Chapter

Polymer Thermodynamics

Volume 238 of the series Advances in Polymer Science pp 1-66

Date:

Making Floryr–Huggins Practical: Thermodynamics of Polymer-Containing Mixtures

  • Bernhard A. WolfAffiliated withInstitut für Physikalische Chemie der Johannes Gutenberg-Universität Mainz Email author 

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Abstract

The theoretical part of this article demonstrates how the original Flory–Huggins theory can be extended to describe the thermodynamic behavior of polymer-containing mixtures quantitatively. This progress is achieved by accounting for two features of macromolecules that the original approach ignores: the effects of chain connectivity in the case of dilute solutions, and the ability of polymer coils to change their spatial extension in response to alterations in their molecular environment. In the general case, this approach leads to composition-dependent interaction parameters, which can for most binary systems be described by means of two physically meaningful parameters; systems involving strongly interacting components, for instance via hydrogen bonds, may require up to four parameters. The general applicability of these equations is illustrated in a comprehensive section dedicated to the modeling of experimental findings. This part encompasses all types of phase equilibria, deals with binary systems (polymer solutions and polymer blends), and includes ternary mixtures; it covers linear and branched homopolymers as well as random and block copolymers. Particular emphasis is placed on the modeling of hitherto incomprehensible experimental observations reported in the literature.

Keywords

Modeling Mixed solvents Phase diagrams Polymer blends Polymer solutions Ternary mixtures Thermodynamics