Carbon nanotechnology in an 17th century Damascus sword

Originally published in National Geographic

In medieval times, crusading Christian knights cut a swathe through the Middle East in an attempt to reclaim Jerusalem from the Muslims. The Muslims in turn cut through the invaders using a very special type of sword, which quickly gained a mythical reputation among the Europeans. These “Damascus blades” were extraordinarily strong, but still flexible enough to bend from hilt to tip. And they were reputedly so sharp that they could cleave a silk scarf floating to the ground, just as readily as a knight’s body.

They were superlative weapons that gave the Muslims a great advantage, and their blacksmiths carefully guarded the secret to their manufacture. The secret eventually died out in the eighteenth century and no European smith was able to fully reproduce their method.

Two years ago, Marianne Reibold and colleagues from the University of Dresden uncovered the extraordinary secret of Damascus steel – carbon nanotubes. The smiths of old were inadvertently using nanotechnology.

Damascus blades were forged from small cakes of steel from India called ‘wootz’. All steel is made by allowing iron with carbon to harden the resulting metal. The problem with steel manufacture is that high carbon contents of 1-2% certainly make the material harder, but also render it brittle. This is useless for sword steel since the blade would shatter upon impact with a shield or another sword. Wootz, with its especially high carbon content of about 1.5%, should have been useless for sword-making. Nonetheless, the resulting sabres showed a seemingly impossible combination of hardness and malleability.

Reibold’s team solved this paradox by analysing a Damascus sabre created by the famous blacksmith Assad Ullah in the seventeenth century, and graciously donated by the Berne Historical Museum in Switzerland. They dissolved part of the weapon in hydrochloric acid and studied it under an electron microscope. Amazingly, they found that the steel contained carbon nanotubes, each one just slightly larger than half a nanometre. Ten million could fit side by side on the head of a thumbtack.

Carbon nanotubes are cylinders made of hexagonally-arranged carbon atoms. They are among the strongest materials known and have great elasticity and tensile strength. In Reibold’s analysis, the nanotubes were protecting nanowires of cementite (Fe₃C), a hard and brittle compound formed by the iron and carbon of the steel. That is the answer to the steel’s special properties – it is a composite material at a nanometre level. The malleability of the carbon nanotubes makes up for the brittle nature of the cementite formed by the high-carbon wootz cakes.

It isn’t clear how ancient blacksmiths produced these nanotubes, but the researchers believe that the key to this process lay with small traces of metals in the wootz including vanadium, chromium, manganese, cobalt and nickel. Alternating hot and cold phases during manufacture caused these impurities to segregate out into planes. From there, they would have acted as catalysts for the formation of the carbon nanotubes, which in turn would have promoted the formation of the cementite nanowires. These structures formed along the planes set out by the impurities, explaining the characteristic wavy bands, or damask (see image at top), that patterns Damascus blades.

By gradually refining their blade-making skills, these blacksmiths of centuries past were using nanotechnology at least 400 years before it became the scientific buzzword of the twenty-first century. The ore used to produce wootz came from Indian mines that were depleted in the eighteenth century. As the particular combination of metal impurities became unavailable, the ability to manufacture Damascus swords was lost. Now, thanks to modern science, we may eventually be able how to replicate these superb weapons and more importantly, the unique steel they were shaped from.