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Study on the structure evolution and temperature zone regulation mechanism of polyacrylonitrile fibers during pre-oxidation process

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Abstract

By regulating the holding time of the temperature zone, the structure evolution and structural defect source of polyacrylonitrile fibers were investigated under two distinct pre-oxidation processes but the same heat treatment time. The chemical structure, crystal structure, bulk density, element content change and cross section relative O content of the pre-oxidized fiber were characterized by FTIR, XRD, sink-float method, EA and SEM techniques, respectively. It was found that as the temperature rose, the chemical structure of polyacrylonitrile fibers changed to heat-resistant trapezoidal structure faster, which improved the production efficiency of their pre-oxidation process. However, when the temperature rose to a certain value, if the polyacrylonitrile fiber contained a large amount of uncyclized C≡N functional groups, some of them would be thermally decomposed and released small molecules of CH4, NH3 and HCN. The thermal decomposition of C≡N groups resulted in the chain breaking of the macromolecular chain, and it was difficult to form a disordered graphite network structure with high degree of cross-linking. Meanwhile, the overflow of the small molecules gases increased the microscopic pores of the fibers. In the other hand, rapid cyclic exothermic reaction occurred, which promoted oxidation reaction. The fibers took the initiative to form a dense layer in their skin as O diffused from the fiber skin to its core, which hindered further O diffusion to the core and aggravated the non-uniformity of the transverse structure. Therefore, if the polyacrylonitrile fiber can quickly complete the cyclization reaction at a higher temperature that can withstand the cyclization reaction by regulating the holding time in the temperature zone, the production efficiency in the pre-oxidation stage and the structural defects of the polyacrylonitrile fibers can be effectively improved.

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References

  1. Frank E, Hermanutz F, Buchmeiser MR (2012) Carbon fibers: precursors, manufacturing, and properties. Macromol Mater Eng 297:493–501

    Article  CAS  Google Scholar 

  2. 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 

  3. 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 

  4. Zhou H, Li M, Zhu J, Chen R, Wang X, Wang H-L (2022) Exploring polymer precursors for low-cost high performance carbon fiber: a materials genome approach to finding polyacrylonitrile-co-poly(N-vinyl formamide). Polymer 243:124570

    Article  CAS  Google Scholar 

  5. Lee S, Cho SY, Chung YS, Choi YC, Lee S (2022) High electrical and thermal conductivities of a PAN-based carbon fiber via boron-assisted catalytic graphitization. Carbon 199:70–79

    Article  CAS  Google Scholar 

  6. Choi J, Kim S-S, Chung Y-S, Lee S (2020) Evolution of structural inhomogeneity in polyacrylonitrile fibers by oxidative stabilization. Carbon 165:225–237

    Article  CAS  Google Scholar 

  7. Zhao G, Zhang C, Lv L, Liu J, Guo S (2022) Research on dynamic microwave low-temperature carbonization of high performance carbon fiber. Diam Relat Mater 125:108989

    Article  CAS  Google Scholar 

  8. Jin X, Feng C, Creighton C, Hameed N, Parameswaranpillai J, Salim NV (2021) On the structural evolution of textile grade polyacrylonitrile fibers during stabilization and carbonization: towards the manufacture of low-cost carbon fiber. Polym Degrad Stabil 186:109536

    Article  CAS  Google Scholar 

  9. Rahaman MSA, Ismail AF, Mustafa A (2007) A review of heat treatment on polyacrylonitrile fiber. Polym Degrad Stabil 92:1421–1432

    Article  CAS  Google Scholar 

  10. Lee J-E, 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 

  11. CattaPreta IF, Sakata SK, Garcia G, Zimmermann JP, Galembeck F, Giovedi C (2007) Thermal behavior of polyacrylonitrile polymers synthesized under different conditions and comonomer compositions. J Therm Anal Calorim 87:657–659

    Article  CAS  Google Scholar 

  12. Devasia R, Nair CPR, Sivadasan P, Katherine BK, Ninan KN (2003) Cyclization reaction in poly(acrylonitrile/itaconic acid) copolymer: an isothermal differential scanning calorimetry kinetic study. J Appl Polym Sci 88:915–920

    Article  CAS  Google Scholar 

  13. Noh J-Y, Kuk Y-S, Kim T-E, Kim S-R, Kim K-Y, Lim J-H, Kim K-M (2021) Effect of comonomer composition and content on the polymerization and thermal behavior of polyacrylonitrile-based carbon fiber precursors. Polym Korea 45:793–802

    Article  CAS  Google Scholar 

  14. Wang Y-F, Wang Y-W, Xu L-H, Wang Y (2021) Regulating the radial structure of polyacrylonitrile fibers during pre-oxidation and its effect on the mechanical properties of the resulting carbon fibers. New Carbon Mater 36:827–834

    Article  CAS  Google Scholar 

  15. Soulis S, Simitzis J (2005) Thermomechanical behaviour of poly[acrylonitrile-co-(methyl acrylate)] fibres oxidatively treated at temperatures up to 180 °C. Polym Int 54:1474–1483

    Article  CAS  Google Scholar 

  16. Lee S-W, Lee H-Y, Jang S-Y, Jo S, Lee H-S, Choe W-H, Lee S (2013) Efficient preparation of carbon fibers using plasma assisted stabilization. Carbon 55:361–365

    Article  CAS  Google Scholar 

  17. Bertran X, Labrugère C, Dourges MA, Rabillat F (2013) Oxidation behavior of PAN-based carbon fibers and the effect on mechanical properties. Oxid Met 80:299–309

    Article  CAS  Google Scholar 

  18. Xu Z, Huang Y, Min C, Chen L, Chen L (2010) Effect of γ-ray radiation on the polyacrylonitrile based carbon fibers. Radiat Phys Chem 79:839–843

    Article  CAS  Google Scholar 

  19. Miao P, Wu D, Zeng K, Xu G, Ce Z, Yang G (2010) Influence of electron beam pre-irradiation on the thermal behaviors of polyacrylonitrile. Polym Degrad Stabil 95:1665–1671

    Article  CAS  Google Scholar 

  20. Aggour YA, Aziz MS (2000) Degradation of polyacrylonitrile by low energy ion beam and UV radiation. Polym Test 19:261–267

    Article  CAS  Google Scholar 

  21. Naskar AK, Walker RA, Proulx S, Edie DD, Ogale AA (2005) UV assisted stabilization routes for carbon fiber precursors produced from melt-processible polyacrylonitrile terpolymer. Carbon 43:1065–1072

    Article  CAS  Google Scholar 

  22. Yu M-J, Bai Y-J, Wang C-G, Xu Y, Guo P-Z (2007) A new method for the evaluation of stabilization index of polyacrylonitrile fibers. Mater Lett 61:2292–2294

    Article  CAS  Google Scholar 

  23. Gupta VB, Kumar S (1981) The effect of heat setting on the structure and mechanical properties of poly(ethylene terephthalate) fiber. II. The elastic modulus and its dependence on structure. J Appl Polym Sci 26:1877–1884

    Article  CAS  Google Scholar 

  24. Hinrichsen G (1972) Structural changes of drawn polyacrylonitrile during annealing. J Polym Sci Part C Polym Symp 38:303–314

    Article  Google Scholar 

  25. Wang B, Wang Y, Li C, Gao A (2022) Evolution and regulation of radial structure of PAN pre-oxidized fiber based on the fine denier model. Materials 15:1409

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  26. Chen R, Li Z, Shi Y, Liu LZ, Li D, Zhao Y, Lv B (2022) In situ study of the preoxidation of polyacrylonitrile fibers. J Appl Cryst 55:901–910

    Article  CAS  Google Scholar 

  27. Chen R, Huang W, Li Z, Shi Y, Liu L-Z, Li D, Lv B (2022) Furnace for in-situ characterization of the preoxidation of polyacrylonitrile (PAN) fibers by wide angle X-ray scattering (WAXS). Instrum Sci Technol 50:321–333

    Article  CAS  Google Scholar 

  28. Chen SS, Herms J, Peebles LH, Uhlmann DR (1981) Oxidative stabilization of acrylic fibres. J Mater Sci 16:1490–1510

    Article  CAS  Google Scholar 

  29. Groetsch T, Maghe M, Rana R, Hess R, Nunna S, Herron J, Buckmaster D, Creighton C, Varley RJ (2021) Gas emission study of the polyacrylonitrile-based continuous pilot-scale carbon fiber manufacturing process. Ind Eng Chem Res 60:17379–17389

    Article  CAS  Google Scholar 

  30. Gao Q, Wang C (2022) New insight into structure-property correlation of polyacrylonitrile precursor fibers and resultant carbon fibers. J Polym Res 29:233

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by Yunnan Fundamental Research Projects (NO. 202101AT070093) and the Construction of High-level Talents of Kunming University of Science and Technology [Grant number KKKP201763019].

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Authors and Affiliations

  1. Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, 650093, China

    Jiabin Zeng, Jianhua Liu & Guozhen Zhao

  2. State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming, 650093, China

    Jianhua Liu & Guozhen Zhao

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  1. Jiabin Zeng
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  2. Jianhua Liu
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Correspondence to Jianhua Liu or Guozhen Zhao.

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Zeng, J., Liu, J. & Zhao, G. Study on the structure evolution and temperature zone regulation mechanism of polyacrylonitrile fibers during pre-oxidation process. Iran Polym J 32, 1511–1522 (2023). https://doi.org/10.1007/s13726-023-01214-4

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