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The very long-term physical aging of glassy polymers

Abstract

The thermodynamic behavior of glasses well below the glass transition temperature ($T_g$) is scarcely explored due to the long time scales required for such investigation. Here, we characterize the thermodynamic state of several polymer glasses aged for about 30 years at room temperature, that is, at more than 100 K below their respective $T_g$(s). To this aim we employ differential scanning calorimetry (DSC), which, via the specific heat, allows characterizing the enthlapy attained after a certain aging protocol and the way the glass with such enthalpy devitrifies when heated. We complement these results with extensive DSC studies on these polymers aged in the same conditions of temperature for time scales ranging from minutes to months. The main outcome of the present work is that these polymers aged in these conditions reach a plateau in the enthalpy with partial enthalpy recovery and devitrify well below $T_g$. This result provides compelling evidence for the existence of a fast mechanism of equilibrium recovery, beyond the standard slow one in proximity of $T_g$. The analogy with other kind of glasses is highlighted, stigmatizing the universality of such behavior. Finally, the way the fast mechanism of equilibrium recovery could be exploited to obtain glasses with low energy state is discussed.

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Publication details

The article was received on 26 Mar 2018, accepted on 17 Apr 2018 and first published on 17 Apr 2018


Article type: Communication
DOI: 10.1039/C8CP01940A
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    The very long-term physical aging of glassy polymers

    N. G. Perez-De Eulate and D. Cangialosi, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP01940A

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