Crystallization of Bulk Polymers With Chain Folding: Theory of Growth of Lamellar Spherulites.

A systematic study of the problem of spherulitic growth in linear polymers in bulk has been carried out. A calculation of the radial growth of polymer spherulites is given for four models. These concern growth where the surface nuclei that control the rate are (1) bundlelike and coherent, (2) chain folded and coherent, (3) chain folded and noncoherent, and (4) bundlelike and noncoherent. The required modifications of nucleation theory are given. Then the radial growth rate laws are derived for each model, and the type of "spherulite" that would be formed discussed. The model with chain folded and coherent growth nuclei leads to a typical lamellar spherulite. The properties of the individual chain folded lamellae that form the spherulite are predicted, including the change of step height with growth temperature, melting behavior, and the behavior on recrystallization. (Chain folded lamellae may also occur in specimens that are not obviously spherulitic.) Under certain conditions, the noncoherent model with chain folds can lead to a modified lamellar spherulite. None of the bundlelike models will lead to a typical lamellar spherulite, though a spherical microcrystalline object might be formed. It is concluded that lamellar spherulites consist largely of chain folded structures. The factors that could cause chain folded crystals to appear in profusion in bulk polymers are discussed. The case of homogeneous initiation is considered first. Homogeneous initiation of chain folded nuclei in bulk will prevail if the end surface free energy of the bundlelike nucleus exceeds that of the folded. It is shown that the end surface free energy of the bundlelike nucleus, as calculated with a density gradient model, will be larger than had been supposed previously. It is therefore considered to be theoretically possible that the end surface free energy of the bundlelike nucleus may in some cases exceed that of the folded nucleus. Attention is given to the possibility that folded structures appear in large numbers because cumulative strain or large chain ends prevent the growth of bundlelike nuclei to large size, even when the latter type of nucleus is energetically favored when small. Heterogeneous initiation of folded structures is then considered. Other topics mentioned include: (1) Conditions that might lead to nonlamellar or nonspherulitic crystallization in bulk, (2) the origin of the twist that is frequently exhibited by the lamellae in spherulites, (3) the transitions that may sometimes occur in the radial growth rate law, and (4) interlamellar links.