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I've been meaning to actually do this for a year, and I finally did it. I painted the brake calipers on my Sebring. I'll try to post pix. Not too sure how but we'll give it a try. It's an old car (2001) and the northern winters have taken their toll on the undercarriage. This would have been a lot easier with a new car or new calipers to work with.
I decided to paint the calipers red and the mounting brackets aluminum and then clearcoat over both. The problem arises in preparing the surface for painting. I removed the brake pads and rotors and re-mounted the calipers to have a solid mount to work on. That also keeps the sliding pins covered and sealed against the onslaught of brake cleaner and sand.
After washing them down with brake cleaner, and masking off areas not to be painted, and covering the wheel hubs against the sand, I attacked the rusty old calipers and brackets first with a wire brush cup on my drill motor, then with sandblasting. Sandblasting is a gawd-awful messy job. One more wash with brake cleaner and then spray-painted the aluminum (Rust-Oleum high temperature aluminum.) 3 coats.
Then with a brush, I applied 3 coats of red to the calipers. The top coat was 3 coats of clear gloss caliper paint (spray by VHT). Then I put it back together, trying not to scratch the new paint too much.
This was a two day job, with all the taking apart and putting together. If you had nice new calipers to work with, the job could easily be done in an afternoon as there would not be a need to pull it all apart for the surface prep.
The three pictures show the right front caliper in process. The first one shows the "before" condition. The middle one show the caliper wire brushed and sandblasted, ready to paint. The third is "after". Worth all the work? Not sure. I'll see if anybody notices.
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Engineer and current owner of two Sebrings.