I thought I may chime in cause I am somewhat "expert" on this subject as an neolithic and bronze age archaeologist. I have participated several excavations in Anatolia, dating from 8. millennium BC to Hellenistic period. Therefore I had a chance to investigate the methods of metallurgy in different periods first hand.
The first metal objects found are malachite (a copper ore), heated on wood fire and hammered to shape with stone hammers. They were usually for ornaments from neolithic age (10th to 8th mil. BC). This way people understood the difference of ordinary stone and metal. This lead to casting copper mostly from malachite ores in Chalcolithic (copper+stone) age. Anatolia was very rich for copper mines these times but some of copper frits were contaminated with arsenic. The early casters found that these ores with arsenic produced very strong and durable metals. This invention lead to the bronze age. The arsenic was not intentionally added to copper but it was thought that was a different metal. Arsenic bronze have diminished in use as tin bronze was introduced from Mesopotamia at 3rd and 2nd Mil. BC. This trade has empowered the Assyrian and Hittite empires. Tin was coming from southern Mesopotamia and Copper was coming from Southern Taurus Mountains and Cyprus. These developments have linked the empires of Hittite, Egypt and Assyrian Empires. The copper ingots were carried by large ships from Cyprus to the heart of Hittite empire. They were cast to weapons with the addition of tin from Assyria.
Casting was relatively simple method. Early times the molds were consisted from two slabs of soft stones. The inner parts of stones were carved negative images of weapons.
Here is an axe head, produced with two part mold method, from Sapinuva -an important imperial city at around 13th century BC.
But the most intricate weapons with beautiful reliefs were cast with the "lost wax method".
Sorry for babbling, I wanted to share my knowledge on this subject...