Experimental Test of Tammann's Nuclei Development Approach in Crystallization of Macromolecules

Prediction of the supermolecular structure and with that of properties of crystallizable polymers requires in-depth knowledge about the crystallization behavior, in particular the temperature-dependence of the nucleation kinetics. Typically, at low supercooling of the melt the nucleation rate/nuclei density often is assessed by optical microscopy, through an analysis of the evolution of the spherulitic superstructure. This approach fails if the nuclei density is too high, or if nuclei formation is not followed by growth due to chain-mobility constraints. In such cases, Tammann's two-stage crystal nuclei development method can be applied. It includes the formation of crystal nuclei at high supercooling of the melt, and their detection at higher temperature, after their growth to crystals. Though initially developed for analysis of low molecular mass compounds, this approach has recently also successfully been employed for analysis of the nucleation behavior of polymers, which is demonstrated here on the examples of poly (L-lactic acid) (PLLA), and poly (epsilon-caprolactone) (PCL). While in case of PLLA the ability to gain information about isothermal and non-isothermal nucleation is explained, in case of PCL new information about the thermal stability of nuclei is presented. The importance of such analyses in the context of understanding structure formation of polymers at processing-relevant cooling conditions is discussed.