Effect of pre⁃oxidation degree on structure and properties of polyacrylonitrile thermal oxidative stabilized fiber

doi:10.19491/j.issn.1001-9278.2024.11.009

Abstract

Abstract:

Thermal oxidative stabilized （TOS） fibers with different pre⁃oxidation degrees were prepared by using constant draft polyacrylonitrile （PAN） fibers under air atmosphere according to the pre⁃oxidation degree obtained from the relative cyclization rate determined by Fourier⁃transform infrared spectroscopy. The effect of pre⁃oxidation degree on the chemical and crystal structures， microstructure， and mechanical properties of the resultant TOS fibers were investigated. The results indicated that the conjugated carbonyl groups began to form at a pre⁃oxidation degree greater than 54.7 % and tended to increase gradually. The TOS fibers exhibited new diffuse peaks and ordered structures at a pre⁃oxidation degree of 83.2 %， and their cross section presented an obvious radial non⁃uniform structure， so⁃called “skin⁃core structure” along with a decrease in the elongation at break. Therefore， the TOS fibers obtained a cyclization degree of 72 %， thus resulting in fewer structural defects and better performance.

Key words: polyacrylonitrile, pre?oxidation degree, skin?core structure, mechanical property

CLC Number:

TQ325

WANG Jun, GE Yuan, CAO Anran, ZHANG Shoulei, YAN Zetong. Effect of pre⁃oxidation degree on structure and properties of polyacrylonitrile thermal oxidative stabilized fiber[J]. China Plastics, 2024, 38(11): 53-56.

Figures/Tables 5

Fig.1. FTIR spectra of thermal oxidative stabilized fibers treated for 30 and 60 min， respectively

Fig.2. Effect of heat treatment temperature and time on cyclization degree of the samples

Fig.3. XRD patterns of the fibers of different thermal oxidative stabilization degree

Fig.4. SEM images of the fibers with different thermal oxidative stabilization degree

Fig.5. Relationship between tensile strength and elongation at break and thermal oxidative stabilization degree

References 19

1	Lee J E， Choi J， Jang D， et al. Processing⁃controlled radial heterogeneous structure of carbon fibers and primary factors determining their mechanical properties［J］. Carbon， 2023， 206： 16⁃25.
2	Zeng J， Zhao G， Liu J， et al. Interaction between thermal stabilization temperature program， oxidation reaction， and mechanical properties of polyacrylonitrile （PAN） based carbon fibers［J］. Diamond and Related Materials， 2024， 141： 110588.
3	秦显营.聚丙烯腈纤维在热处理过程中的结构演变与控制［D］.上海：东华大学，2012.
4	Zhou H， Zhu J， Wang H L. Tuning of structural/functional feature of carbon fibers： New insights into the stabilization of polyacrylonitrile［J］. Polymer， 2023， 282： 126157.
5	Choi J， Kim S S， Chung Y S， et al. Evolution of structural inhomogeneity in polyacrylonitrile fibers by oxidative stabilization［J］. Carbon， 2020， 165： 225⁃237.
6	Jang D， Lee M E， Choi J， et al. Strategies for the production of PAN⁃based carbon fibers with high tensile strength［J］. Carbon， 2022， 186： 644⁃677.
7	顾红星，王浩静，范立东，等.聚丙烯腈预氧丝预氧化程度表征分析［J］.化工学报，2015，66（03）：1 228⁃1 233.
	GU H X， WANG H J， FAN L D，et al. Evaluation and analysis of pre⁃oxidation extent of polyacrylonitrile fiber［J］. CIESC Journal，2015，66（03）：1 228⁃1 233.
8	Son S Y， Jo A Y， Jung G Y， et al. Accelerating the stabilization of polyacrylonitrile fibers by UV irradiation［J］. Journal of Industrial and Engineering Chemistry， 2019， 73： 47⁃51.
9	Wang Y， Wang C， Gao Q， et al. Study on the relationship between chemical structure transformation and morphological change of polyacrylonitrile based preoxidized fibers［J］. European Polymer Journal， 2021， 159： 110742.
10	Terra B M， de Andrade D A， de Mesquita R N. Characterization of polyacrylonitrile thermal stabilization process for carbon fiber production using intelligent algorithms［J］. Polymer Testing， 2021， 100： 107238.
11	杨志军，黄有平，马雷，等.聚丙烯腈纤维热稳定化程度的评估分析［J］.化工新型材料，2021，49（09）：89⁃92.
	YANG Z J， HUANG Y P， MA L，et al. Evaluation on the extent of thermal stabilization of polyacrylonitrile fiber［J］. New Chemical Materials，2021，49（09）：89⁃92.
12	Wang Y， Wang Y， Xu L， et al. Regulating the radial structure of polyacrylonitrile fibers during pre⁃oxidation and its effect on the mechanical properties of the resulting carbon fibers［J］. New Carbon Materials， 2021， 36（4）： 827⁃834.
13	Wang B， Li C， Cao W. Effect of polyacrylonitrile precursor orientation on the structures and properties of thermally stabilized carbon fiber［J］. Materials， 2021， 14（12）： 3237.
14	Ogawa H， Saito K. Oxidation behavior of polyacrylonitrile fibers evaluated by new stabilization index［J］. Carbon， 1995， 33（6）： 783⁃788.
15	Shirolkar N， Patwardhan P， Rahman A， et al. Investigating the efficacy of machine learning tools in modeling the continuous stabilization and carbonization process and predicting carbon fiber properties［J］. Carbon， 2021， 174： 605⁃616.
16	Khayyam H， Jazar R N， Nunna S， et al. PAN precursor fabrication， applications and thermal stabilization process in carbon fiber production： Experimental and mathematical modelling［J］. Progress in Materials Science， 2020， 107： 100575.
17	陈秋飞，郭鹏宗，陈晓，等.张力对PAN预氧化纤维结构和性能的影响［J］.高科技纤维与应用，2022，47（06）：33⁃38.
	CHEN Q F， GUO P Z， CHEN X，et al. Effect of tensionon the structure and properties of pre⁃oxidized PAN fibers［J］. Hi⁃Tech Fiber and Application，2022，47（06）：33⁃38.
18	杨翔麟，陈秋飞，刘高君，等.预氧化温度对大丝束碳纤维性能的影响［J］.高科技纤维与应用，2023，48（04）：29⁃32.
	YANG X L， CHEN Q F， LIU G J，et al. Effect of preoxidation temperature on properties of large tow fiber bundles［J］. Hi⁃Tech Fiber and Application，2023，48（04）：29⁃32.
19	Ge Y， Zhang H， Yu H， et al. Effect of structural evolution in high⁃temperature thermal oxidative stabilized polyacrylonitrile fibers on carbonized fibers［J］. Journal of Applied Polymer Science， 2023， 140（47）： e54692.

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