Aging phenomena in poly(methyl methacrylate) thin films: Memory and rejuvenation effects

The aging dynamics in thin films of poly(methyl methacrylate) (PMMA) have been investigated through dielectric measurements for different types of aging processes. The dielectric constant was found to decrease with increasing aging time at an aging temperature in many cases. An increase in the dielectric constant was also observed in the long-time region (>= 11 h) near the glass transition temperature for thin films with thickness less than 26 nm. In the constant-rate mode including a temporary stop at a temperature T-a, the memory of the aging at T-a was found to be kept and then to be recalled during the subsequent heating process. In the negative-temperature cycling process, a strong rejuvenation effect has been observed after a temperature shift from the initial temperature T-1 to the second temperature T-2 (=T-1+Delta T) when Delta T approximate to-20 K. Furthermore, a full memory effect has also been observed for the temperature shift from T-2 to T-1. This suggests that the aging at T-1 is totally independent of that at T-2 for Delta T approximate to-20 K. As \Delta T\ decreases, the independence of the aging between the two temperatures was found to be weakened-i.e., the effective time, which is a measure of the contribution of the aging at T-1 to that at T-2, is a decreasing function of \Delta T\ in the negative region of Delta T. As the film thickness decreases from 514 nm to 26 nm, the parallel to Delta T parallel to dependence of the effective time was found to become much stronger. The contribution of the aging at T-2 to that at T-1 disappears more rapidly with increasing \Delta T\ in thin-film geometry than in the bulk state.