Co2O3/Ni2O3密着剂对搪瓷涂层界面行为及密着机制的影响

洪昊; 李文生; 李翠霞; 俞雷; 张婷

doi:10.16490/j.cnki.issn.1001-3660.2025.16.007

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表面技术 ›› 2025, Vol. 54 ›› Issue (16) : 92-99. DOI: 10.16490/j.cnki.issn.1001-3660.2025.16.007

腐蚀与防护

Co₂O₃/Ni₂O₃密着剂对搪瓷涂层界面行为及密着机制的影响

洪昊¹, 李文生^1,2,*, 李翠霞¹, 俞雷², 张婷¹

作者信息 +

Effect of Co₂O₃/Ni₂O₃ Adhesives on the Interfacial Behavior and Adhesion Mechanism of Enamel Coatings

HONG Hao¹, LI Wensheng^1,2,*, LI Cuixia¹, YU Lei², ZHANG Ting¹

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文章历史 +

摘要

目的以镍、钴氧化物密着剂为基础,探索其协同作用及氧化态对碳钢搪瓷涂层密着界面反应过程的影响机制,以期进一步提升搪瓷涂层的密着性能。方法采用磨加法在Q235钢基体上制备了分别含有质量分数为1%Ni₂O₃、1%Co₂O₃、0.5%Ni₂O₃+0.5%Co₂O₃和0.5%NiO+0.5%CoO密着剂（组合）的4种搪瓷涂层,通过落重冲击和拉脱附实验评价了涂层的结合性能,采用扫描电子显微镜、能谱仪和电子探针对涂层界面反应和元素扩散机制进行分析。结果 Co₂O₃比Ni₂O₃密着剂更易在界面处形成沉积层,Ni₂O₃在烧结过程中释放的氧气会促进钴的密着反应,Co²⁺/Co³⁺向界面处扩散促进了Ni²⁺的扩散并在界面处形成沉积层,可见同时磨加镍、钴氧化物密着剂具有一定的协同促进作用。Co³⁺高的标准电极电位促进了釉层与基体的电偶腐蚀反应,使界面处的枝晶数量增加。结论钴密着剂具有比镍密着剂更优的密着性能,高价态氧化物有利于促进界面密着反应,因此Ni₂O₃+Co₂O₃密着剂组合比NiO+CoO具有更优的密着效应。

Abstract

An effective coating/substrate interface bond is crucial for impeding the interfacial diffusion of corrosive media and prolonging the service life of the coating. It is therefore of great significance to improve the adhesion of the enamel coating in order to expand the application fields and service conditions of the enamel coating. The adhesion of a carbon steel-based enamel coating is contingent upon the utilization of an adhesive agent, which can facilitate the formation of an adhesion layer through the promotion of interfacial reactions between the metal and the enamel, thereby enhancing the bond strength of the enamel coating. CoO and NiO, as the most commonly used adhesive agents, significantly enhance the adhesion of the enamel coating when added at concentrations of 0.3wt.% to 1.6wt.%. Meanwhile, studies have demonstrated that high-valent oxides can introduce additional electron vacancies and oxygen, which are expected to further enhance the interfacial adhesion reactions and improve the bonding performance of enamel coatings.
Based on this, the work aims to investigate their synergistic effect and the mechanism of effects of oxidation state on the reactive process of the enamel/metal interface from the perspective of nickel and cobalt oxide adhesive agents, in order to further improve the adhesive properties of carbon steel enamel coatings. Four enamel slurries containing 1wt.% Ni₂O₃, 1wt.% Co₂O₃, 0.5wt.% Ni₂O₃ + 0.5wt.% Co₂O₃ and 0.5wt.% NiO + 0.5wt.% CoO adhesives were prepared with the mill additive method. The coatings were prepared on Q235 steel substrate by a manual one-step enameling method. The frit used was a borosilicate system (SiO₂-B₂O₃-Na₂O-SrO), and the sintering temperature was 850 ℃ for 10 minutes. The adhesion properties of the four coatings were evaluated by falling-weight impact and pull-off adhesion test, and the impact craters and pull-off morphologies were analyzed through optical microscope (OM) and scanning electron microscopy (SEM) to study the failure mechanisms. The interfacial reaction process and element diffusion mechanism of the coatings were analyzed with SEM, energy dispersive spectroscopy (EDS) and electron probe X-ray micro analyzer (EPMA) to clarify the effect mechanism of the four adhesive agents (combinations) on the enamel/metal interfacial reaction.
The results indicate that Co₂O₃ adhesive agent is more prone to forming a deposition layer at the interface compared to Ni₂O₃ adhesive agent. However, the oxygen released during the sintering process of Ni₂O₃ promotes the cobalt adhesion reaction. Meanwhile, the diffusion of Co²⁺/Co³⁺ facilitates the diffusion of Ni²⁺ to the interface, resulting in the formation of a deposit layer. This indicates that the simultaneous Co₂O₃ and Ni₂O₃ adhesive agents as mill additives have synergistic effects. Co³⁺ with high standard electrode potential also promotes the galvanic corrosion reaction with the substrate, which in turn increases the number of dendrites at the interface. Overall, cobalt adhesive agents have better adhesion properties than nickel adhesive agents, and high-valent oxide adhesive agents also help to promote adhesion reactions at the enamel/metal interface. The combination of Ni₂O₃ and Co₂O₃ adhesive agents exhibits a better interfacial adhesion effect for enamel coatings compared to NiO and CoO adhesive agents.

导出引用

洪昊, 李文生, 李翠霞, 俞雷, 张婷. Co₂O₃/Ni₂O₃密着剂对搪瓷涂层界面行为及密着机制的影响[J]. 表面技术. 2025, 54(16): 92-99 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.16.007

HONG Hao, LI Wensheng, LI Cuixia, YU Lei, ZHANG Ting. Effect of Co₂O₃/Ni₂O₃ Adhesives on the Interfacial Behavior and Adhesion Mechanism of Enamel Coatings[J]. Surface Technology. 2025, 54(16): 92-99 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.16.007

中图分类号： TG174.4

参考文献

[1] FAN L, TANG F J, CHEN G D, et al.Corrosion Resistances of Steel Pipe Coated with Two Types of Enamel by Two Coating Processes[J]. Journal of Materials Engineering and Performance, 2018, 27(10): 5341-5349.
[2] LI Y L, HUANG Z R, ZHONG Q D.Microstructure and Corrosive Behavior of Enamel Coating Modified on Mild Steel[J]. Surface Review and Letters, 2018, 25(4): 1850081.
[3] WEI Z Z, WU L J, LIANG X Y.Properties of Ceramic Coating on Heating Surface of Waste Incineration Boiler Prepared by Slurry Method[J]. Materials, 2022, 15(13): 4574.
[4] TAO J H, HU S B, YAN F, et al.Effect of Crystallization Temperature on the Microstructures and Mechanical Properties of Enamel Substrate RT330[J]. Advanced Engineering Materials, 2017, 19(2): 1600500.
[5] CROLL S G.Surface Roughness Profile and Its Effect on Coating Adhesion and Corrosion Protection: A Review[J]. Progress in Organic Coatings, 2020, 148: 105847.
[6] 陈肯. BTC1钢表面搪瓷涂层的密着和耐硫酸露点腐蚀机制研究[D]. 合肥: 中国科学技术大学, 2019.
CHEN K.Study on Adhesion and Sulfuric Acid Dew Point Corrosion Resistance Mechanism of Enamel Coating on BTC1 Steel Surface[D]. Hefei: University of Science and Technology of China, 2019.
[7] BOROM M P, PASK J A.Role of “Adherence Oxides” in the Development of Chemical Bonding at Glass-Metal Interfaces[J]. Journal of the American Ceramic Society, 1966, 49(1): 1-6.
[8] 芶文彬. 搪瓷基础教程[M]. 重庆: 轻工业部全国搪瓷技术进修班试用教材, 1982.
GOU W B.Enamelling Basics Tutorial[M]. Chongqing: Ministry of Light Industry National Enamelling Technology Training Course Trial Textbook, 1982.
[9] KARL K.Molybdenum in Enamels: I, Adherence Produced with Molybdenum Compounds[J]. Journal of the American Ceramic Society, 1940, 23(10): 283-287.
[10] HOUSLEY W L, KING R M.Mechanics of Enamel Adherence, Xi[J]. Journal of the American Ceramic Society, 1935, 18(1/2/3/4/5/6/7/8/9/10/11/12): 319-320.
[11] KING B W, TRIPP H P, DUCKWORTH W H.Nature of Adherence of Porcelain Enamels to Metals[J]. Journal of the American Ceramic Society, 1959, 42(11): 504-525.
[12] BODAGHI M, DAVARPANAH A.The Influence of Cobalt on the Microstructure and Adherence Characteristics of Enamel on Steel Sheet[J]. Processing and Application of Ceramics, 2011, 5(4): 215-222.
[13] 洪昊, 李文生, 汤上, 等. 搪瓷涂层的耐腐蚀及改良方法研究进展[J]. 表面技术, 2023, 52(11): 155-170.
HONG H, LI W S, TANG S, et al.Corrosion Resistance and Improvement Method of Enamel Coating[J]. Surface Technology, 2023, 52(11): 155-170.
[14] 国家质量监督检验检疫总局, 中国国家标准化管理委员会. 搪玻璃层耐机械冲击试验方法: GB/T 7990——2013[S]. 北京: 中国标准出版社, 2014.
General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China, Standardization Administration of the People’s Republic of China. Vitreous and Porcelain Enamels—Determination of Resistance to Impact: GB/T 7990—2013[S]. Beijing: Standards Press of China, 2014.
[15] DMITRUK A, MAYER P, PACH J.Pull-off Strength and Abrasion Resistance of Anti-Corrosive Polymer and Composite Coatings[J]. International Journal of Surface Science and Engineering, 2019, 13(1): 50.
[16] TANG F J, CHENG X M, CHEN G D, et al.Electrochemical Behavior of Enamel-Coated Carbon Steel in Simulated Concrete Pore Water Solution with Various Chloride Concentrations[J]. Electrochimica Acta, 2013, 92: 36-46.
[17] 李翠霞, 杨晓永, 瞿学炜, 等. 石英与长石对搪瓷涂层组织和摩擦磨损性能的影响[J]. 表面技术, 2021, 50(10): 221-229.
LI C X, YANG X Y, QU X W, et al.Effects of Quartz and Feldspar on Microstructure and Friction and Wear Properties of Enamel Coating[J]. Surface Technology, 2021, 50(10): 221-229.
[18] YANG X, JHA A, BRYDSON R, et al.An Analysis of the Microstructure and Interfacial Chemistry of Steel-Enamel Interface[J]. Thin Solid Films, 2003, 443(1/2): 33-45.
[19] CHEN K, CHEN M H, WANG Q C, et al.Micro-Alloys Precipitation in NiO- and CoO-Bearing Enamel Coatings and Their Effect on Adherence of Enamel/Steel[J]. International Journal of Applied Glass Science, 2018, 9(1): 70-84.
[20] DOMASHEVSKAYA É P, RYABTSEV S V, TEREKHOV V A, et al.XPS Study of the Oxidation of Nanosize Ni/Si(100) Films[J]. Journal of Structural Chemistry, 2011, 52(1): 115-122.
[21] 彭容秋. 镍冶金[M]. 长沙: 中南大学出版社, 2005.
PENG R Q.Nickel Metallurgy[M]. Changsha: Central South University Press, 2005.
[22] Neil Birks, Gerald H.Meier, Frederick S.Pettit. 金属高温氧化导论[M]. 辛丽, 王文, 译. 北京: 高等教育出版社, 2010.
NEIL B, GERALD H M, FREDERICK S P.Introduction to the High-Temperature Oxidation of Metals[M]. XIN L, WANG W. Translated, Beijing: Higher Education Press, 2010.
[23] ZHU G X, SUN H Q, WEI X W, et al.Synthesis and Characterization of Fe-Ni/Poly(methyl methacrylate) Nanocomposites[J]. Chemistry Letters, 2005, 34(12): 1680-1681.
[24] MURALLES M, OH J T, CHEN Z.Influence of V Addition on the Mechanical Properties of FeCo Alloys: A Molecular Dynamics Study[J]. Materialia, 2023, 27: 101670.