Radiation-induced functionalization of ferroelectric poly(vinylidene fluoride) was studied by ESR spectroscopy. The samples were irradiated in the high vacuum of a Van de Graaff accelerator with 1.0 MeV and 1.5 MeV electrons at room temperature and the decay of free radicals was studied after transferring the samples into the air. The samples exhibit a multicomponent ESR spectrum that can be decomposed into: a large asymmetric signal in the centre related to peroxy radicals, a quintet with hyperfine splitting A F = 4.3 mT centred at g = 2.004, assigned to the in-chain radical (-CF2-C• H-CF2-), and a triplet due to an end-chain (-C • H2) radical with A H = 1.6 mT and g = 2.009.
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