Hierarchical microstructure changes and the molecular mechanism of polypropylene under a critical failure strain during creep

- The molecular deformation mechanism of polypropylene during creep including three stages is proposed.
- The mechanism explains the transition point during creep deformation.
- Positron annihilation lifetime spectroscopy is a powerful microanalytical technique to explore the microstructure changes.
- The disaggregation-recrystallization process would lead the free volume to increase in number while decrease in size.

The hierarchical microstructure evolution of polypropylene during creep was explored via various methods, such as differential scanning calorimetry (DSC), scanning electron microscope (SEM), two-dimensional small-angle X-ray scattering (2D-SAXS), two-dimensional wide angle X-ray diffraction (2D-WAXD) and positron annihilation lifetime spectroscopy (PALS). The results revealed a correlation among the changes of micron-scale spherulites, nano-scale lamellae, crystalline blocks, atomic scale free volume and the deformation of polypropylene during creep. The elongation of micron-scale spherulites along the creep direction, accompanying with the increase of nano-scale lamellar long spacing, as well as the enlargement and amalgamation of atomic scale free volume were observed at ε below 17%; the imperfect fibrillar crystallites with polymer chains preferentially oriented along the creep direction, formed in the stress-induced crystalline block disaggregation-recrystallization process, were proved by SEM and 2D-SAXS results when ε was between 17% and 55%; the further orientation of polypropylene chains led to a higher degree of orientation and crystallinity. The molecular deformation mechanism of polypropylene during creep included three stages: the intralamellar slipping of crystalline blocks, accompanying with the enlargement and amalgamation of free volume, was activated at small strain (ε ≤ 17%); whereas the stress-induced crystalline block disaggregation-recrystallization process as well as the rearrangement and orientation of chains were proceeded at medium strain (17% < ε ≤ 55%); at last, orientation-induced crystallization occurred at larger strain (ε > 55%).

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