A High-Field EPR Study of the Accelerated Dynamics of the Amorphous Fraction of Semicrystalline Poly(dimethylsiloxane) at the Melting Point

The reorientation of a small paramagnetic tracer in poly(dimethylsiloxane) (PDMS) has been investigated by high-field electron paramagnetic resonance spectroscopy at a Larmor frequency of 285 GHz. The tracer is confined in the disordered phase of the semicrystalline PDMS. A sudden change of the rotational dynamics is observed close to the melting point (213 K) of the crystallites. This points to strong coupling between the crystalline and the disordered fractions of PDMS. Below the glass transition (Tg similar to 150K), the tracer reorientation occurs via small angle jumps, with no apparent distribution of the correlation times. Above Tg, a power-law distribution of correlation times is evidenced.