Yaotao Wang

Lamellar Thickness and Stretching Temperature Dependency of Cavitation in Semicrystalline Polymers

Polybutene-1 (PB-1), a typical semicrystalline polymer, in its stable form I shows a peculiar temperature dependent strain-whitening behavior when being stretched at temperatures in between room temperature and melting temperature of the crystallites where the extent of strain-whitening weakens with the increasing of stretching temperature reaching a minima value followed by an increase at higher stretching temperatures. Correspondingly, a stronger strain-hardening phenomenon was observed at higher temperatures. The strain-whitening phenomenon in semicrystalline polymers has its origin of cavitation process during stretching. In this work, the effect of crystalline lamellar thickness and stretching temperature on the cavitation process in PB-1 has been investigated by means of combined synchrotron ultrasmall-angle and wide-angle X-ray scattering techniques. Three modes of cavitation during the stretching process can be identified, namely “no cavitation” for the quenched sample with the thinnest lamellae where only shear yielding occurred, “cavitation with reorientation” for the samples stretched at lower temperatures and samples with thicker lamellae, and “cavitation without reorientation” for samples with thinner lamellae stretched at higher temperatures. The mode “cavitation with reorientation” occurs before yield point where the plate-like cavities start to be generated within the lamellar stacks with normal perpendicular to the stretching direction due to the blocky substructure of the crystalline lamellae and reorient gradually to the stretching direction after strain-hardening. The mode of “cavitation without reorientation” appears after yield point where ellipsoidal shaped cavities are generated in those lamellae stacks with normal parallel to the stretching direction followed by an improvement of their orientation at larger strains. X-ray diffraction results reveal a much improved crystalline orientation for samples with thinner lamellae stretched at higher temperatures. The observed behavior of microscopic structural evolution in PB-1 stretched at different temperatures explains above mentioned changes in macroscopic strain-whitening phenomenon with increasing in stretching temperature and stress-strain curves.

Mechanism of polymorph selection during crystallization of random butene-1/ethylene copolymer

Starting from an initial sample of butene-1/ethylene copolymer with stable form I’, we examined the nucleation of different crystalline polymorphs (here metastable form II and stable form I’) at different isothermal crystallization temperatures after being melted at different melt temperature (Tmelt). When Tmelt was just above the melting temperature (Tm) of the crystallites, self-seeding took place. There, residue crystallites served as nuclei leading to the crystallization of the same crystalline phase. When Tmelt was a few degrees above the Tm, self-seeding was disabled due to complete melting of the initial crystals. Upon crystallization, the selection of the different polymorphs in this random copolymer was found to depend on an interplay between the domain size of segregated long crystallizable sequences and the size and energy barrier of the critical nucleus of the respective crystalline forms. Our results provide a clear understanding of the polymorphs selection during crystallization of a random copolymer as well as homo-polymers under confinement.

Crystallization, Recrystallization, and Melting Lines in Syndiotactic Polypropylene Crystallized from Quiescent Melt and Semicrystalline State Due to Stress-Induced Localized Melting and Recrystallization

Crystalline lamellar thickness in syndiotactic polypropylene (sPP) during crystallization from either isothermal molten or stretching induced localized melt states and during subsequent heating was investigated by means of temperature dependent small-angle X-ray scattering techniques. Well-defined crystallization lines where the reciprocal lamellar thickness is linearly dependent on crystallization temperature were observed. Unlike in the case of polybutene-1 where stretching crystallization line was shifted to direction of much smaller lamellar thickness (Macromolecules 2013, 46, 7874), the stretching induced crystallization line for sPP deviates from its corresponding isothermal crystallization line only slightly. Such phenomenon could be attributed to the fact that both crystallization processes from quiescent melt and stress induced localized melt are mediated in a mesomorphic phase in sPP. Subsequent heating of sPP after crystallization revealed the same melting behavior in both systems for the two kinds of crystallites obtained from either quiescent melt or stretching induced localized melt. Both of them underwent melting and recrystallization when the lamellar thickness was smaller than a critical value and melting directly without changing in thickness when the lamellar thickness was larger than the critical value. The melting behavior in sPP systems can be understood by considering the chain relaxation ability within crystalline phase and also can be used as evidence that the crystallization from molten state and stress-induced crystallization passed through the intermediate phase before forming crystallites.