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Journal of Chinese Society for Corrosion and protection  2025, Vol. 45 Issue (3): 664-674    DOI: 10.11902/1005.4537.2024.150
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Preparation of CeO2@Zr-MOF Composites and Their Effect on Corrosion Protectiveness of Epoxy Coatings on Galvanized Steel Plate
CHEN Lijuan1, CHAO Liuwei2, ZHAO Jingmao2()
1.Beijing Engineering Branch, China Petroleum Engineering & Construction Co., Ltd., Beijing 100085, China
2.College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Cite this article: 

CHEN Lijuan, CHAO Liuwei, ZHAO Jingmao. Preparation of CeO2@Zr-MOF Composites and Their Effect on Corrosion Protectiveness of Epoxy Coatings on Galvanized Steel Plate. Journal of Chinese Society for Corrosion and protection, 2025, 45(3): 664-674.

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Abstract  

In this study, CeO2 was synthesized on zirconium metal oxide skeleton (Zr-MOF) material by hydrothermal synthesis with Ce(NO3)3 as cerium source, ammonia as precipitant, and ethylene glycol as dispersant. The micro-morphology, structureand chemical composition of the composites were characterized by means of scanning electron microscope, transmission electron microscope, X-ray diffractometer, FTIR spectroscopy, X-ray photoelectron spectroscopy, and specific surface area analyzer. Then, as a filler, different amount of CeO2@Zr-MOF was mixed with epoxy resin to prepare variouse CeO2@Zr-MOF-epoxy rein coatings on galvanized steel plate. Afterwards, the effect of CeO2@Zr-MOF on the protectiveness, mechanical properties and hydrophobicityof the CeO2@Zr-MOF coatings were investigated via electrochemical test, salt spray test, hardness test, adhesion test, and contact angle test etc. The results show that CeO2 particles were successfully deposited on the surface of Zr-MOF, while the prepared CeO2@Zr-MOF has a regular morphology with CeO2 particles of mean diameter 200 nm uniformly distributed on the surface, which presents a uniform and dense porous structure with pore size ranging 5-20 nm, and average specific surface area of 99.48 m2/g; The hardness of the epoxy resin coating with CeO2@Zr-MOF is about 11HV, which is about 111% higher than that of pure epoxy resin coating. The adhesion of the coating is about 3 MPa, which is about 18% higher than that of the pure epoxy resin coating, and the contact angle is about 70º for water, which is 12°-14° higher than that of the pure epoxy resin coating; The anticorrosive performance of CeO2@Zr-MOF epoxy resin coating is significantly better than that of pure epoxy resin coating. Among them, the impedance modulus value of the epoxy resin coating with 1%CeO2@Zr-MOF is 5.49 × 1010 Ω·cm2 at frequency 0.01 Hz after 60 d of immersion in 3.5% NaCl solution, which is three orders of magnitude higher than that of the pure epoxy resin coating. Furthermore after 400 h of salt spray test, the coating is almost no signs of corrosion, showing better protectiveness for galvanized steel plate
Key words:  Zr-MOF      CeO2      organic coating      ZMA coated steel      corrosion and protection     
Received:  14 May 2024      32134.14.1005.4537.2024.150
ZTFLH:  TG174.4  
Fund: National Natural Science Foundation of China(52371046)
Corresponding Authors:  ZHAO Jingmao, E-mail: jingmaozhao@126.com
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CHEN Lijuan
CHAO Liuwei
ZHAO Jingmao

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https://www.jcscp.org/EN/10.11902/1005.4537.2024.150     OR     https://www.jcscp.org/EN/Y2025/V45/I3/664

Fig.1  Schematic flow diagram of the preparation of Zr-MOF
Fig.2  Schematic flow diagram of the preparation of CeO2@Zr-MOF
Fig.3  SEM images of CeO2@Zr-MOF in different magnification: (a) low image, (b) high image
Fig.4  TEM images of CeO2@Zr-MOFin different magnification(a-d) and TEM-EDS results of CeO2@Zr-MOF (e-h): (e) carbon, (f) oxygen, (g) zirconium, (h) cerium
Fig.5  XRD pattern of CeO2@Zr-MOF
Fig.6  FTIR spectrum of MOF and CeO2@Zr-MOF
Fig.7  XPS spectrum of CeO2@Zr-MOF material (a), Zr 3d high-resolution XPS spectrum of CeO2@Zr-MOF material (b) and Ce 3d (c)
Fig.8  Nitrogen adsorption-desorption curve for CeO2@Zr-MOF
Fig.9  Chemical structural formula of Zr-MOF[18]
Fig.10  Hardness of epoxy coatings after adding different ratios of CeO2@Zr-MOF
Fig.11  Adhesion strengths of CeO2@Zr-MOF epoxy coatings with different ratios on zinc-magnesium-aluminum steel substrate
Fig.12  Results of contact angle tests of epoxy coatings with different ratios of CeO2@Zr-MOF
Fig.13  EIS test results of CeO2@Zr-MOF epoxy coatings with different additions: (a1-a3) EP, (b1-b3) 0.5%CeO2@Zr-MOF/EP, (c1-c3) 1%CeO2@Zr-MOF/EP, (d1-d3) 2%CeO2@Zr-MOF/EP
Fig.14  Equivalent circuit diagram for CeO2@Zr-MOF epoxy coating
SamplesTime / dCPEcRc / Ω·cm2Cc / F·cm2CPEdlRct / Ω·cm2Cc / F·cm2
Y1 / Ω-1·cm-2·s nn1Y2 / Ω-1·cm-2·s nn2
EP07.00 × 10-1114.24 × 1087.00 × 10-111.34 × 10-1017.59 × 1091.34 × 10-10
128.99 × 10-110.974.11 × 1088.12 × 10-111.44 × 10-100.848.05 × 1091.48 × 10-10
246.54 × 10-110.984.61 × 1086.09 × 10-118.37 × 10-110.798.18 × 1088.36 × 10-11
367.08 × 10-1118.91 × 1077.08 × 10-111.73 × 10-1013.30 × 1081.73 × 10-10
489.71 × 10-110.953.35 × 1077.38 × 10-112.45 × 10-70.788.14 × 1073.30 × 10-7
607.83 × 10-110.963.16 × 1076.49 × 10-111.60 × 10-80.331.40 × 1073.63 × 10-8
0.5%CeO2@Zr-MOF06.03 × 10-1111.94 × 1096.03 × 10-113.89 × 10-100.773.03 × 10105.44 × 10-11
126.69 × 10-110.972.57 × 1096.34 × 10-111.13 × 10-100.768.00 × 10101.11 × 10-10
246.66 × 10-110.973.86 × 1096.24 × 10-113.92 × 10-100.539.06 × 10102.45 × 10-10
366.52 × 10-110.984.60 × 1096.31 × 10-113.16 × 10-110.741.68 × 10113.63 × 10-11
484.87 × 10-1112.60 × 1094.87 × 10-114.27 × 10-110.741.60 × 10115.47 × 10-11
604.69 × 10-110.983.21 × 1094.72 × 10-113.31 × 10-1113.94 × 10103.31 × 10-11
1%CeO2@Zr-MOF05.70 × 10-1114.49 × 1095.70 × 10-111.47 × 10-1112.93 × 10101.47 × 10-11
127.00 × 10-1116.73 × 1097.00 × 10-117.61 × 10-1118.90 × 10107.61 × 10-11
245.01 × 10-110.997.69 × 1094.98 × 10-111.18 × 10-100.709.85 × 10101.19 × 10-10
366.44 × 10-110.976.27 × 1096.07 × 10-112.47 × 10-110.631.43 × 10113.74 × 10-11
485.84 × 10-1112.39 × 1095.84 × 10-113.58 × 10-110.721.34 × 10114.99 × 10-11
606.20 × 10-110.986.11 × 1095.98 × 10-112.70 × 10-110.681.11 × 10113.86 × 10-11
2%CeO2@Zr-MOF06.68 × 10-110.974.34 × 1096.69 × 10-112.54 × 10-110.966.34 × 10102.58 × 10-11
126.80 × 10-110.975.74 × 1096.70 × 10-112.46 × 10-110.648.27 × 10101.10 × 10-11
244.90 × 10-110.986.15 × 1094.75 × 10-111.03 × 10-110.851.04 × 10111.10 × 10-11
366.75 × 10-110.971.72 × 1096.38 × 10-114.79 × 10-110.672.11 × 10104.83 × 10-11
484.68 × 10-1114.54 × 1094.68 × 10-111.81 × 10-1111.52 × 10101.81 × 10-11
609.64 × 10-110.984.74 × 1099.52 × 10-113.85 × 10-110.801.87 × 10103.62 × 10-11
Table 1  EIS fitting parameters of pure EP coatings immersed in 3.5%NaCl solution for different times and different additions of CeO2@Zr-MOF/EP coatings on ZMA coated steel
Fig.15  Rc (a) and Rct (b) values of CeO2@Zr-MOF epoxy coatings with different additions at different immersion times
Fig.16  Salt spray experimental results of Zr-MOF scratch coatings 0 h (a1-d1) and after 400 h (a2-d2): EP (a), 0.5% CeO2@Zr-MOF/EP (b), 1%CeO2@Zr-MOF/EP (c) and 2%CeO2@Zr-MOF/EP (d)
Fig.17  Schematic diagram of corrosion protection mechanism of CeO2@Zr-MOF coating
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