Different materials have different tendencies to attract or give up electrons depending on their chemical properties.
Human skin has a greater tendency to give up electrons than wool, so when we wear a woolen sweater and our skin rubs against the sweater, our skin loses electrons to the sweater. Our skin gains charge, and the sweater gains charge.
Wool has a greater tendency to give up electrons than a plastic comb, so when we rub a sweater with a plastic comb, the sweater gains charge and comb gains charge.
When we rub our skin with a comb, what charge can we expect the comb to gain?
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Human skin gives up electrons more easily than wool, and wool in turn gives up electrons more easily than the plastic comb. Therefore, human skin gives up electrons more easily than plastic comb. As a result, our skin loses electrons and gains positive charge, and the comb gains negative charge.