1852 of knights, 1861, of warships, American English, from iron (n.) + clad. Figuratively, of contracts, etc., "very rigid or strict, allowing no evasion or escape," from 1884. As a noun meaning "iron-clad ship," it is attested from 1862.
an ironclad rule
iron
Iron Age
Iron Cross
iron curtain
iron-bound
ironclad
iron-gray
ironic
ironing
ironmonger
iron-on