Protably a few over the couple of thousand years where meteorites were the primary and in some cases, the only source of workable iron!!!

As I implied before, most civilizations had at least played with smiling iron by between 1500 and 1200BC, but it really didn't become THe material until that later period and in some places, bronze was still the metal of choice for a lot of applications for even longer if you had access to tin. IIRC, a lot of the parts for the crossbows and other "industrially produced" weapons from the era of Emperor Qin Shihuang Di and his terra-cotta army circa 220 BC were still made form cast bronze.