Evolution of surface functional groups and aromatic ring degradation upon treatment of polystyrene with hydroxyl radicals

The surface properties of hydrocarbon polymers are inadequate for numerous applications. Hence, they require alteration via functionalisation with desired functional groups. Hydroxyl groups are often preferred, since they enable appropriate polarity for the irreversible grafting of desired molecules. In this study, the surface kinetics resulting from the treatment of polystyrene with hydroxyl (OH) radicals from the gas phase was fundamentally investigated through a precisely-designed experiment. Polystyrene samples were exposed to various known fluences of OH radicals, and the evolution of surface functional groups versus the OH fluence was monitored using high-resolution X-ray photoelectron spectroscopy (XPS). The fluences of OH radicals varied between 1 × 1018 and 4 × 1023 m−2 in the process of finding a threshold fluence for the formation of specific groups. The surface concentration of carbonyl (C=O) groups could be measured using XPS at a fluence of approximately 5 × 1020 m−2. The C=O groups became measurable at a fluence of approximately 1.5 × 1021 m−2, and carboxyl (COOH)/ester groups at approximately 4 × 1021 m−2. As deduced from the XPS, a concentration of C=O groups at approximately 5 % occurred before the degradation of the aromatic ring. The formation of other oxygen-functional groups required opening of the aromatic ring. The results have been explained using a two-step process, considering available theories vis-a-vis initial stages in the functionalisation of PS with polar functional groups.