The origin of the faster mechanism of partial enthalpy recovery deep in the glassy state of polymers

Literature Information

Publication Date 2021-05-24
DOI 10.1039/D1CP01445E
Impact Factor 3.676
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Abstract

A novel finding made by Cangialosi and coworkers in the physical aging of several polymers way below the glass transition temperature Tg is that equilibrium recovery occurs by reaching a plateau in the enthalpy with partial enthalpy recovery. This observation points to the existence of a much faster mechanism capable of partial equilibrium recovery deep in the glassy state. A similar phenomenon was found in different glassy materials. The generality of the phenomenon indicates that the faster mechanism of equilibrium recovery is universal and fundamental. In this paper the faster mechanism is identified to be the universal JG β-relaxation having dynamic and thermodynamic properties analogous to the α-relaxation, and thus capable of effecting enthalpy and volume recovery far below Tg in several high-Tg polymers. The JG β-relaxation is also the mechanism responsible for the first step of two steps in the approach to equilibrium found in another polymer with much lower Tg. The Coupling Model is used to explain why the first step transpires far below Tg in some polymers but much closer to Tg in another polymer.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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