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you have the right idea on how the heat transfer works, I can only assume that with the higher temp/boiling point there is little steam in the radiator, again assuming there could be small pockets. This could give the coolant a free flowing path. Kind of like cleaning out a blocked artery. Cooling then could be better with the heat out to the air passing in the radiator.
I'm sure we could nuke this problem out to it's fullest.
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