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Can NM (AKA "Romex") cable reliably sustain contact with hot water pipe so that the water pipe never gets so hot as to melt the insulation and pick up electric current?

I'm crossing pipes and cable at 90° and it's hard to avoid contact.

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NMB is rated for 90c so your water pipe should not be a problem, if running in close contact you would have to derate the ampacity but crossing at a 90 it should not be a problem, I would throw a chunk or piece of insulation in between just to be extra safe.

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