Assessing Fast Structure Formation Processes in Isotactic Polypropylene with a Combination of Nanofocus X-ray Diffraction and In Situ Nanocalorimetry

A combination of in situ nanocalorimetry with simultaneous nanofocus 2D Wide-Angle X-ray Scattering (WAXS) was used to study polymorphic behaviour and structure formation in a single micro-drop of isotactic polypropylene (iPP) with defined thermal history. We were able to generate, detect, and characterize a number of different iPP morphologies using our custom-built ultrafast chip-based nanocalorimetry instrument designed for use with the European Synchrotron Radiation Facility (ESRF) high intensity nanofocus X-ray beamline facility. The detected iPP morphologies included monoclinic alpha-phase crystals, mesophase, and mixed morphologies with different mesophase/crystalline compositional ratios. Monoclinic crystals formed from the mesophase became unstable at heating rates above 40 K s(-1) and showed melting temperatures as low as similar to 30 K below those measured for iPP crystals formed by slow cooling. We also studied the real-time melt crystallization of nanogram-sized iPP samples. Our analysis revealed a mesophase nucleation time of around 1 s and the co-existence of mesophase and growing disordered crystals at high supercooling <= 328 K. The further increase of the iPP crystallization temperature to 338 K changed nucleation from homogeneous to heterogeneous. No mesophase was detected above 348 K. Low supercooling (>= 378 K) led to the continuous growth of the alpha-phase crystals. In conclusion, we have, for the first time, measured the mesophase nucleation time of supercooled iPP melted under isothermal crystallization conditions using a dedicated experimental setup designed to allow simultaneous ultrafast chip-based nanocalorimetry and nanofocus X-ray diffraction analyses. We also provided experimental evidence that upon heating, the mesophase converts directly into thermodynamically stable monoclinic alpha-phase crystals via perfection and reorganization and not via partial melting. The complex phase behaviour of iPP and its dependence on both crystallization temperature and time is presented here using a time-temperature-transformation (TTT) diagram.

Automated summary

The study combined in situ nanocalorimetry with simultaneous nanofocus 2D Wide-Angle X-ray Scattering to investigate the polymorphic behavior and structure formation of isotactic polypropylene (iPP). Various iPP morphologies were detected, including monoclinic alpha-phase crystals and mesophase, with different compositional ratios. The complex phase behavior of iPP was explored under different crystallization conditions, providing insights into its dependence on temperature and time.