Mechanistic insights into low-temperature oxidation of carbon fibers: Influence of hydrogen defects and crystallite size

Brubaker, Zach E.; Moseley, Duncan H.; Neu, Jenn; Kearney, Logan; Miskowiec, Andrew J.; Niedziela, Jennifer L.

doi:10.1016/j.carbon.2026.121310

Title: Mechanistic insights into low-temperature oxidation of carbon fibers: Influence of hydrogen defects and crystallite size

Journal Article · Sat Jan 24 00:00:00 UTC 2026 · Carbon

DOI: https://doi.org/10.1016/j.carbon.2026.121310 · OSTI ID:3017006

^[1];

^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Although oxidation mechanisms have been exhaustively studied for graphite, similar analyses of carbon fibers are comparatively sparse. Most prior work has focused on quantifying weight loss or assessing protective surface coatings designed to slow oxidation. The use of optical spectroscopic techniques for oxidation analyses is comparatively unexplored, but such techniques could provide an early indicator of fiber oxidation that would undermine carbon fiber performance. Here, in this work, we applied Raman spectroscopy to study oxidation-induced spectral alterations in 16 carbon fiber types from 7 manufacturers oxidized at 300 °C for 72 h, 400 °C for 8 h, and 500 °C for 1 h. We connect these results with structural properties of the carbon fibers obtained through wide-angle X-ray scattering, identifying a linear dependence between the reactivity of carbon fibers and the crystallite size of the unperturbed fibers. We then demonstrate that substituted hydrogen defects are likely removed from the fiber surface during oxidation and use the relative defect concentration to predict the Raman spectral change as a function of temperature and time, assuming Arrhenius behavior.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 3017006

Journal Information:: Carbon, Journal Name: Carbon Vol. 250; ISSN 0008-6223

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Carbon Fibers: Precursor Systems, Processing, Structure, and Properties Frank, Erik; Steudle, Lisa M.; Ingildeev, Denis Angewandte Chemie International Edition, Vol. 53, Issue 21 https://doi.org/10.1002/anie.201306129	journal	March 2014
Surface characterization and electrical property of carbon fibers modified by air oxidation Li, Weiwei; Li, Ruipei; Li, Chunyang Surface and Interface Analysis, Vol. 47, Issue 3 https://doi.org/10.1002/sia.5711	journal	November 2014
Characterization of PAN-based carbon fibres with laser Raman spectroscopy: Part I Effect of processing variables on Raman band profiles Melanitis, N.; Tetlow, P. L.; Galiotis, C. Journal of Materials Science, Vol. 31, Issue 4 https://doi.org/10.1007/BF00352882	journal	February 1996
Carbon fibre compressive strength and its dependence on structure and morphology Kumar, S.; Anderson, D. P.; Crasto, A. S. Journal of Materials Science, Vol. 28, Issue 2 https://doi.org/10.1007/BF00357820	journal	January 1993
Effect of microstructure on the modulus of PAN-based carbon fibers during high temperature treatment and hot stretching graphitization Li, Dongfeng; Wang, Haojing; Wang, Xinkui Journal of Materials Science, Vol. 42, Issue 12 https://doi.org/10.1007/s10853-006-0519-4	journal	February 2007
Effect of microstructure on the mechanical properties of PAN-based carbon fibers during high-temperature graphitization Liu, Fujie; Wang, Haojing; Xue, Linbing Journal of Materials Science, Vol. 43, Issue 12 https://doi.org/10.1007/s10853-008-2633-y	journal	June 2008
The effect of heat treatment temperature and time on the microstructure and mechanical properties of PAN-based carbon fibers Xiao, Hao; Lu, Yonggen; Zhao, Weizhe Journal of Materials Science, Vol. 49, Issue 2 https://doi.org/10.1007/s10853-013-7762-2	journal	October 2013
Quantitative analysis of Raman spectral parameters for carbon fibers: practical considerations and connection to mechanical properties Brubaker, Z. E.; Langford, J. J.; Kapsimalis, R. J. Journal of Materials Science, Vol. 56, Issue 27 https://doi.org/10.1007/s10853-021-06225-1	journal	June 2021
Insights into the thermal history of carbon fibers using Raman spectroscopy and a novel kinetic model Brubaker, Zach E.; Miskowiec, Andrew; Niedziela, Jennifer L. Journal of Materials Science, Vol. 58, Issue 18 https://doi.org/10.1007/s10853-023-08512-5	journal	May 2023
Raman spectroscopic characterization of graphites: A re-evaluation of spectra/ structure correlation Nikiel, Leszek; Jagodzinski, Paul W. Carbon, Vol. 31, Issue 8, p. 1313-1317 https://doi.org/10.1016/0008-6223(93)90091-N	journal	January 1993
Oxidation protection of carbon fibers by coatings Wang, Yu-Qing; Zhou, Ben-Lian; Wang, Zuo-Ming Carbon, Vol. 33, Issue 4 https://doi.org/10.1016/0008-6223(94)00167-X	journal	January 1995
The oxidation of carbon fibres in air between 230° and 375°C Eckstein, Bernard H. Fibre Science and Technology, Vol. 14, Issue 2 https://doi.org/10.1016/0015-0568(81)90037-3	journal	February 1981
Reactions of NO, O2, H2O, and CO2 with the basal plane of graphite Chu, X.; Schmidt, L. D. Surface Science, Vol. 268, Issue 1-3 https://doi.org/10.1016/0039-6028(92)90972-9	journal	January 1992
Kinetic study by TGA of the effect of oxidation inhibitors for carbon–carbon composite Cairo, C. A. A.; Florian, M.; Graça, M. L. A. Materials Science and Engineering: A, Vol. 358, Issue 1-2 https://doi.org/10.1016/S0921-5093(03)00302-2	journal	October 2003
Influence of the carbon fiber surface microstructure on the surface chemistry generated by a thermo-chemical surface treatment Vautard, F.; Ozcan, S.; Paulauskas, F. Applied Surface Science, Vol. 261 https://doi.org/10.1016/j.apsusc.2012.08.038	journal	November 2012
A reconsideration of the relationship between the crystallite size La of carbons determined by X-ray diffraction and Raman spectroscopy Zickler, Gerald A.; Smarsly, Bernd; Gierlinger, Notburga Carbon, Vol. 44, Issue 15 https://doi.org/10.1016/j.carbon.2006.06.029	journal	December 2006
Microstructure difference between core and skin of T700 carbon fibers in heat-treated carbon/carbon composites Zhou, Gengheng; Liu, Yequn; He, Lianlong Carbon, Vol. 49, Issue 9 https://doi.org/10.1016/j.carbon.2011.02.025	journal	August 2011
A Raman study to obtain crystallite size of carbon materials: A better alternative to the Tuinstra–Koenig law Mallet-Ladeira, Philippe; Puech, Pascal; Toulouse, Constance Carbon, Vol. 80 https://doi.org/10.1016/j.carbon.2014.09.006	journal	December 2014
High resolution transmission electron microscopy study on polyacrylonitrile/carbon nanotube based carbon fibers and the effect of structure development on the thermal and electrical conductivities Newcomb, Bradley A.; Giannuzzi, Lucille A.; Lyons, Kevin M. Carbon, Vol. 93 https://doi.org/10.1016/j.carbon.2015.05.037	journal	November 2015
High performance carbon fibers from very high molecular weight polyacrylonitrile precursors Morris, E. Ashley; Weisenberger, Matthew C.; Abdallah, Mohamed G. Carbon, Vol. 101 https://doi.org/10.1016/j.carbon.2016.01.104	journal	May 2016
Tensile failure phenomena in carbon fibres Okuda, Haruki; Young, Robert J.; Tanaka, Fumihiko Carbon, Vol. 107 https://doi.org/10.1016/j.carbon.2016.06.037	journal	October 2016
Investigating nanostructures in carbon fibres using Raman spectroscopy Okuda, Haruki; Young, Robert J.; Wolverson, Daniel Carbon, Vol. 130 https://doi.org/10.1016/j.carbon.2017.12.108	journal	April 2018
Developing a novel evaluation technique of Raman spectra for PAN-based carbon fibers using dependence of excitation wavelength and differential spectra Senda, Takahiro; Tanaka, Fumihiko; Ishikawa, Toru Carbon, Vol. 234 https://doi.org/10.1016/j.carbon.2024.119970	journal	March 2025
Spatial distribution of sp3 defects in carbon fibers via time-of-flight secondary ion mass spectrometry Dwyer, Derek B.; Brubaker, Zachary E.; Ievlev, Anton V. Carbon, Vol. 245 https://doi.org/10.1016/j.carbon.2025.120735	journal	October 2025
Computational investigation of hydrogen-induced phonon changes in carbon fiber Isbill, Sara B.; Brubaker, Zach E.; Shields, Ashley E. Computational Materials Science, Vol. 216 https://doi.org/10.1016/j.commatsci.2022.111884	journal	January 2023
Tensile properties of carbon fibres and carbon fibre–polymer composites in fire Feih, S.; Mouritz, A. P. Composites Part A: Applied Science and Manufacturing, Vol. 43, Issue 5 https://doi.org/10.1016/j.compositesa.2011.06.016	journal	May 2012
Processing, structure, and properties of carbon fibers Newcomb, Bradley A. Composites Part A: Applied Science and Manufacturing, Vol. 91 https://doi.org/10.1016/j.compositesa.2016.10.018	journal	December 2016
AFM characterization of the interfacial properties of carbon fiber reinforced polymer composites subjected to hygrothermal treatments Wang, Ying; Hahn, Thomas H. Composites Science and Technology, Vol. 67, Issue 1 https://doi.org/10.1016/j.compscitech.2006.03.030	journal	January 2007
Oxidation kinetics of polyacrylonitrile-based carbon fibers in air and the effect on their tensile properties Tong, Yuanjian; Wang, Xiaoqian; Su, Hua Corrosion Science, Vol. 53, Issue 8 https://doi.org/10.1016/j.corsci.2011.04.004	journal	August 2011
Understanding the reaction of nuclear graphite with molecular oxygen: Kinetics, transport, and structural evolution Kane, Joshua J.; Contescu, Cristian I.; Smith, Rebecca E. Journal of Nuclear Materials, Vol. 493 https://doi.org/10.1016/j.jnucmat.2017.06.001	journal	September 2017
Kinetics and Transport of Hydrogen in Graphite at High Temperature and the Effects of Oxidation, Irradiation and Isotopics Vergari, Lorenzo; Scarlat, Raluca O. Journal of Nuclear Materials https://doi.org/10.1016/j.jnucmat.2021.153142	journal	July 2021
Microstructure and properties of polyacrylonitrile based carbon fibers Lu, Junshan; Li, Weiwei; Kang, Hongliang Polymer Testing, Vol. 81 https://doi.org/10.1016/j.polymertesting.2019.106267	journal	January 2020
Oxidation protection of carbon fibers by a reaction sintered nanostructured SiC coating Kang, P. C.; Chen, G. Q.; Zhang, B. Surface and Coatings Technology, Vol. 206, Issue 2-3 https://doi.org/10.1016/j.surfcoat.2011.07.016	journal	October 2011
Review Carbon fibers for composites Chand, S. Journal of Materials Science, Vol. 35, Issue 6, p. 1303-1313 https://doi.org/10.1023/A:1004780301489	journal	January 2000
Comparative performance of X-ray diffraction and Raman microprobe techniques for the study of carbon materials Cuesta, A.; Dhamelincourt, P.; Laureyns, J. Journal of Materials Chemistry, Vol. 8, Issue 12 https://doi.org/10.1039/a805841e	journal	January 1998
Raman Spectrum of Graphite Tuinstra, F.; Koenig, J. L. The Journal of Chemical Physics, Vol. 53, Issue 3 https://doi.org/10.1063/1.1674108	journal	August 1970
General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy Cançado, L. G.; Takai, K.; Enoki, T. Applied Physics Letters, Vol. 88, Issue 16 https://doi.org/10.1063/1.2196057	journal	April 2006
Acrylic Precursors for Carbon Fibers Gupta, A. K.; Paliwal, D. K.; Bajaj, Pushpa Polymer Reviews, Vol. 31, Issue 1 https://doi.org/10.1080/15321799108021557	journal	February 1991
X-Ray Diffraction in Random Layer Lattices Warren, B. E. Physical Review, Vol. 59, Issue 9 https://doi.org/10.1103/PhysRev.59.693	journal	May 1941
Origin of dispersive effects of the Raman D band in carbon materials Matthews, M. J.; Pimenta, M. A.; Dresselhaus, G. Physical Review B, Vol. 59, Issue 10 https://doi.org/10.1103/PhysRevB.59.R6585	journal	March 1999
Interpretation of Raman spectra of disordered and amorphous carbon Ferrari, A. C.; Robertson, J. Physical Review B, Vol. 61, Issue 20, p. 14095-14107 https://doi.org/10.1103/PhysRevB.61.14095	journal	May 2000
Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon Ferrari, A. C.; Robertson, J. Physical Review B, Vol. 64, Issue 7 https://doi.org/10.1103/PhysRevB.64.075414	journal	July 2001
Determination of crystallite size in polished graphitized carbon by Raman spectroscopy Maslova, O. A.; Ammar, M. R.; Guimbretière, G. Physical Review B, Vol. 86, Issue 13 https://doi.org/10.1103/PhysRevB.86.134205	journal	October 2012
Making Strong Fibers Chae, Han Gi; Kumar, Satish Science, Vol. 319, Issue 5865 https://doi.org/10.1126/science.1153911	journal	February 2008
Characterization of diamond films by Raman spectroscopy Knight, Diane S.; White, William B. Journal of Materials Research, Vol. 4, Issue 2 https://doi.org/10.1557/JMR.1989.0385	journal	April 1989
Microstructural changes of polyacrylonitrile-based carbon fibers (T300 and T700) due to isothermal oxidation (1): focusing on morphological changes using scanning electron microscopy Oh, Seong-Moon; Lee, Sang-Min; Kang, Dong-Su Carbon letters, Vol. 18 https://doi.org/10.5714/CL.2016.18.018	journal	April 2016

Similar Records

Raman spectroscopy of thermally perturbed carbon fibers: Discriminating spectral responses of modulus classes and defect types

Journal Article · Thu Jul 21 00:00:00 UTC 2022 · Physical Review Materials · OSTI ID:1879960

Brubaker, Zach E.; Miskowiec, Andrew; Niedziela, Jennifer L.

Computational investigation of hydrogen-induced phonon changes in carbon fiber

Journal Article · Wed Nov 02 00:00:00 UTC 2022 · Computational Materials Science · OSTI ID:1897847

Isbill, Sara B.; Brubaker, Zach E.; Shields, Ashley E.; +1 more

Insights into the thermal history of carbon fibers using Raman spectroscopy and a novel kinetic model

Journal Article · Wed May 03 00:00:00 UTC 2023 · Journal of Materials Science · OSTI ID:1975352

Brubaker, Zach E.; Miskowiec, Andrew; Niedziela, Jennifer L.

Related Subjects

Carbon fiber
Crystallite size
Hydrogen defects
Oxidation
Raman spectroscopy

Title: Mechanistic insights into low-temperature oxidation of carbon fibers: Influence of hydrogen defects and crystallite size

Citation Formats

References (46)

Similar Records

Related Subjects