I am sure the great LE Dudeman will have a spectacular presentation on this subject, but here is another theory to ponder-
The head started from birth in a small French villa. His mom knew it would come in handy some day. She wanted him to become a bagel chef. But he could stack but three bagels at a time on his head. Other conehead babies could stack as many as 8 bagels.
But his head was recognized by a local youth club and so it began......from a little boy playing on the beaches of Normandy, it is said that little Zidane would constantly head butt rocks across the shoreline. He progressed to headbutting lizards and frogs and finally cats. And then............soccer balls.
His head grew
......and grew.......... into quite a weapon as he matured
But now to your question about the phantom head butt against Italy. You can tell from this angle that Materazzi was trying to knee Zidane in the groin, and Zidane had to protect himself
As Materazzi's knee comes forward Zidane expertly (as usual) avoids the knee by bringing his head swiftly forward, just like on a corner.
Finally you can tell by the way Materazzi falls (face first) that the blow could not have come from the front, but from the rear. As in the Kennedy assasination, there had to be a second butter from the rear to cause the face to hit first.
So, therefore, no card should have been given.
Just a theory.