Aging phenomena in PMMA thin films -- memory and rejuvenation effects

TL;DR

This study investigates aging, memory, and rejuvenation effects in PMMA thin films through dielectric measurements, revealing thickness-dependent dynamics and temperature shift effects that differ from bulk behavior.

Contribution

It provides new insights into the thickness-dependent aging and memory effects in PMMA thin films, highlighting differences from bulk properties and the impact of temperature shifts.

Findings

Dielectric constant decreases with aging time in most cases.

Memory effects are retained during temperature cycling.

Rejuvenation effects are stronger in thinner films.

Abstract

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 ($\ge$11h) near the glass transition temperature for thin films with thickness less than 26nm. 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 the temperature shift from the initial temperature $T_1$ to the second temperature $T_2$($=T_1+\Delta T$) when $\Delta T\approx -20$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 $\Delta T\approx -20$K. As $|\Delta T|$ decreases, the independence of the aging between the two temperatures was found to be weaken, $i.e.,$ 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 514nm to 26nm, the $|\Delta T|$ 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.