间苯二胺-氧化石墨烯/有机涂层的制备及防腐性能研究

doi:10.11902/1005.4537.2020.272

中国腐蚀与防护学报

2021, Vol. 41

Issue (2): 161-168 DOI: 10.11902/1005.4537.2020.272

研究报告

本期目录 | 过刊浏览

间苯二胺-氧化石墨烯/有机涂层的制备及防腐性能研究

栾浩¹, 孟凡帝¹(

), 刘莉¹(

), 崔宇², 刘叡³, 郑宏鹏¹, 王福会¹

^1.沈阳材料科学国家研究中心东北大学联合研究分部沈阳 110819
^2.中国科学院金属研究所师昌绪先进材料创新中心沈阳 110016
^3.中国科学院金属研究所沈阳材料科学国家研究中心沈阳 110016

Preparation and Anticorrosion Performance of M-phenylenediamine-graphene Oxide/Organic Coating

LUAN Hao¹, MENG Fandi¹(

), LIU Li¹(

), CUI Yu², LIU Rui³, ZHENG Hongpeng¹, WANG Fuhui¹

^1.Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China
^2.Shi -changxu Innovation Center for Advanced Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
^3.Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

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摘要:

针对有机涂层中氧化石墨烯 (GO) 分散性差、与树脂相容性不好的问题，本工作选择间苯二胺作为“桥接物质”，利用其分子上的两个胺基与GO和环氧树脂的环氧基团分别键合，从而改善GO与环氧树脂间的相容性。同时，利用间苯二胺的空间位阻效应有效改善了GO的团聚问题，提高在环氧树脂中的分散性。采用化学接枝法得到间苯二胺表面改性的GO(M-GO)，并制备了M-GO与环氧树脂E-44复合涂料 (EP/M-GO)。结果表明，间苯二胺的胺基能够成功与GO表面的环氧基团键合，且在透射电镜下可以观察到M-GO呈现出少量片层的状态，团聚现象明显改善。另一方面，涂层截面形貌表明M-GO与基料树脂之间结合良好。复合涂料在12 d的盐雾实验后仍然能够为金属基底提供保护，且浸泡1000 h后的阻抗模值 (|Z^{|_{0.01 Hz}) 仍可达10⁹数量级，防腐性能明显提高。}

关键词 ：氧化石墨烯, 有机涂层, 防腐性能

Abstract：

In order to solve the problems of poor dispersion of graphene oxide (GO) in organic coatings and poor compatibility with resins, m-phenylenediamine, taking as the so called "bridge" material, was grafted on the surface of graphene oxide (GO) via a chemical means to obtain M-GO composite materials. Then the M-GO/epoxy resin E-44 composite anticorrosion coatings were also prepared. The results of FTIR, Raman and TGA showed that amine groups of m-phenylenediamine were successfully bonded with the epoxy group. A few layers of the M-GO composite particulates of lamellar morphology can be observed by transmission electron microscope (TEM), indicating that the dispersibility of GO was improved through m-phenylenediamine-grafting. On the other hand, the cross-sectional morphology of the coating showed that the M-GO composite material also has good compatibility with epoxy resin. In comparison with the epoxy resin coating GO/EP with the inherent graphene oxide GO, the M-GO/EP coating shows far more better anti-corrosion performance, namely, after 1000 h of immersion in 3.5% (mass fraction) NaCl solution, the impedance modulus (|Z^{|_{0.01 Hz}) value of EP/M-GO stayed at 1.0×10⁹ Ω·cm², and after salt spray test for 12 d, the M-GO/EP coating could still provide effective protection for the metal substrate. The results show that the m-phenylenediamine modified graphene oxide/organic coatings present significantly enhanced anti-corrosion performance.}

Key words： graphene oxide organic coating anti-corrosion performance

收稿日期: 2020-12-24

ZTFLH:

TQ323.5

基金资助:国家自然科学基金(51901040);博士后科学基金(2020M680962);辽宁省兴辽英才计划(XLYC1807076)

通讯作者: 孟凡帝,刘莉 E-mail: fandimeng@mail.neu.edu.cn;liuli@mail.neu.edu.cn

Corresponding author: MENG Fandi,LIU Li E-mail: fandimeng@mail.neu.edu.cn;liuli@mail.neu.edu.cn

作者简介: 栾浩，男，1995年生，硕士生

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引用本文:

栾浩, 孟凡帝, 刘莉, 崔宇, 刘叡, 郑宏鹏, 王福会. 间苯二胺-氧化石墨烯/有机涂层的制备及防腐性能研究[J]. 中国腐蚀与防护学报, 2021, 41(2): 161-168.
Hao LUAN, Fandi MENG, Li LIU, Yu CUI, Rui LIU, Hongpeng ZHENG, Fuhui WANG. Preparation and Anticorrosion Performance of M-phenylenediamine-graphene Oxide/Organic Coating. Journal of Chinese Society for Corrosion and protection, 2021, 41(2): 161-168.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2020.272 或 https://www.jcscp.org/CN/Y2021/V41/I2/161

图1 间苯二胺表面改性氧化石墨烯的实验原理图

图2 GO与M-GO的红外光谱图

图3 GO与M-GO的热重曲线图

图4 GO与M-GO的Raman谱图

图5 水滴在GO与M-GO表面的接触角图

图6 GO与M-GO在树脂溶液中沉降不同时间的照片

图7 GO与M-GO的TEM像

图8 EP/GO与EP/M-GO涂层的截面SEM像

图9 EP/GO与EP/M-GO涂层的吸水率曲线

图10 EP/GO与EP/M-GO涂层在3.5%NaCl溶液中浸泡不同时间后的电化学阻抗谱

图11 EP/GO与EP/M-GO涂层的等效电路图

图12 两种有机涂层的涂层电阻Rc随浸泡时间的变化

图13 EP/GO与EP/M-GO涂层的拉伸曲线

图14 EP/GO与EP/M-GO涂层经不同时间盐雾实验后的宏观照片

1	Ye Y W, Zhang D W, Zou Y J, et al. A feasible method to improve the protection ability of metal by functionalized carbon dots as environment-friendly corrosion inhibitor [J]. J. Clean. Prod., 2020, 264: 121682
2	Ye Y W, Yang D P, Chen H, et al. A high-efficiency corrosion inhibitor of N-doped citric acid-based carbon dots for mild steel in hydrochloric acid environment [J]. J. Hazard. Mater., 2020, 381: 121019
3	Rahman O U, Ahmad S. Physico-mechanical and electrochemical corrosion behavior of soy alkyd/Fe₃O₄ nanocomposite coatings [J]. RSC Adv., 2014, 4: 14936
4	Ramezanzadeh B, Ghasemi E, Mahdavian M, et al. Covalently-grafted graphene oxide nanosheets to improve barrier and corrosion protection properties of polyurethane coatings [J]. Carbon, 2015, 93: 555
5	Su Y, Kravets V G, Wong S L, et al. Impermeable barrier films and protective coatings based on reduced graphene oxide [J]. Nat. Commun., 2014, 5: 4843
6	Berry V. Impermeability of graphene and its applications [J]. Carbon, 2013, 62: 1
7	Mohammadi S, Roohi H. Influence of functionalized multi-layer graphene on adhesion improvement and corrosion resistance performance of zinc-rich epoxy primer [J]. Corros. Eng. Sci. Technol., 2018, 53: 422
8	Chang C I, Chang K H, Shen H H, et al. A unique two-step Hummers method for fabricating low-defect graphene oxide nanoribbons through exfoliating multiwalled carbon nanotubes [J]. J. Taiwan Inst. Chem. Eng., 2014, 45: 2762
9	Tang L C, Wan Y J, Yan D, et al. The effect of graphene dispersion on the mechanical properties of graphene/epoxy composites [J]. Carbon, 2013, 60: 16
10	Huang G J, Chen Z G, Li M D, et al. Surface functional modification of graphene and graphene oxide [J]. Acta Chim. Sin., 2016, 74: 789
10	黄国家, 陈志刚, 李茂东等. 石墨烯和氧化石墨烯的表面功能化改性 [J]. 化学学报, 2016, 74: 789
11	Cui G, Bi Z X, Zhang R Y, et al. A comprehensive review on graphene-based anti-corrosive coatings [J]. Chem. Eng. J., 2019, 373: 104
12	Ding R, Chen S, Lv J, et al. Study on graphene modified organic anti-corrosion coatings: a comprehensive review [J]. J. Alloy. Compd., 2019, 806: 611
13	Lerf A, He H Y, Riedl T, et al. ¹³C and ^1H MAS NMR studies of graphite oxide and its chemically modified derivatives [J]. Solid State Ion., 1997, 101-103: 857
14	Tararan A, Zobelli A, Benito A M, et al. Revisiting graphene oxide chemistry via spatially-resolved electron energy loss spectroscopy [J]. Chem. Mater., 2016, 28: 3741
15	Qiu S H, Liu G, Li W, et al. Noncovalent exfoliation of graphene and its multifunctional composite coating with enhanced anticorrosion and tribological performance [J]. J. Alloy. Compd., 2018, 747: 60
16	Liu C B, Qiu S H, Du P, et al. An ionic liquid-graphene oxide hybrid nanomaterial: Synthesis and anticorrosive applications [J]. Nanoscale, 2018, 10: 8115
17	Parhizkar N, Ramezanzadeh B, Shahrabi T. Corrosion protection and adhesion properties of the epoxy coating applied on the steel substrate pre-treated by a sol-gel based silane coating filled with amino and isocyanate silane functionalized graphene oxide nanosheets [J]. Appl. Surf. Sci., 2018, 439: 45
18	Ramezanzadeh B, Niroumandrad S, Ahmadi A, et al. Enhancement of barrier and corrosion protection performance of an epoxy coating through wet transfer of amino functionalized graphene oxide [J]. Corros. Sci., 2016, 103: 283
19	Layek R K, Nandi A K. A review on synthesis and properties of polymer functionalized graphene [J]. Polymer, 2013, 54: 5087
20	Wang S, Chia P J, Chua L L, et al. Band‐like transport in surface‐functionalized highly solution‐processable graphene nanosheets [J]. Adv. Mater., 2008, 20: 3440
21	Stankovich S, Piner R D, Nguyen S T, et al. Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets [J]. Carbon, 2006, 44: 3342
22	Jiang T W, Kuila T, Kim N H, et al. Enhanced mechanical properties of silanized silica nanoparticle attached graphene oxide/epoxy composites [J]. Compos. Sci. Technol., 2013, 79: 115
23	Parhizkar N, Shahrabi T, Ramezanzadeh B. A new approach for enhancement of the corrosion protection properties and interfacial adhesion bonds between the epoxy coating and steel substrate through surface treatment by covalently modified amino functionalized graphene oxide film [J]. Corros. Sci., 2017, 123: 55
24	Hu Z, Huang Y D, Zhang C H, et al. Graphene-polydopamine-C₆₀ nanohybrid: An efficient protective agent for NO-induced cytotoxicity in rat pheochromocytoma cells [J]. J. Mater. Chem., 2014, 2B: 8587
25	Lu X N, Li L Y, Song B, et al. Mechanistic investigation of the graphene functionalization using p-phenylenediamine and its application for supercapacitors [J]. Nano Energy, 2015, 17: 160
26	Cai K W, Zuo S X, Luo S P, et al. Preparation of polyaniline/graphene composites with excellent anti-corrosion properties and their application in waterborne polyurethane anticorrosive coatings [J]. RSC Adv., 2016, 6: 95965
27	Zhou X N, Huang H W, Zhu R, et al. Facile modification of graphene oxide with Lysine for improving anti-corrosion performances of water-borne epoxy coatings [J]. Prog. Org. Coat., 2019, 136: 105200
28	Wang C Y, Lan Y F, Yu W T, et al. Preparation of amino-functionalized graphene oxide/polyimide composite films with improved mechanical, thermal and hydrophobic properties [J]. Appl. Surf. Sci., 2016, 362: 11
29	Zheng H P, Guo M Y, Shao Y W, et al. Graphene oxide-poly (urea-formaldehyde) composites for corrosion protection of mild steel [J]. Corros. Sci., 2018, 139: 1
30	Liu X L, Shao Y W, Zhang Y J, et al. Using high-temperature mechanochemistry treatment to modify iron oxide and improve the corrosion performance of epoxy coating-I. High-temperature ball milling treatment [J]. Corros. Sci., 2015, 90: 451

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