Polymer, Vol.44, No.3, 783-791, 2003
The effect of gamma irradiation on the pressure dependence of the room temperature transition in PTFE
Some of the effect of gamma irradiation on the pneumatic pressure dependence of the well established room temperature transition (ca. 19 degreesC) in polytetra(fluoroethylene) are described. The experiments, conducted up to a maximum gamma dosage of 60 Mrad and a superimposed nitrogen pressure of 48.3 MPa indicate a significant reduction in the room temperature transition as well as its pressure dependence with the increasing of the gamma dosage. These data, combined with the observed and reported reduction in the free volume (actually net volume) are consistent with the proposition that irradiation process results in a reduction in the 'effective internal pressure' due to extensive bond scission. The latter process is manifested in an observed dramatic decrease in the molecular weight. Data on the compressibility and coefficient of thermal expansion, accompanied by thermodynamic arguments, indicate that the room temperature transition more closely resembles a second order transition as gamma dosage increases. This is consistent with a change in system behaviour progressing from a viscoelastic to that of a brittle glassy polymer as confirmed by monitoring the polymer creep behaviour following rapid pressurisation. Data for the 'freshly' irradiated specimens indicate highly transient post-irradiation induced changes in the polymer morphology.