Fe+Cr及Si含量对Zr-4合金耐腐蚀性能的影响

岳慧芳; 庞华; 高博; 高士鑫; 罗倩倩; 赵艳丽; 蒋有荣

doi:10.13832/j.jnpe.2024.03.0146

Fe+Cr及Si含量对Zr-4合金耐腐蚀性能的影响

doi: 10.13832/j.jnpe.2024.03.0146

1.
中国核动力研究设计院核反应堆系统设计技术重点实验室，成都，610213
2.
国核宝钛锆业股份公司陕西省核级锆材重点实验室，陕西宝鸡，721013

详细信息

作者简介:
岳慧芳（1991—），女，硕士研究生，现主要从事核燃料材料设计与研究工作，E-mail: 1130005792@qq.com

中图分类号: TL34
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出版历程
- 收稿日期: 2023-11-08
- 修回日期: 2024-01-23
- 刊出日期: 2024-06-13

Effect of Fe+Cr and Si Contents on Corrosion Resistance of Zircaloy-4

1.
Science and Technology on Reactor System Design Technology Laboratory, Nuclear Power Institute of China, Chengdu, 610213, China
2.
State Nuclear Bao Ti Zirconium Industry Company, Shaanxi Key Laboratory of Nuclear Grade Zirconium Material, Baoji, Shaanxi, 721013, China

摘要

摘要: 为了优化国产Zr-4合金的耐腐蚀性能，在420℃、10.3 MPa的高温高压水蒸气加速腐蚀条件下，研究了合金元素Fe+Cr以及杂质元素Si对国产Zr-4合金耐腐蚀性能的影响。结果表明：在美国材料实验学会（ASTM）规定的Fe+Cr含量范围内（0.28 wt%~0.37 wt%，wt%表示质量分数），Fe+Cr含量越高，析出的第二相数目越多、尺寸越大，越有利于材料耐腐蚀性能提升。在420℃水蒸气中腐蚀126 d后，当Fe+Cr含量从0.28 wt%增加到0.37 wt%时，Zr-4合金的腐蚀增重降低约30%。Zr-4合金在1100℃淬火时，当Si含量低至10 mg/kg时，形成粗大的平行板条结构；而增加Si含量到100 mg/kg后，析出的细小Zr₃Si为α相提供形核位置，使得组织中出现网篮结构和细小的平行板条结构。网篮结构能促使组织中第二相分布更均匀弥散，因此，高Si含量的Zr-4合金表现出更优良的耐腐蚀性能。
- Zr-4合金 /
- Fe+Cr含量 /
- Si含量 /
- 耐腐蚀性能
Abstract: In order to optimize the corrosion resistance of domestic Zr-4 alloy, the effects of alloying element Fe+Cr and impurity element Si on the corrosion resistance of domestic Zr-4 alloy were studied under the accelerated corrosion condition of high temperature and high pressure steam at 420℃ and 10.3 MPa. The results show that within the range of Fe+Cr content specified by ASTM (0.28 wt%-0.37 wt%, with wt% representing mass percentage), the higher the Fe+Cr content, the larger the number and size of the precipitated second phases, which is beneficial to the improvement of the corrosion resistance of the material. When the content of Fe+Cr increases from 0.28 wt% to 0.37 wt%, the corrosion weight gain of Zr-4 alloy decreases by about 30% after 126 d of corrosion in steam at 420℃. When the Si content of Zr-4 alloy is as low as 10 mg/kg during quenching at 1100℃, the coarse parallel-plate structure is formed. When the Si content is increased to 100 mg/kg, the precipitated fine Zr₃Si provides nucleation sites for α phase, which leads to the appearance of basketweave structure and fine parallel-plate structure in the microstructure. The basketweave structure can promote the distribution of the second phase in the structure to be more uniform and diffuse, so the Zr-4 alloy with high Si content shows better corrosion resistance.
- Zr-4 alloy /
- Fe+Cr content /
- Si content /
- Corrosion resistance

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图 1 不同Fe+Cr含量的Zr-4合金的典型微观组织图

Figure 1. Typical Microstructure of Zr-4 Alloys with Different Fe+Cr Content

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图 2 不同Fe+Cr含量的Zr-4合金的第二相直径及分布面积　　　

Figure 2. Second Phase Diameter and Area Fraction of Zr-4 Alloys with Different Fe+Cr Content

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图 3 Zr-4合金样品的TEM明场像及第二相P1、 P2、P3对应的SAED花样

Figure 3. TEM Bright Field Image of Zr-4 Sample and SAED Patterns of the Second Phase Particles P1, P2, P3

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图 4 不同Fe+Cr含量的Zr-4合金在420℃腐蚀后的增重及腐蚀126 d的表观形貌

Figure 4. Weight Gains and 126 Days of Corrosion Appearance of Zr-4 Alloys with Different Fe+Cr Content after Corrosion at 420℃

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图 5 锆合金第二相粒子平均直径与腐蚀速率的依赖关系^[21]　　

Figure 5. Dependence of Mean Diameter of Zircaloy Second Phase Particles on Corrosion Rate

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图 6 不同Si含量Zr-4合金淬火组织形态

Figure 6. Quenching Microstructure of Zr-4 Alloy with Different Si Content

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图 7 锆合金中β/β+硅化物物相转变图^[22]

Figure 7. Phase Transition Diagram of β/β+silicide in Zircaloy

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图 8 Zr-4合金淬火组织的SEM图及EDS分析

Figure 8. SEM and EDS Analysis of Quenched Microstructure of Zr-4 Alloys

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图 9 不同Si含量Zr-4合金在420℃的腐蚀增重曲线

Figure 9. Corrosion Weight Gain Curves of Zr-4 Alloys with Different Si Contents at 420℃

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表 1 ASTM B811规定的Zr-4合金主要成分范围^[16]

Table 1. Primary Element Range of Zr-4 Alloy Specified by ASTM B811^[16]

合金成分	Sn	Fe+Cr	C	Si
标准范围/wt%	1.2~1.7	0.28~0.37	＜0.027	＜0.012
wt%表示质量分数

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表 2 样品成分

Table 2. Composition of the Samples

样品编号	Fe+Cr 含量/wt%	Fe/Cr 比值	C含量/ (mg·kg⁻¹)	P含量/ (mg·kg⁻¹)	Si含量/ (mg·kg⁻¹)
样品1	0.28	2.1	150	＜10	100
样品2	0.32	1.9	150	＜10	100
样品3	0.37	2.1	150	＜10	100
样品4	0.32	1.9	30	＜10	10
样品5	0.32	1.9	30	＜10	100

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表 3 Zr-4合金样品中第二相P1、 P2、 P3的EDS分析（对应图3）

Table 3. EDS Analyses of Second Phase Particles P1, P2, P3 in the Zr-4 Sample (Corresponding to Fig. 3)

第二相	化学成分/at%
第二相	Zr	Fe	Cr	Sn	Fe/Cr比值
P1	47.29	34.22	18.24	0.25	1.88
P2	45.55	34.76	19.47	0.22	1.79
P3	51.34	31.17	17.38	0.11	1.79
at%表示原子百分比

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