Swift heavy ion modification of polymers

We have studied the effects of dense electronic excitations on vinyl linear polymers, by performing swift heavy ion, SHI, irradiations. We used different ion beams, from C to Pb, provided by the GANIL accelerator at energies of a few MeV/u. We mainly studied the physico-chemical modifications induced in polyethylene (PE), but the role of chemical substitutions has also been investigated by studying the swift heavy ion induced damage in polyvinylidene fluoride (PVDF) and polystyrene (PS). The irradiated samples were analysed ex-situ by means of Fourier transform infrared spectroscopy in the transmission mode. Any contact with air was avoided: oxidation does not occur. Swift heavy ion irradiations are characterised by a significant increase of the yield of chain scission associated with unsaturated end groups. Moreover, we have evidences for specific modifications, i.e. modifications which are never observed when using low ionising particles as electrons or gamma-rays; namely the creation of alkyne and allene end groups. These specific modifications are little sensitive to chemical substitutions. For instance, alkyne formation is observed in PE, PVDF and PS. A simultaneous ionisation of the different atoms of a constituting monomer is likely needed for triggering the formation of the specific swift heavy ion induced modifications. On the other hand, if we pay attention to the physico-chemical modifications which are easily induced by low ionising particles, it is observed that increasing the electronic stopping power does not significantly modify the creation yield of, for instance in PE, trans-vinylene or trans-trans diene groups.