Chemical transformations and changes in free volume holes in high-energy proton irradiated low-density polyethylene (LDPE)

Low-density polyethylene (LDPE) was irradiated with 4 MeV protons at different ion fluences. Chemical modifications were studied by UV–vis and Fourier transformed infrared (FT-IR) spectroscopy. Further, the changes in free volume holes were studied using positron annihilation lifetime spectroscopy. The different UV–vis absorption spectra show the maximum absorption at around 280 nm for the lower fluences whereas at the highest fluence a red shift is observed. This indicates formation of chromophoric groups that have the maximum absorption in that region. The formation of vinylidine, trans-vinylene, end-vinyl group, unsaturated linkage and carbonyl group were detected from FT-IR spectra. Positron annihilation lifetime spectroscopy reveals that the free volume hole size and their relative fraction first decrease, attaining a minimum value and subsequently increases with increase in ion fluence. These changes in free volume holes have been well correlated with the observed chemical transformations.