Frank Rijkaard, Spitting Mad (Italy 1990)
Dutch defender Frank Rijkaard saw red when he was booked for fouling German player Rudi Voller in the second-round matchup between old rivals Netherlands and Germany. Angered by the call, Rijkaard spat into Voller's spongy locks. When Voller complained, the ref penalized the German. Later Voller and Rijkaard got into an argument near the goal and Rijkaard spat on him again. Both men were sent off, with Rijkaard giving one more gob to Voller on their way out.