Comparative Study on Corrosion Resistance of TaSiCN, TaAlSiCN and TaCrSiCN Coatings in NaCl-KCl Molten Salt
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摘要: 为探究Al、Cr元素掺杂的TaSiCN涂层在NaCl-KCl熔盐中的耐腐蚀性能，利用射频磁控溅射技术并通过调控Ar和N2混合气体的比例在Ta合金基体上制备了近似N原子百分比的TaSiCN、TaAlSiCN和TaCrSiCN纳米复合涂层。系统研究了涂层的微观结构、化学组成和耐NaCl-KCl熔盐的腐蚀性能。结果表明：所有沉积态的涂层均由TaN、TaC和Ta(C,N)纳米晶相以及SiCx、SiNx、CNx和sp2无定型态碳等非晶相组成，其中掺杂元素Al、Cr也以非晶的形式存在于涂层之中。腐蚀后的涂层表面主要由Ta(C,N)、Ta2O5、Na2Ta4O11晶相成分和一些非晶相成分构成。涂层在NaCl-KCl熔盐中的腐蚀行为主要以氧化腐蚀为主，熔盐侵蚀为辅。通过对比发现，涂层耐腐蚀性顺序为：TaAlSiCN＞TaSiCN＞TaCrSiCN。本研究可为熔盐电解坩埚表面涂层技术的开发提供一种具有应用潜力的候选涂层材料。
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关键词:
- TaSiCN涂层 /
- 磁控溅射技术 /
- Ta合金 /
- NaCl-KCl熔盐 /
- 抗腐蚀性
Abstract: In order to explore the corrosion resistance of Al and Cr doped TaSiCN coatings in NaCl-KCl molten salt, nano-composite coatings of TaSiCN, TaAlSiCN and TaCrSiCN with approximately N atomic percent were prepared on Ta alloy substrate by using RF magnetron sputtering technology and adjusting the ratio of Ar and N2 mixed gases. The microstructure, chemical composition and corrosion resistance of the coating in NaCl-KCl molten salt were systematically studied. The results show that all as-deposited coatings are composed of TaN, TaC and Ta(C,N) nanocrystals and amorphous carbon such as SiCx, SiNx, CNx and sp2, among which the doped Al and Cr elements also exist in the coatings in amorphous form. After corrosion, the coating surface is mainly composed of crystalline components such as Ta(C,N), Ta2O5 and Na2Ta4O11, and other amorphous components. The corrosion behavior of coating in NaCl-KCl molten salt is mainly oxidation corrosion, supplemented by molten salt corrosion. Through comparison, it is found that the order of corrosion resistance of three coatings is: TaAlSiCN > TaSiCN > TaCrSiCN. This study can provide a potential candidate coating material for the development of surface coating technology of molten salt electrolytic crucible.-
Key words:
- TaSiCN coating /
- Magnetron sputtering /
- Ta alloy /
- NaCl-KCl molten salt /
- Corrosion resistance
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图 2 TaSiCN、TaAlSiCN和TaCrSiCN涂层的XRD图谱
α—Ta；β—Ta(C,N)；2θ—衍射角
Figure 2. XRD Patterns of TaSiCN, TaAlSiCN and TaCrSiCN Coatings
图 4 腐蚀4 h后涂层表面和截面SEM图像
Figure 4. SEM Images of Coating Surface and Cross-section after 4 h Corrosion
图 5 腐蚀4 h后涂层的XRD图谱
γ—Ta2O5；ε—Na2Ta4O11
Figure 5. XRD Patterns of Coatings after 4 h Corrosion
图 6 腐蚀4 h后涂层的XPS图谱
图6a能级谱图中从上到下依次为TaSiCN、TaAlSiCN、TaCrSiCN涂层
Figure 6. XPS Core Level Spectra of Coatings after 4 h Corrosion
图 7 腐蚀12 h后涂层的SEM图像和EDS谱
Figure 7. SEM Images and EDS Spectra for Coatings after 12 h Corrosion
图 8 腐蚀16 h后涂层典型表面、截面SEM图像和EDS图谱
Figure 8. Typical Surface, Cross-section SEM Images and EDS Spectra after 16 h Corrosion
表 1 TaSiCN、TaAlSiCN和TaCrSiCN涂层的EDS元素分析
Table 1. EDS Elemental Composition of TaSiCN, TaAlSiCN and TaCrSiCN Coatings
试样 气体流量/(mL·min−1) 元素原子百分比/% Ar N2 Ta Si C N Al Cr TaSiCN 48 6 26 6 40 29 0 0 TaAlSiCN 48 6 22 8 34 26 10 0 TaCrSiCN 48 6 21 9 33 24 0 13 
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表 2 TaSiCN、TaAlSiCN和TaCrSiCN涂层表面和截面内部的EDS元素分析
Table 2. EDS Element Analysis of Surface and Cross Section of TaSiCN, TaAlSiCN and TaCrSiCN Coatings
分析区域 元素原子百分比/% Ta Si C N O Al Cr Cl Na K 涂层表面 TaSiCN 18.1 4.4 20.7 4.3 44.2 0.6 6.8 0.9 TaAlSiCN 12.8 4.8 28.2 6.6 40.5 3.2 0.5 6.8 1.4 TaCrSiCN 17.9 4.9 25.5 13.3 24.7 9.6 0.1 3.8 0.2 涂层截面内部 TaSiCN 19.9 8.5 25.8 38.4 5.6 0 1.8 0 TaAlSiCN 21.6 6.3 26.1 32.2 3.8 9.8 0 0.2 0 TaCrSiCN 17.9 7.9 23.1 31.2 7.2 10.3 0 2.4 0
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