镀锌层的硅酸盐无铬钝化研究
摘要
为了减少电镀业使用铬酸盐所造成的环境污染,本文研究了用于碱性镀锌层蓝白钝化的新型无铬钝化液工艺配方。该钝化液以硅酸盐为主要原料,并含有双氧水和氟离子等物质。采用正交优化与单因素优化相结合的方法,讨论硅酸盐型钝化液各组分对镀锌层钝化膜的影响。并且对镀锌硅酸盐钝化工艺技术进行了系统的研究,讨论了钝化液成分、钝化温度、钝化时间、钝化液pH值、空停时间、活化时间、出光时间对钝化成膜及膜层耐蚀性的影响。钝化液的组成及工艺条件为：
Na2Si03·9H2 18g/L
HNO3 15ml/L
ZnSO4·7H2O 28 g/L
NaF 2.4g/L
H2O2 10ml/L
钝化时间20s
pH值2-3
钝化温度25℃
空停时间0-1s
活化时问25s
出光时间5s
干燥条件热风吹干
实验材料为碱性电镀锌钢板,用上述溶液钝化后,通过中性盐雾试验(NSS试验),硫酸铜点滴试验,盐水浸泡试验及电化学测试等方法对该硅酸盐钝化样品的耐蚀性进行了研究,并通过扫描电镜及XPS对钝化膜进行表征。
研究表明,该硅酸盐钝化工艺可在镀锌层表面得到光泽度好、耐蚀性高的蓝白色钝化膜,可代替传统铬盐钝化工艺从而解决其环境污染问题,具有良好的应用前景。
In order to reduce the environmental pollution caused by the electroplating industry in use of chromate salt, this paper studies a novel chromium-free passivating liquid technological formulation used for bright blue passivation of alkaline galvanized layer. This passivating liquid takes silicate as main raw materials and contains substances such as hydrogen peroxide, fluorin ion and others. Using the method of combining orthogonal optimization and single factor optimization, the impact of all the components of Silicate type passivation liquid upon galvanized layer passivation membrane is discussed. Besides, the systematic research on galvanized silicate passivation technology is carried on, and the impact of passivation solution composition, passivation temperature, passivation time, passivation solution pH value, time of pause, Activation time, glaring time upon the passivation membrane and membrane layer noncorrodibility. Passivation solution composition and process conditions is as the followed:
Na2SiO3·9H2O 18g/L
HNO3 15ml/L
ZnSO4·7H2O 28 g/L
NaF 2.4 g/L
H2O2 10ml/L
Passivation Time 20 s
pH Value 2-3
Passivation temperature 25℃
Time of pause 0-1 s
Activation time 25 s
Glaring time 5 s
Dry conditions Blowing dry
with Hot air
Experimental material is an alkaline electricity galvanized steel plate. After the above mentioned solution is passivated,the noncorrodibility of this silicate passivation samples has been researched by way of neutral salt spray test(NSS test), acid copper dropping test, salt water immersion test and electrochemical test, etc. and the passivation membrane is characterized by scanning electron microscope and XPS.
The research shows that by this silicate passivation technology bright blue passivation membrane with good gloss and high noncorrodibility can be acquired in the surface of galvanized layer, which can replace traditional chrome salt passivation technology so as to solve the problem of environmental pollution, and has good application prospect.
Na2Si03·9H2 18g/L
HNO3 15ml/L
ZnSO4·7H2O 28 g/L
NaF 2.4g/L
H2O2 10ml/L
钝化时间20s
pH值2-3
钝化温度25℃
空停时间0-1s
活化时问25s
出光时间5s
干燥条件热风吹干
实验材料为碱性电镀锌钢板,用上述溶液钝化后,通过中性盐雾试验(NSS试验),硫酸铜点滴试验,盐水浸泡试验及电化学测试等方法对该硅酸盐钝化样品的耐蚀性进行了研究,并通过扫描电镜及XPS对钝化膜进行表征。
研究表明,该硅酸盐钝化工艺可在镀锌层表面得到光泽度好、耐蚀性高的蓝白色钝化膜,可代替传统铬盐钝化工艺从而解决其环境污染问题,具有良好的应用前景。
In order to reduce the environmental pollution caused by the electroplating industry in use of chromate salt, this paper studies a novel chromium-free passivating liquid technological formulation used for bright blue passivation of alkaline galvanized layer. This passivating liquid takes silicate as main raw materials and contains substances such as hydrogen peroxide, fluorin ion and others. Using the method of combining orthogonal optimization and single factor optimization, the impact of all the components of Silicate type passivation liquid upon galvanized layer passivation membrane is discussed. Besides, the systematic research on galvanized silicate passivation technology is carried on, and the impact of passivation solution composition, passivation temperature, passivation time, passivation solution pH value, time of pause, Activation time, glaring time upon the passivation membrane and membrane layer noncorrodibility. Passivation solution composition and process conditions is as the followed:
Na2SiO3·9H2O 18g/L
HNO3 15ml/L
ZnSO4·7H2O 28 g/L
NaF 2.4 g/L
H2O2 10ml/L
Passivation Time 20 s
pH Value 2-3
Passivation temperature 25℃
Time of pause 0-1 s
Activation time 25 s
Glaring time 5 s
Dry conditions Blowing dry
with Hot air
Experimental material is an alkaline electricity galvanized steel plate. After the above mentioned solution is passivated,the noncorrodibility of this silicate passivation samples has been researched by way of neutral salt spray test(NSS test), acid copper dropping test, salt water immersion test and electrochemical test, etc. and the passivation membrane is characterized by scanning electron microscope and XPS.
The research shows that by this silicate passivation technology bright blue passivation membrane with good gloss and high noncorrodibility can be acquired in the surface of galvanized layer, which can replace traditional chrome salt passivation technology so as to solve the problem of environmental pollution, and has good application prospect.
引文
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[4]石磊,于登文,王清,王士磊.镀锌层蓝白钝化工艺泛彩故障的防治[J].材料保护.2003,36(4).
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[7]孔纲,卢锦堂,车淳山,等.热镀锌钢白锈产生原因分析及预防[J].腐蚀与防护,2005,26(10)：450-452.
[8]莫耀忠.电镀锌层白色腐蚀现象的腐蚀机理[J].表面技术,1994,23(3)：139-141.
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[11]周金保.镀锌层无铬钝化工艺的新进展[J].电镀与环保,1991,12(1)：33-35.
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[13]韩克平,叶向荣,方景礼.镀锌层表面硅酸盐防腐膜的研究[J],腐蚀科学与防护技术,1997,9(20)：167-170.
[14]李广超.硫脲对镀锌层硅酸盐钝化作用的影响[J].电镀与涂饰,2007,26(1)：10.
[15]李广超.镀锌层硅酸盐钝化工艺研究[J],电镀与精饰,2007,39(2)：31-33.
[16]Dalbin S,Maurin G,Nogueira R P. Silica-based coating for corrosion p rotection of electrogalvanized steel [J]. Surface & Coatings Technology,2005, (194):363.
[17]Dikinis V, Niaura G, Rezaite V, et al. Formation of conversion silicate films on Zn and their p roperties [J].Transactions of the Institute of Metal Finishing,2007,85 (2):87-93.
[18]满瑞林,梁永煌,彭天兰等.镀锌钢板表面无铬钝化研究进展[J],河南化工,2008,25：6-10.
[19]安成强,郝建军,牟世辉.镀锌钢板无铬钝化技术的发展[J],表面技术,2003,32(2)：6-8.
[20]Wilcox G D,Gabe D R. Chemicalm olybatec onversiont eratments for zinc[J]. Metal Finishing,1988,86(9):71-74.
[21]L. Thiery, N. Pommier, Hexavalent Chromate-free Passivation Treatments in the Automotiv industry, Coventya SAS 51 rue Pierre[P],Clichy-France,92111,2004.
[22]T Peter, Tang etc., To Chromating 2L9 iL2 Molybdate-Based Alternatives W As a Passivation Treatment for Zinc[J]. Plating and Surface Finishing.1994,21(11):20-23.
[23]Wilcox GD, Wharton J A, A Review of Chromate-Free Passivation Treatments for Zinc and Zinc Alloys[J], Trans IMF,1997,75(6):131-140.
[24]Tang P T, Bech-Nielsen G, Moller P M. Molybdate based altenraitves to chromating as a passivaiton treatment for zinc[J]. Plating and Surface Finishing,1994,81 (11):20-23.
[25]Tang P T, Bech-Nielsen G Moller P M. Molybdate based passivation of zinc[J].Transacitons of the Institute of Metal Finishing,1997,75 (4):144-148.
[26]Bech-Nielsen G, Tang P T.A method for post-treatment of an article with a metallic surface as well as a treatment solution to be used in the mehtdo [P].US:560721,1997.
[27]刘小虹,颜肖慈.镀锌层钼酸盐转化摸及其耐蚀机理[J],电镀与环保,2002,22(11)：17-20.
[28]肖鑫,龙有前,钟萍.镀锌层钼酸盐-氟化锆体系钝化工艺研究[J],腐蚀科学与防护技术,2005,17(3)：184-186.
[29]Kurosawa K, Fukushima T, Effects of pH of a Na2Mo4-H3PO4 type aqueous solution on the formation of chemical conversion coatings no steels[J]. Corrosion Science,1989,29 (9):1103-111.
[30]方景礼,刘琴,韩克平,等.不锈钢上蓝色铝酸盐转化膜的研究[J].材料保护,1995,28(5)：3-5.
[31]Wilcox G D, Gabe D R. Passivation studies using group.VIA anions. V cathodic treatment of zinc[J]. British Corrosion Jounral,1987,22 (4):254-258.
[32]韩克平,方景礼.用XPS和AES研究锌表面彩色防腐蚀膜明[J].中国腐蚀与防护学报,1997,7(1)：41-50.
[33]吴海江,陈锦虹,卢锦堂.镀锌层无铬钝化耐蚀机理的研究进展[J],材料保护,2004,37(3)：43.
[34]C.G. da, Silva etc., Study of conversion coatings obtained from tungstate-phosphoric acid solutions[J],Corrosion Science,2005,47(5):709-722.
[35]Cowicson D R, Scholefield A R. Passivation of tin-zinc alloy coated steel[J],Trans IMF,1985,63(2):56-58.
[36]Bijimi D, Gabe D R. Passivation Studies Using Group VIA Anions Anodic Treatment of Zinc[J],British Corrosion Journal,1983,18(3):138-140.
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