杂质对高速镀锌层微观形貌及耐蚀性的影响
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摘要
硫酸盐镀锌液具有成分简单、电流效率高(接近100%)、沉积速度快等优点,常用于高速电镀。镀锌层在长期贮藏过程中表面出现黑色或茶褐色膜层的现象,称之为黑变。这种黑色膜层严重影响了钢板的外观质量。为了降低镀锌层的黑变影响并探讨镀锌层黑变的产生机理,本文对高速电镀锌工艺进行了优化,并通过加速腐蚀试验、金相显微观察、SEM微观形貌观察及X射线衍射等方法分别研究了静态和动态条件下镀液中杂质离子对镀层微观形貌,镀层结晶取向度以及镀层耐黑变性能的影响,同时研究了环境因素对镀层耐黑变性能的影响,并提出了缓解黑变的措施。
试验了在静态下,电流密度为15A/dm2时,镀层的耐黑变性能最强;杂质对镀层外观质量、微观形貌和耐黑变性能有负面影响,镀液对杂质的容忍范围为:铜离子0~1.0mg/L;镍离子0~400mg/L;铁离子0~800mg/L;铝离子对镀层的影响不大。
在动态下,镀层的结晶大小比静态时的要小很多,耐黑变性能也增强了。随着镀液流速和电流密度的增大,降低了浓差极化同时增大电化学极化,镀层结晶变得更加细致,耐黑变性能有所提高,晶面(002)、(004)择优取向度逐渐减小,其他晶面的择优取向度逐渐增大;其他工艺参数对镀层耐黑变性能影响相对较小,得出最佳工艺条件为:电流密度50A/dm~2、流速大于3.2m/s、Zn~(2+)浓度120g/L、温度40℃、pH为2.2。相对静态下,镀液对杂质的容忍范围变宽。
另外,在镀锌之前闪镀一层镍能够增强镀锌层耐黑变性能,并且当闪镀镍量为100mg/m2时,晶面(002)、(004)择优取向度最小,耐黑变性能最强,涂防锈油也具有较好的耐黑变作用。
Zinc sulphate electrolytes are used for continuous high speed plating on account of their simple ingredient, high current efficiency and quick deposition rate. When galvanized sheet steel is stored for a long time, a kind of black or brown film is formed on the surface. The phenomenon is went by the name of black patina. The black film seriously affects the appearance of surface. In this paper, high speed electrogalvanizing process is optimized and the influence of metallic impurities on the performances of coating, including black patina resistance, micromorphology and degree of orientation of crystal face, is researched by humid-hot-test, microscopicexamination and XRD analyses in static state and dynamic state respectively. It is to decrease degree of black patina and investigate the formation mechanism of black patina film. The influence of environmental factors on coating is researched and the measures which relieve black patina are proposed.
In static state, black patina resistance of coating is the best when current density is 15A/dm2. impurities affect the performances of coating, including appearance of surface, black patina resistance and micromorphology, negatively. The tolerant scopes of electrolyte to impurities are as follows: copper ion 0~1.0mg/L; nickel ion 0~400mg/L; iron ion 0~800mg/L; influence of aluminium ion on zinc electrowinning is neglectable.
When electrolyte is flowing, the crystal size of coating is smaller than coating’s in static state and black patina resistance is enhanced. Concentration polarization is decreasing and electrochemical polarization is increasing with increasing flow rate of solution and current density, at the same time, crystal size become smaller and black patina resistance is enhanced; degree of orientation of crystal face (002), (004) is decreased and other’s is increased gradually. The effect of other technological parameters on coating is less relatively. The best process condition is: current density (50A/dm2), flow rate (>3.2m/s), concentration of zinc ion (120g/L), temperature (40℃), pH(2.2). The tolerant scopes of electrolyte to impurities are wider than the scopes in static state.
Besides, nickel electroplating can enhance black patina resistance before zinc electrowinning, and when the quantity of nickel electroplating is 100mg/m2, degree of orientation of crystal face (002), (004) is least, black patina resistance is best. Painting pickling oil can also enhance black patina resistance.
试验了在静态下,电流密度为15A/dm2时,镀层的耐黑变性能最强;杂质对镀层外观质量、微观形貌和耐黑变性能有负面影响,镀液对杂质的容忍范围为:铜离子0~1.0mg/L;镍离子0~400mg/L;铁离子0~800mg/L;铝离子对镀层的影响不大。
在动态下,镀层的结晶大小比静态时的要小很多,耐黑变性能也增强了。随着镀液流速和电流密度的增大,降低了浓差极化同时增大电化学极化,镀层结晶变得更加细致,耐黑变性能有所提高,晶面(002)、(004)择优取向度逐渐减小,其他晶面的择优取向度逐渐增大;其他工艺参数对镀层耐黑变性能影响相对较小,得出最佳工艺条件为:电流密度50A/dm~2、流速大于3.2m/s、Zn~(2+)浓度120g/L、温度40℃、pH为2.2。相对静态下,镀液对杂质的容忍范围变宽。
另外,在镀锌之前闪镀一层镍能够增强镀锌层耐黑变性能,并且当闪镀镍量为100mg/m2时,晶面(002)、(004)择优取向度最小,耐黑变性能最强,涂防锈油也具有较好的耐黑变作用。
Zinc sulphate electrolytes are used for continuous high speed plating on account of their simple ingredient, high current efficiency and quick deposition rate. When galvanized sheet steel is stored for a long time, a kind of black or brown film is formed on the surface. The phenomenon is went by the name of black patina. The black film seriously affects the appearance of surface. In this paper, high speed electrogalvanizing process is optimized and the influence of metallic impurities on the performances of coating, including black patina resistance, micromorphology and degree of orientation of crystal face, is researched by humid-hot-test, microscopicexamination and XRD analyses in static state and dynamic state respectively. It is to decrease degree of black patina and investigate the formation mechanism of black patina film. The influence of environmental factors on coating is researched and the measures which relieve black patina are proposed.
In static state, black patina resistance of coating is the best when current density is 15A/dm2. impurities affect the performances of coating, including appearance of surface, black patina resistance and micromorphology, negatively. The tolerant scopes of electrolyte to impurities are as follows: copper ion 0~1.0mg/L; nickel ion 0~400mg/L; iron ion 0~800mg/L; influence of aluminium ion on zinc electrowinning is neglectable.
When electrolyte is flowing, the crystal size of coating is smaller than coating’s in static state and black patina resistance is enhanced. Concentration polarization is decreasing and electrochemical polarization is increasing with increasing flow rate of solution and current density, at the same time, crystal size become smaller and black patina resistance is enhanced; degree of orientation of crystal face (002), (004) is decreased and other’s is increased gradually. The effect of other technological parameters on coating is less relatively. The best process condition is: current density (50A/dm2), flow rate (>3.2m/s), concentration of zinc ion (120g/L), temperature (40℃), pH(2.2). The tolerant scopes of electrolyte to impurities are wider than the scopes in static state.
Besides, nickel electroplating can enhance black patina resistance before zinc electrowinning, and when the quantity of nickel electroplating is 100mg/m2, degree of orientation of crystal face (002), (004) is least, black patina resistance is best. Painting pickling oil can also enhance black patina resistance.
引文
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[3]俞钢强.中国镀锌工业的发展及对锌的需求[J].世界有色金属.1999.8:19-21
[4] M.Alfanzazi,D.B.Dreisinger.The role of zinc and sulfuric acid concentrations on zinc electrowinning from industrial sulfate based electrolyte[J].Journal of Applied Electrochemistry.2001.31:641-646
[5] B.C.Tripathy.Zinc electrowinning from acidic sulphate solutions Part IV: ffects of perfluorocarboxylic acids[J].Journal of Electroanalytical Chemistry.2004. 565:49-56
[6] V.Jiricny,A.Roy.Electrodeposition of Zinc from Sodium Zincate/Hydroxide ele- ctrolytes in a Spouted Bed Electrode[J].Metallurgical and Material Transaction. 2000.31:753-764
[7] R.Sekar.Characteristics of zinc electrodeposits from acetate solutions[J].Journal of Applied Electrochemistry.2006.36:591-597
[8] A.C.Scott,R.M.Pitblado.Experimental determination of the factor affecting zinc electrowinning efficiency[J].Journal of Applied electrochemistry.1985.15:953- 960
[9]罗耀宗.常见镀锌液性能比较[J].电镀与精饰,2003.25(2):20-21
[10]郑瑞庭.锌酸盐镀锌工艺中一些问题的探讨[J].电镀与涂饰.2001.20(3):65- 68
[11] S.Gurmen.A laboratory-scale investigation of alkaline zinc electrowinning[J]. Minerals engineering.2003.16:559-562
[12] A.E.Saba.Continuous electrowinning of zinc[J].Hydrometallurgy.2000.54:91- 106
[13] Y.F.YUAN.Effects of stannous ions on the electrochemical performance of the alkaline zinc electrode[J].Journal of Applied Electrochemistry.2007.37:249- 253
[14]尚书定.新型氯化钾镀锌工艺[J].电镀与精饰.2006.28(4):38-40
[15]任广军.电镀原理与工艺[M].第一版.沈阳:东北大学出版社.2001.71-80
[16] Alejandro recendiz.Current efficiency studies of the zinc electrowinning process on aluminum rotating cylinder electrode in sulfuric acid medium: Influence of different additives[J]. Electrochimica Acta.2007.52:6880-6887
[17]肖鑫,郭贤烙,易翔.光亮硫酸盐镀锌工艺研究[J].腐蚀与防护.2000.21(11): 498-501
[18] P.Guilume.Investigation of optimal conditions for zinc electrowinning from aqueous sulfuric acid electrolytes[J].Appl Electrochem.2007.37:1237-1243
[19]王孝镕,邹常诗,郭振良等.一种新的硫酸盐镀锌光亮剂的研制[J].表面技术.2003.32(3):46-48
[20] K.Raeissi,A.Saatchi.Texture and surface morphology in zinc electrodeposits[J]. Journal of Applied Electrochemistry.2004.34:1249-1258
[21]王远,安成强,郝建军.高速电镀锌研究现状[J].广西轻工业.2007.17(9):36-37
[22] R.Winand.Electrocrystallization: fundamental considerations and application to high current density continuous steel sheet plating[J]. Journal of Applied Elec- trochemistry.1991.21:377-385
[23] V.Jiricny,H.Choi,J.W.Evans.Zinc electrodeposit morphology under conditions of fluctuating current density[J].Journal of Applied Electrochemistry.1987.17: 91-103
[24] M.Karavasteva,S.Karaivanov.Electrowinning of zinc at high current density in the presence of some surfactants[J].Journal of Applied Electrochemisty.1993. 23:763-765
[25]李宁,武刚,黎德育等.采用明度法确定高速电镀锌工艺参数[J].材料科学与工艺.2001.9(4):420-423
[26]李宁,黎德育,朱晓东等.镀液流速对高速镀锌层粗糙度及织构的影响[J].电镀与环保.2005.25(4):12-17
[27]朱晓东,李宁,黎德育等.高速电镀锌工艺对镀层粗糙度及微观形貌的影响[J].中国有色金属学报.2005.15(1):146-152
[28]吴志良,任玉苓.高速电镀锌工艺实验及其镀层性能[J].宝钢技术.2001.1: 27-30
[29]朱晓东,李宁,黎德育等.高速电镀锌工艺对镀层粗糙度及织构的影响[J].电镀与环保.2004.24(4):14-16
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