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I'm trying to get a black sludge on ultra sun but whenever I use thief on the Pokemon that can have it, they mainly faint so I am worried that this is preventing me from getting the item.

No, it should work after your enemy faints because there will be some dialog saying that your Pokémon stole an item.

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Yes it will still work.

I know this from experience, as I used this method to get Heart Scales from Luvdisc in ORAS, and I doubt the mechanics have changed since then. I suggest leading with a Pokemon with the ability Frisk, though, as it will mean you are not wasting your time attacking Pokemon that aren't holding an item.

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Even though you're probably just getting unlucky, I would recommend you check to make sure your Pokémon isn't holding anything, since that will prevent Thief's secondary effect.