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

Abstract

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 providemore » guidance for accurate nanofiber characterization to improve fundamental understanding and accelerate development of nanofibers and related nanostructured materials produced by electrospinning or other methods. Overall, 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.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [2];  [3];  [4];  [5];  [6];  [3];  [2]; ORCiD logo [7];  [8]; ORCiD logo [9]; ORCiD logo [1]
  1. Univ. of Nebraska - Lincoln, Lincoln, NE (United States). Dept. of Mechanical and Materials Engineering; Univ. of Nebraska - Lincoln, Lincoln, NE (United States). Nebraska Center for Materials and Nanoscience
  2. Normandie Univ., Rouen (France). Département Systèmes Désordonnés et Polymères, Equipe Internationale de Recherche et de Caractérisation des Amorphes et des Polymères
  3. Univ. of Nebraska - Lincoln, Lincoln, NE (United States). Dept. of Mechanical and Materials Engineering
  4. Division of HORIBA Instruments, Inc.,Piscataway, NJ (United States)
  5. Univ. of Nebraska - Lincoln, Lincoln, NE (United States). Dept. of Mechanical and Materials Engineering; Univ. of Nebraska Medical Center, Omaha, NE (United States). Dept. of Surgery
  6. Univ. of Nebraska - Lincoln, Lincoln, NE (United States). Dept. of Mechanical and Materials Engineering; Huazhong Univ. of Science and Technology, Wuhan, Hubei (China). Dept. of Mechanics
  7. Northwestern Univ., Evanston, Illinois (United States). Dept. of Materials Science and Engineering
  8. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  9. Univ. de Montréal, Montréal (Canada). Département de chimie
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Natural Sciences and Engineering Research Council of Canada (NSERC); US Department of the Navy, Office of Naval Research (ONR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1562281
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 13; Journal Issue: 5; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 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

Citation Formats

Papkov, Dimitry, Delpouve, Nicolas, Delbreilh, Laurent, Araujo, Steven, Stockdale, Taylor, Mamedov, Sergey, Maleckis, Kaspars, Zou, Yan, Andalib, Mohammad Nahid, Dargent, Eric, Dravid, Vinayak P., Holt, Martin V., Pellerin, Christian, and Dzenis, Yuris A. Quantifying Polymer Chain Orientation in Strong and Tough Nanofibers with Low Crystallinity: Toward Next Generation Nanostructured Superfibers. United States: N. p., 2019. Web. doi:10.1021/acsnano.8b08725.
Papkov, Dimitry, Delpouve, Nicolas, Delbreilh, Laurent, Araujo, Steven, Stockdale, Taylor, Mamedov, Sergey, Maleckis, Kaspars, Zou, Yan, Andalib, Mohammad Nahid, Dargent, Eric, Dravid, Vinayak P., Holt, Martin V., Pellerin, Christian, & Dzenis, Yuris A. Quantifying Polymer Chain Orientation in Strong and Tough Nanofibers with Low Crystallinity: Toward Next Generation Nanostructured Superfibers. United States. https://doi.org/10.1021/acsnano.8b08725
Papkov, Dimitry, Delpouve, Nicolas, Delbreilh, Laurent, Araujo, Steven, Stockdale, Taylor, Mamedov, Sergey, Maleckis, Kaspars, Zou, Yan, Andalib, Mohammad Nahid, Dargent, Eric, Dravid, Vinayak P., Holt, Martin V., Pellerin, Christian, and Dzenis, Yuris A. Tue . "Quantifying Polymer Chain Orientation in Strong and Tough Nanofibers with Low Crystallinity: Toward Next Generation Nanostructured Superfibers". United States. https://doi.org/10.1021/acsnano.8b08725. https://www.osti.gov/servlets/purl/1562281.
@article{osti_1562281,
title = {Quantifying Polymer Chain Orientation in Strong and Tough Nanofibers with Low Crystallinity: Toward Next Generation Nanostructured Superfibers},
author = {Papkov, Dimitry and Delpouve, Nicolas and Delbreilh, Laurent and Araujo, Steven and Stockdale, Taylor and Mamedov, Sergey and Maleckis, Kaspars and Zou, Yan and Andalib, Mohammad Nahid and Dargent, Eric and Dravid, Vinayak P. and Holt, Martin V. and Pellerin, Christian and Dzenis, Yuris A.},
abstractNote = {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. Overall, 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.},
doi = {10.1021/acsnano.8b08725},
journal = {ACS Nano},
number = 5,
volume = 13,
place = {United States},
year = {Tue Apr 30 00:00:00 EDT 2019},
month = {Tue Apr 30 00:00:00 EDT 2019}
}

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