Pressure effects on the $α$ and $α′$ relaxations in polymethylphenylsiloxane

In some polymers, in addition to the usual structural $α$ relaxation, a slower $α′$ relaxation is observed with a non-Arrhenius temperature dependence. In order to understand better the molecular origin of this $α′$ relaxation in poly(methylphenylsiloxane) (PMPS) we have studied, for the first time, the pressure dependence of its relaxation time, together with the usual temperature dependence, by means of dynamic light scattering (DLS). For the same material the $α$ relaxation was also studied by means of DLS and dielectric spectroscopy (DS) in broad temperature and pressure ranges. We find that the temperature dependence of both $α$ and $α′$ relaxation times, at all pressures studied, can be described by a double Vogel-Fulcher-Tammann (VFT) law. The pressure dependence of the characteristic temperatures $Tg$ (glass transition temperature) and $T0$ (Vogel temperature) as well as the activation volumes for both $α$ and $α′$ processes are very similar, indicating, that both relaxation processes originate from similar local molecular dynamics. Additionally, for both $α$ and $α′$ relaxations the combined temperature and pressure dependences of the relaxation times can be described using a parameter $Γ=ρn∕T$ with the same value of the exponent $n$⁠.