Most studies of old iron begin with the Celts or the Viking age, with a few digressions on exotic eastern steels like the nickel-steel daggers from Tutankhamun’s mummy, wootz from India, krises from the jungles of southeast Asia, and katanas from Japan. In fact, there are a number of studies of very early iron from the Aegean and the Near East. One of the first of these examined a spearhead from the cemetery at Deve Hüyük on the upper Euphrates. (There is some dispute about which country the site is in right now). It was badly rusted and mineralized, but enough elemental iron remained to understand the composition.
This smith took a bar made from about 50 layers with different composition, probably by placing different pieces side-by-side, heating and hammering them, and repeatedly folding and stretching until they were evenly mixed (Gärben or faggoting). Over time, smiths and smelters learned to combine pieces with different properties to take advantage of their different natures, such as forging an axehead from a sandwich of hard steel for the edge and soft, foldable iron for the back and socket. So far, the first traces of techniques like this (or baking iron with carbon to enrich the surface with carbon) appear in the last few centuries BCE, while this grave at Deve Hüyük dates to around the 5th century. This spear has an average composition of 0.18% C, 0.32% N, 0.1% Si, and various trace elements, but the composition is different at any given spot. The iron contains particles of cinders and slag and other useless matter. The Vickers diamond hardness of the steel ranged from 108 to 153 depending on where it was tested (it might be worth making sure that this test in 1956 is the same as the modern Vickers Pyramid Hardness test). The finished spearhead would have been similar to one forged from a modern mild steel, but ancient steels and irons were nothing like the homogeneous cast and rolled steels that come out of modern smelters. Iron production was a mysterious art and deeply connected to the peculiarities of the local ore and fuel.
Iron spearheads were revolutionary, because iron can be bent into all kinds of shapes and welded to itself. Casting a socketed spearhead from bronze is a fussy, delicate process, but forging one does not take an apprentice smith more than a few hours. The smith hammers a bar flat, wraps the socket around a form (mandrel) with more hammer blows, and then closes the overlap: this smith brazed the join in the socket closed with copper. The new weapons were not sharper or harder or tougher than bronze equivalents, but by the 6th century BCE they were much cheaper. Until the 19th century, smiths seem to have been more interested in soft, forgeable, consistent irons than hard, uncooperative ones. Medium-carbon steels are easy to produce in a simple furnace, but they were harder to shape into the desired form, and low-carbon blades, their edges hardened with hammering or phosphorus, did the job. From the 8th century BCE to the 16th century of our era, the iron spear was the queen of weapons and the soldier’s basic tool. I hope that more archaeolometallurgists analyse irons from the ancient Near East.
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If You Want to Know More: You can find the original study from 1956 in Coghlan, H.H. (1956) Notes on Prehistoric and Early Iron in the Old World. Occasional Papers on Technology, 8. Oxford University Press: Oxford.
You can learn more about Deve Hüyük in Moorey, P. R. S. (1980) Cemeteries of the First Millennium BCE at Deve Hüyük, near Carchemish, salvaged by T.E. Lawrence and C.L. Wooley in 1913. British Archaeological Reports 87 (Oxford). http://digital.library.stonybrook.edu/cdm/ref/collection/amar/id/157174
For a summary of other studies of ancient near eastern iron and steel see Moorey, P.R.S. (1999) Ancient Mesopotamian Materials and Industries: The Archaeological Evidence. Winona Lake, Indiana: Eisenbrauns.