a.State Key Lab of Oil & Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China
b.School of Material Science and Engineering, Southwest Petroleum University, Chengdu 610500, China
c.National Synchrotron Radiation Lab, Key Laboratory of Soft Matter Chemistry, Chinese Academy of Sciences, University of Science and Technology of China, Hefei 230029, China
Yun-tao Li(李云涛), E-mail:yuntaoli@swpu.edu.cn
Liang-bin Li(李良彬), E-mail:lbli@ustc.edu.cn
收稿:2017-03-07,
修回:2017-4-10,
录用:2017-4-17,
纸质出版:2017-11-05
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Yi-kun Ren, Yun-tao Li, Liang-bin Li. A Theoretical Interpretation of Free Volume at Glass Transition[J]. Chinese Journal of Polymer Science, 2017,35(11):1415-1427.
Yi-kun Ren, Yun-tao Li, Liang-bin Li. A Theoretical Interpretation of Free Volume at Glass Transition[J]. Chinese Journal of Polymer Science, 2017, 35(11): 1415-1427.
Yi-kun Ren, Yun-tao Li, Liang-bin Li. A Theoretical Interpretation of Free Volume at Glass Transition[J]. Chinese Journal of Polymer Science, 2017,35(11):1415-1427. DOI: 10.1007/s10118-017-1968-8.
Yi-kun Ren, Yun-tao Li, Liang-bin Li. A Theoretical Interpretation of Free Volume at Glass Transition[J]. Chinese Journal of Polymer Science, 2017, 35(11): 1415-1427. DOI: 10.1007/s10118-017-1968-8.
We device a relaxed lattice model (RLM) to study the mechanism of glass transition
which unifies the cage-effects from particle-particle interaction and entropy. By analyzing entropy in RLM with considering the influence of interactions on equilibrium
we demonstrate that glass transition is a second-order phase transition. For a perfect one-dimensional linked particle system like linear polymer under normal pressure
the free volume at glass transition is rigorously deduced out to be 2.6%
which provides a theoretical basis for the iso-free volume of 2.5% given by Willian
Landel and Ferry (WLF) equation. Extending to system with dead particles linked with higher dimensions like branched or cross-linked chains under positive or negative pressure
free volume at glass transition is varied
based on which we construct a phase diagram of glass transition in the space of free volume-dead particle-pressure. This demonstrates that free volume is not the single parameter determining glass transition
while either dead particles like cross-linked points or external force fields like pressure can vary free volume at the glass transition.
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