石墨烯掺杂环氧复合涂层的制备及防腐性能的研究

田泳; 关振威; 李静

doi:10.3981/j.issn.1000-7857.2022.05.004

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科技导报 ›› 2022, Vol. 40 ›› Issue (5) : 34-43. DOI: 10.3981/j.issn.1000-7857.2022.05.004

专题：航空材料腐蚀与防护技术

石墨烯掺杂环氧复合涂层的制备及防腐性能的研究

作者信息 -

中国航发北京航空材料研究院第九研究室, 北京 100095

作者简介:

田泳，工程师，研究方向为特种涂层，电子信箱：tiany158@163.com

Preparation of graphene-doped epoxy composite coatings and their anti-corrosion properties

Author information -

AECC Beijing Institute of Aeronautical Materials, the Ninth Laboratory, Beijing 100095, China

摘要

通过简单的化学反应，将3-氨丙基三乙氧基硅烷和3-缩水甘油醚氧丙基三甲氧基硅烷接枝在氧化石墨烯上，制备成复合材料（GO-APTES与GO-GPTES）。2种表面改性剂使氧化石墨烯更易于与环氧-胺树脂产生化学键。通过微观电镜以及可见-近红外全波段透过率测试实验，发现改性剂作用后的氧化石墨烯能均匀分散在树脂体系中。相比较于纯的环氧-胺树脂涂层，GO-APTES/Resin涂层的蒸汽透过率降低30%，形成“迷宫效应”，对水蒸气具有良好的阻隔效果。通过 Bode和 Nyquist图谱研究了复合涂层的防腐机理。添加改性氧化石墨烯后的涂层对腐蚀介质的屏蔽性增强，腐蚀介质穿透涂层的能力降低，因此在涂层与金属的界面处改性氧化石墨烯分散的树脂涂层能够更好的附着，电化学腐蚀的面积更小，表现出更优秀的腐蚀防护性。中性盐雾实验表明，经过7000 h，涂层表面无起泡，无脱落。

Abstract

Through simple chemical reactions, 3-aminopropyl triethoxysilane and 3-glycidyl ether oxypropyl trimethoxysilane have been successfully grafted onto graphene oxide to prepare composite of a sandwich structure. The two surface modifiers make it easier for the graphene oxide to form chemical bonds with epoxy resin/polyamine. Through electron microscope and visibleinfrared full-band transmittance tests it is found that the graphene oxide treated by the modifier can evenly disperse in the resin system. Compared with the pure epoxy amine resin coating, the water vapor transmittance of the GO-APTES/Resin coating is reduced by 30%. A "labyrinth effect" is formed, which is a good barrier against water vapor. Moreover, the anti-corrosion mechanism of the composite coating is studied by Bode and Nyquist spectra. The shielding of the coating against the corrosive medium is enhanced after adding modified graphene oxide, and the ability of the corrosive medium to penetrate the coating is reduced. Therefore, the coating is better attached to the metal and the area of electrochemical corrosion is smaller, having a better corrosion protection ability. Neutral salt spray test shows that the coating surface will not fall off or present blister after 7000 hours.

导出引用

田泳, 关振威, 李静. 石墨烯掺杂环氧复合涂层的制备及防腐性能的研究[J]. 科技导报, 2022, 40(5): 34-43 https://doi.org/10.3981/j.issn.1000-7857.2022.05.004

TIAN Yong, GUAN Zhenwei, LI Jing. Preparation of graphene-doped epoxy composite coatings and their anti-corrosion properties[J]. Science & Technology Review, 2022, 40(5): 34-43 https://doi.org/10.3981/j.issn.1000-7857.2022.05.004

参考文献

[1] Wu Y, Zhao W, Qiang Y, et al.π-π interaction between fluorinated reduced graphene oxide and acridizinium ion-ic liquid:Synthesis and anti-corrosion application[J].Car-bon, 2020, 159:292-302.
[2] Ding J H, Zhao H R, Shao Z Z, et al.Bioinspired smart anticorrosive coatings with an emergency-response clos-ing function[J].ACS Applied Materials and Interfaces, 2019, 11(45):42646-42653.
[3] Chang K C, Hsu M H, Lu H I, et al.Room-temperature cured hydrophobic epoxy/graphene composites as corro-sion inhibitor for cold-rolled steel[J].Carbon, 2014, 66:144-153.
[4] Ding J H, Zhao H R, Ji D, et al.Achieving long-term an-ticorrosion:Via the inhibition of graphene's electrical ac-tivity[J].Journal of Materials Chemistry A, 2019, 7(6):2864-2874.
[5] Ding J H, Zhao H R, Zheng Y, et al.A long-term anti-corrsive coating through graphene passivation[J].Carbon, 2018, 138:197-206.
[6] Wang X, Li Y, Li C, et al.Highly orientated graphene/ep-oxy coating with exceptional anti-corrosion performance for harsh oxygen environments[J].Corrosion Science, 2020, 176:109049.
[7] Skorb E V, Andreeva D V.Layer-by-Layer approaches for formation of smart self-healing materials[J].Polymer Chemistry, 2013, 4(18):4834-4845.
[8] Andreeva D V, Fix D, Möhwald H, et al.Self-healing an-ticorrosion coatings based on pH-sensitive polyelectrolyte/inhibitor sandwichlike nanostructures[J].Advanced Materi-als, 2008, 20(14):2789-2794.
[9] Wei H, Wang Y, Guo J, et al.Advanced micro/nanocap-sules for self-healing smart anticorrosion coatings[J].Jour-nal of Materials Chemistry A, 2015, 3(2):469-480.
[10] Ding J H, Zhao H R, Yu H B.Epidermis microstructure inspired mica-based coatings for smart corrosion protec-tion[J].Progress in Organic Coatings, 2021, 152:106-126.
[11] Prasai D, Tuberquia J C, Bolotin K I, et al.Graphene:Corrosion-inhibiting coating[J].ACS Nano, 2012, 6(2):1102-1108.
[12] Schriver M, Regan W, Gannett W J, et al.Graphene as a long-term metal oxidation barrier:Worse than nothing[J].ACS Nano, 2013, 7(7):5763-5771.
[13] Abhishek T, Singh R R.Durable corrosion resistance of copper due to multi-layer graphene[J].Materials, 2017, 10(10):1112-1119.
[14] Sun W, Wang L, Wu T, et al.Synthesis of low-electri-cal-conductivity graphene/pernigraniline composites and their application in corrosion protection[J].Carbon, 2014, 79(1):605-614.
[15] Ding J H, Zhao H R, Yu H B.Superior to graphene:Su-per-anticorrosive natural mica nanosheets[J].Nanoscale, 2020, 12(30):16253-16261.
[16] Zhu X B, Zhao H C, Wang L P, et al.Bioinspired ultra-thin graphene nanosheets sandwiched between epoxy lay-ers for high performance of anticorrosion coatings[J].Chemical Engineering Journal, 2021, 410:128301.
[17] Ding J H, Zhao H R, Xu B Y, et al.Superanticorrosive graphene nanosheets through πdeposition of boron ni-tride nanodots[J].ACS Sustainable Chemistry and Engi-neering, 2019, 7(12):10900-10911.
[18] Ding J H, Zhao H R, Yu H B.A water-based green ap-proach to large-scale production of aqueous compatible graphene nanoplatelets[J].Scientific Reports, 2018, 8(1):5567.
[19] Zhao H R, Xu B Y, Ding J H, et al.Natural amino ac-ids:high-efficiency intercalants for graphene exfoliation[J].ACS Sustainable Chemistry and Engineering, 2019, 7(23):18819-18825.
[20] Alajmi A F, Ramulu M.Solid particle erosion of gra-phene-based coatings[J].Wear, 2021:203686.
[21] Chang K C, Ji W F, Lai M C, et al.Correction:Synergis-tic effects of hydrophobicity and gas barrier properties on the anticorrosion property of PMMA nanocomposite coatings embedded with graphene nanosheets[J].Poly-mer Chemistry, 2014, 5(23):6865.
[22] Mai Y J, Chen F X, Zhou M P, et al.Anchored gra-phene nanosheet films towards high performance solid lubricants[J].Materials & design, 2018, 160:861-869.
[23] Qi X, Yang L, Zhu J, et al.Stiffer but more healable ex-ponential layered assemblies with boron nitride nano-platelets[J].ACS Nano, 2016, 10(10):9434-9445.
[24] Su S, Xu B Y, Ding J H, et al.Large-yield exfoliation of few-layer black phosphorus nanosheets in liquid[J].New Journal of Chemistry, 2019, 43(48):19365-19371.
[25] Qi X, Zhang D, Ma Z, et al.An epidermis-like hierar-chical smart coating with a hardness of tooth enamel[J].ACS Nano, 2018, 12(2):1062-1073.
[26] Zhou F, Li Z T, Shenoy G J, et al.Enhanced room-tem-perature corrosion of copper in the presence of graphene[J].ACS Nano, 2013, 7(8):6939-6947.
[27] Li S, Wang A, Long W, et al.Study on the properties of epoxy resin filled with graphene oxide and silane cou-pling agent modified graphene oxide[J].Plastics Science and Technology, 2015, 43(6):40-45.
[28] Shu S S, Wu L, Liu J M, et al.Synthesis and corrosion resistance of silane coupling agent modified graphene ox-ide/waterborne polyurethane[J].IOP Conference Series:Materials Science and Engineering, 2019, 631(2):022058.
[29] Cui M, Ren S, Zhao H, et al.Polydopamine coated gra-phene oxide for anticorrosive reinforcement of waterborne epoxy coating[J].Chemical Engineering Journal, 2018, 335:255-266.