Modifications induced by energetic ions have been investigated in the regime of electronic stopping power by X-ray photoemission spectroscopy (XPS), infrared absorption spectroscopy (IRAS) and differential scanning calorimetry (DSC). Stacks of thin foils of polyvinylidene fluoride (PVDF) have been exposed to ion beams with energies ranging from 1 to 50 MeV/amu and with different atomic number Z ( 16 O, 84 Kr, 129 Xe) . XPS measurements provide information about the surface modifications of irradiated PVDF: (1) oxygen ions bombardment leads to the creation of cumulene compounds (CCC) n following hydrogen fluoride desorption, the intensity of which increases with the irradiation dose δE, the fluence φt of the ion and the energy loss ΔE in the polymer; (2) for krypton or xenon irradiation, no changes can be detected on the surface composition. Differential scanning calorimetry (DSC) performed on a pristine sample and on PVDF irradiated with xenon ions shows a decrease of the melting point T Fand of the enthalpy ΔH F with the irradiation dose δE. This behaviour is characteristic of a loss of crystallinity due to the internal reorganization of the polymer (creation of polyallenic compounds, chain scission, decrease of the molecular weight). Infrared transmission spectra (IRAS) and attenuated total reflexion spectroscopy (ATR) show that only surface modifications are induced by oxygen ions. For energetic heavy ions (Kr, Xe), the bulk of the polymer is loaded with unsaturated compounds like allenes (2038, 1720, 1610 and 1560 cm −1), and is depleted in fluorine atoms. On the other hand, the PVDF surface studied in ATR mode exibits a much smaller evolution. There results are consistent with XPS data. All these experimental data can be explained by gas formation and desorption, migration in the bulk of reactive species like free radicals and internal recombinations.
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