含硼水溶液上方蒸汽对奥氏体不锈钢的腐蚀行为

doi:10.19964/j.issn.1006-4990.2021-0225

摘要/Abstract

摘要：

硼酸应用广泛,其对设备腐蚀不容忽视。针对核电站含硼水溶液循环体系中设备顶端腐蚀的实际情况,取304奥氏体不锈钢为研究对象,研究了在给定温度和一定硼浓度水溶液存在下,溶液上方含硼水蒸气对奥氏体不锈钢的腐蚀行为,并将其与相应的溶液腐蚀对比。采用扫描电子显微镜（SEM）、X射线衍射仪（XRD）和X射线光电子能谱仪（XPS）分析了试样表面氧化膜。结果表明：在180 ℃下腐蚀1 200 h后,304不锈钢在含硼水蒸气中的腐蚀程度高于相应含硼水溶液的腐蚀程度;尽管两种环境中的试样表面均形成了双层氧化膜,但在含硼水蒸气中形成的氧化膜表层富铁镍,而在含硼水溶液中形成的氧化膜表层富铬,并用氧化膜形成机理解释了此现象。

关键词: 奥氏体不锈钢, 含硼水蒸气, 氧化膜

Abstract:

With the widespread use of boric acid,the corrosion problem of equipments exposed to boric acid-containing medi-um cannot be ignored.Based on the actual situation of the equipment tip corrosion in the boron-containing solution circulating system of nuclear power plant,the corrosion behavior of 304 austenitic stainless steel exposed to the vapor above boron-con-taining solution at a given temperature and a certain boron concentration was studied,and contrasting the vapor phase corro-sion with the corresponding solution corrosion was also discussed.The oxide films formed on the surface of specimens were characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS）.The result indicated that the corrosion of 304 stainless steel exposed to boron-containing vapor was more serious than that exposed to boron-containing solution at 180 ℃ when the corrosion test was carried out for 1 200 h.In spite of forming double-layer oxide films on the samples in both boron-containing vapor and solution,it was noted that the surface layer of the oxide film formed in boron-containing vapor was rich in Fe and Ni,while the surface layer of the oxide film formed in boron-containing solution was rich in Cr.This phenomenon was elucidated by the formation mechanism of oxide film.

Key words: austenitic stainless steel, boron-containing vapor, oxide film

中图分类号:

TQ128.5

魏丁丁,仲剑初,宁桂玲. 含硼水溶液上方蒸汽对奥氏体不锈钢的腐蚀行为[J]. 无机盐工业, 2022, 54(2): 85-89.

WEI Dingding,ZHONG Jianchu,NING Guiling. Corrosion behavior of austenitic stainless steel exposed to the vapor above boron-containing solution[J]. Inorganic Chemicals Industry, 2022, 54(2): 85-89.

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参考文献 15

[1]	范柄辰. 压水堆核电站一回路主要活化腐蚀产物及水化学控制措施[J]. 中国核电, 2020, 13(3):356-362.
[2]	许咏丽, 张道德, 张锡林, 等. 硼酸生产设备的腐蚀破裂[J]. 腐蚀与防护, 1985(4):38-39.
[3]	郑越, 卢可可, 雷欣, 等. 乏燃料干法贮存运输容器用B₄C/Al 复合材料板的高温老化和硼酸腐蚀行为[J]. 机械工程材料, 2017, 41(10):63-68.
[4]	XIAO Q, JANG C, KIM C, et al. Corrosion behavior of stainless st-eels in simulated PWR primary water:The effect of composition and matrix phases[J]. Corrosion Science, 2020, 177.Doi: 10.1016/j.corsci.2020.108991.
[5]	彭德全, 胡石林, 张平柱, 等. 304L在模拟压水堆一回路条件下长期均匀腐蚀性能的研究[J]. 中国腐蚀与防护学报, 2013, 33(4):288-292.
[6]	LIU X H, WU X Q, HAN N H. Effect of Zn injection on established surface oxide films on 316 L stainless steel in borated and lithiated high temperature water[J]. Corrosion Science, 2012, 65:136-144.
[7]	TERACHI T, FUJII K, ARIOKA K. Microstructural characterization of SCC crack tip and oxide film for SUS 316 stainless steel in simu-lated PWR primary water at 320 ℃[J]. Journal of Nuclear Science & Technology, 2005, 42(2):225-232.
[8]	BRUGGEMAN A, BRAET J.Method for separating boric acid:US,5468347[P]. 1995-11-21.
[9]	申罡, 应红. 核电站硼酸腐蚀泄露监检测技术[J]. 全面腐蚀控制, 2016, 30(1):16-19.
[10]	王正品, 王静, 要玉宏, 等. Z3CN20-09M钢高温高压水蒸气腐蚀行为研究[J]. 西安工业大学学报, 2016, 36(4):310-316.
[11]	茹祥坤, 吕战鹏, 杨乘东, 等. 高温水中不同Fe含量Ni-Cr-Fe合金的氧化膜特性[J]. 腐蚀与防护, 2020, 41(11):8-21.
[12]	DICKINSON T, POVEY A F, SHERWOOD P M A. Dissolution and passivation of nickel.An X-ray photoelectron spectroscopic stu-dy[J]. Journal of the Chemical Society Faraday Transactions, 1977, 73:327-343.
[13]	刘东, 向红亮, 刘春育. 含Ag抗菌双相不锈钢表面腐蚀产物的XPS分析[J]. 中国腐蚀与防护学报, 2018, 38(6):533-542.
[14]	STELLWAG B. The mechanism of oxide film formation on austeni-tic stainless steels in high temperature water[J]. Corrosion Sci-ence, 1998, 40(2/3):337-370.
[15]	翟金坤. 金属高温腐蚀[M]. 北京: 北京航空航天大学出版社, 1994.

腐蚀环境	O原子分数/%	Cr原子分数/%	Fe原子分数/%	Ni原子分数/%
180 ℃含硼水溶液	20.25	16.58	57.20	5.97
180 ℃含硼水蒸气	65.24	4.44	27.11	3.22

化学状态		含硼水溶液腐蚀			含硼水蒸气腐蚀
化学状态		结合能/ eV	半峰宽/ eV	峰面积（S）/ （CPS·eV）	结合能/ eV	半峰宽/ eV	峰面积（S）/ （CPS·eV）
Fe 2p_3/2	Fe（Ⅱ）氧化物	709.6	1.7	1 085.6	709.6	1.3	9 032.2
	Fe（Ⅲ）氧化物	710.9	1.7	9 558.1	710.8	1.8	13 208.5
	Fe（Ⅲ）氢氧化物	712.4	2.4	8 407.9	712.3	3.1	16 481.7
Cr 2p_3/2	Cr（Ⅲ）氧化物	576.4	2.3	20 784.2	576.3	2.0	4 397.9
Cr 2p_3/2	Cr（Ⅲ）氢氧化物	578.1	1.9	2 690.9	577.9	1.9	854.1
Ni 2p_3/2	Ni单质	852.8	2.5	992.4	—	—	—
Ni 2p_3/2	Ni（Ⅱ）氧化物/氢氧化物	855.3	2.1	2 192.7	855.6	2.2	33 233.9
O 1s	M—O	529.6	1.2	31 310.9	529.6	1.0	30 363.4
O 1s	M—OH	531.0	2.1	48 414.7	531.1	2.2	60 668.2

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