The continuous cooling transformation (CCT) as a flexible tool to investigate polymer crystallization under processing conditions

An experimental route for investigating polymer crystallization over a wide range of cooling rates (from 0.01 to 1000◦C/s) and pressures (from 0.1 to 40 MPa) is illustrated, using a method that recalls the approach adopted in metallurgy for studying structure development in metals. Two types of experimental setup were used, namely an apparatus for fast cooling of thin films (100–200 μm thick) at various cooling rates under atmospheric pressure and a device (based on a on-purpose modified injection molding machine) for quenching massive samples (about 1–2 cm3) under hydrostatic pressure fields. In both cases, ex situ characterization experiments were carried out to probe the resulting structure, using techniques such as density measurements and wide-angle x-ray diffraction (WAXD) patterns. The cooling mechanism and temperature distribution across the sample thickness were analyzed. Results show that the final structure is determined only by the imposed thermal history and pressure. Experimental results for isotactic polypropylene (iPP), poly(ethylene terephthalate) (PET), polyamide 6 (PA6), and syndiotactic polystyrene (sPS) are reported, showing the reliability of this experimental approach to assess not only quantitative information but also a qualitative description of the crystallization behavior of different classes of semicrystalline polymers. The present study gives an opportunity to evaluate how the combined effect of the cooling rate and pressure influences the crystallization kinetics for various classes of polymer of commercial interest. An increase in the cooling rate translates into a decrease in crystallinity and density, which both experience a sudden drop around the specific “crystallizability” (or “critical cooling rate”) of the material examined. The exception is sPS where competition among the various crystalline modifications determines a minimum in the plot of density vs. cooling rate. As for the effect of pressure, iPP exhibits a “negative dependence” of crystallization kinetics upon pressure, with a decrease of density and degree of crystallinity with increasing pressure, owing to kinetic constraints. PA6 and PET, on the other hand, due to thermodynamic factors resulting in an increase in Tm with pressure, exhibits a “positive dependence” of crystallization kinetics upon pressure. Finally, recent original results concerning sPS have shown that the minimum in the density vs. cooling rate curve shifts toward larger cooling rates upon increasing pressure.