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can be either or. For the MDF i would soak it with a few applications of epoxy resin, then sand, fill and put on a 2K clearcoat. doesn't need to be epoxy, but 1K is asking for trouble in most cases.
No experience with oak but would assume it will work in the same way.
Then as mould release on paint i like to use a wax based system (I use formula five). I had better luck with that than with a chemical mould release. PVA would be the safest way, but will leave you with a mediocre finish.
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