Stability and corrosion behavior of AlO<sub><i>x</i></sub> coating on T91 steel and SIMP steel in static liquid Pb-Bi eutectic at 600 ℃

Liao Qing; Li Bing-Sheng; Ge Fang-Fang; Zhang Hong-Peng; Shen Tie-Long; Mao Xue-Li; Wang Ren-Da; Sheng Yan-Bin; Chang Hai-Long; Wang Zhi-Guang; Xu Shuai; Chen Li-Ming; He Xiao-Xun

doi:10.7498/aps.71.20220356

Abstract

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1. 引　言
2. 实验过程
2.1 实验材料和涂层制备工艺
2.2 静态腐蚀实验
3. 实验结果
4. 讨　论
4.1 氧化层的形成原因
4.2 氧化铝涂层的作用与稳定性分析
5. 结　论

References

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Abstract

Ferritic/martensitic steels, such as T91 steel and SIMP steel, are chosen as the main candidates of structural materials for the Generation IV lead-cooled fast reactors and accelerator driven system. However, the compatibility between container steel and liquid Pb-Bi eutectic (LBE) at high temperature limits their applications. The corrosion of ferritic/martensitic steels is serious in LBE at 600 ℃. In order to avoid corroding the ferritic/martensitic steels in LBE, it is proposed to coat AlO_x (x < 1.5) on the steel surface. The AlO_x coating is conducted on T91 steel and SIMP steel by magnetron sputtering. In this exploratory work, the corrosion results of AlO_x coating steel are compared with the corrosion results of the uncoated steel in LBE with a saturated oxygen concentration at 600 ℃ for 300 h and 700 h. The results show that the AlO_x coating can effectively prevent the iron chromium and oxygen from diffusing, so the oxide scale of the coated steel is thinner than that of the uncoated steel. However, the coating cracks after 700 h corrosion in LBE. Meanwhile, T91 steel and SIMP steel also suffer serious oxidative corrosion, indicating that the coating can protect the substrate from being corroded by 600 ℃ static LBE in a short time. However, the coating cannot keep stable for a long time in LBE at 600 ℃. This may be due to the weak film base bonding force of AlO_x coating prepared under the experimental conditions, or a large number of metal aluminum and structural defects existing in AlO_x coating. It is needed to further study the stability of AlO_x coating in LBE at elevated temperature.

Keywords:

PACS:

61.66.Dk	(Alloys)
61.72.-y	(Defects and impurities in crystals; microstructure)
68.18.-g	(Langmuir-Blodgett films on liquids)
68.35.Fx	(Diffusion; interface formation)

Authors and contacts

1.
State Key Laboratory for Environment-friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, China
2.
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
3.
Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000, China
4.
School of science, Southwest University of Science and Technology, Mianyang 621010, China
5.
School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, China

Corresponding author: Li Bing-Sheng, libingshengmvp@163.com

Funds: Project supported by the National Nature Science Foundation of China (Grant Nos. U1832133, 12075194) and the Scientific Research Fundation of the Science and Technology Department of Sichuan Province, China (Grant No. 2020ZYD055).

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1. 引　言

液态重金属铅合金凭借其良好的中子学性能、较低的化学活性、良好的传热性和固有安全性, 被认为是加速器驱动系统(ADS)和铅冷快堆等第4代核反应堆的主要候选材料之一^[1-3]. 液态铅铋共晶(LBE)作为铅合金的重要组成, 其在加速器驱动系统(ADS)和铅冷快堆等方向同样具有广阔的应用前景, 然而在高温下LBE对容器材料会造成腐蚀. 腐蚀主要可分为溶解腐蚀, 如奥氏体不锈钢中镍元素溶解到铅铋溶液中、铅铋流动造成的侵蚀、冲刷, 以及组分元素在固液两相中的迁移、腐蚀产物和杂质的化学反应等^[4,5]. 主要腐蚀机理如下: 氧化腐蚀、铅铋渗透和溶解腐蚀以及高速的LBE流动产生的加速腐蚀. 容器材料的腐蚀会导致结构承载能力的降低, 甚至危及反应堆的安全. 故此, 提高容器材料耐腐蚀性能至关重要. 研究表明, 提高材料耐腐蚀性能的方法有以下5种:

1) 通过控制反应体系中的氧浓度, 在钢表面形成稳定的氧化铁和氧化铬保护膜^[6,7]. 当温度低于500 ℃时, 该方法可以达到良好的保护效果. 然而当温度高于500 ℃时, 由于氧化物快速生长, 导致材料热导率迅速降低. 另外氧化膜在高温流动铅铋溶液中, 很容易被冲刷掉, 导致铅铋流场发生变化, 因此该方法在高温铅铋溶液中将不再适用^[8,9].

2)使用耐腐蚀材料, 确定冷却剂运行参数的适当范围, 包括温度和溶解氧浓度. 迄今为止, 候选结构材料主要包括铁素体/马氏体钢、奥氏体不锈钢、纳米氧化物弥散强化钢(ODS)和陶瓷材料^[10,11].

3)含有特殊元素(如硅和铝)的合金钢可以促进致密氧化层的形成.

4)钢铁表面处理技术, 例如渗铝表面处理^[12,13], 电子束处理的FeCrAl和FeCrAl涂层^[14,15], 甚至包括Fe-12Cr-2Si^[16]和ODS钢^[17-19]在内的新合金, 以增强材料的耐腐蚀性. 一些研究表明, 表面上的氧化铝薄层可以保护钢材^[20,21].

5)向液态金属中加入抑制剂^[9].

尽管做出了许多努力, 但在高温下保护结构钢免受材料腐蚀仍然是一个未完全解决的问题. 近年来, 表面改性技术在防止材料腐蚀方面得到了广泛的应用, 已经开发了几种涂层制备技术来保护钢材免受腐蚀. 例如通过真空等离子喷涂、化学气相沉积、脉冲激光沉积和物理气相沉积来沉积不同类型的涂层, 如金属合金(FeAl)、氧化物(主要是硅和铝)、碳化物和氮化物^[8,22,23].

研究表明, 氧化铝难溶于液态铅铋溶液中, 并且金属原子和氧原子在氧化铝中扩散速率较低, 可以作为铁素体/马氏体钢的良好防腐涂层^[14,24]. Ferré等^[25]的研究表明, 脉冲激光沉积生长的氧化铝涂层具有良好的界面结合能力. 此外, 氧化铝涂层在550 ℃的饱和氧浓度下具有良好的稳定性能, 并能在浸泡500 h后保护T91钢免受液态铅铋腐蚀. 氧化铝涂层制备方法将影响涂层结构和组分, 决定了涂层防护效果. 本研究采用磁控溅射法沉积AlO_x涂层, 该方法具有设备简单、易于控制、涂层面积大、附着力强等优点. 选择T91钢和SIMP钢是由于其具有优异的高温性能、低辐照肿胀性和高的导热率, 是先进能源系统(如核反应堆)结构部件的主要结构候选材料^[26].

本文的目的是探索AlO_x涂层是否能在600 ℃ LBE中保持结构完整性, 从而提高T91钢和SIMP钢耐腐蚀性. 该研究有助于理解AlO_x涂层和T91钢、SIMP钢在核动力系统中的应用. 本文采用磁控溅射法在T91钢和SIMP钢表面制备了AlO_x涂层, 然后在600 ℃饱和氧浓度的铅铋溶液中浸泡300 h和700 h, 利用X射线衍射(XRD)、扫描电子显微镜(SEM)和能量色散光谱(EDS)对腐蚀样品进行表征.

2. 实验过程

2.1 实验材料和涂层制备工艺

实验中使用的T91钢和SIMP钢由中国科学院近代物理研究所提供. 表1列出了T91钢和SIMP钢的主要成分. 通过线切割将T91钢和SIMP钢处理成规格为20 mm×10 mm×5 mm, 使用600—4000#的砂纸和氧化铝喷雾对T91钢和SIMP钢进行抛光, 达到镜面抛光效果, 采用中频脉冲磁控溅射法在T91钢和SIMP钢上制备出厚度为1—2 μm的AlO_x涂层(该涂层含有丰富的铝原子, 以提高涂层在基体上的稳定性). 磁控溅射法制备AlO_x薄膜的工艺参数如表2所列.

表 1 研究钢材的化学成分(质量分数)

Table 1. Chemical compositions of the studied steels (mass fraction%)

元素	Fe	Cr	Ni	Mo	V	Si	C	Nb	N	Ta	W
T91	Bal	8.50	0.25	0.95	0.19	0.20	0.10	0.067	0.05	—	—
SIMP	Bal	10.50	—	—	0.20	1.40	0.20	0.01	—	0.15	1.50

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表 2 磁控溅射制备AlO_x薄膜的典型工艺参数(1 sccm = 1 mL/min)

Table 2. Typical process parameters of the AlO_x films prepared by magnetron sputtering

靶功率/W	频率 /kHz	O₂ 流量/sccm	氩气流量/sccm	靶温度/℃	沉积速率/(nm·min^–1)
400	350	8.6	32	25	9

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2.2 静态腐蚀实验

将样品放入静态腐蚀实验装置中, 实验装置的简易结构示意如图1所示. 该装置主要由炉体、真空泵和控制箱组成, 其具有良好的密封性和耐液态金属腐蚀性, 可以在不同温度下进行静态腐蚀实验. 根据高温工况的设计参数, 实验温度选择为600 ℃, 腐蚀时间分别为300 h和700 h. 腐蚀实验后, 在170 ℃下用甘油清洗表面上残留的铅和铋, 随后在超声波中用乙醇清洗. 通过XRD分析了试样表面腐蚀产物的相组成. 除此之外, 使用SEM探究了试样表面和截面上的腐蚀形貌和氧化层结构, 并用EDS检测了腐蚀产物的化学成分和氧化层的元素组成.

$图 1 腐蚀实验设备的简单示意图\r\nFig. 1. A simple schematic diagram of the corrosion test equipment.$

图 1 腐蚀实验设备的简单示意图

Fig. 1. A simple schematic diagram of the corrosion test equipment.

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根据经验公式^[27], LBE中的氧溶解浓度计算公式为

$\text{lg}\;{ {C}}_{\text{0}}=1.2-\frac{\text{3400}}{ {T}} ~~(673 < T < 973),$

(1)

式中, C₀是静态非氧控(饱和氧)条件下LBE中的氧质量浓度, T是LBE的温度. 在600 ℃时, LBE中的氧质量浓度为2.02×10^–3%. 根据图2^[28]中报告的简化埃林厄姆图分析可知, 系统中的氧分压决定了不同氧化物的化学势. 目前LBE中氧质量浓度可以防止PbO和Bi₂O₃的形成.

$图 2 简化的Ellingham图, 铁、铅、铬和铝氧化物的热力学数据见文献[8]\r\nFig. 2. Experimental condition of thermodynamics in a simplified Ellingham diagram. Thermodynamic data for Fe, Pb, Cr and Al oxides are obtained in Ref. [8].$

图 2 简化的Ellingham图, 铁、铅、铬和铝氧化物的热力学数据见文献[8]

Fig. 2. Experimental condition of thermodynamics in a simplified Ellingham diagram. Thermodynamic data for Fe, Pb, Cr and Al oxides are obtained in Ref. [8].

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3. 实验结果

图3所示为T91钢和SIMP钢在600 ℃饱和氧浓度的LBE中分别浸泡300 h和700 h后的XRD图谱. 通过分析衍射峰可以看出, 在XRD衍射图中未发现沉积的AlO_x薄膜的衍射峰, 这是因为室温下通过磁控溅射获得的AlO_x薄膜结构是非晶的^[25]. XRD图谱表明, T91钢和SIMP钢上形成两种氧化物: Fe-Cr尖晶石([Fe,Cr]₂O₄)和磁铁矿Fe₃O₄. 此外, 还发现了残余铋的一些衍射峰. 另外在600 ℃的LBE中腐蚀300 h后, 表面有涂层的T91钢和SIMP钢显示出基体铁的衍射峰, 而表面无涂层的T91钢和SIMP钢上已经显示出Fe₃O₄/(Fe,Cr)₂O₄物质的衍射峰. 这一结果表明, 涂层可以阻碍钢表面氧化物的形成. 但当腐蚀时间达到700 h后, 在T91钢和SIMP钢的涂层面和无涂层表面上均检测到氧化物的衍射峰. 通过比较衍射峰的半高全宽(FWHM), 发现表面有涂层的T91钢和SIMP钢的半高全宽值较宽. 利用谢乐公式, 可以得出表面有涂层的钢表面的氧化物晶粒尺寸较小, 这是因为在样品表面有涂层时氧化物生长更缓慢. 以上结果表明, 在600 ℃下, AlO_x涂层可以防止LBE中的铁素体/马氏体钢上形成氧化物.

$图 3 T91钢和SIMP钢在600 ℃ LBE中暴露300 h和700 h后的X射线衍射图　(a) T91钢; (b) SIMP钢\r\nFig. 3. X-ray diffraction patterns of T91 steel and SIMP steel after exposing in oxygen-saturated static liquid LBE at 600 ℃ for 300 h and 700 h: (a) T91 steel; (b) SIMP.$

图 3 T91钢和SIMP钢在600 ℃ LBE中暴露300 h和700 h后的X射线衍射图　(a) T91钢; (b) SIMP钢

Fig. 3. X-ray diffraction patterns of T91 steel and SIMP steel after exposing in oxygen-saturated static liquid LBE at 600 ℃ for 300 h and 700 h: (a) T91 steel; (b) SIMP.

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图4显示了T91钢和SIMP钢在600 ℃的LBE中腐蚀300 h和700 h后的表面形貌. 图4(a)和图4(c)显示了表面无AlO_x涂层的T91钢和SIMP钢样品典型区域的腐蚀形态. 腐蚀300 h后, 钢表面光滑, 表面生成一层黑色氧化膜. 为精确观察化合物的形态, 将图4(a)和图4(c)放大, 如图4(a)和图4(c)右上角放大图所示, 可以清楚地观察到一层竹叶状的氧化膜. 表明氧化处于早期阶段. 随着腐蚀时间的增加, 如图4(e)和图4(g)所示, 当腐蚀时间达到700 h后, 钢表面出现颗粒状氧化物, 并且在钢表面发现一些孔洞, 说明钢表面形成的氧化物在LBE中腐蚀700 h后容易脱落. 由此可知, T91钢和SIMP钢在600 ℃的LBE中, 样品表面首先形成细小的氧化物, 随着腐蚀时间的延长, 细小的氧化物逐渐长大, 生成凸起的氧化物. 当腐蚀时间进一步延长时, 钢表面的氧化层可能会断裂或脱落. 为了进一步了解表面氧化物的化学成分, 对图4中A, C, E和G点进行了元素扫描, 数据如表3所列. 元素分析结果表明, A, C, E和G点主要由铁、氧、硅和铅元素组成. 这里铅是由于钢表面形成的磁铁矿松散多孔, 导致少量铅渗入.

$图 4 T91钢和SIMP钢在600 ℃的LBE中腐蚀300 h和700 h后的表面SEM图　 (a) LBE中腐蚀300 h后无涂层的T91钢表面; (b) LBE中腐蚀300 h后有涂层的T91钢表面; (c) LBE中腐蚀300 h后无涂层的SIMP钢表面; (d) LBE中腐蚀300 h后有涂层的SIMP钢表面; (e) LBE中腐蚀700 h后无涂层的T91钢表面; (f) LBE中腐蚀700 h后有涂层的T91钢表面; (g) LBE中腐蚀700 h后无涂层的SIMP钢表面; (h) LBE中腐蚀700 h后无涂层的SIMP钢表面\r\nFig. 4. SEM images showing the surface morphology of SIMP and T91 steels after 300 h and 700 h corrosion in LBE at 600 ℃: (a) The uncoated surface of T91 steel in LBE for 300 h; (b) the coated surface of T91 steel in LBE for 300 h; (c) the uncoated surface of SIMP steel in LBE for 300 h; (d) the coated surface of SIMP steel in LBE for 300 h; (e) the uncoated surface of T91 steel in LBE for 700 h; (f) the coated surface of T91 steel in LBE for 700 h; (g) the uncoated surface of SIMP steel in LBE for 700 h; (h) the coated surface of SIMP steel in LBE for 700 h.$

图 4 T91钢和SIMP钢在600 ℃的LBE中腐蚀300 h和700 h后的表面SEM图　 (a) LBE中腐蚀300 h后无涂层的T91钢表面; (b) LBE中腐蚀300 h后有涂层的T91钢表面; (c) LBE中腐蚀300 h后无涂层的SIMP钢表面; (d) LBE中腐蚀300 h后有涂层的SIMP钢表面; (e) LBE中腐蚀700 h后无涂层的T91钢表面; (f) LBE中腐蚀700 h后有涂层的T91钢表面; (g) LBE中腐蚀700 h后无涂层的SIMP钢表面; (h) LBE中腐蚀700 h后无涂层的SIMP钢表面

Fig. 4. SEM images showing the surface morphology of SIMP and T91 steels after 300 h and 700 h corrosion in LBE at 600 ℃: (a) The uncoated surface of T91 steel in LBE for 300 h; (b) the coated surface of T91 steel in LBE for 300 h; (c) the uncoated surface of SIMP steel in LBE for 300 h; (d) the coated surface of SIMP steel in LBE for 300 h; (e) the uncoated surface of T91 steel in LBE for 700 h; (f) the coated surface of T91 steel in LBE for 700 h; (g) the uncoated surface of SIMP steel in LBE for 700 h; (h) the coated surface of SIMP steel in LBE for 700 h.

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表 3 T91钢和SIMP钢在600 ℃静态LBE下表面氧化物在图4标记位置的EDS点分析

Table 3. EDS analyses of the surface oxides of T91 and SIMP steel exposed to static LBE at 600 ℃ in Fig. 4.

原子分数/%	元素
原子分数/%	Fe	Cr	O	Al	Pb	Si
Point A	43.89	—	55.12	—	0.34	0.65
Point B	0.89	—	61.9	36.4	—	0.81
Point C	42.7	—	54.37	—	0.38	2.55
Point D	3.01	—	58.63	34.6	—	3.76
Point E	44.21	—	54.30	—	0.88	0.61
Point F	41.17	—	58.26	—	—	0.57
Point G	40.59	—	55.23	—	0.60	3.58
Point H	32.51	—	63.80	—	—	3.69

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图4(b)和图4(d)显示了表面有AlO_x涂层的T91钢和SIMP钢样品典型区域的腐蚀形态, 涂层部分区域已经剥离, 露出基底, 且SIMP钢涂层剥离面积大于T91钢. 对裸露区域细致地观察, 如图4(b)和图4(d)右上角放大图所示, 看到涂层缺口呈多边形, 说明涂层具有较好的韧性. 对图4中标记的B点和D点位置进行元素分析, 结果如表3所列. B点和D点的主要元素是铁、铝、氧和硅. 为了进一步了解暴露基底和表面氧化膜的成分, 对其进行EDS元素分析, 结果如图5所示. 根据表面扫描分析结果可知, 表面氧化物主要由铝和氧元素组成, 而基体的裸露部分不含铝和氧元素, 仅含铁和铬元素. 另外, 在T91钢和SIMP钢的涂层表面上观察到裂纹, 如图6所示. 裂纹路线很不规则, T91钢表面涂层裂纹宽度要大于SIMP钢, 这也可解释T91钢表面涂层剥离面积小于SIMP钢. 当腐蚀时间到达700 h后, 涂层T91钢表面形成了脊状氧化膜. 对图4(f)中F点位置元素分析表明, 该化合物主要由铁和氧组成. 另外, 在涂层SIMP钢上也观察到类似的氧化物. 对图4(h)中H点的元素分析表明, 该化合物主要由铁、硅和氧组成. 从以上结果可以看出, 涂层T91钢和SIMP钢表面的AlO_x薄膜在600 ℃的LBE中腐蚀300 h后相对稳定, 当腐蚀时间达到700 h后, 钢表面上未检测到AlO_x薄膜.

$图 5 在600 ℃的LBE中腐蚀300 h后SIMP钢涂层表面的SEM显微照片和表框区域Al, O, Cr和Fe分布图\r\nFig. 5. SEM micrograph of the coated surface of SIMP steel after 300 h corrosion in LBE at 600 ℃ and the elemental mapping images of Al, O, Cr and Fe.$

图 5 在600 ℃的LBE中腐蚀300 h后SIMP钢涂层表面的SEM显微照片和表框区域Al, O, Cr和Fe分布图

Fig. 5. SEM micrograph of the coated surface of SIMP steel after 300 h corrosion in LBE at 600 ℃ and the elemental mapping images of Al, O, Cr and Fe.

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$图 6 涂层T91钢和SIMP钢在600 ℃的 LBE中腐蚀300 h后表面扫描电子显微镜显微照片　(a) T91钢; (b) SIMP钢\r\nFig. 6. SEM micrograph of the coated surface of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃: (a) T91 steel; (b) SIMP steel$

图 6 涂层T91钢和SIMP钢在600 ℃的 LBE中腐蚀300 h后表面扫描电子显微镜显微照片　(a) T91钢; (b) SIMP钢

Fig. 6. SEM micrograph of the coated surface of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃: (a) T91 steel; (b) SIMP steel

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为研究氧化层厚度和结构, 对样品进行截面观察. 将样品切割开, 露出横截面竖直向上. 用树脂保护样品, 然后进行机械抛光. 图7为T91钢和SIMP钢在LBE中腐蚀300 h后形成的氧化层剖面SEM图像和EDS元素分析结果. 图7(d)和图7(h)分别为表面无AlO_x涂层的T91钢和SIMP钢元素线扫描结果, 无涂层时表面形成了明显的氧化层. 对于T91钢, 氧化层厚度约为25 μm, 而SIMP钢氧化层厚度约为18 μm, 这说明了SIMP钢抗腐蚀性能要优于T91钢. 元素随样品深度测试表面, 氧化层中存在铁和氧, 而铬富集在氧化层底部区域, 这与文献[29-31]报道一致. 氧化层由两层组成, 内层为相对致密光滑的铁铬尖晶石层([Fe,Cr]₂O₄), 外层为松散的磁铁矿层(Fe₃O₄). 但是, 图7(a)和图7(e)未看到明显的氧化层, 能谱测试发现表面有铝元素(见图7(b)和图7(f)), 这说明了材料表面有氧化铝膜时, 能够较好地保护基体免受铅铋腐蚀. 图8中面扫描结果进一步证实了氧化铝膜良好的保护性能.

$图 7 在600 ℃的LBE中腐蚀300 h后T91钢和SIMP钢的横截面SEM图像和EDS线性分析(扫描方向从左到右)　(a), (b)涂层T91钢; (c), (d)无涂层T91钢; (e), (f)涂层SIMP钢; (g), (h)无涂层SIMP钢\r\nFig. 7. Cross-sectional SEM images and EDS linear analysis of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃: (a), (b) The coated T91; (c), (d) the uncoated T91; (e), (f) the coated SIMP; (g), (h) the uncoated SIMP.$

图 7 在600 ℃的LBE中腐蚀300 h后T91钢和SIMP钢的横截面SEM图像和EDS线性分析(扫描方向从左到右)　(a), (b)涂层T91钢; (c), (d)无涂层T91钢; (e), (f)涂层SIMP钢; (g), (h)无涂层SIMP钢

Fig. 7. Cross-sectional SEM images and EDS linear analysis of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃: (a), (b) The coated T91; (c), (d) the uncoated T91; (e), (f) the coated SIMP; (g), (h) the uncoated SIMP.

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$图 8 在600 ℃的LBE中腐蚀LBE中腐蚀300 h后T91钢和SIMP钢的SEM 图和EDS图谱　(a)涂层T91钢; (b)涂层SIMP钢\r\nFig. 8. Cross-sectional SEM image and EDS mapping of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃ : (a) The coated T91 steel; (b) coated SIMP steel.$

图 8 在600 ℃的LBE中腐蚀LBE中腐蚀300 h后T91钢和SIMP钢的SEM 图和EDS图谱　(a)涂层T91钢; (b)涂层SIMP钢

Fig. 8. Cross-sectional SEM image and EDS mapping of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃ : (a) The coated T91 steel; (b) coated SIMP steel.

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图9显示了T91钢和SIMP钢在600 ℃ LBE中腐蚀700 h后形成的氧化层结构和元素分布. 图9(a)和图9(e)分别显示了表面有AlO_x涂层的T91钢和SIMP钢腐蚀层剖面图, 氧化层平均厚度分别约为38 μm和22 μm. 图9(c)和图9(g)分别显示了表面无AlO_x涂层的T91钢和SIMP钢腐蚀层剖面图, 此时氧化层平均厚度约分别为53 μm和30 μm. 元素分布说明氧化层由内层铁铬尖晶石和外层磁铁矿组成. 外层磁铁矿(Fe₃O₄)与内层Fe-Cr尖晶石层的厚度比约为1.11, 略低于其他报道的1.2^[32]. 这是因为磁铁矿很松散, 高温LBE中很容易脱落. 需要说明的是, T91钢和SIMP钢在600 ℃的LBE中腐蚀700 h后, EDS元素结果中未检测到铝, 说明氧化铝涂层已经脱落了. 但是, T91钢和SIMP钢两面腐蚀层厚度明显不同, 氧化铝涂层在脱落前还是减缓了材料腐蚀速率. 此外, T91钢和SIMP钢的氧化层厚度随着腐蚀时间的延长而增大, T91钢氧化层厚度增大速度大于SIMP钢.

$图 9 T91钢和SIMP钢在600℃的LBE中腐蚀700 h后的横截面SEM图像和EDS线性分析(扫描方向从左到右)　(a), (b)涂层T91钢; (c), (d)无涂层T91钢; (e), (f)涂层SIMP钢; (g), (h)无涂层SIMP钢.\r\nFig. 9. Cross-sectional SEM images and EDS linear analysis of T91 and SIMP steels after 700 h corrosion in LBE at 600 ℃: (a), (b) The coated T91; (c), (d) the uncoated T91; (e), (f) the coated SIMP; (g), (h) the uncoated SIMP.$

图 9 T91钢和SIMP钢在600℃的LBE中腐蚀700 h后的横截面SEM图像和EDS线性分析(扫描方向从左到右)　(a), (b)涂层T91钢; (c), (d)无涂层T91钢; (e), (f)涂层SIMP钢; (g), (h)无涂层SIMP钢.

Fig. 9. Cross-sectional SEM images and EDS linear analysis of T91 and SIMP steels after 700 h corrosion in LBE at 600 ℃: (a), (b) The coated T91; (c), (d) the uncoated T91; (e), (f) the coated SIMP; (g), (h) the uncoated SIMP.

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4. 讨　论

4.1 氧化层的形成原因

研究表明, 在饱和氧浓度下, 钢表面多层氧化物形成机理如下: 高温下铁原子从材料内部向外扩散, 被氧化形成磁铁矿层, 从而导致材料中出现铁空位. 氧气分子穿过磁铁矿层到达基底, 与材料中铁、铬原子反应形成铁铬尖晶石内层^[32,33]. 表面无涂层的T91钢和SIMP钢在600 ℃的LBE中腐蚀300 h和700 h后, 形成厚度不同的氧化层, 但氧化层都分为内外两层. 外层为磁铁矿, 内层为铁铬尖晶石. 一般来说, 在高温LBE环境中的腐蚀时间越长, 表面形成的氧化层越厚. 而表面有涂层的T91钢和SIMP钢经过300 h腐蚀, 表面没有形成双氧化层. 这说明了AlO_x涂层对提高钢的抗LBE腐蚀性能起到了有效的作用, 这与文献[34]中报道的结果一致.

T91钢和SIMP钢在600 ℃ LBE中腐蚀700 h后, 表面有涂层和无涂层表面都形成了双氧化层, 但氧化层厚度不同, 如图9(b)和图9(d)所示. 涂层钢的表面上的氧化膜厚度约为38 μm, 而无涂层钢表面上的氧化膜厚度约为53 μm. 类似地, 如图9(f)和图9(h)所示, 表面有涂层的SIMP钢表面的氧化膜厚度约为22 μm, 而表面无涂层的SIMP钢表面的氧化膜厚度约为30 μm. SEM和EDS结果中未检测到氧化铝, 这表明在600 ℃的LBE中腐蚀700 h后, 钢表面上的AlO_x涂层剥落.

综上所述, 在600 ℃的饱和氧浓度的LBE中腐蚀300 h后, 如图7(d)和图7(h)所示, 表面无AlO_x涂层的T91钢和SIMP钢表面形成了明显的氧化层. 对于T91钢, 氧化层厚度约为25 μm, 而SIMP钢氧化层厚度约为18 μm, 同样T91钢和SIMP钢在600 ℃ LBE中腐蚀700 h后, 表面无AlO_x涂层的T91钢和SIMP钢形成的氧化层厚度分别为53 μm和30 μm, 表面有AlO_x涂层的T91钢和SIMP钢形成的氧化层厚度分别为38 μm和22 μm, 对比以上结果可知, 在腐蚀时间为300 h和700 h时, T91钢横截面上形成的氧化膜都比SIMP钢厚, 说明SIMP钢抗腐蚀性能要优于T91钢. 而这里SIMP钢具有更好耐蚀性的原因与氧化层内层铁铬尖晶石有关^[35]. T91钢和SIMP钢之间的主要区别在于材料元素成分, 材料成分对LBE中钢的腐蚀行为有显著的影响^[36]. T91钢和SIMP钢之间Fe-Cr尖晶石的显著差异是铁向外扩散留下的孔隙分布, 以及Fe-Cr尖晶石和基体之间界面的不规则性(图9), 这是由T91钢和SIMP钢之间的Cr和Si含量以及微观结构的差异造成的. SIMP钢中的Cr的质量分数约为10.50%, T91钢中的Cr的质量分数约为8.50%, SIMP钢中的Si的质量分数约为T91钢的7倍(如表1所示). 与Fe相比, Cr和Si在Fe-Cr尖晶石^[37]的八面体位置非常稳定, 这导致尖晶石结构更加紧密. 致密的尖晶石结构可抑制铁离子向外扩散. Fe-Cr尖晶石中Cr和Si的含量越高, Fe的扩散速率越低^[38-40]. SIMP钢中的碳化物存在于板条和晶界中, 并聚集形成链状结构^[41], 通过沿板条和晶界的氧扩散被氧化. 同时, 由于氧化物具有热力学稳定性, 形成了富铬和富硅氧化物网络扩散层^[42], 从而防止铁向外迁移, 形成磁铁矿. 以上两点可解释SIMP钢的耐腐蚀性优于T91钢.

4.2 氧化铝涂层的作用与稳定性分析

根据上述结果, 在600 ℃的LBE中腐蚀300 h后, 表面有AlO_x涂层的钢表面没有形成双层氧化膜. 当腐蚀时间达到700 h时, 表面有AlO_x涂层的钢表面的氧化膜厚度低于无涂层钢表面的氧化膜厚度. 根据磁铁矿和Fe-Cr尖晶石的形成机理, Fe-Cr尖晶石生长速率的实验结果可以用以下机制来解释: 铁原子从材料内部向磁铁矿/Pb-Bi界面迁移, 导致材料内部形成空位, 与此同时, 铅铋溶液中氧分子通过磁铁矿向里扩散, 到达基体. 根据Ellingham图, 氧与基体中富集的铁和铬反应, 形成Fe-Cr尖晶石. 因此铁和铬原子从基体向表面扩散, 导致大量空位形成, 这正好解释了氧化层与基体界面处存在明显的裂纹^[33]. 因此, Fe-Cr尖晶石生长速度取决于氧在磁铁矿层中的迁移, 以及铁和铬在铁铬尖晶石层中迁移, 而磁铁矿生长主要由铁原子在铁铬尖晶石层中迁移决定的^[32,33,43]. 通常磁铁矿结构较为疏松, 氧分子很容易进入, 而铁铬尖晶石结构较为致密, 能够较好地阻挡铁、铬和氧的扩散. 因此, 腐蚀层生长速度主要取决于铁、铬和氧的迁移率. 表面有涂层的钢和无涂层的钢在600 ℃的LBE中腐蚀300 h和700 h腐蚀结果表明, AlO_x层保护钢免受LBE腐蚀, 这主要是AlO_x涂层一方面在铅铋溶液中难以腐蚀, 另外一方面铁、铬和氧在氧化铝中迁移率低共同的作用.

如图5所示, 在600 ℃ LBE中腐蚀300 h后, SIMP钢的表面形貌表明, SIMP钢的表面涂层部分脱落. SEM和EDS结果见图8(a), 铝涂层的边缘不规则. 此外, 在600 ℃ LBE中腐蚀700 h后, 通过SEM和EDS分析可知, 钢表面未发现铝涂层. 且表面有涂层的T91钢和SIMP钢在600 ℃ LBE下暴露300 h后表面出现裂纹(图6). 上述结果表明, AlO_x涂层在腐蚀过程中是不稳定的. AlO_x膜不稳定的可能原因如下: 1) LBE腐蚀后形成的裂纹可能与基体之间的晶格应力有关^[43]. 这是因为薄膜和衬底材料之间热膨胀系数差异会引起的热应力^[26]. 在涂层制备过程中, 当基材和薄膜同时加热到一定温度, 然后冷却到初始温度时, 由于薄膜材料和基材的膨胀系数不同, 系统(薄膜+合金)的完整性会受到影响. 据报道, Fe-Cr合金在298—973 K时的热膨胀系数在10×10^–6—13×10^–6 K^–1之间, 且热膨胀系数随合金中Cr含量的增大而略有增大^[44-46]. 在100—1000 K温度下, α-Al₂O₃的热膨胀系数在0.79×10^–6—10.3×10^–6 K^–1范围内^[43-45]. 氧化铝的杨氏弹性模量为390 GPa, 氧化铝膜的泊松比为0.25^[46]. T91钢的杨氏弹性模量为187 GPa^[47], SIMP钢的杨氏弹性模量为172 GPa. 涂层和基体参数, 如热膨胀系数、泊松比和弹性模量, 对残余热应力有显著影响. 残余热应力的计算公式如下^[48]:

${\sigma}_{\text{th}}=\frac{{E}\left({\Delta } {T}\right)}{\left(\text{1}-\mu\right)}\left({\alpha}_{\text{s}}-{\alpha}_{\text{c}}\right)\text{, }$

(2)

式中, E是涂层和基材的弹性模量, ∆T是温差, α_c和α_s分别是涂层和基体的热膨胀系数, μ是泊松比. 在600 ℃时, 氧化铝的热膨胀系数约为7.59 × 10^–6 K^–1[49]. 因此, 冷却后, σ_th在–1617.59 MPa至–720.59 MPa范围内, T91钢中的σ_th在–831.01 MPa至–370.191 MPa范围内, SIMP钢中的σ_th在–764.36 MPa至–340.50 MPa范围内. 根据胡克定律^[50]: ε = σ/E, 其中E是弹性模量, σ是热应力, ε是应变. 因此, 涂层中的ε在0.184%—0.415%之间, 基体中的ε在0.198%—0.444%之间. 根据上述数据分析, 涂层和基体的应力值相差不大, 冷却后涂层和基体的收缩程度相差也不大. 因此, 热膨胀系数的差异引起的热应力不是导致AlO_x涂层断裂的主要原因. 2)腐蚀缺陷的累积和晶界附近元素的偏析, 导致涂层中晶界能结合能降低, 沿晶界形成裂纹. 3)制备的AlO_x涂层, 里面存在大量的金属铝和结构缺陷, 金属铝在高温铅铋溶液中氧化, 形成氧化铝, 导致晶格膨胀, 涂层出现裂纹. 另外, 液态铅铋沿着裂纹进入基体, 从而形成氧化膜. 氧化膜生长时向外挤压涂层, 导致涂层局部区域脱落, 如图5所示. 本文制备AlO_x涂层, 而不是Al₂O₃涂层, 主要是基于两方面考虑, 一方面是AlO_x涂层中存在金属铝, 能够提高涂层的韧性, 这一点从涂层中裂纹扩展路径就能看出; 另一方面涂层具有自修复功能, 氧与铝反应形成氧化铝, 能够修复涂层中的裂纹. 然而, 本次实验中并没有看到裂纹修复, 相反涂层发生了剥离. 这主要是因为铅和铋原子半径较大, 进入涂层中导致裂纹宽度变大. 另外, 基体被氧化, 也会产生向外的张应力, 导致涂层中裂纹快速生长. 正如Miorin等^[34]所报道的, 涂层是通过射频磁控溅射制备的. 氧化铝膜仅被熔融金属略微润湿, 腐蚀1200 h后其厚度保持不变. 此外, 氧化铝膜可以用作铅渗透到基体中的屏障. 该结果表明, 氧化铝涂层在550 ℃的铅中腐蚀1200 h后仍具有良好的稳定性. 与目前的实验结果相比, AlO_x涂层在600 ℃的LBE腐蚀700 h后, 无法保持其稳定性. 最有可能的原因是AlO_x涂层的结构不均匀, 膜基结合力不够和薄膜内部自身存在残余应力所导致的. 下一步, 将改进制造技术, 如通过调节制备温度、电压和制备后热处理等方式以获得高质量的AlO_x涂层, 以满足高温LBE中T91和SIMP钢长期运行的耐腐蚀性.

5. 结　论

在600 ℃饱和氧浓度的LBE中腐蚀300 h和700 h后, T91钢和SIMP钢的腐蚀实验结果表明:

1)在相同的实验条件下, SIMP钢比T91钢具有更好的耐腐蚀性. T91钢和SIMP钢在600 ℃饱和氧浓度的LBE中腐蚀300 h和700 h后均发生氧化腐蚀, 并在试样表面形成氧化层, 这不仅可以保护基体免受液态铅铋的渗透, 还可以抑制基体元素向铅铋溶液中的扩散, 从而有效地抑制溶解腐蚀的发生. 然而, T91钢不适用于温度高于600 ℃的LBE, 因为它会形成更厚的氧化层, 导致导热系数快速降低. 更重要的是, 当磁铁矿生长到一定厚度时, 氧化层很容易脱落.

2) 在600 ℃饱和氧浓度的LBE中腐蚀300 h后, AlO_x涂层阻止了铁和铬在基体中的外扩散和氧的内扩散, 因此没有形成双氧化膜, 但涂层已经出现裂纹和部分脱落. 在600 ℃饱和氧浓度的LBE中腐蚀700 h后, 发现表面有涂层的样品的氧化膜与基体结合更好, 氧化膜更薄, 但涂层已经基本完全脱落.

基于以上结果, 可以进一步优化磁控溅射工艺参数, 如沉积温度、气体流量、溅射功率和靶基距离, 以获得质量更好的氧化铝薄膜. 涂层对LBE腐蚀行为的影响有待进一步评估.

References

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[22]	Ferré F G, Mairov A, Iadicicco D, Vanazzi M, Bassini S, Utili M, Tarantino M, Bragaglia M, Lamastra F R, Nanni F, Ceseracciu L, Serruys Y, Trocellier P, Beck L, Sridharan K, Beghi M G , Di Fonzo F 2017 Corros. Sci. 124 80 Google Scholar
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[25]	Ferré G, Ormellese M, Fonzo F D, Beghi M G 2013 Corros. Sci. 77 375 Google Scholar
[26]	Sordo F, Abánades A, Lafuente A, Martínez-Val J M, Perlado M 2009 Nucl. Eng. Des. 239 2573 Google Scholar
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[32]	Martinelli L, Balbaud-Célérier F, Terlain A, Bosonnet S, Picard G, Santarini G 2008 Corros. Sci. 50 2537 Google Scholar
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[37]	Li B S, Liao Q, Zhang H P, Shen T L, Ge F F, Nabil D 2021 Corros. Sci. 187 109477 Google Scholar
[38]	Zhang L L, Yan W, Shi Q Q, Li Y F, Shen Y Y, Yang K 2020 Corros. Sci. 167 108519 Google Scholar
[39]	Liu J, Yan W, Sha W, Wang W, Shan Y Y, Yang K 2016 J. Nucl. Mater. 473 189 Google Scholar
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1.	叶怀波，孙琨，李六六，吴冰洁. 合金元素(Cr、Ni、Mn、Cu)增强T91钢耐蚀性机理的第一性原理计算研究. 西安交通大学学报. 2024(09): 205-212 . 百度学术
2.	周涛，唐剑宇，蒋屹. 基于灰色关联度的棒束通道内液态铅铋合金中颗粒物运动沉积研究. 核技术. 2023(07): 103-112 . 百度学术

其他类型引用(2)

图 1 腐蚀实验设备的简单示意图

Figure 1. A simple schematic diagram of the corrosion test equipment.

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图 2 简化的Ellingham图, 铁、铅、铬和铝氧化物的热力学数据见文献[8]

Figure 2. Experimental condition of thermodynamics in a simplified Ellingham diagram. Thermodynamic data for Fe, Pb, Cr and Al oxides are obtained in Ref. [8].

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图 3 T91钢和SIMP钢在600 ℃ LBE中暴露300 h和700 h后的X射线衍射图　(a) T91钢; (b) SIMP钢

Figure 3. X-ray diffraction patterns of T91 steel and SIMP steel after exposing in oxygen-saturated static liquid LBE at 600 ℃ for 300 h and 700 h: (a) T91 steel; (b) SIMP.

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Figure 4. SEM images showing the surface morphology of SIMP and T91 steels after 300 h and 700 h corrosion in LBE at 600 ℃: (a) The uncoated surface of T91 steel in LBE for 300 h; (b) the coated surface of T91 steel in LBE for 300 h; (c) the uncoated surface of SIMP steel in LBE for 300 h; (d) the coated surface of SIMP steel in LBE for 300 h; (e) the uncoated surface of T91 steel in LBE for 700 h; (f) the coated surface of T91 steel in LBE for 700 h; (g) the uncoated surface of SIMP steel in LBE for 700 h; (h) the coated surface of SIMP steel in LBE for 700 h.

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图 5 在600 ℃的LBE中腐蚀300 h后SIMP钢涂层表面的SEM显微照片和表框区域Al, O, Cr和Fe分布图

Figure 5. SEM micrograph of the coated surface of SIMP steel after 300 h corrosion in LBE at 600 ℃ and the elemental mapping images of Al, O, Cr and Fe.

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图 6 涂层T91钢和SIMP钢在600 ℃的 LBE中腐蚀300 h后表面扫描电子显微镜显微照片　(a) T91钢; (b) SIMP钢

Figure 6. SEM micrograph of the coated surface of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃: (a) T91 steel; (b) SIMP steel

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Figure 7. Cross-sectional SEM images and EDS linear analysis of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃: (a), (b) The coated T91; (c), (d) the uncoated T91; (e), (f) the coated SIMP; (g), (h) the uncoated SIMP.

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图 8 在600 ℃的LBE中腐蚀LBE中腐蚀300 h后T91钢和SIMP钢的SEM 图和EDS图谱　(a)涂层T91钢; (b)涂层SIMP钢

Figure 8. Cross-sectional SEM image and EDS mapping of T91 and SIMP steels after 300 h corrosion in LBE at 600 ℃ : (a) The coated T91 steel; (b) coated SIMP steel.

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Figure 9. Cross-sectional SEM images and EDS linear analysis of T91 and SIMP steels after 700 h corrosion in LBE at 600 ℃: (a), (b) The coated T91; (c), (d) the uncoated T91; (e), (f) the coated SIMP; (g), (h) the uncoated SIMP.

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表 1 研究钢材的化学成分(质量分数)

Table 1. Chemical compositions of the studied steels (mass fraction%)

元素	Fe	Cr	Ni	Mo	V	Si	C	Nb	N	Ta	W
T91	Bal	8.50	0.25	0.95	0.19	0.20	0.10	0.067	0.05	—	—
SIMP	Bal	10.50	—	—	0.20	1.40	0.20	0.01	—	0.15	1.50

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表 2 磁控溅射制备AlO_x薄膜的典型工艺参数(1 sccm = 1 mL/min)

Table 2. Typical process parameters of the AlO_x films prepared by magnetron sputtering

靶功率/W	频率 /kHz	O₂ 流量/sccm	氩气流量/sccm	靶温度/℃	沉积速率/(nm·min^–1)
400	350	8.6	32	25	9

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表 3 T91钢和SIMP钢在600 ℃静态LBE下表面氧化物在图4标记位置的EDS点分析

Table 3. EDS analyses of the surface oxides of T91 and SIMP steel exposed to static LBE at 600 ℃ in Fig. 4.

原子分数/%	元素
原子分数/%	Fe	Cr	O	Al	Pb	Si
Point A	43.89	—	55.12	—	0.34	0.65
Point B	0.89	—	61.9	36.4	—	0.81
Point C	42.7	—	54.37	—	0.38	2.55
Point D	3.01	—	58.63	34.6	—	3.76
Point E	44.21	—	54.30	—	0.88	0.61
Point F	41.17	—	58.26	—	—	0.57
Point G	40.59	—	55.23	—	0.60	3.58
Point H	32.51	—	63.80	—	—	3.69

DownLoad: CSV

[1]	Sar F, Mhiaoui S, Gasser J G 2007 J. Non. Cryst. Solids. 353 3622 Google Scholar
[2]	Sobolev V 2007 J. Nucl. Mater. 362 235 Google Scholar
[3]	Zhang J 2014 Adv. Eng. Mater. 16 349 Google Scholar
[4]	Zhang J, Ning L 2008 J. Nucl. Mater. 373 351 Google Scholar
[5]	Xu Y C, Zhang Y G, Li X Y, Liu W, Li D D, Liu C S, Pan B C, Wang Z G 2017 Corros. Sci. 118 1 Google Scholar
[6]	Barbier F, Rusanov A 2001 J. Nucl. Mater. 296 231 Google Scholar
[7]	Martinelli L, Jean-Louis C, Fanny B C 2011 Nucl. Eng. Des. 241 1288 Google Scholar
[8]	Concetta F 2015 Handbook on Lead-bismuth Eutectic Alloy and Lead Properties, Materials Compatibility, Thermal-hydraulics and Technologies (2015 Edition-Introduction) (OECD Nuclear Energy Agency)
[9]	Zhang J 2009 Corros. Sci. 51 1207 Google Scholar
[10]	Takaya S, Furukawa T, Müller G, Heinzel A, Jianu A, Weisenburger A, Aoto K, Inoue M, Okuda T, Abe F, Ohnuki S, Fujisawa T, Kimura A 2012 J. Nucl. Mater. 428 125 Google Scholar
[11]	Srinivasan P B, Kumar M 2009 Mater. Chem. Phys. 115 179 Google Scholar
[12]	Müller G, Schumacher G, Zimmermann F 2000 J. Nucl. Mater. 278 85 Google Scholar
[13]	Deloffre P, Balbaud-Célérier F, Terlain A 2004 J. Nucl. Mater. 335 180 Google Scholar
[14]	Weisenburger A, Heinzel A, Müller G, Muscher H, Rousanov A 2008 J. Nucl. Mater. 376 274 Google Scholar
[15]	Fetzer R, Weisenburger A, Jianu A, Müller G 2012 Corros. Sci. 55 213 Google Scholar
[16]	Short M P, Ballinger R G, Hänninen H E 2013 J. Nucl. Mater. 434 259 Google Scholar
[17]	Hosemann P, Thau H T, Johnson A L, Maloy S A, Li N 2008 J. Nucl. Mater. 373 246 Google Scholar
[18]	Takaya S, Furukawa T, Aoto K, Müller G, Weisenburger A, Heinzel A, Inoue M, Okuda T, Abe F, Ohnuki S, Fujisawa T and Kimura A 2009 J. Nucl. Mater. 386–388 507 Google Scholar
[19]	Takaya S, Furukawa T, Inoue M, Fujisawa T, Okuda T, Abe F, Ohnuki S, Kimura A 2010 J. Nucl. Mater. 398 132 Google Scholar
[20]	Heinzel A, Kondo M, Takahashi M 2006 J. Nucl. Mater. 350 264 Google Scholar
[21]	Kurata Y, Futakawa M, Saito S 2004 J. Nucl. Mater. 335 501 Google Scholar
[22]	Ferré F G, Mairov A, Iadicicco D, Vanazzi M, Bassini S, Utili M, Tarantino M, Bragaglia M, Lamastra F R, Nanni F, Ceseracciu L, Serruys Y, Trocellier P, Beck L, Sridharan K, Beghi M G , Di Fonzo F 2017 Corros. Sci. 124 80 Google Scholar
[23]	Glasbrenner H, Gröschel F 2006 J. Nucl. Mater. 356 213 Google Scholar
[24]	Weisenburger A, Jianu A, Doyle S, Bruns M, Fetzer R, Heinzel A, Del Giacco M, An W, Müller G 2013 J. Nucl. Mater 437 282 Google Scholar
[25]	Ferré G, Ormellese M, Fonzo F D, Beghi M G 2013 Corros. Sci. 77 375 Google Scholar
[26]	Sordo F, Abánades A, Lafuente A, Martínez-Val J M, Perlado M 2009 Nucl. Eng. Des. 239 2573 Google Scholar
[27]	Borgstedt H U, Frees G 1995 Liquid Metal Systems. (New York: Springer) p339
[28]	Ellingham H J T 1994 J. Soc. Chem. Ind. 63 125
[29]	Yeliseyeva O, Tsisar V, Zhou Z 2013 J. Nucl. Mater. 442 434 Google Scholar
[30]	Weisenburger A, Schroer C, Jianu A, Heinzel A, Konys J, Steiner H, Müller G, Fazio C, Gessi A, Babayan S, Kobzova A, Martinelli L, Ginestar K, Balbaud-Célerier F, Martín-Muñoz F J, Soler Crespo L 2011 J. Nucl. Mater. 415 260 Google Scholar
[31]	Weisenburger A, Mansani L, Schumacher G, Müller G 2014 Nucl. Eng. Des. 273 584 Google Scholar
[32]	Martinelli L, Balbaud-Célérier F, Terlain A, Bosonnet S, Picard G, Santarini G 2008 Corros. Sci. 50 2537 Google Scholar
[33]	Martinelli L, Balbaud-Célérier F, Picard G, Santarini G 2008 Corros. Sci. 50 2549 Google Scholar
[34]	Miorin E, Montagner F, Zin V, Giuranno D, Deambrosis S M 2019 Surf. Coat. Technol. 377 124890 Google Scholar
[35]	Comstock M 2009 J. Nucl. Mater. 382 272 Google Scholar
[36]	Tan L, Machut M T, Sridharan K 2007 J. Nucl. Mater. 371 161 Google Scholar
[37]	Li B S, Liao Q, Zhang H P, Shen T L, Ge F F, Nabil D 2021 Corros. Sci. 187 109477 Google Scholar
[38]	Zhang L L, Yan W, Shi Q Q, Li Y F, Shen Y Y, Yang K 2020 Corros. Sci. 167 108519 Google Scholar
[39]	Liu J, Yan W, Sha W, Wang W, Shan Y Y, Yang K 2016 J. Nucl. Mater. 473 189 Google Scholar
[40]	Li Y, Wang S, Sun P, Xu D, Ren M, Guo Y, Lin G 2017 Corros. Sci. 128 241 Google Scholar
[41]	Shi Q, Liu J, Luan H, Yang Z, Wang W, Yan W, Shan Y, Yang K 2015 J. Nucl. Mater. 457 135 Google Scholar
[42]	Behnamian Y, Mostafaei A, Kohandehghan A, Amirkhiz B S, Serate D, Sun Y, Liu S, Aghaie E, Zeng Y, Chmielus M, Zheng W, Guzonas D 2016 Corros. Sci. 106 188 Google Scholar
[43]	Martinelli L, Balbaud-Célérier F, Terlian A, Delpech S, Santarini G, Favergeon J, Moulin G, Tabarant M, Picard G 2008 Corros. Sci. 50 2523 Google Scholar
[44]	Bian L Z, Chen Z Y, Wang L J, Li F S, Chou K C 2017 J. Iron. Steel. Res. Int. 24 77 Google Scholar
[45]	Huntz A M, Maréchal L, Lesage B, Molins R 2006 Appl. Surf. Sci. 252 7781 Google Scholar
[46]	Melander A 1997 Int. J. Fatigue 19 13 Google Scholar
[47]	Wang Q S, Wang W Q, Shi Z M 2018 E. Science. 113 012146 Google Scholar
[48]	Echsler H, Martinez E A, Singheiser L, Quadakkers W J 2004 Mater. Sci. Eng. A 384 1 Google Scholar
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