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We have measured the linear and nonlinear dielectric responses of S-methoxypropylene carbonate, a highly polar glass-former, for which it has been reported that the “hump,” which is typical of third harmonic susceptibilities, disappears across a 5 K temperature change. To understand this unusual feature, we have measured the responses to high amplitude ac and dc electric fields at the fundamental frequency. The static limits of these results are entered into a model aimed at reproducing nonlinear dielectric susceptibility spectra using the concept of a fictive electric field. This model reproduces the “hump” in the third-harmonic response and its seeming disappearance. It is revealed that the “hump” is predominantly the result of reduced time constants, a consequence of the energy the sample absorbs from the electric field. At elevated temperatures, the “hump” only appears to vanish because its reduced amplitude submerges below the extraordinarily high level of polarization saturation of this liquid. 

Physical vapor deposition can prepare organic glasses with high kinetic stability. When heated, these glassy solids slowly transform into supercooled liquid in a process known as rejuvenation. In this study, we anneal vapor-deposited glasses of methyl-m-toluate for 6 h at 0.98Tg to observe rejuvenation using dielectric spectroscopy. Glasses of moderate stability exhibited partial or full rejuvenation in 6 h. For highly stable glasses, prepared at substrate temperatures of 0.85Tg and 0.80Tg, the 6 h annealing time is ∼2% of the estimated transformation time, and no change in the onset temperature for the α relaxation process was observed, as expected. Surprisingly, for these highly stable glasses, annealing resulted in significant increases in the storage component of the dielectric susceptibility, without corresponding increases in the loss component. These changes are interpreted to indicate that short-term annealing rejuvenates a high frequency relaxation (e.g., the boson peak) within the stable glass. We compare these results to computer simulations of the rejuvenation of highly stable glasses generated by using the swap Monte Carlo algorithm. The in silico glasses, in contrast to the experiment, show no evidence of rejuvenation within the stable glass at times shorter than the alpha relaxation process. 

Glassy films of methyl-m-toluate have been vapor deposited onto a substrate equipped with interdigitated electrodes, facilitating in situ dielectric relaxation measurements during and after deposition. Samples of 200 nm thickness have been deposited at rates of 0.1 nm/s at a variety of deposition temperatures between 40 K and Tg = 170 K. With increasing depth below the surface, the dielectric loss changes gradually from a value reflecting a mobile surface layer to that of the kinetically stable glass. The thickness of this more mobile layer varies from below 1 to beyond 10 nm as the deposition temperature is increased, and its average fictive temperature is near Tg for all deposition temperatures. Judged by the dielectric loss, the liquid-like portion of the surface layer exceeds a thickness of 1 nm only for deposition temperatures above 0.8Tg, where near-equilibrium glassy states are obtained. After deposition, the dielectric loss of the material positioned about 5–30 nm below the surface decreases for thousands of seconds of annealing time, whereas the bulk of the film remains unchanged. 

Upon heating, ultrastable glassy films transform into liquids via a propagating equilibration front, resembling the heterogeneous melting of crystals. A microscopic understanding of this robust phenomenology is, however, lacking because experimental resolution is limited. We simulate the heterogeneous transformation kinetics of ultrastable configurations prepared using the swap Monte Carlo algorithm, thus allowing a direct comparison with experiments. We resolve the liquid–glass interface both in space and in time as well as the underlying particle motion responsible for its propagation. We perform a detailed statistical analysis of the interface geometry and kinetics over a broad range of temperatures. We show that the dynamic heterogeneity of the bulk liquid is passed on to the front that propagates heterogeneously in space and intermittently in time. This observation allows us to relate the averaged front velocity to the equilibrium diffusion coefficient of the liquid. We suggest that an experimental characterization of the interface geometry during the heterogeneous devitrification of ultrastable glassy films could provide direct experimental access to the long-sought characteristic length scale of dynamic heterogeneity in bulk supercooled liquids. 

The discovery of ultrastable glasses raises novel challenges about glassy systems. Recent experiments studied the macroscopic devitrification of ultrastable glasses into liquids upon heating but lacked microscopic resolution. We use molecular dynamics simulations to analyze the kinetics of this transformation. In the most stable systems, devitrification occurs after a very large time, but the liquid emerges in two steps. At short times, we observe the rare nucleation and slow growth of isolated droplets containing a liquid maintained under pressure by the rigidity of the surrounding glass. At large times, pressure is released after the droplets coalesce into large domains, which accelerates devitrification. This two-step process produces pronounced deviations from the classical Avrami kinetics and explains the emergence of a giant lengthscale characterizing the devitrification of bulk ultrastable glasses. Our study elucidates the nonequilibrium kinetics of glasses following a large temperature jump, which differs from both equilibrium relaxation and aging dynamics, and will guide future experimental studies.