Molecular motion and relaxation below glass transition temperature in poly (methyl methacrylate) studied by positron annihilation

• PMMA was irradiated by 22Na positron source at room temperature, 225 K and 16 K.
• Irradiation at 225 K and 16 K introduces free radicals and trapped electrons, respectively.
• Ester and main chain methyl group rotations lead to detrapping of accumulated electrons.
• A new method for detection of molecular motion below glass transition is developed.

In this paper, we present the study of local molecular motions in poly (methyl methacrylate) (PMMA) below glass transition temperature by measuring the ortho-positronium (o-Ps) intensity. Two series of experiments were performed: (1) the PMMA sample was irradiated by 22Na positron source with elongated time at room temperature, 225 K and 16 K, respectively, and positron lifetime spectra were measured as a function of irradiation time and (2) Positron lifetime and Doppler broadening spectra were measured as a function of temperature from 16 to 350 K after positron irradiation at 16 K for more than 350 h. While the o-Ps lifetime always shows no change with elapsed time, decrease and increase of o-Ps intensity I3 are observed at 225 K and 16 K, which are interpreted as the result of positron irradiation-induced free radicals and trapped electrons, respectively. With temperature increasing from 16 K, there is a continuous drop of I3 beginning at around 100 K. This is due to some local group movements such as the ester and main chain methyl group rotations, which lead to the detrapping of accumulated electrons. These local motions do not need additional free volume, so we observed no change of the o-Ps lifetime. Some other structural relaxations such as β-relaxation are also observed and discussed.