Particle Concentration Promotes Flow-Induced Crystallization of High-Molecular-Weight Isotactic Polypropylene

Intervals of shear flow that stretch polymer chains form flow-induced precursors which accelerate crystallization and transform the crystalline morphology from isotropic spherulites to anisotropic structures. The flow-induced crystallization of two commercial samples of isotactic polypropylene with nearly identical molecular weight distributions, differing in concentrations of catalyst residue particles, was investigated by using dynamic rheology and ex situ Synchrotron X-ray scattering. Upon the application of flow, the sample with higher particle concentration crystallized at faster rates relative to the sample with lower levels of heterogeneous impurities. The nucleation ability of these particles was particularly pronounced at lower levels of deformation, while flow effects became prominent as larger deformations were applied. For sufficiently strong flows (γ̇ ≤ 145 s-1), a lower critical shear stress (∼0.096 MPa) was observed for the formation of shish-kebab structures in the sample with higher concentrations of particles. In this work, we have also identified the formation of shish-kebab structures in the presence of weak flow (γ̇ ≤ 0.3 s-1) when sheared for long durations of time. For equivalent levels of specific work within both flow regimes, the morphologies of these anisotropic structures were found to be characteristically distinct from one another. The long period and degree of crystallinity were also found to increase with shear stress above the stress level needed for the formation of shish-kebab structures.

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Work Title Particle Concentration Promotes Flow-Induced Crystallization of High-Molecular-Weight Isotactic Polypropylene
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Open Access
Creators
  1. Benson J. Jacob
  2. Xiaoshi Zhang
  3. Jongkyeong Kim
  4. Jason D. Alexander
  5. Manoela E. Cangussú
  6. Alicyn M. Rhoades
  7. Ralph H. Colby
Keyword
  1. Crystal Structure
  2. Crystallization
  3. Nucleation
  4. Stress
  5. X-Ray Scattering
License CC BY 4.0 (Attribution)
Work Type Article
Publisher
  1. Macromolecules
Publication Date April 16, 2024
Publisher Identifier (DOI)
  1. 10.1021/acs.macromol.4c00413
Deposited October 22, 2024

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Version 1
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  • Created
  • Updated
  • Added Creator Benson J. Jacob
  • Added Creator Xiaoshi Zhang
  • Added Creator Jongkyeong Kim
  • Added Creator Jason D. Alexander
  • Added Creator Manoela E. Cangussú
  • Added Creator Alicyn M. Rhoades
  • Added Creator Ralph H. Colby
  • Updated Work Title, Publisher, Publisher Identifier (DOI), and 2 more Show Changes
    Work Title
    • Particle Concentration Promotes Flow-Induced Crystallization of High Molecular Weight Isotactic Polypropylene
    • Particle Concentration Promotes Flow-Induced Crystallization of High-Molecular-Weight Isotactic Polypropylene
    Publisher
    • Macromolecules
    Publisher Identifier (DOI)
    • 10.1021/acs.macromol.4c00413
    Description
    • <p>Intervals of shear flow that stretch polymer chains form flow-induced precursors which accelerate crystallization and transform the crystalline morphology from isotropic spherulites to anisotropic structures. The flow-induced crystallization of two commercial samples of isotactic polypropylene with nearly identical molecular weight distributions, differing in concentrations of catalyst residue particles, was investigated by using dynamic rheology and ex situ Synchrotron X-ray scattering. Upon the application of flow, the sample with higher particle concentration crystallized at faster rates relative to the sample with lower levels of heterogeneous impurities. The nucleation ability of these particles was particularly pronounced at lower levels of deformation, while flow effects became prominent as larger deformations were applied. For sufficiently strong flows (γ̇ ≤ 145 s<sup>-1</sup>), a lower critical shear stress (∼0.096 MPa) was observed for the formation of shish-kebab structures in the sample with higher concentrations of particles. In this work, we have also identified the formation of shish-kebab structures in the presence of weak flow (γ̇ ≤ 0.3 s<sup>-1</sup>) when sheared for long durations of time. For equivalent levels of specific work within both flow regimes, the morphologies of these anisotropic structures were found to be characteristically distinct from one another. The long period and degree of crystallinity were also found to increase with shear stress above the stress level needed for the formation of shish-kebab structures.</p>
    Publication Date
    • 2024-05-14
  • Updated
  • Updated
  • Updated Creator Benson J. Jacob
  • Updated Creator Xiaoshi Zhang
  • Updated Creator Jongkyeong Kim
  • Updated Creator Jason D. Alexander
  • Updated Creator Manoela E. Cangussú
  • Updated Creator Alicyn M. Rhoades
  • Updated Creator Ralph H. Colby
  • Added iPP Particle Manuscript March 2024_Final.pdf
  • Updated License Show Changes
    License
    • https://creativecommons.org/licenses/by/4.0/
  • Published
  • Updated
  • Updated Keyword, Publication Date Show Changes
    Keyword
    • Crystal Structure , Crystallization , Nucleation , Stress , X-Ray Scattering
    Publication Date
    • 2024-05-14
    • 2024-04-16