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Black Knight Chronology

https://en.wikipedia.org/wiki/Black_Knight

Marvel Age Introductions by On-Sale Date
1963	NOV 05	TTA052	Tales to Astonish	[Giant-Man • The Wasp] [Tales of the Wasp] [INTROBlack Knight]
1964	MAY 05	AVN006	The Avengers	[AVNROS•Captain America • Giant-Man • Iron Man • Mighty Thor • The Wasp] [INTROMOEROS•Masters of Evil • Baron Zemo • Black Knight • The Melter • Radioactive Man][Paste-Pot Pete•Trapster]
1964	AUG 11	TOS059A	Tales of Suspense	[Iron Man][INTROEdwin Jarvis] [The Avengers•AVNROS•Captain America • Giant-Man • Mighty Thor • The Wasp][Black Knight]
1965	FEB 11	AVN015	The Avengers	[AVNROS•Captain America • Giant-Man • Iron Man • Mighty Thor • The Wasp][MOEROS•Masters of Evil • Baron Zemo • Black Knight • Enchantress • The Executioner • The Melter]
1965	MAR 11	AVN016	The Avengers	[AVNROS•Captain America • Giant-Man • Iron Man • Mighty Thor • The Wasp] New Lineup[AVNROS•Captain America • Hawkeye • Quicksilver • Scarlet Witch] xo[Sub-Mariner][Immortus][Kang the Conquerer][Mole Man][MOEROS•Masters of Evil • Baron Zemo • Black Knight • Enchantress • The Executioner • The Melter]]
1965	OCT 12	TOS073A	Tales of Suspense	[Iron Man][Black Knight]
1967	OCT 10	AVN047	The Avengers	[AVNROS•Captain America • Goliath • Hawkeye •Hercules • Quicksilver • Scarlet Witch • The Wasp [Black Widow]•Dane Whitman • Black Knight]
1967	NOV 9	AVN048	The Avengers	[AVNROS•Goliath • Hawkeye • Hercules • Quicksilver • Scarlet Witch • The Wasp] [Aragorn][Black Knight]
1968	AUG 13	MSH017	Marvel Super-Heroes	[Black Knight]
1968	DEC 5	DOC178	Doctor Strange	xo[Black Knight][Tiboro]
1969	OCT 14	AVN071	The Avengers	[AVNROS•Black Knight • Black Panther • Captain America • Goliath(Hawkeye) • Iron Man • Mighty Thor • The Vision • The Wasp • Yellowjacket][Black Knight joins][Kang the Conquerer][Original Human Torch]