Effects of High Molecular Weight Species on Shear-Induced Orientation and Crystallization of Isotactic Polypropylene

Journal Article · Sun Jan 01 04:00:00 EST 2006 · Polymer

DOI:https://doi.org/10.1016/j.polymer.2004.12.066· OSTI ID:914338

Somani, R; Yang, L; Hsiao, B

In situ rheo-SAXS (small-angle X-ray scattering) and rheo-WAXD (wide-angle X-ray diffraction) techniques were used to investigate the role of high molecular weight species on the evolution of oriented microstructure in isotactic polypropylene (iPP) melt under shear flow. The two iPP samples, designated as PP-A and PP-B, respectively, had the same number-average (M{sub n}) but different weight-average (M{sub w}) and Z-average (M{sub z}) molecular weights. Molecular weight distribution (MWD) of PP-A and PP-B was such that for MW<10{sup 5} the MWD curves overlapped; whereas in the high MW tail region, the amount of high molecular weight species was higher in PP-B than PP-A. Both samples were subjected to an identical shear condition (rate=60 s{sup -1}, duration=5 s, T=155 degC). In situ 2D SAXS and WAXD images allowed the tracking of shear-induced oriented structures in the melt. It was found that the shish structures evolved much earlier, and the degree of crystal orientation and oriented crystal fractions were higher in PP-B than PP-A. Moreover, PP-B exhibited faster crystallization kinetics than PP-A. These results, along with the predictions of double reptation models of chain motion and experimental studies of chain conformation dynamics in dilute solutions under flow, suggest the following: When a polymer melt that consists of entangled chains of different lengths is deformed, the chain segments aligned with the flow eigenvector can undergo the abrupt coil-stretch-like transition, while other segments would remain in the coiled state. Since, flow-induced orientation decays much more slowly for long chains than for short chains, oriented high molecular weight species play a prominent role in formation of the stretched sections, where shish originates. Our experimental results are strong evidence of the hypothesis that even a small increase in the concentration of high molecular weight species causes a significant increase in the formation, stability and concentration of the flow-induced oriented microstructure.

• Research Organization: Brookhaven National Laboratory (BNL) National Synchrotron Light Source
• Sponsoring Organization: Doe - Office Of Science
• DOE Contract Number: AC02-98CH10886
• OSTI ID: 914338
• Report Number(s): BNL--78906-2007-JA
• Journal Information: Polymer, Journal Name: Polymer Journal Issue: 15 Vol. 47; ISSN 0032-3861; ISSN POLMAG
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
CRYSTALLIZATION
KINETICS
MICROSTRUCTURE
MOLECULAR WEIGHT
ORIENTATION
POLYPROPYLENE
SHEAR
SMALL ANGLE SCATTERING
X-RAY DIFFRACTION
national synchrotron light source