强γ辐照下Q235碳钢在甘肃北山地区地下水模拟液中的腐蚀行为
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摘要
利用1.11×10~(16) Bq(30万Ci)高强度~(60)Co源γ辐照装置,对甘肃北山地区地下水模拟液中高放废物处置罐候选材料Q235碳钢进行了辐照腐蚀试验。采用水化学参数分析、称重、扫描电镜(SEM)、X射线能谱(EDS)和红外光谱(FT-IR)等技术手段,分析了辐照剂量(时间)对辐照腐蚀演化的影响规律,并与未辐照试验进行了对比。结果表明,在长时间强γ辐照下,模拟液辐照分解导致氧化性增强、pH值由弱碱性变为酸性、电导率下降明显,而未辐照的模拟液pH值和电导率未见明显变化;利用质量变化率计算得到的辐照腐蚀速率约为未辐照腐蚀速率的5.5倍,辐照明显加速了Q235碳钢的腐蚀。SEM-EDS和FT-IR分析表明,随着辐照剂量的增加,腐蚀层中出现泡状或针状产物,表面由致密变为稀疏;腐蚀层化学组成以Fe、O为主,含有不同相的羟基氧化铁(α-FeOOH和γ-FeOOH)和氧化铁(α-Fe_2O_3)。
Q235 carbon steel is a candidate material of the high level waste(HLW) disposal container. The irradiation corrosion test of Q235 carbon steel was carried out with the high-strength ~(60)Co radioactive device(1.11×10~(16) Bq) in the simulated groundwater in Gansu Beishan aera. Water chemical parameter analysis, weighing, scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS) and Fourier transform infrared spectroscopy(FT-IR) were used to analyze the effects of irradiation dose(time) on the evolution of irradiation corrosion. The results show that the oxidizability of the simulated groundwater is enhanced, the pH value changes from 7.81 to 4.75, which means that the solution changes from weakly alkaline to strongly acidic under the long-term high-strength γ irradiation. Besides, the electrical conductivity decreases obviously, but there is no significant change for the pH value and electrical conductivity of the non-irradiated solution, and the irradiation corrosion rate calculated by mass change rate is about 5.5 times that of non-irradiation. SEM-EDS and FT-IR analysis shows that bubbles or needles appeare in the corrosion layer. The corrosion layer surface changes from dense to sparse as the radiation dose increases. The chemical composition of the corrosion layer is mainly Fe and O, and the corrosion layer contains different phases of iron oxyhydroxide(α-FeOOH and γ-FeOOH) and iron oxide(α-Fe_2O_3).
Q235 carbon steel is a candidate material of the high level waste(HLW) disposal container. The irradiation corrosion test of Q235 carbon steel was carried out with the high-strength ~(60)Co radioactive device(1.11×10~(16) Bq) in the simulated groundwater in Gansu Beishan aera. Water chemical parameter analysis, weighing, scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS) and Fourier transform infrared spectroscopy(FT-IR) were used to analyze the effects of irradiation dose(time) on the evolution of irradiation corrosion. The results show that the oxidizability of the simulated groundwater is enhanced, the pH value changes from 7.81 to 4.75, which means that the solution changes from weakly alkaline to strongly acidic under the long-term high-strength γ irradiation. Besides, the electrical conductivity decreases obviously, but there is no significant change for the pH value and electrical conductivity of the non-irradiated solution, and the irradiation corrosion rate calculated by mass change rate is about 5.5 times that of non-irradiation. SEM-EDS and FT-IR analysis shows that bubbles or needles appeare in the corrosion layer. The corrosion layer surface changes from dense to sparse as the radiation dose increases. The chemical composition of the corrosion layer is mainly Fe and O, and the corrosion layer contains different phases of iron oxyhydroxide(α-FeOOH and γ-FeOOH) and iron oxide(α-Fe_2O_3).
引文
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[21]NORRFORS K K,BJRKBACKA,KESSLERA,et al.γ-radiation induced corrosion of copper in bentonite-water systems under anaerobic conditions[J].Radiation Physics and Chemistry,2018,144:8-12.
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[23]BJRKBACKA,HOSSEINPOUR S,JOHN-SON M,et al.Radiation induced corrosion of copper for spent nuclear fuel storage[J].Radiation Physics and Chemistry,2013,92:80-86.
[24]陈旎,魏强林,杨波,等.地下水对放射性废物地质处置库的影响[J].环境科技,2014,27(4):75-78.CHEN Ni,WEI Qianglin,YANG Bo,et al.The effects of underground water on radioactive waste disposal system[J].Environmental Science and Technology,2014,27(4):75-78(in Chinese).
[25]黄贤黎.γ辐照条件下水的辐照分解研究[D].南昌:东华理工大学,2014.
[26]杨波.高放射性废物包装容器安全评价研究[D].北京:中国原子能科学研究院,2017.
[27]DAUB K,ZHANG X,NOL J J,et al.Gamma-radiation-induced corrosion of carbon steel in neutral and mildly basic water at 150℃[J].Corros Sci,2011,53(1):11-16.
[28]WINSLEY R J,SMART N R,RANCE A P,et al.Further studies on the effect of irradiation on the corrosion of carbon steel in alkaline media[J].Corros Eng Sci Techn,2011,46(2):111-116.
[29]FUJITA N,AKIYAMA M,TAMURA T.Stress corrosion cracking of sensitized type 304stainless steel in high temperature water under gamma ray irradiation[J].Corrosion,1981,37(6):335-341.
[30]KONDOU K,HASEGAWA A,ABE K.Study on irradiation induced corrosion behavior in austenitic stainless steel using hydrogen-ion bombardment[J].Journal of Nuclear Materials,2004,329-333(1-3):652-656.
[31]YAMAMOTO T,TSUKUI S,OKAMOTO S,et al.Gamma-ray irradiation effects on corrosion rates of stainless steel in boiling nitric acid containing ionic additives[J].Journal of Nuclear Science and Technology,1998,35(5):353-356.
[32]JU W,RUI S U,WEIMING C,et al.Deep geological disposal of high-level radioactive wastes in China[J].Chinese Journal of Rock Mechanics and Engineering,2006,25(4):649-658.
[33]闵茂中,张卫东,蒋浩生,等.水辐解产物对深处置高放废物容器侵蚀模拟研究[J].原子能科学技术,1993,27(5):458-463.MIN Maozhong,ZHANG Weidong,JIANG Haosheng,et al.A simulated experimental study in corrosion of water radiolysis products on container in the condition of deep geological disposal[J].Atomic Energy Science and Technology,1993,27(5):458-463(in Chinese).
[34]郑珉,黄彦良,路东柱,等.中国高放废物处置库甘肃北山预选区腐蚀研究用代表性地下水成分的确定[J].中国腐蚀与防护学报,2016,36(2):185-189.ZHENG Min,HUANG Yanliang,LU Dongzhu,et al.Determination of representative groundwater components for corrosion study in Beishan preselected area of high-level radioactive waste disposal repository[J].Journal of Chinese Society for Corrosion and Protection,2016,36(2):185-198(in Chinese).
[35]DAS S.Critical review of water radiolysis processes,dissociation products,and possible impacts on the local environment:A geochemist’s perspective[J].Australian Journal of Chemistry,2013,66(5):522-529.
[36]PAN Y M,BROSSIA C S,CRAGNOLINO GA,et al.Evolution of solution chemistry through interactions with waste package internal structural components[J].Scientific Basis for Nuclear Waste Management,2002,713:121-127.
[37]VCLAV C,MU'V,POSPIL M,et al.Radiation induced corrosion of nuclear fuel and materials[M]∥REVANKAR S T.Advances in Nuclear Fuel.London:Intechopen Limited,2012:27-48.
[38]EWING R C.Long-term storage of spent nuclear fuel[J].Nature Materials,2015,14(3):252-257.
[39]杨晓梅.碳钢和低合金钢大气腐蚀锈层的红外光谱研究[J].宁夏大学学报:自然科学版,1999,20(1):46-48.YANG Xiaomei.The research of infrared spectrum on carbon steel and low-alloy steel rusty layer from atmosphere corrosion[J].Journal of Ningxia University:Natural Science Edition,1999,20(1):46-48(in Chinese).
[2]王长罡,董俊华,柯伟,等.硼酸缓冲溶液中pH值和Cl-浓度对Cu腐蚀行为的影响[J].金属学报,2011,47(3):354-360.WANG Changgang,DONG Junhua,KE Wei,et al.Effect of pH and Cl-concentration on the corrosion behavior of copper in boric acid buffer solution[J].Acta Metallurgica Sinica,2011,47(3):354-360(in Chinese).
[3]魏欣,董俊华,柯伟.工业纯Ti在模拟高放废物地质处置环境中的缝隙腐蚀行为[J].金属学报,2013,49(6):675-681.WEI Xin,DONG Junhua,KE Wei.Crevice corrosion of grade-2Ti in simulated groundwater for geological disposal of high-level radioactive nuclear waste[J].Acta Metallurgica Sinica,2013,49(6):675-681(in Chinese).
[4]魏欣,董俊华,柯伟.模拟高放废物处置环境中钛的缝隙腐蚀敏感性[C]∥第四届废物地下处置学术研讨会论文集.北京:中国岩石力学与工程学会废物地下处置专业委员会,2012.
[5]徐秋发,王薇,庞晓露,等.4种材料在地下水模拟溶液中的腐蚀行为[J].工程材料,2014,13(1):28-33.XU Qiufa,WANG Wei,PANG Xiaolu,et al.Corrosion behavior of four kinds of materials in simulated groundwater[J].Journal of Engineering Materials,2014,13(1):28-33(in Chinese).
[6]郑珉,黄彦良,西方笃,等.Q235钢在甘肃北山地区地下水模拟液及高压实膨润土环境下的腐蚀行为[J].中国腐蚀与防护学报,2016,36(5):398-406.ZHENG Min,HUANG Yanliang,XI Fangdu,et al.Corrosion behavior of Q235steel in simulated underground water and highly compacted bentonite environment of Beishan area[J].Journal of Chinese Society for Corrosion and Protection,2016,36(5):398-406(in Chinese).
[7]黄彦良,余秀明,曲文娟,等.深地质处置核废物储罐备选材料不锈钢和镍基合金的腐蚀研究现状[C]∥第5届废物地下处置学术研讨会论文集.北京:中国岩石力学与工程学会废物地下处置专业委员会,2014.
[8]阳靖峰.高放废物地质处置环境下金属处置罐材料的腐蚀行为[D].北京:中国科学院金属研究所,2011.
[9]徐秋发.地下水环境中典型金属材料腐蚀行为的研究[D].北京:北京科技大学,2016.
[10]王薇.核废料包装容器材料腐蚀行为的研究[D].北京:北京科技大学,2013.
[11]GLASS R S,OVERTURF G E,KONYNEN-BURG A V,et al.Gamma radiation effects on corrosion,Ⅰ:Electrochemical mechanisms for the aqueous corrosion processes of austenitic stainless steels relevant to nuclear waste disposal in tuff[J].Corrosion Science,1986,26(8):577-590.
[12]ONOFREI M,SHOESMITH D W.Corrosion of iron-based materials for nuclear-fuel waste immobilization containers[J].Cim Bulletin,1987,80:93-94.
[13]MARSH G P,HARKER A H,TAYLOR K J.Corrosion of carbon steel nuclear waste containers in marine sediment[J].Corrosion,1989,45(7):579-589.
[14]ROSBORG B,KRANJC A,KUHAR V,et al.Corrosion rate of pure copper in an oxic bentonite/saline groundwater environment[J].Corrosion Engineering,Science and Technology,2011,46(2):148-152.
[15]ROY A K,FLEMING D L,FREEMAN D C,et al.Stress corrosion cracking of alloy C-22and TiGr-12 using double-cantilever-beam technique[J].Micron,1999,30(6):649-654.
[16]CLARKE C F,HARDIE D,IKEDA B M.The effect of hydrogen content on the fracture of precracked titanium specimens[J].Corros Sci,1994,36(3):487-509.
[17]GIORDANO C M,RINCO’N-ORTI’Z M,RO-DRI’GUEZ M A,et al.Crevice corrosion testing methods for measuring repassivation potential of alloy 22[J].Corrosion Engineering,Science and Technology,2011,46(2):129-133.
[18]DUNN D S,SRIDHAR N,CRAGNOLINO GA.Long-term prediction of localized corrosion of alloy 825in high-level nuclear waste repository environments[J].Corrosion,1996,52(2):115-124.
[19]NAKAYAMA G,SAKAKIBARA Y,KAWA-KAMI S.Long term integrity against corrosion of titanium used for TRU waste container[J].Corrosion Engineering,Science and Technology,2011,46(2):159-164.
[20]L’HOSTIS V,FOCT F,DILLMANN P.Corrosion behaviour of reinforced concrete:Laboratory experiments and archaeological analogues for long-term predictive modeling[J].Journal of Nuclear Materials,2008,379(1-3):124-132.
[21]NORRFORS K K,BJRKBACKA,KESSLERA,et al.γ-radiation induced corrosion of copper in bentonite-water systems under anaerobic conditions[J].Radiation Physics and Chemistry,2018,144:8-12.
[22]IBRAHIM B,ZAGIDULIN D,SMITH J M,et al.Radiolytic corrosion of Cu nuclear waste containers[C]∥17th International Conference on Environmental Degradation of Materials in Nuclear Power Systems-Water Reactors.Ottawa:[s.n.],2015.
[23]BJRKBACKA,HOSSEINPOUR S,JOHN-SON M,et al.Radiation induced corrosion of copper for spent nuclear fuel storage[J].Radiation Physics and Chemistry,2013,92:80-86.
[24]陈旎,魏强林,杨波,等.地下水对放射性废物地质处置库的影响[J].环境科技,2014,27(4):75-78.CHEN Ni,WEI Qianglin,YANG Bo,et al.The effects of underground water on radioactive waste disposal system[J].Environmental Science and Technology,2014,27(4):75-78(in Chinese).
[25]黄贤黎.γ辐照条件下水的辐照分解研究[D].南昌:东华理工大学,2014.
[26]杨波.高放射性废物包装容器安全评价研究[D].北京:中国原子能科学研究院,2017.
[27]DAUB K,ZHANG X,NOL J J,et al.Gamma-radiation-induced corrosion of carbon steel in neutral and mildly basic water at 150℃[J].Corros Sci,2011,53(1):11-16.
[28]WINSLEY R J,SMART N R,RANCE A P,et al.Further studies on the effect of irradiation on the corrosion of carbon steel in alkaline media[J].Corros Eng Sci Techn,2011,46(2):111-116.
[29]FUJITA N,AKIYAMA M,TAMURA T.Stress corrosion cracking of sensitized type 304stainless steel in high temperature water under gamma ray irradiation[J].Corrosion,1981,37(6):335-341.
[30]KONDOU K,HASEGAWA A,ABE K.Study on irradiation induced corrosion behavior in austenitic stainless steel using hydrogen-ion bombardment[J].Journal of Nuclear Materials,2004,329-333(1-3):652-656.
[31]YAMAMOTO T,TSUKUI S,OKAMOTO S,et al.Gamma-ray irradiation effects on corrosion rates of stainless steel in boiling nitric acid containing ionic additives[J].Journal of Nuclear Science and Technology,1998,35(5):353-356.
[32]JU W,RUI S U,WEIMING C,et al.Deep geological disposal of high-level radioactive wastes in China[J].Chinese Journal of Rock Mechanics and Engineering,2006,25(4):649-658.
[33]闵茂中,张卫东,蒋浩生,等.水辐解产物对深处置高放废物容器侵蚀模拟研究[J].原子能科学技术,1993,27(5):458-463.MIN Maozhong,ZHANG Weidong,JIANG Haosheng,et al.A simulated experimental study in corrosion of water radiolysis products on container in the condition of deep geological disposal[J].Atomic Energy Science and Technology,1993,27(5):458-463(in Chinese).
[34]郑珉,黄彦良,路东柱,等.中国高放废物处置库甘肃北山预选区腐蚀研究用代表性地下水成分的确定[J].中国腐蚀与防护学报,2016,36(2):185-189.ZHENG Min,HUANG Yanliang,LU Dongzhu,et al.Determination of representative groundwater components for corrosion study in Beishan preselected area of high-level radioactive waste disposal repository[J].Journal of Chinese Society for Corrosion and Protection,2016,36(2):185-198(in Chinese).
[35]DAS S.Critical review of water radiolysis processes,dissociation products,and possible impacts on the local environment:A geochemist’s perspective[J].Australian Journal of Chemistry,2013,66(5):522-529.
[36]PAN Y M,BROSSIA C S,CRAGNOLINO GA,et al.Evolution of solution chemistry through interactions with waste package internal structural components[J].Scientific Basis for Nuclear Waste Management,2002,713:121-127.
[37]VCLAV C,MU'V,POSPIL M,et al.Radiation induced corrosion of nuclear fuel and materials[M]∥REVANKAR S T.Advances in Nuclear Fuel.London:Intechopen Limited,2012:27-48.
[38]EWING R C.Long-term storage of spent nuclear fuel[J].Nature Materials,2015,14(3):252-257.
[39]杨晓梅.碳钢和低合金钢大气腐蚀锈层的红外光谱研究[J].宁夏大学学报:自然科学版,1999,20(1):46-48.YANG Xiaomei.The research of infrared spectrum on carbon steel and low-alloy steel rusty layer from atmosphere corrosion[J].Journal of Ningxia University:Natural Science Edition,1999,20(1):46-48(in Chinese).
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