铜封端负载<strong>8-HQ</strong>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

doi:10.11902/1005.4537.2025.161

中国腐蚀与防护学报

2026, Vol. 46

Issue (2): 511-522 CSTR: 32134.14.1005.4537.2025.161 DOI: 10.11902/1005.4537.2025.161

研究报告

本期目录 | 过刊浏览

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

施艳¹, 饶智航¹, 缪程平¹, 张洋¹, 陈赵扬², 屠晓华¹(

), 李加友¹, 褚有群²(

)

^1.嘉兴大学生物与化学工程学院嘉兴 314001
^2.浙江工业大学化工学院杭州 310014

Preparation and Corrosion Resistance of a Copper-capped 8-HQ-loaded Halloysite Nanotube-based Self-healing Coating on Mg-alloy via Micro-arc Oxidation

SHI Yan¹, RAO Zhihang¹, MIAO Chengping¹, ZHANG Yang¹, CHEN Zhaoyang², TU Xiaohua¹(

), LI Jiayou¹, CHU Youqun²(

)

^1.College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, China
^2.College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

引用本文:

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.
Yan SHI, Zhihang RAO, Chengping MIAO, Yang ZHANG, Zhaoyang CHEN, Xiaohua TU, Jiayou LI, Youqun CHU. Preparation and Corrosion Resistance of a Copper-capped 8-HQ-loaded Halloysite Nanotube-based Self-healing Coating on Mg-alloy via Micro-arc Oxidation[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(2): 511-522.

全文: PDF(19371 KB) HTML

摘要:

埃洛石纳米管(HNTs)是一种具有管状结构的天然粘土矿物，可作为负载缓蚀剂的纳米容器。本研究通过超声负载法将8-羟基喹啉(8-HQ)装载到HNTs中，并利用Cu²⁺与8-HQ之间的相互作用，在HNTs末端形成不溶性Cu-8-HQ络合物，成功制备缓蚀剂可控释放的Cu-8-HQ-HNTs纳米容器。通过系列表征手段研究该纳米容器的形貌、组成及释放性能。在碱性硅酸盐电解液中，添加纳米容器制备镁合金微弧氧化涂层。利用扫描电子显微镜(SEM)、能谱(EDX)和X射线衍射仪(XRD)表征了涂层的形貌与组成；利用开路电位测试(OCP)以及电化学阻抗谱(EIS)研究耐蚀性能。结果表明，由于具备较好的自修复作用，添加Cu-8-HQ-HNTs纳米容器制备的镁合金微弧氧化涂层耐蚀性能最佳；通过原位掺杂缓蚀纳米容器制备自修复微弧氧化涂层，在镁合金腐蚀防护方面具有较好的应用前景。

关键词 ：镁合金, 埃洛石纳米管, 微弧氧化, 自修复

Abstract：

Halloysite nanotubes (HNTs), as natural clay minerals with tubular structures, serve as nanocontainers for loading corrosion inhibitors. In this study, 8-hydroxyquinoline (8-HQ) was loaded into HNTs via an ultrasonic loading method. By utilizing the interaction between Cu²⁺ and 8-HQ, the insoluble Cu-8-HQ complexes were introduced at the ends of HNTs to prepare the enclosed Cu-8-HQ-HNTs nanocontainers with controlled release properties. The morphologies, compositions, and release behavior of the nanocontainers were systematically characterized. Subsequently, the micro-arc oxidation (MAO) coating on AZ31 Mg-alloy was fabricated in an alkaline silicate electrolyte containing these nanocontainers. The morphology and composition of the coatings were analyzed using scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive X-ray spectroscopy (EDX). Its corrosion resistance was evaluated through open circuit potential (OCP) measurement and electrochemical impedance spectroscopy (EIS). The results indicated that the MAO coating incorporated with Cu-8-HQ-HNTs exhibited optimal corrosion performance due to its superior self-healing capability. This strategy of in situ doping corrosion-inhibiting nanocontainers to prepare self-healing MAO coatings holds significant potential for corrosion protection of Mg-alloys.

Key words： Mg-alloy halloysite nanotube micro-arc oxidation self-healing

收稿日期: 2025-05-27 32134.14.1005.4537.2025.161

ZTFLH:

TG174.4

基金资助:浙江省自然科学基金(LGN22C200009);嘉兴市科技计划(2025AC010);浙江省高校国内访问学者“教师专业发展”项目(FX2024047)

通讯作者: 屠晓华，E-mail：tuxiaohua@zjxu.edu.cn，研究方向为镁合金的腐蚀与防护;
褚有群，E-mail：chuyq@zjut.edu.cn，研究方向为电化学合成、液流电池及材料的腐蚀与防护

作者简介: 施艳，女，2001年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.161 或 https://www.jcscp.org/CN/Y2026/V46/I2/511

图1 Cu-8-HQ-HNTs制备过程示意图和不同HNTs的SEM形貌图、XRD图谱及FTIR谱

图2 8-HQ-HNTs和Cu-8-HQ-HNTs在pH = 3、7、11条件下中的释放曲线

图3 镁合金MAO过程中电压与时间变化关系曲线及不同涂层膜厚和粗糙度的变化关系

图4 4种MAO涂层的表面SEM形貌

图5 4种MAO涂层的XRD谱

图6 4种MAO涂层表面的元素面分布图

图7 4种MAO涂层在3.5%NaCl溶液中的开路电位-时间变化曲线。

图8 4种MAO涂层在3.5%NaCl溶液中的Nyquist和Bode图、等效拟合电路及其Rp值随浸泡时间的变化

表1 4种MAO涂层表面元素含量的EDX分析 (atomic fraction / %)

表2 4种MAO涂层EIS数据的拟合结果

图9 Cu-8-HQ-HNTs-MAO在NaCl中的自修复过程机理

[1]	Bai J Y, Yang Y, Wen C, et al. Applications of magnesium alloys for aerospace: A review [J]. J. Magnesium Alloy., 2023, 11: 3609
[2]	Kulekci M K. Magnesium and its alloys applications in automotive industry [J]. Int. J. Adv. Manuf. Technol., 2008, 39: 851
[3]	Shi L T, Hu J, Lin X D, et al. A robust superhydrophobic PPS-PTFE/SiO₂ composite coating on AZ31 Mg alloy with excellent wear and corrosion resistance properties [J]. J. Alloy. Compd., 2017, 721: 157
[4]	Atrens A, Song G L, Liu M, et al. Review of recent developments in the field of magnesium corrosion [J]. Adv. Eng. Mater., 2015, 17: 400
[5]	Wei R, Jiang Q T, Sun C, et al. A review on corrosion and protection of Mg-alloy in marine environment [J]. J. Chin. Soc. Corros. Prot., 2025, 45: 533
[5]	魏然, 蒋全通, 孙琛等. 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: 533
[6]	Huang J F, Song G L. Research progress on corrosion testing and analysis of Mg-alloys [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 519
[6]	黄居峰, 宋光铃. 镁合金腐蚀测试与分析研究进展 [J]. 中国腐蚀与防护学报, 2024, 44: 519
[7]	Parsons R. Atlas of electrochemical equilibria in aqueous solutions: By Marcel Pourbaix, Pergamon Press, Oxford etc, Cebelcor, Brussels, 1966, 644 pages, £12 [J]. J. Electroanal. Chem. Interfacial Electrochem., 1967, 13: 471
[8]	Wei R, Jiang Q T, Sun C, et al. A review on corrosion and protection of Mg-alloy in marine environment [J]. J. Chin. Soc. Corros. Prot., 2025, 45: 533
[8]	魏然, 蒋全通, 孙琛等. 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: 533
[9]	Chen J Y, Chen X B, Li J L, et al. Electrosprayed PLGA smart containers for active anti-corrosion coating on magnesium alloy AMlite [J]. J. Mater. Chem., 2014, 2A: 5738
[10]	Gnedenkov A S, Sinebryukhov S L, Mashtalyar D V, et al. Protective properties of inhibitor-containing composite coatings on a Mg alloy [J]. Corros. Sci., 2016, 102: 348
[11]	Duan H P, Du K Q, Yan C W, et al. Electrochemical corrosion behavior of composite coatings of sealed MAO film on magnesium alloy AZ91D [J]. Electrochim. Acta, 2006, 51: 2898
[12]	King A D, Birbilis N, Scully J R. Accurate electrochemical measurement of magnesium corrosion rates; a combined impedance, mass-loss and hydrogen collection study [J]. Electrochim. Acta, 2014, 121: 394
[13]	Lu F M, Ma A B, Jiang J H, et al. Significantly improved corrosion resistance of heat-treated Mg-Al-Gd alloy containing profuse needle-like precipitates within grains [J]. Corros. Sci., 2015, 94: 171
[14]	Tian M Z, Wang Y, Li T, et al. Effect of electrical parameters on energy consumption and corrosion resistance of micro-arc oxidation coating on AZ31B Mg-alloy [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 1064
[14]	田梦真, 王勇, 李涛等. 电参数对AZ31B镁合金微弧氧化膜能耗及耐蚀性的影响 [J]. 中国腐蚀与防护学报, 2024, 44: 1064
[15]	Wu Y, An Y Q, Wang L W, et al. Atmospheric corrosion behavior of Mg-alloys AZ31B and AZ91D in simulated low temperature environments [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 1001
[15]	吴洋, 安易强, 王力伟等. 镁铝合金在模拟低温条件下大气腐蚀行为研究 [J]. 中国腐蚀与防护学报, 2024, 44: 1001
[16]	Yang B, Wang P, Hu J, et al. Improving structure and corrosion resistance of micro-arc oxidation coatings formed on aluminum alloy with the addition of La₂O₃ [J]. Int. J. Mater. Res., 2022, 113: 693
[17]	Zhu J Y, Jia H J, Liao K J, et al. Improvement on corrosion resistance of micro-arc oxidized AZ91D magnesium alloy by a pore-sealing coating [J]. J. Alloy. Compd., 2021, 889: 161460
[18]	Ly X, Yang S, Nguyen T. Effect of equal channel angular pressing as the pretreatment on microstructure and corrosion behavior of micro-arc oxidation (MAO) composite coating on biodegradable Mg-Zn-Ca alloy [J]. Surf. Coat. Technol., 2020, 395: 125923
[19]	Wang R, Ni S L, Ma L, et al. Porous construction and surface modification of titanium-based materials for osteogenesis: A review [J]. Front. Bioeng. Biotechnol., 2022, 10: 973297
[20]	Hussein R O, Northwood D O, Nie X. The influence of pulse timing and current mode on the microstructure and corrosion behaviour of a plasma electrolytic oxidation (PEO) coated AM60B magnesium alloy [J]. J. Alloy. Compd., 2012, 541: 41
[21]	Hwang D Y, Kim Y M, Park D Y, et al. Corrosion resistance of oxide layers formed on AZ91 Mg alloy in KMnO₄ electrolyte by plasma electrolytic oxidation [J]. Electrochim. Acta, 2009, 54: 5479
[22]	Li H, Lu S T, Qin W, et al. Improving the wear properties of AZ31 magnesium alloy under vacuum low-temperature condition by plasma electrolytic oxidation coating [J]. Acta Astronaut., 2015, 116: 126
[23]	Sun M, Matthews A, Yerokhin A. Plasma electrolytic oxidation coatings on cp-Mg with cerium nitrate and benzotriazole immersion post-treatments [J]. Surf. Coat. Technol., 2018, 344: 330
[24]	Wang T C, Zhao D Y, Xiang X Y, et al. Degradation behavior of an epoxy corrosion-resistant coating in NaCl solution [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 1361
[24]	王天丛, 赵东杨, 向雪云等. 一种环氧耐蚀涂层在NaCl溶液中的劣化行为研究 [J]. 中国腐蚀与防护学报, 2024, 44: 1361
[25]	Liu D, Han E H, Song Y W, et al. Enhancing the self-healing property by adding the synergetic corrosion inhibitors of Na₃PO₄ and 2-mercaptobenzothiazole into the coating of Mg alloy [J]. Electrochim. Acta, 2019, 323: 134796
[26]	Zhu W, Li W F, Mu S L, et al. Comparative study on Ti/Zr/V and chromate conversion treated aluminum alloys: Anti-corrosion performance and epoxy coating adhesion properties [J]. Appl. Surf. Sci., 2017, 405: 157
[27]	Zeng R C, Liu L J, Luo K J, et al. In vitro corrosion and antibacterial properties of layer-by-layer assembled GS/PSS coating on AZ31 magnesium alloys [J]. Trans. Nonferrous Met. Soc. China, 2015, 25: 4028
[28]	Mingo B, Guo Y, Němcová A, et al. Incorporation of halloysite nanotubes into forsterite surface layer during plasma electrolytic oxidation of AM50 Mg alloy [J]. Electrochim. Acta, 2019, 299: 772
[29]	Nazeer A A, Madkour M. Potential use of smart coatings for corrosion protection of metals and alloys: A review [J]. J. Mol. Liq., 2018, 253: 11
[30]	Bhavsar D, Gajjar J, Sawant K. Formulation and development of smart pH responsive mesoporous silica nanoparticles for breast cancer targeted delivery of anastrozole: In vitro and in vivo characterizations [J]. Microporous Mesoporous Mater., 2019, 279: 107
[31]	Liu C B, Zhao H C, Hou P M, et al. Efficient graphene/cyclodextrin-based nanocontainer: Synthesis and host-guest inclusion for self-healing anticorrosion application [J]. ACS Appl. Mater. Interfaces, 2018, 10: 36229
[32]	Shchukina E, Shchukin D, Grigoriev D. Halloysites and mesoporous silica as inhibitor nanocontainers for feedback active powder coatings [J]. Prog. Org. Coat., 2018, 123: 384
[33]	Zuo J D, Wu B, Luo C Y, et al. Preparation of MgAl layered double hydroxides intercalated with nitrite ions and corrosion protection of steel bars in simulated carbonated concrete pore solution [J]. Corros. Sci., 2019, 152: 120
[34]	Chen Y, Gong C B, Wang S G, et al. Microstructures, microhardness and corrosion properties of nanocrystalline 304 stainless steel plate [J]. Acta Metall. Sin., 2024, DOI: 10.11900/0412.1961.2024.00253
[34]	陈园, 宫春波, 王胜刚等. 纳米晶304不锈钢板材微观组织、显微硬度与腐蚀性能 [J]. 金属学报, 2024, DOI: 10.11900/0412.1961.2024.00253
[35]	Wu H, Yang G H, Tang C, et al. Corrosion resistance of TiN nanoparticle-reinforced aluminum alloy [J]. Spec. Cast. Nonferrous Alloy., 2025, 45: 1815
[35]	吴昊, 杨光恒, 汤超等. TiN纳米颗粒增强铝合金的耐腐蚀性能研究 [J]. 特种铸造及有色合金, 2025, 45: 1815
[36]	Yu D, Wang J, Hu W, et al. Preparation and controlled release behavior of halloysite/2-mercaptobenzothiazole nanocomposite with calcined halloysite as nanocontainer [J]. Mater. Des., 2017, 129: 103
[37]	Guzmán E, Cavallo J A, Chuliá-Jordán R, et al. pH-induced changes in the fabrication of multilayers of poly (acrylic acid) and chitosan: Fabrication, properties, and tests as a drug storage and delivery system [J]. Langmuir, 2011, 27: 6836
[38]	Lvov Y, Abdullayev E. Functional polymer-clay nanotube composites with sustained release of chemical agents [J]. Prog. Polym. Sci., 2013, 38: 1690
[39]	Shchukin D G, Lamaka S V, Yasakau K A, et al. Active anticorrosion coatings with halloysite nanocontainers [J]. J. Phys. Chem., 2008, 112C: 958
[40]	Xing X T, Wang J H, Hu W B, et al. Synthesis and inhibition behavior of acid stimuli-responsive Ca-Na₂MoO₄-HNTs nanocomposite [J]. Colloids Surf., 2018, 553A: 305
[41]	Fan H Y, Liang K, Bai R, et al. Enhanced corrosion resistance of PEO coating on AZ31B Mg alloys with delayed corrosion and slow diffusion [J]. Surf. Coat. Technol., 2025, 496: 131630
[42]	Zhang A B, Pan L, Zhang H Y, et al. Effects of acid treatment on the physico-chemical and pore characteristics of halloysite [J]. Colloids Surf., 2012, 396A: 182
[43]	Badiei A, Goldooz H, Ziarani G M. A novel method for preparation of 8-hydroxyquinoline functionalized mesoporous silica: Aluminum complexes and photoluminescence studies [J]. Appl. Surf. Sci., 2011, 257: 4912
[44]	Haase M F, Grigoriev D, Moehwald H, et al. Encapsulation of amphoteric substances in a pH-sensitive Pickering emulsion [J]. J. Phys. Chem., 2010, 114C: 17304
[45]	Guo J, Wang L P, Wang S C, et al. Preparation and performance of a novel multifunctional plasma electrolytic oxidation composite coating formed on magnesium alloy [J]. J. Mater. Sci., 2009, 44: 1998
[46]	Lee K M, Shin K R, Namgung S, et al. Electrochemical response of ZrO₂-incorporated oxide layer on AZ91 Mg alloy processed by plasma electrolytic oxidation [J]. Surf. Coat. Technol., 2011, 205: 3779
[47]	Wu W X, Wang W P, Lin H C. A study on corrosion behavior of micro-arc oxidation coatings doped with 2-aminobenzimidazole loaded halloysite nanotubes on AZ31 magnesium alloys [J]. Surf. Coat. Technol., 2021, 416: 127116
[48]	Gao Y H, Yerokhin A, Matthews A. Effect of current mode on PEO treatment of magnesium in Ca- and P-containing electrolyte and resulting coatings [J]. Appl. Surf. Sci., 2014, 316: 558
[49]	Zhang R F, Zhang S F, Yang N, et al. Influence of 8-hydroxyquinoline on properties of anodic coatings obtained by micro arc oxidation on AZ91 magnesium alloys [J]. J. Alloy. Compd., 2012, 539: 249
[50]	Sun M, Yerokhin A, Bychkova M Y, et al. Self-healing plasma electrolytic oxidation coatings doped with benzotriazole loaded halloysite nanotubes on AM50 magnesium alloy [J]. Corros. Sci., 2016, 111: 753
[51]	Qiang Y J, Guo L, Zhang S T, et al. Synergistic effect of tartaric acid with 2, 6-diaminopyridine on the corrosion inhibition of mild steel in 0.5 M HCl [J]. Sci. Rep., 2016, 6: 33305
[52]	Cen H Y, Cao J J, Chen Z Y, et al. 2-Mercaptobenzothiazole as a corrosion inhibitor for carbon steel in supercritical CO₂-H₂O condition [J]. Appl. Surf. Sci., 2019, 476: 422

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