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One of the best tools I own.Vacuum fill is the best way to go if you have the tools. There can't be any air in the system if it's under vacuum.
Just browsing and skimming looking for Intake Gasket and didn't see it until here. But yes, this would have been my first go to and check on any 60 degree V6 GM engine. Even the 90 degree 3.8 has this issue but not near as common on the 2.8 3.1 and 3.4s. This problem will show it's face usually between 80,000-100,000 miles. DexCool is part of the problem. So if and when you get this problem found and fixed flush that DexCool out and replace it with all green. DO NOT MIX DexCool with the Green. Flush the system first.If a leaking intake manifold gasket is letting air into the cooling system it'll boil where the coolant and air meet. The 3.1 & 3.4 are notorious for leaking intakes and it's not dexcool it's the intake gaskets.
This would fit the symptoms except for the fact that it's holding 20psi.
Maybe a combination of a bad intake gasket, and an intake valve not totally seating.I know these engines have LIM gasket issues but I'm struggling to see how intake gaskets would cause the coolant to push out of the radiator though almost instantly after I start it cold with the water pump disabled.
Maybe a combination of a bad intake gasket, and an intake valve not totally seating.