Thermodynamics of polyisobutylene solutions. III. Thermal behavior and polymer order

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Abstract
Considerations based on the Maron theory show that for solutions of an amorphous polymer in a solvent the values of A obtained from heats of solution, heats of dilution, osmotic pressure, and vapor pressure should all be identical. Here λ = (aWaT)2, where μ is the Maron theory interaction parameter, T the temperature, and v2 the volume fraction. On the other hand, for solutions of a crystalline polymer in a solvent the A's obtained from heats of solution should always differ from those given by the other measurements. The difference is due to the heat of fusion involved in melting the crystalline portion of the polymer. A method is presented by means of which this heat of fusion can be found from the observed heats of solution, and this heat of fusion can either be used as a relative measure of crystallinity, or it can be converted to percent crystallinity when the heat of fusion of the completely crystalline polymer is known. The method described is very precise, and highly sensitive to low degrees of order.

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