POLYMER CRYSTALLIZATION FROM THE MELT AT LARGE UNDERCOOLINGS

This paper is concerned with the theories of polymer crystallization. Consideration of crystallization kinetics in high-molecular-weight polymers shows that adjacent reentry is unlikely in melt crystallization and that sections of individual chains will crystallize concurrently at several sites. Hence the characteristic crystallization process will be that of a loop of chain with both ends attached to different sites on the crystal surface. Analysis of this process leads to predictions of crystallinity values for various conditions of chanin mobility in the crystal and of entanglements in the amorphous regions. Observations on polymers crystallized at high undercoolings where a crystallinity of about 30% is usually observed suggest that the common case is that of a highly entangled amorphous layer and rapid, local annealing of the chains but with no long-range motion in the crystal. This model of loop crystallization is shown to agree with available small-angle neutron scattering data. The overall crystallization kinetics are in accord with surface nucleation controlled growth which also arises out of the Lauritzen-Hoffman adjacent reentry model and has been shown to fit experimental results on growth rates.