Crystallization of polymers
partial alignment of polymer molecular chains, resulting in "semi-crystalline" structures
Crystallization of polymers is a process associated with partial alignment of their molecular chains. These chains fold together and form ordered regions called lamellae, which compose larger spheroidal structures named spherulites. Polymers can crystallize upon cooling from melting, mechanical stretching or solvent evaporation. Crystallization affects optical, mechanical, thermal and chemical properties of the polymer. The degree of crystallinity is estimated by different analytical methods and it typically ranges between 10 and 80%, with crystallized polymers often called "semi-crystalline". The properties of semi-crystalline polymers are determined not only by the degree of crystallinity, but also by the size and orientation of the molecular chains.
Crystallization mechanisms
Solidification from the melt
Polymers are composed of long molecular chains which form irregular, entangled coils in the melt. Some polymers retain such a disordered structure upon freezing and readily convert into amorphous solids. In other polymers, the chains rearrange upon freezing and form partly ordered regions with a typical size of the order 1 micrometer. Although it would be energetically favorable for the polymer chains to align parallel, such alignment is hindered by the entanglement.
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