Relaxation processes in a glassy polymer containing methanol molecules

The interaction of small guest molecules with the molecular degrees of freedom of a glassy polymer matrix is investigated, i.e. (i) the dynamics of these guest molecules and (ii) their effect on the secondary ‘β’ and main ‘α’ relaxations of the host polymeric matrix. The system considered here is the glassy poly(methyl metacrylate) modified by introduction and desorption of methanol. The dynamics of the system is observed by means of low-frequency mechanical and wide band dielectric spectroscopies. The presence of small molecules in the PMMA glassy matrix induces several effects, namely (i) a strong relaxation peak develops at low temperature (near 120 K at 1 Hz and called αm in the following), (ii) the strength of the β relaxation is increased while the temperature of the maximum shifts towards the low temperatures, (iii) a sharp peak appears superimposed on the β peak, and finally (iv) the α relaxation shifts towards the low temperatures. Dielectric and mechanical spectroscopies results are in agreement and make it possible to capture the dynamical behavior in a wide frequency range (eight decades). The experimental results are explained on the basis of physical concepts recently introduced in the physics of glassy matter: cooperativity and nanoheterogeneity. In particular, the low-temperature relaxation process αm is attributed to cooperative motions in methanol clusters which form in the nanoheterogeneous polymeric matrix, in agreement with small angle X-rays scattering and low-frequency Raman scattering observations recently reported.