Mechanical properties and the evolution of matrix molecules in PTFE upon irradiation with MeV alpha particles

The morphology, chemical composition, and mechanical properties in the surface region of α-irradiated polytetrafluoroethylene (PTFE) have been examined and compared to unirradiated specimens. Samples were irradiated with 5.5 MeV ⁴ He ²⁺ ions from a tandem accelerator to doses between 1 × 10 ⁶ and 5 × 10 ¹⁰ Rad. Static time-of-flight secondary ion mass spectrometry (ToF-SIMS), using a 20 keV C ₆₀ ⁺ source, was employed to probe chemical changes as a function of α dose. Chemical images and high resolution spectra were collected and analyzed to reveal the effects of α particle radiation on the chemical structure. Residual gas analysis (RGA) was utilized to monitor the evolution of volatile species during vacuum irradiation of the samples. Scanning electron microscopy (SEM) was used to observe the morphological variation of samples with increasing α particle dose, and nanoindentation was engaged to determine the hardness and elastic modulus as a function of α dose. The data show that PTFE nominally retains its innate chemical structure and morphology at α doses <10 ⁹ Rad. At α doses ≥10 ⁹ Rad the polymer matrix experiences increased chemical degradation and morphological roughening which are accompanied by increased hardness and declining elasticity. At α doses >10 ¹⁰ Rad the polymer matrix suffers severe chemical degradation and material loss. Chemical degradation is observed in ToF-SIMS by detection of ions that are indicative of fragmentation, unsaturation, and functionalization of molecules in the PTFE matrix. The mass spectra also expose the subtle trends of crosslinking within the α-irradiated polymer matrix. ToF-SIMS images support the assertion that chemical degradation is the result of α particle irradiation and show morphological roughening of the sample with increased α dose. High resolution SEM images more clearly illustrate the morphological roughening and the mass loss that accompanies high doses of α particles. RGA confirms the supposition that the outcome of chemical degradation in the PTFE matrix with continuing irradiation is evolution of volatile species resulting in morphological roughening and mass loss. Finally, we reveal and discuss relationships between chemical structure and mechanical properties such as hardness and elastic modulus.