Cerium Oxide Nanoparticles as an Accelerating Agent for Zinc Phosphate Coatings with Enhanced Corrosion Resistance

Document Type : Research Paper


Department of Engineering, Shahrekord University, Shahrekord, Iran


Cerium oxide (ceria, CeO2) is a biocompatible ceramic oxide with a wide range of applications as catalysts, fuel cell systems, and sensors. In the present study, CeO2 NPs were added to a zinc phosphate bath as an accelerator. The microstructural, morphological, and phase studies of coatings formed in the phosphating bath with and without CeO2 NPs, were performed by scanning electron microscopy (SEM), field emission-SEM (FE-SEM), and X-ray diffraction spectroscopy (EDS). Besides, the corrosion behavior of phosphate coatings containing 0, 0.04, 0.07, and 0.1 g/L of CeO2 NPs was evaluated using the Tafel polarization method and electrochemical impedance spectroscopy (EIS). The results showed significant differences in the microstructure, roughness, and phase structure of phosphate coatings with and without CeO2 NPs. The optimum addition of CeO2 NPs to the phosphating bath was equal to 0.07 g/L, in which, as compared to typical phosphate coating, the coating weight increased from 0.51 to 1.73 mg/cm2 while the corrosion current density decreased from 12.5 to 2.2 µA/cm2. Furthermore, the coating porosity decreased from 13.9 to 1.7 percent due to creating a denser coating with much better coverage by CeO2 NPs.


Main Subjects

[1] L. Niu, R. Guo, C. Tang, H. Guo, J. Chen, "Surface characterization and corrosion resistance of fluoferrite conversion coating on carbon steel" Surface and Coatings Technology, Vol.  300, 2016, pp. 110.
[2] C.-c. Jiang, Y.-k. Cao, G.-y. Xiao, R.-f. Zhu, Y.-p. Lu, "A review on the application of inorganic nanoparticles in chemical surface coatings on metallic substrates" RSC advances, Vol.  7, 2017, pp. 7531.
[3] O. Girčienė, R. Ramanauskas, L. Gudavičiūtė, A. Martušienė, "The effect of phosphate coatings on carbon steel protection from corrosion in a chloride-contaminated alkaline solution" J. of CHEMIJA, Vol.  24, 2013, pp. 251.
[4] B. Ramezanzadeh, M. Akbarian, M. Ramezanzadeh, M. Mahdavian, E. Alibakhshi, P. Kardar, "Corrosion protection of steel with zinc phosphate conversion coating and post-treatment by hybrid organic-inorganic sol-gel based silane film" Journal of The Electrochemical Society, Vol.  164, 2017, pp. C224.
[5] S. Eidivandi, B.S. Boroujeny, A. Dustmohammadi, E. Akbari, "The effect of surface mechanical attrition treatment (SMAT) time on the crystal structure and electrochemical behavior of phosphate coatings" Journal of Alloys and Compounds, Vol.  821, 2020, pp. 153252.
[6] C. Galvan-Reyes, J. Fuentes-Aceituno, A. Salinas-Rodríguez, "The role of alkalizing agent on the manganese phosphating of a high strength steel part 1: The individual effect of NaOH and NH4OH" Surface and Coatings Technology, Vol.  291, 2016, pp. 179.
[7] B. Ramezanzadeh, H. Vakili, R. Amini, "The effects of addition of poly (vinyl) alcohol (PVA) as a green corrosion inhibitor to the phosphate conversion coating on the anticorrosion and adhesion properties of the epoxy coating on the steel substrate" Applied Surface Science, Vol.  327, 2015, pp. 174.
[8] M. Morks, P. Corrigan, N. Birbilis, I. Cole, "A green MnMgZn phosphate coating for steel pipelines transporting CO2 rich fluids" Surface and Coatings Technology, Vol.  210, 2012, pp. 183.
[9] M. Farias, C. Santos, Z. Panossian, A. Sinatora, "Friction behavior of lubricated zinc phosphate coatings" Wear, Vol.  266, 2009, pp. 873.
[10] G. Parker, Encyclopedia of materials: science and technology, 2001.
[11] N. Bay, Metal forming and lubrication, Encyclopedia of Materials: Science and Technology, Elsevier2000, pp. 5377-5380.
[12] M. Fouladi, A. Amadeh, "Effect of phosphating time and temperature on microstructure and corrosion behavior of magnesium phosphate coating" Electrochimica Acta, Vol.  106, 2013, pp. 1.
[13] J. Popić, B. Jegdić, J. Bajat, Đ. Veljović, S. Stevanović, V. Mišković-Stanković, "The effect of deposition temperature on the surface coverage and morphology of iron-phosphate coatings on low carbon steel" Applied Surface Science, Vol.  257, 2011, pp. 10855.
[14] A. Valanezhad, K. Tsuru, M. Maruta, G. Kawachi, S. Matsuya, K. Ishikawa, "Zinc phosphate coating on 316L-type stainless steel using hydrothermal treatment" Surface and Coatings Technology, Vol.  205, 2010, pp. 2538.
[15] S. Jegannathan, T.S. Narayanan, K. Ravichandran, S. Rajeswari, "Formation of zinc phosphate coating by anodic electrochemical treatment" Surface and Coatings Technology, Vol.  200, 2006, pp. 6014.
[16] B.-i. LIN, J.-T. Lu, K. Gang, L. Jun, "Growth and corrosion resistance of molybdate modified zinc phosphate conversion coatings on hot-dip galvanized steel" Transactions of Nonferrous Metals Society of China, Vol.  17, 2007, pp. 755.
[17] T.S. Narayanan, S. Jegannathan, K. Ravichandran, "Corrosion resistance of phosphate coatings obtained by cathodic electrochemical treatment: Role of anode–graphite versus steel" Progress in organic coatings, Vol.  55, 2006, pp. 355.
[18] G. Li, L. Niu, J. Lian, Z. Jiang, "A black phosphate coating for C1008 steel" Surface and Coatings Technology, Vol.  176, 2004, pp. 215.
[19] M. Sheng, Y. Wang, Q. Zhong, H. Wu, Q. Zhou, H. Lin, "The effects of nano-SiO2 additive on the zinc phosphating of carbon steel" Surface and Coatings Technology, Vol.  205, 2011, pp. 3455.
[20] F. Fang, J.-h. Jiang, S.-Y. Tan, A.-b. Ma, J.-q. Jiang, "Characteristics of a fast low-temperature zinc phosphating coating accelerated by an ECO-friendly hydroxylamine sulfate" Surface and Coatings Technology, Vol.  204, 2010, pp. 2381.
[21] Y. Tian, W. Qiu, Y. Xie, H. Huang, J. Hu, L. Zhong, X. Jiang, X. Zhang, "Melatonin as an accelerating agent for phosphate chemical conversion coatings on mild steel with enhanced corrosion resistance" Journal of the Electrochemical Society, Vol., 2020, pp.
[22] C.-c. Jiang, R.-f. Zhu, G.-y. Xiao, Y.-z. Zheng, L.-l. Wang, Y.-p. Lu, "Effect of nano-SiO2 particles and sol on phosphate conversion coatings on 35CrMnSi steel" Journal of The Electrochemical Society, Vol.  163, 2016, pp. C571.
[23] X. Tan, F. Nan, Performance of Modified Nano-SiO2 Composite Phosphating Coating on the Surface of Steel, IOP Conference Series: Materials Science and Engineering, IOP Publishing, 2020, p. 012002.
[24] M. Tamilselvi, P. Kamaraj, M. Arthanareeswari, S. Devikala, J.A. Selvi, "Development of nano SiO2 incorporated nano zinc phosphate coatings on mild steel" Applied Surface Science, Vol.  332, 2015, pp. 12.
[25] S. Shibli, F. Chacko, "Development of nano TiO2-incorporated phosphate coatings on hot dip zinc surface for good paintability and corrosion resistance" Applied Surface Science, Vol.  257, 2011, pp. 3111.
[26] K. Mašek, J. Beran, V. Matolín, "RHEED study of the growth of cerium oxide on Cu (1 1 1)" Applied Surface Science, Vol.  259, 2012, pp. 34.
[27] T. Montini, M. Melchionna, M. Monai, P. Fornasiero, "Fundamentals and catalytic applications of CeO2-based materials" Chemical reviews, Vol.  116, 2016, pp. 5987.
[28] B.C. Nelson, M.E. Johnson, M.L. Walker, K.R. Riley, C.M. Sims, "Antioxidant cerium oxide nanoparticles in biology and medicine" Antioxidants, Vol.  5, 2016, pp. 15.
[29] C. Walkey, S. Das, S. Seal, J. Erlichman, K. Heckman, L. Ghibelli, E. Traversa, J.F. McGinnis, W.T. Self, "Catalytic properties and biomedical applications of cerium oxide nanoparticles" Environmental Science: Nano, Vol.  2, 2015, pp. 33.
[30] K.A. Ledwa, L. Kępiński, "Dispersion of ceria nanoparticles on γ-alumina surface functionalized using long chain carboxylic acids" Applied Surface Science, Vol.  400, 2017, pp. 212.
[31] S. Ranganatha, T. Venkatesha, K. Vathsala, "Electrochemical studies on Zn/nano-CeO2 electrodeposited composite coatings" Surface and Coatings Technology, Vol.  208, 2012, pp. 64.
[32] J. Huiming, S. Jiang, L. Zhang, "Structural characterization and corrosive property of Ni-P/CeO2 composite coating" Journal of Rare Earths, Vol.  27, 2009, pp. 109.
[33] W.-c. Sun, J.-M. Xu, Y. Wang, F. Guo, Z.-W. Jia, "Effect of Cerium Oxide on Morphologies and Electrochemical Properties of Ni-WP Coating on AZ91D Magnesium" Journal of Materials Engineering and Performance, Vol.  26, 2017, pp. 5753.
[34] L. Ecco, M. Fedel, A. Ahniyaz, F. Deflorian, "Influence of polyaniline and cerium oxide nanoparticles on the corrosion protection properties of alkyd coating" Progress in Organic Coatings, Vol.  77, 2014, pp. 2031.
[35] E. Banczek, P. Rodrigues, I. Costa, "The effects of niobium and nickel on the corrosion resistance of the zinc phosphate layers" Surface and Coatings Technology, Vol.  202, 2008, pp.
[36] N. Rezaee, M. Attar, B. Ramezanzadeh, "Studying corrosion performance, microstructure and adhesion properties of a room temperature zinc phosphate conversion coating containing Mn2+ on mild steel" Surface and Coatings Technology, Vol.  236, 2013, pp. 361.
[37] F. Saberi, B.S. Boroujeny, A. Doostmohamdi, A.R. Baboukani, M. Asadikiya, "Electrophoretic deposition kinetics and properties of ZrO2 nano coatings" Materials Chemistry and Physics, Vol.  213, 2018, pp. 444.
[38] A. Standard, "Zeta potential of colloids in water and waste water" ASTM Standard D, Vol., 1985, pp. 4187.
[39] A. KozŁowski, "Dry friction of manganese phosphate coatings on steel and cast iron" Electrodeposition and Surface Treatment, Vol.  2, 1974, pp. 109.
[40] K. Chandrasekaran, S.N. TS Nellaiappan, R. Kulandaivelu, M.H. Lee, "Improving the reactivity and receptivity of alloy and tool steels for phosphate conversion coatings: role of surface mechanical attrition treatment" Industrial & Engineering Chemistry Research, Vol.  53, 2014, pp. 20124.
[41] L. Qihai, L. Zili, Z. Xinhua, L. Cuijin, D. Jiao, "Hydrogen production by steam reforming of ethanol over copper doped Ni/CeO2 catalysts" Journal of Rare Earths, Vol.  29, 2011, pp. 872.
[42] R. Pérez-Hernández, Catalytic Ni/CeO 2 Nanorods and Ag/CeO 2 Nanotubes for Hydrogen Production by Methanol Reforming, Advanced Catalytic Materials: Current Status and Future Progress, Springer2019, pp. 167-190.
[43] M. Tamilselvi, P. Kamaraj, M. Arthanareeswari, S. Devikala, "Nano zinc phosphate coatings for enhanced corrosion resistance of mild steel" Applied Surface Science, Vol.  327, 2015, pp. 218.
[44] M. Manna, A. Shah, S. Kulkarni, "Development of phosphate coating on the surface of TMT rebar: an option to study the effect of n-SiO2 as an additive" Ironmaking & Steelmaking, Vol.  44, 2017, pp. 666.
[45] D.B. Freeman, phosphating and metal pre-treatment: a guide to modern processes and practice, Woodhead-Faulkner, Cambridge, 1986.
[46] R. De Levie, "The influence of surface roughness of solid electrodes on electrochemical measurements" Electrochimica Acta, Vol.  10, 1965, pp. 113.