Chain growth, polymer crystal nucleation

Polymers crystallize from the molten state by the two-step process of nucleation and crystal growth. Nucleation initiates crystallization, followed by the addition of linear chain segments to the crystal nucleus. 

Polymer crystallization is usually divided into two separate processes primary nucleation and crystal growth [1]. The primary nucleation typically occurs in three-dimensional (3D) homogeneous disordered phases such as the melt or solution. The elementary process involved is a molecular transformation from a random-coil to a compact chain-folded crystallite induced by the changes in ambient temperature, pH, etc. Many uncertainties (the presence of various contaminations) and experimental difficulties have long hindered quantitative investigation of the primary nucleation. However, there are many works in the literature on the early events of crystallization by var-... 

Polymer crystal growth is predominantly in the lateral direction, because folds and surface entanglements inhibit crystalliza- 4 don in the thickness direction. Neverthe-1 less, there is a considerable increase in the fold period behind the lamellar front during crystallization from the melt and, as we have j seen, polymers annealed above their crys-tallization temperature but below Tm also irreversibly thicken. Nevertheless, in most theories of secondary nucleation, the most i widely used being the theory of Lauritzen and Hoffman,28 it is assumed that once a part of a chain is added to the growing crystal, its. fold period remains unchanged. 

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