There’s a step before the time you’ve imagined. There’s places where the metals one can find are so naturally pure that no metallurgy is required. For example, there’s a place on Lake Huron where the copper is pure enough that you can work it without any complex extraction.
It seems to me that step would be first. Then, once demand for metals spreads to where very pure raw materials are in short supply, that’s when you’d start experimenting with ways to make use of progressively inferior ore through more and more sophisticated refinement. But you’d start with the only slightly defective ore so you’d only need incremental advances in your refinement technology.
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