Studies of reaction mechanisms during stabilization of electrospun polyacrylonitrile carbon nanofibers
Abstract
Various reaction mechanisms such as cyclization, oxidation, dehydrogenation, and crosslinking are studied during stabilization of electrospun polyacrylonitrile nanofibers using different in situ techniques such as differential scanning calorimetry (DSC), shrinkage measurement, and dynamic mechanical analysis (DMA). DSC results show that oxidation preferentially occurs in cyclized structure. It is also found that the cyclization reaction has the highest activation energy followed by oxidation/dehydrogenation and crosslinking reactions. In situ shrinkage measurement and DMA data are used to study the extent of cyclization and cross-linking reactions, respectively, in air. Comparing the in situ shrinkage measurement with DSC data, it is found that cyclization reaction in air progresses in two different mechanisms such as radical cyclization, which depends only on the temperature and ionic cyclization, which is limited by the rate of oxygen diffusion. In conclusion, it is found that complete cyclization time occurs at about 189 min for isothermal heat treatment at 260 °C with 5 °C/min ramp, while cross-linking reaction becomes dominant at 132 min.
- Authors:
-
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Univ. of Oklahoma, Norman, OK (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- University of Oklahoma; USDOE Office of Science (SC)
- OSTI Identifier:
- 1489823
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Polymer Engineering and Science
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 8; Journal ID: ISSN 0032-3888
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; carbon nanofiber; cyclization; electrospinning; polyacrylonitrile; stabilization
Citation Formats
Barua, Bipul, and Saha, Mrinal C. Studies of reaction mechanisms during stabilization of electrospun polyacrylonitrile carbon nanofibers. United States: N. p., 2017.
Web. doi:10.1002/pen.24708.
Barua, Bipul, & Saha, Mrinal C. Studies of reaction mechanisms during stabilization of electrospun polyacrylonitrile carbon nanofibers. United States. doi:https://doi.org/10.1002/pen.24708
Barua, Bipul, and Saha, Mrinal C. Fri .
"Studies of reaction mechanisms during stabilization of electrospun polyacrylonitrile carbon nanofibers". United States. doi:https://doi.org/10.1002/pen.24708. https://www.osti.gov/servlets/purl/1489823.
@article{osti_1489823,
title = {Studies of reaction mechanisms during stabilization of electrospun polyacrylonitrile carbon nanofibers},
author = {Barua, Bipul and Saha, Mrinal C.},
abstractNote = {Various reaction mechanisms such as cyclization, oxidation, dehydrogenation, and crosslinking are studied during stabilization of electrospun polyacrylonitrile nanofibers using different in situ techniques such as differential scanning calorimetry (DSC), shrinkage measurement, and dynamic mechanical analysis (DMA). DSC results show that oxidation preferentially occurs in cyclized structure. It is also found that the cyclization reaction has the highest activation energy followed by oxidation/dehydrogenation and crosslinking reactions. In situ shrinkage measurement and DMA data are used to study the extent of cyclization and cross-linking reactions, respectively, in air. Comparing the in situ shrinkage measurement with DSC data, it is found that cyclization reaction in air progresses in two different mechanisms such as radical cyclization, which depends only on the temperature and ionic cyclization, which is limited by the rate of oxygen diffusion. In conclusion, it is found that complete cyclization time occurs at about 189 min for isothermal heat treatment at 260 °C with 5 °C/min ramp, while cross-linking reaction becomes dominant at 132 min.},
doi = {10.1002/pen.24708},
journal = {Polymer Engineering and Science},
number = 8,
volume = 58,
place = {United States},
year = {2017},
month = {9}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Correlative study of critical reactions in polyacrylonitrile based carbon fiber precursors during thermal-oxidative stabilization
journal, January 2013
- Xue, Yan; Liu, Jie; Liang, Jieying
- Polymer Degradation and Stability, Vol. 98, Issue 1
Electrochemical properties of carbon nanofiber web as an electrode for supercapacitor prepared by electrospinning
journal, August 2003
- Kim, C.; Yang, K. S.
- Applied Physics Letters, Vol. 83, Issue 6
An investigation on structure characterization of thermally stabilized polyacrylonitrile precursor fibers pretreated with guanidine carbonate prior to carbonization
journal, November 2011
- Karacan, İsmail; Erdoğan, Gülhan
- Polymer Engineering & Science, Vol. 52, Issue 5
Carbon nanofibers for composite applications
journal, January 2004
- Hammel, E.; Tang, X.; Trampert, M.
- Carbon, Vol. 42, Issue 5-6
Nanometre diameter fibres of polymer, produced by electrospinning
journal, September 1996
- Reneker, Darrell H.; Chun, Iksoo
- Nanotechnology, Vol. 7, Issue 3
A review of heat treatment on polyacrylonitrile fiber
journal, August 2007
- Rahaman, M. S. A.; Ismail, A. F.; Mustafa, A.
- Polymer Degradation and Stability, Vol. 92, Issue 8
Development of carbon nanofibers from aligned electrospun polyacrylonitrile nanofiber bundles and characterization of their microstructural, electrical, and mechanical properties
journal, June 2009
- Zhou, Zhengping; Lai, Chuilin; Zhang, Lifeng
- Polymer, Vol. 50, Issue 13
Carbon Nanofibers Prepared via Electrospinning
journal, April 2012
- Inagaki, Michio; Yang, Ying; Kang, Feiyu
- Advanced Materials, Vol. 24, Issue 19
Kinetic study of the dehydrogenation reaction in polyacrylonitrile-based carbon fiber precursors during thermal stabilization
journal, May 2012
- Xue, Yan; Liu, Jie; Liang, Jieying
- Journal of Applied Polymer Science, Vol. 127, Issue 1
Kinetic analysis of derivative curves in thermal analysis
journal, September 1970
- Ozawa, T.
- Journal of Thermal Analysis, Vol. 2, Issue 3
Investigation on jet stability, fiber diameter, and tensile properties of electrospun polyacrylonitrile nanofibrous yarns
journal, January 2015
- Barua, Bipul; Saha, Mrinal C.
- Journal of Applied Polymer Science, Vol. 132, Issue 18
Correlation of chemical shrinkage of polyacrylonitrile fibres with kinetics of cyclization
journal, January 2008
- Simitzis, Johannis; Soulis, Spyridon
- Polymer International, Vol. 57, Issue 1
Polyacrylonitrile-based nanofibers—A state-of-the-art review
journal, March 2012
- Nataraj, S. K.; Yang, K. S.; Aminabhavi, T. M.
- Progress in Polymer Science, Vol. 37, Issue 3
Comparative study of the cure kinetics of an unsaturated polyester resin using different procedures
journal, March 1996
- Salla, Josep M.; Ramis, Xavier
- Polymer Engineering & Science, Vol. 36, Issue 6
The Explanation of the Increase in Slope at the T g in the Plot of d‐Spacing Versus Temperature in Polyacrylonitrile
journal, February 2005
- Bashir, Z.; Rastogi, Sanjay
- Journal of Macromolecular Science, Part B, Vol. 44, Issue 1
The processing, properties, and structure of carbon fibers
journal, February 2005
- MInus, Marilyn; Kumar, Satish
- JOM, Vol. 57, Issue 2
Cyclization kinetics of poly(acrylonitrile)
journal, January 1996
- Beltz, L. A.; Gustafson, R. R.
- Carbon, Vol. 34, Issue 5
A critical review of the stabilisation of polyacrylonitrile
journal, January 1991
- Bashir, Z.
- Carbon, Vol. 29, Issue 8
Mechanical and structural characterization of electrospun PAN-derived carbon nanofibers
journal, August 2005
- Zussman, E.; Chen, X.; Ding, W.
- Carbon, Vol. 43, Issue 10
Preparation and Application of Carbon-Nanofiber Based Microstructured Materials as Catalyst Supports
journal, June 2007
- Chinthaginjala, J. K.; Seshan, K.; Lefferts, L.
- Industrial & Engineering Chemistry Research, Vol. 46, Issue 12
IR studies of PAN fibres thermally stabilized at elevated temperatures
journal, January 1994
- Mittal, J.; Bahl, O. P.; Mathur, R. B.
- Carbon, Vol. 32, Issue 6
Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part I: Effect of carbon nanotubes on stabilization
journal, November 2011
- Liu, Yaodong; Chae, Han Gi; Kumar, Satish
- Carbon, Vol. 49, Issue 13
Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part II: Stabilization reaction kinetics and effect of gas environment
journal, November 2011
- Liu, Yaodong; Chae, Han Gi; Kumar, Satish
- Carbon, Vol. 49, Issue 13
Strong carbon nanofibers from electrospun polyacrylonitrile
journal, April 2011
- Arshad, Salman N.; Naraghi, Mohammad; Chasiotis, Ioannis
- Carbon, Vol. 49, Issue 5
Mechanism and kinetics of the stabilization reactions of itaconic acid-modified polyacrylonitrile
journal, August 2008
- Ouyang, Qin; Cheng, Lu; Wang, Haojing
- Polymer Degradation and Stability, Vol. 93, Issue 8
Optimization of stabilization and carbonization treatment of PAN fibres and structural characterization of the resulting carbon fibres
journal, January 1986
- Fitzer, E.; Frohs, W.; Heine, M.
- Carbon, Vol. 24, Issue 4
Polyacrylonitrile/acrylamide-based carbon fibers prepared using a solvent-free coagulation process: Fiber properties and its structure evolution during stabilization and carbonization
journal, October 2011
- Yusof, N.; Ismail, A. F.
- Polymer Engineering & Science, Vol. 52, Issue 2
Kinetic study of the degradation of a new aromatic polyethersulfone
journal, May 2000
- Abate, L.; Pappalardo, A.; Recca, A.
- Polymer Engineering & Science, Vol. 40, Issue 5
Nanostructured Carbon and Carbon Nanocomposites for Electrochemical Energy Storage Applications
journal, February 2010
- Su , Dang Sheng; Schlögl, Robert
- ChemSusChem, Vol. 3, Issue 2
Mechanism of oxidisation of polyacrylonitrile fibres
journal, September 1975
- Watt, W.; Johnson, W.
- Nature, Vol. 257, Issue 5523
The influence of oxygen on the chemical reactions during stabilization of pan as carbon fiber precursor
journal, February 1975
- Fitzer, E.; Müller, D. J.
- Carbon, Vol. 13, Issue 1
Reaction Kinetics in Differential Thermal Analysis
journal, November 1957
- Kissinger, H. E.
- Analytical Chemistry, Vol. 29, Issue 11
Polybenzimidazole nanofiber produced by electrospinning
journal, May 1999
- Kim, Jong-Sang; Reneker, Darrell H.
- Polymer Engineering & Science, Vol. 39, Issue 5
A review on polymer nanofibers by electrospinning and their applications in nanocomposites
journal, November 2003
- Huang, Zheng-Ming; Zhang, Y.-Z.; Kotaki, M.
- Composites Science and Technology, Vol. 63, Issue 15, p. 2223-2253
Inter-versus intramolecular oligomerization of nitrile groups in polyacrylonitrile
journal, October 1981
- Henrici-Oliv�, G.; Oliv�, S.
- Polymer Bulletin, Vol. 5, Issue 8
Influence of humidity, temperature, and annealing on microstructure and tensile properties of electrospun polyacrylonitrile nanofibers
journal, June 2017
- Barua, Bipul; Saha, Mrinal C.
- Polymer Engineering & Science, Vol. 58, Issue 6
Viscoelastic properties of polyacrylonitrile terpolymers during thermo‐oxidative stabilization (cyclization)
journal, July 2008
- Suresh, K. I.; Thomas, K. Saji; Rao., B. S.
- Polymers for Advanced Technologies, Vol. 19, Issue 7
Works referencing / citing this record:
Structure evolution mechanism of polyacrylonitrile films incorporated with graphene oxide during oxidative stabilization
journal, March 2019
- Li, Fengmei; Chen, Yankun; Li, Mengzhu
- Journal of Applied Polymer Science, Vol. 136, Issue 26
Wet Relaxation of Electrospun Nanofiber Mats
journal, February 2019
- Grothe, Timo; Sabantina, Lilia; Klöcker, Michaela
- Technologies, Vol. 7, Issue 1
Figures / Tables found in this record: