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It's a form of electroplating.

In electroplating, you put the thing you want to plate in an electrolyte and connect the positive cable from a DC power source to it, a piece of the metal you want to plate it with (call it "donor metal") in the electrolyte and connect the negative cable, turn on the power and stand back as metal atoms flow from the donor metal to the item you're plating.

In electrolytic cleaning, you hook up the cables "backwards"--the positive to the item you're trying to clean, the negative to a bar of metal--and when you turn the juice on, metal atoms will flow from the item you're cleaning to the bar of metal...taking the crud with them.

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