화학공학소재연구정보센터
Fluid Phase Equilibria, Vol.417, 144-157, 2016
Non-equilibrium thermodynamics of glassy polymers: Use of equations of state to predict gas solubility and heat capacity
The use of Non-Equilibrium Thermodynamics for Glassy Polymers (NET-GP) model to predict infinite dilution gas solubility coefficient is revised in this work and its extension to the analysis of apparent constant pressure heat capacity in polymeric materials below the glass transition temperature T-g is developed. Use is made of different Equations of State (EoS), in the class of tangent-hard-spheres-chain theories, to predict the thermal expansion coefficient below Tg, resulting in consistent representations of the Henry's coefficient for gaseous species in the same temperature range, for the case of different versions of Statistical Associating Fluid Theory (SAFT) EoS. With reference to calorimetric properties, the analysis here performed indicates that NET-GP endowed with EoS tuned on melt phase equilibrium properties does not allow for the prediction of the bulk modulus of the glassy polymeric phase, and only qualitative behavior for the apparent heat capacity are reproduced. On the other hand, after the use of experimental data from structural relaxation experiments to evaluate the bulk modulus in glassy state, a satisfactory prediction of the excess heat capacity is obtained within the same framework, for the case of different non-equilibrium conditions. Conclusion are finally drawn for the need to account for additional order parameters in NET-GP approach in order to address the representation of the complex calorimetric behavior exhibited by glassy polymeric materials. (C) 2016 Elsevier B.V. All rights reserved.