Abstract
In this study, the effect of chemical structural transformation on the microstructure and mechanical properties of polyacrylonitrile precursor fibers in thermal oxidative stabilization (TOS) process was investigated. The chemical transformation was tracked quantitatively by combining the curve-fitting and second-derivative operations in Fourier transform infrared spectroscopy spectra. The aggregation and radial structural changes in the fibers were investigated by wide-angle X-ray diffraction and scanning electron microscope analysis. It was found that the degree of stabilization of thermal treated fibers in chemical evolution increased with the increase in TOS temperature and time. The increase in the extent of cyclization promoted the formation of conjugated carbonyls, whereas it decreased the crystallinity and crystallite size. Under the action of diffusion process, oxidation reaction caused the fracture morphology of radial structure transformed from ductility to brittleness. The extent of cyclization of fibers controlled in an appropriate range resulted in the high degree of oxidation stabilization and good structural properties, not the higher, the better. This result was evidenced by the excessive oxidative and cross-linking reaction in the skin of fibers resulted in the phenomenon that more obvious skin–core structure and reduced elongation at break when the cyclization degree was more than 83%.
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Frank E, Steudle L, Ingildeev D, Spoerl J, Buchmeiser M (2014) Carbon fibers: precursor systems, processing, structure, and properties. Angew Chem Int Ed 53:5262–5298
Liu Y, Kumar S (2012) Recent progress in fabrication, structure, and properties of carbon fibers. Polym Rev 52:234–258
Salim N, Blight S, Creighton C, Nunna S, Atkiss S, Razal J (2018) The role of tension and temperature for efficient carbonization of polyacrylonitrile fibers: toward low cost carbon fibers. Ind Eng Chem Res 57:4268–4276
Takaku A, Hashimoto T, Miyoshi T (1985) Tensile properties of carbon fibers from acrylic fibers stabilized under isothermal conditions. J Appl Polym Sci 30:1565–1571
Yu M, Wang C, Bai Y, Zhu B, Ji M, Xu Y (2008) Microstructural evolution in polyacrylonitrile fibers during oxidative stabilization. Polym Sci Part B Polym Phys 46:759–765
Fu Z, Gui Y, Cao C, Liiu B, Zhou C, Zhang H (2014) Structure evolution and mechanism of polyacrylonitrile and related copolymers during the stabilization. J Mater Sci 49:2864–2874. https://doi.org/10.1007/s10853-013-7992-3
Suresh K, Thomas K, Rao B, Nair C (2008) Viscoelastic properties of polyacrylonitrile terpolymers during thermo-oxidative stabilization (cyclization). Polym Adv Technol 19:831–837
Gupta A, Harrison I (1997) New aspects in the oxidative stabilization of PAN-based carbon fibers: II. Carbon 35:809–818
Bahl OP, Manocha LM (1975) Effect of preoxidation conditions on mechanical properties of carbon fibres. Carbon 13:297–300
Warner S, Peebles L, Uhlmann D (1979) Oxidative stabilization of acrylic fibres. J Mater Sci 14:556–564. https://doi.org/10.1007/BF00551029
Jain M, Abhiraman A (1987) Conversion of acrylonitrile-based precursor fibres to carbon fibres. J Mater Sci 22:278–300. https://doi.org/10.1007/BF01160584
Wang B, Zhao C, Xiao S, Zhang J, Xu L (2012) Effect of the aggregation structure on the thermal shrinkage of polyacrylonitrile fibers during the heat-treatment process. J Appl Polym Sci 125:3545–3551
Liu X, Chen W, Hong Y, Yuan S, Kuroki S, Miyoshi T (2015) Stabilization of atactic-polyacrylonitrile under nitrogen and air as studied by solid-state NMR. Macromolecules 48:5300–5309
Arbab S, Zeinolebadi A (2013) A procedure for precise determination of thermal stabilization reactions in carbon fiber precursors. Polym Degrad Stab 98:2537–2545
Badii K, Church J, Golkarnarenji G, Naebe M, Khayyam H (2016) Chemical structure based prediction of PAN and oxidized PAN fiber density through a non-linear mathematical model. Polym Degrad Stab 131:53–61
Zhou Y, Han X, Hu X, Xu L, Cao W (2017) Evolution of the structural orientation in polyacrylonitrile precursors during stabilization revealed by in situ synchrotron wide-angle X-ray diffraction and polarized infrared spectroscopy. High Perform Polym 29:1158–1164
Nunna S, Creighton C, Hameed N, Naebe M, Henderson L, Setty M, Fox B (2017) Radial structure and property relationship in the thermal stabilization of PAN precursor fibres. Polym Test 59:203–211
Nguyen-Thai N, Hong S (2013) Structural evolution of poly (acrylonitrile-co-itaconic acid) during thermal oxidative stabilization for carbon materials. Macromolecules 46:5882–5889
Ghorpade R, Cho D, Hong S (2017) Effect of controlled tacticity of polyacrylonitrile (co) polymers on their thermal oxidative stabilization behaviors and the properties of resulting carbon films. Carbon 121:502–511
Fu Z, Liu B, Li B, Liu Y, Zhang H (2018) Comprehensive and quantitative study on the thermal oxidative stabilization reactions in poly (acrylonitrile-co-itaconic acid) copolymer. J Appl Polym Sci 135:45934
Zhao W, Lu Y, Wang J, Chen Q, Zhou L, Jiang J, Chen L (2016) Improving crosslinking of stabilized polyacrylonitrile fibers and mechanical properties of carbon fibers by irradiating with γ-ray. Polym Degrad Stab 133:16–26
Yu M, Wang C, Bai Y, Xu Y, Zhu B (2008) Effect of oxygen uptake and aromatization on the skin–core morphology during the oxidative stabilization of polyacrylonitrile fibers. J Appl Polym Sci 107:1939–1945
Watt W, Johnson W (1975) Mechanism of oxidation of polyacrylonitrile fibres. Nature 257:210–212
Layden G (1972) Retrograde core formation during oxidation of polyacrylonitrile filaments. Carbon 10:59–63
Wang J, Hu L, Yang C, Zhao W, Lu Y (2016) Effects of oxygen content in the atmosphere on thermal oxidative stabilization of polyacrylonitrile fibers. RSC Adv 6:73404–73411
Nunna S, Naebe M, Hameed N, Fox B, Creighton C (2016) Evolution of radial heterogeneity in polyacrylonitrile fibres during thermal stabilization: an overview. Polym Degrad Stab 136:20–30
Lv M, Ge H, Chen J (2008) Study on the chemical structure and skin-core structure of polyacrylonitrile-based fibers during stabilization. J Polym Res 16:513–517
Ge H, Liu H, Chen J, Wang C (2009) The microstructure of polyacrylonitrile-stabilized fibers. J Appl Polym Sci 113:2413–2417
Liu X, Zhu C, Guo J, Liu Q, Dong H, Gu Y, Liu R, Zhao N et al (2014) Nanoscale dynamic mechanical imaging of the skin–core difference: from PAN precursors to carbon fibers. Mater Lett 128:417–420
Nunna S, Creighton C, Fox B, Naebe M, Maghe M, Tobin M, Bambery K et al (2017) The effect of thermally induced chemical transformations on the structure and properties of carbon fibre precursors. J Mater Chem A 5:7372–7382
Gerasimowicz WV, Byler DM, Susi H (1986) Resolution-enhanced FT-IR spectra of soil constituents: humic acid. Appl Spectrosc 40:504–507
Wu S, Gao A, Wang Y, Xu L (2018) Modification of polyacrylonitrile stabilized fibers via post-thermal treatment in nitrogen prior to carbonization and its effect on the structure of carbon fibers. J Mater Sci 53:8627–8638. https://doi.org/10.1007/s10853-017-1894-8
Gupta V, Kumar S (1981) The effect of heat setting on the structure and mechanical properties of poly (ethylene terephthalate) fiber. I. Structural changes. J Appl Polym Sci 26:1865–1876
Gupta A, Paliwal D, Bajaj P (1991) Acrylic precursors for carbon fibers. J Macromol Sci Polym Rev 31:1–89
Silverstein R, Webster F, Kiemle D (2005) Spectrometric identification of organic compounds, 7th edn. Wiley, Hoboken
Ouyang Q, Lu C, Wang H, Li K (2008) Mechanism and kinetics of the stabilization reactions of itaconic acid-modified polyacrylonitrile. Polym Degrad Stab 93:1415–1421
Kakida H, Tashiro K, Kobayashi M (1996) Mechanism and kinetics of stabilization reaction of polyacrylonitrile and related copolymers I. Relationship between isothermal DSC thermogram and FTIR spectral change of an acrylonitrile/methacrylic acid copolymer. Polym J 28:30–34
Nabais J, Carrott P, Carrott M (2005) From commercial textile fibres to activated carbon fibres: chemical transformations. Mater Chem Phys 93:100–108
Loginova E, Mikheev I, Volkov D, Proskurnin M (2016) Quantification of copolymer composition (methyl acrylate and itaconic acid) in polyacrylonitrile carbon-fiber precursors by FTIR-spectroscopy. Anal Methods 8:371–380
Bunsell A, Hearle J, Konopasek L, Lomas B (1974) A preliminary study of the fracture morphology of acrylic fibers. J Appl Polym Sci 18:2229–2242
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This research was supported by National Key R&D Program of China (2017YFB1401805).
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Ge, Y., Fu, Z., Deng, Y. et al. The effects of chemical reaction on the microstructure and mechanical properties of polyacrylonitrile (PAN) precursor fibers. J Mater Sci 54, 12592–12604 (2019). https://doi.org/10.1007/s10853-019-03781-5
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DOI: https://doi.org/10.1007/s10853-019-03781-5