Man you'd need a lot of exhaust gas back through the EGR to generate that much heat, but I suppose it is possible...
Going the really obvious route, are we sure the cap itself isn't cracked or have some similar malfunction? My Lincoln LS is known for coolant tank malfunctions at random. Same thing here maybe?
Since you're saying the coolant is clean, I can't see how the gasket could be leaking and not have it show up. It's not like you're just pumping air into it, it's air and fuel, and eventually exhaust.
Going the really obvious route, are we sure the cap itself isn't cracked or have some similar malfunction? My Lincoln LS is known for coolant tank malfunctions at random. Same thing here maybe?
Since you're saying the coolant is clean, I can't see how the gasket could be leaking and not have it show up. It's not like you're just pumping air into it, it's air and fuel, and eventually exhaust.