Abstract
Theta (Θ) conditions in binary and multicomponent polymer solutions are calculated using a perturbed hard-sphere-chain (PHSC) equation of state. Θ conditions are identified by roots of the spinodal criterion in the limit of infinite polymer molecular weight and zero polymer-segment fraction. Because the thermodynamic properties of mixtures are described by an equation of state, both upper and lower Θ temperatures can be calculated. For binary systems (one polymer and one solvent), experimentally determined Θ conditions and the critical solution temperature for a single polymer molecular weight are used to obtain equation-of-state parameters. Parameters obtained in this manner yield nearly quantitative representation of upper and lower Θ temperatures as a function of pressure and upper and lower critical solution temperatures as a function of polymer molecular weight. For ternary systems (two solvents and one polymer), the dependence of the Θ temperature on solvent composition can be described using parameters obtained from binary data.
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