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If you use non-fire rated paint, it will likely peel off and look horrible once the fireplace is used for fire, again. It will do so even if you subsequently re-paint it with fire-rated paint. The worst-case scenario is that it will burn off and the entire fireplace surface will catch on fire, but the flamable chemicals will likely (but not necessarily) have evaporated by then, so the more likely result is that it will just flake off. Any painted surface is only as strong as its weakest link, so if you have non fire-rated paint anywhere in the layers of paint, it will fail when put to the test and flake off.
[This message has been edited by Lawrence (edited September 14, 2002).]