A Molecular Theory of the Thermal Transitions of Polymers. II.

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  • A Molecular Theory of the Thermal Transitions of Polymers. I.

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A lattice theory is developed for melting and glass transition of polymers. Each chain segment is assumed to occupy a site on a hexagonal lattice. A polymer chain in crystalline state exists in an extended form with trans conformation. In molten or rubbery state holes are formed in the lattice and the chain becomes flexible having the mixed forms of trans and gauche; in glassy state the chain conformations are frozen in. The partition functions are set up. The equations to give melting temperature and glass transition temperature are derived from them with appropriate criteria for these transitions. Variations of thermodynamic properties at the transition points are also evaluated; the Prigogine-Defay relation is obtained. The results of the theory fairly agree with the available experimental data on polyethylene.

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