The first team to wear plastic helmets in a game was Northwestern when they did so in their 1940 season opener at Syracuse. A few other teams had access to plastic helmets that year, but restrictions on plastics during WWII meant teams relied on leather helmets for the duration. (Click here for a story on the plastic helmets used by WWII paratroopers.)
After the war, plastic helmets proved popular, yet they were bitterly opposed by some who believed they caused more injuries than they prevented. Notre Dame, for example, wore leather helmets during the 1956 season when Paul Hornung won the Heisman Trophy. They wore their yellow leather helmets with green straps again in 1957, before switching to plastic “golden dome” bonnets in 1958.
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