Using the Flory-Huggins equation it is possible to account for the equilibrium thermodynamic properties of polymer solutions, particularly the large negative deviations from Raoult's Law, phase-separation and fractionation behaviour, melting-point depressions in crystalline polymers, and swelling of networks. However, whilst the theory is able to predict general trends, precise agreement with experimental data is not achieved. The deficiencies of the theory result from the limitations both of the model and of the assumptions employed in its derivation. The use of a single type of lattice for pure solvent, pure polymer and their mixtures is unrealistic and requires there to be no volume change upon mixing. The mathematical procedure used to calculate the total number of possible conformations of a polymer molecule in the lattice does not exclude self-intersections of the chain, which clearly is physically unrealistic. Furthermore, the use of a mean-field approximation to facilitate this calculation for placement of a polymer molecule in a partly-filled lattice, is satisfactory only when the volume fraction, ¢2, of polymer is high. In view of this, Flory-Huggins theory is least satisfactory for dilute polymer solutions because the polymer molecules in such solutions are isolated from each other by regions of pure solvent, i.e. the segments are not uniformly distributed in the lattice. Additionally, the interaction parameter, X, introduced to account for the effects of contact interactions, is not a simple parameter. Equation (3.20) resulted from a recognition that X contains both enthalpy and entropy contributions, and X also has been shown to depend upon ¢2. Despite these shortcomings, Flory-Huggins lattice theory was a major step forward towards understanding the thermodynamics of polymer solutions, and is the basis of many other theories. The theory will be developed further in subsequent sections since the relationships obtained are instructive, though the above limitations must be borne in mind when applying the resulting equations. Some of the more refined theories developed since the advent of Flory-Huggins lattice theory will be given brief consideration, but in general are beyond the scope of this book.
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