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Mine stays on the bolt when I remove it but I guess if it came off I would put the beveled side of the washer towards the head of the bolt.
In aviation there are Belleville bolts with matching washers. The radius under the head of the bolt where it meets the shank is is much larger than normal bolts and the washer has a matching radius. Normally the item the bolt is connecting to is flat and has no need of a bevel.