电解液氧化性对高模量碳纤维表面处理效果影响研究

doi:10.19936/j.cnki.2096-8000.20251228.012

摘要/Abstract

摘要： 电化学阳极氧化表面处理是提升高模量碳纤维表面活性的重要手段,为探究此过程中电解液的氧化性对高模量碳纤维表面处理效果的影响,采用五种氧化性不同的电解液(NaOH,NH₄HCO₃,H₂SO₄,NaNO₂,HNO₃)对聚丙烯腈基高模量碳纤维进行电化学阳极氧化表面处理,并系统讨论了其对碳纤维表面物理化学结构及界面性能的影响规律。结果表明,随着电解液氧化性的增强,碳纤维表面石墨片层膨胀愈发加剧,sp³碳结构及含氧官能团含量呈升高趋势,表面化学活性显著增强。本文揭示了电解液氧化性在碳纤维阳极氧化过程中的关键作用,为高模量碳纤维表面结构优化提供更多理论依据。

关键词: 碳纤维, 电解液, 氧化性, 表面处理, 电化学阳极氧化

Abstract: Electrochemical anodic oxidation is an important method for enhancing the surface activity of high-modulus carbon fibers. To investigate the influence of electrolyte oxidizability on the surface treatment performance, five electrolytes with different oxidation potentials (NaOH, NH₄HCO₃, H₂SO₄, NaNO₂, and HNO₃) were employed to modify polyacrylonitrile-based high-modulus carbon fibers via anodic oxidation. The effects of electrolyte oxidizability on the physicochemical surface structure and interfacial properties of the fibers were systematically analyzed. The results show that with increasing oxidizability, the graphite layer expansion becomes more pronounced, the content of sp³ carbon structures and oxygen-containing functional groups increases, and the surface chemical reactivity is significantly enhanced. This study reveals the key role of electrolyte oxidizability in the anodic oxidation process of carbon fibers and provides a theoretical basis for optimizing the surface structure of high-modulus carbon fibers.

Key words: carbon fiber, electrolyte, oxidizability, surface treatment, electrochemical anodic oxidation

中图分类号:

TB332

高东晓, 康永朝, 王梦梵. 电解液氧化性对高模量碳纤维表面处理效果影响研究[J]. 复合材料科学与工程, 2025, 0(12): 88-95.

GAO Dongxiao, KANG Yongchao, WANG Mengfan. Effect of electrolyte oxidizability on the surface treatment of high-modulus carbon fibers[J]. COMPOSITES SCIENCE AND ENGINEERING, 2025, 0(12): 88-95.

参考文献

[1] 徐樑华, 王宇. 国产高性能聚丙烯腈基碳纤维技术特点及发展趋势[J]. 科技导报, 2018, 36(19): 43-51.
[2] SOULIS S, KONSTANTOPOULOS G, KOUMOULOS E P, et al. Impact of alternative stabilization strategies for the production of PAN-based carbon fibers with high performance[J]. Fibers, 2020, 8(6): 33.
[3] LU J S, LI W W, KANG H L, et al. Microstructure and properties of polyacrylonitrile based carbon fibers[J]. Polymer Testing, 2020, 81: 106267.
[4] LI W, LONG D H, MIYAWAKI J, et al. Structural features of polyacrylonitrile-based carbon fibers[J]. Journal of Materials Science, 2012, 47(2): 919-928.
[5] 杨燕宁, 张亮儒, 董经经, 等. 高模量碳纤维复合材料在卫星结构上的应用[J]. 高科技纤维与应用, 2022, 47(4): 11-15.
[6] CHAE H G, NEWCOMB B A, GULGUNJE P V, et al. High strength and high modulus carbon fibers[J]. Carbon, 2015, 93: 81-87.
[7] LI W, GUO Q F. Application of carbon fiber composites to cosmonautic fields[J]. Chinese Optics, 2011, 4(3): 201-212.
[8] SHARMA M, GAO S L, MDER E, et al. Carbon fiber surfaces and composite interphases[J]. Composites Science and Technology, 2014,102: 35-50.
[9] WU S, LIU Y Q, GE Y C, et al. Surface structures of PAN-based carbon fibers and their influences on the interface formation and mechanical properties of carbon-carbon composites[J]. Composites Part A: Applied Science and Manufacturing, 2016, 90: 480-488.
[10] ISHITANI A. Application of X-ray photoelectron spectroscopy to surface analysis of carbon fiber[J]. Carbon, 1981, 19(4): 269-275.
[11] 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(4): 29-32.
[12] 康素梅. PAN基高模量碳纤维的表面涂层改性研究[D]. 北京: 北京化工大学, 2011.
[13] DENG C, JIANG J J, LIU F A, et al. Influence of graphene oxide coatings on carbon fiber by ultrasonically assisted electrophoretic deposition on its composite interfacial property[J]. Surface and Coatings Technology, 2015, 272: 176-181.
[14] FANG C Q, WU J X, WANG J L, et al. Modification of carbon fiber surfaces via grafting with Meldrum’s acid[J]. Applied Surface Science, 2015, 356: 9-17.
[15] YAO Z Q, WANG C G, QIN J J, et al. Interfacial improvement of carbon fiber/epoxy composites using one-step method for grafting carbon nanotubes on the fibers at ultra-low temperatures[J]. Carbon, 2020, 164: 133-142.
[16] LIN J P, SUN C C, MIN J Y, et al. Effect of atmospheric pressure plasma treatment on surface physicochemical properties of carbon fiber reinforced polymer and its interfacial bonding strength with adhesive[J]. Composites Part B: Engineering, 2020, 199: 108237.
[17] LI W W, LI R P, LI C Y, et al. Surface characterization and electrical property of carbon fibers modified by air oxidation[J]. Surface and Interface Analysis, 2015, 47(3): 325-330.
[18] LI J. Interfacial studies on the O₃ modified carbon fiber-reinforced polyamide 6 composites[J]. Applied Surface Science, 2008, 255(5): 2822-2824.
[19] WANG X Y, QIAN X, ZHANG Y G, et al. Surface oxidation of PAN-based ultrahigh modulus carbon fibers (UHMCFs) and its effect on the properties of UHMCF/EP composites[J]. Carbon Letters, 2021, 31: 449-461.
[20] TIWARI S, BIJWE J, PANIER S. Tribological studies on polyetherimide composites based on carbon fabric with optimized oxidation treatment[J]. Wear, 2011, 271(9/10): 2252-2260.
[21] 李磊, 沈志刚, 屠晓萍, 等. 聚丙烯腈基高强高模碳纤维表面处理研究进展[J]. 上海纺织科技, 2024, 52(2): 1-6.
[22] WANG Z K, HUANG X Y, XIAN G J, et al. Effects of surface treatment of carbon fiber: tensile property, surface characteristics, and bonding to epoxy[J]. Polymer Composites, 2016, 37(10): 2921-2932.
[23] SUN Y, LU Y G, YANG C L. Stripping mechanism of PAN-based carbon fiber during anodic oxidation in NaOH electrolyte[J]. Applied Surface Science, 2019, 486: 128-136.
[24] LIANG Y C, ZHANG X H, WEI X H, et al. Contributions of surface roughness and oxygen-containing groups to the interfacial shear strength of carbon fiber/epoxy resin composites[J]. Carbon, 2024, 218: 118683.
[25] CAO H L, HUANG Y D, ZHANG Z Q, et al. Uniform modification of carbon fibers surface in 3-D fabrics using intermittent electrochemical treatment[J]. Composites Science and Technology, 2005, 65(11/12): 1655-1662.
[26] GAO D T, YANG H L, LIU G, et al. Effect of electrochemical oxidation degree of carbon fiber on the interfacial properties of carbon fiber-reinforced polyaryletherketone composites[J]. Journal of Reinforced Plastics and Composites, 2023, 42(21/22): 1107-1118.
[27] QIAN X, CHEN L Q, HUANG J, et al. Effect of carbon fiber surface chemistry on the interfacial properties of carbon fibers/epoxy resin composites[J]. Journal of Reinforced Plastics and Composites, 2013, 32(6): 393-401.
[28] FU Y P, LU Y K, YOU T, et al. Study on multistage anodization for high-modulus carbon fiber[J]. Surface and Interface Analysis, 2019, 51(8): 798-808.
[29] MA Y J, WANG J L, CAI X P. The effect of electrolyte on surface composite and microstructure of carbon fiber by electrochemical treatment[J]. International Journal of Electrochemical Science, 2013, 8(2): 2806-2815.
[30] BAUER M, BERATZ S, RUHLAND K, et al. Anodic oxidation of carbon fibers in alkaline and acidic electrolyte: quantification of surface functional groups by gas-phase derivatization[J]. Applied Surface Science, 2020, 506: 144947.
[31] SUN Y, YANG C L, LU Y G. Weak layer exfoliation and an attempt for modification in anodic oxidation of PAN-based carbon fiber[J]. Journal of Materials Science, 2020, 55(6): 2372-2379.
[32] XIAO J, TIAN S Y, ZHOU H, et al. Construction of polar functional groups on the surface of a high-modulus carbon fiber and its effect on the interfacial properties of composites[J]. ACS Omega, 2023, 8(32): 29262-29269.
[33] 周相武, 汪晓军, 刘姣, 等. 次氯酸钠溶液的氧化性研究[J]. 氯碱工业, 2006(8): 28-30.