Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Spatial inhomogeneity of chain orientation associated with strain-induced density fluctuations in polyethylene

Polymer Journal volume 54, pages 243–248 (2022)Cite this article

Subjects

Abstract

We found the spatial inhomogeneity of chain orientation on the submicron scale in polyethylene (PE) under strain by scanning transmission X-ray microscopy (STXM). Our previous study [1] clarified that straininduced density fluctuations on the submicron scale and that density fluctuations strongly affected the mechanical behavior of PE during strain. Strain is expected to induce the spatial inhomogeneity of chain orientation as well as density fluctuations, and the spatial inhomogeneity might also affect the mechanical behavior. However, wide-angle X-ray scattering can be used to explore the spatially averaged local structure, and the spatial inhomogeneity of chain orientation on the submicron scale has not yet been investigated. To clarify the spatial inhomogeneity of chain orientation, we observed near-edge X-ray absorption fine structure (NEXAFS) spectra at the carbon K-edge of stretched PE, with a resolution on the order of 10 nm, by STXM and investigated the spatial inhomogeneity of chain orientation as well as density fluctuations. The intensity of the NEXAFS spectra revealed that the chains were more oriented in the low-density region under stretching. The orientation was induced by the stretching of the polymer chains mechanically melted.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

References

  1. Kishimoto M, Mita K, Ogawa H, Takenaka M. Effect of submicron structures on the mechanical behavior of polyethylene. Macromolecules. 2020;53:9097–107. https://doi.org/10.1021/acs.macromol.0c00896.

    Article  CAS  Google Scholar 

  2. Wilchinsky ZW. Orientation in crystalline polymers related to deformation. Polymer. 1964;5:271–81. https://doi.org/10.1016/0032-3861(64)90144-2.

    Article  CAS  Google Scholar 

  3. Fu Q, Men Y, Strobl G. A molar mass induced transition in the yielding properties of linear polyethylene. Polymer. 2003;44:1941–7. https://doi.org/10.1016/S0032-3861(03)00036-3.

    Article  CAS  Google Scholar 

  4. Che J, Locker CR, Lee S, Rutledge GC, Hsiao BS, Tsou AH. Plastic deformation of semicrystalline polyethylene by X-ray scattering: comparison with atomistic simulations. Macromolecules. 2013;46:5279–89. https://doi.org/10.1021/ma4005007.

    Article  CAS  Google Scholar 

  5. Strobl GR, Hagedorn W. Raman spectroscopic method for determining the crystallinity of polyethylene. J Polym Sci: Polym Phys Ed. 1978;16:1181–93. https://doi.org/10.1002/pol.1978.180160704.

    Article  CAS  Google Scholar 

  6. Doi M, Onuki A. Dynamic coupling between stress and composition in polymer solutions and blends. J Phys II Fr. 1992;2:1631–56. https://doi.org/10.1051/jp2:1992225.

    Article  CAS  Google Scholar 

  7. Furukawa A, Tanaka H. Inhomogeneous flow and fracture of glassy materials. Nat Mater. 2009;8:601–9. https://doi.org/10.1038/nmat2468.

    Article  CAS  PubMed  Google Scholar 

  8. Hashimoto T, Kume T. “Butterfly” light scattering pattern in shear-enhanced concentration fluctuations in polymer solutions and anomaly at high shear rates. J Phys Soc Jpn. 1992;61:1839–43. https://doi.org/10.1143/JPSJ.61.1839.

    Article  CAS  Google Scholar 

  9. Bastide J, Leibler L, Prost J. Scattering by deformed swollen gels: butterfly isointensity patterns. Macromolecules. 1990;23:1821–5. https://doi.org/10.1021/ma00208a044.

    Article  CAS  Google Scholar 

  10. Mendes E, Oeser R, Hayes C, Boué F, Bastide J. Small-angle neutron scattering study of swollen elongated gels: butterfly patterns. Macromolecules. 1996;29:5574–84. https://doi.org/10.1021/ma960043t.

    Article  CAS  Google Scholar 

  11. Kilcoyne AL, Tyliszczak T, Steele WF, Fakra S, Hitchcock P, Franck K, et al. Interferometer-controlled scanning transmission X-ray microscopes at the advanced light source. J Synchrotron Radiat. 2003;10:125–36. https://doi.org/10.1107/s0909049502017739.

    Article  CAS  PubMed  Google Scholar 

  12. Takeichi Y, Inami N, Suga H, Ono K, Takahashi Y. Development of a compact scanning transmission X-ray microscope (STXM) at the photon factory. Chem Lett. 2014;43:373–5. https://doi.org/10.1246/cl.130948.

    Article  CAS  Google Scholar 

  13. Ohigashi T, Arai H, Araki T, Kondo N, Shigemasa E, Ito A, et al. Construction of the scanning transmission X-ray microscope beamline at UVSOR. J Phys: Conf Ser. 2013;463:012006 https://doi.org/10.1088/1742-6596/463/1/012006.

    Article  CAS  Google Scholar 

  14. Masunaga H, Ogawa H, Takano T, Sasaki S, Goto S, Tanaka T, et al. Multipurpose soft-material SAXS/WAXS/GISAXS beamline at SPring-8. Polym J. 2011;43:471–7. https://doi.org/10.1038/pj.2011.18.

    Article  CAS  Google Scholar 

  15. Fu J, Urquhart SG. Effect of chain length and substrate temperature on the growth and morphology of n-alkane thin films. Langmuir. 2007;23:2615–22. https://doi.org/10.1021/la0630007.

    Article  CAS  PubMed  Google Scholar 

  16. Takahashi Y, Ishida T, Furusaka M. Monoclinic-to-orthorhombic transformation in polyethylene. J Polym Sci Part B: Polym Phys. 1988;26:2267–77. https://doi.org/10.1002/polb.1988.090261107.

    Article  CAS  Google Scholar 

  17. Flory PJ, Yoon DY. Molecular morphology in semicrystalline polymers. Nature. 1978;272:226–9. https://doi.org/10.1038/272226a0.

    Article  CAS  Google Scholar 

  18. Lucas JC, Failla MD, Smith FL, Mandelkern L, Peacock AJ. The double yield in the tensile deformation of the polyethylenes. Polym Eng Sci. 1995;35:1117–23. https://doi.org/10.1002/pen.760351308.

    Article  CAS  Google Scholar 

  19. Wang Y, Zou Y, Araki T, Lüning J, Kilcoyne ALD, Sokolov J, et al. Probing the chain and crystal lattice orientation in polyethylene thin films by near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Macromolecules. 2010;43:8153–61. https://doi.org/10.1021/ma101213h.

    Article  CAS  Google Scholar 

  20. Ohta T, Seki K, Yokoyama T, Morisada I, Edamatsu K. Polarized XANES studies of oriented polyethylene and fluorinated polyethylenes. Phys Scr. 1990;41:150–3. https://doi.org/10.1088/0031-8949/41/1/036.

    Article  CAS  Google Scholar 

  21. Stöhr J. NEXAFS spectroscopy. Vol. 25. Springer Science & Business Media; 1992.

  22. Hernández Cruz D, Rousseau M-E, West MM, Pézolet M, Hitchcock AP. Quantitative mapping of the orientation of fibroin β-Sheets in B. mori cocoon fibers by scanning transmission X-ray microscopy. Biomacromolecules. 2006;7:836–43. https://doi.org/10.1021/bm050943u.

    Article  CAS  PubMed  Google Scholar 

  23. Fu J, Urquhart SG. Linear dichroism in the X-ray absorption spectra of linear n-alkanes. J Phys Chem A. 2005;109:11724–32.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The synchrotron USAXS/SAXS/WAXD experiments were performed at BL03XU in SPring-8 (Proposal Nos. 2019 A7215, 2019B7264, 2020A7213, and 2021A7213), which was constructed by the Consortium of Advanced Softmaterial Beamline (FSBL) with the approval of the Japan Synchrotron Radiation Research Institute (JASRI). The authors thank Dr. Taizo Kabe and Dr. Hiroyasu Masunaga (JASRI/SPring-8) for their assistance in the experiments on the BL03XU beamline. The STXM measurements were conducted at BL-19A of the Photon Factory (Proposal Nos. 2020G091 and 2020Y016). The authors thank Dr. Yasuo Takeichi, Dr. Shohei Yamashita, and Dr. Daisuke Wakabayashi (KEK-PF) for supporting STXM operation.

Author information

Authors and Affiliations

  1. Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan

    Masato Arakawa, Mizuki Kishimoto, Yohei Nakanishi & Mikihito Takenaka

  2. Mitsui Chemicals Inc., 580-32 Nagaura, Sodegaura, Chiba, 299-0265, Japan

    Mizuki Kishimoto & Kazuki Mita

Authors
  1. Masato Arakawa
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mizuki Kishimoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yohei Nakanishi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kazuki Mita
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Mikihito Takenaka
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contributed to the writing of this manuscript. All authors have given approval to the final version of the manuscript.

Corresponding authors

Correspondence to Yohei Nakanishi or Mikihito Takenaka.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Arakawa, M., Kishimoto, M., Nakanishi, Y. et al. Spatial inhomogeneity of chain orientation associated with strain-induced density fluctuations in polyethylene. Polym J 54, 243–248 (2022). https://doi.org/10.1038/s41428-021-00601-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41428-021-00601-z

Search

Advanced search

Quick links