If you rub your hair with a balloon, the balloon gets negatively charged.
How do charges move between the balloon and the hair when they are rubbed together?
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Balloon and hairs were initially neutral due to the balance of positively charged protons and negatively charged electrons. When the balloon and the hairs are rubbed together then due to the difference in their electron affinity electrons travel from one of them to the other.
As it is mentioned in the question that due to rubbing the balloon becomes negative therefore it can be concluded that either the electrons have traveled from the hairs to the balloon or the protons have traveled from the balloon to the hairs.
Protons or atoms are not free to move inside a solid although some of the electrons (high energy electrons) are free. These electrons are called the free electrons and are also responsible for carrying the current. When the two objects are rubbed together, these electrons easily travel from one object to the another. Therefore, we may conclude that they are the electrons that move from the hairs to the balloon to make it negative.