Zr-Nb系合金在360 ℃/20 MPa溶氧水中的腐蚀行为
Corrosion Behavior of Zr-Nb Alloys in 360 ℃/20 MPa Water with Dissolved Oxygen
摘 要
通过高温高压（360℃/20 MPa）动态循环水回路系统，研究了在含1.5 mg/L溶解氧的水中，Zr-Nb系合金（M5和E110）的早期腐蚀行为。利用透射电子显微镜（TEM）分析了两种锆合金氧化膜的显微特性，以及氧化膜/基体（O/M）界面特性和靠近界面处β-Nb相的腐蚀行为。结果表明：腐蚀60 d后M5与E110合金表面的氧化膜厚度分别为3.2 μm与2.1 μm。M5合金的腐蚀已经发生转折，而E110合金的未发生转折。两种合金O/M界面处的结构有很大差异，在E110合金的O/M界面处存在ZrO过渡层，这与其氧化膜较慢的生长速率相关。两种合金中靠近O/M界面处的β-Nb相均被部分氧化，溶解氧（DO）可以加速β-Nb相的氧化。
腐蚀
溶解氧
显微组织
腐蚀行为
zirconium alloy
corrosion
dissolved oxygen
microstructure
corrosion behavior
Abstract
Early corrosion behavior of Zr-Nb alloys (M5 and E110) in 1.5 mg/L dissolved oxygen water was studied through a high temperature and high pressure (360 ℃/20 MPa) dynamic circulating water loop system. The microscopic characteristics of oxide films of two zirconium alloys, oxide film/matrix (O/M) interface characteristics and corrosion behavior of β-Nb phase near interface were analyzed by transmission electron microscopy (TEM). The results show that the thicknesses of the oxide films on the surface of M5 and E110 alloys reached 3.2 μm and 2.1 μm respectivly, after corrosion of 60 days. The corrosion of M5 alloy had already turned, while that of E110 alloy had not. The structures of O/M interface of the two alloys were very different. There was a ZrO transition layer at the O/M interface of E110, which was related to the slower growth rate of the oxide film. The β-Nb phases near the O/M interface in oxide films of the two alloys were partially oxidized, and dissolved oxygen (DO) could accelerate the oxidation of β-Nb phase.
中图分类号 TG174 DOI 10.11973/fsyfh-202103001
所属栏目 试验研究
基金项目 国家重点研发计划（2018YFB1900405）
收稿日期 2019/5/21
修改稿日期
网络出版日期
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引用该论文: ZHANG Hao,LIU Zhu,LAI Ping,GUO Xianglong,ZHANG Lefu. Corrosion Behavior of Zr-Nb Alloys in 360 ℃/20 MPa Water with Dissolved Oxygen[J]. Corrosion & Protection, 2021, 42(3): 1
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参考文献
【1】曾奇锋,朱丽兵,袁改焕,等. CAP1400燃料组件用新锆合金研究[J]. 核技术,2017,40(3):61-67.
【2】BEIE H,MITWALSKY A,GARZAROLLI F,et al. Examinations of the corrosion mechanism of zirconium alloys[C]//Zirconium in the nuclear industry:Tenth International Symposium. West Conshohocken,PA:ASTM International,1994:615-643.
【3】QIN W,NAM C,LI H L,et al. Tetragonal phase stability in ZrO2 film formed on zirconium alloys and its effects on corrosion resistance[J]. Acta Materialia,2007,55(5):1695-1701.
【4】杨文斗. 反应堆材料学(修订版)[M]. 北京:原子能出版社,2006.
【5】李中奎. 有金属材料与工程[J]. 1999;28(2):101.
【6】刘文庆,李强,周邦新. 锆锡合金腐蚀转折机理的讨论[J]. 稀有金属材料与工程,2001,30(2):81-84.
【7】YILMAZBAYHAN A,BREVAL E,MOTTA A T,et al. Transmission electron microscopy examination of oxide layers formed on Zr alloys[J]. Journal of Nuclear Materials,2006,349(3):265-281.
【8】NI N,LOZANO-PEREZ S,SYKES J,et al. Quantitative EELS analysis of zirconium alloy metal/oxide interfaces[J]. Ultramicroscopy,2011,111(2):123-130.
【9】NI N,HUDSON D,WEI J,et al. How the crystallography and nanoscale chemistry of the metal/oxide interface develops during the aqueous oxidation of zirconium cladding alloys[J]. Acta Materialia,2012,60(20):7132-7149.
【10】PROFF C,ABOLHASSANI S,LEMAIGNAN C. Oxidation behaviour of zirconium alloys and their precipitates-A mechanistic study[J]. Journal of Nuclear Materials,2013,432(1/2/3):222-238.
【11】TEJLAND P,ANDRÉN H O. Origin and effect of lateral cracks in oxide scales formed on zirconium alloys[J]. Journal of Nuclear Materials,2012,430(1/2/3):64-71.
【12】KIM H G,CHOI B K,PARK J Y,et al. Analysis of oxidation behavior of the β-Nb phase formed in Zr-1.5Nb alloy by using the HVEM[J]. Journal of Alloys and Compounds,2009,481(1/2):867-871.
【13】王荣山,柏广海,翁立奎,等. 含Nb锆合金第二相及其与腐蚀行为关系研究进展[J]. 稀有金属材料与工程,2014,43(12):3188-3192.
【14】COX B. Some thoughts on the mechanisms of in-reactor corrosion of zirconium alloys[J]. Journal of Nuclear Materials,2005,336(2/3):331-368.
【15】ZHOU B X,YAO M Y,LI Z K,et al. Optimization of N18 zirconium alloy for fuel cladding of water reactors[J]. Journal of Materials Science & Technology,2012,28(7):606-613.
【16】BOJINOV M,KARASTOYANOV V,KINNUNEN P,et al. Influence of water chemistry on the corrosion mechanism of a zirconium-niobium alloy in simulated light water reactor coolant conditions[J]. Corrosion Science,2010,52(1):54-67.
【17】KUMAR M K,AGGARWAL S,KAIN V,et al. Effect of dissolved oxygen on oxidation and hydrogen pick up behaviour-Zircaloy vs Zr-Nb alloys[J]. Nuclear Engineering and Design,2010,240(5):985-994.
【18】韦天国,林建康,龙冲生,等. 蒸汽中的溶解氧对锆合金腐蚀行为的影响[J]. 金属学报,2016,52(2):209-216.
【19】CHOO K N,KANG Y H,PYUN S I,et al. Effect of composition and heat treatment on the microstructure and corrosion behavior of Zr-Nb alloys[J]. Journal of Nuclear Materials,1994,209(3):226-235.
【20】MOTTA A T. Waterside corrosion in zirconium alloys[J]. Journal of the Minerals,Metals&Materials Society,2011,63(8):59-63.
【21】YAO M Y,GAO C Y,HUANG J,et al. Oxidation behavior of β-Nb precipitates in Zr-1Nb-0.2Bi alloy corroded in lithiated water at 360℃[J]. Corrosion Science,2015,100:169-176.
【22】PREUSS M, FRANKEL P,LOZANO-PEREZ S,et al. Studies regarding corrosion mechanisms in zirconium alloys[J]. Journal of ASTM International,2011,8(9):103246.
【23】GRIGGS B,MAFFEI H P,SHANNON D W. Multiple rate transitions in the aqueous corrosion of zircaloy[J]. Journal of the Electrochemical Society,1962,109(8):665.
【24】TEJLAND P,THUVANDER M,ANDRÉN H O,et al. Detailed analysis of the microstructure of the metal/oxide interface region in zircaloy-2 after autoclave corrosion testing[C]//Zirconium in the Nuclear Industry:16th International Symposium. West Conshohocken,PA:ASTM International,2011:595-619.
【25】HU J,GARNER A,NI N,et al. Identifying suboxide grains at the metal-oxide interface of a corroded Zr-1.0% Nb alloy using (S) TEM,transmission-EBSD and EELS[J]. Micron,2015,69:35-42.
【26】YARDLEY S S,MOORE K L,NI N,et al. An investigation of the oxidation behaviour of zirconium alloys using isotopic tracers and high resolution SIMS[J]. Journal of Nuclear Materials,2013,443(1/2/3):436-443.
【27】ANADA H,TAKEDA K. Microstructure of oxides on zircaloy-4,1.0Nb zircaloy-4,and zircaloy-2 formed in 10.3-MPa steam at 673 K[C]//Zirconium in the Nuclear Industry:Eleventh International Symposium. West Conshohocken,PA:ASTM International,1996:35-54.
【28】BOSSIS P,LELIÈVRE G,BARBERIS P,et al. Multi-scale characterization of the metal-oxide interface of zirconium alloys[C]//Zirconium in the Nuclear Industry:Twelfth International Symposium. West Conshohocken,PA:ASTM International,2000:918-918-27.
【29】MARDON J P,GARNER G L,HOFFMANN P B. M5® a breakthrough in Zr alloy[C]//Proceedings of International Conference on Light Water Reactor Fuel Performance (Top Fuel 2010), La Grange Park,IL:ANS,2010.
【30】GODLEWSKI J,BOUVIER P,LUCAZEAU G,et al. Stress distribution measured by Raman spectroscopy in zirconia films formed by oxidation of Zr-based alloys[C]//Zirconium in the Nuclear Industry:Twelfth International Symposium. West Conshohocken,PA:ASTM International,2000:877-877-24.
【31】刘建章. 核结构材料[M]. 北京:化学工业出版社,2007.
【32】周邦新,李强,姚美意,等. 锆-4合金在高压釜中腐蚀时氧化膜显微组织的演化[J]. 核动力工程,2005,26(4):364-371.
【2】BEIE H,MITWALSKY A,GARZAROLLI F,et al. Examinations of the corrosion mechanism of zirconium alloys[C]//Zirconium in the nuclear industry:Tenth International Symposium. West Conshohocken,PA:ASTM International,1994:615-643.
【3】QIN W,NAM C,LI H L,et al. Tetragonal phase stability in ZrO2 film formed on zirconium alloys and its effects on corrosion resistance[J]. Acta Materialia,2007,55(5):1695-1701.
【4】杨文斗. 反应堆材料学(修订版)[M]. 北京:原子能出版社,2006.
【5】李中奎. 有金属材料与工程[J]. 1999;28(2):101.
【6】刘文庆,李强,周邦新. 锆锡合金腐蚀转折机理的讨论[J]. 稀有金属材料与工程,2001,30(2):81-84.
【7】YILMAZBAYHAN A,BREVAL E,MOTTA A T,et al. Transmission electron microscopy examination of oxide layers formed on Zr alloys[J]. Journal of Nuclear Materials,2006,349(3):265-281.
【8】NI N,LOZANO-PEREZ S,SYKES J,et al. Quantitative EELS analysis of zirconium alloy metal/oxide interfaces[J]. Ultramicroscopy,2011,111(2):123-130.
【9】NI N,HUDSON D,WEI J,et al. How the crystallography and nanoscale chemistry of the metal/oxide interface develops during the aqueous oxidation of zirconium cladding alloys[J]. Acta Materialia,2012,60(20):7132-7149.
【10】PROFF C,ABOLHASSANI S,LEMAIGNAN C. Oxidation behaviour of zirconium alloys and their precipitates-A mechanistic study[J]. Journal of Nuclear Materials,2013,432(1/2/3):222-238.
【11】TEJLAND P,ANDRÉN H O. Origin and effect of lateral cracks in oxide scales formed on zirconium alloys[J]. Journal of Nuclear Materials,2012,430(1/2/3):64-71.
【12】KIM H G,CHOI B K,PARK J Y,et al. Analysis of oxidation behavior of the β-Nb phase formed in Zr-1.5Nb alloy by using the HVEM[J]. Journal of Alloys and Compounds,2009,481(1/2):867-871.
【13】王荣山,柏广海,翁立奎,等. 含Nb锆合金第二相及其与腐蚀行为关系研究进展[J]. 稀有金属材料与工程,2014,43(12):3188-3192.
【14】COX B. Some thoughts on the mechanisms of in-reactor corrosion of zirconium alloys[J]. Journal of Nuclear Materials,2005,336(2/3):331-368.
【15】ZHOU B X,YAO M Y,LI Z K,et al. Optimization of N18 zirconium alloy for fuel cladding of water reactors[J]. Journal of Materials Science & Technology,2012,28(7):606-613.
【16】BOJINOV M,KARASTOYANOV V,KINNUNEN P,et al. Influence of water chemistry on the corrosion mechanism of a zirconium-niobium alloy in simulated light water reactor coolant conditions[J]. Corrosion Science,2010,52(1):54-67.
【17】KUMAR M K,AGGARWAL S,KAIN V,et al. Effect of dissolved oxygen on oxidation and hydrogen pick up behaviour-Zircaloy vs Zr-Nb alloys[J]. Nuclear Engineering and Design,2010,240(5):985-994.
【18】韦天国,林建康,龙冲生,等. 蒸汽中的溶解氧对锆合金腐蚀行为的影响[J]. 金属学报,2016,52(2):209-216.
【19】CHOO K N,KANG Y H,PYUN S I,et al. Effect of composition and heat treatment on the microstructure and corrosion behavior of Zr-Nb alloys[J]. Journal of Nuclear Materials,1994,209(3):226-235.
【20】MOTTA A T. Waterside corrosion in zirconium alloys[J]. Journal of the Minerals,Metals&Materials Society,2011,63(8):59-63.
【21】YAO M Y,GAO C Y,HUANG J,et al. Oxidation behavior of β-Nb precipitates in Zr-1Nb-0.2Bi alloy corroded in lithiated water at 360℃[J]. Corrosion Science,2015,100:169-176.
【22】PREUSS M, FRANKEL P,LOZANO-PEREZ S,et al. Studies regarding corrosion mechanisms in zirconium alloys[J]. Journal of ASTM International,2011,8(9):103246.
【23】GRIGGS B,MAFFEI H P,SHANNON D W. Multiple rate transitions in the aqueous corrosion of zircaloy[J]. Journal of the Electrochemical Society,1962,109(8):665.
【24】TEJLAND P,THUVANDER M,ANDRÉN H O,et al. Detailed analysis of the microstructure of the metal/oxide interface region in zircaloy-2 after autoclave corrosion testing[C]//Zirconium in the Nuclear Industry:16th International Symposium. West Conshohocken,PA:ASTM International,2011:595-619.
【25】HU J,GARNER A,NI N,et al. Identifying suboxide grains at the metal-oxide interface of a corroded Zr-1.0% Nb alloy using (S) TEM,transmission-EBSD and EELS[J]. Micron,2015,69:35-42.
【26】YARDLEY S S,MOORE K L,NI N,et al. An investigation of the oxidation behaviour of zirconium alloys using isotopic tracers and high resolution SIMS[J]. Journal of Nuclear Materials,2013,443(1/2/3):436-443.
【27】ANADA H,TAKEDA K. Microstructure of oxides on zircaloy-4,1.0Nb zircaloy-4,and zircaloy-2 formed in 10.3-MPa steam at 673 K[C]//Zirconium in the Nuclear Industry:Eleventh International Symposium. West Conshohocken,PA:ASTM International,1996:35-54.
【28】BOSSIS P,LELIÈVRE G,BARBERIS P,et al. Multi-scale characterization of the metal-oxide interface of zirconium alloys[C]//Zirconium in the Nuclear Industry:Twelfth International Symposium. West Conshohocken,PA:ASTM International,2000:918-918-27.
【29】MARDON J P,GARNER G L,HOFFMANN P B. M5® a breakthrough in Zr alloy[C]//Proceedings of International Conference on Light Water Reactor Fuel Performance (Top Fuel 2010), La Grange Park,IL:ANS,2010.
【30】GODLEWSKI J,BOUVIER P,LUCAZEAU G,et al. Stress distribution measured by Raman spectroscopy in zirconia films formed by oxidation of Zr-based alloys[C]//Zirconium in the Nuclear Industry:Twelfth International Symposium. West Conshohocken,PA:ASTM International,2000:877-877-24.
【31】刘建章. 核结构材料[M]. 北京:化学工业出版社,2007.
【32】周邦新,李强,姚美意,等. 锆-4合金在高压釜中腐蚀时氧化膜显微组织的演化[J]. 核动力工程,2005,26(4):364-371.
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