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I've found atleast five so far.

Most of them you have to defeat them in combat to unlock them 

Giant rat (got to defeat the giant rat in the sewer to unlock)

Lime Slime ( got to find a lime slime in the cave east of town and give them a potion and they can be found outside once you leave, will be the only friendly one in the cave but randomly spawns 

Barrel Master: Tip over the big barrel by the gate

Chimera: Found down by the docks 

Raving Fan: Defeat their former boss (can easily be found when looking for the left arm)

Concerning the Raving Fan. I think it's important to point out that the more you beat their boss, the bigger their boss becomes.

Any tips on how to get the giant rat key? been unable to find it

Just beat the Giant Rat once. It drops automatically when you do.

Where is it? I can't find em

Sewer Dungeon, Floor 5.

Thanks i managed! if i gave the key to the fake is that irreversible?

I didn't get to give him the key but you can still find the fake and beat him outside the city so I guess it is reversible ?

No, but it doesn't really matter tbh. They'll run off when you rescue the real blacksmith but not with the entire inventory. 

You can find the bandit later outside of the cathedral dungeon, just past the bridge and towards the back of the open field.