With regards to metals, I have no doubt someone, be it a kid apprentice or a master smelter, experimented with melting different rocks to see what comes out. After all, if you already know that different rocks spew out different metals (copper, tin, etc..) it logically follows that there may be more.
And then someone, be it the same person or a different person entirely, would've surely conducted experiments. After all, you already have Tin, Copper, and Bronze which combines both of them; all with different properties. Of course someone will want to know how this new shiny metal the smelter spewed out fares compared with other existing ones.
Then some smith will want to try making something with that metal, new things are exciting. Many people here are familiar with the desire to try out a new Programming language or framework just for the sake of it, and a Bronze age smith is no different. Then someone will give that mee Iron sword/knife/axe a try , duel a friend, ruin their bronze weapon, and said friend will be like "holy shit I want an iron sword too it's way too good" and bam you got a meme.