Kovacs effect in PMMA observed by low-frequency Raman scattering (boson peak)

The physical aging of the poly(methyl methacrylate) glass (PMMA) is described by its effects on the refractive index, that reflects the change of mean specific volume, and, on the other hand, on the low-frequency Raman scattering, i.e., on the boson peak. The boson peak depends mainly on the cohesion fluctuations. The memory or so-called Kovacs effect is observed by the appearance of a minimum of refractive index (i.e. a maximum of volume) as a function of the aging time at a higher temperature subsequent to an aging at lower temperature. The minimum of refractive index corresponds to a maximum of the boson peak intensity. However, the cohesion is not directly related to the volume, so that the evolution of the refractive index does not mimic exactly that of the boson peak intensity. Information on the change of cohesion by aging is obtained by enthalpy measurement. The obtained experimental results are discussed in the frame of the heterogeneous cohesion or elasticity at the nanometric scale. This clarifies the phenomenon of physical aging and the consequent Kovacs effect.