Pardon me, sir, would you like some more Wootz?

[timmy]

Gentlemen:

I came across this paper; it's too lengthy to quote here, but I felt that it may interest some:

http://met.iisc.ernet.in/~rangu/text.pdf

[Moin.]

An excellent article Timmy, thanks for sharing.

Regards
Moin.

[timmy]

Another issue of Wootz!

Damascus Sword - An Ancient Product of Nanotechnology







C. Srinivasan

Emeritus Professor

Department of Materials Science, School of Chemistry,

Swords were used as weapons in battlefields till 19th century and the use of better version of daggers was invariably regarded as an advantage for a victory. In this respect Damascus swords were considered to be the best and the strongest swords ever made in history. These swords, which possess distinguishing water marking in the blade, probably involved complex metallurgy and sword smithing. It is believed that these swords are manufactured from wootz steel which confers the great hardness, incredible super elasticity (unequaled by any other steel) and the ability to cut other swords in half without dulling the blade.1 It is claimed that a Damascus steel blade could cut a piece of silk in half as it fell to the ground. Damascus swords became very valued possession because of their mechanical strength, flexibility and sharpness. Though initial development of these sword is accredited to India (about 300 AD), Syria took the lead and introduced to the Western world between 1000 AD and 1300 AD. During Crusade times, the Christian warriors of Europe encountered Muslim armies and the Europeans discovered that the Muslims had steel swords superior to their own steel swords. Historical accounts claim that the swords were encountered by Europeans in Damascus.

Several reasons are attributed for the name Damascus. It refers to swords forged in Damascus, Syria. Another reason is that the swordsmith, Damasqui made this type of blades. In Arabic damas refers to the surface pattern of moiré ripples, which resemble turbulent water and is also found in some Damascus swords (Figure 1). The beautiful Damascus sword has a wavy pattern on its surface and it looks like wood grain. Some of the old swords are kept in museums like Berne Historical Museum, Switzerland.2

In the production of steel, if iron is loaded up to 2 % carbon, hard and brittle steel will be produced while soft and malleable steel is obtained by the addition of about 0.5% carbon. The Damascus steel is both hard and malleable.1 These features are important - hard to hold an edge once sharpened, but malleable so that it would not break when hitting other metal in combat. This was not possible with normal processes. It is hard to believe that the blades of these swords can be bent to about 90o.



Damascus sword

It is learnt that the swords were prepared by forging small cakes of steel called wootz steel manufactured in southern India and exported to other countries.1 Wootz is the anglicized version of ukku in many south Indian languages of a term denoting steel. A systematic survey of literature indicates that the steel from the southern part of the Indian subcontinent was exported to Europe, China, the Arab world and the Middle East. It is astonishing to note numerous early literary references to steel produced in India are from Mediterranean sources including one from the time of Alexander (3rd c. BC) who was said to have been presented with Indian steel.3 There was a great reputation of Indian iron and steel in Greek and Rome in that period and perhaps that promoted the export of high quality iron and steel from ancient India.4 Archaeological evidence from the region of Tamil Nadu suggests that the Indian crucible steel process is likely to have started before the Christian era from that region.5,6 The manufacture of steel in south India by a crucible process at several locales including Mysore, Malabar and Golconda was observed by various European travellors.7,8 By the late 1600's shipments running into tens of thousands of wootz ingots were traded from the Coromandel coast to Persia.

Wootz steel was one of the advanced materials of early period exhibiting properties such as superplasticity and high impact hardness. The recipe for the manufacture wootz steel was an enigma. In the Indian method of preparation of wootz steel cake, it is believed that some particular ingredients were essential like wood from Cassia auriculata and leaves of Calotropis gigantean and ores from particular mines. Wootz steel was produced as roughly 2.3 kg ingots, commonly referred to as cakes, which are solidified in a closed crucible. It was a relatively high-purity iron steel with 1.5% carbon. The cakes were shipped to Damascus. The smiths repeatedly heated and hammered the cake till it was stretched and flattened into a blade. During this process the wavy pattern was formed on the surface of the blade. Verhoeven found that the swords contained band of iron carbide particles, Fe3C, known as cementite.1 It is a mystery how the inherent brittleness of cementite was overcome by the Indians in their preparation of wootz steel. The production of this type of steel almost vanished possibly because of the depletion of the particular ores. Unfortunately, the technique of producing wootz Damascus steel blades is a lost art. The date of the last blades produced with the highest-quality damascene patterns is uncertain, but is probably around 1750. Debate has persisted in the metallurgy community over the past 200 years as to how these blades were made and why the surface pattern appeared. Success eluded the hands of European swordsmiths to produce steel similar to wootz. Recently, Vorhoeven, an Emeritus Distinguished Professor of Materials Science and Engineering at Iowa State University, USA, produced a steel which when forged into a blade had all the characteristics of Damascus blade.1,9 Their recipe includes iron, carbon and other elements in trace amounts such as vanadium and molybdenum (which are referred to as impurity elements) in addition to rare-earth elements.

It is strange that in spite of the presence of about 1.5% carbon in wootz steel, the blades produced from it is not only strong but also malleable. This appears to be a mystery. Does the carbon play a new role? To understand this let us examine the recent studies on various forms of carbon. Buckminsterfullerene (C60), the third form of carbon, was first reported from Rice University, Houston in 1985 by Smalley and co-workers.10 After the announcement of the large-scale preparation of C60 by electric arc discharge method, several amazing discoveries followed soon. It is not an exaggeration to state that the invention of fullerene is solely responsible for the discovery of carbon nanotubes (CNTs). A careful examination of the carbon cathode used in the arc discharge process for preparing small carbon clusters by Sumio Iijima12 in 1991 resulted in the historical discovery of CNTs, the name of ultra-thin carbon fibres with nanometre size diameter and micrometre size length. Iijima originally obtained only multiwalled carbon nanotubes (MWCNTs) and that is indeed a milestone in the study of different forms of carbon. Subsequently, Iijima and Ichihashi12 and Bethune et al.14 reported the production of single-walled carbon nanotubes (SWCNTs). CNTs have been recognized as the quintessential nanomaterials and have acquired the status of one of the most active fields of nanoscience and nanotechnology. The MWCNT is composed of 2-30 concentric graphitic layers, the diameters of which range from 10 to 50 nm and length more than 10 μm. On the other hand, SWCNT is much thinner, with diameter ranging from 1.0 to 1.4 nm (Figure 2). CNTs exhibit unique electronic, mechanical and thermal properties. CNTs are very strong and the Young's modulus of them is almost 6 to 10 times that of steel. Tensile strength of CNTs is about 20 times higher than that of steel. Thus CNTs are strong, even though they are light weight. When CNTs are bent, they are very resilient They buckle like straws but do not break and can be straightened without any damage.



Structrues of (a) SWCNT and (b) MWCNT

The high mechanical properties and flexibility features of Damascus blades resemble those of CNTs and these characteristics probably motivated German scientists Reibold et al. to probe whether a genuine Damscus sabre contains CNTs by using high-resolution transmission electron microscopy (HRTEM).15 A specimen was taken from one of the swords kept in Berne Museum, Switzerland and dissolved in hydrochloric acid and the remnants examined by HRTEM revealed the presence of MWCNTs with the characteristic distance of 0.34 nm and also bent CNTs (Figure 3a & 3b). Figure 3c shows remnants of cementite nanowires encapsulated by CNTs which prevents the wires from dissolving in acid.

Scientists are not surprised to find the presence of CNTs in these swords as it is now well known that CNTs can be produced from carbon at high temperature - the laser ablation and arc-discharge methods involve high temperature. Probably the repeated heating and hammering (forging) results in band formation from segregation at a microscopic level of some impurity elements (metals). These elements may also be responsible for the growth of CNTs which in turn initiate formation of cementite nanowires and coarse cementite particles. A question to be answered is whether the high mechanical strength and flexibility of Damascus blade arise due to the presence of CNTs. It is needless to state that further detailed studies may provide answer to the question. However, we can be proud of the fact that even several centuries ago Indians are aware of the importance of wootz steel and Damascus sword, which are now proved to contain carbon nanostructures.













Figure 3. HRTEM images of remnants from the dissolution of a sample of genuine Damasus sabre in hydrochloric acid. a, b MWCNTs with the characteristic distance of d = 0.34 nm. In b, the tubes are bent like a rope. c. Remnants of cementite nanowires encapsulated by CNTs, which prevent wires from dissolving in acid. Scale bars: 5 nm (a) & (c) and (b) 10 nm reproduced from ref. 15 ( with permission from P. Paufler).

References

1. J. D. Verhoeven, A. H. Pendray, and W. E. Dauksch, The key role of impurities of ancient Damascus steel blades, JOM, 1998, 50, 58-64.

2. C. Srinivasan, Do Damascus swords reveal India's mastery of nanotechnology?,

Curr. Sci., 2007, 92, 279-280.

3.G. N. Pant, Indian Arms and Armour, Vol. I and II, National Museum, 1980, New Delhi

4. B. Bronson, The making and selling of wootz, a crucible steel of India, Archaeomaterials, 1986, 1, 13-51.

S. Srinivasan, Wootz Crucible steel: a newly discovered production site in South India, Papers from the Institute of Archaeology, University College London, London, 1994, 5, 49-61.

A. K. Biswas, Iron and steel in pre-modern India- a critical review, Indian Journal of History of Science, 1994, 29 , 579-610.

F. Buchanan, A Journey from Madras Through the Countries of Mysore, Canara and Malabar, Vol. I, II, II, 1807, London .

H. W. Voysey, Description of the native manufacture of steel in southern India. Journal of the Asiatic Society of Bengal, 1832, 1, 245-247.

J. D. Verhoeven, The mystery of Damascus blades, Sci. Am., 2001, January, 74-79

10. H. W. Kroto, J. R. Heath, S. O'Brien, R. F. Curl and R. F.Smalley, Nature,1985,

318, 162-163.

11. W. Kratschmer, L. D. Lamb, K. Fostiropoulos, and D. R. Huffman, Nature,1990,

347, 354-358.

12. S. Iijima, Nature, 1991, 354, 56.

13. S. Iijima, and T. Ichihashi, Nature, 1993, 363, 603.

14. D. S. Bethune, C. H. Kiang, M. S. m.de Vries, G. Gorman, R. Savoy, F. Vasquez

and R. Bayers, Nature, 1993, 363, 605.

15. M. Reibold, P. Paufler, A. A. Levin, W. Kochmann, N. Patzke. and D. C.Meyer,

Nature, 2006, 444, 286.

Contributed by

C. Srinivasan

Emeritus Professor

Department of Materials Science, School of Chemistry,

Madurai Kamaraj University, Madurai - 625 021, India

For the pictures, you will have to go here:
http://www.steelguru.com/article/detail ... Sword.html

[brihacharan]

Hi timmy,
> Thanks for sharing - made very interesting read
Briha

[timmy]

I think of those fellows on the hillside, working over their furnace centuries ago, making steel that we only are just understanding today. They didn't understand the science of it, something which took the combined work of generations, but they were plenty smart and produced some wonderful things, didn't they? It is a marvel to me.

[TwoRivers]

Yes indeed! Those craftsmen of old did amazing work. As to the article, I find it difficult to imagine how "ukku" can become anglicized as "wootz". The term wootz is used in Afghanistan and Iran, and surely did not come from English.

[Grumpy]

It is remarkable what these ancient artisans were able to produce and such a shame that the technology to produce Wootz steel was lost around 1800. Why that came about isn`t yet understood but it must have had something to do with the loss of one ( or more ) primary ingredients.
The misunderstandings that occur regarding the differences between Wootz steel, Damascus blades and pattern welded steel ( so-called `Damascus` steel ) are so frequently encountered that they`ve become boring. Damascus blades are made from Wootz steel. They are NOT pattern welded - the pattern is produced during the forging of the steel and not by multiple foldings.
`Damascus` barrels are NOT made from Damascus steel or from Wootz steel. They are produced from pattern welded steel which is steel subjected to multiple foldings and hammerings to produce the distinctive patterns. Those patterns are vaguely similar to those in Wootz steel which is how the mis-naming came about. The same applies to ancient ( and modern ) pattern welded blades which which are invariably described as being made of `Damascus` steel.
One of the most frequently encountered mistakes is when someone mentions Damascus steel in the context of gun barrels or modern blades and is told that the correct term is actually `pattern welded` steel ( which is absolutely right ) and then someone chimes in with the information that `actually` THE correct term is `Wootz` steel ( which is WRONG ! )
I agree with TwoRivers that the Anglicisation of `urukku`, `urukke` or `ukku` into `wootz` is unlikely ..... actually I think it`s pretty well impossible as the word is extremely un-English in form ( there`s a `Z` in it for goodness sake ! ) Another fact that should be taken into consideration is that the word `wootz` to describe this type of steel only came into being around 200 years ago .... about the time that production of wootz steel ceased in fact. Is that a coincidence ? The British were in India a long time before 1800 so why should this `Anglicised` form suddenly occur ? It seems much more likely to me also that the word is Persian ( or possibly Afghani ) in origin.
The John. D. Verhoeven Scientific American article referred to in the bibliography above ( Should be No.9 but the number has been omitted ) is excellent and I`ll post a link to it under a new heading to save it being lost in this thread.

[timmy]

I think that those links have been posted, but I will search for them again. Moin has talked about this in the past, and I had a number of links, some from Verhoeven, I believe, a few years back. Anyway, Grumpy, post away, as this subject is so fascinating! Nanotubes, yet!

As I understand it, the ore body from which wootz was derived played out. I believe the key component in that ore was a small percentage of vanadium.

[timmy]

Here we go! This was the original wootz thread from a few years back:

http://indiansforguns.com/viewtopic.php?f=20&t=7029

urukku -- wootz!
Postby timmy » Thu Jul 30, 2009 14:05

I have been poking about into the subject of what English speakers would call "Wootz steel." Many many years ago, I asked my Dad (who was deeply involved in the steel making industry) about the legendary "blades of Damascus" and he said that any kind of steel could be made today (which was maybe 45 years ago). Some people claim that the Russian Pavel Anosov may (or may not) have duplicated the properties of Wootz steel in his Bulat steel.

A couple of years ago, while I was in college, I read an interesting article in Nature, where one investigator hypothesized that Wootz steel, besides its already-noted cemetite formations (making it similar to a ceramic blade), also had carbon nanotubes, which allowed it to keep such a sharp edge.

I am fascinated to read that archeologists have so far discovered that the manufacture of Wootz was occurring at least as early as 300 BC in Tamil Nadu and Sri Lanka, where the temperatures achieved by the ancient kilns were achieved with stronger drafts aided by monsoon winds.

I would have liked to have written something up about Wootz, but I feel I'm still learning. Here are some very interesting academic papers I've found on the subject, for those of you who might be interested:

Carbon nanotechnology in an 17th century Damascus sword A blog article that pretty much duplicates the original Nature article.

The Key Role of Impurities in Ancient Damascus Steel Blades

Historical Background of Damascus blades (There are other copies of this on the web -- faced with the choice of posting one with pictures, as opposed to footnotes, I chose the one with pictures.)

(This is a pdf file -- 1.7 MB. It probably isn't modem friendly, but it is one great read in the academic sense!) Microstructure of a genuine Damascus sabre (This was the research on which the Nature article of a couple of years ago regarding carbon nanotubes was based.)

Wootz Steel: An advanced material of the ancient world (an article from the Indian Institute of Science, Bangalore)

This is a more complete document from the Indian Institute of Science (this is a pdf of ~500 KB)

Duplication of Wootz at a Swedish University

The Replication of Wootz (A USA college student's project, duplicating Wootz)

My question is, does anyone have any experience regarding real (not simulated) edged weapons made of Wootz, whether ancient or modern? I have seen knives made to look like Wootz, but I am referring to the real thing.

I confess a real admiration and interest in the mastery of metallurgy at such an early date. Although nobody understood that traces of vanadium were the essential "secret ingredient" of Wootz (something discovered only relatively recently), those early metal workers surely understood the desirable properties inherent in this, the most modern carbon nanotube technology!

The links did not come through, but anyone interested can click on the original link.

[Grumpy]

It is most likely that the source of ore for wootz steel ran out but there were obviously alternative supplies of iron ore because steel was still being produced into the 1850s ............. when it was banned by the British because of deforestation. It could be that the specific source for the ore that produced the wootz steel was very localised - possibly vein within a larger area of iron ore.
Yes, vanadium seems to be key to the production of wootz steel.
Alfred H. Pendray, the Florida bladesmith who collaborated with John. D. Verhoeven on the production of wootz steel went on to produce and sell knives made from the wootz steel he produced but his workshop burned down around 2008 and I haven`t seen anything about him since.
It is a fascinating subject isn`t it ?
Old technologies that developed because of impurities in the base materials. The eventual production of wootz steel must have have been subject to years of experimentation.

[timmy]

I am guessing that part of this process was serendipitous (no pun intended). Similarly, Swedish steels are always noted for being good and credit is given to Swedes, yet my understanding is that the composition of Swedish ore lent itself to superior grades of steel in the days when the Bessemer process was used to make steel, before the Siemens "open hearth" process became prevalent. (cf. complaints about the brittleness of Titanic's plates, caused by impurities. I don't think that was a cause of Titanic's sinking, but those impurities did make her steel more brittle than today's products.)

The trade routes between the Malabar Coast and the western peoples, such as Greeks and Romans, was a well-trod path in ancient times. The Arabs got the credit in older Western literature, but now we know that Metallurgy, Chemistry, Mathematics, and a whole bunch of other learning, which the West derived from the Middle East, had, in turn, come from India.

[Grumpy]

It is an absolute fact that India was, for far too long, regarded as being of little significance as far as the development and utilisation of technologies is concerned but the earliest production of smelted iron - for example - was almost certainly in Anatolia ( Turkey ) although India`s Ganges valley was not many centuries behind.
To ignore the role of the near and middle East in the development of many aspects of science, technology and medicine would be foolish however - complex mathematics ( arithmetic, basic algebra, geometry, etc ) were first developed and used by both the Mesopotamians and Egyptians c.3000 BC.
The earliest proven location for the high temperature production of copper is Serbia ( S.E.Europe ) c. 5,000 BC.
Proven writing was first developed in Sumer ( Mesopotamia ) c.3200 BC although some now claim Egypt c.3400 BC. The Indus Valley also has a claim for c.3200 BC although that script is undecipherable and might be a signing system/proto language. Proto writing dates back to at least 6,000-7,000 BC in China followed by many other examples throughout Europe and Asia. Obviously the development of proto writing into actual writing cannot be dated exactly as most proto writing is undecipherable
The earliest known literature is Egyptian. c. 2400 BC.
The earliest bronze was probably produced by the Maikop Culture in the Caucasus c.3500 BC but that was arsenical bronze which is a natural alloy. Where the first tin bronze was produced is very difficult to say ..... Logically that ought to be somewhere that both bronze and tin occurred naturally - which very much limits the possible locations but as tin was found in N.E.Spain/Portugal, N.E.France, S.W.England and on the German/Czech border ... with a small amount in N.E.Italy it rather suggests that it wasn`t any of those locations. It has been suggested - but not proven - that tin might have been found in very small deposits in Egypt, Persia and Syria. It is known that the Egyptians mined copper in Sinai. The likelyhood is that tin bronze was first developed either in Mesopotamia/Sumer or Egypt however, again, it was being produced by the Indus valley civilisation not long afterwards.
All of which is a rather rambling essay to confirm that ancient Indian civilisations might not have been first to innovate new technologies but they were often very close behind when it came to utilising them.
India definitely has not received credit for the ancient development of science and technology but the same can also be said for Turkey, Iraq ( Mesopotamia and Sumer in particular ) Iran ( Persia ) - the major civilisation of the `classical` period was not Athens which was a tiny city state but Persia which was a huge empire - Pakistan ( both as part of the Persian Empire and as part of the Indus Valley Civilisations ) and even Afghanistan - again as a part of those same two civilisations .... and more than a dozen separate kingdoms have had their capitals within the borders of what is now Afghanistan.
Arab people live in Arabia, N.Africa and the horn of Africa. Not a huge amount of scientific/technological innovation is credited to them.

[timmy]

True enough, Grumpy -- but the point I was making was a bit different.

The analogy I would draw here would be, who discovered America (as the question is often inaccurately put). The answer, though technically correct, is not St. Brendan, or some Viking, or Basque fishermen, but Columbus -- the earth-changing explorations and settlements were undoubtedly kicked off by Coumbus, whoever was really "first," and despite the fact that he thought he was somewhere else.

Similarly, many discoveries might have been "first" on the time line, but the ones that influenced Western Civilization were the target of my comments. When it comes to language, at least, it may have started in a number of places, simultaneously or not, but Western languages have "Indo" in their roots for a reason.

Before turning in, I'd also like to mention that there are sometimes two trains of thought in these matters. One train of thought has it that a major discovery is so rare and precious that it only happens once, and somehow it gets passed on to everyone else. The other train of thought (and the one to which I tend to subscribe) has it that discoveries often take place in multiple places, independent of one another.

This second case is still true today, for when we clear away the Horatio Alger bootstrap claptrap meant for the encouragement of cultural and national myths, we have Bell beating Grey to the patent office by mere hours, and other such stories.

Have to turn in now, but this would be a fun topic to pursue.

[Grumpy]

I agree that the independent development of technologies and inventions can take simultaneously or almost so - that`s proven. It`s also a fact that things have been re-invented time and time again in different locations around the planet. It`s also the case however that there have been a great many `one-off` type inventions that have appeared almost `out of the blue` Something else to remember is that a difference of 200 years 5000 years ago seems almost simultaneous and of no consequence now but new technologies could transfer from one location to another a very long way off over the course of 200 years.
Let`s not talk about that crook Bell.....................

[Kittu]

Gentlemen:

I came across this paper; it's too lengthy to quote here, but I felt that it may interest some:

http://met.iisc.ernet.in/~rangu/text.pdf

Anyone have this file? link is broken,not working
regards