If you activate his shields whilst another is active the previous one is replaced by the new one. So say you've got 1,2,3 or 4 charges of physical resistance and you dodge back and hold block, all of the physical resistance charges will be replaced by armour up ones instead.
Not necessarily, it will Reduce the damage it does but there are no guarantees. Rocket has low health also so there's a good chance it might still knock you out, depends how high your opponents attack is. It yes it's possible for the emergency shield to save you from a third special, just don't expect it to happen every time.
Usually i don't bother to activate any because he'll take big damage if he gets hit anyway. But the physical resistance offers more protection than the armour up but only reduces physical damage, energy attacks etc just ignore it entirely. Armour up protects you from all types of attacks as long as there's no true damage, true strike and so on. If you accidentally make a mistake it can help if you only take a couple of hits but rocket is an amazing champion if you're good at avoiding direct hits. Imo, it's not worth taking the chip damage to activate the shields unless there's a gap where the AI isn't attacking.
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Raccoon is big time glass cannon, so is the 1st and 2nd shield any use then?