Physical aging in poly(methyl methacrylate) glass: densification via density fluctuation

Abstract

The physical aging in poly(methyl methacrylate) during annealing just below T g was investigated by light scattering and oscillating-DSC in which a sinusoidal temperature rise was imposed over the conventional linear temperature rise. Light scattering intensity decreased monotonously with increasing scattering angle. The intensity was found to increase rapidly and then to decrease gradually with annealing time t a. The correlation length and the mean-square density fluctuations by Debye–Bueche plot increased at an early stage and then decreased with t a. The width of the glass transition, obtained by the Fourier transform treatment of the oscillated DSC heat flow, increased with t a at an early stage and then decreased. The endothermic peak, given by the non-reversing part of the oscillating DSC heat flow, appeared even at an early stage of the aging. These results suggest that: (1) as-quenched PMMA glass is partially densified to yield an inhomogeneity in density with a correlation length about 200 nm; (2) by the annealing, the density fluctuations grow at first by a decrease in density at the low density regions and an expansion of the low density regions to increase the correlation length; and (3) the densification then proceeds at the low density regions to reduce the correlation length and to get higher density as a whole, by approaching a rather homogeneous glassy state.