Structure and Properties of Crystalline Polymers: Supramolecular structure is complex, can be controlled, and influences mechanical properties

Through control of the crystallization process many polymers can be made to exhibit a broad spectrum of structural possibilities, ranging from a state of high disorder to one of high order. Emphasis has been placed on bulk-crystallized polymers which normally fall near the center of this spectrum. This was done in part because polymers are most commonly fabricated in this manner, and also because the amount of attention given in recent years to crystals grown from dilute solution has tended to obscure important aspects of the structure of bulk-crystallized polymers. Differences in the structure of the interlamellar regions account most reasonably for many of the variations in mechanical properties that crystalline polymers can be made to display. The interlamellar amorphous model, proposed here as a structural model for bulk-crystallized polymers, largely neglects the lamellae themselves, because so little is known about the structure of the lamellae of bulk-crystallized polymers and how variations in lamellar structure can affect properties. This model is intended, therefore, as both a working hypothesis to aid further investigation and as an outline to be filled in as more is learned about the supramolecular structure of crystalline polymers (31).