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Direct measurement of microfibril structures in polyacrylonitrile fibers during carbon fiber manufacturing process

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Abstract

The exceptional tensile strength and modulus of high-performance carbon fibers are determined by the microstructure evolution during the manufacturing process. The comprehension of the internal morphology of polyacrylonitrile (PAN) fibers is crucial for establishing the robust structure–property relationship and achieving superior mechanical properties in the fibers. In this work, a combination method of the ultrathin sectioning and electron microscopy technique was developed and employed for the analysis of internal structure features of the nascent fibers, precursor fibers, pre-oxidized fibers and carbon fibers. The microfibril elements were already formed during the coagulation stage and further developed within the carbon fibers through spinning, thermal stabilization and carbonization processes. Subsequently, the unoriented microfibrillar network underwent a transformation into dense fibrils, and the crystal layers within these microfibrils experienced a conversion into the turbostratic graphite structures. Based on the Nano-IR2-FS results, the morphological changes of the microfibrils were found to be intricately associated with the evolution of chemical structure, implying a strong correction between them. Through analysis of the modulus differences, it became possible to distinguish between the crystalline domains and amorphous regions, facilitating the establishment of a relationship between the mechanical strength and the microfibril structures. This work presented a direct measurement method for unraveling the complex hierarchical structures of polymer fibers, which held great potential for developing high-performance polymer fibers.

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Data availability

The data that support the findings of this study are available from the corresponding author,  upon reasonable request.

References

  1. Khayyam H, Jazar RN, Nunna S, Golkarnarenji G, Badii K, Fakhrhoseini SM, Kumar S, Naebe M (2020) PAN precursor fabrication, applications and thermal stabilization process in carbon fiber production: experimental and mathematical modelling. Prog Mater Sci 107:100575

    Article  CAS  Google Scholar 

  2. Shirolkar N, Maffe A, DiLoreto E, Gulgunje P, Gupta K, Park JG, Kirmani MH, Liang RC, Kumar S (2023) Continuous small diameter carbon fibers. Carbon 201:1193–1199

    Article  CAS  Google Scholar 

  3. Liao X, Dulle M, Silva J, Wehrspohn RB, Agarwal S, Forster S, Hou HQ, Smith P, Greiner A (2019) High strength in combination with high toughness in robust and sustainable polymeric materials. Science 366:1376–1379

    Article  CAS  PubMed  Google Scholar 

  4. Yang J, Sun W, Ju J, Tan Y, Yuan H (2023) Facile fabrication of superwetting PVDF membrane for highly efficient oil/water separation. Polymers 15:327

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Al Aiti M, Jehnichen D, Fischer D, Brunig H, Heinrich G (2018) On the morphology and structure formation of carbon fibers from polymer precursor systems. Prog Mater Sci 98:477–551

    Article  CAS  Google Scholar 

  6. Zhao GZ, Chen J, Zhang C, Zeng JB, Zhou ZQ, Liu JH, Guo SH (2023) Study on the relationship between ring formation and properties of pre-oxidized polyacrylonitrile-based fibres. J Mol Struct 1284:135412

    Article  CAS  Google Scholar 

  7. Liu J, Yue Z, Hao F (2009) Continuous nanoscale carbon fibers with superior mechanical strength. Small 5:536–542

    Article  CAS  PubMed  Google Scholar 

  8. Gulgunje PV, Newcomb BA, Gupta K, Chae HG, Tsotsis TK, Kumar S (2015) Low-density and high-modulus carbon fibers from polyacrylonitrile with honeycomb structure. Carbon 95:710–714

    Article  CAS  Google Scholar 

  9. Morris EA, Weisenberger MC, Abdallah MG, Vautard F, Grappe H, Ozcan S, Paulauskas FL, Eberle C, Jackson D, Mecham SJ, Naskar AK (2016) High performance carbon fibers from very high molecular weight polyacrylonitrile precursors. Carbon 101:245–252

    Article  CAS  Google Scholar 

  10. He M, Arefev MI, Joshi K, Zhigilei LV (2023) Atomistic modeling of tensile deformation and fracture of carbon fibers: nanoscale stress redistribution, effect of local structural characteristics and nanovoids. Carbon 202:528–546

    Article  CAS  Google Scholar 

  11. Jang D, Lee ME, Choi J, Cho SY, Lee S (2022) Strategies for the production of PAN-based carbon fibers with high tensile strength. Carbon 186:644–677

    Article  CAS  Google Scholar 

  12. Wu T, Lu C, Sun T, Li Y, Yuan S, Li D, Wang G, Ren X (2021) New discovery on the relationship between microstructure and tensile strength of PAN-based carbon fibers. Microporous Mesoporous Mater 330:111584

    Article  Google Scholar 

  13. Gao Q, Wang C, Zhao S (2022) Interior morphological feature of PAN nascent fibers and precursor fibers revealed by ultrathin section and solution etching. Polymer 239:124431

    Article  CAS  Google Scholar 

  14. Xu SS, Zhou J, Pan PJ (2023) Strain-induced multiscale structural evolutions of crystallized polymers: from fundamental studies to recent progresses. Prog Polym Sci 140:101676

    Article  CAS  Google Scholar 

  15. Liu X, Makita Y, Hong Y, Nishiyama Y, Miyoshi T (2017) Chemical reactions and their kinetics of atactic-polyacrylonitrile as revealed by solid-State C-13 NMR. Macromolecules 50:244–253

    Article  CAS  Google Scholar 

  16. Gao B, Wang MF (2023) Multistep structure evolution during the coagulation of PAN/DMSO solution studied by in-situ FTIR spectroscopy. Polymer 283:126221

    Article  CAS  Google Scholar 

  17. Zhou H, Lan ZC, Xiao J, Wang Y, Xu LH (2023) Effect of oxygen content on the preoxidation structure of polyacrylonitrile fibers. J Appl Polym Sci 140:54241

    Article  Google Scholar 

  18. Gupta AK, Singhal RP (1983) Effect of co-polymerization and heat-treatment on the structure and X-ray-diffraction of polyacrylonitrile. J Polym Sci Polym Phys 21:2243–2262

    Article  CAS  Google Scholar 

  19. Chen L, Chen J, Shen ZG, Liu J, Wang XX (2022) New insights into the radial structural differences of polyacrylonitrile fibres during thermal stabilization by the synchronous processing adjustment of time and temperature. Rsc Adv 12:13339–13346

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  20. Lee JE, Chae YK, Lee DJ, Choi J, Chae HG, Kim TH, Lee S (2022) Microstructural evolution of polyacrylonitrile fibers during industry-mimicking continuous stabilization. Carbon 195:165–173

    Article  CAS  Google Scholar 

  21. Tian Y, Zhu CZ, Gong JH, Yang SL, Ma JH, Xu J (2014) Lamellae break induced formation of shish-kebab during hot stretching of ultra-high molecular weight polyethylene precursor fibers investigated by in situ small angle X-ray scattering. Polymer 55:4299–4306

    Article  CAS  Google Scholar 

  22. Ouyang Q, Chen Y, Wang X, Ma H, Li D, Yang J (2015) Supramolecular structure of highly oriented wet-spun polyacrylonitrile fibers used in the preparation of high-performance carbon fibers. J Polym Res 22:229–238

    Article  Google Scholar 

  23. Henry CK, Sandoz-Rosado E, Roenbeck MR, Magagnosc DJ, Palmese GR, Strawhecker KE, Alvarez NJ (2020) Direct measure of crystalline domain size, distribution, and orientation in polyethylene fibers. Polymer 202:122589

    Article  CAS  Google Scholar 

  24. Strawhecker KE, Sandoz-Rosado EJ, Stockdale TA, Laird ED (2016) Interior morphology of high-performance polyethylene fibers revealed by modulus mapping. Polymer 103:224–232

    Article  CAS  Google Scholar 

  25. Kunzmann C, Schmidt-Bilkenroth G, Moosburger-Will J, Horn S (2018) Microscopic investigation of polyacrylonitrile fiber fibrils separated by ultrasonic etching. J Mater Sci 53:4693–4704

    Article  CAS  Google Scholar 

  26. Gao Q, Jing M, Wang C, Chen M, Zhao S, Wang W, Qin J (2019) Correlation between fibril structures and mechanical properties of polyacrylonitrile fibers during the dryjet wet spinning process. J Appl Polym Sci 136:47336

    Article  Google Scholar 

  27. Li C, Jiang T, Wang J, Wu H, Guo S, Zhang X, Li J, Shen J, Chen R, Xiong Y (2017) In situ formation of microfibrillar crystalline superstructure: achieving high-performance polylactide. ACS Appl Mater Interfaces 9:25818–25829

    Article  CAS  PubMed  Google Scholar 

  28. Wang Y, Wang C, Gao Q, Wang Y, Zhao S, Cui B, Yue Y (2021) Study on the relationship between chemical structure transformation and morphological change of polyacrylonitrile based preoxidized fibers. Eur Polym J 159:110742

    Article  CAS  Google Scholar 

  29. Gao Q, Jing M, Wang C, Chen M, Zhao S, Wang W, Qin J (2019) Mesopores variation in polyacrylonitrile fibers during dry-jet wet spinning process. Iran Polym J 28:259–269

    Article  CAS  Google Scholar 

  30. Gong Y, Du R, Mo G, Xing X, Lu C, Wu Z (2018) Nanostructural hereditability in polyacrylonitrile based fibers studied by small angle X-ray scattering. Polymer 153:485–497

    Article  CAS  Google Scholar 

  31. Gao Q, Jing M, Zhao S, Wang Y, Qin J, Yu M, Wang C (2020) From microfibrillar network to lamellae during the coagulation process of polyacrylonitrile fiber: visualization of intermediate structure evolution. Macromolecules 53:8663–8673

    Article  CAS  Google Scholar 

  32. Wang W, Wang C, Gao Q, Chen M, Wang Y, Yao Z (2019) A new perspective on the internal structure of polyacrylonitrile-based preoxidized fibers through ultrathin sections. Polym Degrad Stabil 167:269–276

    Article  Google Scholar 

  33. Hu X, Wang C, Tang X, Han N, Xu J (2017) Fibrillar structure development of polyacrylonitrile fibers treated by ultrasonic etching in oxidative stabilization. Polym Adv Technol 28:1038–1043

    Article  CAS  Google Scholar 

  34. Watt W, Johnson W (1969) High temperature resistant fibers from organic polymer. Appl Polym Symp 9:229–243

    Google Scholar 

  35. Diefendorf RJ, Tokarsky E (1975) High-performance carbon fibers. Polym Eng Sci 15:150–159

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation, China (Grant No. 52303057), the Natural Science Foundation of Ningxia, China (No. 2023AAC03012) and the Key Research and Development Program of Ningxia, China (No. 2022BSB03073). We would like to thank Mr Weitao Xia at Analysis and Testing Center of Ningxia University for their assistance with SEM analysis.

Funding

This work was funded by The National Natural Science Foundation, China, 52303057, Quan Gao, Natural Science Foundation of Ningxia Province, 2023AAC03012, Quan Gao, and The Key Research and Development Program of Ningxia, China, 2022BSB03073, Quan Gao.

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Authors and Affiliations

  1. Ningxia Key Laboratory of Photovoltaic Materials, School of Materials and New Energy, Ningxia University, Yinchuan, 750021, China

    Quan Gao, Zhihan Wang, Yongfa Zhou & Jiang Ren

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  1. Quan Gao
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  2. Zhihan Wang
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Correspondence to Quan Gao.

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Gao, Q., Wang, Z., Zhou, Y. et al. Direct measurement of microfibril structures in polyacrylonitrile fibers during carbon fiber manufacturing process. Iran Polym J (2024). https://doi.org/10.1007/s13726-024-01317-6

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