Preparation and anti-corrosion research of graphene oxide modified by L-glutamic acid composite epoxy resin coating

doi:10.16085/j.issn.1000-6613.2024-0065

Abstract

Abstract:

Graphene oxide (GO) was modified with L-glutamic acid (L-Glu) to improve the dispersibility of GO, and the modified graphene oxide (L-GO) was used as a filler doped into epoxy resin (EP) to prepare L-GO/EP coating. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were used to analyze the morphology and surface properties of GO before and after the modification. The hardness and adhesion of the coatings were identified, and the physical properties of the coatings were evaluated. The thermal stability and anticorrosion properties of L-GO/EP were investigated by using thermogravimetric analyzer (TG), electrochemical alternating impedance (EIS) and polarization curve (Tafel). The results showed that compared with GO, the modified L-GO nanosheet layer spacing increased by 0.115nm, the I_D/I_G value increased from 0.98 to 1.01 and L-GO had a higher level of disorder. L-Glu attached to the surface of GO, which increased the dispersion of GO in the epoxy resin. The agglomeration problem of GO was solved and the stability of the coating was improved. Compared with EP and GO/EP coatings, L-GO/EP coating offered the highest hardness (5 H), abrasion resistance (0.9L/μm), flexibility (3mm), impact strength (50cm) and adhesion (Class 1). Compared with EP, the corrosion current density of L-GO/EP coating decreased from 2.85×10^-6A/cm² to 7.65×10^-8A/cm² and the polarization resistance increased from 2.06×10⁴Ω·cm² to 5.79×10⁵Ω·cm², respectively. The improvement of anticorrosive properties of L-GO/EP coating were closely related to the increase of dispersion and physical barrier properties of L-GO.

Key words: corrosion, graphene oxide, epoxy resin coating, composite coating, dispersion, physical property

摘要：

采用L-谷氨酸（L-Glu）对氧化石墨烯（GO）进行改性以提高GO的分散性，改性后的氧化石墨烯（L-GO）作为填料掺杂至环氧树脂（EP）中，制备L-GO/EP涂层。采用X射线衍射仪（XRD）、傅里叶红外光谱仪（FTIR）和扫描电镜（SEM）等分析改性前后GO的形貌结构和表面特性；识别涂层的硬度、耐磨性和附着力等指标的变化，评价涂层的物理性能；利用热重分析仪（TG）、电化学交流阻抗（EIS）和极化曲线（Tafel）考察L-GO/EP的热稳定性和防腐性能。结果表明：与GO相比，改性后的L-GO纳米片层间距增加0.115nm，I_D/I_G由0.98增加至1.01，L-GO具有更高的无序水平；L-Glu附着于GO表面，增加了GO在环氧树脂中的分散性，解决了GO的团聚问题，提高了涂层的稳定性。与EP和GO/EP相比，L-GO/EP涂层具有最高的硬度（5H）、耐磨性（0.9L/μm）、柔韧性（3mm）、耐冲击强度（50cm）和附着力（1级）。与EP相比，L-GO/EP涂层的腐蚀电流密度由2.85×10^-6A/cm²下降到7.65×10^-8A/cm²，极化电阻由2.06×10⁴Ω·cm²增加到5.79×10⁵Ω·cm²。L-GO/EP涂层的防腐性能提高与L-GO分散性和物理阻隔性能增加紧密相关。

关键词: 腐蚀, 氧化石墨烯, 环氧树脂涂料, 复合涂层, 分散性, 物理性能

CLC Number:

TQ633.9

DING Wei, DU Wei, GUO Tiebin, GUAN Xiaozhuo, WANG Tiezheng, GAO Jiantong, ZHANG Nan, LI Da, ZHANG Lanhe. Preparation and anti-corrosion research of graphene oxide modified by L-glutamic acid composite epoxy resin coating[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 424-435.

丁伟, 杜伟, 郭铁滨, 关潇卓, 王铁铮, 高健桐, 张楠, 李达, 张兰河. L-谷氨酸改性氧化石墨烯复合环氧树脂涂层的制备及防腐性能[J]. 化工进展, 2025, 44(1): 424-435.

Figures/Tables 16

References 32

1	朱钰, 王飞, 张立军. 辽宁地区雷电活动与输电线路雷害故障特点[J]. 东北电力技术, 2012, 33(8): 35-38.
	ZHU Yu, WANG Fei, ZHANG Lijun. Analysis of characteristcs of lightning activity and lightning flashover failure of transmission lines in Liaoning[J]. Northeast Electric Power Technology, 2012, 33(8): 35-38.
2	申学德, 程克娜, 梁永东. 盐渍土地区高压输电线路杆塔接地装置腐蚀分析[J]. 东北电力技术, 2015, 36(6): 20-23.
	SHEN Xuede, CHENG Kena, LIANG Yongdong. Corrosion analysis of high-voltage transmission line tower grounding device in saline soil area[J]. Northeast Electric Power Technology, 2015, 36(6): 20-23.
3	张万友, 隋兴东. 天津市变电站土壤腐蚀性分析[J]. 东北电力大学学报, 2019, 39(1): 56-61.
	ZHANG Wanyou, SUI Xingdong. Analysis of Tianjin substation soil corrosion[J]. Journal of Northeast Electric Power University, 2019, 39(1): 56-61.
4	曹英, 刘磊, 曹默, 等. 接地网材料在四种典型土壤中的电化学腐蚀研究[J]. 东北电力大学学报, 2014, 34(1): 35-38.
	CAO Ying, LIU Lei, CAO Mo, et al. Grounding grid materical of electrochemical corrosion research in four kinds of typical soil[J]. Journal of Northeast Electric Power University, 2014, 34(1): 35-38.
5	马骏, 孙冬, 张明爽, 等. 氧化石墨烯改性环氧树脂涂料的制备及防腐性能[J]. 化工进展, 2021, 40(8): 4456-4462.
	MA Jun, SUN Dong, ZHANG Mingshuang, et al. Preparation of graphene oxide modified epoxy resin coating and research on its anti-corrosive performance[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4456-4462.
6	张治财, 齐福刚, 赵镍, 等. 环氧树脂防腐涂料的研究进展及发展趋势[J]. 功能材料, 2021, 52(6): 6069-6075.
	ZHANG Zhicai, QI Fugang, ZHAO Nie, et al. Research progress and development trend of epoxy resin anticorrosive coatings[J]. Journal of Functional Materials, 2021, 52(6): 6069-6075.
7	RAMEZANZADEH B, GHASEMI E, MAHDAVIAN M, et al. Characterization of covalently-grafted polyisocyanate chains onto graphene oxide for polyurethane composites with improved mechanical properties[J]. Chemical Engineering Journal, 2015, 281: 869-883.
8	POURHASHEM Sepideh, VAEZI Mohammad Reza, RASHIDI Alimorad, et al. Distinctive roles of silane coupling agents on the corrosion inhibition performance of graphene oxide in epoxy coatings[J]. Progress in Organic Coatings, 2017, 111: 47-56.
9	郝松松, 孙晓峰, 宋巍, 等. 石墨烯改性环氧树脂涂层的制备及其性能[J]. 中国表面工程, 2018, 31(3): 108-115.
	HAO Songsong, SUN Xiaofeng, SONG Wei, et al. Preparation and properties of graphene modified epoxy resin coating[J]. China Surface Engineering, 2018, 31(3): 108-115.
10	HUSSAIN Ahmed Khalid, SEETHARAMAIAH Nuthalapati, PICHUMANI Moorthi, et al. Research progress in organic zinc rich primer coatings for cathodic protection of metals — A comprehensive review[J]. Progress in Organic Coatings, 2021, 153: 106040.
11	UZOMA Paul C, LIU Fuchun, XU Long, et al. Superhydrophobicity, conductivity and anticorrosion of robust siloxane-acrylic coatings modified with graphene nanosheets[J]. Progress in Organic Coatings, 2019, 127: 239-251.
12	QIU Zhaozhong, WANG Rui, WU Jinzhu, et al. Graphene oxide as a corrosion-inhibitive coating on magnesium alloys[J]. RSC Advances, 2015, 5(55): 44149-44159.
13	ZHANG Lanhe, WANG Sen, WANG Junqi, et al. Preparation of a fluorescent composite coating and its anticorrosive and indicative performance[J]. Journal of the Chinese Chemical Society, 2023, 70(9): 1773-1783.
14	LIU Chengbao, DU Peng, ZHAO Haichao, et al. Synthesis of L-histidine-attached graphene nanomaterials and their application for steel protection[J]. ACS Applied Nano Materials, 2018, 1(3): 1385-1395.
15	GANJAEE SARI Morteza, SHAMSHIRI Mohammadreza, RAMEZANZADEH Bahram. Fabricating an epoxy composite coating with enhanced corrosion resistance through impregnation of functionalized graphene oxide-co-montmorillonite nanoplatelet[J]. Corrosion Science, 2017, 129: 38-53.
16	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]. Corrosion Science, 2016, 103: 283-304.
17	HELAL N H, EL-RABIEE M M, Gh M Abd EL-HAFEZ, et al. Environmentally safe corrosion inhibition of Pb in aqueous solutions[J]. Journal of Alloys and Compounds, 2008, 456(1/2): 372-378.
18	Vadivel MURUGAN A, MURALIGANTH T, MANTHIRAM A. Rapid, facile microwave-solvothermal synthesis of graphene nanosheets and their polyaniline nanocomposites for energy strorage[J]. Chemistry of Materials, 2009, 21(21): 5004-5006.
19	李仕友, 伍随意, 张考, 等. L-谷氨酸改性氧化石墨烯对Cu²⁺的吸附[J]. 化工环保, 2020, 40(4): 418-424.
	LI Shiyou, WU Suiyi, ZHANG Kao, et al. Adsorption of Cu²⁺ on L-glutamic acid modified graphene oxide[J]. Environmental Protection of Chemical Industry, 2020, 40(4): 418-424.
20	Ashok Kumar DAS, SRIVASTAV Manish, LAYEK Rama K, et al. Iodide-mediated room temperature reduction of graphene oxide: A rapid chemical route for the synthesis of a bifunctional electrocatalyst[J]. Journal of Materials Chemistry A, 2014, 2(5): 1332-1340.
21	HU Zhen, HUANG Yudong, ZHANG Chunhua, et al. Graphene-polydopamine-C₆₀ nanohybrid: An efficient protective agent for NO-induced cytotoxicity in rat pheochromocytoma cells[J]. Journal of Materials Chemistry B, 2014, 2(48): 8587-8597.
22	STANKOVICH Sasha, DIKIN Dmitriy A, PINER Richard D, et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide[J]. Carbon, 2007, 45(7): 1558-1565.
23	赵书华, 崔佳伟, 段云飞, 等. 多巴胺改性氧化石墨烯对环氧富锌涂层性能的影响[J]. 腐蚀与防护, 2022, 43(8): 1-7.
	ZHAO Shuhua, CUI Jiawei, DUAN Yunfei, et al. Effect of dopamine modified GO on properties of epoxy zinc-rich coatings[J]. Corrosion & Protection, 2022, 43(8): 1-7.
24	ZHOU Xingnan, HUANG Haowei, ZHU Rui, et al. Facile modification of graphene oxide with lysine for improving anti-corrosion performances of water-borne epoxy coatings[J]. Progress in Organic Coatings, 2019, 136: 105200.
25	WANG Zhiyu, DONG Yanfeng, LI Hongjiang, et al. Enhancing lithium-sulphur battery performance by strongly binding the discharge products on amino-functionalized reduced graphene oxide[J]. Nature Communications, 2014, 5: 5002.
26	Barbara PILCH-PITERA, Łukasz BYCZYŃSKI. Study on the thermal behavior of new blocked polyisocyanates for polyurethane powder coatings[J]. Progress in Organic Coatings, 2016, 101: 240-244.
27	ZHANG Yuanya, HE Yu, ZHOU Yongjun, et al. Fabrication of RGO/CNTs/MXene 3D skeleton structure for enhancing thermal and tribological properties of epoxy composites[J]. Tribology International, 2023, 179: 108172.
28	陈虹雨, 于倩倩, 杨建军, 等. 氨基化氧化石墨烯/磺化聚苯胺的制备及在水性环氧防腐涂料的应用[J]. 精细化工, 2022, 39(4): 837-843.
	CHEN Hongyu, YU Qianqian, YANG Jianjun, et al. Preparation of amino-functionalized graphene oxide/sulfonated polyaniline and its application in waterborne epoxy anticorrosive coatings[J]. Fine Chemicals, 2022, 39(4): 837-843.
29	杨金鑫, 吕培斌, 刘文杰, 等. 氧化石墨烯(GO)/水性环氧富锌涂料的制备及性能研究[J]. 中国涂料, 2022, 37(11): 15-26.
	YANG Jinxin, Peibin LYU, LIU Wenjie, et al. A study on preparation and properties of graphene oxide(GO)/waterborne epoxy zinc-rich coatings[J]. China Coatings, 2022, 37(11): 15-26.
30	ZHU Yanfang, XIONG Jinping, TANG Yuming, et al. EIS study on failure process of two polyurethane composite coatings[J]. Progress in Organic Coatings, 2010, 69(1): 7-11.
31	WANG Na, ZHANG Yinan, CHEN Junsheng, et al. Dopamine modified metal-organic frameworks on anti-corrosion properties of waterborne epoxy coatings[J]. Progress in Organic Coatings, 2017, 109: 126-134.
32	JIANG Meiyan, WU Liankui, HU Jiming, et al. Silane-incorporated epoxy coatings on aluminum alloy (AA2024). Part 1: Improved corrosion performance[J]. Corrosion Science, 2015, 92: 118-126.

组分	原料	质量分数/%
甲组分	环氧树脂	68~72
	分散剂	0.4~0.8
	L-GO	2~2.5
乙组分	固化剂	18~22
	丙二醇甲醚	3~5
	消泡剂	0.5~1.2
	润湿剂	0.8~1.5
	膨润土	0.3~0.5

组分	原料	质量分数/%
甲组分	环氧树脂	68~72
	分散剂	0.4~0.8
	L-GO	2~2.5
乙组分	固化剂	18~22
	丙二醇甲醚	3~5
	消泡剂	0.5~1.2
	润湿剂	0.8~1.5
	膨润土	0.3~0.5

样品	原子分数/%
样品	C	N	O
GO	47.06	0	51.49
L-GO	53.26	0.56	46.05

样品	原子分数/%
样品	C	N	O
GO	47.06	0	51.49
L-GO	53.26	0.56	46.05

指标	EP	GO/EP	L-GO/EP
黏度/mPa·s	1650	2420	3400
固含量/%	99.0	99.4	99.3
涂层厚度/μm	200±10	200±10	200±10
硬度	4H	4H	5H
耐磨性/L·μm^-1	0.6	0.8	0.9
柔韧性/mm	4	4	3
抗冲击强度/cm	40	45	50
附着力/级	2	1	1