Study of the glass transition in the amorphous interlamellar phase of highly crystallized poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) is a semi--crystalline polymer that can be crystallized to different degrees heating from the amorphous state. Even when primary crystallization has been completed, secondary crystallization can take place with further annealing and modify the characteristics of the amorphous interlamellar phase. In this work we study the glass transition of highly crystallized PET and in which way it is modified by secondary crystallization. Amorphous PET samples were annealed for 4 hours at temperatures between 140C and 180C. The secondary crystallization process was monitored by differential scanning calorimetry and the glass transition of the remaining interllamelar amorphous phase was studied by Thermally Stimulated Depolarization Currents measurements. Non--isothermal window polarization is employed to resolve the relaxation in modes with a well--defined relaxation time that are subsequently adjusted to several standard models. Analysis of experimental results, show that cooperativity is reduced to a great extend in the interlamellar amorphous regions. The evolution of the modes on crystallization temperature reveals that large scale movements are progressively replaced by more localized ones, with higher frequency, as crystallization takes place at higher temperatures. As a consequence, the glass transition temperature of the amorphous interlamellar phase tends to lower values for higher annealing temperatures. Evolution of calorimetric scans of the glass transition are simulated from the obtained results and show the same behaviour. The interpretation of these results in terms of current views about secondary crystallization is discussed.Comment: 30 pages, 5 tables, 12 figures; figure 5 modifie

Relaxation of isolated quantum systems beyond chaos

In classical statistical mechanics there is a clear correlation between relaxation to equilibrium and chaos. In contrast, for isolated quantum systems this relation is -- to say the least -- fuzzy. In this work we try to unveil the intricate relation between the relaxation process and the transition from integrability to chaos. We study the approach to equilibrium in two different many body quantum systems that can be parametrically tuned from regular to chaotic. We show that a universal relation between relaxation and delocalization of the initial state in the perturbed basis can be established regardless of the chaotic nature of system.Comment: 4+ pages, 4 figs. Closest to published versio

Lyapunov decay in quantum irreversibility

The Loschmidt echo -- also known as fidelity -- is a very useful tool to study irreversibility in quantum mechanics due to perturbations or imperfections. Many different regimes, as a function of time and strength of the perturbation, have been identified. For chaotic systems, there is a range of perturbation strengths where the decay of the Loschmidt echo is perturbation independent, and given by the classical Lyapunov exponent. But observation of the Lyapunov decay depends strongly on the type of initial state upon which an average is done. This dependence can be removed by averaging the fidelity over the Haar measure, and the Lyapunov regime is recovered, as it was shown for quantum maps. In this work we introduce an analogous quantity for systems with infinite dimensional Hilbert space, in particular the quantum stadium billiard, and we show clearly the universality of the Lyapunov regime.Comment: 8 pages, 6 figures. Accepted in Phil. Trans. R. Soc.