Theoretical aspects of polymer crystallization with chain folds: Bulk polymers

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Abstract
The Theory of Crystallization of bulk linear polymers with chain folding is discussed in terms of recent developments. Specific topics covered are: (a) Rate of crystal growth and size of folded nuclei, (b) theoretical and experimental estimates of the fold surface free energy, and estimates of the surface free energy of “friged micelle” and “switchbord” type crystals, (c) basic causes of essentially regular folding in bulk, (d) rejection of short chain species during crystallization, (e) melting behavior of thin chain‐folded lamellae, (f) gradual thickening of lamellae on isothermal storage, (g) homogeneous, pseudohomogeneous, and heterogeneous nucleation, (h) voids and included point defects as a paret of the concept of the degree of crystallinity, and (i) phenomena occurring in stage 1 and stage 2 of bulk crystallization isotherms (annealing). A comparison of theory and experiment is carried out using data, some previously unpublished, on polyethylene and polychlorotrifluoroethylene. The theory with essentially regular golding is found to be satisfactory.

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