We investigate the relaxation behavior of thin films of a polyamide random copolymer, PA66/6I, with various film thicknesses using dielectric relaxation spectroscopy. Two dielectric signals are observed at high temperatures, the $alpha$-process and t
he relaxation process due to electrode polarization (the EP-process). The relaxation time of the EP-process has a Vogel-Fulcher-Tammann type of temperature dependence, and the glass transition temperature, $T_{rm g}$, evaluated from the EP-process agrees very well with the $T_{rm g}$ determined from the thermal measurements. The fragility index derived from the EP-process increases with decreasing film thickness. The relaxation time and the dielectric relaxation strength of the EP-process are described by a linear function of the film thickness $d$ for large values of $d$, which can be regarded as experimental evidence for the validity of attributing the observed signal to the EP-process. Furthermore, there is distinct deviation from this linear law for thicknesses smaller than a critical value. This deviation observed in thinner films is associated with an increase in the mobility and/or diffusion constant of the charge carriers responsible for the EP-process. The $alpha$-process is located in a high frequency region than the EP-process at high temperatures, but merges with the EP-process at lower temperatures near the glass transition region. The thickness dependence of the relaxation time of the $alpha$-process is different from that of the EP-process. This suggests that there is decoupling between the segmental motion of the polymers and the translational motion of the charge carriers in confinement.
Glassy dynamics was investigated for thin films of atactic polystyrene by complex electric capacitance measurements using dielectric relaxation spectroscopy. During the isothermal aging process the real part of the electric capacitance increased with
time, whereas the imaginary part decreased with time. It follows that the aging time dependences of real and imaginary parts of the electric capacitance were primarily associated with change in volume (film thickness) and dielectric permittivity, respectively. Further, dielectric permittivity showed memory and rejuvenation effects in a similar manner to those observed for poly(methyl methacrylate) thin films. On the other hand, volume did not show a strong rejuvenation effect.
The aging behavior of polymer glass, poly(methyl methacrylate), has been investigated through the measurement of ac dielectric susceptibility ata fixed frequency after a temperature shift $Delta T$ ($le $ 20 K)between two temperatures, $T_1$ and $T_2
$. A crossover from cumulative aging to non-cumulative aging could be observed with increasing $Delta T$ using a twin temperature ($T$-) shift measurement. Based on a growth law of a dynamical coherent length given by activated dynamics, we obtained a unique coherent length for positive and negative $T$-shifts. The possibility of the existence of temperature chaos in polymer glasses is discussed.
The glass transition temperature and relaxation dynamics of the segmental motions of thin films of polystyrene labeled with a dye, 4-[N-ethyl-N-(hydroxyethyl)]amino-4-nitraozobenzene (Disperse Red 1, DR1) are investigated using dielectric measurement
s. The dielectric relaxation strength of the DR1-labeled polystyrene is approximately 65 times larger than that of the unlabeled polystyrene above the glass transition, while there is almost no difference between them below the glass transition. The glass transition temperature of the DR1-labeled polystyrene can be determined as a crossover temperature at which the temperature coefficient of the electric capacitance changes from the value of the glassy state to that of the liquid state. The glass transition temperature of the DR1-labeled polystyrene decreases with decreasing film thickness in a reasonably similar manner to that of the unlabeled polystyrene thin films. The dielectric relaxation spectrum of the DR1-labeled polystyrene is also investigated. As thickness decreases, the $alpha$-relaxation time becomes smaller and the distribution of the $alpha$-relaxation times becomes broader. These results show that thin films of DR1-labeled polystyrene are a suitable system for investigating confinement effects of the glass transition dynamics using dielectric relaxation spectroscopy.
The aging behavior is investigated for thin films of atactic polystyrene through measurements of complex electric capacitance. During isothermal aging process the real part of the electric capacitance increases with aging time, while the imaginary pa
rt decreases with aging time. This result suggests that the aging time dependence of the real and imaginary parts are mainly associated with change in thickness and dielectric permittivity, respectively. In thin films, the thickness depends on thermal history of aging even above the glass transition. Memory and `rejuvenation effects are also observed in the thin films.
