You wanna completely paint them I assume?
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Clean with a degreaser and/or brake cleaner to remove brake dust and grease (especially in the corners and on the wheel face
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Sand the painting area
-if you need to do serious smoothing, start with a hard grit (200-400) and finish with a softer one (600-1000)
You NEED some surface texture for... -
Spray light base coat and wait for it to dry to touch (this should be on the can)
Start your Spray OFF of the wheel and bring the flowing spray to it. Do NOT start to spray directly on the wheel
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Spray medium coats to get full coverage.
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Dry to touch or better (hour+)
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Clear coat. Same deal. Light coat first..dry a few min...medium coats after