The coming of metals
The coming of metals started with copper towards the end of the Neolithic age about 6,000 BCE in Switzerland, 4,500 BCE in Mesopotamia, 4,000 BCE in Egypt, and 3,100 BCE in the ruins of Ur. The Age of Metals began not with their discovery, but with their transformation to human purpose by fire and working. Apparently about 3500 BCE in the region around the Eastern Mediterranean men discovered the art of smelting, of extracting metals from their ores. Then, towards 1500 BCE (as we may judge from bas-reliefs on the tomb of Rekh-mara in Egypt), they proceeded to cast metal: dropping the molten copper into a clay or sand receptacle, they let it cool into some desired form like a spear-head or an axe. That process, once discovered, was applied to a great variety of metals. and provided man with those doughty elements that were to build his greatest industries, and give him his conquest of the earth, the sea, and the air.
Source: Durant, Will, The Story of Civilization, Vol. 1: Our Oriental Heritage, A history of civilization in Egypt and the Near East to the Death of Alexander, and in India, China, and Japan from the beginning. New York: Simon & Schuster, 1954.
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Full disclosure, I may occasionally borrow a sentence from Will Durant's Story of Civilization. I absolutely love that collection!