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The itchy sensation you feel when a wound heals is coming from sensitive nerve cells that are reacting to both chemicals being released and structural stretch on the surrounding skin and wound tissue.
Another possible explanation is that pain and itch engage many of the same areas of the brain. When you scratch an itch, you cause yourself enough pain to relive the itch, temporarily. Regardless, itches are best left unscratched. Find out what happens to your skin when you develop an itch.