Spherulite (polymer Physics) - Formation

Formation

If a molten linear polymer (such as polyethylene) is cooled down rapidly, then the orientation of its molecules, which are randomly aligned, curved and entangled remain frozen and the solid has disordered structure. However, upon slow cooling, some polymer chains take on a certain orderly configuration: they align themselves in plates called crystalline lamellae.

Growth from the melt would follow the temperature gradient (see figure). For example, if the gradient is directed normal to the direction of molecular alignment then the lamella growth sideward into a planar crystallite. However, in absence of thermal gradient, growth occurs radially, in all directions resulting in spherical aggregates, that is spherulites. The largest surfaces of the lamellae are terminated by molecular bends and kinks, and growth in this direction results in disordered regions. Therefore, spherulites have semicrystalline structure where highly ordered lamellae plates are interrupted by amorphous regions.

The size of spherulites varies in a wide range, from micrometers up to 1 centimeter and is controlled by the nucleation. Strong supercooling or intentional addition of crystallization seeds results in relatively large number of nucleation sites; then spherulites are numerous and small and interact with each other upon growth. In case of fewer nucleation sites and slow cooling, a few larger spherulites are created.

The seeds can be induced by impurities, plasticizers, fillers, dyes and other substances added to improve other properties of the polymer. 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.