The most likely answer is that we placed rocks in or around a fire to help us with cooking. We noticed that some of the rocks melted when exposed to heat, and when they cooled off the rocks became hard again. From there, it wouldn’t take much to realize that we can manipulate the rock while it is liquid, forming it into shapes that are useful to us when it hardens.
The most likely first substance we discovered this with is lead. Lead melts at a fairly low temperature – 327 C – which is _easily_ achieved by your average campfire. From there, it wouldn’t take much ingenuity to realize that other rocks might produce similar effects if you get them hot enough.
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