Determination of trace silicon in high-purity tantalum, high-purity tungsten and high-purity molybdenum by inductively coupled plasma tandem mass spectrometry
WANG Zhiqing1, HOU Yanxia1,2, YANG Guowu1,2, QI Rong1, QIAO Lili1, LOU Jinhui1
1. NCS Testing Technology Co.,Ltd.,Beijing 100081,China; 2. Central Iron and Steel Research Institute Co.,Ltd.,Beijing 100081,China
Abstract：During the determination of trace silicon (Si) in high-purity tantalum, high-purity tungsten and high-purity molybdenum by single quadrupole inductively coupled plasma tandem mass spectrometry (SQ-ICP-MS), it will be interfered by 14N14N+ and 12C16O+, which seriously affects the determination results. This problem has always been a research difficulty in determining low-content Si by ICP-MS. In this study, the sample was digested in aqua regia-hydrofluoric acid system. In series quadrupole (MS/MS) mode, the mass-to-charge ratio (m/z) of the first-stage mass filter (Q1) was set to 28, and then hydrogen was introduced into the collision/reaction cell. At this time, Si did not react with hydrogen, but the interfering ions would react with hydrogen to generate polyatomic ions with mass-to-charge ratio not equal to 28. The mass-to-charge ratio (m/z) of the secondary mass filter (Q2) was set to 28, and only 28Si+ passed through and was then detected by the detector. Therefore, the mass spectrometry interference of 14N14N+ and 12C16O+ could be avoided. Based on this, a method for the determination of Si in high purity tantalum, high purity tungsten and high purity molybdenum by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) was established. The hydrogen flow rate was optimized and determined to be 4 mL/min. The effects of different mass concentrations of Mo, Ta and W matrixes on the determination of Si were investigated. The experimental results showed that the matrix effects of these three matrices were remarkable, and the matrix effects could be overcome after correction with Sc as the internal standard. The linear range of the method was 1-100 μg/L, and the linear correlation coefficients were 1.000. The limit of detection was 0.33 μg/L, and the limit of quantification was 1.11 μg/L. The content of Si in high-purity tantalum, high-purity tungsten and high-purity molybdenum was determined according to the experimental method. Meanwhile, the recovery test was also carried out. The relative standard deviation (RSD, n=7) of the determination results was less than 5%, and the spiked recoveries were in range of 94%-111%. High-purity molybdenum (>99.99%), high-purity tantalum (>99.99%) and high-purity tungsten (>99.99%) samples from different production enterprises were determined according to the experimental methods, and the determination results were basically consistent with the Si content range provided by the enterprises.
[1] 张颖.高纯钨、钼、钽、铌工业分析进展[J].湖南有色金属,2012,28(6):71-76. ZHANG Ying.Development of high pure tungsten molybdenum tantalum and niobium industrial analysis[J].Hunan Nonferrous Metals,2012,28(6):71-76. [2] 赵秦生.国外高纯钨粉和钨材制备[J].稀有金属与硬质合金,2003,31(4):56-57. ZHAO Qinsheng.Preparation of ultra-pure tungsten powder and tungsten material abroad[J].Rare Metals and Cemented Carbides,2003,31(4):56-57. [3] 李仲香,杨国启,陈学清,等.溅射钽靶材用高纯钽粉工艺研究[J].材料开发与应用,2017,32(3):67-72. LI Zhongxiang,YANG Guoqi,CHEN Xueqing,et al.Study on production process of high pure tantalum powder for tantalum target[J].Material Development and Application,2017,32(3):67-72. [4] 杨帆,王快社,胡平,等.高纯钼溅射靶材的研究现状及发展趋势[J].热加工工艺,2013,42(24):10-12. YANG Fan,WANG Kuaishe,HU Ping,et al.Research status and development trend of high purity molybdenum sputtering target material[J].Hot Working Technology,2013,42(24):10-12. [5] 华海霞,于慧国,刘德君.硅钼蓝比色法测定植株中的硅[J].现代农业科技,2013(24):173-174. HUA Haixia,YU Huiguo,LIU Dejun.Determination of silicon concentration in the plants by colorimetric molybdenum blue method[J].Modern Agricultural Science and Technology,2013(24):173-174. [6] 袁秉鉴,戴祥胜.分光光度法快速测定钢铁中的锰、磷、硅[J].化学分析计量,2001,10(4):24-26. YUAN Bingjian,DAI Xiangsheng.Quick determination of Mn,P and Si in the steel and iron by spectrophotometry[J].Chemical Analysis and Meterage,2001,10(4):24-26. [7] 张众,李亚琴,王淑梅.电感耦合等离子体原子发射光谱法测定钒中铁、硅、铝[J].材料开发与应用,2018,33(1):16-19. ZHANG Zhong,LI Yaqin,WANG Shumei.Determination of iron,silicon and aluminum elements in vanadium by inductively coupled plasma atomic emission spectrometry[J].Material Development and Application,2018,33(1):16-19. [8] 杨海岸,罗舜,刘英波,等.辉光放电质谱法测定高纯钴中痕量杂质元素[J].云南冶金,2015,44(3):61-65. YANG Haian,LUO Shun,LIU Yingbo,et al.Determination of the trace impurity elements in high purity cobalt by glow discharge mass spectrometry[J].Yunnan Metallurgy,2015,44(3):61-65. [9] 杨海岸,罗舜,闫豫昕,等.辉光放电质谱法测定高纯镍中16种痕量杂质元素[J].冶金分析,2015,35(5):1-6. YANG Haian,LUO Shun,YAN Yuxin,et al.Determination of sixteen trace impurity elements in high-purity nickel by glow discharge mass spectrometry[J].Metallurgical Analysis,2015,35(5):1-6. [10] 王长华,李继东,潘元海.电感耦合等离子体质谱法测定高纯钼中12种杂质元素[J].分析试验室,2011,30(7):18-21. WANG Changhua,LI Jidong,PAN Yuanhai.The determination of 12 trace-impurities in high purity molybdenum by inductively coupled plasma mass spectrometry[J].Chinese Journal of Analysis Laboratory,2011,30(7):18-21. [11] 张萍,符靓,聂西度.ICP-MS法测定MnZn铁氧体中Si和P[J].光谱学与光谱分析,2014,34(3):808-811. ZHANG Ping,FU Liang,NIE Xidu.Determination of Si and P in MnZn ferrites by inductively coupled plasma mass spectrometry[J].Spectroscopy and Spectral Analysis,2014,34(3):808-811. [12] 刘园,周婉笛,李亚慧,等.电感耦合等离子体质谱法间接测定粉尘中游离二氧化硅含量[J].中国工业医学杂志,2014,27(1):67-68. LIU Yuan,ZHOU Wandi,LI Yahui,et al.Indirect determination of free silica content in dust by inductively coupled plasma mass spectrometry[J].Chinese Journal of Industrial Medicine,2014,27(1):67-68. [13] 刘慧琴,张文媚,钟少芳,等.微波消解-电感耦合等离子-质谱法测定船用燃料油中钒、铝、钙、锌、镍、钠、铁和硅[J].光谱实验室,2010,27(5):2056-2059. LIU Huiqin,ZHANG Wenmei,ZHONG Shaofang,et al.Determination of V,Al,Ca,Zn,Ni,Na,Fe and Si in marine fuel oil by ICP-MS with microwave-assisted digestion[J].Chinese Journal of Spectroscopy Laboratory,2010,27(5):2056-2059. [14] 刘元元,胡净宇.电感耦合等离子体串联质谱法测定高纯钼中痕量镉[J].冶金分析,2018,38(5):1-6. LIU Yuanyuan,HU Jingyu.Deterination of trace cadmium in high-purity molybdenum by inductively coupled plasma tandem mass spectrometry[J].Metallurgical Analysis,2018,38(5):1-6. [15] 墨淑敏,邱长丹,李爱嫦,等.电感耦合等离子体串联质谱法测定高纯铪中钪铱铂[J].冶金分析,2022,42(9):9-15. MO Shumin,QIU Changdan,LI Aichang,et al.Determination of scandium, iridium and platinum in high purity hafnium by inductively coupled plasma tandem mass spectrometry[J].Metallurgical Analysis,2022,42(9):9-15. [16] 郭红巧,胡净宇,侯艳霞,等.电感耦合等离子体串联质谱法测定高温合金中痕量砷[J].冶金分析,2021,41(5):35-40. GUO Hongqiao,HU Jingyu,HOU Yanxia,et al.Determination of trace arsenic in superalloys by inductively coupled plasma tandem mass spectrometry[J].Metallurgical Analysis,2021,41(5):35-40. [17] 张珂,张钦龙,张蜀,等.电感耦合等离子体串联质谱法测定实验室纯水中痕量硅[J].化学分析计量,2019,28(5):61-64. ZHANG Ke,ZHANG Qinlong,ZHANG Shu,et al.Determination of trace silicon in lab pure water by inductively coupled plasma mass spectrometry[J].Chemical Analysis and Meterage,2019,28(5):61-64. [18] 符靓,施树云,唐有根,等.高纯钼粉中超痕量杂质的质谱分析[J].光谱学与光谱分析,2018,38(8):2588-2594. FU Liang,SHI Shuyun,TANG Yougen,et al.Analysis of ultra-trace impurities in high purity molybdenum powder through inductively coupled plasma tandem mass spectrometry[J].Spectroscopy and Spectral Analysis,2018,38(8):2588-2594. [19] 张安余,张经,张瑞峰,等.多接收电感耦合等离子体质谱仪测定稳定硅同位素[J].分析化学,2015,43(9):1353-1359. ZHANG Anyu,ZHANG Jing,ZHANG Ruifeng,et al.Determination of stable silicon isotopes using multi-collector inductive coupled plasma mass spectrometry[J].Chinese Journal of Analytical Chemistry,2015,43(9):1353-1359.
