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Honestly, Vit E isn't going to do much. As a rule of thumb I dont reccomend that to anyone. Vit E has gotten this mythic property that it cures everything and has no side effects.
However, a recent study showed that there is an increased mortality (death) with people taking Vit E supplements. Especialy those taking too much (defined as 150 IU/day).
Plus, it has never been showed to be of benefit however theorhetically it should work.
For bad sunburns, cool compresses will provide the most symptom releif. Like dirtyrascal7 found out, the skin will get better on its own. Though, do avoid any more sun. Sometimes I will give someone a quick steroid burst if the sunburn is extensive.
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