锆合金表面复合陶瓷涂层的制备与性能表征

朱燕辉; 刘祥; 张吉阜; 陈嘉杰; 陈东初

doi:10.16490/j.cnki.issn.1001-3660.2025.15.008

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表面技术 ›› 2025, Vol. 54 ›› Issue (15) : 86-95. DOI: 10.16490/j.cnki.issn.1001-3660.2025.15.008

技术及应用

锆合金表面复合陶瓷涂层的制备与性能表征

朱燕辉^{1, 2}, 刘祥^{1, 2}, 张吉阜^{1, 2, *}, 陈嘉杰³, 陈东初^{1, 2}

作者信息 +

Preparation and Characterization of Composite Ceramic Coatings on Zirconium Alloy Surfaces

ZHU Yanhui^{1, 2}, LIU Xiang^{1, 2}, ZHANG Jifu^{1, 2, *}, CHEN Jiajie³, CHEN Dongchu^{1, 2}

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文章历史 +

摘要

目的解决核反应堆锆合金包壳在高温水蒸气环境下的氧化腐蚀问题,采用原位陶瓷化技术构建复合陶瓷涂层,以提高锆合金的抗高温氧化性、耐水汽腐蚀性能及事故容错能力（ATF）。方法采用微弧氧化（MAO）与大气等离子喷涂（APS）相结合的工艺制备复合陶瓷涂层,并优化MAO底层膜结构。通过筛选不同微弧氧化电源模式,包括单向脉冲（UP）、双向脉冲（BP）、两步脉冲（TS）,调整氧化膜的微观结构和成分。利用扫描电子显微镜（SEM）、X射线衍射（XRD）、X射线光电子能谱（XPS）等表征手段,分析MAO膜的微观形貌、物相组成及化学成分。同时,通过划痕试验、高温水汽腐蚀试验等测试复合陶瓷涂层的结合强度和抗高温氧化性能,以评估其服役性能。结果采用两步脉冲（TS）模式制备的MAO底层膜由ZrO₂和Al_0.52Zr_0.48O_1.74混合相组成,形成了梯度致密结构,显著降低了裂纹密度。基于TS模式制备的涂层的结合强度达到16 MPa,相较于UP（7 MPa）和BP（4 MPa）模式,分别提高了128%、300%。高温水汽腐蚀测试（1 200 ℃、4 000 s）结果表明,厚度为30 μm的涂层的氧化增量速率最低,且结构完整,而80 μm的涂层因热应力的累积,出现了剥落现象。结论通过调控微弧氧化过程中的电源模式,可优化MAO底层膜的结构和性能,实现喷涂沉积层与氧化膜的有效结合,从而在锆合金表面获得结合牢固、结构致密且厚度可控的复合陶瓷涂层,提高了它在核反应堆环境中的服役稳定性。

Abstract

To address the oxidation and corrosion challenges of zirconium alloy claddings in nuclear reactors under high-temperature steam environments, the work aims to employ in situ ceramicization technology to fabricate a composite ceramic coating, so as to enhance the high-temperature oxidation resistance, steam corrosion resistance, and accident tolerance performance (Accident Tolerant Fuel, ATF) of zirconium alloys. A hybrid fabrication process combining micro-arc oxidation (MAO) and atmospheric plasma spraying (APS) was developed to prepare the composite ceramic coating system, with particular emphasis on optimizing the microstructure of the MAO interlayer. The experimental protocol involved systematic screening of different MAO power supply modes, including unipolar pulse (UP), bipolar pulse (BP), and two-step pulse (TS), to regulate the microstructural evolution and compositional characteristics of the oxide layer. Subsequent APS deposition was performed to establish a multilayered protective architecture. Comprehensive material characterization techniques, such as scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), were employed to analyze the morphological features, phase composition, and chemical states of the MAO-derived oxide layers. Mechanical integrity and environmental resistance were evaluated through scratch testing and high-temperature steam corrosion experiments, providing quantitative assessment of interfacial bonding strength and long-term durability. Experimental results demonstrate that the MAO base layer fabricated via the two-step pulse (TS) mode consists of a mixed phase of ZrO₂ and Al_0.52Zr_0.48O_1.74, forming a gradient dense structure that significantly reduces crack density. The coating prepared under the TS mode exhibits an interfacial bonding strength of 16 MPa, representing a 128% and 300% improvement compared to the unipolar pulse (UP, 7 MPa) and bipolar pulse (BP, 4 MPa) modes, respectively. High-temperature steam corrosion tests (1 200 ℃, 4 000 s) reveal that the 30 μm-thick coating shows the lowest oxidation weight gain rate and maintains structural integrity, while the 80 μm-thick coating experiences spallation due to accumulated thermal stress. Microstructural analysis reveals that the TS power mode facilitates controlled plasma discharge behavior during MAO process, promoting the formation of a gradient oxide structure with reduced microcrack density and improves phase stability. The mechanism underlying performance enhancement can be attributed to two synergistic effects. Firstly, the MAO-derived oxide layer acts as an effective diffusion barrier, suppressing oxygen penetration and hydrogen absorption at the substrate-coating interface. Secondly, the tailored surface morphology and chemical compatibility of the MAO interlayer create favorable conditions for APS coating adhesion through mechanical interlocking and chemical bonding. By precisely regulating the electrical parameters during MAO process, this study establishes a methodology for achieving optimal interfacial compatibility between the metallic substrate and ceramic coating system and provides critical insights into surface engineering strategies for nuclear-grade zirconium alloys. The developed composite coating architecture demonstrates threefold advantages of enhanced interfacial integrity through MAO layer optimization, superior environmental resistance via multilayered ceramic protection, and controllable thickness for maintaining neutron economy in reactor applications. The TS-mode MAO process proves particularly effective in balancing coating density and residual stress distribution, addressing the longstanding challenge of ceramic coating spallation under thermal cycling conditions. Further investigation should focus on long-term stability assessment under simulated loss-of-coolant accident (LOCA) scenarios and neutron irradiation effects. Nevertheless, the current findings establish a viable pathway for developing advanced ATF cladding materials through hybrid surface modification techniques, potentially extending the operational safety margins of nuclear reactors under both normal and accident conditions.

导出引用

朱燕辉, 刘祥, 张吉阜, 陈嘉杰, 陈东初. 锆合金表面复合陶瓷涂层的制备与性能表征[J]. 表面技术. 2025, 54(15): 86-95 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.15.008

ZHU Yanhui, LIU Xiang, ZHANG Jifu, CHEN Jiajie, CHEN Dongchu. Preparation and Characterization of Composite Ceramic Coatings on Zirconium Alloy Surfaces[J]. Surface Technology. 2025, 54(15): 86-95 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.15.008

中图分类号： TG174.453

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