AZ91D镁合金表面双层硅烷膜的制备及其性能研究
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摘要
采用γ-氨丙基三乙氧基硅烷(KH-550)和双-1,2-[γ-三乙氧基硅丙基]-四硫化物(BTESPT)两种硅烷在AZ91D镁合金表面制备双层硅烷膜,通过正交试验选出了最佳制备工艺,即在KH-550硅烷中浸泡90 s,在BTESPT硅烷中浸泡5 min,再于80℃下固化90 min,得到550+BTESPT双层硅烷膜试样。通过接触角测试仪和动电位极化技术对试样进行润湿性和耐蚀性测试,通过扫描电子显微镜(SEM)、X射线能谱分析仪(EDS)对硅烷膜进行微观形貌和成分表征,通过X射线光电子能谱(XPS)对膜层元素的存在形式进行分析,结果表明:550+BTESPT双层硅烷膜表面接触角107.3°,表现为疏水性;在3.5%的NaCl溶液中,腐蚀电流密度为0.169μA/cm~2;硅烷膜表面形貌致密,主要有Mg、O、Si、S 4种元素组成;膜层中元素主要以Si—O—Si, Si—O—Mg, Si—O—X 3种形式存在。
Two-layer silane films have been prepared on the surface of AZ91 D magnesium alloy by using KH-550 and BTESPT. The best preparation process, selected on the basis of orthogonal tests, was found to involve immersion in KH-550 silane for 90 s, followed by immersion in BTESPT silane for 5 min, and curing at 80 ℃ for 90 min. The wettability and corrosion resistance of samples were tested by contact angle measurements and potentiodynamic polarization, the morphology and composition of the silane film were characterized by scanning electron microscopy(SEM) and energy dispersive spectroscopy(EDS), and the elemental composition was analyzed by X-ray photoelectron spectroscopy(XPS). The results showed that the 550+BTESPT double-layer silane film was hydrophobic, with a surface contact angle of 107.3°; in 3.5% NaCl solution, the corrosion current density was 0.169 μA/cm~2; the surface morphology is dense, and the silane film mainly consists of four elements: Mg, O, Si, and S; the elements in the film layer are mainly present in the forms Si—O—Si, Si—O—Mg, and Si—O—X.
Two-layer silane films have been prepared on the surface of AZ91 D magnesium alloy by using KH-550 and BTESPT. The best preparation process, selected on the basis of orthogonal tests, was found to involve immersion in KH-550 silane for 90 s, followed by immersion in BTESPT silane for 5 min, and curing at 80 ℃ for 90 min. The wettability and corrosion resistance of samples were tested by contact angle measurements and potentiodynamic polarization, the morphology and composition of the silane film were characterized by scanning electron microscopy(SEM) and energy dispersive spectroscopy(EDS), and the elemental composition was analyzed by X-ray photoelectron spectroscopy(XPS). The results showed that the 550+BTESPT double-layer silane film was hydrophobic, with a surface contact angle of 107.3°; in 3.5% NaCl solution, the corrosion current density was 0.169 μA/cm~2; the surface morphology is dense, and the silane film mainly consists of four elements: Mg, O, Si, and S; the elements in the film layer are mainly present in the forms Si—O—Si, Si—O—Mg, and Si—O—X.
引文
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[2] 朱阮利,魏博,胡小涛,等.硅烷膜固化方式对AZ91镁合金耐蚀性的影响[J].沈阳工业大学学报,2016,38(1):36- 41.ZHU R L,WEI B,HU X T,et al.Effect of curing methods of silane film on corrosion resistance of AZ91 magnesium alloy[J].Journal of Shenyang University of Technology,2016,38(1):36- 41.(in Chinese)
[3] 冯英宁.镁合金表面硅烷化处理的研究[D].长春:长春工业大学,2015.FENG Y N.Study on silanization treatment on the surface of magnesium alloy [D].Changchun:Changchun University of Technology,2015.(in Chinese)
[4] ZHANG W,PAN F S,YANG M B,et al.Influence of KH- 550 silane treatment on the corrosion resistance of AZ31 magnesium alloy[C]//Sino-US Materials International Symposium.Chongqing,2008:927- 930.
[5] PALANIVEL V,ZHU D Q,VAN OOIJ W J.Nanoparticle-filled silane films as chromate replacements for aluminum alloys[J].Progress in Organic Coatings,2003,47(3/4):384- 392.
[6] SHEFFER M,GROYSMAN A,MANDLER D.Electrodeposition of sol-gel films on Al for corrosion protection[J].Corrosion Science,2003,45(12):2893- 2904.
[7] SHACHAM R,AVNIR D,MANDLER D.Electrodeposition of methylated sol-gel films on conducting surfaces[J].Advanced Materials,1999,11(5):384- 388.
[8] MONTEMOR M F,PINTO R,FERREIRA M G S.Chemical composition and corrosion protection of silane films modified with CeO2 nanoparticles[J].Electrochimica Acta,2009,54(22):5179- 5189.
[9] MONTEMOR M F,CABRAL A M,ZHELUDKEVICH M L,et al.The corrosion resistance of hot dip galvanized steel pretreated with bis-functional silanes modified with microsilica[J].Surface and Coatings Technology,2006,200(9):2875- 2885.
[10] 赵瑾,申忠宇.研究弱极化区极化曲线来估算腐蚀过程的电化学动力学参数[J].腐蚀与防护,1998,19(2):69- 72.ZHAO J,SHEN Z Y.Estimation of electrochemical kinetic parameters of corrosion processes by studying polarization curve in weak polarization region[J].Corrosion and Protection,1998,19(2):69- 72.(in Chinese)
[11] 宋莹莹.镁锂合金表面硅烷预处理及其腐蚀与防护研究[D].哈尔滨:哈尔滨工程大学,2013.SONG Y Y.Corrosion protection of Mg- Li alloy pretreated by silanes[D].Harbin:Harbin Engineering University,2013.(in Chinese)
[12] 高晓辉.镁锂合金表面硅烷复合耐蚀膜层的制备及性能研究[D].哈尔滨:哈尔滨工程大学,2017.GAO X H.Preparation and properties of silane composite anticcorrosion coatings on Mg- Li alloy[D].Harbin:Harbin Engineering University,2017.(in Chinese)
[13] 雷黎.镁合金铈转化膜与铈/硅烷复合转化膜的成膜机理及腐蚀行为[D].青岛:中国海洋大学,2015.LEI L.Formation mechanism and corrosion behavior of the cerium and cerium/silane conversion coatings for magnesium alloy[D].Qingdao:Ocean University of China,2015.(in Chinese)
[14] 窦庆乐.铝基超疏水表面制备方法研究[D].大连:大连理工大学,2010.DOU Q L.Research on fabrication of superhydrophobic surface on aluminum substrat[D].Dalian:Dalian University of Technology,2010.(in Chinese)
[15] ARNOTT D R,RYAN N E,HINTON B R W,et al.Auger and XPS studies of cerium corrosion inhibition on 7075 aluminium alloy[J].Applications of Surface Science,1985,22/23(85):236- 251.
[16] BOUVIER Y,MUTEL B,GRIMBLOT J.Use of an Auger parameter for characterizing the Mg chemical state in different materials[J].Surface and Coatings Technology,2004,180/181(2):169- 173.
[17] 威姆.硅烷偶联剂在金属上的应用[J].傅德生,傅原,译.表面技术,1998,28(4):37- 40.VAN OOIJ W J.Application of silane coupling agents to metals[J].FU D S,FU Y,trans.Surface Technology,1998,28(4):37- 40.(in Chinese)
[18] CORREA P S,MALFATTI C F,AZAMBUJA D S.Corrosion behavior study of AZ91 magnesium alloy coated with methyltriethoxysilane doped with cerium ions[J].Progress in Organic Coatings,2011,72(4):739- 747.