Hi,
I had my TR4 heater box nicely powdercoated, and agree that the original was likely just paint, possibly baked on enamel at most.
One consideration: To powdercoat it you'll have to completely disassemble the box. Might have to fiddle with some clearance issues a bit during reassembly, too, since the PC will add a bit of thickness.
Sad to say, after all that work restoring the TR4's heater box to like-new appearance and function, it's carefully packed away in storage. I've decided at least for the time being to not reinstall it. Instead, the heater pipe connections on the head and water pump housing are being used to increase coolant flow to the rear of the engine.
Of course, here in Calif. we're a bit spoiled and A/C is generally more desirable than heat! (Well, I suppose the heater's help defogging the windscreen would be nice, on some rainy day.)
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