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Thermodynamic description of geometrical confinement. Application to the glassy state and the glass transition of amorphous polymers

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  • Zeng, Yiming
  • Shi, Yanqiao
  • Chen, Guanwen

Abstract

Based on the analysis of the geometrical confinements and the interactions between neighbor segments in polymeric systems, besides the quasi-lattice model used in Gibbs–DiMarzio entropy theory, an alternative theoretical method was developed here to investigate the thermodynamic aspect of the glassy state and the glass transition of amorphous polymers. A glass forming process through solvent evaporation from amorphous polymer-good solvent system was investigated, and the functional relationship between the glass transition temperature (Tg) and Kauzmann temperature (TK) at which configurational entropy equals zero was derived. The ratio Tg/TK=e1/4 was also deduced as a good approximation for a large amount of glassy polymers. The ratio is consistent with the empirical result Tg/TK=1.30±8.4%, which was proposed by Adam and Gibbs. The theoretical method presented here was also applied to investigate the compositional variation of glass transition temperatures; equations, which are consistent with experiments, were also derived.

Suggested Citation

  • Zeng, Yiming & Shi, Yanqiao & Chen, Guanwen, 2003. "Thermodynamic description of geometrical confinement. Application to the glassy state and the glass transition of amorphous polymers," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 319(C), pages 80-98.
    • Handle: RePEc:eee:phsmap:v:319:y:2003:i:c:p:80-98
    DOI: 10.1016/S0378-4371(02)01500-5
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