石墨烯改性无铬达克罗涂层的组织及耐腐蚀性能
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摘要
达克罗凭借优异的耐腐蚀性能,广泛应用于汽车、航海、风电等领域,但其所含铬酸盐存在严重的污染问题。采用硅烷偶联剂代替铬酸盐的无铬达克罗解决了污染问题,但相对于达克罗,其硬度低、附着力差、耐腐蚀性较差。通过加入硝酸铈铵和石墨烯对无铬达克罗涂料进行改性,并采用X射线衍射仪、扫描电镜、拉曼光谱仪、快速腐蚀试验、极化曲线试验研究了涂层的物相组成、组织形貌、耐腐蚀性能。结果表明:涂层表面主要是片状锌粉、片状铝粉,致密性好;涂层截面层状堆叠结构清晰。石墨烯添加量为200 mg/L时,改性无铬达克罗涂层的耐腐蚀性能最佳,耐腐蚀时间(5 h)最长,腐蚀电流密度(0.124μA/cm2)最小,腐蚀电压(-0.82 V)最正。硝酸铈铵通过对金属粉的钝化、粘结作用提高涂层的耐腐蚀性能;石墨烯通过物理屏蔽作用、促进牺牲阳极保护作用提高涂层的耐腐蚀性能。
Dacromet is an effective corrosion-resistant coating widely used in automobiles,ships and wind-power generators.However,it contains chromate which may cause severe environmental pollution.Chromium-free dacromet coating has been developed to address the pollution problem by replacing chromate with safe silane coupling agent.However,the hardness,adhesion strength and corrosion resistance of the chromium-free dacromet coating is worse than that of dacromet.Thus,diammonium cerium(IV) nitrate and graphene was used to modify the chromium-free dacromet coating.Various characterizations including X-ray diffraction,scanning electron microscopy,Raman spectroscopy,rapid corrosion test and electrochemical polarization show that the top layer of the coating is mainly composed by compact flake zinc powder and flake aluminum powder and the cross section of the coating shows a clear multi-layer structure.With a concentration of 200 mg/L graphene,the modified chromium-free dacromet coating has the best corrosion resistance,evidenced by the longest corrosion resistance time(5 h),the minimum corrosion current density(0.124 μA/cm2),and the most positive corrosion voltage(-0.82 V).The improved corrosion resistance can be ascribed to the passivizing and powder-bonding effects of diammonium cerium(IV) nitrate as well as the physical shielding and increased sacrificial anode protection from graphene.
Dacromet is an effective corrosion-resistant coating widely used in automobiles,ships and wind-power generators.However,it contains chromate which may cause severe environmental pollution.Chromium-free dacromet coating has been developed to address the pollution problem by replacing chromate with safe silane coupling agent.However,the hardness,adhesion strength and corrosion resistance of the chromium-free dacromet coating is worse than that of dacromet.Thus,diammonium cerium(IV) nitrate and graphene was used to modify the chromium-free dacromet coating.Various characterizations including X-ray diffraction,scanning electron microscopy,Raman spectroscopy,rapid corrosion test and electrochemical polarization show that the top layer of the coating is mainly composed by compact flake zinc powder and flake aluminum powder and the cross section of the coating shows a clear multi-layer structure.With a concentration of 200 mg/L graphene,the modified chromium-free dacromet coating has the best corrosion resistance,evidenced by the longest corrosion resistance time(5 h),the minimum corrosion current density(0.124 μA/cm2),and the most positive corrosion voltage(-0.82 V).The improved corrosion resistance can be ascribed to the passivizing and powder-bonding effects of diammonium cerium(IV) nitrate as well as the physical shielding and increased sacrificial anode protection from graphene.
引文
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[15]QI X,CAI Y S,JIA Y Y,et al.Microstructure evolution of a Zn-Al coating Co-deposited on low-carbon steel by pack cementation[J].Journal of Alloys and Compounds,2016,699(1):1012-1021.
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[19]周文娟,许立坤,王佳,等.碳钢表面硅烷锌铝涂层的腐蚀电化学行为[J].金属学报,2007(9):983-988.ZHOU W J,XU L K,WANG J,et al.Corrosion electrochemical behavior of Zn-Al silane coating on carbon steel[J].Acta Metallurgica Sinica,2007(9):983-988(in Chinese).
[2]乔静飞.达克罗(Dacromet)涂层的制备及性能研究[D].新乡:河南师范大学,2016:3-6.QIAO J F.Study on the preparation and properties of dacromet coating[D].Xinxiang Henan Normal University,2016:3-6(in Chinese).
[3]安恩朋,李相波,程旭东,等.达克罗涂层研究现状[J].腐蚀科学与防护技术,2014,26(1):73-76.AN E P,LI X B,CHENG X D,et al.Status of dacromet coating[J].Corrosion Science and Protection Technology,2014,26(1):73-76(in Chinese).
[4]王青,裴政,童鹤,等.达克罗涂层技术进展研究[J].兵器材料科学与工程,2013,36(2):138-142.WANG Q,FEI Z,TONG H,et al.Research progress in dacromet coating technique[J].Ordnance Material Science and Engineering,2013,36(2):138-142(in Chinese).
[5]LIU J,GONG G P,YAN C W.EIS study of corrosion behaviour of organic coating/dacromet composite systems[J].Electrochimica Acta,2004,50(16):3320-3332.
[6]周次心,周雅.达克罗涂层的现状及发展[J].南昌航空大学学报(自然科学版),2014,28(2):43-49.ZHOU C X,ZHOU Y.Status and development of dacromet coating[J].Journal of Nanchang Hangkong University(Natural Sciences),2014,28(2):43-49(in Chinese).
[7]张旭明,刘春明,王建军,等.无铬达克罗成膜物质的研究进展[J].材料与冶金学报,2012,11(1):58-63.ZHOU X M,LIU C M,WANG J J,et al.Research progress on materials to form the chromium-free dacromet film[J].Journal of Materials and Metallurgy,2012,11(1):58-63(in Chinese).
[8]陈丽姣.无铬达克罗工艺及耐蚀性的研究[D].哈尔滨:哈尔滨工业大学,2007:28-32.CHEN L J.The Study on process and corrosion resistance of chrome-free dracromet coating[D].Journal of Harbin Institute of Technology,2007:28-32(in Chinese).
[9]LIU J G,GONG G P,YAN C W.Enhancement of the erosion-corrosion resistance of dacromet with hybrid SiO2sol-gel[J].Surface&Coatings Technology,2005,200(16):4967-4975.
[10]WANG D H,TANG X,QIU Y Y,et al.A study of the film formation kinetics on zinc in different acidic corrosion inhibitor solutions by quartz crystal microbalance[J].Corrosion Science,2005,47(9):2157-2172.
[11]崔廷昌.无铬达克罗技术的研究及应用进展[J].材料保护,2018,51(3):98-102.CUI T C.Application development of non-chormium dacroment technology[J].Materials Protection,2018,51(3):98-102(in Chinese).
[12]李新波,曾鹏,谢光荣,等.稀土镧盐对水性锌铝涂层的钝化作用[J].材料保护,2011,44(10):19-22.LI X B,ZENG P,XIE R G,et al.Passivation of rare earth cerium salts on water-based Zn-Al coatings[J].Materials Protection,2011,44(10):19-22(in Chinese).
[13]黄平,唐长林,范梅梅,等.汽车制动盘涂覆石墨烯改性锌铝水性涂料工艺[J].汽车工艺与材料,2017(4):15-17.HUANG P,TANG C L,FAN M M,et al.Process for coating brake-coated graphene modified water-based Zn-Al coatings on automobile brake disc[J].Automobile Technology&Material,2017(4):15-17(in Chinese).
[14]蒋穹,高欣,季铁安,等.纳米微粒增强水性无铬锌铝合金涂层的制备及其性能[J].中国表面工程,2018,31(1):123-130.JIANG Q,GAO X,JI T A,et al.Preparation and properties of water-based chromium-free Zn-Al alloy coatings enhanced by nanoparticles[J].China Surface Engineering,2018,31(1):123-130(in Chinese).
[15]QI X,CAI Y S,JIA Y Y,et al.Microstructure evolution of a Zn-Al coating Co-deposited on low-carbon steel by pack cementation[J].Journal of Alloys and Compounds,2016,699(1):1012-1021.
[16]HU H L,LI N,CHENG J N,et al.Corrosion behavior of chromium-free dacromet coating in seawater[J].Journal of Alloys and Compounds,2008,472(1):219-224.
[17]ZHANG K B,ZHANG M M,QIAO J F,et al.Enhancement of the corrosion resistance of Zn-Al-Cr coating with cerium nitrate[J].Journal of Alloys and Compounds,2017,692(1):460-464.
[18]舒畅,刘彬,周漪.锌铝/富铝复合涂层在海洋环境中的耐蚀性研究[J].表面技术,2012,41(5):56-59.SHU C,LIU B,ZHOU Y.Zn-Al/rich-Al composite coatings in marine environment[J].Surface Technology,2012,41(5):56-59(in Chinese).
[19]周文娟,许立坤,王佳,等.碳钢表面硅烷锌铝涂层的腐蚀电化学行为[J].金属学报,2007(9):983-988.ZHOU W J,XU L K,WANG J,et al.Corrosion electrochemical behavior of Zn-Al silane coating on carbon steel[J].Acta Metallurgica Sinica,2007(9):983-988(in Chinese).
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