Abstract
Polystyrene samples, incorporated with halogen elements (F, Cl, Br, I) on the para-position of the benzene ring, were studied using positron annihilation lifetime spectroscopy. It was found that the free-volume hole size is significantly affected by the internal Coulombic interaction of the halogen group, and is mainly related to the electronegativity of halogen–carbon bonds. In addition, it is found that the free-volume is secondarily modified by the steric effect of the side groups. The intensity of o-Ps has a linear relationship with the strength of the C–X bond and is strongly affected by the chemical environment in a halogenated styrene polymer system.
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