搪瓷涂层在600 ℃熔融MgCl2-NaCl-KCl中热腐蚀行为研究

doi:10.11902/1005.4537.2024.186

中国腐蚀与防护学报

2025, Vol. 45

Issue (1): 155-163 CSTR: 32134.14.1005.4537.2024.186 DOI: 10.11902/1005.4537.2024.186

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搪瓷涂层在600 ℃熔融MgCl₂-NaCl-KCl中热腐蚀行为研究

杨啸东¹, 李雪², 喻政²(

), 杨莎莎², 陈明辉², 王福会²

1 国家国防科技工业局军工项目审核中心北京 100039
2 东北大学腐蚀与防护中心沈阳 110819

Corrosion Behavior of Enamel Coatings in Molten Salts MgCl₂-KCl-NaCl at 600 ^oC

YANG Xiaodong¹, LI Xue², YU Zheng²(

), YANG Shasha², CHEN Minghui², WANG Fuhui²

1 State Administration of Science, Technology and Industry for National Defence, Beijing 100039, China
2 Corrosion and Protection Center, Northeastern University, Shenyang 110819, China

引用本文:

杨啸东, 李雪, 喻政, 杨莎莎, 陈明辉, 王福会. 搪瓷涂层在600 ℃熔融MgCl₂-NaCl-KCl中热腐蚀行为研究[J]. 中国腐蚀与防护学报, 2025, 45(1): 155-163.
Xiaodong YANG, Xue LI, Zheng YU, Shasha YANG, Minghui CHEN, Fuhui WANG. Corrosion Behavior of Enamel Coatings in Molten Salts MgCl₂-KCl-NaCl at 600 ^oC[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(1): 155-163.

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摘要:

以T92钢为基体制备了助熔剂(Na₂O、K₂O和B₂O₃)不同质量分数B₂O₃ (11.78%、14.78%和17.78%)的3种搪瓷涂层，研究了它们在600 ℃熔融MgCl₂-NaCl-KCl中的腐蚀行为。结果表明，涂层的腐蚀抗性随着B₂O₃含量的升高而升高。经500 h腐蚀后，B₂O₃含量为11.78%的搪瓷涂层在腐蚀性盐的物理溶解和化学侵蚀的共同作用下遭受了平均82.7 μm的厚度损失和14.44 mg/cm²的质量损失，涂层在内部不断生成的气态腐蚀产物的作用下由原始的82.7 ± 0.5 μm膨胀至253.9 ± 44.9 μm；提高B₂O₃含量至14.78%，涂层的厚度和质量损失降低至约12.5 μm和3.69 mg/cm²并且避免了因快速腐蚀而发生膨胀。17.78%B₂O₃含量的涂层腐蚀非常轻微，厚度损失小于1 μm，质量损失最终降低至仅为0.16 mg/cm²。

关键词 ：搪瓷涂层, T92钢, 腐蚀, 熔融氯盐

Abstract：

Three enamel coatings with identical total quantities of flux Na₂O, K₂O, and B₂O₃, but varying B₂O₃ mass fractions (11.78%, 14.78% and 17.78%) were prepared on on T92 ferritic steel. Their corrosion behaviorwas studied in molten salts MgCl₂-NaCl-KCl at 600 ^oC in air. Results show that the corrosion severity of the enamel coatings gradually decreases with the increasing amount of B₂O₃ in enamels. After corrosion for 500 h, the enamel coating with the lowest mass fraction of B₂O₃ (11.78%) suffered from a thickness loss of about 82 μm and a mass loss of about 14.44 mg/cm² under the combined action of physical dissolution and chemical attack of corrosive salts. Meanwhile, under the action of continuously generated gaseous corrosion products inside the coating, the coating was swelled, as a result, its thickness is expanded from 82.7 ± 0.5 μm of the original to 253.9 ± 44.9 μm. By increasing B₂O₃ content to 14.78%, the thickness- and mass-loss of the enamel coating were significantly reduced to about 12 μm and 3.69 mg/cm² respectively, while the volume expansion caused by rapid corrosion is eliminated. Comparatively, the enamel coating with the highest mass fraction of B₂O₃ (17.78%) showed excellent corrosion resistance with a thickness loss of less than 1 μm, and mass loss is eventually reduced to only 0.16 mg/cm².

Key words： enamel coating T92 steel corrosion melt chloride salts

收稿日期: 2024-06-17 32134.14.1005.4537.2024.186

ZTFLH:

TG17

基金资助:兴辽英才项目(XLYC2203133);教育部中央高校基本科研业务费项目(N2302018);宁波余姚市科技创新项目

通讯作者: 喻政，E-mail：yuzheng_199501@163.com，研究方向为高温腐蚀与防护涂层

Corresponding author: YU Zheng, E-mail: yuzheng_199501@163.com

作者简介: 杨啸东，男，1994年生，工程师

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表1 3种搪瓷涂层的名义成分 (mass fraction / %)

图1 3种成分搪瓷粉末的DSC曲线及制备态搪瓷涂层的XRD谱

图2 搪瓷涂层制备态的截面和表面SEM像

图3 搪瓷涂层在600 ℃下MgCl2-KCl-NaCl熔盐中热腐蚀500 h前后的宏观形貌

图4 搪瓷涂层在600 ℃下MgCl2-KCl-NaCl熔盐中腐蚀500 h后的质量损失

图5 搪瓷涂层在600 ℃下MgCl2-KCl-NaCl熔盐中腐蚀500 h后的XRD谱

图6 搪瓷涂层在600 ℃下MgCl2-KCl-NaCl熔盐中腐蚀500 h后的表面SEM像

表2 图6中各区域的元素成分分析 (atomic fraction / %)

图7 搪瓷涂层在600 ℃下MgCl2-KCl-NaCl熔盐中腐蚀500 h后的截面SEM像

图8 B15和B18搪瓷涂层在600 ℃下MgCl2-KCl-NaCl熔盐中腐蚀500 h 后距原始表面不同深度处元素含量的EDS点分析结果变化曲线

图9 搪瓷涂层在600 ℃下MgCl2-KCl-NaCl熔盐中腐蚀500 h后的表面3D模型图

图10 搪瓷组分中相关反应方程式的热力学数据

图11 B12和B18搪瓷的热腐蚀过程示意图

1	Bonk A, Sau S, Uranga N, et al. Advanced heat transfer fluids for direct molten salt line-focusing CSP plants [J]. Prog. Energy Combust. Sci., 2018, 67: 69
2	Vignarooban K, Xu X H, Arvay A, et al. Heat transfer fluids for concentrating solar power systems-a review [J]. Appl. Energy, 2015, 146: 383
3	Wu J J, Wang Y L. Hot corrosion and protection of structural materials in molten salt reactor [J]. J. Chin. Soc. Corros. Prot., 2022, 42: 193
3	吴家杰, 王艳丽. 熔盐堆用结构材料的热腐蚀及防护 [J]. 中国腐蚀与防护学报, 2022, 42: 193 doi: 10.11902/1005.4537.2021.070
4	Bauer T, Pfleger N, Laing D, et al. High-temperature molten salts for solar power application [A]. LantelmeF, GroultH. Molten Salts Chemistry: From Lab to Applications [M]. Amsterdam: Elsevier, 2013: 415
5	Peiró G, Gasia J, Miró L, et al. Influence of the heat transfer fluid in a CSP plant molten salts charging process [J]. Renew. Energy, 2017, 113: 148
6	Villada C, Ding W J, Bonk A, et al. Engineering molten MgCl₂-KCl-NaCl salt for high-temperature thermal energy storage: review on salt properties and corrosion control strategies [J]. Sol. Energy Mater. Sol. Cells, 2021, 232: 111344
7	Ding W J, Shi H, Jianu A, et al. Molten chloride salts for next generation concentrated solar power plants: mitigation strategies against corrosion of structural materials [J]. Sol. Energy Mater. Sol. Cells, 2019, 193: 298
8	Mohan G, Venkataraman M B, Coventry J. Sensible energy storage options for concentrating solar power plants operating above 600^oC [J]. Renew. Sustain. Energy Rev., 2019, 107: 319
9	Mohan G, Venkataraman M, Gomez-Vidal J, et al. Thermo-economic analysis of high-temperature sensible thermal storage with different ternary eutectic alkali and alkaline earth metal chlorides [J]. Sol. Energy, 2018, 176: 350
10	Mohan G, Venkataraman M, Gomez-Vidal J, et al. Assessment of a novel ternary eutectic chloride salt for next generation high-temperature sensible heat storage [J]. Energy Convers. Manage., 2018, 167: 156
11	Pandey C, Giri A, Mahapatra M M. Evolution of phases in P91 steel in various heat treatment conditions and their effect on microstructure stability and mechanical properties [J]. Mater. Sci. Eng., 2016, 664A: 58
12	Zhang X H, Zeng Y P, Cai W H, et al. Study on the softening mechanism of P91 steel [J]. Mater. Sci. Eng., 2018, 728A: 63
13	Zhang M Y, Ge J B, Yin, T Q, et al. Erratum—redox potential measurements of Cr(II)/Cr Ni(II)/Ni and Mg(II)/Mg in molten MgCl₂-KCl-NaCl mixture [J. Electrochemi Soc., 167, 116505 (2020)] [J]. J. Electrochem. Soc., 2021, 168: 079001
14	Feng X K, Melendres C A. Anodic corrosion and passivation behavior of some metals in molten LiCl-KCl containing oxide ions [J]. J. Electrochem. Soc., 1982, 129: 1245
15	Zaikov Y P, Batukhtin V P, Shurov N I, et al. Calcium production by the electrolysis of molten CaCl₂-part I. Interaction of calcium and copper-calcium alloy with electrolyte [J]. Metall. Mater. Trans., 2014, 45B: 961
16	Fernández A G, Cabeza L F. Corrosion evaluation of eutectic chloride molten salt for new generation of CSP plants. Part 1: thermal treatment assessment [J]. J. Energy Storage, 2020, 27: 101125
17	Grégoire B, Oskay C, Meißner T M, et al. Corrosion mechanisms of ferritic-martensitic P91 steel and Inconel 600 nickel-based alloy in molten chlorides. Part II: NaCl-KCl-MgCl₂ ternary system [J]. Sol. Energy Mater. Sol. Cells, 2020, 216: 110675
18	Ding W J, Shi H, Xiu Y L, et al. Hot corrosion behavior of commercial alloys in thermal energy storage material of molten MgCl₂/KCl/NaCl under inert atmosphere [J]. Sol. Energy Mater. Sol. Cells, 2018, 184: 22
19	Yuan L, Xie X, Chen M H, et al. Air oxidation and NaCl corrosion behavior of 20 steel without and with enamel coating at 400 ^oC [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 890
19	袁磊, 谢新, 陈明辉等. 20钢及其搪瓷涂层在400 ℃下的氧化和NaCl腐蚀行为研究 [J]. 中国腐蚀与防护学报, 2023, 43: 890
20	Chen M H, Li W B, Shen M L, et al. Glass-ceramic coatings on titanium alloys for high temperature oxidation protection: oxidation kinetics and microstructure [J]. Corros. Sci., 2013, 74: 178
21	Chen M H, Li W B, Shen M L, et al. Glass coatings on stainless steels for high-temperature oxidation protection: mechanisms [J]. Corros. Sci., 2014, 82: 316
22	Ullah F, Ameen M, Hasrat K. Experimental study on optimization of heat storage and melting salts of solar energy [J]. J. Food Process. Preserv., 2018, 43: e13685
23	Zuo Y, Cao M P, Shen M, et al. Effect of Mg on corrosion of 316H stainless steel in molten salts MgCl₂-NaCl-KCl [J]. J. Chin. Soc. Corros. Prot., 2021, 41: 80
23	左勇, 曹明鹏, 申淼等. MgCl₂-NaCl-KCl熔盐体系中金属Mg对316H不锈钢的缓蚀性能研究 [J]. 中国腐蚀与防护学报, 2021, 41: 80
24	Liu S J, Wang R D, Wang L, et al. Corrosion behavior of iron-based and Ni-based alloys melted in NaCl-MgCl₂-KCl mixed molten salt under vacuum atmosphere [J]. J. Mater. Res. Technol., 2024, 28: 1915
25	Wang B, Cunning B V, Park S Y, et al. Graphene coatings as barrier layers to prevent the water-induced corrosion of silicate glass [J]. ACS Nano, 2016, 10: 9794 pmid: 27704789
26	Wang H, Zhang C, Jiang C Y, et al. Evaluation of glass coatings with various silica content corrosion in a 0.5 M HCl water solution [J]. Crystals, 2021, 11: 346
27	Zhan J, Chen G M, Zhang Q. Study on the corrosion mechanism of HVOF silicate glass coating in 36%HCl and 10 mol/L NaOH solution [J]. Optoelectron. Adv. Mater. Rapid Commun., 2010, 4: 1170
28	Zhang H, Zhang J J, Wang Z Q. Corrosion resistance of plasma-sprayed ceramic coatings doped with glass in different proportions [J]. J. Therm. Spray Technol., 2023, 32: 1286
29	Shao G X, Gou W B, Wen R C, et al. Enamel [M]. Beijing: China Light Industry Press, 1983: 360
29	邵规贤, 芶文彬, 闻瑞昌等. 搪瓷学 [M]. 北京: 轻工业出版社, 1983: 360
30	Huang Q Z, Lu G M, Wang J, et al. Thermal decomposition mechanisms of MgCl₂·6H₂O and MgCl₂·H₂O [J]. J. Anal. Appl. Pyrolysis, 2011, 91: 159
31	Chen K, Chen M H, Yu Z D, et al. Simulating sulfuric acid dew point corrosion of enamels with different contents of silica [J]. Corros. Sci., 2017, 127: 201
32	Bunker B C. Molecular mechanisms for corrosion of silica and silicate glasses [J]. J. Non-Cryst. Solids, 1994, 179: 300
33	Gin S, Ribet I, Couillard M. Role and properties of the gel formed during nuclear glass alteration: importance of gel formation conditions [J]. J. Nucl. Mater., 2001, 298: 1

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