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中国腐蚀与防护学报  2026, Vol. 46 Issue (5): 1497-1507     CSTR: 32134.14.1005.4537.2025.333      DOI: 10.11902/1005.4537.2025.333
  研究报告 本期目录 | 过刊浏览 |
Al2O3 磨加量对铝合金搪瓷涂层组织结构及腐蚀性能的影响
齐晓涵1, 翟海民1, 李文生1,2,3(), 洪昊1, 曹元1, 俞雷2, 陈博瀚2
1.兰州理工大学材料科学与工程学院 兰州 730050
2.西北师范大学物理与电子工程学院 兰州 730070
3.兰州资源环境职业技术大学冶金工程学院 兰州 730015
Influence of Adding Nano-Al2O3 to Wet Enamel Frit Powder Slurry on Microstructure and Corrosion Resistance Enamel Coatings Applied on Al-alloy
QI Xiaohan1, ZHAI Haimin1, LI Wensheng1,2,3(), HONG Hao1, CAO Yuan1, YU Lei2, CHEN Bohan2
1.School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, China
2.College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou 730070, China
3.School of Metallurgical Engineering, Lanzhou Resources & Environment Voc-Tech University, Lanzhou 730015, China
引用本文:

齐晓涵, 翟海民, 李文生, 洪昊, 曹元, 俞雷, 陈博瀚. Al2O3 磨加量对铝合金搪瓷涂层组织结构及腐蚀性能的影响[J]. 中国腐蚀与防护学报, 2026, 46(5): 1497-1507.
Xiaohan QI, Haimin ZHAI, Wensheng LI, Hao HONG, Yuan CAO, Lei YU, Bohan CHEN. Influence of Adding Nano-Al2O3 to Wet Enamel Frit Powder Slurry on Microstructure and Corrosion Resistance Enamel Coatings Applied on Al-alloy[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(5): 1497-1507.

全文: PDF(9907 KB)   HTML
摘要: 

Zn-Al复合涂层为ORV换热管表面防护常采用的方式,但其易损伤老化且服役寿命短,搪瓷涂层作为一种性能表现优异的无机非金属材料已应用于石化管道等领域,有望为ORV换热管表面防护提供一种新思路。本文采用手工湿法喷搪工艺,制备了Al2O3磨加量分别为0%、2%、4%和6%的4种铝合金搪瓷涂层。利用红外光谱仪(FTIR)、Raman光谱仪、热重-差示扫描量热分析仪(TG-DSC)、X射线光电子能谱仪(XPS)、激光共聚焦显微镜和扫描电子显微镜(SEM)对涂层的组织结构和表面形貌进行了系统表征,同时在3.5%NaCl溶液中进行浸泡腐蚀实验,结合电化学测试,探讨磨加Al2O3对搪瓷涂层耐腐蚀性能的影响机制。结果表明,Al2O3在烧结过程中可夺取硅氧网络中的非桥氧,形成[AlO4]结构并进入非晶网络,发挥补网作用,提高网络结构致密度。当Al2O3添加量为4%时,涂层表现出最优异的耐腐蚀性能,其致密的网络结构有效阻碍了腐蚀介质的渗透,延缓了裂纹扩展路径,抑制了腐蚀反应的进行。

关键词 : 搪瓷涂层,  Al2O3,  组织结构,  耐腐蚀性,  非晶网络    
Abstract:

Zn-Al composite coatings are widely used as protective coating for heat exchanger tube of open rack vaporizer, but suffered from corrosion damage and thus limited its service life. Enamel coatings, a high-performance inorganic non-metallic material, widely adopted in petrochemical industry, represent a promising alternative approach. Therefore, four types of enamel slurries were prepared by adding nano-Al2O3 particulates in the designed wet frit power, namely the frit powder with 0, 2, 4 and 6 mass% nano-Al2O3 particulates were prepared respectively, which were further ground by ball mill, subsequently applied on Al-alloy by cold spraying method and finally sintered at 550℃ to gain coatings/Al-alloy. The microstructure and surface morphology of the coatings were characterized using. Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermogravimetric-differential scanning calorimetry (TG-DSC), X-ray photoelectron spectroscopy (XPS), laser confocal microscopy, and scanning electron microscopy (SEM). Their corrosion behavior was comparatively examined via immersion tests in 3.5%NaCl solution whilst with electrochemical measurement. The results indicate that during the sintering process, Al2O3 incorporates into the silicate network by capturing non-bridging oxygen and forming [AlO4] structural units, thereby promoting the expansion and densification of the amorphous network. Among others, the coating containing 4%Al2O3 exhibits the best corrosion resistance, which may be ascribed to its dense network structure that acts as an effective barrier against corrosive medium penetration, extends the diffusion path, and suppresses crack initiation and propagation.

Key words: enamel coating    Al2O3    microstructure    corrosion resistance    amorphous network
收稿日期: 2025-10-28      32134.14.1005.4537.2025.333
ZTFLH:  TG174  
基金资助:国家自然科学基金国际合作研究项目(W2412069);国家“111”学科创新引智基地项目(D21032)
通讯作者: 李文生,E-mail:liws@nwnu.edu.cn,研究方向为金属表面防护
Corresponding author: LI Wensheng, E-mail: liws@nwnu.edu.cn
作者简介: 齐晓涵,女,2000年生,硕士生
SampleFritHBO3K2CO3Al2O3
0% coating10030.20
2% coating10030.22
4% coating10030.24
6% coating10030.26
表1  搪瓷浆料组成 (g)
图1  不同Al2O3磨加量搪瓷涂层的表面形貌及截面形貌
图2  不同Al2O3磨加量搪瓷涂层的粗糙度及硬度变化
图3  不同Al2O3磨加量的搪瓷涂层红外和拉曼光谱
图4  不同Al2O3磨加量涂层的TG-DSC曲线
图5  不同Al2O3磨加量涂层的XPS图谱Al 2p轨道分峰拟合结果
图6  不同Al2O3磨加量搪瓷涂层不同浸泡时间的EIS
图7  搪瓷涂层腐蚀等效电路示意图
图8  不同Al2O3磨加量搪瓷涂层腐蚀参数对比
图9  不同Al2O3磨加量搪瓷涂层腐蚀30 d后表面形貌
图10  磨加4%Al2O3搪瓷涂层腐蚀30 d后XPS数据分析结果
图11  未磨加Al2O3涂层磨加Al2O3涂层的腐蚀机理示意图
[1] Xu Y, Ma M J, Zhu M, et al. Research of the open rack vaporizer operation [J]. Chem. Eng. Oil Gas, 2019, 48(4): 57
[1] 许 燕, 马敏吉, 朱 明 等. 海水开架式气化器运行工况研究 [J]. 石油与天然气化工, 2019, 48(4): 57
[2] Liu J J, Zhang D W, Wang J K, et al. Corrosion factor analysis of heat exchange tubes of open rack vaporizer [J]. Dev. Appl. Mater., 2022, 37(3): 57
[2] 刘景俊, 张大伟, 王剑琨 等. 开架式气化器换热管腐蚀影响因素分析 [J]. 材料开发与应用, 2022, 37(3): 57
[3] Guo Y N. Operation and maintenance of seawater open-rack vaporizer [J]. Petrochem. Ind. Technol., 2023, 30(7): 15
[3] 郭勇男. 海水开架式气化器的运行与维护 [J]. 石化技术, 2023, 30(7): 15
[4] Hou H L, Hou J G, Wang X L, et al. Corrosion analysis of LNG terminals [J]. Paint Coat. Ind., 2020, 50(3): 83
[4] 侯海龙, 侯建国, 王秀林 等. LNG接收站腐蚀情况分析 [J]. 涂料工业, 2020, 50(3): 83
[5] Fan Z B, Gao Z Y, Zong L J, et al. Corrosion behaviour and characteristics of 1050A al-alloy exposed in typical atmospheres of Shandong Province [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 1055
[5] 樊志彬, 高智悦, 宗立君 等. 1050A铝合金在山东不同典型环境中的大气腐蚀行为特征研究 [J]. 中国腐蚀与防护学报, 2024, 44: 1055
doi: 10.11902/1005.4537.2023.321
[6] Mao Y C, Zhu Y, Sun S K, et al. Localized corrosion of 5083 al-alloy in simulated marine splash zone [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 47
[6] 毛英畅, 祝 钰, 孙圣凯 等. 5083铝合金在模拟海洋浪花飞溅区的局部腐蚀行为 [J]. 中国腐蚀与防护学报, 2023, 43: 47
doi: 10.11902/1005.4537.2022.162
[7] Zeng W, Wang L J, Wu Y Z, et al. Coating failure analysis of open rack vaporizers [J]. Total Corros. Control, 2015, 29(4): 36
[7] 曾 伟, 王良军, 吴永忠 等. 开架式海水汽化器(ORV)涂层失效分析 [J]. 全面腐蚀控制, 2015, 29(4): 36
[8] Hu S W. Research on environmental pollution prevention in sandblasting operations within China's ship repair industry [J]. Chin. Sci. Technol. J. Database (Citat. Ed.) Eng. Technol., 2016, (11): 00032
[8] 胡世武. 我国修船业喷砂作业环境污染防治研究 [J]. 中文科技期刊数据库(引文版)工程技术, 2016, (11): 00032
[9] Chen J J, Liang J L, Xie H Q, et al. Heavy metals content and pollution evaluation in seawater of Hainan eucheuma provincial nature reserve [J]. Trop. Agric. Eng., 2023, 47(6): 109
[9] 陈积杰, 梁计林, 谢海群 等. 海南麒麟菜省级自然保护区海水重金属含量与污染评价 [J]. 热带农业工程, 2023, 47(6): 109
[10] Zhang G Y. Bidden danger of enamel reactor and the protective measures [J]. Guangzhou Chem. Ind., 2008, 36(1): 55
[10] 张广宇. 搪瓷反应釜的隐患及防护措施 [J]. 广州化工, 2008, 36(1): 55
[11] Shao W G, Wang L Q. Metal-glass (glaze) thermal spray composite anti-corrosion piping [P]. Chin Pat, 891078568, 1989
[11] 邵文古, 王理泉. 金属-玻璃(釉)热喷复合防腐管道 [P]. 中国专利, 891078568, 1989)
[12] Rossi S, Fedel M, Deflorian F, et al. Abrasion and chemical resistance of composite vitreous enamel coatings with hard particles [J]. Surf. Interface Anal., 2016, 48: 827
doi: 10.1002/sia.v48.8
[13] Rossi S, Calovi M, Velez D, et al. Influence of addition of hard particles on the mechanical and chemical behavior of vitreous enamel [J]. Surf. Coat. Technol., 2019, 357: 69
doi: 10.1016/j.surfcoat.2018.09.062
[14] Shu M Y, Yin H Y, Zhong Q D, et al. Effect of glass powder on acid resistance of enamel coating [J]. Surf. Rev. Lett., 2017, 24: 1750036
doi: 10.1142/S0218625X17500366
[15] Wang Y, Tian W, Zhang T, et al. Microstructure, spallation and corrosion of plasma sprayed Al2O3-13%TiO2 coatings [J]. Corros. Sci., 2009, 51: 2924
doi: 10.1016/j.corsci.2009.08.005
[16] Kim G H, Sohn I. Effect of Al2O3 on the viscosity and structure of calcium silicate-based melts containing Na2O and CaF2 [J]. J. Non-Cryst. Solids, 2012, 358: 1530
doi: 10.1016/j.jnoncrysol.2012.04.009
[17] Aronne A, Esposito S, Pernice P. FTIR and DTA study of lanthanum aluminosilicate glasses [J]. Mater. Chem. Phys., 1997, 51: 163
doi: 10.1016/S0254-0584(97)80287-8
[18] Hrma P. Arrhenius model for high-temperature glass-viscosity with a constant pre-exponential factor [J]. J. Non-Cryst. Solids, 2008, 354: 1962
doi: 10.1016/j.jnoncrysol.2007.11.016
[19] Allu A R, Gaddam A, Ganisetti S, et al. Structure and crystallization of alkaline-earth aluminosilicate glasses: Prevention of the alumina-avoidance principle [J]. J. Phys. Chem., 2018, 122B: 4737
[20] Wang C. Raman spectroscopy study of silicate and aluminosilicate minerals [D]. Beijing: China University of Geosciences (Beijing), 2005: 7
[20] 王 晨. 硅酸盐及含铝硅酸盐矿物的拉曼光谱研究 [D]. 北京: 中国地质大学(北京), 2005: 7
[21] Zagrajczuk B, Dziadek M, Olejniczak Z, et al. Structural investigation of gel-derived materials from the SiO2-Al2O3 system [J]. J. Mol. Struct., 2018, 1167: 23
doi: 10.1016/j.molstruc.2018.04.085
[22] Sun W, Mu R, Luo X, et al. Effect of chloride salt, freeze-thaw cycling and externally applied load on the performance of the concrete [J]. Cem. Concr. Res., 2002, 32: 1859
doi: 10.1016/S0008-8846(02)00769-X
[23] Guo H W, Zhao C C, Chi L X, et al. Effect of Al2O3 content on the structure of alkali-free aluminoborosilicate glass network [J]. Glass, 2019, 46(4): 1
[23] 郭宏伟, 赵聪聪, 池龙兴 等. Al2O3含量对无碱铝硼硅玻璃网络结构的影响 [J]. 玻璃, 2019, 46(4): 1
[24] Walter G W. A review of impedance plot methods used for corrosion performance analysis of painted metals [J]. Corros. Sci., 1986, 26: 681
doi: 10.1016/0010-938X(86)90033-8
[25] Presa M J R, Tucceri R I, Florit M I, et al. Constant phase element behavior in the poly (o-toluidine) impedance response [J]. J. Electroanal. Chem., 2001, 502: 82
doi: 10.1016/S0022-0728(00)00512-X
[26] Hirschorn B, Orazem M E, Tribollet B, et al. Determination of effective capacitance and film thickness from constant-phase-element parameters [J]. Electrochim. Acta, 2010, 55: 6218
doi: 10.1016/j.electacta.2009.10.065
[27] Zhu C F, Xie R, Xue J H, et al. Studies of the impedance models and water transport behaviors of cathodically polarized coating [J]. Electrochim. Acta, 2011, 56: 5828
doi: 10.1016/j.electacta.2011.04.068
[28] Zhang J T, Hu J M, Zhang J Q, et al. Studies of water transport behavior and impedance models of epoxy-coated metals in NaCl solution by EIS [J]. Prog. Org. Coat., 2004, 51: 145
doi: 10.1016/j.porgcoat.2004.08.001
[29] Cao M, Liu L, Fan L, et al. Influence of temperature on corrosion behavior of 2A02 Al alloy in marine atmospheric environments [J]. Materials, 2018, 11: 235
doi: 10.3390/ma11020235
[30] Wu P N, Niu G J, Xi J J, et al. Study affection of nano-Al2O3 additive on the corrosion resistance of micro-arc oxidation film of titanium alloy TC4 [J]. Adv. Mater. Res., 2012, 472: 2707
[31] Jiang W Z, Li Y J. Enamel and Glass-Lined [M]. Beijing: China Light Industry Press, 2015: 33
[31] 蒋伟忠, 厉益骏. 搪瓷与搪玻璃 [M]. 北京: 中国轻工业出版社, 2015: 33
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