Please wait a minute...
中国腐蚀与防护学报  2026, Vol. 46 Issue (4): 1218-1226     CSTR: 32134.14.1005.4537.2025.308      DOI: 10.11902/1005.4537.2025.308
  研究报告 本期目录 | 过刊浏览 |
镁合金的一种致密微弧氧化涂层工艺及性能的研究
张晓晨1,2(), 杨闯1, 姜旭1, 陈永生1, 赵佳祥1, 赵阳2, 周鹏2, 张涛2, 王福会2
1.黑龙江工程学院材料科学与工程学院 哈尔滨 150050
2.东北大学 数字钢铁全国重点实验室 沈阳 110819
Preparation and Properties of a Novel Compact Micro-arc Oxidation Coating on AZ91D Mg-alloy
ZHANG Xiaochen1,2(), YANG Chuang1, JIANG Xu1, CHEN Yongsheng1, ZHAO Jiaxiang1, ZHAO Yang2, ZHOU Peng2, ZHANG Tao2, WANG Fuhui2
1.School of Material Science and Engineering, Heilongjiang Institute of Technology, Harbin 150050, China
2.State Key Laboratory of Digital Steel, Northeastern University, Shenyang 110819, China
引用本文:

张晓晨, 杨闯, 姜旭, 陈永生, 赵佳祥, 赵阳, 周鹏, 张涛, 王福会. 镁合金的一种致密微弧氧化涂层工艺及性能的研究[J]. 中国腐蚀与防护学报, 2026, 46(4): 1218-1226.
Xiaochen ZHANG, Chuang YANG, Xu JIANG, Yongsheng CHEN, Jiaxiang ZHAO, Yang ZHAO, Peng ZHOU, Tao ZHANG, Fuhui WANG. Preparation and Properties of a Novel Compact Micro-arc Oxidation Coating on AZ91D Mg-alloy[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(4): 1218-1226.

全文: PDF(19646 KB)   HTML
摘要: 

通过在锆盐电解溶液中掺杂聚苯胺颗粒(PAN),以制备致密的AZ91D合金表面微弧氧化膜。采用扫描电镜(SEM)、X射线衍射仪(XRD)表征涂层的微观形貌、晶体结构;采用百格法和摩擦磨损实验表征涂层的力学性能;,还采用动电位极化曲线、阻抗、析氢、盐雾实验评定了涂层的耐腐蚀性能。结果表明:当掺杂量为3.0 g时,涂层的孔隙率从未经掺杂的13.16%降低到了4.81%,其摩擦系数小,粘附力等级0级;涂层的自腐蚀电位-1.558 V,自腐蚀电流密度39.3 μA·cm-2,电阻44037.9 Ω·cm2,涂层的合金在3.5%NaCl溶液中浸泡120 h的析氢量仅为1.7 mL,120 h盐雾腐蚀等级为10 G。综上,聚苯胺颗粒的掺杂有利于致密微弧氧化涂层的形成,随着掺杂量的增加,涂层的微观结构和耐腐蚀性能都得到了明显的改善,即通过聚苯胺颗粒掺杂制备致密的微弧氧化涂层是提高镁合金耐蚀性能的有效方法。

关键词 镁合金微弧氧化电解液聚苯胺耐蚀性能    
Abstract

Herewith a new process was proposed for preparing micro-arc oxidation coating on the surface of AZ91D Mg-alloy. The coating is formed in a modified zirconium salt-based electrolyte that incorporates properly polyaniline (PAN) particles. Then its microscopic morphology and crystal structure were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). Mechanical properties were evaluated through the Shore A scale method and friction-wear tests, while corrosion resistance was assessed via galvanostatic polarization curves, impedance measurements, hydrogen evolution experiments, and salt spray testing. The results show, that when the doping amount of polyaniline particles is 3.0 g, the porosity of the coating is reduced from the 13.16% for the coating prepared in the un-modified electrolyte to 4.81%, the friction coefficient is small, and the adhesion grade is 0; the coating has free-corrosion potential of -1.558 V, free-corrosion current density of 39.3 μA·cm-2, resistance of 44037.9 Ω·cm2, and hydrogen evolution of only 1.7 mL after immersion in 3.5%NaCl solution for 120 h, and a salt spray corrosion grade of 10G after 120 h. In conclusion, the doping of polyaniline particles is beneficial to the formation of a compact micro-arc oxidation coating. As the doping amount increases, the microstructure and corrosion resistance of the coating are significantly improved. Thus, preparing compact micro-arc oxidation coatings through polyaniline particle doping is an effective method to enhance the corrosion resistance of Mg-alloys.

Key wordsMg-alloy    micro-arc oxidation    electrolyte    polyaniline    corrosion resistance
收稿日期: 2025-09-30      32134.14.1005.4537.2025.308
ZTFLH:  TG174  
基金资助:国家自然科学基金(52201066);国家自然科学基金(U21A2045);教育部重点实验室开放基金(NEU-ATM-2024-3*);龙江工程雏燕创新团队项目(2024CYQN01);黑龙江省自然科学基金(LH2024E116);黑龙江省高校科研基本经费(2022GJ07);黑龙江省高校科研基本经费(2023GJ09)
通讯作者: 张晓晨,E-mail:zxc161616@126.com,研究方向为金属腐蚀与防护
Corresponding author: ZHANG Xiaochen, E-mail: zxc161616@126.com
作者简介: 张晓晨,女,1982年生,博士,副教授
图1  不同掺杂聚苯胺颗粒样品表面形貌测试结果
图2  不同掺杂聚苯胺颗粒样品截面形貌测试结果
图3  掺杂3.0 g聚苯胺颗粒样品表面元素分析
图4  掺杂3.0 g聚苯胺颗粒样品截面元素分析
图5  不同掺杂聚苯胺颗粒样品的XRD图谱
图6  不同掺杂聚苯胺颗粒样品的粘附力测试结果
AdhesionAdhesion levelCoating shedding
PAN, wt0.0 g1Partial shedding
PAN, wt0.8 g1Partial shedding
PAN, wt1.5 g0Almost no shedding
PAN, wt2.2 g0Almost no shedding
PAN, wt3.0 g0Almost no shedding
表1  不同掺杂聚苯胺颗粒微弧氧化涂层与基体镁合金的粘附力等级统计结果
图7  不同掺杂聚苯胺颗粒样品的摩擦磨损系数
图8  不同掺杂聚苯胺颗粒样品的动电位极化曲线测试结果
Polyaniline contentEcorr / VIcorr / μA·cm-2
PAN, wt0.0 g-1.50492.1
PAN, wt0.8 g-1.51288.2
PAN, wt1.5 g-1.52572.6
PAN, wt2.2 g-1.53655.1
PAN, wt3.0 g-1.55839.3
表2  动电位极化曲线的Tafel的外推结果
ParameterRs / Ω·cm2CPEf / μS·s-n·cm-2n1Rf / Ω·cm2CPEdl / μS·s-n·cm-2n2Rct / Ω·cm2
PAN, wt0.0 g13.792.1440.887877.850.36280.9635793
PAN, wt0.8 g16.492.2150.8009141.60.105117160
PAN, wt1.5 g25.461.5680.81328157142.811284
PAN, wt2.2 g67.010.66060.782623700631.60.776712
PAN, wt3.0 g31.380.26670.7145847.95.6950.881943190
表3  不同掺杂聚苯胺颗粒微弧氧化样品EIS测试的电化学参数
图9  不同掺杂聚苯胺颗粒样品的阻抗测试结果
图10  不同掺杂聚苯胺颗粒样品析氢测试结果
图11  不同掺杂聚苯胺颗粒样品120 h的盐雾实验结果
[1] Zhao S M. Preparation and performance study of conversion coating of AZ91D magnesium alloy [D]. Shenyang: Shenyang Ligong University, 2017
[1] 赵思萌. AZ91D镁合金转化膜的制备及性能研究 [D]. 沈阳: 沈阳理工大学, 2017
[2] Jiang B L, Liu D J. Scientific aspects of restricting development and application of micro-arc oxidation technology [J]. Chin. J. Nonferrous Met., 2011, 21: 2402
doi: 10.1016/S1003-6326(11)61027-3
[2] 蒋百灵, 刘东杰. 制约微弧氧化技术应用开发的几个科学问题 [J]. 中国有色金属学报, 2011, 21: 2402
[3] Huang Z Y, Guan Y C. Preliminary study of laser surface modification techniques for magnesium alloys [J]. Aeronaut. Manuf. Technol., 2020, 63(13): 32
[3] 黄泽亚, 管迎春. 浅谈几种典型镁合金激光表面改性技术 [J]. 航空制造技术, 2020, 63(13): 32
[4] Zhang X, Zhang K. Research advances on corrosion behavior and mechanism of magnesium alloys [J]. Corros. Sci. Prot. Technol., 2015, 27: 78
[4] 张 新, 张 奎. 镁合金腐蚀行为及机理研究进展 [J]. 腐蚀科学与防护技术, 2015, 27: 78
[5] Zhao Z. The reaearch on micro arc oxidation experiments and its reaction mechanism [D]. Beijing: Tsinghua University, 2015
[5] 赵 拯. 微弧氧化技术实验设备的研制及其反应机理研究 [D]. 北京: 清华大学, 2015
[6] Song R G. Development and applications of micro-arc oxidation technology [J]. J. Mater. Eng., 2019, 47(3): 50
[6] 宋仁国. 微弧氧化技术的发展及其应用 [J]. 材料工程, 2019, 47(3): 50
doi: 10.11868/j.issn.1001-4381.2018.000582
[7] Lei X, Lin N M, Zou J J, et al. Research progress of micro-arc oxidation on aluminum alloys [J]. Surf. Technol., 2019, 48(12): 10
[7] 雷 欣, 林乃明, 邹娇娟 等. 铝合金微弧氧化的研究进展 [J]. 表面技术, 2019, 48(12): 10
[8] Chen M. Research on the local arc discharge mechanism and the characteristics of power supply in micro-arc oxidation of magnesium alloy [D]. Lanzhou: Lanzhou University of Technology, 2010
[8] 陈 明. 镁合金微弧氧化微区电弧放电机理及电源特性的研究 [D]. 兰州: 兰州理工大学, 2010
[9] Yao W H, Wu L, Wang J F, et al. Micro‐arc oxidation of magnesium alloys: A review [J]. J. Mater. Sci. Technol., 2022, 118: 158
doi: 10.1016/j.jmst.2021.11.053
[10] Yue X J, Xu K N, Wang S Y, et al. SLM magnesium alloy micro-arc oxidation coating [J]. Materials, 2024, 17: 4988
doi: 10.3390/ma17204988
[11] Zhang X X, Yang L, Lu X Q, et al. Characterization and property of dual-functional Zn-incorporated TiO2 micro-arc oxidation coatings: the influence of current density [J]. J. Alloy. Compd., 2019, 810: 151893
doi: 10.1016/j.jallcom.2019.151893
[12] Wang D Y, Dong Q, Chen C Z, et al. Recent progress of micro-arc oxidation technique [J]. J. Chin. Ceram. Soc., 2005, 33: 1133
[12] 王德云, 东 青, 陈传忠 等. 微弧氧化技术的研究进展 [J]. 硅酸盐学报, 2005, 33: 1133
[13] Jiang Y, Chen Z M, Xin B J, et al. Research progress of polyaniline-based conductive functional fabrics [J]. Adv. Text. Technol., 2019, 27(4): 58
[13] 姜 宇, 陈卓明, 辛斌杰 等. 聚苯胺基导电功能性织物研究进展 [J]. 现代纺织技术, 2019, 27(4): 58
[14] Huang H, Guo Z C. Preparation and Application of Conductive Polyaniline [M]. Beijing: Science Press, 2010: 22
[14] 黄 惠, 郭忠诚. 导电聚苯胺的制备及应用 [M]. 北京: 科学出版社, 2010: 22
[15] Xu H, Yan W, Feng J T. Development of synthesis and polymerization mechanism of polyaniline [J]. Chem. Ind. Eng. Prog., 2008, 27: 1561
[15] 徐 浩, 延 卫, 冯江涛. 聚苯胺的合成与聚合机理研究进展 [J]. 化工进展, 2008, 27: 1561
[16] Wu H E, Fei G T, Gao X D, et al. Research progress on preparation and application of polyaniline and its composite materials [J]. China Powder Sci. Technol., 2023, 29(5): 70
[16] 吴红娥, 费广涛, 高旭东 等. 聚苯胺及其复合材料的制备及应用研究进展 [J]. 中国粉体技术, 2023, 29(5): 70
[17] Korovin A N, Kubar'kov A V, Milakin K A, et al. Synthesis and properties of latex particles with polyaniline shells [J]. Colloid J., 2016, 78: 772
doi: 10.1134/S1061933X16060077
[18] Zheng C, Dong Y Z, Liu Y, et al. Enhanced stimuli-responsive electrorheological property of poly (ionic liquid) s-capsulated polyaniline particles [J]. Polymers, 2017, 9: 385
doi: 10.3390/polym9090385
[19] Li Y L, Li Y. Preparation of conductive polyaniline by surfactant-free microemulsion and its coating properties on organic materials [J]. China Dyeing Finish., 2024, 50(8): 54
[19] 李衍隆, 李 勇. 无表面活性剂微乳液制备导电聚苯胺及对有机材料的包覆性能 [J]. 印染, 2024, 50(8): 54
[20] Peng H C, Chen S, Yan B. Electrochromic electrode based on polyaniline and silver nanowires based localized surface plasmon resonance [J]. Acta Chim. Sin., 2024, 82: 797
[20] 彭红超, 陈 胜, 阎 斌. 基于聚苯胺和银纳米线基局部表面等离子体共振的电致变色电极 [J]. 化学学报, 2024, 82: 797
doi: 10.6023/A24020062
[21] Tang M Q, Feng Z Q, Wu X Y, et al. Microarc oxidation coatings containing TiC and NbC on magnesium alloy [J]. Surf. Eng., 2020, 36: 1171
doi: 10.1080/02670844.2019.1635803
[22] Tang M Q, Xin C, Feng Z Q, et al. Review of oxide coatings containing ZrO2 on magnesium alloys by microarc oxidation [J]. Trans. Indian Inst. Met., 2023, 76: 875
doi: 10.1007/s12666-022-02813-0
[23] Huang Z Q, Bai S, Wang Y Q, et al. Effect of polytetrafluoroethylene-assisted microarc oxidation on corrosion and wear characteristics of AZ91 magnesium alloy surface coating [J]. J. Mater. Eng. Perform, 2025, 34: 21893
doi: 10.1007/s11665-025-10869-4
[24] Shang W, Wu F, Jiang S Q, et al. Effect of hydrophobicity on the corrosion resistance of microarc oxidation/self-assembly/nickel composite coatings on magnesium alloys [J]. J. Mol. Liq., 2021, 330: 115606
doi: 10.1016/j.molliq.2021.115606
[25] Wu Y Z, Zhu B W, Zhang X Z, et al. Preparation and characterization of Y-doped microarc oxidation coating on AZ31 magnesium alloys [J]. J. Biomater. Appl., 2022, 37: 930
doi: 10.1177/08853282221121886
[26] Wang X F, Zhang T, Li Y L, et al. Study on characterization technology of porosity and fractal dimension of micro-arc oxidation coating [J]. Mater. Res. Express, 2023, 10: 076514
[27] Zhang Y, Chen Y, Duan X Y, et al. Long time corrosion test of AZ31B Mg alloy via micro-arc oxidation (MAO) technology [J]. Mater. Res. Express, 2019, 6: 126416
doi: 10.1088/2053-1591/ab57e1
[28] Li D L, Li C W, Chen H, et al. Preparation of microarc oxidation coating containing graphene combined with micro-arc oxidation and electrophoretic deposition [J]. Mater. Chem. Phys., 2022, 290: 126598
doi: 10.1016/j.matchemphys.2022.126598
[29] Cheng B, Lu H L, Bai K Y, et al. Formation of ceramic coatings on non-valve metal low carbon steel using micro-arc oxidation technology [J]. Ceram. Int., 2024, 50: 23541
doi: 10.1016/j.ceramint.2024.04.076
[30] Li X Y, Li X G, Li Y, et al. Growth mechanism of micro-arc oxidation film on 6061 aluminum alloy [J]. Mater. Res. Express, 2019, 6: 066404
[1] 赖漾, 徐清亮, 罗群, 李谦. 酸洗致基板表面状态变化对镀锡板耐蚀性的影响[J]. 中国腐蚀与防护学报, 2026, 46(2): 393-404.
[2] 张云, 张宇鹏, 董泽华, 张欣欣. 再生镁合金表面微弧氧化/水滑石复合膜层的一步法制备及其耐蚀性能研究[J]. 中国腐蚀与防护学报, 2026, 46(2): 441-449.
[3] 施艳, 饶智航, 缪程平, 张洋, 陈赵扬, 屠晓华, 李加友, 褚有群. 铜封端负载8-HQ埃洛石纳米管镁合金微弧氧化自修复涂层的制备及耐蚀性能[J]. 中国腐蚀与防护学报, 2026, 46(2): 511-522.
[4] 许诗源, 孟鑫, 杨亚璋, 刘辰, 张昭, 方晓祖. 腐蚀形貌对镁合金电化学阻抗谱特征的影响研究[J]. 中国腐蚀与防护学报, 2025, 45(6): 1589-1598.
[5] 何江海, 杨子钰, 刘琦, 马子骅, 何伟, 陈飞. 在电解液中添加陶瓷颗粒对钛合金表面微弧氧化膜层改性的研究进展[J]. 中国腐蚀与防护学报, 2025, 45(5): 1175-1186.
[6] 蔡科涛, 季磊, 张震, 冯强, 邓伟林, 兰贵红, 何莎, 赵占勇, 白培康. Mg-Gd-Y-Zn-Zr合金在NaClNa2SO4 溶液中腐蚀行为研究[J]. 中国腐蚀与防护学报, 2025, 45(5): 1289-1299.
[7] 张雄斌, 党恩, 于晓婧, 汤玉斐, 赵康. 油气田用马氏体不锈钢腐蚀性能研究现状与进展[J]. 中国腐蚀与防护学报, 2025, 45(4): 837-848.
[8] 翟亚如, 熊金平, 赵景茂. 3.5%NaCl溶液中硝基巴比妥酸对AZ31BAZ91D镁合金腐蚀的缓蚀作用及机理研究[J]. 中国腐蚀与防护学报, 2025, 45(4): 916-926.
[9] 周谦永, 赖漾, 李谦. 酸洗工艺对不同锡量二次冷轧镀锡板耐蚀性能的影响[J]. 中国腐蚀与防护学报, 2025, 45(4): 939-946.
[10] 陈宇强, 冉光林, 陆丁丁, 黄磊, 曾立英, 刘阳, 支倩. 循环强化对7075铝合金腐蚀行为的影响[J]. 中国腐蚀与防护学报, 2025, 45(4): 1051-1060.
[11] 魏然, 蒋全通, 孙琛, 王伟伟, 段继周, 侯保荣. 镁合金在海洋环境中的腐蚀与防护研究[J]. 中国腐蚀与防护学报, 2025, 45(3): 533-547.
[12] 郑微, 曲冬阳, 孙中辉, 牛利. 锌离子电池的锌金属负极和电解液的研究进展[J]. 中国腐蚀与防护学报, 2025, 45(3): 548-562.
[13] 张超, 陈俊航, 邹士文, 张欢, 李曌亮, 肖葵. Mg-Gd-Y-Zr合金在模拟沿海贮存环境下的腐蚀行为与机理研究[J]. 中国腐蚀与防护学报, 2025, 45(3): 731-738.
[14] 安燕, 荆永良, 刘涛, 张玉良, 类延华, 李晓峰, 董丽华. 聚苯胺光热超疏水防冰涂层的制备及其防冰除冰性能[J]. 中国腐蚀与防护学报, 2024, 44(6): 1485-1494.
[15] 魏珂正, 蒋文龙, 龚奕维, 裘欣, 丁汉林, 项重辰, 王子健. 时效时间对锻态AZ80镁合金第二相析出及柱面取向表面腐蚀性能的影响[J]. 中国腐蚀与防护学报, 2024, 44(6): 1557-1565.