The ceramic coater will definitely blast all the rust off the headers, but the real question will be what are they going to look like after surface is prepped, and if there are any thru holes or thin spots. They might look like ceramic coated pits. They are not going to smooth the metal, just remove the rust.
Also, if you are going to coat the headers, get the pipes down stream of the headers coated as well. They can mask off the mufflers if they are welded to the pipes.
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