Plasma-induced surface radicals of low-density polyethylene studied by electron spin resonance

Plasma-induced low-density polyethylene (LDPE) radicals were studied in detail by electron spin resonance (ESR) by its comparison with ESR of high-density polyethylene (HDPE). The observed ESR spectra of plasma-irradiated LDPE are largely different in pattern from those of HDPE. The systematic computer simulation disclosed that such observed spectra consist of three kinds of radicals, midchain alkyl radical (1), allylic radical (2) as discrete radical species, and a large amount of dangling bond sites (DBS) (3) at an intra-and intersegmental cross-linked region. All these component radicals are essentially identical to those of HDPE. One of the most special features unique to plasma-irradiated LDPE, however, is the fact that thermally stable DBS (3) is a major component radical instead of a midchain alkyl radical in HDPE. This can be ascribed to the difference in polymer morphology between LDPE and HDPE: branched structure with a large amount of amorphous region for LDPE and linear structure with a large amount of crystalline region for HDPE. Since one of the characteristics of plasma irradiation is the fact that it is surface-limited, LDPE would undergo the radical formation preferentially on the surface-branched structural moiety followed by facile cross-link reactions resulting in the formation of DBS. Thus, the nature of radical formation of PE was found to be affected by the polymer morphology in a very sensitive manner.