurgy of the time. By 1600 BC to 1200 BC, iron was used increasingly in the Middle East, but did not supplant the dominant use of bronze.
In the period from the 12th to 10th century, there was a rapid transition in the Middle East from bronze to iron tools and weapons. The critical factor in this transition does not appear to be the sudden onset of a superior ironworking technology, but instead the disruption of the supply of tin. This period of transition, which occurred at different times in different parts of the world, is the ushering in of an age of civilization called the Iron Age.
Concurrent with the transition from bronze to iron was the discovery of carburization, which was the process of adding carbon to the irons of the time. Iron was recovered as sponge iron, a mix of iron and slag with some carbon and/or carbide, which was then repeatedly hammered and folded over to free the mass of slag and oxidise out carbon content, so creating the product wrought iron. Wrought iron was very low in carbon content and was not easily hardened by quenching. The people of the Middle East found that a much harder product could be created by the long term heating of a wrought iron object in a bed of charcoal, which was then quenched in water or oil. The resulting product, which had a surface of steel, was harder and less brittle than the bronze it began to replace.
In China the first irons used were also meteoric iron, with archeological evidence for items made of wrought iron appearing in the northwest, near Xinjiang, in the 8th century BC. These items were made of wrought iron, created by the same processes used in the Middle East and Europe, and were thought to be imported by non-Chinese people.
In the later years of the Zhou Dynasty (ca 550 BC), a new iron manufacturing capability began because of a highly developed kiln technology. Producing blast furnaces capable of temperatures exceeding 1300 K, the Chinese developed the manufacture of cast, or pig iron. If iron ores are heated with carbon to 1420-1470 K, a molten liquid is formed, an alloy of about 96.5% iron and 3.5% carbon. This product is strong, can be cast into intricate shapes, but is too brittle to be worked, unless the product is decarburized to remove most of the carbon. The vast majority of Chinese iron manufacture, from the Zhou dynasty onward, was of cast iron. Iron, however, remained a pedestrian product, used by farmers for hundreds of years, and did not really affect the nobility of China until the Qin dynasty (ca 221 BC).
Cast iron development lagged in Europe, as the smelters could only achieve temperatures of about 1000 K. Through a good portion of the Middle Ages, in Western Europe, iron was still being made by the working of sponge iron into wrought iron. Some of the earliest casting of iron in Europe occurred in Sweden, in two sites, Lapphyttan and Vinarhyttan, between 1150 and 1350 AD. There are suggestions by scholars that the practice may have followed the Mongols across Russia to these sites, but there is no clear proof of this hypothesis. In any event, by the late fourteenth century, a market for cast iron goods began to form, as a demand developed for cast iron cannonballs.
Early iron smelting (as the process is called) used charcoal as both the heat source and the reducing agent. In 18th century England, wood supplies ran down and coke, a fossil fuel, was used as an alternative. This innovation by Abraham Darby supplied the energy for the Industrial Revolution.
Occurrence
Iron is one of the more common elements on Earth, making up about 5% of the Earth's crust.
Iron is extracted from the ore hematite, which is mainly Fe2O3. The iron is separated from the ore by reduction with carbon - a more reactive element. This process takes place in a blast furnace at temperatures of about 2000°C.
First coke, mainly carbon, is entered in to the furnace and reacts with the oxygen to form carbon dioxide:
- C + O2 → CO2
Then the carbon dioxide reacts with more carbon to form carbon monoxide:
- CO2 + C → 2CO
Carbon monoxide goes on to actually react with the haematite ore:
- 3CO + Fe2O3 → 2Fe + 3CO2
The iron is tapped off as a liquid. However it is still not pure, the main impurity being