High-Field Electron Paramagnetic Resonance Reveals a Stable Glassy Fraction up to Melting in Semicrystalline Poly(dimethylsiloxane)

The reorientation of the guest 4-methoxy-TEMPO (spin probe) in the disordered fraction of semicrystalline poly(dimethylsiloxane) (PDMS) is investigated by high-field electron paramagnetic resonance (HF-EPR) at 190 and 285 GHz. Accurate numerical simulations of the HF-EPR lineshapes evidence that the reorientation times of the spin probes are distributed between the melting temperature Tm and Tm-30 K. The distribution exhibits, in addition to a broad component, a narrow component with low mobility up to the PDMS melting point. It is shown that the temperature dependence of the reorientation time of the spin probes with low mobility is the same of the spin probes in glassy PDMS. The result suggests that the low-mobility fraction is localized in the so-called rigid amorphous fraction.