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Captain America's shield is made of vibranium and is often called unbreakable, but it obviously isn't as suggested by this.

The linked answer mentions various people who have broken Captain America's shield.

When was the first time Captain America's shield was broken? Whatever the reason - fighting someone or maybe protecting himself from something.

Here, by "break" I mean divided into two or more pieces. Denting it or scratching it doesn't count.

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    Note that in the comics, the shield isn't made of pure vibranium like it is in the MCU; it's an alloy of vibranium and another metal, dubbed proto-adamantium by Marvel's Official Handbooks. Also, in the comics, adamantium is alot more durable than vibranium. Vibranium is an unusually tough metal, but its primary attribute in the comics is not its durability but rather its ability to absorb and negate vibrations. Jun 19, 2023 at 15:20

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The Avengers #215 may be the first case, with Molecule Man disintegrating the shield with his powers.

In The Avengers #215–216 (1982), the Molecule Man used his total control over matter to disintegrate the shield, along with Thor's hammer, Iron Man's armor, and the Silver Surfer's board. After he does so, he comments that the board's molecules are "weird", and while there are "odd forces interweaving" among the hammer's molecules, the shield is "weirdest of all". He later reassembles these items, with the exception of the armor, as the electronic circuits are too complicated for him to understand at that time

The first time it was actually broken into discrete pieces was Secret Wars #11 in 1985.

During the 1984-1985 Secret Wars limited series, the shield is partially destroyed by Doctor Doom, who has stolen the power of the godlike being known as the Beyonder. Even broken, Rogers is able to wield what is left as an effective weapon, with the shield largely retaining its balance when thrown. When the Beyonder reclaims its power, the heroes are temporarily granted the ability to realize their wishes. Rogers uses this to reconstruct the shield.

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  • I think it's fair to say that this is the first case where his canonically unbreakable shield has been broken. It was entirely vaporised in the 1960's, but that was retconned to be a different, albeit identical-looking shield.
    – Valorum
    Jun 21, 2023 at 10:02
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Captain America's shield was completely disintegrated by the Living Laser in "The Light That Failed!" published in December, 1966 in The Avengers #35.

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This was latterly retconned. Tony Stark reveals a few episodes later that he 'borrowed' Cap's actual shield and replaced it with one that was made from mere hardened steel

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