Zirconium-Doped Ceria Nanoparticles as Anticorrosion Pigments in Waterborne Epoxy–Polymer Coatings

Cite this: ACS Appl. Nano Mater. 2021, 4, 1, 834–849
Publication Date (Web):December 22, 2020
Copyright © 2020 American Chemical Society
Article Views
Read OnlinePDF (10 MB)
Supporting Info (1)»


The use of anticorrosion pigments in polymeric coatings is an effective way for the prevention of corrosion of metals. Ceria nanoparticle-based pigments are excellent replacement for conventional chromate-based inhibitors that create severe toxicity and health hazards. The corrosion inhibition mechanism of ceria is associated with its Ce4+ ↔ Ce3+ redox shuttle and ability to form insoluble precipitates over the metallic substrate. Zirconium doping in ceria can enhance its redox properties by creating a large number of oxygen vacancies. However, corrosion inhibition properties of zirconium-doped ceria are not studied yet. In the present work, ceria–zirconia solid solutions (CexZr1–xO2 nanoparticles) with different doping concentrations of Zr have been prepared using coprecipitation synthesis. X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy studies revealed the formation of ceria–zirconia solid solutions with increased oxygen defect density. Thermogravimetric analysis exhibited enhanced oxygen storage capacity for Ce–Zr solid solutions. CexZr1–xO2 nanoparticle-filled waterborne epoxy resin coating has been prepared on a mild steel substrate using the spin-coating technique. Electrochemical corrosion measurements were employed to analyze the corrosion inhibition properties of the coatings. Tafel polarization results and electrochemical impedance spectroscopy analysis show excellent corrosion resistance for zirconium-doped ceria nanoparticle-filled epoxy coating. The corrosion resistance of the zirconium-doped ceria-epoxy coating increased with an increase in the doping concentration of Zr for Ce-rich Ce–Zr solid solutions (0.6 ≤ x ≤ 0.8). The corrosion inhibition property of ceria–zirconia solid solutions is attributed to the improvement in their redox properties due to a large number of oxygen vacancies.

Supporting Information

Jump To

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsanm.0c03162.

  • FE-SEM images, EDAX spectra, Williamson Hall plot, and TGA graph of CexZr1–xO2 nanoparticles; FE-SEM images, EDAX spectra and maps, Bode phase angle plot, and EIS equivalent circuit parameters for the coatings; and optical microscopy images of the corroded mild steel surface (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By

This article is cited by 4 publications.

  1. Edgar Andrés Chavarriaga, Tiago Bender Wermuth, Alex Arbey Lopera. Nanomaterials for Inorganic Pigments. 2022,,, 185-194. https://doi.org/10.1007/978-3-030-86901-4_11
  2. Ziyang Zhou, Xiaohong Ji, Sepideh Pourhashem, Jizhou Duan, Baorong Hou. Investigating the effects of g-C3N4/Graphene oxide nanohybrids on corrosion resistance of waterborne epoxy coatings. Composites Part A: Applied Science and Manufacturing 2021, 149 , 106568. https://doi.org/10.1016/j.compositesa.2021.106568
  3. Chenyang Zhang, Wen Li, Cong Liu, Chunfeng Zhang, Lin Cao, Debao Kong, Wei Wang, Shougang Chen. Effect of Covalent Organic Framework Modified Graphene Oxide on Anticorrosion and Self-healing Properties of Epoxy Resin Coatings. Journal of Colloid and Interface Science 2021, 320 https://doi.org/10.1016/j.jcis.2021.10.024
  4. Natthapong Pongpichayakul, Kanlayawat Wangkawong, Paralee Waenkaew, Li Fang, Burapat Inceesungvorn, Jaroon Jakmunee, Surin Saipanya. Pt electrodeposited on CeZrO4/MCNT as a new alternative catalyst for enhancement of ethanol oxidation. International Journal of Hydrogen Energy 2021, 46 (46) , 23682-23693. https://doi.org/10.1016/j.ijhydene.2021.04.168