Glass transition sorption and swelling the g d and nelf approaches
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Glass Transition, Sorption and Swelling: The G-D and NELF approaches. Costas Panayiotou University of Thessaloniki, Greece. The salient features of the development:. The glass transition and glass densification. The Gibbs-DiMarzio + EOS approach. The NELF approach. The Glass – Transition I.

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Glass transition sorption and swelling the g d and nelf approaches

Glass Transition, Sorption and Swelling:The G-D and NELF approaches

Costas Panayiotou

University of Thessaloniki, Greece


The salient features of the development:

The glass transition and glass densification

The Gibbs-DiMarzio + EOS approach

The NELF approach




Effect of pressure on tg
Effect of pressure on Tg

  • The pressure increases the Tg of pure polymers

  • The presence of a solvent decreases the Tg of the polymer (plasticization)

  • What will happen when a SCF is interacting with a polymer at high pressures?



Plasticization of glassy polymers:

Retrograde vitrification


Handling the Glassy State with EOS

  • Density: An order parameter for the non-equilibrium glassy state. Thus:

    (Macromolecules 1998, 31, 7915; IEC Res. 2004, 43, 6841)

  • The Gibbs-DiMarzio criterion:

    S 0 at Tg


Handling the Glassy State with EOS

The Gibbs-DiMarzio Approach

  • The Gibbs-DiMarzio criterion:

  • The key LF equations:

S 0 at Tg


Handling the Glassy State with EOS

The Gibbs-DiMarzio Approach

  • The Gibbs-DiMarzio criterion:

  • Calculation of entropy:

S 0 at Tg


Handling the Glassy State with EOS

The Gibbs-DiMarzio Approach


Handling the Glassy State with EOS

The Gibbs-DiMarzio Approach


Handling the Glassy State with EOS

The Gibbs-DiMarzio Approach












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