Inconel 601合金在高温硼硅酸盐核废物玻璃熔体中的腐蚀行为
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摘要
研究了Inconel 601合金在普通硼硅酸盐核废物玻璃(MW)和添加ZnO、Mn_2O_3改性的硼硅酸盐玻璃(MZMF)的1060℃高温熔体中浸泡168 h和336 h的腐蚀行为,利用扫描电子显微镜和能谱仪、X射线衍射分析仪,研究了合金与玻璃的腐蚀界面的表面形貌、元素组成以及相结构变化。结果表明:合金表面生成了Cr_2O_3层,其中合金在MW中的腐蚀深度比在MZMF中大10μm;在MW熔体中,MgO、Fe_2O_3和Cr_2O_3反应生成MgCr_2O_4和FeCr_2O_4,破坏了合金和玻璃之间的Cr_2O_3层,使该层呈碎片状。在MZMF高温熔体中长期浸泡后,合金表面形成的Cr_2O_3层呈连续均匀的状态,并且Cr_2O_3层外附着一层含B、O、Fe、Mn、Zn的锯齿状化合物,阻碍了Cr_2O_3层与MgO或其他化学物质反应,减缓了合金的腐蚀速率。
The corrosion behaviors of Inconel 601 alloy immersed in the borosilicate glass( MW glass) and in ZnO,Mn_2O_3 modified borosilicate glasses( MZMF glass) containing simulant nuclear waste at 1060 ℃ for 168 h and 336 h were studied. The surface morphology,chemical composition of elements and the change of phase structure of the corrosion interface between the alloy and glass were studied by means of scanning electron microscopy( SEM),energy disperse spectroscopy( EDS) and X-ray diffraction( XRD). The results show that the Cr_2O_3 layer is formed on the alloy surface,and the corrosion depth of the Inconel 601 in MW waste glass melt is about 10μm greater than that in the MZMF glass melt. In the MW glass,the Cr_2O_3 layer between the alloy and glass is fragmented because of the reaction among MgO,Fe_2O_3 and Cr_2O_3,which forms the crystal phase MgCr_2O_4 and FeCr_2O_4. After immersing in the MZMF waste glasses for long time,the Cr_2O_3 layer formed on the surface of the alloy shows a continuous uniform state,and a thin( B,O,Fe,Mn,Zn)-containing zigzag layer formed on the surface of the Cr_2O_3 layer may prevent Cr_2O_3 from reacting with MgO or other constituents,and slow down the corrosion rate of the Inconel 601 alloy.
The corrosion behaviors of Inconel 601 alloy immersed in the borosilicate glass( MW glass) and in ZnO,Mn_2O_3 modified borosilicate glasses( MZMF glass) containing simulant nuclear waste at 1060 ℃ for 168 h and 336 h were studied. The surface morphology,chemical composition of elements and the change of phase structure of the corrosion interface between the alloy and glass were studied by means of scanning electron microscopy( SEM),energy disperse spectroscopy( EDS) and X-ray diffraction( XRD). The results show that the Cr_2O_3 layer is formed on the alloy surface,and the corrosion depth of the Inconel 601 in MW waste glass melt is about 10μm greater than that in the MZMF glass melt. In the MW glass,the Cr_2O_3 layer between the alloy and glass is fragmented because of the reaction among MgO,Fe_2O_3 and Cr_2O_3,which forms the crystal phase MgCr_2O_4 and FeCr_2O_4. After immersing in the MZMF waste glasses for long time,the Cr_2O_3 layer formed on the surface of the alloy shows a continuous uniform state,and a thin( B,O,Fe,Mn,Zn)-containing zigzag layer formed on the surface of the Cr_2O_3 layer may prevent Cr_2O_3 from reacting with MgO or other constituents,and slow down the corrosion rate of the Inconel 601 alloy.
引文
[1]Michael I O,William E L.Glassy wasteforms for nuclear waste immobilization[J].Metallurgical and Materials Transactions A,2011,42:837-851.
[2]陈明周,张瑞峰,吕永红,等.放射性固体废物玻璃固化技术综述[J].热力发电,2012,41(3):1-6.CHEN Ming-zhou,ZHANG Rui-feng,LYong-hong,et al.A summary of glass-solidification technology for radioactive solid wastages[J].Thermal Power Generation,2012,41(3):1-6.
[3]罗上庚,姜耀中,柳得橹.模拟高放废物玻璃固化体的析晶行为研究[J].核科学与工程,1990,10(2):154-159.LUO Shang-geng,JIANG Yao-zhong,LIU De-lu.Study on the devitrification behaviour of simulated HLW-glassforms[J].Chinese J Nucl Sci Eng,1990,10(2):154-159.
[4]黄文旵,周萘,Day D E,等.高放射性核废料玻璃固化体结构与化学稳定性[J].同济大学学报(自然科学版),2005,33(5):654-658.HUANG Wen-hai,ZHOU Nai,Day D E,et al.Glass structure and chemical durability of phosphate glass wasteforms containing high level radioactive nuclear waste[J].J Tongji Univer(Natural Science),2005,33(5):654-658.
[5]黄文旵,周萘,Day D E,等.磷酸盐玻璃固化体化学耐蚀性研究[J].硅酸盐学报,2004,32(4):460-469.HUANG Wen-hai,ZHOU Nai,Day D E,et al.Study on chemical durability of phosphate glass wasteform[J].J the Chinese Ceramic Society,2004,32(4):460-469.
[6]丁新更,李平广,杨辉,等.硼硅酸盐玻璃固化体结构及化学稳定性研究[J].稀有金属材料与工程,2013,42(增刊1):325-328.DING Xin-geng,LI Ping-guang,YANG Hui,et al.Study on structure and leaching resistance performance of borosilicate glass[J].Rare Metal Mater Eng,2013,42(S1):325-328.
[7]胡唐华,宋崇立,徐世平,等.模拟铯废物玻璃固化体组成对浸出性能的影响[J].辐射防护,2002,22(5):306-312.HU Tang-hua,SONG Chong-li,XU Shi-ping,et al.Effect of composition of titanium silicate glass containing simulated Cs-loaded HLW on the Leaching Behavior[J].Radiation Protection,2002,22(5):306-312.
[8]刘小青,何峰,房玉.硼硅酸盐玻璃结构与其熔体性质研究[J].硅酸盐通报,2013,32(5):804-807.LIU Xiao-qing,HE Feng,FANG Yu.Structures and melt properties of borosilicate glasses[J].Bulletin of the Chinese Ceramic Society,2013,32(5):804-807.
[9]刘丽君,周慧,郄东生,等.硼硅酸盐废物玻璃中硫形态的拉曼光谱[J].原子能科学技术,2009,43(2):103-107.LIU Li-jun,ZHOU Hui,QIE Dong-sheng,et al.Raman spectroscopy of sulfur structure in borosilicate waste glasses[J].Atomic Energy Science and Technology,2009,43(2):103-107.
[10]李红霞,赵会峰,王桂荣,等.硼硅酸盐玻璃对耐火材料的侵蚀研究[J].玻璃,2007(6):5-6.LI Hong-xia,ZHAO Hui-feng,WANG Gui-rong,et al.Study on attack of borosilicate glass upon refractory[J].Glass,2007(6):5-6.
[11]陈民芳,孙家枢,由臣,等.铬、硅含量对镍基高温合金组织及耐蚀性的影响[J].天津理工学院学报,2000,16(1):6-10.CHEN Min-fang,SUN Jia-shu,YOU Chen,et al.Effect of chromium and silicon on microstructure and corrosion resistance of Ni-based superalloy[J].J Tianjin Institute Tech,2000,16(1):6-10.
[12]田素贵,卢旭东,孙振东.高Cr镍基合金的高温内氧化和内氮化行为[J].中国有色金属学报,2012,22(2):408-415.TIAN Sui-gui,LU Xu-dong,SUN Zhen-dong.Internal oxidation and internal nitridation of Ni-base alloy with high Cr contents during high temperature exposure[J].The Chinese Journal of Nonferrous Metals,2012,22(2):408-415.
[13]Sengupta P,Kaushik C P,Mishra R K,et al.Microstructural characterization and role of glassy layer developed on Inconel 690 during a nuclear highlevel waste vitrification process[J].J Ameri Ceramic Soc,2007,90:3057-3062.
[14]Sengupta P,Kaushik C P,Kale G B,et al.Evaluation of Alloy 690 process pot at the contact with borosilicate melt pool during vitrification of high level nuclear waste[J].J Nucl Mater,2009,392:379-385.
[15]Dutta R S,Yusufali C,Paul B,et al.Formation of diffusion barrier coating on Superalloy 690 substrate and its stability in borosilicate melt at elevated temperature[J].J Nucl Mater,2013,432:72-77.
[16]Jen H H,Joseph W N,Cheol W K,et al.Corrosion of inconel 690 and inconel 693 in an iron phosphate glass melt[J].Corrosion Science,2013,75:148-157.
[17]Michael J E,Lisa J M,Tracy R W.A methodology for post operational clean out of a highly active facility including solids behavior[C]∥WM2012Conference,February 26-March 1,2012,Phoenix,Arizona,USA,1-9.
[18]Dunnett B F,Gribble N R,Short R,et al.Vitrification of high molybdenum waste[J].Glass Technol:Eur J Glass Sci Technol A,2012,53(4):166-171.
[19]Henry N,Deniard P,Jobic S,et al.Heat treatments versus micro-structure in a molybdenum-rich borosilicate[J].J Non-Crystal Solids,2004,333:199-205.
[2]陈明周,张瑞峰,吕永红,等.放射性固体废物玻璃固化技术综述[J].热力发电,2012,41(3):1-6.CHEN Ming-zhou,ZHANG Rui-feng,LYong-hong,et al.A summary of glass-solidification technology for radioactive solid wastages[J].Thermal Power Generation,2012,41(3):1-6.
[3]罗上庚,姜耀中,柳得橹.模拟高放废物玻璃固化体的析晶行为研究[J].核科学与工程,1990,10(2):154-159.LUO Shang-geng,JIANG Yao-zhong,LIU De-lu.Study on the devitrification behaviour of simulated HLW-glassforms[J].Chinese J Nucl Sci Eng,1990,10(2):154-159.
[4]黄文旵,周萘,Day D E,等.高放射性核废料玻璃固化体结构与化学稳定性[J].同济大学学报(自然科学版),2005,33(5):654-658.HUANG Wen-hai,ZHOU Nai,Day D E,et al.Glass structure and chemical durability of phosphate glass wasteforms containing high level radioactive nuclear waste[J].J Tongji Univer(Natural Science),2005,33(5):654-658.
[5]黄文旵,周萘,Day D E,等.磷酸盐玻璃固化体化学耐蚀性研究[J].硅酸盐学报,2004,32(4):460-469.HUANG Wen-hai,ZHOU Nai,Day D E,et al.Study on chemical durability of phosphate glass wasteform[J].J the Chinese Ceramic Society,2004,32(4):460-469.
[6]丁新更,李平广,杨辉,等.硼硅酸盐玻璃固化体结构及化学稳定性研究[J].稀有金属材料与工程,2013,42(增刊1):325-328.DING Xin-geng,LI Ping-guang,YANG Hui,et al.Study on structure and leaching resistance performance of borosilicate glass[J].Rare Metal Mater Eng,2013,42(S1):325-328.
[7]胡唐华,宋崇立,徐世平,等.模拟铯废物玻璃固化体组成对浸出性能的影响[J].辐射防护,2002,22(5):306-312.HU Tang-hua,SONG Chong-li,XU Shi-ping,et al.Effect of composition of titanium silicate glass containing simulated Cs-loaded HLW on the Leaching Behavior[J].Radiation Protection,2002,22(5):306-312.
[8]刘小青,何峰,房玉.硼硅酸盐玻璃结构与其熔体性质研究[J].硅酸盐通报,2013,32(5):804-807.LIU Xiao-qing,HE Feng,FANG Yu.Structures and melt properties of borosilicate glasses[J].Bulletin of the Chinese Ceramic Society,2013,32(5):804-807.
[9]刘丽君,周慧,郄东生,等.硼硅酸盐废物玻璃中硫形态的拉曼光谱[J].原子能科学技术,2009,43(2):103-107.LIU Li-jun,ZHOU Hui,QIE Dong-sheng,et al.Raman spectroscopy of sulfur structure in borosilicate waste glasses[J].Atomic Energy Science and Technology,2009,43(2):103-107.
[10]李红霞,赵会峰,王桂荣,等.硼硅酸盐玻璃对耐火材料的侵蚀研究[J].玻璃,2007(6):5-6.LI Hong-xia,ZHAO Hui-feng,WANG Gui-rong,et al.Study on attack of borosilicate glass upon refractory[J].Glass,2007(6):5-6.
[11]陈民芳,孙家枢,由臣,等.铬、硅含量对镍基高温合金组织及耐蚀性的影响[J].天津理工学院学报,2000,16(1):6-10.CHEN Min-fang,SUN Jia-shu,YOU Chen,et al.Effect of chromium and silicon on microstructure and corrosion resistance of Ni-based superalloy[J].J Tianjin Institute Tech,2000,16(1):6-10.
[12]田素贵,卢旭东,孙振东.高Cr镍基合金的高温内氧化和内氮化行为[J].中国有色金属学报,2012,22(2):408-415.TIAN Sui-gui,LU Xu-dong,SUN Zhen-dong.Internal oxidation and internal nitridation of Ni-base alloy with high Cr contents during high temperature exposure[J].The Chinese Journal of Nonferrous Metals,2012,22(2):408-415.
[13]Sengupta P,Kaushik C P,Mishra R K,et al.Microstructural characterization and role of glassy layer developed on Inconel 690 during a nuclear highlevel waste vitrification process[J].J Ameri Ceramic Soc,2007,90:3057-3062.
[14]Sengupta P,Kaushik C P,Kale G B,et al.Evaluation of Alloy 690 process pot at the contact with borosilicate melt pool during vitrification of high level nuclear waste[J].J Nucl Mater,2009,392:379-385.
[15]Dutta R S,Yusufali C,Paul B,et al.Formation of diffusion barrier coating on Superalloy 690 substrate and its stability in borosilicate melt at elevated temperature[J].J Nucl Mater,2013,432:72-77.
[16]Jen H H,Joseph W N,Cheol W K,et al.Corrosion of inconel 690 and inconel 693 in an iron phosphate glass melt[J].Corrosion Science,2013,75:148-157.
[17]Michael J E,Lisa J M,Tracy R W.A methodology for post operational clean out of a highly active facility including solids behavior[C]∥WM2012Conference,February 26-March 1,2012,Phoenix,Arizona,USA,1-9.
[18]Dunnett B F,Gribble N R,Short R,et al.Vitrification of high molybdenum waste[J].Glass Technol:Eur J Glass Sci Technol A,2012,53(4):166-171.
[19]Henry N,Deniard P,Jobic S,et al.Heat treatments versus micro-structure in a molybdenum-rich borosilicate[J].J Non-Crystal Solids,2004,333:199-205.