Effect of electrolyte oxidizability on the surface treatment of high-modulus carbon fibers

doi:10.19936/j.cnki.2096-8000.20251228.012

Abstract

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

CLC Number:

TB332

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.

References

[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.