Applications of graphene in anti-corrosion of metal surface

Guo Xiao-Meng; Qing Fang-Zhu; Li Xue-Song

doi:10.7498/aps.70.20210349

Abstract

As an emerging material, graphene has become a research hotspot in the field of anti-corrosion because of its excellent chemical inertia and permeability resistance. In this paper, combined with the latest research results, the applications of graphene film and graphene powders in the field of anti-corrosion are discussed more comprehensively. First, the anti-corrosion mechanisms of graphene (mainly including barrier effect, shielding effect, corrosion inhibition synergy, enhancement of coating adhesion, cathodic protection, and self-healing effect) and its corresponding coating preparation methods (graphene film prepared by chemical vapor deposition method and composite coatings prepared with graphene powders) are introduced. Then, the influences of different factors such as defects, conductivity, oxidation degree, flake size, and content of graphene on the anti-corrosion performance are discussed. Finally, various methods are comprehensively compared with each other, and future development is prospected. This paper not only reviews the existing work, but also has a certain reference value for preparing graphene materials with better corrosion resistance in the future.

Keywords:

Authors and contacts

1.
State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Electronic Science and Engineering, University of Electronic Science and Technology of China, Chengdu 610054, China
2.
School of Chemistry and Environmental Engineering, University of Wuhan Institute of Technology, Wuhan 430074, China

Corresponding author: Qing Fang-Zhu, qingfz@uestc.edu.cn ; Li Xue-Song, lxs@uestc.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 51802036, 51772043)

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Cited By

图 1 石墨烯防腐作用机理　(a) 阻隔作用^[13]; (b) 屏蔽作用^[17]; (c) 缓蚀作用^[18]; (d) 加固作用^[19]; (e) 阴极保护作用^[20]; (f) 自修复作用^[21]

Figure 1. Anticorrosion mechanism of graphene: (a) Barrier effect^[13]; (b) shielding effect^[17]; (c) corrosion inhibition synergy^[18]; (d) enhancement of coating adhesion^[19]; (e) cathodic protection^[20]; (f) self-healing effect^[21].

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图 2 CVD石墨烯防腐性能^[24]　(a) 石墨烯作为化学惰性扩散阻挡层示意图; (b) 硬币经过H₂O₂浸泡(30%, 2 min)后的照片; (c) 带有和不带有石墨烯涂层的铜和铜镍合金在空气中退火(200 °C, 4 h)的照片

Figure 2. Performance of CVD graphene as an anticorrosion layer^[24]: (a) Schematics of graphene as a chemically inert diffusion barrier; (b) photograph showing graphene coated (upper) and uncoated (lower) penny after H₂O₂ treatment (30%, 2 min); (c) photographs of Cu and Cu/Ni foils with and without graphene coating taken before and after annealing in air (200 °C, 4 h).

DownLoad: Full-Size Img PowerPoint

图 3 不锈钢球包覆石墨烯涂层制备过程示意图^[31]

Figure 3. Schematics of the preparation of graphene coated stainless steel balls^[31].

DownLoad: Full-Size Img PowerPoint

图 4 溶液中FGO对碳钢表面的缓蚀机理示意图^[39]

Figure 4. Schematics of inhibition mechanism on carbon steel surface for FGO in solution^[39].

DownLoad: Full-Size Img PowerPoint

图 5 DETA, GO 和DETA-GO的HOMO和LUMO分布图^[40]　(a) HOMO图; (b) LUMO图

Figure 5. HOMO and LUMO distribution maps of DETA, GO and DETA-GO^[40]: (a) LUMO; (b) HOMO.

DownLoad: Full-Size Img PowerPoint

图 6 装有BTA的覆盆子状空心聚合物微球的制备示意图^[41]

Figure 6. Schematics of the preparation of raspberry-like hollow polymeric microspheres loaded with BTA^[41].

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图 7 石墨烯基纳米容器的制备工艺^[42]

Figure 7. Preparation process of graphene-based nanocontainer^[42].

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图 8 8-PG-BTA/EP涂层的防腐蚀机理^[42]　(a) 完整涂层; (b) 缺陷; (c) 腐蚀反应; (d) 自愈行为

Figure 8. Corrosion protection mechanism of 8-PG-BTA/EP coating^[42]: (a) Intact coating; (b) defect; (c) corrosion reaction; (d) self-healing behavior.

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图 9 石墨烯薄膜的缺陷促进金属腐蚀^[14]

Figure 9. Defects of graphene films promote the corrosion of metals^[14].

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图 10 在单层石墨烯(SLG)和多层石墨烯(FLG)中进行分子扩散的原子尺度模拟示意图^[52]　(a) 水分子在有缺陷的SLG中扩散需要的能量和示意图; (b) 氧气和水分子等物质易在SLG中扩散并使Cu表面氧化的情况示意图; (c) 水分子在有缺陷的双层石墨烯(BLG)中扩散需要的能量和示意图; (d) 示意图显示即使三层石墨烯包含多个晶界(GB)缺陷, 氧气和水分子也难以穿过多晶三层石墨烯并与下面的Cu表面接触

Figure 10. Atomic-scale simulations of molecular diffusion through SLG and FLG^[52]: (a) Schematics and the calculated energy barrier for a water molecule to diffuse through a defective SLG; (b) schematic showing the easiness of reactive species such as oxygen and water molecules to diffuse through SLG and oxidize the Cu surface; (c) schematics and the calculated energy barrier for a water molecule to diffuse through a defective BLG; (d) schematic showing the difficulties for oxygen and water molecules to diffuse through polycrystalline trilayer graphene and contact with the underlying Cu surface, even when the trilayer graphene contains multiple GB defects.

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图 11 (a)−(c) 在含有0.1 mol/L KCl溶液的5 mmol/L K₃[Fe(CN)₆]溶液中通过循环伏安法修饰玻碳电极(GCE)上的GO样品(S-1至S-6); (d) 具有不同氧化水平的样品的I_pc^[56]

Figure 11. (a)−(c) Cyclic voltammetry of GO samples (S-1 to S-6) modified on GCE in 5 mmol/L K₃[Fe(CN)₆] containing 0.1 mol/L KCl solution; (d) I_pcof the samples with different oxidation levels^[56].

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图 12 PU/GnP复合材料的横截面SEM图像(质量分数为1%的GnP, 其中(a)−(d)为低倍率; (e)−(f)为高倍率)　(a), (e) PU/H100; (b), (f) PU/M25; (c), (g) PU/M5; (d), (h) PU/C750^[59]

Figure 12. Cross-sectional SEM images for the PU/GnP composites (GnP with weight fraction of 1%, (a)−(d) low magnification, (e)−(f) high magnification): (a), (e) PU/H100; (b), (f) PU/M25; (c), (g) PU/M5; (d), (h) PU/C750^[59].

DownLoad: Full-Size Img PowerPoint

图 13 腐蚀介质在含有质量分数为1% GnP的PU复合材料层中的渗透示意图^[59]

Figure 13. Schematic model for the permeation of the corrosive agent passing through the coating layer of the PU composite containing GnP with weight fraction of 1%^[59].

DownLoad: Full-Size Img PowerPoint

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Vol. 70, Issue 9 - 2021-05-05

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