Abstract: Polymeric materials are widely used in applications where the environmental conditions entail their exposure to different sources of irradiation (in most cases ultraviolet or low dose of electromagnetic irradiation for sterilization). In contrast, in this study we have assessed the modifications undergone by a series of polyurethane joints exposed to high radioactive doses of either X-rays or gamma rays (with doses of 20.5, 100, 300 and 900?kGy) or neutron irradiation (with a fluence of 7.23·1010 n/cm2) which are typical of the environment of nuclear reactors. Tensile tests were carried out to assess the change in mechanical properties derived from the radioactive exposure. Three mechanical parameters were used to monitor the evolution of strength, ductility and toughness: the tensile strength (?max), the strain corresponding to ?max (??max) and the density of energy absorbed prior to maximum load (U?max). With regards to X and gamma rays, a negative impact of radiation on strength, ductility and toughness was observed. The detailed statistical analysis of the results has shown that a threshold dose of 300?kGy must be overcome to trigger the damage process. For the fluence employed in this study, neutron irradiation produced very little change in the mechanical properties. The SEM fractographic study has allowed the influence of irradiation on the material failure mechanisms to be identified. Thus, the fracture surface of unirradiated samples shows evidence of plastic deformation and ductile tearing. In contrast, the fracture surface of those samples exposed to a dose of 900?kGy corresponds to brittle fracture. In a consistent way, samples exposed to neutron irradiation have a fracture surface similar to that of the non-irradiated material. In summary, electromagnetic radiation for doses above the threshold leads to the embrittlement of polyurethane. Raman spectroscopy was employed to identify the microstructural changes induced by the different sources of radiation at the molecular level. The band corresponding to the vibration of the C-H bending bonds present in the polyurethane was measured as a function of the dose, finding a strong correlation between its vibration frequency and the dose of exposure to electromagnetic radiation. This shift is more sensitive than the mechanical material response since the frequency is affected at doses of 100?kGy, below the threshold previously identified for any of the mechanical properties. This correlation opens the door for the use of Raman spectroscopy as a novel non-destructive tool to characterize the microstructural effect of irradiation on polyurethane.

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