Zinedine Zidane was a French World Cup champion in 1998, however it was is was 2006 World Cup that sparked controversy. When the game went into over-time, Zidane proceeded to head-butt Marco Materazzi of Italy following an insult from the Italian player, according to ESPN. Zidane was sent off the field and France went on to lose the game. Charges were discussed for the incident, but were never filed.
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