Please wait a minute...
Just Accepted | Current Issue | Archive | Featured Articles | Special Issue | Most Read | Most Downloaded | Most Cited
Chinese Journal of Materials Research  2018, Vol. 32 Issue (8): 607-615    DOI: 10.11901/1005.3093.2017.372
ARTICLES Current Issue | Archive | Adv Search |
Effect of Different Molar Ratio of SiO2 to Na2O on Silicate Conversion Film Prepared on Hot-dip Zn-5%Al Coating
Lu XU, Chunshan CHE(), Gang KONG, Yanqi WANG, Zujun CAO
School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China
Cite this article: 

Lu XU, Chunshan CHE, Gang KONG, Yanqi WANG, Zujun CAO. Effect of Different Molar Ratio of SiO2 to Na2O on Silicate Conversion Film Prepared on Hot-dip Zn-5%Al Coating. Chinese Journal of Materials Research, 2018, 32(8): 607-615.

Download:  HTML  PDF(4269KB) 
Export:  BibTeX | EndNote (RIS)      
Abstract  

Silicate conversion film was prepared on Zn-5%Al hot dip galvanized Q235 steel by dipping in sodium silicate solution with different molar ratio of SiO2 to Na2O in the range of 1.0-4.5. The surface morphology and microstructure, as well as the corrosion resistance of the conversion film were characterized by scanning electron microscopy (SEM) with energy dispersive spectrometer (EDS), transmission infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS), as well as electrochemical impedance spectroscopy (EIS). The results show that in the solution of molar ratio 4.0, the prepared film is uniform and smooth with the highest electrochemical impedance up to 204.22 kΩ?cm2. However, the film formed in the solution of molar ratio 2.0 exhibits a large number of cracks, which presents the lowest corrosion performance. The silicate conversion film consists of zinc silicate, aluminosilicate, silicon dioxide, aluminum oxide/hydroxide and zinc oxide/hydroxide. Finally, the formation mechanism of silicate conversion film on the Zn-5%Al hot dip galvanized steel was also discussed.
Key words:  surface and interface in the materials      hot-dip Zn-5%Al      conversion film      silicate      corrosion resistance     
Received:  31 August 2017     
ZTFLH:  TB304  
  TG174  
Fund: Supported by National Natural Science Foundation of China (Nos. 21573077 & 51373055), and International Lead and Zinc Study Group (No. ILZRO/IZA//CN201212)
Service
E-mail this article
Add to citation manager
E-mail Alert
RSS
（）
Articles by authors
Lu XU
Chunshan CHE
Gang KONG
Yanqi WANG
Zujun CAO

URL: 

https://www.cjmr.org/EN/10.11901/1005.3093.2017.372     OR     https://www.cjmr.org/EN/Y2018/V32/I8/607

Fig.1  SEM images of Zn-5%Al (a) and silicate coatings on M2 (b) and M4 (c)
Analytic area Morphology Zn/% Al/% O/% Si/%
1 swell 72.11 4.20 18.49 5.20
2 the edge of crack 66.71 4.19 23.31 5.79
3 crack 90.58 3.79 4.31 1.32
4 flat 86.63 4.27 7.02 2.09
5 swell 85.84 5.23 7.37 1.56
6 flat 89.75 4.99 4.37 0.89
7 flat 91.20 4.28 4.52 -
Table 1  EDS analysis of the area in Fig.1
Fig.2  XPS spectrum of the surface of the silicate conversion coating on M2 (a) and M4 (b)
Fig.3  High resolution spectra of Na1s (a), O1s (b), Si2p (c) on M2 and Na1s (d), O1s (e), Si2p (f), Al2p (g), Zn2p (h) on M4
Fig.4  FT-IR spectra of silicate coating sample of M2 and M4
Fig.5  EIS of Zn-5%Al and the silicate coating samples with different SiO2:Na2O molar ration in 5%NaCl solution (a) Nyquist plots, (b) local amplification of Fig.5a and (c, d) bode diagrams
Fig.6  Electrical circuit used to fit the EIS results of the Zn-5%Al and silicate coating samples
Sample Rs/kΩcm2 R1/kΩcm2 CPE1 R2/kΩcm2 CPE2
Y1/10-6Ω-1cm-2s-n n1 Y2/10-5Ω-1cm-2s-n n2
Zn-5%Al 1.16 0.49 8.13 0.88 4.66 46.71 0.60
M=2.0 0.72 0.34 77.18 0.75 1.36 24.31 0.69
M=3.0 0.42 8.45 17.58 0.84 16.28 6.36 0.69
M=3.5 1.16 32.38 6.13 0.91 45.19 2.80 0.82
M=4.0 5.38 204.22 6.61 0.91 - - -
M=4.5 15.49 0.96 5.86 0.66 9.42 42.90 0.61
Table 2  Values of the elements related to Zn-5%Al and the silicate coatings, determined from the fit to mode of Fig.6
[1] Liang Y L, Wang Z B, Zhang J B, et al.Formation of interfacial compounds and the effects on stripping behaviors of a cold-sprayed Zn-Al coating on interstitial-free steel[J]. Appl. Surf. Sci., 2015, 340: 89
[2] Liu Z, Li R, Jiang R, et al.Effects of Al addition on the structure and mechanical properties of Zn alloys[J]. J. Alloys Compd., 2016, 687:885.
[3] Wang Y Q, Kong G, Che C S.Corrosion behavior of Zn-Al alloys in saturated Ca(OH)2 solution[J]. Corros. Sci., 2016, 112: 679
[4] Prosek T, Hagstr?m J, Dan P, et al.Effect of the microstructure of Zn-Al and Zn-Al-Mg model alloys on corrosion stability[J]. Corros. Sci., 2016, 110: 71
[5] Shen T H, Tsai C Y, Lin C S.Growth behavior and properties of Zn-Al pack cementation coatings on carbon steels[J]. Surf. Coat. Technol., 2016, 306: 455
[6] Cao Z J, Kong G, Che C S.Effect of Nd addition on microstructure and corrosion resistance of Zn-5%Al alloy[J]. Chin. J. Nonferrous. Met., 2017(01): 24(曹祖军, 孔纲, 车淳山. 稀土Nd对Zn-5%Al合金显微组织和耐蚀性的影响[J].中国有色金属学报, 2017(01): 24)
[7] Kato T, Nunome K, Kaneko K, et al.Formation of the ζ phase at an interface between an Fe substrate and a molten 0.2 mass% Al-Zn during galvannealing[J]. Acta Mater., 2000, 48(9): 2257
[8] Elechower M, Kli J, Augustyn E, et al.The Microstructure of Annealed Galfan Coating on Steel Substrate[J]. Arch. Metall. Mater., 2012, 57(2): 517
[9] Wu X X, Kong G, Sun Z W, et al.Preparation and corrosion performance of lanthanum nitrate conversion coating on hot-dip galfan steel[J]. Chin. J. Mater. Res., 2016(04): 269(吴晓晓, 孔纲, 孙子文等.热浸镀Galfan表面镧盐转化膜的生长和耐腐蚀性能的研究[J].材料研究学报, 2016(04): 269)
[10] Golabadi M, Aliofkhazraei M, Toorani M, et al.Corrosion and cathodic disbondment resistance of epoxy coating on zinc phosphate conversion coating containing Ni2+ and Co2+ [J]. J. Ind. and Eng.Chem., and Eng. Chem., 2016, 47: 154
[11] Zhang S H, Kong G, Sun Z W, et al.Effect of formulation of silica-based solution on corrosion resistance of silicate coating on hot-dip galvanized steel[J]. Surf. Interface Anal., 2016, 48(3): 132
[12] Ramanauskas R, Gir?ien? O, Gudavi?iūt? L, et al.The interaction of phosphate coatings on a carbon steel surface with a sodium nitrite and silicate solution[J]. Appl. Surf. Sci., 2015, 327: 131
[13] Xu Q Y, Wang H X, Jiang R.Formation and corrosion resistance of titanium containing conversion film on hot-dip galvanized steel[J]. Chin. J. Mater. Res., 2014(07): 521(许乔瑜, 王海霞, 姜瑞. 热浸镀锌层钛盐转化膜的制备和耐蚀性能[J]. 材料研究学报, 2014(07): 521)
[14] Pommiers S, Frayret J, Castetbon A, et al.Alternative conversion coatings to chromate for the protection of magnesium alloys[J]. Corros. Sci., 2014, 84(8): 135
[15] Gupta R K, Mensah-Darkwa K, Kumar D.Effect of Post Heat Treatment on Corrosion Resistance of Phytic Acid Conversion Coated Magnesium[J]. J. Mater. Sci., Technol. 2013, 29(2): 180
[16] Hamlaoui Y, Tifouti L, Pedraza F.Corrosion behaviour of molybdate-phosphate-silicate coatings on galvanized steel[J]. Corros. Sci., 2009, 51(10): 2455
[17] Jiang L, Wolpers M, Volovitch P, et al.An atomic emission spectroelectrochemical study of passive film formation and dissolution on galvanized steel treated with silicate conversion coatings[J]. Surf. Coat. Technol., 2012, 206(13): 3151
[18] Yuan M, Lu J, Kong G, et al.Effect of silicate anion distribution in sodium silicate solution on silicate conversion coatings of hot-dip galvanized steels[J]. Surf. Coat. Technol., 2011, 205(19): 4466
[19] Yuan M, Lu J, Kong G.Effect of SiO2:Na2O molar ratio of sodium silicate on the corrosion resistance of silicate conversion coatings[J]. Surf. Coat. Technol., 2010, 204(8): 1229
[20] Yuan M, Lu J, Kong G, et al.Self healing ability of silicate conversion coatings on hot dip galvanized steels[J]. Surf. Coat. Technol., 2011, 205(19): 4507
[21] Kazemi M, Danaee I, Zaarei D.Deposition and corrosion behavior of silicate conversion coatings on aluminum alloy 2024[J]. Materialwiss. Werkstofftech., 2014, 45(7): 574
[22] Kazemi M, Danaee I, Zaarei D.The effect of pre-anodizing on corrosion behavior of silicate conversion coating on AA2024[J]. Mater. Chem. Phys., 2014, 148(1-2): 223
[23] Kim H, Jang J.Infrared spectroscopic study of SiOx film formation and decomposition of vinyl silane derivative by heat treatment. II. on copper surface[J]. J. Appl. Polym. Sci., 1998, 68: 785
[24] Labbe J P, Pagetti J.Study of an inhibiting aluminosilicate interface by infrared reflection spectroscopy[J]. Thin Solid Films., 1981, 82(1): 113
[25] Yuan M R.Silicate conversion coatings on hot-dip galvanized steel [D]. South China University of Technology, 2011(袁美蓉. 热浸镀锌层表面硅酸盐转化膜的研究[D]. 华南理工大学, 2011)
[26] Wu Z F, Li S J.Infrared spectra characteristics of zinc hydroxide and zinc oxide[J]. Chin. J. spectrosc. Lab., 2012, 29(4): 2172(武志富, 李素娟. 氢氧化锌和氧化锌的红外光谱特征[J]. 光谱实验室, 2012, 29(4): 2172)
[27] Gaggiano R, Moriamé P, Biesemans M, et al.Mechanism of formation of silicate thin films on porous anodic alumina[J]. Surf. Coat. Technol., 2011, 205(21-22): 5210
[28] Beverskog B, Puigdomenech I.Revised pourbaix diagrams for zinc at 25-300℃[J]. Corros Sci., 1997, 39(1): 107
[29] Yang Z H, Xu N, Qiu Z X.Measurement of aluminum corrosive potential-pH and the polarization curve[J].J. Northeast. Univ., 2000(04): 401(杨振海, 徐宁, 邱竹贤. 铝的电位-pH图及铝腐蚀曲线的测定[J].东北大学学报, 2000(04): 401)
[30] Xu H,Van Deventer J S J. The geopolymerisation of alumino-silicate minerals[J]. Int. J. Miner. Process., 2000, 59(3): 247
[31] Swaddle T W, Salerno J, Tregloan P A.Aqueous aluminates, silicates, and aluminosilicates[J]. Chem. Soc. Rev., 1994, 23(5): 319
[32] Vu T N, Volovitch P, Ogle K.The effect of pH on the selective dissolution of Zn and Al from Zn-Al coatings on steel[J]. Corros Sci., 2013, 67: 42
[33] Nordstr?m J, Sundblom A, Jensen G V, et al.Silica/alkali ratio dependence of the microscopic structure of sodium silicate solutions[J]. J. Colloid Interface Sci., 2013, 397: 9
[1] WANG Qian, PU Lei, JIA Caixia, LI Zhixin, LI Jun. Inhomogeneity of Interface Modification of Carbon Fiber/Epoxy Composites[J]. 材料研究学报, 2023, 37(9): 668-674.
[2] LU Yimin, MA Lifang, WANG Hai, XI Lin, XU Manman, YANG Chunlai. Carbon-base Protective Coating Grown by Pulsed Laser Deposition on Copper Substrate[J]. 材料研究学报, 2023, 37(9): 706-712.
[3] FENG Ye, CHEN Zhiyong, JIANG Sumeng, GONG Jun, SHAN Yiyin, LIU Jianrong, WANG Qingjiang. Effect of a NiCrAlSiY Coating on Cyclic Oxidation and Room Temperature Tensile Properties of Ti65 Alloy Plate[J]. 材料研究学报, 2023, 37(7): 523-534.
[4] LI Pengyu, LIU Zitong, KANG Shumei, CHEN Shanshan. Effect of Plasma Treatment on Performance of Polybutylene Adipate Coating on Biomedical AZ31 Mg-alloy[J]. 材料研究学报, 2023, 37(4): 271-280.
[5] LIAO Hongyu, JIA Yongxin, SU Ruiming, LI Guanglong, QU Yingdong, LI Rongde. Effect of Retrogression Times on Microstructure and Corrosion Resistance of 2024 Aluminum Alloy[J]. 材料研究学报, 2023, 37(4): 264-270.
[6] CHEN Kaiwang, ZHANG Penglin, LI Shuwang, NIU Xianming, HU Chunlian. High-temperature Tribological Properties for Plasma Spraying Coating of Ni-P Plated Mullite Powders[J]. 材料研究学报, 2023, 37(1): 39-46.
[7] SHAN Weiyao, WANG Yongli, LI Jing, XIONG Liangyin, DU Xiaoming, LIU Shi. High Temperature Oxidation Resistance of Cr Based Coating on Zirconium Alloy[J]. 材料研究学报, 2022, 36(9): 699-705.
[8] CHEN Jie, LI Hongying, ZHOU Wenhao, ZHANG Qingxue, TANG Wei, LIU Dan. Effect of Heat Input on Low Temperature Toughness and Corrosion Resistance of Q1100 Steel Welded Joints[J]. 材料研究学报, 2022, 36(8): 617-627.
[9] ZHANG Hongliang, ZHAO Guoqing, OU Junfei, Amirfazli Alidad. Superhydrophobic Cotton Fabric Based on Polydopamine via Simple One-Pot Immersion for Oil Water Separation[J]. 材料研究学报, 2022, 36(2): 114-122.
[10] LI Yufeng, ZHANG Nianfei, LIU Lishuang, ZHAO Tiantian, GAO Wenbo, GAO Xiaohui. Preparation of Phosphorus-containing Graphene and Corrosion Resistance of Composite Coating[J]. 材料研究学报, 2022, 36(12): 933-944.
[11] CUI Li, SUN Lili, GUO Peng, MA Xin, WANG Shuyuan, WANG Aiying. Effect of Deposition Time on Structure and Performance of Diamond-like Carbon Films on PEEK[J]. 材料研究学报, 2022, 36(11): 801-810.
[12] LI Jianzhong, ZHU Boxuan, WANG Zhenyu, ZHAO Jing, FAN Lianhui, YANG Ke. Preparation and Properties of Copper-carrying Polydopamine Coating on Ureteral Stent[J]. 材料研究学报, 2022, 36(10): 721-729.
[13] LI Rui, WANG Hao, ZHANG Tiangang, NIU Wei. Microstructure and Properties of Laser Clad Ti2Ni+TiC+Al2O3+CrxSy Composite Coating on Ti811 Alloy[J]. 材料研究学报, 2022, 36(1): 62-72.
[14] LI Xiuxian, QIU Wanqi, JIAO Dongling, ZHONG Xichun, LIU Zhongwu. Promotion Effect of α-Al2O3 Seeds on Low-temperature Deposition of α-Al2O3 Films by Reactive Sputtering[J]. 材料研究学报, 2022, 36(1): 8-12.
[15] WANG Peng, LU Xilong, CAO Chun-e, CHEN Yunxia, SHEN Huarong, ZHANG Xu. Influence of Nucleation-growth Liquid-liquid Phase Partition on Properties of Lead-free Low Temperature Frit[J]. 材料研究学报, 2021, 35(9): 657-666.
No Suggested Reading articles found!

Copyright © 2017 Acta Metallurgica Sinica, All Rights Reserved.
Editorial Office: Acta Metallurgica Sinica, 72 Wenhua Rd., Shenyang 110016, China
Tel: +86- 024-23971286, Fax: +86-024-23843760 　E-mail: jsxb@imr.ac.cn
Powered by Beijing Magtech