氮气调控微弧氧化: 锆合金涂层的致密化与耐蚀性

doi:10.15541/jim20250406

无机材料学报 ›› 2026, Vol. 41 ›› Issue (8): 1095-1102.DOI: 10.15541/jim20250406

氮气调控微弧氧化: 锆合金涂层的致密化与耐蚀性

纪若男¹(), 魏大庆¹(), 王庆宇¹, 李永昶¹, 张田¹, 杜青²

¹ 哈尔滨工程大学核科学与技术学院, 哈尔滨 150001
² 哈尔滨理工大学建筑工程学院, 哈尔滨 150080

收稿日期:2025-10-16 修回日期:2025-12-19 出版日期:2026-08-20 网络出版日期:2025-12-19
通讯作者: 魏大庆, 教授. E-mail: daqingwei@hrbeu.edu.cn
作者简介:纪若男(1994-), 女, 讲师. E-mail: 1327952321@qq.com
基金资助:
基本科研业务费(2522050205A0015)

Nitrogen Modulation of Micro-arc Oxidation: Densification and Corrosion Resistance of Zirconium Alloy Coatings

JI Ruonan¹(), WEI Daqing¹(), WANG Qingyu¹, LI Yongchang¹, ZHANG Tian¹, DU Qing²

¹ College of Nuclear Science and Technology, Harbin Engineering University, Harbin 150001, China
² School of Architecture and Civil Engineering, Harbin University of Science and Technology, Harbin 150080, China

Received:2025-10-16 Revised:2025-12-19 Published:2026-08-20 Online:2025-12-19
Contact: WEI Daqing, professor. E-mail: daqingwei@hrbeu.edu.cn
About author:JI Ruonan (1994-), female, lecturer. E-mail: 1327952321@qq.com
Supported by:
Fundamental Research Funds for the Academy of Sciences(2522050205A0015)

摘要/Abstract

摘要：

核用锆合金在反应堆失水事故工况下易发生剧烈的锆水反应, 而传统微弧氧化(MAO)涂层因孔隙率高, 难以提供足够保护。本研究在MAO过程中创新性地引入氮气, 利用氮气氛围抑制电弧集中, 实现涂层结构优化与氮元素掺杂。实验结果表明, 该方法成功制备出致密氧化锆涂层, 其孔隙率显著降至4.96%(降幅62%), 表面粗糙度降低, 且与基体结合紧密、无明显裂纹; 同步实现氮元素晶格固溶, 并形成特征性Zr-O-N键合结构。得益于此微观结构与化学组成的协同优化, 致密涂层在0.1 mol/L LiOH溶液中的腐蚀电流密度低至1.61×10^-8 A·cm^-2, 较常规MAO涂层降低一个数量级。本研究证实, 氮气氛围可同步实现结构调控与化学改性, 为开发高性能事故容错锆合金包壳涂层提供了新途径。

关键词: 锆合金, 微弧氧化, 氮掺杂, 耐腐蚀性能

Abstract:

Zirconium alloys used in nuclear reactors undergo severe zirconium-water reaction during loss-of-coolant accidents. Conventional micro-arc oxidation (MAO) coatings, limited by their high porosity, offer insufficient protection. In this study, nitrogen was innovatively introduced into the MAO process to suppress arc concentration, thereby achieving simultaneous structural optimization and nitrogen doping of the coating. Experimental results demonstrate the successful fabrication of a dense zirconium oxide coating through this approach. The porosity is significantly reduced to 4.96% (representing a 62% reduction), surface roughness is decreased, and a tight, crack-free bond with the substrate is achieved. Simultaneously, nitrogen is incorporated into the crystal lattice, forming a characteristic Zr-O-N bonding structure. Benefiting from this synergistic optimization of the microstructure and chemical composition, the dense coating exhibits a corrosion current density as low as 1.61×10^-8 A·cm^-2 in a 0.1 mol/L LiOH solution, which is one order of magnitude lower than that of a conventional MAO coating. This work confirms that a nitrogen atmosphere can simultaneously facilitate structural regulation and chemical modification, providing a new pathway for developing high-performance accident-tolerant zirconium alloy cladding coatings.

Key words: zirconium alloy, micro-arc oxidation, nitrogen doping, corrosion resistance

中图分类号:

TG174

纪若男, 魏大庆, 王庆宇, 李永昶, 张田, 杜青. 氮气调控微弧氧化: 锆合金涂层的致密化与耐蚀性[J]. 无机材料学报, 2026, 41(8): 1095-1102.

JI Ruonan, WEI Daqing, WANG Qingyu, LI Yongchang, ZHANG Tian, DU Qing. Nitrogen Modulation of Micro-arc Oxidation: Densification and Corrosion Resistance of Zirconium Alloy Coatings[J]. Journal of Inorganic Materials, 2026, 41(8): 1095-1102.

图/表 9

图1 (a) MAO和(b) MAO-N2涂层的微观形貌以及ImageJ二值化处理图

Fig. 1 Micro-morphologies and ImageJ binarization processed images of (a) MAO and (b) MAO-N2 coatings

图2 (a) MAO和(b) MAO-N2涂层的截面形貌及元素能谱分析

Fig. 2 Cross-sectional morphologies and corresponding element distributions of (a) MAO and (b) MAO-N2 coatings Colorful figures are available on website

图3 (a) OES总谱图和(b)涂层的XRD谱图

Fig. 3 (a) OES full spectra and (b) XRD patterns of coatings

图4 MAO和MAO-N2涂层的XPS谱图

Fig. 4 XPS spectra of MAO and MAO-N2 coatings (a) XPS full spectra; (b, c) N1s XPS spectra of (b) MAO and (c) MAO-N2 coatings before and after etching; (d) O1s, (e) N1s and (f) Zr3d XPS spectra of MAO and MAO-N2 coatings

图5 MAO-N2涂层的TEM结果

Fig. 5 TEM results of MAO-N2 coating (a) TEM image and EDS mappings; (b) HRTEM images; (c) FFT pattern

表1 图5(a)所示区域的元素组成

Table 1 Chemical composition of the area presented in Fig. 5(a)

Element	C	N	O	Si	Zr
Chemical composition/ % (in atom)	14.05	3.70	45.35	1.58	35.32

图6 极化曲线和EIS测试结果

Fig. 6 Results of polarization curves and EIS tests (a) Potentiodynamic polarization curves; (b) Bode plots of |Z| vs. frequency and the equivalent circuit model; (c) Nyquist plots; (d) Bode plots of phase angle vs. frequency

表2 极化曲线分析结果

Table 2 Polarization analysis

Coating	E_corr/V	I_corr/(A·cm⁻²)	b_a/V	b_c/V	R_p/(Ω·cm²)
MAO	-0.175	5.51×10^-7	0.1944	-0.2004	5.116×10⁶
MAO-N₂	-0.605	1.61×10^-8	0.2287	-0.1576	1.371×10⁷

表3 EIS数据拟合结果

Table 3 Fitting results of EIS data

Coating	R_s/(Ω·cm²)	R_p/(Ω·cm²)	Q_p/(F·cm⁻²)	n_p	R_ct/(Ω·cm²)	Q_dl/(F·cm⁻²)	n_dl
MAO	82	4.26×10⁴	1.83×10^-6	0.55	3.92×10⁴	2.91×10³	0.50
MAO-N₂	82	1.54×10⁵	9.20×10^-7	0.58	5.05×10⁴	3.75×10^-5	0.75

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氮气调控微弧氧化: 锆合金涂层的致密化与耐蚀性

Nitrogen Modulation of Micro-arc Oxidation: Densification and Corrosion Resistance of Zirconium Alloy Coatings

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