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硫酸环境下电流强度对碳纤维表面电化学活化的影响

马崇攀 张洋 张恒 高爱君 王宇

马崇攀, 张洋, 张恒, 等. 硫酸环境下电流强度对碳纤维表面电化学活化的影响[J]. 复合材料学报, 2024, 41(4): 1788-1797. doi: 10.13801/j.cnki.fhclxb.20230822.002
引用本文: 马崇攀, 张洋, 张恒, 等. 硫酸环境下电流强度对碳纤维表面电化学活化的影响[J]. 复合材料学报, 2024, 41(4): 1788-1797. doi: 10.13801/j.cnki.fhclxb.20230822.002
MA Chongpan, ZHANG Yang, ZHANG Heng, et al. Effect of current intensity on electrochemical activation of carbon fibers surface in sulfuric acid environment[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1788-1797. doi: 10.13801/j.cnki.fhclxb.20230822.002
Citation: MA Chongpan, ZHANG Yang, ZHANG Heng, et al. Effect of current intensity on electrochemical activation of carbon fibers surface in sulfuric acid environment[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1788-1797. doi: 10.13801/j.cnki.fhclxb.20230822.002

硫酸环境下电流强度对碳纤维表面电化学活化的影响

doi: 10.13801/j.cnki.fhclxb.20230822.002
详细信息
    通讯作者:

    王宇,博士,副教授,硕士生导师,研究方向为聚丙烯腈基碳纤维及其复合材料 E-mail: wangy@mail.buct.edu.cn

  • 中图分类号: TB332

Effect of current intensity on electrochemical activation of carbon fibers surface in sulfuric acid environment

  • 摘要: 碳纤维的碳含量在90%以上,表面惰性强,表面活化处理是其制备过程中的重要工艺。研究采用XPS、Raman、动态接触角、单丝拉伸和界面剪切强度等测试方法,借助非接触式阳极氧化装置,明确了稀H2SO4作为电解液时电流强度对电化学活化碳纤维表面结构和性能的影响。结果表明:活性氧[O]进攻碳纤维表面使其含氧活性官能团含量增加,在本研究范围内电流越大活化效果越显著;处于阳极附近的碳纤维,受静电与扩散作用影响,SO4 2−和S2O8 2−进入碳结构内部间隙,碳纤维表面S/C升高,直径增大。在SO4 2−刻蚀作用下,碳纤维表面无序碳结构脱落而缺陷减少,石墨化程度降低;SO4 2−和S2O8 2−插层进入碳结构内部,通过静电作用形成缔合结构,在刻蚀和插层的共同作用下,碳纤维的单丝拉伸强度提升,最高提高了16.77%。0.5 A电流处理后,碳纤维表面粗糙度提升,表面可与环氧树脂基体反应的羟基、羧基官能团含量最高,碳纤维表面极性最强,与去离子水的动态接触角由未处理时的89.9°降低到50.6°,相应的复合材料界面剪切强度提高了47.70%。

     

  • 图  1  非接触式电化学氧化处理装置示意图

    Figure  1.  Schematic diagram of a non-contact electrochemical treatment unit

    CF—Carbon fiber

    图  2  (a) 复合材料界面评价装置;碳纤维表面树脂微滴的脱粘过程:(b) 脱粘前;(c) 脱粘后

    Figure  2.  (a) Composite interface evaluation device; Debonding process of epoxy microdroplet on carbon fiber surface: (b) Before debonding;(c) After debonding

    图  3  不同电流处理后碳纤维的XPS全谱图

    Figure  3.  XPS full spectra of carbon fiber after different current treatment

    图  4  不同电流强度处理后碳纤维表面O/C比

    Figure  4.  Oxygen-carbon element ratio of carbon fiber treated with different current intensities

    图  5  不同电流处理后碳纤维的XPS的C1s分峰拟合

    Figure  5.  C1s curves fitting for XPS of carbon fiber after different current treatment

    图  6  不同电流强度处理后的碳纤维的S/C比

    Figure  6.  Sulfur-carbon elemental ratio of carbon fiber treated with different current intensities

    图  7  碳纤维直径随电流强度变化

    Figure  7.  Variation of carbon fiber diameter with current intensity

    图  8  硫酸溶液电化学处理碳纤维直径胀大机制示意图

    Figure  8.  Schematic diagram of the expansion mechanism of carbon fiber diameter expansion treated by sulfuric acid solution electrochemically

    d, d'—Carbon fiber diameter before and after intercalation; GIC—Graphite intercalation on compounds; e—Electron

    图  9  不同电流强度处理后碳纤维表面拉曼光谱与石墨化程度R

    Figure  9.  Raman spectra and the degree of graphitization R values of carbon fibers treated with different current intensities

    图  10  接触角测试(a)和不同电流强度处理后的碳纤维表面与去离子水的动态接触角(b)

    Figure  10.  Contact angle test process (a) and dynamic contact angle between carbon fiber surface treated with different current intensities and deionized water (b)

    图  11  不同电流强度处理后碳纤维的拉伸强度

    Figure  11.  Tensile strength of carbon fiber treated with different current intensities

    图  12  不同电流处理后碳纤维的界面剪切强度(IFSS)

    Figure  12.  Interfacial shear strength (IFSS) of carbon fiber treated with different current intensities

    图  13  碳纤维表面活性官能团与环氧树脂结合机制

    Figure  13.  Bonding mechanism of active functional groups of carbon fiber surface and epoxy resin

    图  14  用硫酸电解质电化学处理前后碳纤维表面的原子力显微镜图像

    Figure  14.  Atomic force microscopy images of carbon fiber surfaces before and after electrochemical treatment with sulfuric acid electrolyte

    表  1  碳纤维表面官能团含量

    Table  1.   Surface functional group contents of carbon fibers

    Current intensity
    /A
    Content of functional group/%
    C=CC—CC—OHC=OCOOH
    Untreated 0.0 A 70.33 9.07 6.95 3.72 9.93
    H2SO4 0.1 A 68.26 11.80 7.75 5.19 7.01
    H2SO4 0.3 A 60.03 14.53 11.21 4.70 9.52
    H2SO4 0.5 A 56.31 10.41 16.83 5.72 10.74
    下载: 导出CSV

    表  2  氧化前后碳纤维的表面粗糙度

    Table  2.   Surface roughness of carbon fibers before and after oxidation

    Surface roughnessDifferent current intensities of electrochemical oxidation
    Untreated 0 AH2SO4 0.1 AH2SO4 0.5 A
    Ra/nm36.439.741.3
    RMS/nm42.146.747.7
    Notes: Ra—Arithmetic mean of the absolute value of the roughness curve relative to the center line; RMS—Root-mean-square deviation of the roughness curve profile.
    下载: 导出CSV
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  • 收稿日期:  2023-07-05
  • 修回日期:  2023-07-31
  • 录用日期:  2023-08-03
  • 网络出版日期:  2023-08-22
  • 刊出日期:  2024-04-15

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