They did, under the watchful eye of Baron Zemo, and became his Masters of Evil, a group with a long history, which began soon after the Avengers formed (and continues to this day….).
The Leader of the Pack
Avengers #4 (March 1964), and not even seen until Avengers #6 (July, 1964, both Avengers issues by Stan Lee and Jack Kirby, wherein Zemo formed the Masters of Evil). Zemo also appeared in Sgt. Fury and his Howling Commandos #8 (by Stan Lee and Dick Ayers) at the same publishing time as Avengers #6, but that story was set in World War II. Zemo was a Nazi scientist who created many items for his leader…including the one he wish he didn’t…Adhesive X. In battle with Captain America, Heinrich had his mask permanently stuck to his head as Cap threw his shield to break a vat of the adhesive, dousing Zemo in it. Zemo was responsible for Cap being on the plane took him over the Arctic Ocean, where Bucky was thought to be killed, and leading Cap to be found by the Avengers (who had been searching for the Sub-Mariner) decades later.
The Heat Is On
The Melter had damaged Iron Man’s armor (his next red and gold suite premiered in the very next issue…though it wasn’t specifically the Melter’s damage that caused the replacement, it might have been the inspiration for Stark to do just that!). Still, the Melter wasn’t much of a villain, having that odd chest-melting beam (Iron Man hasn’t had the best foes, has he?).
A Dark Knight
Wasp first in Tales to Astonish #52 (February, 1964, by Lee and Dick Ayers).
The professor had been arrested for treason by Hank Pym’s alter ego, but developed a winged horse and special lance to take on the identity of the Black Knight…and be defeated by Giant-Man and the Wasp. After facing this large man and his diminutive sidekick, working for Zemo was a breeze…but, Garrett switched individual foes, facing Iron Man more instead, until his wayward ways caught up to him, and he passed along the mantle of the Black Knight to Dane Whitman.
A Night Light
Lu exposed himself to radiation until he became…radioactive (thus, the name). Thor was able to defeat him in the ultimate throwdown between science and mythology, but the Radioactive Man was recruited by Zemo for his Masters of Evil (and he liked it so much, he also remained a member when others led the Masters).
Odd, isn’t it? It’s not like you could HAVE a title focused on the Masters of Evil….could you? That would be like getting hit with a Thunderbolt out of the blue…