IngentaConnect Statistical thermodynamics predictions of the solubility paramete...

Authors: Utracki L.¹; Simha R.²

Source: Polymer International, Volume 53, Number 3, March 2004 , pp. 279-286(8)

Abstract:

The Simha and Somcynsky (S-S) lattice-hole theory has been shown to represent accurately the pressure–volume–temperature (PVT) surface of chain molecular melts and their mixtures. The characteristic scaling parameters, P*, T* and V*, extracted from equation of state (eos) measurements, are known for a large number of polymers. On this basis it is possible to compute the configurational internal energy density and thus the solubility parameter delta

as a function of temperature and pressure, delta

(T, P). In the first part of this paper it is shown that the theory leads to an energy approximately proportional to the first power of density, that is of the van der Waals type, as found for low molar mass fluids by Hildebrand. We continue with a computation of delta

for a series of polymer melts at two levels of temperature, namely T = 25 °C and T = T_g + 300 K. Next, the results are compared with those listed in reference publications, all at ambient pressure. The theoretical values extrapolated from the melt to 25 °C were systematically higher than those listed. However, good correlation is obtained with the high-temperature calculations for a large variety of polymers. Arguments for this low–high temperature correlation are presented in terms of corresponding levels of molecular mobility and packing in solution and in bulk. Copyright © 2004 Society of Chemical Industry

Keywords: cohesive energy; solubility parameter; free volume; equation of state; corresponding states; lattice-hole; Simha-Somcynsky theory

Document Type: Research article

DOI: 10.1002/pi.1365

Affiliations: 1: National Research Council Canada, Industrial Materials Institute, 75 de Mortagne, Boucherville, QC, Canada, J4B 6Y4 2: Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, Ohio 44106-7202, USA

The full text electronic article is available for purchase. You will be able to download the full text electronic article after payment.

$31.49 plus tax

Statistical thermodynamics predictions of the solubility parameter