Quantifying Polymer Chain Orientation in Strong and Tough Nanofibers with Low Crystallinity: Toward Next Generation Nanostructured Superfibers

Dimitry Papkov, Nicolas Delpouve, Laurent Delbreilh, Steven Araujo, Taylor Stockdale, Sergey Mamedov, Kaspars Maleckis, Yan Zou, Mohammad Nahid Andalib, Eric Dargent, Vinayak P. Dravid, Martin V. Holt, Christian Pellerin, Yuris A. Dzenis

Research output: Contribution to journalReview articlepeer-review

40 Scopus citations


Advanced fibers revolutionized structural materials in the second half of the 20th century. However, all high-strength fibers developed to date are brittle. Recently, pioneering simultaneous ultrahigh strength and toughness were discovered in fine (<250 nm) individual electrospun polymer nanofibers (NFs). This highly desirable combination of properties was attributed to high macromolecular chain alignment coupled with low crystallinity. Quantitative analysis of the degree of preferred chain orientation will be crucial for control of NF mechanical properties. However, quantification of supramolecular nanoarchitecture in NFs with low crystallinity in the ultrafine diameter range is highly challenging. Here, we discuss the applicability of traditional as well as emerging methods for quantification of polymer chain orientation in nanoscale one-dimensional samples. Advantages and limitations of different techniques are critically evaluated on experimental examples. It is shown that straightforward application of some of the techniques to sub-wavelength-diameter NFs can lead to severe quantitative and even qualitative artifacts. Sources of such size-related artifacts, stemming from instrumental, materials, and geometric phenomena at the nanoscale, are analyzed on the example of polarized Raman method but are relevant to other spectroscopic techniques. A proposed modified, artifact-free method is demonstrated. Outstanding issues and their proposed solutions are discussed. The results provide guidance for accurate nanofiber characterization to improve fundamental understanding and accelerate development of nanofibers and related nanostructured materials produced by electrospinning or other methods. We expect that the discussion in this review will also be useful to studies of many biological systems that exhibit nanofilamentary architectures and combinations of high strength and toughness.

Original languageEnglish (US)
Pages (from-to)4893-4927
Number of pages35
JournalACS Nano
Issue number5
StatePublished - May 28 2019


  • chain orientation quantification
  • characterization of subwavelength-diameter nanofibers
  • continuous nanofibers
  • electrospinning
  • low crystallinity
  • macromolecular orientation
  • nanoscale-related artifacts
  • simultaneously strong and tough nanofibers
  • size effects in nanofibers

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)


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