热镀锌板双硅烷无铬钝化膜性能的研究
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摘要
目的为进一步提高热镀锌板无铬钝化膜的耐腐蚀性能。方法以偏钒酸铵和氟钛酸作为无机组分,添加主要成膜物质苯丙乳液,通过硅烷偶联剂KH-560和KH-570将两者紧密连接,在热镀锌板表面获得一层耐腐蚀性较强的双硅烷无铬钝化膜。采用中性盐雾试验、电化学试验、扫描电镜(SEM)、傅里叶红外光谱(FTIR)等表征钝化膜的耐腐蚀性能。结果热镀锌板-双硅烷无铬钝化膜经96 h中性盐雾试验,腐蚀面积在2%~4%,腐蚀电流密度比热镀锌板基体降低一个数量等级,这表明双硅烷无铬钝化膜能提供良好的耐腐蚀能力。SEM分析表明在热镀锌板表面生成了一层均匀、连续、致密的钝化薄膜,钝化膜的厚度大约在3μm。FTIR分析表明,双硅烷无铬钝化膜中存在—(CH_2)_n—、C=O、Si—O、Si—O—Si、Si—O—Zn键。结论在热镀锌板表面生成了一层均匀、致密的钝化膜,使热镀锌板呈现良好的耐腐蚀性能,且满足工业应用标准。
The work aims to further improve corrosion resistance of chromium-free passive film on hot-dip galvanized steel. With H_2TiF_6 and NH_4VO_3 as proper inorganic constituents and styrene-acrylic emulsion as major film-forming material, a layer of corrosive bis-silane chromium-free passive film was obtained on hot-dip galvanized steel by binding the constituents tightly using silicon coupling agent(KH-560, KH-570). Corrosion resistance of the bis-silane chromium-free passive film was characterized by neutral salt spray test, electrochemical test, scanning electron microscopy and Fourier infrared spectroscopy. Corrosion area of the film accounted for approximately 2%~4% after 96 h neutral salt spray test, and corrosion current density was one order of magnitude lower than that of untreated hot-dip galvanized steel, indicating that the bis-silane chromium-free passive film could exhibit excellent corrosion resistance. SEM analysis showed that a nearly 3 μm thick uniform, continuous and compact passive film took shape on the surface of hot-dip galvanized steel. FTIR analysis indicated that —(CH_2)_n—, C=O, Si—O, Si—O—Si and Si—O—Zn bonds were present in the passive film. The hot-dip galvanized steel exhibits excellent cor-rosion resistance and meets requirements of industrial application since a layer of uniform and compact passive film takes shape on the surface of hot-dip galvanized steel.
The work aims to further improve corrosion resistance of chromium-free passive film on hot-dip galvanized steel. With H_2TiF_6 and NH_4VO_3 as proper inorganic constituents and styrene-acrylic emulsion as major film-forming material, a layer of corrosive bis-silane chromium-free passive film was obtained on hot-dip galvanized steel by binding the constituents tightly using silicon coupling agent(KH-560, KH-570). Corrosion resistance of the bis-silane chromium-free passive film was characterized by neutral salt spray test, electrochemical test, scanning electron microscopy and Fourier infrared spectroscopy. Corrosion area of the film accounted for approximately 2%~4% after 96 h neutral salt spray test, and corrosion current density was one order of magnitude lower than that of untreated hot-dip galvanized steel, indicating that the bis-silane chromium-free passive film could exhibit excellent corrosion resistance. SEM analysis showed that a nearly 3 μm thick uniform, continuous and compact passive film took shape on the surface of hot-dip galvanized steel. FTIR analysis indicated that —(CH_2)_n—, C=O, Si—O, Si—O—Si and Si—O—Zn bonds were present in the passive film. The hot-dip galvanized steel exhibits excellent cor-rosion resistance and meets requirements of industrial application since a layer of uniform and compact passive film takes shape on the surface of hot-dip galvanized steel.
引文
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[2]于元春,李宁,胡会利,等.无铬钝化与三价铬钝化的研究进展[J].表面技术,2005,34(5):6—9.YU Yuan-chun,LI Ning,HU Hui-li,et al.Research Progress of Chromium-free and Trivalent Chromium Passiv-ation[J].Surface Technology,2005,34(5):6—9.
[3]FEDEL M,OLIVIER M,POELMAN M,et al.Corrosion Protection Properties of Silane Pre-treated Powder Coated Galvanized Steel[J].Progress in Organic Coatings,2009,66(2):118—128.
[4]卢琳,李晓刚,宫丽,等.镀锌层无铬(Ⅵ)钝化的现状与发展趋向[J].轧钢,2007,24(5):41—44.LU Lin,LI Xiao-gang,GONG Li,et al.Research Status and Development Trend of Chromium-free(Ⅵ)Passivation on Galvanized Steel[J].Steel Rolling,2007,24(5):41—44.
[5]马健权,田冰,程兴德.镀锌钢板有机无铬钝化技术研究的进展[J].轧钢,2007,24(1):36—38.MA Jian-quan,TIAN Bing,CHEN Xing-de.Research Progress of Organic Chromium-free Passivation on Galvanized Steel[J].Steel Rolling,2007,24(1):36—38.
[6]DEFLORIAN F,ROSSI S,FEDEL M,et al.Electrochemical Investigation of High-performance Silane SolGel Films Containing Clay Nanoparticles[J].Progress in Organic Coating,2010,69(2):158—166.
[7]徐丽萍,胡丰,杨兴亮,等.无机-有机硅烷复合无铬钝化膜的性能[J].材料保护,2011,44(12):8—11.XU Li-ping,HU Feng,YANG Xing-liang,et al.Research Properties of Inorganic-Organic Composite Chromiumfree Passivation Films[J].Material Protection,2011,44(12):8—11.
[8]王磊,刘常升,安成强.镀锌层无机物与有机物复合无铬钝化研究进展[J].电镀与精饰,2011,33(3):22—26.WANG Lei,LIU Chang-sheng,AN Cheng-qiang.Research progress of Inorganic and Organic Composite Chromium-free Passivation on Galvanized Steel[J].Plating&Finishing,2011,33(3):22—26.
[9]PALANIVCL V,ZHU D Q,OOIJ W J V.Nanoparticle-filled Silane Films as Chromate Replacements for Aluminum Alloys[J].Progress in Organic Coatings,2003,47(3):384—392.
[10]徐斌,满瑞林,彭天兰,等.镀锌钢板的硅烷复合膜表面改性[J].腐蚀科学与防护技术,2008,20(2):135—139.XU Bin,MAN Rui-lin,PENG Tian-lan,et al.Surface Modification of Silane Composite Films on Galvanized Steel[J].Corrosion Science and Protection Technology,2008,20(2):135—139.
[11]ZHU D Q,OOIJ W J V.Corrosion Protection of Metals by Water-based Silane Mixtures of Bis-(trimethoxysilylpropyl)amine and Vinyltriacetoxysilane[J].Progress in Organic Coatings,2004,49(1):42—53.
[12]SONG Y K,MANSFELD F.Development of a Molybdate-Phosphate-Silane-Silicate(MPSS)Coating Process for Electrogalvanized Steel[J].Corrosion Science,2006,48(1):154—164.
[13]易德莲,王静,李宇鹏,等.镀锌板的复合钝化[J].腐蚀与防护,2010,31(2):142—145.YI De-lian,WANG Jing,LI Yu-peng,et al.Composite Passivation of Galvanized Steel[J].Corrosion&Protection,2010,31(2):142—145.
[14]BIERWAGEN G,TALLMAN D,LI J P,et al.EIS Studies of Coated Metals in Accelerated Exposure[J].Progress in Organic Coatings,2003,46(2):149—158.
[15]潘琦,伍林,易德莲,等.镀锌钢板表面无机-有机复合无铬钝化膜[J].电镀与涂饰,2013,32(10):37—42.PAN Qi,WU Lin,YI De-lian,et al.Inorganic-Organic Composite Chromium-free Passivation Films of Galvanized Steel Surface[J].Plating&Finishing,2013,32(10):37—42.
[16]BECCARIA A M,CHIARUTTINI L.The Inhibitive Action of Metacryloxypropylmethoxy-silane(MAOS)on Aluminium Corrosion in Na Cl Solutions[J].Corrosion Science,1999,41(5):885—899.