A new theory for polymer/solvent mixtures based on hard-sphere limit

Based on hard-sphere limit of binary mixtures with different molecular size of components a theory has been developed for calculating activities of solvents in polymer/solvent mixtures. The theory considers various chain configurations for polymer molecules, varying from extended chain to the coiled chain. According to this theory the activity of solvent can be calculated from molecular weights (MWs) and densities as the only input data. The only adjustable parameter in the calculations, is the hard-sphere diameter of polymer, which provides useful criteria for the judgement on the chain configuration of polymer. The activity calculations have been performed for seven binary mixtures of polymer/solvent and compared with experimental data at various temperatures and for a varying range of MWs of polymers. The solvents in the mixtures were both of polar and nonpolar natures. The activity calculations for the same systems were performed by the well-known Flory–Huggins theory. Comparing the results of calculations with those of Flory– Huggins theory indicates that, the proposed theory is able to predict the activities of the solvent with good accuracy. The radius of gyration, excluded volume and interaction parameter for polymer chain have been calculated using the parameter obtained in the new theory. The calculated interaction parameter in the new theory, is interpreted in terms of attraction, repulsion and interchange energy of polymer and solvent in the mixture. 2003 Elsevier Science Ltd. All rights reserved.