Simulation of possible Bronze Age copper-iron alloy production by smelting dead-roasted ferruginous sulphidic copper ores

This experiment was carried out to see whether copper-iron ingots from Late Bronze Age hoards could have been produced by smelting ferruginous copper ores. Since ferruginous copper-ores are chalcopyritic, chalcopyritic concentrate from a present day copper mine was dead roasted in our experiment in lieu of a rich chalcopyritic ore. Charcoal was used as a reducing agent in the reduction of calcine (i.e., a product of dead-roasting), and quartz sand was used as a flux. Two separate metallic solutions, a copper-base and an iron-base alloy, were obtained as a result of two factors: the presence of carbon and the miscibility gap in the Cu-Fe-C system. The metallic melts appeared in a form of bigger or smaller droplets, enclosed by a molten slag which, during the cooling, solidified into metallic beads. The presence of both metals was noticed in the majority of the examined beads. It was therefore concluded that calcine consisted of an intimate mixture of oxides of both metals which were simultaneously reduced during the reduction process. Due to the miscibility gap in the Cu-Fe-C system, separate iron and copper regions were formed in the beads. In both regions, sulphide inclusions were found. The formed molten copper and molten iron solution were found to be saturated solutions. The metallographic analysis revealed the precipitation of iron out of copper and that of copper out of iron during the cooling and solidification of melts. The formed slag contained little iron and no copper oxide.