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I’m about to replace my old cooper pipes to PEX. There’s a steam pipe and a branch attached in 90 degree to release some steams. The thing is, the cold and hot water pipes are right above the steam pipe. These pipes are hot and wet all the time when we turn the boiler on. It seems okay with cooper pipes for now, but I’m not sure if PEX could endure the high temperature steams every day. enter image description here

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Yes pex is fine. Because you are going to vent your steam pipes during the pex replacement in a more suitable way - and something that is code.

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