Organization of macromolecules in the solid state: A personal approach

The purpose of the article is to highlight the existence of large‐scale regular organizations in high polymers in order to provide a contrast with the more traditional conceptions based on randomness in the solid polymeric state. The selection adopted in this article is highly personal. Not unnaturally the author's own material forms the backbone of the survey; other material featured is quoted selectively to fit into the spirit of the narrative. It is hoped nevertheless that the overall impression given will be a balanced view, particularly in the more controversial aspects of the subject, emphasizing the complementary part played by order and disorder in a solid polymer. The material selected ranges from “historical” items to most recent developments, some still unpublished, which perhaps in retrospect are not as far apart as it may appear at first sight. Most of the material quoted is concerned with crystallization. The main items featured are macroscopic single crystals obtained by solid‐state polymerization, spherulites, chain‐folded lamellae with current issues relating to the nature of the fold surface, fibrous crystals, and the range of validity of the fringed micelle concept. In the course of this the nature of disorder in all these systems is also outlined and an appreciation is given of the usual technological material. The final section is devoted to some examples of remarkably regular organizations in twophase amorphous block copolymers.