电感耦合等离子体质谱法测定高纯五氧化二铌中25种痕量杂质元素
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摘要
采用电感耦合等离子体质谱法(ICP-MS)测定高纯五氧化二铌中痕量Mg、K、Ca、Cr、Fe时,因质谱干扰严重,从而导致其背景等效浓度值(BEC)较高进而无法准确测定。实验采用氢氟酸-硝酸体系以微波消解方式消解样品,以标准加入法补偿基体效应,控制基体质量浓度为500μg/mL,建立了ICP-MS测定高纯五氧化二铌中包括Mg、K、Ca、Cr、Fe在内的25种痕量杂质元素的分析方法。研究表明:采用屏蔽矩冷等离子体技术,在500μg/mL的五氧化二铌基体溶液中,Na、Mg、Al、K、Ca、Cr、Fe、Cu、Co、Ni、Mn的BEC得到明显改善,尤其是Mg、K、Ca、Cr、Fe的BEC改善效果最为显著,由常规模式下的56.5～194ng/mL降至冷等离子体模式下的0.012～0.203ng/mL;使用经实验室亚沸蒸馏提纯的电子级氢氟酸及硝酸可有效地降低试剂空白值。各元素校准曲线线性相关系数均大于0.999 0;方法中各元素的检出限在0.001～0.010μg/g之间,测定下限在0.003～0.033μg/g之间。采用实验方法对高纯五氧化二铌样品中25种杂质元素进行测定,结果表明,各元素测定结果的相对标准偏差(RSD,n=11)为0.90%～12.7%,回收率为91%～111%。方法应用于两批纯度为99.999%的超高纯五氧化二铌实际样品分析,结果与辉光放电质谱法(GD-MS)基本一致。
During the determination of trace Mg,K,Ca,Cr and Fe in high purity niobium pentoxide by inductively coupled plasma mass spectrometry(ICP-MS),these impurity elements could not be accurately determined due to the high background equivalent concentrations(BECs)which were caused by the serious mass spectral interferences.After the sample was treated by microwave digestion with HF-HNO_3 system and the matrix effect was corrected by the standard addition method,an analysis method of 25 trace impurity elements(including Mg,K,Ca,Cr,Fe,etc)in high-purity niobium pentoxide by ICP-MS was established with matrix mass concentration at 500μg/mL.The results indicated that BECs of Na,Mg,Al,K,Ca,Cr,Fe,Cu,Co,Ni and Mn were obviously improved in 500μg/mL niobium pentoxide matrix solution by the shield torch cool plasma technology.Particularly,the improvement effect of BECs of Mg,K,Ca,Cr and Fe were the most significant,which were reduced from 56.5-194 ng/mL at normal mode to 0.012-0.203 ng/mL at cool plasma mode.The reagent blank could be effectively reduced by the electronic-grade HF and HNO3 purified in laboratory by sub boiling distillation.The linear correlation coefficients of calibration curves of elements were all higher than 0.999 0.The detection limits of elements in this method were in the range of 0.001-0.010μg/g,and the low limits of determination were between 0.003μg/g and 0.033μg/g.The contents of 25 impurity elements in high purity niobium pentoxide sample were determined according to the experimental method.The results showed that the relative standard deviations of determination results(RSD,n=11)were between 0.9% and 12.7%,and the spiked recoveries were between 91%and 111%.The proposed method was applied for the analysis of two batches of actual ultrapure niobium pentoxide samples(the purity was 99.999%).The results were basically consistent with those obtained by GD-MS.
During the determination of trace Mg,K,Ca,Cr and Fe in high purity niobium pentoxide by inductively coupled plasma mass spectrometry(ICP-MS),these impurity elements could not be accurately determined due to the high background equivalent concentrations(BECs)which were caused by the serious mass spectral interferences.After the sample was treated by microwave digestion with HF-HNO_3 system and the matrix effect was corrected by the standard addition method,an analysis method of 25 trace impurity elements(including Mg,K,Ca,Cr,Fe,etc)in high-purity niobium pentoxide by ICP-MS was established with matrix mass concentration at 500μg/mL.The results indicated that BECs of Na,Mg,Al,K,Ca,Cr,Fe,Cu,Co,Ni and Mn were obviously improved in 500μg/mL niobium pentoxide matrix solution by the shield torch cool plasma technology.Particularly,the improvement effect of BECs of Mg,K,Ca,Cr and Fe were the most significant,which were reduced from 56.5-194 ng/mL at normal mode to 0.012-0.203 ng/mL at cool plasma mode.The reagent blank could be effectively reduced by the electronic-grade HF and HNO3 purified in laboratory by sub boiling distillation.The linear correlation coefficients of calibration curves of elements were all higher than 0.999 0.The detection limits of elements in this method were in the range of 0.001-0.010μg/g,and the low limits of determination were between 0.003μg/g and 0.033μg/g.The contents of 25 impurity elements in high purity niobium pentoxide sample were determined according to the experimental method.The results showed that the relative standard deviations of determination results(RSD,n=11)were between 0.9% and 12.7%,and the spiked recoveries were between 91%and 111%.The proposed method was applied for the analysis of two batches of actual ultrapure niobium pentoxide samples(the purity was 99.999%).The results were basically consistent with those obtained by GD-MS.
引文
[1]国家发展和改革委员会.YS/T 548—2007高纯五氧化二铌[S].北京:中国标准出版社,2008.
[2]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 15076—2008钽铌化学分析方法[S].北京:中国标准出版社,2008.
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[6]马晓敏,王辉,李波,等.直流电弧原子发射光谱法测定铌、钽中硅含量[J].理化检验:化学分册,2015,51(6):859-861.MA Xiao-min,WANG Hui,LI Bo,et al.Determination of silicon in niobium and tantalum by DC-Arc AES[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2015,51(6):859-861.
[7]任凤莲,李淑兰,邓培,等.离子交换分离铌ICP-AES法测定高纯Nb2O5中杂质元素[J].冶金分析,2000,20(6):21-23.REN Feng-lian,LI Shu-lan,DENG Pei,et al.Determination of impurity elements in high-purity niobium pentoxide by ICP-AES[J].Metallurgical Analysis,2000,20(6):21-23.
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[9]田孔泉,郝红梅,张卫杰,等.ICP-MS测定超高纯钽铌及其化合物中痕量杂质元素[J].光谱实验室,2004,21(3):551-555.TIAN Kong-quan,HAO Hong-mei,ZHANG Wei-jie,et al.Determination of trace impurities in high-purity niobium and tantalum matrices by inductively coupled plasma mass spectrometry[J].Chinese Journal of Spectroscopy Laboratory,2004,21(3):551-555.
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[11]李宝城,刘英,童坚,等.GD-MS法和ICP-MS法测定高纯铌中痕量元素[J].分析试验室,2012,31(6):39-42.LI Bao-cheng,LIU Ying,TONG Jian,et al.Determination of trace amounts of elements in high purity niobium by GD-MS and ICP-MS[J].Chinese Journal of Analysis Laboratory,2012,31(6):39-42.
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[15]王小如.电感耦合等离子体质谱应用实例[M].北京:化学工业出版社,2005.
[16]靳兰兰,王秀季,李会来,等.电感耦合等离子体质谱技术进展及其在冶金分析中的应用[J].冶金分析,2016,36(7):1-14.JIN Lan-lan,WANG Xiu-ji,LI Hui-lai,et al.Progress in inductively coupled plasma mass spectrometry technology and its application in metallurgical analysis[J].Metallurgical Analysis,2016,36(7):1-14.
[17]宋金华,戴和平,廖丹.电感耦合等离子质谱法测定钽粉中杂质[J].稀有金属与硬质合金,2012,40(2):68-71.SONG Jin-hua,DAI He-ping,LIAO Dan.Determination of impurities int tantalum powder by inductively coupled plasma mass spectrometry[J].Rare Metals and Cemented Carbides,2012,40(2):68-71.
[18]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 Yuan-yuan,HU Jing-yu.Determination of trace cadmium in high-purity molybdenum by inductively coupled plasma tandem mass spectrometry[J].Metallurgical Analysis,2018,38(5):1-6.
[19]Quemet A,Brennetot R,Chevalier E,et al.Analysis of twenty five impurities in uranium matrix by ICP-MS with iron measurement optimized by using reaction collision cell,cold plasma or medium resolution[J].Talanta,2012,99:207-212.
[20]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 Shu-yun,TANG You-gen,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.
[21]李继东,王长华,郑永章.动态反应池-电感耦合等离子体质谱法测定高纯锑中23种痕量杂质元素[J].冶金分析,2011,31(12):21-25.LI Ji-dong,WANG Chang-hua,ZHENG Yong-zhang.Determination of twenty-three trace impurity elements in high purity antimony by dynamic reaction cell inductively coupled plasma mass spectrometry[J].Metallurgical Analysis,2011,31(12):21-25.
[22]钟胜贤,卢现友,刘景麟,等.电感耦合等离子体质谱法测定磷酸铁锂中杂质元素[J].冶金分析,2015,35(3):19-24.ZHONG Sheng-xian,LU Xian-you,LIU Jing-lin,et al.Determination of impurity elements in lithium iron phosphate by inductively coupled plasma mass spectrometry[J].Metallurgical Analysis,2015,35(3):19-24.
[2]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 15076—2008钽铌化学分析方法[S].北京:中国标准出版社,2008.
[3]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.
[4]裘立奋.现代难熔金属和稀散金属分析[M].北京:化学工业出版社,2007.
[5]张仁惠,伏军胜,李继宏.直流电弧光谱仪在铌杂质分析中的应用研究[J].稀有金属与硬质合金,2014,42(6):58-60.ZHANG Ren-hui,FU Jun-sheng,LI Ji-hong.Study on application of DC arc spectrometer in impurity analysis of niobium[J].Rare Metals and Cemented Carbides,2014,42(6):58-60.
[6]马晓敏,王辉,李波,等.直流电弧原子发射光谱法测定铌、钽中硅含量[J].理化检验:化学分册,2015,51(6):859-861.MA Xiao-min,WANG Hui,LI Bo,et al.Determination of silicon in niobium and tantalum by DC-Arc AES[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2015,51(6):859-861.
[7]任凤莲,李淑兰,邓培,等.离子交换分离铌ICP-AES法测定高纯Nb2O5中杂质元素[J].冶金分析,2000,20(6):21-23.REN Feng-lian,LI Shu-lan,DENG Pei,et al.Determination of impurity elements in high-purity niobium pentoxide by ICP-AES[J].Metallurgical Analysis,2000,20(6):21-23.
[8]张颖.电感耦合等离子体原子发射光谱法测定高纯氧化铌中13种杂质元素[J].理化检验:化学分册,2008,44:1097-1098,1102.ZHANG Ying.ICP-AES determination of 13impurityelements in high-purity niobium oxide[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2008,44:1097-1098,1102.
[9]田孔泉,郝红梅,张卫杰,等.ICP-MS测定超高纯钽铌及其化合物中痕量杂质元素[J].光谱实验室,2004,21(3):551-555.TIAN Kong-quan,HAO Hong-mei,ZHANG Wei-jie,et al.Determination of trace impurities in high-purity niobium and tantalum matrices by inductively coupled plasma mass spectrometry[J].Chinese Journal of Spectroscopy Laboratory,2004,21(3):551-555.
[10]Kozono S,Haraguchi H.Determination of ultratrace impurity elements in high purity niobium materials by on-line matrix separation and direct injection/inductively coupled plasma mass spectrometry[J].Talanta,2007,72(5):1791-1799.
[11]李宝城,刘英,童坚,等.GD-MS法和ICP-MS法测定高纯铌中痕量元素[J].分析试验室,2012,31(6):39-42.LI Bao-cheng,LIU Ying,TONG Jian,et al.Determination of trace amounts of elements in high purity niobium by GD-MS and ICP-MS[J].Chinese Journal of Analysis Laboratory,2012,31(6):39-42.
[12]马玉莉.电感耦合等离子质谱法测定氧化钽、氧化铌中钾量和钠量[J].江西有色金属,2009,23(3):46-48.MA Yu-li.Determination of the quantity of kalium and natrium in tantalum oxide and niobium oxide by inductively coupled plasma mass spectrometry[J].Jiangxi Nonferrous Metals,2009,23(3):46-48.
[13]刘洁,陈忠颖,刘巍,等.电感耦合等离子体质谱法测定高纯铌中20种痕量杂质元素[J].理化检验:化学分册,2018,54(10):1158-1162.LIU Jie,CHEN Zhong-ying,LIU Wei,et al.Determination of 20trace impurity elements in high-purity niobium by inductively coupled plasma mass spectrometry[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2018,54(10):1158-1162.
[14]李宝城.高纯铌、铋、钨的辉光放电质谱多元素分析[D].北京:北京有色金属研究总院,2012.
[15]王小如.电感耦合等离子体质谱应用实例[M].北京:化学工业出版社,2005.
[16]靳兰兰,王秀季,李会来,等.电感耦合等离子体质谱技术进展及其在冶金分析中的应用[J].冶金分析,2016,36(7):1-14.JIN Lan-lan,WANG Xiu-ji,LI Hui-lai,et al.Progress in inductively coupled plasma mass spectrometry technology and its application in metallurgical analysis[J].Metallurgical Analysis,2016,36(7):1-14.
[17]宋金华,戴和平,廖丹.电感耦合等离子质谱法测定钽粉中杂质[J].稀有金属与硬质合金,2012,40(2):68-71.SONG Jin-hua,DAI He-ping,LIAO Dan.Determination of impurities int tantalum powder by inductively coupled plasma mass spectrometry[J].Rare Metals and Cemented Carbides,2012,40(2):68-71.
[18]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 Yuan-yuan,HU Jing-yu.Determination of trace cadmium in high-purity molybdenum by inductively coupled plasma tandem mass spectrometry[J].Metallurgical Analysis,2018,38(5):1-6.
[19]Quemet A,Brennetot R,Chevalier E,et al.Analysis of twenty five impurities in uranium matrix by ICP-MS with iron measurement optimized by using reaction collision cell,cold plasma or medium resolution[J].Talanta,2012,99:207-212.
[20]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 Shu-yun,TANG You-gen,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.
[21]李继东,王长华,郑永章.动态反应池-电感耦合等离子体质谱法测定高纯锑中23种痕量杂质元素[J].冶金分析,2011,31(12):21-25.LI Ji-dong,WANG Chang-hua,ZHENG Yong-zhang.Determination of twenty-three trace impurity elements in high purity antimony by dynamic reaction cell inductively coupled plasma mass spectrometry[J].Metallurgical Analysis,2011,31(12):21-25.
[22]钟胜贤,卢现友,刘景麟,等.电感耦合等离子体质谱法测定磷酸铁锂中杂质元素[J].冶金分析,2015,35(3):19-24.ZHONG Sheng-xian,LU Xian-you,LIU Jing-lin,et al.Determination of impurity elements in lithium iron phosphate by inductively coupled plasma mass spectrometry[J].Metallurgical Analysis,2015,35(3):19-24.