Narrowing Down When Humans Began Hurling Spears

The history of ironworking in general is a total mess: Not only were the best techniques(at any given time and place) some combination of trade secrets and National Security Stuff, leading to dubious recordkeeping, iron and most iron alloys corrode enthusiastically, often leaving archeologists to stare at an intriguing-looking rust stain and puzzle from there.

Then(as in the case of Damascus steel, as you mention) the properties of iron(actually a pretty lousy material, pure) change quite dramatically with the addition of relatively small amounts of various alloying agents, frequently ones that weren't even identified as distinct substances(much less 'identified' as 'elements') until centuries later, in addition to being sensitive to heating/cooling parameters and any other treatments affecting crystal structure.

There were improvements over time, of course; but until fairly recently, with modern metallurgy and chemistry, even a good-faith effort by the original craftsman to share his technique would likely leave us with considerable puzzling left to do.

Source: http://rss.slashdot.org/~r/Slashdot/slashdotScience/~3/_kP6fWSPEmw/story01.htm

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