Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (08): 107-115.doi: 10.13475/j.fzxb.20230501501

• Fiber Materials • Previous Articles     Next Articles

Process optimization and properties of petroleum pitch/polyacrylonitrile electrospun carbon nanofibers

WANG Yongzheng1, HUANG Lintao1,2, SONG Fuquan1,3()   

  1. 1. School of Petrochemical Engineering and Environment, Zhejiang Ocean University, Zhoushan, Zhejiang 316022, China
    2. Ningbo Shanshan Silicon Base Material Co., Ltd., Ningbo, Zhejiang 315100, China
    3. School of Oil and Gas Engineering, Changzhou University, Changzhou, Jiangsu 213000, China
  • Received:2023-05-05 Revised:2023-11-03 Online:2024-08-15 Published:2024-08-21
  • Contact: SONG Fuquan E-mail:songfuquan@cczu.edu.cn

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Abstract:

Objective Due to the complexity of its own components and structure, long-term low-value utilization of petroleum pitch often causes it to become an environmental pollutant. The research aims to achieve the high-value utilization of petroleum pitch by preparing pitch based composite carbon nanofibers, reducing the production cost and environmental pollution, and providing a reliable preparation method and process support for the application of carbon nanofibers in adsorption, energy storage and other fields.

Method Petroleum pitch and polyacrylonitrile were dissolved in various solvents and mixed at different ratios to prepare the spinning solution for composite nanofiber production. Electrospinning technology was utilized to create the nanofibers from the solutions, and the spinning parameters including flow rate, voltage, and tip-to-collector distance were optimized using Box-Behnken response surface methodology. The composite nanofibers then underwent pre-oxidation and carbonization treatments at varying temperatures. The structural transformation of the fibers was analyzed by X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscope, and Raman spectroscopy. The effect of petroleum pitch ratio and carbonization temperature on the graphitization degree of the carbon nanofibers was investigated.

Results The main factors affecting the fiber diameter were found to be the flow rate, spinning voltage and tip-to-collector distance, in descending order of significance. The optimal electrospinning conditions were obtained to be 0.64 mL/h flow rate, 15.28 kV voltage, and 13.08 cm distance, resulting in an average fiber diameter of 342.43 nm with a relative error of 9.13% compared to the predicted value. The regression model was found to have high reliability and accuracy, as demonstrated by the response surface analysis and verification experiments. The structural transformation of the composite fibers during pre-oxidation and carbonization was analyzed systematically. The aromaticity index of the pre-oxidized fibers was found to be significantly affected by the pre-oxidation temperature, reaching the maximum value of 77.56% at 250 ℃. The linear structure of polyacrylonitrile was verified to convert into a ladder-shaped structure during pre-oxidation, and dehydrogenation reaction occurred in the molecular chain of the pre-oxidized fibers. The effect of petroleum pitch ratio and carbonization temperature on the graphitization degree of the carbon nanofibers was investigated. It was found that increasing the petroleum pitch ratio could improve the graphitization degree to some extent, and that the minimum value of R (the intensity ratio of D peak to G peak in Raman spectra) was obtained when the pitch ratio was 20%-30%. Increasing the carbonization temperature was found to reduce the fiber diameter and increase the crystallite size and interlayer spacing of the carbon nanofibers, indicating a gradual increase in the ordered structure of graphite with the increase in heat treatment temperature.

Conclusion Petroleum pitch/polyacrylonitrile composite carbon nanofibers were successfully prepared using the electrospinning technology, and the spinning parameters were optimized using response surface methodology. The structural transformation and graphitization degree of the composite fibers during pre-oxidation and carbonization processes were investigated. It was found that the optimal pre-oxidation temperature was 250 ℃, and increasing the petroleum pitch ratio and carbonization temperature could improve the graphitization degree of the carbon nanofibers to some extent. Potential applications of the composite carbon nanofibers were identified in adsorption, energy storage, and catalyst support fields. Further research is needed to explore their performance and mechanism in these fields. Some challenges and limitations of the research method were also pointed out, including the difficulty of controlling the uniformity and orientation of the fibers, and the influence of solvent selection and environmental factors on the fiber morphology.

Key words: petroleum pitch, polyacrylonitrile, electrospinning, carbon nanofiber, Box-Behnken response surface method

CLC Number: 

  • TQ127.1

Tab.1

Coding level of electrospinning process parameters"

因素
水平		 推流速度/(mL·h-1) 纺丝电压/kV 接收距离/cm
-1 0.6 13 11
0 0.9 15 13
1 1.2 17 15

Tab.2

Response surface methodology experimental design and results"

实验
序号		 推流速度/
(mL·h-1)		 纺丝电
压/kV		 接收距
离/cm		 纤维直
径/nm
1 1.2 15 15 615.04
2 0.9 17 11 982.83
3 1.2 17 13 405.58
4 0.6 13 13 261.84
5 0.9 13 15 851.93
6 0.9 13 11 1 002.82
7 0.9 15 13 571.90
8 0.9 15 13 613.21
9 1.2 15 11 425.12
10 0.9 17 15 1 234.09
11 0.6 17 13 250.75
12 0.6 15 15 207.33
13 0.9 15 13 563.07
14 0.6 15 11 296.04
15 1.2 13 13 385.82

Tab.3

Variance analysis of regression model of fiber diameter"

方差来源 平方和 自由度 均方 F值 P值
模型 1.34×106 9 1.49×105 29.37 0.000 8
A 8.32×104 1 8.32×104 16.39 0.009 8
B 1.72×104 1 1.72×104 3.39 0.125 1
C 5.08×103 1 5.08×103 1.00 0.363 0
AB 237.93 1 237.93 0.046 9 0.837 1
AC 1.94×104 1 1.94×104 12.82 0.147 9
BC 4.04×104 1 4.04×104 7.97 0.037 0
A2 7.29×105 1 7.29×105 143.69 <0.000 1
B2 1.30×105 1 1.30×105 25.62 0.003 9
C2 2.26×105 1 2.26×105 44.59 0.001 1
残差 2.54×104 5 5.07×103 — —
失拟项 2.39×104 3 7.98×103 11.14 0.083 5
误差 1.43×103 2 716.42 — —
总和 1.37×106 14 — — —
R2=0.981 4 信噪比=17.272 1

Fig.1

Response surface diagram of influence of factor interaction on fiber diameter. (a) Recieving distance interacts with pushing velocity; (b) Spinning voltage interactes with pushing velocity; (c) Recieving distance interacts with spinning voltage"

Fig.2

XRD patterns of pitch/PAN composite nanofibers at different temperatures"

Tab.4

Aromatization index of pre-oxidized fibers at different pre-oxidation temperature"

预氧化温度/℃ 芳构化指数/% 晶粒尺寸/nm
220 73.22 0.92
250 77.56 1.01
280 76.40 1.07
310 75.04 1.15

Fig.3

FT-IR spectra of pre-oxidized fibers at different pre-oxidation temperature"

Fig.4

SEM images and diameter distribution of pitch/PAN carbon nanofibers at different temperatures"

Fig.5

XRD patterns of composite carbon nanofibers at different carbonization temperatures"

Tab.5

XRD analysis data of pitch/PAN carbon nanofibers"

炭化温度/℃ d002/nm Lc/nm La/nm
700 0.367 1.24 1.34
900 0.360 1.28 1.68
1 100 0.351 1.31 2.17
1 300 0.349 1.39 2.89

Fig.6

Raman spectra of carbon fibers corresponding to different pitch ratios"

Fig.7

Raman spectra and Gaussian peak fitting spectra of carbon nanofibers at different carbonization temperature"

Tab.6

Raman parameters of carbon nanofibers at different temperature"

炭化温
度/℃		 R WD/
cm-1		 WG/
cm-1		 FWHM(D)/
cm-1		 FWHM(G)/
cm-1
700 1.349 1 357.82 1 580.86 351.35 261.64
900 1.100 1 348.19 1 585.43 308.20 117.09
1 100 1.046 1 342.68 1 578.55 286.35 108.24
1 300 1.006 1 337.43 1 579.07 264.56 105.97
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