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MDF requires a bit of extra prep. Either glue it together first with regular wood glue or leave it in separate panels for easier paint access and glue it after painting is fine, but you need to seal it before you paint it or the paint will soak into the wood and it'll take 3x more paint AND still look awful and blotchy. You can seal it with a sanding sealer like Shellac or, even easier, use an enamel spray paint to prime the MDF. Spray the enamel in an even coat and let it dry completely. Brand doesn't really matter and they make all sorts of different colors but most are gloss finish. Once completely dry, give it a scuff with some fine sandpaper so any additional paints will stick to it and you can paint it like any other model or plastic terrain from there
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