Can't find anything on Tech-line. For Cerakote it seems to be a brush on coating. If that's correct I wouldn't use it on a head. Yes a ceramic coating is thermal barrier. Problem is if you apply it to the outside of the head it can't radiate heat so it becomes trapped in the metal. Headers that are ceramic coated are coated inside and out so it protects the header from the hot exhaust gases. Maybe I'm missing something but that's my take on it.
Are the heads going back into a vette? If not I wouldn't worry about it. A vette engine compartment doesn't provide the best air flow so overheating of the heads is possible. Older Dodge vans had the same problem with their 318 V8's, cracks between the intake and exhaust valves on the rear cylinders. Cooling to the rear of the heads was poor because it was trapped inside that small engine compartment.
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Hank
70 Chevelle SS396(454), M20, 3.73
My Chevelle
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