T2铜及QCr0.5铜合金无铬复配钼酸盐钝化研究
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摘要
采用单一钼酸盐与各种复配钼酸盐钝化液对T2铜与QCr0.5铜合金表面进行钝化处理,分别运用电化学法、硝酸点滴实验、中性盐雾实验、SEM,XRD等手段对不同钝化膜的微观结构与耐蚀性能进行研究,并与铬酸盐钝化结果进行对比。结果表明,双氧水与聚天冬氨酸(PASP)作为添加剂,可以提高钼酸盐的钝化效果,尤其是两者同时加入时显著促进了钝化膜的形成,使两种钢材的溶解及表面形貌的腐蚀程度降低到最低限度,形成以Cu的氧化物为主的钝化膜,显著提高试样的耐蚀性。相比未钝化试样,钝化试样表面光泽较好。钝化试样经过盐雾实验后,表面腐蚀坑较少,存在一定的金属光泽;特别是T2铜的钝化效果最好,其PASP+H_2O_2复配钝化后的自腐蚀电流密度仅为3.10×10~(-6)A/cm~2,近似于铬酸盐钝化的9.06×10~(-7)A/cm~2,达到了与铬酸盐钝化类似的效果。
T2 Cu and QCr0.5 Cu-alloy were passivated in chromate-free solutions with single molybdate and complex molybdate respectively. The formed passivation films were then characterized by electrochemical method, nitric acid drop test, neutral salt spray test, SEM and XRD etc., taking the passivation film prepared with conventional chromate containing solution as comparison. Results show that the addition of polyaspartic acid(PASP) and H_2O_2 could improve the passivation effect of molybdate, especially the addition of the both simultaneously, which promoted the formation of passive film, the decrease of dissolution of Cu-alloy, and thereby the formation of a passivation film of copper oxide-based,significantly improved the corrosion resistance of T2 Cu and QCr0.5 Cu-alloy. After salt spray test, the surface of passivation treated samples presents metallic lustrousness to certain extent, while with less corrosion pits. In particular, the free-corrosion current density for T2 Cu passivated in molybdate solution with PASP + H_2O_2 is only 3.10 × 10~(-6)A/cm~2, which is close to that for the chromate passivation film i.e.9.06×10~(-7)A/cm~2.
T2 Cu and QCr0.5 Cu-alloy were passivated in chromate-free solutions with single molybdate and complex molybdate respectively. The formed passivation films were then characterized by electrochemical method, nitric acid drop test, neutral salt spray test, SEM and XRD etc., taking the passivation film prepared with conventional chromate containing solution as comparison. Results show that the addition of polyaspartic acid(PASP) and H_2O_2 could improve the passivation effect of molybdate, especially the addition of the both simultaneously, which promoted the formation of passive film, the decrease of dissolution of Cu-alloy, and thereby the formation of a passivation film of copper oxide-based,significantly improved the corrosion resistance of T2 Cu and QCr0.5 Cu-alloy. After salt spray test, the surface of passivation treated samples presents metallic lustrousness to certain extent, while with less corrosion pits. In particular, the free-corrosion current density for T2 Cu passivated in molybdate solution with PASP + H_2O_2 is only 3.10 × 10~(-6)A/cm~2, which is close to that for the chromate passivation film i.e.9.06×10~(-7)A/cm~2.
引文
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[2]Sui W J,Zhao W J,Zhang X,et al.Influence of TEOS content on anti-corrosion property of mercapto functional organic silane based sol-gel coatings on copper alloy surface[J].J.Chin.Soc.Corros.Prot.,2016,36:52(睢文杰,赵文杰,张星等.铜合金表面巯基官能有机硅溶胶-凝胶涂层中TEOS含量对其防腐性能的影响[J].中国腐蚀与防护学报,2016,36:52)
[3]Chen J,Zheng Q F,Wen J G.Gray correlation analyses of influence factors on atmospheric corrosion of copper and copper alloys[J].Corros.Prot.,2010,31:917(陈杰,郑弃非,温军国.铜及铜合金大气腐蚀影响因素的灰色关联分析[J].腐蚀与防护,2010,31:917)
[4]Zhao S M,Hao J J,Bi X.Study on the chromium-free passivation solution for copper and copper alloys[J].Plat.Finish.,2016,38(9):13(赵思萌,郝建军,毕祥.铜及其合金无铬钝化液的研究[J].电镀与精饰,2016,38(9):13)
[5]Chu J S.Advances in research on chromate-free passivation for zinc coating[J].Technol.Innov.Appl.,2016,(6):51(储俊生.对镀锌层无铬钝化技术的研究进展探讨[J].科技创新与应用,2016,(6):51)
[6]Zhang M L,Zhao J M.Research progress of synergistic inhibition effect and mechanism[J].J.Chin.Soc.Corros.Prot.,2016,36:1(张漫路,赵景茂.缓蚀剂协同效应与协同机理的研究进展[J].中国腐蚀与防护学报,2016,36:1)
[7]Zhang Z G,Guo D,Zhou H F,et al.Research progress of molybdate-based inhibitors used for nonferrous metals[J].Mater.Prot.,2015,48(4):40(张志刚,郭帝,周华锋等.钼酸盐应用于有色金属缓蚀的研究进展[J].材料保护,2015,48(4):40)
[8]Xiao J,Zhang J D.Study on corrosion inhibition performance of molybdate corrosion inhibitor for copper[J].Silicon Valley,2011,(23):105(肖靖,张剑德.钼酸盐复配缓蚀剂对铜的缓蚀性能研究[J].硅谷,2011,(23):105)
[9]Wang X,Zhang C L.Corrosion inhibition of sodium molybdate and triethanolamine for copper[J].Corros.Sci.Prot.Technol.,2004,16:44(王昕,张春丽.钼酸钠和三乙醇胺对铜的缓蚀作用[J].腐蚀科学与防护技术,2004,16:44)
[10]Zhang S C,Shi W Y,Bai Z M.Chromium-free passivation treatment for copper alloy[J].Corros.Prot.,2005,26:96(张世超,石伟玉,白致铭.铜合金无铬钝化的研究[J].腐蚀与防护,2005,26:96)
[11]Hu Y X,Chen Z L,Liu X,et al.Study on surface treatment of metal copper[J].J.Beijing Inst.Petro-Chem.,2000,8(2):13(胡应喜,陈志玲,刘霞等.金属铜表面处理研究[J].北京石油化工学院学报,2000,8(2):13)
[12]Fu R,Wang S,Zhou R T.Progress on research of passivated galvanized[J].Jiangxi Chem.Ind.,2014,(4):34(付锐,汪晟,周仁韬.镀锌钝化研究进展概述[J].江西化工,2014,(4):34)
[13]Ding Y T,Lu Z H,Hu Y,et al.Oxidation behavior of pure copper and its influencing factors[J].J.Lanzhou Univ.Technol.,2010,36(2):1(丁雨田,卢振华,胡勇等.纯铜的氧化行为及影响因素[J].兰州理工大学学报,2010,36(2):1)
[14]Yu F,Liu G M,Yang L.Study of molybdate-tannic acid passivation on galvanised steel[J].J.Nanchang Hangkong Univ.(Nat.Sci.),2012,26(2):45(于斐,刘光明,杨柳.热镀锌钢板钼酸盐-单宁酸钝化研究[J].南昌航空大学学报(自然科学版),2012,26(2):45)
[15]Yue H W,Wang S L,Liu Y L,et al.Effect of H2O2on the CMP of the copper pattern wafer in the alkaline slurry[J].Micronano.Technol.,2012,49:553(岳红维,王胜利,刘玉岭等.碱性抛光液中H2O2对铜布线CMP的影响[J].微纳电子技术,2012,49:553)
[16]Yang J,Jiang K,Zhang D Q.No-chromium passive treatment for brass surface[J].Corros.Prot.,2001,22:193(杨健,蒋凯,张大全.黄铜表面的非铬钝化处理研究[J].腐蚀与防护,2001,22:193)
[17]Xu Q J,Shan Z H,Zhu L J,et al,Photoelectrochemical study on the complex of poly-aspartate and tungstate as inhibitors against brass corrosion[J].Acta Chim.Sin.,2009,67:618(徐群杰,单贞华,朱律均等.聚天冬氨酸与钨酸钠复配对黄铜缓蚀作用的光电化学研究[J].化学学报,2009,67:618)
[18]Zha F L,Feng B,He T X.Corrosion behavior of copper grounding materials buried in soil at different depths[J].Mater.Prot.,2015,48(3):48(查方林,冯兵,何铁祥.不同埋地深度下铜质接地网材料的腐蚀特性[J].材料保护,2015,48(3):48)
[19]Pan Y,Zhang S P,Zhou J L,et al.Research progress of pitting corrosion initiation of metal materials[J].Equip.Environ.Eng.,2010,7(4):67(潘莹,张三平,周建龙等.金属材料点蚀形核过程研究进展[J].装备环境工程,2010,7(4):67)