So, whenever I occasionally read ASOIAF futurefics, sometimes I see Sam as maester of Winterfell. So here’s my question: if Sam took the maester’s vows, could he be sent anywhere the archmaesters wanted? Obviously the Night’s Watch takes precedence since they don’t have a maester and that’s why Sam was sent to the Citadel in the first place but humor me in this?

No, I think the Night’s Watch oath would still be binding in this situation. 

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