Iron Man: Armored Adventures Season 2 Episode 11 Fugitive of S.H.I.E.L.D.
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Episode Title: Fugitive of S.H.I.E.L.D.
Episode Description: Black Widow returns stealing from Nick Fury and the S.H.I.E.L.D. helicarrier, and by circumstance and some cold calculation Iron Man ends up being hunted by S.H.I.E.L.D. for that deed.
Note #1: Reed Richards is specifically mentioned as a featured lecturing scientist (though he does not appear on camera). No specific mention of the Fantastic Four is made.
Note #2: The vibranium-adamantium alloy is specifically introduced in this episode. Originally this alloy was stated to be the secret metal compound of Captain America's "indestructible" round shield before the shield was retconned to being only vibranium and iron. No specific mention of Captain America is made.
Note #3: Black Widow is shown web-slinging through the city from weblines emitted from her wrist units in the same mannerism as Spider-Man and the "Mutant X" (Earth-1298) Black Widow. No specific mention of Spider-Man is made.
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