Citation: 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 shu

A Theoretical Interpretation of Free Volume at Glass Transition

Yi-kun Ren ^a,b,c ,
Yun-tao Li ^a,b,, ,
Liang-bin Li ^c,,

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

Corresponding author: Yun-tao Li, yuntaoli@swpu.edu.cn Liang-bin Li, lbli@ustc.edu.cn
Received Date: 7 March 2017
Revised Date: 10 April 2017
Accepted Date: 17 April 2017

Fund Project: the National Natural Science Foundation of China 51633009the National Natural Science Foundation of China 51325301

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.
- Glass transition,
- Iso-free volume,
- Relaxed lattice model,
- Predicted phase diagram
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