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the way im thinking is that amaterasu burns what ever it touches. like everyone before has stated that neji has chakra come from the openings on his body for the technique. thus if he manages to use the technique and block amaterasu wouldn't the chakra coming from the openings get burned and cause the flames to move into his body trying to burn the chakra that is flowing out?
This wall is not some thin layer of chakra it is dense powerful chakra that rotates rapidly and it acts as a shield.
Why do you think in the hidden leaf village hyuga are right underneath the uchiha in power it is because of their doujutsu and their techs and their deadly taijutsu. This is why they are the strongest clan in the hidden leaf right now