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 the melt, 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%, thus crystallized polymers are often called 'semicrystalline'. The properties of semicrystalline polymers are determined not only by the degree of crystallinity, but also by the size and orientation of the molecular chains.
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 thus 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. Therefore, within the ordered regions, the polymer chains are both aligned and folded. Those regions are therefore neither crystalline nor amorphous and are classified as semicrystalline. Examples of semi-crystalline polymers are linear polyethylene, polyethylene terephthalate, polytetrafluoroethylene or isotactic polypropylene.
Whether or not polymers can crystallize depends on their molecular structure – presence of straight chains with regularly spaced side groups facilitates crystallization. For example, crystallization occurs much easier in isotactic than in the atactic polypropylene form. Atactic polymers crystallize when the side groups are very small, as in polyvinyl and don't crystallize in case of large substituents like in rubber or silicones.
Nucleation starts with small, nanometer-sized areas where as a result of heat motion some chains or their segments occur parallel. Those seeds can either dissociate, if thermal motion destroys the molecular order, or grow further, if the grain size exceeds a certain critical value.
Apart from the thermal mechanism, nucleation is strongly affected by impurities, dyes, plasticizers, fillers and other additives in the polymer. This is also referred to as heterogeneous nucleation. This effect is poorly understood and irregular, so that the same additive can promote nucleation in one polymer, but not in another. Many of the good nucleating agents are metal salts of organic acids, which themselves are crystalline at the solidification temperature of the polymer solidification.
Crystal growth is achieved by the further addition of folded polymer chain segments and only occurs for temperatures below the melting temperature Tm and above the glass transition temperature Tg. Higher temperatures destroy the molecular arrangement and below the glass transition temperature, the movement of molecular chains is frozen. Nevertheless, secondary crystallization can proceed even below Tg, in the time scale of months and years. This process affects mechanical properties of the polymers and decreases their volume because of a more compact packing of aligned polymer chains.
The chains interact via various types of the van der Waals forces. The interaction strength depends on the distance between the parallel chain segments and it determines the mechanical and thermal properties of the polymer.
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