Study of microstructure of modified polyethylene films with acrylic and methacrylic acids, by positron annihilation spectroscopy

Low density polyethylene (LDPE) was preirradiated with γ -rays and after some contact time with the monomers AA and MAA, suitable graft copolymers were obtained at different grafting grades. After their physical-chemistry characterization, the copolymers were studied using the Positron Annihilation Lifetime Spectroscopy (PALS). Owing to its sensitive and non-destructive nature PALS has proven to be very useful in studying free-volume properties -at the molecular level- during phase transitions in molecular solids, such as the graft copolymers of LDPE/AA and LDPE/MAA. Using PALS it was possible to detect the changes in the melting point of the LDPE as a function of the grafting degree, obtaining thus, valuable information about the microstructure of this kind of copolymers. The increase in the values of the o-Ps lifetime, was interpreted as suggesting that the melting transition is followed by a free-volume cavity expansion as the temperature increased. The o-Ps intensity of formation behavior is in accord with the distortions occurring in the electronic density surrounding the o-Ps as well as the changes in the number of cavities available to the formation of o-Ps. (Author)