Zr-Nb-Fe合金在LiOH溶液中的腐蚀行为
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摘要
利用静态高压釜腐蚀试验研究了Zr-Nb-Fe管状样品在LiOH溶液(360℃,18.6 MPa,0.01 mol/L)中的腐蚀行为;利用OM、SEM和TEM观察了合金和氧化膜的显微组织和氧化膜的形貌。结果表明:Zr-Nb-Fe合金中的第二相为体心立方的β-Nb、面心立方和密排六方的Zr(Nb,Fe)_2。Zr-Nb-Fe管状样品腐蚀150 d时腐蚀增质曲线发生转折,转折后的腐蚀速率显著加快,氧化膜表面出现包状凸起,该包状凸起比片状样品的凸起形貌较圆些,其周围氧化膜明显变厚且较为疏松。转折后样品的吸氢量虽有增加,吸氢分数却明显降低,因而氧化膜中包状凸起的形成与未被锆合金吸收的氢需要通过氧化膜向外逸出有关。
The corrosion behavior of Zr-Nb-Fe in lithiated solution(360 ℃, 18.6 MPa, 0.01 mol/L) was investigated by autoclave tests. The microstructure of Zr-Nb-Fe alloy and the morphology of oxide film were observed by OM, SEM and TEM. The results show that the second phase particles(SPPs) including β-Nb with a body-center cubic(BCC) and Zr(Nb, Fe)_2 with a hexagonal close packed(HCP) structure and face-center cubic(FCC) structure are observed in Zr-Nb-Fe alloy. The corrosion mass curve breaks away when the Zr-Nb-Fe alloy is corroded for 150 d, then the corrosion rate increases rapidly. Cellular bulge morphology is forms on the external surface of oxide film and the surrounding oxide film is thick and loose. Cellular bulge morphology formed on the tube specimen is roundish compare with that formed on the plate specimen. The hydrogen uptake of specimen after breaking away increases but hydrogen uptake fraction decreases. So the formation of cellular bulge morphology is related to the unabsorbed hydrogen diffusing out through oxide film.
The corrosion behavior of Zr-Nb-Fe in lithiated solution(360 ℃, 18.6 MPa, 0.01 mol/L) was investigated by autoclave tests. The microstructure of Zr-Nb-Fe alloy and the morphology of oxide film were observed by OM, SEM and TEM. The results show that the second phase particles(SPPs) including β-Nb with a body-center cubic(BCC) and Zr(Nb, Fe)_2 with a hexagonal close packed(HCP) structure and face-center cubic(FCC) structure are observed in Zr-Nb-Fe alloy. The corrosion mass curve breaks away when the Zr-Nb-Fe alloy is corroded for 150 d, then the corrosion rate increases rapidly. Cellular bulge morphology is forms on the external surface of oxide film and the surrounding oxide film is thick and loose. Cellular bulge morphology formed on the tube specimen is roundish compare with that formed on the plate specimen. The hydrogen uptake of specimen after breaking away increases but hydrogen uptake fraction decreases. So the formation of cellular bulge morphology is related to the unabsorbed hydrogen diffusing out through oxide film.
引文
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[21]NI N,LOZANO-PEREZ S,SYKES J M,SMITH G D W,GROVENOR C R M.Focused ion beam sectioning for the 3D characterisation of cracking in oxide scales formed on commercial ZIRLOTM alloys during corrosion in high temperature pressurised water[J].Corrosion Science,2011,53:4073-4083.
[22]周邦新,李强,刘文庆,姚美意,褚于良.水化学及合金成分对锆合金氧化膜显微组织演化的影响[J].稀有金属材料与工程,2006,35(7):1009-1016.ZHOU Bang-xin,LI Qiang,LIU Wen-qing,YAO Mei-yi,CHU Yu-liang.The effects of water chemistry and composition on the microstructure evolution of oxide films on zirconium alloys during autoclave tests[J].Rare Metal Materials and Engineering,2006,35(7):1010-1016.
[23]HUANG Jiao,YAO Mei-yi,GAO Chang-yuan,HU Peng-fei,LIANG Xue,ZHANG Jin-long,ZHOU Bang-xin,LI Qiang,AHSAN E.Analysis of the oxidized surface of 90Nb-10Zr alloy after exposure tolithiated water with 0.01 M Li OH at 360℃/18.6 MPa[J].Corrosion Science,2016:269-276.
[2]JUNG Y I,LEE M H,KIM H G,PARK J Y,JEONG Y H.Behavior of a recrystallization in HANA-4 and HANA-6zirconium-based alloys[J].Journal of Alloy sand Compounds,2009,479(1/2):423-426.
[3]NIKULINA A V,MARKELOV V A,PEREGUD M M.Zirconium alloy E635 as a material for fuel rod cladding and other components of VVER and RBMK cores[C]//Zirconium in the Nuclear Industry:Eleventh International Symposium.Philadelphia:ASTM STP 1295,1996:785-804.
[4]MARDON J P,CHARQUET D,SENEVAT J.Influence of composition and fabrication process on out-of-pile and in-pile properties of M5 alloy[C]//Zirconium in the Nuclear Industry:Twelfth International Symposium.Philadelphia:ASTM STP1354,2000:505-524.
[5]张金龙,张骏,梁楠,曾奇锋,袁改焕,王练,高博,姚美意,周邦新.退火工艺对Zr-Sn-Nb-Fe-Si合金耐腐蚀性能的影响[J].中国有色金属学报,2017,27(1):97-104.ZHANG Jin-long,ZHANG Jun,LIANG Nan,ZENG Qi-feng,YUAN Gai-huan,WANG Lian,GAO Bo,YAO Mei-yi,ZHOU Bang-xin.Effect of annealing treatments on corrosion resistance of Zr-Sn-Nb-Fe-Si alloy[J].The Chinese Journal of Nonferrous Metals,2017,27(1):97-104.
[6]张金龙,梁楠,赵寒沛,苟少秋,姚美意,周邦新.Pd添加对Zr-4合金在Li OH水溶液中耐腐蚀性能的影响[J].中国有色金属学报,2015,25(3):675-681.ZHANG Jin-long,LIANG Nan,ZHAO Han-pei,GOU Shao-qiu,YAO Mei-yi,ZHOU Bang-xin.Effect of Pd addition on corrosion resistance of Zr-4 alloy in Li OH solution[J].The Chinese Journal of Nonferrous Metals,2015,25(3):675-681.
[7]张金龙,谢兴飞,姚美意,周邦新,彭剑超,李强.Ge含量对Zr-4合金在Li OH水溶液中耐腐蚀性能的影响[J].中国有色金属学报,2013,23(6):1542-1548.ZHANG Jin-long,XIE Xing-fei,YAO Mei-yi,ZHOU Bang-xin,PENG Jian-chao,LI Qiang.Effect of Ge addition on corrosion performance of Zr-4 alloy in lithiated solution[J].The Chinese Journal of Nonferrous Metals,2013,23(6):1542-1548.
[8]NEOGY S,SRIVASTAVA D,CHAKRAVARTTY J K,DEY G K,BANERJEE S.Microstructural Evolution in Zr-1Nb and Zr-1Nb-1Sn-0.1Fe alloys[J].Metal Trans A,2007,38:485-498.
[9]NEGYESI M,BURDA J,KLOUC V,LORIC J,SOPOUSEK J,KABATOVA J,NOVOTNY L,LINHART S,CHMELA T,SIEGL J,VRTILKOVA V.Contribution to the study of the pseudobinary Zr1Nb-oxygen phase diagram by local oxygen measurements of Zr1Nb fuel cladding after high temperature oxidation[J].J Nucl Mater,2012,420:314-319.
[10]EI-SHANSHOURY I A,RUDENKO V A.On the mechanism of oxidation of Zr-1%Nb alloy in pressurized steam[J].Corros Sci,1971,11:779-785.
[11]ARIMA T,MIYATA K,INAGAKI Y,IDEMITSU K.Oxidation properties of Zr-Nb alloys at 500-600℃under low oxygen potentials[J].Corros Sci,2005,47:435-446.
[12]赵寒沛.四种锆合金的耐腐蚀性能和氧化膜中内应力的研究[D].上海:上海大学,2014:71.ZHAO Han-pei.Study on the corrosion resistance and compressive stress in oxide films of four kinds of zirconium alloys[D].Shanghai:Shanghai University,2104:71.
[13]ROOT J H,SMALL W M,KHATAMIAN D,WOO O T.Kinetics of the to zirconium hydride transformation in Zr-2.5Nb[J].Acta Materialia,2003,51(2):2041-2053.
[14]KHATAMIAN D,Hydrogen diffusion in oxides formed on surfaces of zirconium alloys[J].Journal of Alloys and Compounds,1997,253(5):471-474.
[15]王洋.锻件产生白点缺陷的问题分析与预防措施[J].重工与起重技术,2009(4):9-12.WANG-Yang.Analysis and prevention measures of white dot defect problem in forgings[J].Heavy Industrial&Hoisting Machinery,2009(4):9-12.
[16]KUWAE R,SATO K,HIGASHINAKAGAWA E,KAWASHIMA J,NAKAMURA S I.Mechanism of zircaloy nodular corrosion[J].Journal of Nuclear Materials,1983,119(7):229-239.
[17]刘文庆,朱晓勇,王晓姣,李强,姚美意,周邦新.Nb元素和Fe元素对锆合金耐腐蚀性能的影响[J].原子能科学技术,2010,44(12):1477-1481.LIU Wen-qing,ZHU Xiao-yong,WANG Xiao-jiao,LI Qiang,YAO Mei-yi,ZHOU Bang-xin.Effect of Nb and Fe on corrosion resistance of zirconium alloys[J].Atomic Energy Science and Technology,2010,44(12):1477-1481.
[18]KIM J M,JEONG Y H,JUNG Y H.Correlation of heat treatment and corrosion behavior of Zr-Sn-Nb-Fe-Cu alloys[J].J Mat Proc Tech.,2000,104:145-149.
[19]YAO Mei-yi,GAO Chang-yuan,HUANG Jiao,PENG Jian-chao,LIANG Xue,ZHANG Jin-long,ZHOU Bang-xin,LI Qiang.Oxidation behavior ofβ-Nb precipitates in Zr-1Nb-0.2Bi alloy corroded in lithiated water at 360℃[J].Corrosion Science,2015,100:169-176.
[20]PREUSS M,FRANKEL P,LOZANO-PEREZ S,HUDSON D,POLATIDIS E,NI N,WEI J,ENGLISH C,STORER S,CHONG K B,FITZPATRICK M,WANG P,SMITH J,GROVENOR C,SMITH G,SYKES J,COTTIS B,LYON S,HALLSTADIUS L,COMSTOCK R J,AMBARD A,BLAT-YRIEIX M.Studies regarding corrosion mechanisms in zirconium alloys[C]//16th International Symposium on Zirconium in the Nuclear Industry.Philadelphia:ASTM STP,1529,2011:649-679.
[21]NI N,LOZANO-PEREZ S,SYKES J M,SMITH G D W,GROVENOR C R M.Focused ion beam sectioning for the 3D characterisation of cracking in oxide scales formed on commercial ZIRLOTM alloys during corrosion in high temperature pressurised water[J].Corrosion Science,2011,53:4073-4083.
[22]周邦新,李强,刘文庆,姚美意,褚于良.水化学及合金成分对锆合金氧化膜显微组织演化的影响[J].稀有金属材料与工程,2006,35(7):1009-1016.ZHOU Bang-xin,LI Qiang,LIU Wen-qing,YAO Mei-yi,CHU Yu-liang.The effects of water chemistry and composition on the microstructure evolution of oxide films on zirconium alloys during autoclave tests[J].Rare Metal Materials and Engineering,2006,35(7):1010-1016.
[23]HUANG Jiao,YAO Mei-yi,GAO Chang-yuan,HU Peng-fei,LIANG Xue,ZHANG Jin-long,ZHOU Bang-xin,LI Qiang,AHSAN E.Analysis of the oxidized surface of 90Nb-10Zr alloy after exposure tolithiated water with 0.01 M Li OH at 360℃/18.6 MPa[J].Corrosion Science,2016:269-276.