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Register a new userEnergy barriers and cooperative motion at the surface of freestanding glassy polystyrene films
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We investigate the near-surface relaxation of freestanding atactic glsdesc{ps} films with molecular dynamics simulations. As in previous coarse-grained simulations, relaxation times for backbone segments and phenyl rings are linked to their bulk relaxation times via a power law coupling relation. Variation of the coupling exponent with distance from the surface is consistent with depth-dependent activation barriers. We also quantify a reduction of dynamical heterogeneity at the interface which can be interpreted in the framework of cooperative models for glassy dynamics.
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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.
Polymer glasses have numerous advantageous mechanical properties in comparison to other materials. One of the most useful is the high degree of toughness that can be achieved due to significant yield occurring in the material. Remarkably, the onset of plasticity in polymeric materials is very poorly quantified, despite its importance as the ultimate limit of purely elastic behavior. Here we report the results of a novel experiment which is extremely sensitive to the onset of yield and discuss its impact on measurement and elastic theory. In particular, we use an elastic instability to locally bend and impart a textit{local} tensile stress in a thin, glassy polystyrene film, and directly measure the resulting residual stress caused by the bending. We show that plastic failure is initiated at extremely low strains, of order $10^{-3}$ for polystyrene. Not only is this critical strain found to be small in comparison to bulk measurement, we show that it is influenced by thin film confinement - leading to an increase in the critical strain for plastic failure as film thickness approaches zero.
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 part 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.
Thin block copolymer films have attracted considerable academic attention because of their ability to self-assemble into various microstructures, many of which have potential technological applications. Despite the ongoing interest, little effort has focused on the onset of plasticity and failure which are important factors for the eventual adoption of these materials. Here we use delamination to impart a quantifiable local stain on thin films of homopolymer polystyrene and poly(2-vinylpyridine), as well as block copolymers made of styrene and 2-vinylpyridine. Direct observation of the damage caused by bending with atomic force microscopy and laser scanning confocal microscopy, leads to the identification of a critical strain for the onset of plasticity. Moving beyond our initial scaling analysis, the more quantitative analysis presented here shows strain levels for thick films to be comparable to bulk measurements. Monitoring the critical strain leads to several observations: 1.) as-cast PS-P2VP has low critical strain, 2.) annealing slowly increases critical strain as microstructural ordering takes place, and 3.) similar to the homopolymer, both as cast and ordered films both show increasing critical strain under confinement.
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 measurements. 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.
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