Metallurgy of iron and its alloys
Ferrous metallurgy is the metallurgy of iron and its alloys. The earliest surviving prehistoric iron artifacts, from the 4th millennium BC in Egypt, were made from meteoritic iron-nickel. It is not known when or where the smelting of iron from ores began, but by the end of the 2nd millennium BC iron was being produced from iron ores in the region from Greece to India, The use of wrought iron (worked iron) was known by the 1st millennium BC, and its spread defined the Iron Age. During the medieval period, smiths in Europe found a way of producing wrought iron from cast iron, in this context known as pig iron, using finery forges. All these processes required charcoal as fuel.
By the 4th century BC southern India had started exporting wootz steel, with a carbon content between pig iron and wrought iron, to ancient China, Africa, the Middle East, and Europe. Archaeological evidence of cast iron appears in 5th-century BC China. New methods of producing it by carburizing bars of iron in the cementation process were devised in the 17th century. During the Industrial Revolution, new methods of producing bar iron by substituting coke for charcoal emerged, and these were later applied to produce steel, ushering in a new era of greatly increased use of iron and steel that some contemporaries described as a new "Iron Age".
In the late 1850s Henry Bessemer invented a new steelmaking process which involved blowing air through molten pig-iron to burn off carbon, and so producing mild steel. This and other 19th-century and later steel-making processes have displaced wrought iron. Today, wrought iron is no longer produced on a commercial scale, having been displaced by the functionally equivalent mild or low-carbon steel.
Meteoric iron.
Iron was extracted from iron–nickel alloys, which comprise about 6% of all meteorites that fall on the Earth. That source can often be identified with certainty because of the unique crystalline features (Widmanstätten patterns) of that material, which are preserved when the metal is worked cold or at low temperature. Those artifacts include, for example, a bead from the 5th millennium BC found in Iran and spear tips and ornaments from ancient Egypt and Sumer around 4000 BC.
These early uses appear to have been largely ceremonial or decorative. Meteoric iron is very rare, and the metal was probably very expensive, perhaps more expensive than gold. The early Hittites are known to have bartered iron (meteoric or smelted) for silver, at a rate of 40 times the iron's weight, with Assyria in the first centuries of the second millennium BC.
Meteoric iron was also fashioned into tools in the Arctic when the Thule people of Greenland began making harpoons, knives, ulus and other edged tools from pieces of the Cape York meteorite. Typically pea-size bits of metal were cold-hammered into disks and fitted to a bone handle. These artifacts were also used as trade goods with other Arctic peoples: tools made from the Cape York meteorite have been found in archaeological sites more than distant. When the American polar explorer Robert Peary shipped the largest piece of the meteorite to the American Museum of Natural History in New York City in 1897, it still weighed over 33 tons. Another example of a late use of meteoric iron is an adze from around 1000 AD found in Sweden.
Native iron.
Native iron in the metallic state occurs rarely as small inclusions in certain basalt rocks. Besides meteoritic iron, Thule people of Greenland have used native iron from the Disko region.
Iron smelting and the Iron Age.
Iron smelting—the extraction of usable metal from oxidized iron ores—is more difficult than tin and copper smelting. While these metals and their alloys can be cold-worked or melted in relatively simple furnaces (such as the kilns used for pottery) and cast into molds, smelted iron requires hot-working and can be melted only in specially designed furnaces. Iron is a common impurity in copper ores and iron ore was sometimes used as a flux, thus it is not surprising that humans mastered the technology of smelted iron only after several millennia of bronze metallurgy.
The place and time for the discovery of iron smelting is not known, partly because of the difficulty of distinguishing metal extracted from nickel-containing ores from hot-worked meteoritic iron. The archaeological evidence seems to point to the Middle East area, during the Bronze Age in the 3rd millennium BC. However, wrought iron artifacts remained a rarity until the 12th century BC.
The Iron Age is conventionally defined by the widespread replacement of bronze weapons and tools with those of iron and steel. That transition happened at different times in different places, as the technology spread. Mesopotamia was fully into the Iron Age by 900 BC. Although Egypt produced iron artifacts, bronze remained dominant until its conquest by Assyria in 663 BC. The Iron Age began in India about 1200 BC, in Central Europe about 800 BC, and in China about 300 BC. Around 500 BC, the Nubians, who had learned from the Assyrians the use of iron and were expelled from Egypt, became major manufacturers and exporters of iron.
Ancient Near East.
One of the earliest smelted iron artifacts, a dagger with an iron blade found in a Hattic tomb in Anatolia, dated from 2500 BC. About 1500 BC, increasing numbers of non-meteoritic, smelted iron objects appeared in Mesopotamia, Anatolia and Egypt. Nineteen meteoric iron objects were found in the tomb of Egyptian ruler Tutankhamun, who died in 1323 BC, including an iron dagger with a golden hilt, an Eye of Horus, the mummy's head-stand and sixteen models of an artisan's tools. An Ancient Egyptian sword bearing the name of pharaoh Merneptah as well as a battle axe with an iron blade and gold-decorated bronze shaft were both found in the excavation of Ugarit.
Although iron objects dating from the Bronze Age have been found across the Eastern Mediterranean, bronzework appears to have greatly predominated during this period. As the technology spread, iron came to replace bronze as the dominant metal used for tools and weapons across the Eastern Mediterranean (the Levant, Cyprus, Greece, Crete, Anatolia and Egypt).
Iron was originally smelted in bloomeries, furnaces where bellows were used to force air through a pile of iron ore and burning charcoal. The carbon monoxide produced by the charcoal reduced the iron oxide from the ore to metallic iron. The bloomery, however, was not hot enough to melt the iron, so the metal collected in the bottom of the furnace as a spongy mass, or "bloom". Workers then repeatedly beat and folded it to force out the molten slag. This laborious, time-consuming process produced wrought iron, a malleable but fairly soft alloy.
Concurrent with the transition from bronze to iron was the discovery of carburization, the process of adding carbon to wrought iron. While the iron bloom contained some carbon, the subsequent hot-working oxidized most of it. Smiths in the Middle East discovered that wrought iron could be turned into a much harder product by heating the finished piece in a bed of charcoal, and then quenching it in water or oil. This procedure turned the outer layers of the piece into steel, an alloy of iron and iron carbides, with an inner core of less brittle iron.
Theories on the origin of iron smelting.
The development of iron smelting was traditionally attributed to the Hittites of Anatolia of the Late Bronze Age. It was believed that they maintained a monopoly on iron working, and that their empire had been based on that advantage. According to that theory, the ancient Sea Peoples, who invaded the Eastern Mediterranean and destroyed the Hittite empire at the end of the Late Bronze Age, were responsible for spreading the knowledge through that region. This theory is no longer held in the mainstream of scholarship, since there is no archaeological evidence of the alleged Hittite monopoly. While there are some iron objects from Bronze Age Anatolia, the number is comparable to iron objects found in Egypt and other places of the same time period, and only a small number of those objects were weapons.
A more recent theory claims that the development of iron technology was driven by the disruption of the copper and tin trade routes, due to the collapse of the empires at the end of the Late Bronze Age. These metals, especially tin, were not widely available and metal workers had to transport them over long distances, whereas iron ores were widely available. However, no known archaeological evidence suggests a shortage of bronze or tin in the Early Iron Age. Bronze objects remained abundant, and these objects have the same percentage of tin as those from the Late Bronze Age.
Indian subcontinent.
The history of ferrous metallurgy in the Indian subcontinent began in the 2nd millennium BC. Archaeological sites in the Gangetic plains have yielded iron implements dated between 1800 and 1200 BC. By the early 13th century BC, iron smelting was practiced on a large scale in India. In Southern India (present day Mysore) iron was in use 12th to 11th centuries BC. The technology of iron metallurgy advanced in the politically stable Maurya period and during a period of peaceful settlements in the 1st millennium BC.
Iron artifacts such as spikes, knives, daggers, arrow-heads, bowls, spoons, saucepans, axes, chisels, tongs, door fittings, etc., dated from 600 to 200 BC, have been discovered at several archaeological sites of India. The Greek historian Herodotus wrote the first western account of the use of iron in India. The Indian mythological texts, the Upanishads, have mentions of weaving, pottery and metallurgy, as well. The Romans had high regard for the excellence of steel from India in the time of the Gupta Empire.
Perhaps as early as 500 BC, although certainly by 200 AD, high-quality steel was produced in southern India by the crucible technique. In this system, high-purity wrought iron, charcoal, and glass were mixed in a crucible and heated until the iron melted and absorbed the carbon. Iron chain was used in Indian suspension bridges as early as the 4th century.
Wootz steel was produced in India and Sri Lanka from around 300 BC. Wootz steel is famous from Classical Antiquity for its durability and ability to hold an edge. When asked by King Porus to select a gift, Alexander is said to have chosen, over gold or silver, thirty pounds of steel. Wootz steel was originally a complex alloy with iron as its main component together with various trace elements. Recent studies have suggested that its qualities may have been due to the formation of carbon nanotubes in the metal. According to Will Durant, the technology passed to the Persians and from them to Arabs who spread it through the Middle East. In the 16th century, the Dutch carried the technology from South India to Europe, where it was mass-produced.
Steel was produced in Sri Lanka from 300 BC by furnaces blown by the monsoon winds. The furnaces were dug into the crests of hills, and the wind was diverted into the air vents by long trenches. This arrangement created a zone of high pressure at the entrance, and a zone of low pressure at the top of the furnace. The flow is believed to have allowed higher temperatures than bellows-driven furnaces could produce, resulting in better-quality iron. Steel made in Sri Lanka was traded extensively within the region and in the Islamic world.
One of the world's foremost metallurgical curiosities is an iron pillar located in the Qutb complex in Delhi. The pillar is made of wrought iron (98% Fe), is almost seven meters high and weighs more than six tonnes. The pillar was erected by Chandragupta II Vikramaditya and has withstood 1,600 years of exposure to heavy rains with relatively little corrosion.
China.
Historians debate whether bloomery-based ironworking ever spread to China from the Middle East. One theory suggests that metallurgy was introduced through Central Asia. In 2008, two iron fragments were excavated at the Mogou site, in Gansu. They have been dated to the 14th century BC, belonging to the period of Siwa culture, suggesting an independent Chinese origin. One of the fragments was made of bloomery iron rather than meteoritic iron.
The earliest iron artifacts made from bloomeries in China date to end of the 9th century BC. Cast iron was used in ancient China for warfare, agriculture and architecture. Around 500 BC, metalworkers in