Natural attacks generally can't overcome material-based DR. Mineral warrior (Underdark, p97) could be good then. That gives you DR 8/adamantine for +1 LA.
Pitspawn armor (Dungeon Master's Guide II, p278) deals 1 point of damage to anyone who strikes you with a melee weapon. It costs +600 gp. Interestingly, the damage bypasses all DR.
Hamatula barbs (Planar Handbook, p78) deal 1d8 damage to anyone striking you (except with reach weapons). It costs +2 to the effective armor bonus.
A lightning tunic (Magic Item Compendium, p114) doesn't function continuously, but it could deal 2d6 electricity damage to attackers much of the time.