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If the paint cannot hold up to the heat - it won't melt or run, it will just burn and flake off.
Brake system temps vary, the hottest part - the pads, can see operating temps anywhere from 300C-800C, depending on pad materials and driving conditions.
The key with any paint job is the prep work - doesn't matter if you have the best paint you can buy, it will peel off incredibly quickly if the metal wasn't prep'd correctly.
Longest I got hi-temp epoxy paint to last was about a year with the decent degreasing of the caliper on my old 2003 Matrix XRS w/Hawk pads. Was planning to remove the calipers and media blast them to get all the grease/oil/dust off them as well as dig into the surface a bit, but never got a chance to do it. Did that on before on a BB project muscle car - epoxy paint lasted over two years without issue.
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2002 Corolla S, 1.8L 1ZZ-FE VVT-i
2003 Matrix XRS, 1.8L 2ZZ-GE, VVTL-i (RIP)
2009 Matrix XRS, 2.4L 2AZ-FE VVT-i
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