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

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          Abstract

          <p class="first" id="d7617802e210">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 (&lt;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. </p>

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          Author and article information

          Journal
          ACS Nano
          ACS Nano
          American Chemical Society (ACS)
          1936-0851
          1936-086X
          May 10 2019
          May 10 2019
          Affiliations
          [1 ]Department of Mechanical and Materials Engineering, University of Nebraska—Lincoln, Lincoln, Nebraska 68588-0526, United States
          [2 ]Nebraska Center for Materials and Nanoscience, University of Nebraska—Lincoln, Lincoln, Nebraska 68588-0298, United States
          [3 ]Département Systèmes Désordonnés et Polymères, Equipe Internationale de Recherche et de Caractérisation des Amorphes et des Polymères, Normandie Univ, UNIROUEN, INSA ROUEN, CNRS, GPM, 76000 Rouen, France
          [4 ]Division of HORIBA Instruments, Inc., HORIBA Scientific, 20 Knightsbridge Road, Piscataway, New Jersey 08854, United States
          [5 ]Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States
          [6 ]Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, United States
          [7 ]Département de chimie, Université de Montréal, Montréal, QC H3C 3J7, Canada
          Article
          10.1021/acsnano.8b08725
          31038925
          7f2d2df7-8e88-4a0f-a450-d0014cdf79a7
          © 2019
          History

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