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Lastly, enemies might be equipped with it in challenge mode, but i don't know if there are any rules about what masteries can appear in challenge mode.
Third heart is a mastery set, you can find exactly what it requires in the mastery set effect guide but second heart is one of the needed mastery.
Ash has "Phoenix", not "Second Heart". All the same though, "Phoenix" is a component for crafting "Second Heart".