Abstract
Melting of imperfect crystals is treated, using the methods of irreversible thermodynamics. A reproducible limiting heating path of zero entropy production from the metastable solid to the supercooled molten state is described. Experimental evidence shows that this ‘equilibrium’ heating path can often be approximated by heating fast enough so that reorganization and recrystallization in the crystalline aggregates are minimized, but not so fast that superheating is experienced. Expressions for the melting of perfect homopolymer lamellae, defect copolymer lamellae, and for the experimental maximum melting point of copolymers are discussed. For polyethylene a self-consistent set of data based on melting experiments carried out under zero entropy production heating is given. By this method the equilibrium maximum melting point for polyethylene homopolymer is found to be 142°C, while the surface free energy of a (001)-surface of polymer lamellae is about 75 erg/cm 2.
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