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锰铁合金是炼钢过程中用量最多的铁合金之一，定量测定锰铁合金中As、Pb、Sn、Sb、Bi等有害元素的含量，对于调控高附加值品种钢的冶炼过程非常关键。但是这类元素在钢铁中含量极少，成分之间相互干扰严重，检测困难。为此，建立了敞开酸溶-电感耦合等离子体质谱(ICP-MS)法测定锰铁合金中As、Pb、Sn、Sb、Bi的精准方法，在敞开容器中，利用过氧化氢-硝酸-纯化氢氟酸-高氯酸溶解样品。用氢氟酸首先进行两步纯化，有效降低了本底值；过氧化氢既是合金溶解剂，也是As的氧化剂；酒石酸为Sn的络合剂，试剂共同作用，完全溶样的同时，还有效避免了敞开式溶样过程造成的元素挥发损失问题，保证结果准确、可靠。确定了分析元素的同位素质量数为75As、118Sn、121Sb、208Pb、209Bi，内标元素同位素质量数为103Rh和159Tb。在仪器最佳测定条件下测定样品中5种元素的加标回收率为97.0%～107%，相对标准偏差(RSD)<5%，完全满足锰铁合金中5种有害元素的检测要求。该方法也可推广到硅锰合金等其他类型铁合金中5种有害元素的精准检测中。
Abstract：Ferromanganese alloy is one of the most widely used ferroalloys in modern steelmaking,playing a crucial role in enhancing the mechanical properties of steel. However,it often contains low-melting-point metallic elements such as arsenic(As),lead(Pb),tin(Sn),antimony(Sb),and bismuth(Bi). Due to their ultra-low concentrations in the alloy matrix and significant spectral interferences from matrix components,considerable analytical challenges remain. In the experiment,samples were dissolved in an open vessel using a mixed solution of hydrogen peroxide,nitric acid,purified hydrofluoric acid,and perchloric acid,which simultaneously removed carbon(C) and silicon(Si). The hydrofluoric acid underwent a two-stage purification process:initial lowtemperature prolonged distillation followed by high-temperature distillation of the residual solution to reduce impurities such as Pb,Sn,Sb,and Bi,and the purified distillate was subsequently used. Hydrogen peroxide facilitated sample dissolution while oxidizing arsenic to As(Ⅴ),thereby preventing the volatile loss of As(Ⅲ) during heating in the presence of hydrofluoric acid. During digestion,tin ions might react with chloride ions to form volatile SnCl4(boiling point 114 ℃),leading to underestimated analytical results. Tartaric acid was introduced to form stable complexes with tin,preventing volatilization and ensuring accuracy. The synergistic effect of these reagents achieved complete sample dissolution while minimizing elemental loss,thus guaranteeing the accuracy and reliability of the method. The isotopes selected for ICP-MS analysis were 75As,118Sn,121Sb,208Pb,and 209Bi. Internal standards 103Rh and 159Tb were used to correct for matrix effects and instrumental drift. Under the optimized conditions of ICP-MS with a plasma power of 1 300 W,a nebulizer gas flow rate of 1. 00 L/min,a cooling gas flow rate of 13. 0 L/min,and an auxiliary gas flow rate of 0. 80 L/min,an accurate analytical method combining open-vessel acid digestion with ICP-MS was established for the precise quantification of arsenic(As),lead(Pb), tin(Sn),antimony(Sb),and bismuth(Bi) in ferromanganese alloy. The method achieved spike recoveries ranging from 97. 0% to 107%,with relative standard deviations( RSDs) below 5%. Additionally,the analytical values were in good agreement with the standard values,thus meeting the rigorous requirements for analyzing these elements in manganese ferroalloys. Furthermore,this approach can be readily applied to the precise determination of these five detrimental elements in other ferroalloys,such as silicomanganese,and extended to the analysis of additional key elements in metallurgical samples. It establishes a reliable framework for trace element analysis in refractory metal alloys,supporting stringent quality control essential for the production of high-performance steel products.
[1]黎均红，刘晓峰，王少波，等.合金杂质含量分析及合金化工艺优化实践[C]//中国金属学会.第十三届中国钢铁年会论文集.北京：冶金工业出版社，2022:46-50.LI Junhong,LIU Xiaofeng,WANG Shaobo,et al.Analysis of alloy impurity content and optimization of alloying process[C]//China Society for Metals.Proceedings of the 13th China Iron and Steel Annual Conference. Beijing:Metallurgical Industry Press,2022:46-50.
[2]黄丹宇，陶美娟.微波消解-火焰原子吸收光谱法测定锰铁合金中7种微量元素[J].分析仪器，2022(6):6-10.HUANG Danyu,TAO Meijuan. Determination of seven trace elements in ferromanganese alloy by microwave digestion-flame atomic absorption spectrometry[J].Analytical Instrumentation,2022(6):6-10.
[3]何志明，陈溪. ICP-AEC法测定锰铁中铬锑铅锡砷含量[C]//中国金属学会.第十二届中国钢铁年会论文集.北京：冶金工业出版社，2019:111-115.HE Zhiming,CHEN Xi. Determination of chromium,antimony,lead,tin and arsenic in ferromanganese by ICPAEC[C]//China Society for Metals. Proceedings of the12th China Iron and Steel Annual Conference. Beijing:Metallurgical Industry Press,2019:111-115.
[4]冶金工业信息标准研究院标准化研究所.钢铁及铁合金化学分析方法标准汇编（上）[M].第2版.北京：中国标准出版社，2002:296-298.China Metallurgical Information and Standardization Institute. Standard compilation of methods for chemical analysis of steel and ferroalloys（Ⅰ）[M]. 2th Ed. Beijing:Stand Press of China,2002:296-298.
[5]马冲先，刘洁，刘巍.电感耦合等离子体质谱分析应用的新进展[J].分析试验室，2019,38(6):732-760.MA Chongxian,LIU Jie,LIU Wei. Recent advances and applications of inductively coupled plasma mass spectrometry analysis[J]. Chinese Journal of Analysis Laboratory,2019,38(6):732-760.
[6]王铁，亢德华，于媛君.电感耦合等离子体质谱法测定锰铁中痕量铅锡锑[J].冶金分析，2013,33(5):13-16.WANG Tie,KANG Dehua,YU Yuanjun. Determination of trace lead,tin and antimony in ferromanganese by inductively coupled plasma mass spectrometry[J].Metallurgical Analysis,2013,33(5):13-16.
[7]陈靖，张艳，高颂，等. ICP-MS法测定镍基高温合金中的锗、钌、钡、钍、铀含量[J].分析仪器，2021(8):1-4.CHEN Jing,ZHANG Yan,GAO Song,et al.Determination of germanium,ruthenium,barium,thorium and uranium in nickel base superalloy by ICP-MS[J].Analysis Instrumentation,2021(8):1-4.
[8] CHENG Y. ICP-AES determination of 15 kind of impurity elements in the vanadium-aluminum alloy[J].Procedia Engineering,2011,24:447-453.
[9]国家市场监督管理总局，国家标准化管理委员会.锰铁、锰硅合金、氮化锰铁和金属锰、硅、磷和铁含量的测定波长色散X射线荧光光谱法（熔铸玻璃片法）：GB/T5686. 9—2023[S].北京：中国标准出版社，2023.State Administration for Market Regulation,Standardization Administration of the People's Republic of China. Ferromanganese,ferromanganese-silicon,nitrogen-bearing ferromanganese and manganese metaldetermination of manganese,silicon,phosphorus and iron content-wavelength dispersive X-ray fluorescence spectrometry(fused cast bead method):GB/T 5686. 9—2023[S]. Beijing:China Standard Press,2023.
[10]张丽丽，王亚朋，李明明. X荧光压片法测定中高碳锰铁中主成分[J].铁合金，2022,53(5):46-48.ZHANG Lili,WANG Yapeng,LI Mingming.Determination of main components in medium and high carbon ferromanganese by X-ray fluorescence tablet pressing method[J]. Ferro-Alloys,2022,53(5):46-48.
[11]张李斌，刘源，江袁蕾. X射线荧光光谱法快速测定高碳锰铁合金中硅、锰、磷[J].昆明冶金高等专科学校学报，2021,37(1):10-13.ZHANG Libin,LIU Yuan,JIANG Yuanlei. Rapid determination of silicon,manganese and phosphorus in high-carbon ferromanganese alloy by X-ray fluorescence spectrometry[J]. Journal of Kunming Metallurgy College,2021,37(1):10-13.
[12]刘宪彬，张各各，张吉强，等.铬天青S分光光度法测定锰铁合金、锰硅合金、金属锰中铝[J].冶金分析，2020,40(1):75-81.LIU Xianbin,ZHANG Gege,ZHANG Jiqiang,et al.Determination of aluminum in ferromanganese,ferromanganese-silicon and manganese metal by chrome azurol S spectrophotometry[J]. Metallurgical Analysis,2020,40(1):75-81.
[13]国家市场监督管理总局，国家标准化管理委员会.钢铁及合金镧、铈、镨、钕、钐含量的测定电感耦合等离子体质谱法：GB/T 223. 92—2023[S].北京：中国标准出版社，2023.State Administration for Market Regulation,Standardization Administration of the People's Republic of China. Iron,steel and alloy-determination of lanthanum,cerium,praseodymium,neodymium and samarium content-inductively coupled plasma mass spectrometry:GB/T 223. 92—2023[S]. Beijing:China Standard Press,2023.
[14]王丹，李思思，李辉，等.电感耦合等离子体质谱法测定复杂高温合金中微量硅[J].化学分析计量，2024,33(2):77-81.WANG Dan,LI Sisi,LI Hui,et al. Determination of trace silicon in complex superalloys by inductively coupled plasma mass spectrometry[J]. Chemical Analysis and Meterage,2024,33(2):77-81.
[15]罗凤焱，李文强，张庆宇，等.电感耦合等离子体质谱法测定镍基合金中痕量砷、铅、锡、锑[J].核动力工程，2023,44（增刊2）:211-215.LUO Fengyan,LI Wenqiang,ZHANG Qingyu,et al.Determination of trace arsenic,plumbum,stannum and stibium in nickel-based alloys by inductively coupled plasma mass spectrometry[J]. Nuclear Power Engineering,2023,44(Suppl. 2):211-215.
[16]罗琦林，倪海燕，贾海峰，等.电感耦合等离子体质谱法（ICP-MS）测定高纯金属铬中钒铜铝镍锰[J].中国测试，2024,50（增刊1）:100-105.LUO Qilin,NI Haiyan,JIA Haifeng,et al. Determination of vanadium、copper、aluminum、nickel and manganesein high purity chromium by inductively coupled plasma mass spectrometry(ICP-MS)[J]. China Measurement&Test,2024,50(Suppl. 1):100-105.
[17]孙孟华，金倩，陈庆芝，等.半密闭酸溶-电感耦合等离子体质谱（ICP-MS）法测定化探样品中的铬、镍、铜、锌、镉、铅等6种重金属[J].中国无机分析化学，2023,13(4):318-325.SUN Menghua,JIN Qian,CHEN Qingzhi,et al.Determination of chromium,nickel,copper,zinc,cadmium,lead in geological samples by inductively coupled plasma mass spectrometry(ICP-MS)with semiclosed acid solution[J]. Chinese Journal of Inorganic Analytical Chemistry,2023,13(4):318-325.
[18]陈家舒，熊雄，段锦梅，等.碱熔-电感耦合等离子体质谱法测定土壤中全硼[J].质谱学报，2025,46(3):361-369.CHEN Jiashu,XIONG Xiong,DUAN Jinmei,et al.Determination of total boron in soil by alkaline fusioninductively coupled plasma mass spectrometry[J]. Journal of Chinese Mass Spectrometry Society,2025,46(3):361-369.
[19]刘巍，黄丹宇，郅惠博.微波消解-电感耦合等离子体质谱法测定钴基高温合金中银、铋、铅、硼、镧的含量[J].理化检验-化学分册，2021,57(12):1132-1135.LIU Wei,HUANG Danyu,ZHI Huibo. Determination of the contents of silver,bismuth,lead,boron and lanthanum in cobalt-based superalloys by inductively coupled plasma mass spectrometry with microwave digestion[J]. Physical Testing and Chemical Analysis(Part B:Chemical Analysis),2021,57(12):1132-1135.
[20] MI H P,ZHU H M,LI G R,et al. Determination of Pb,Cr,Cd and As in aluminum-plastic packaging materials via inductively coupled plasma-mass spectrometry with microwave digestion[J]. Spectroscopy and Spectral Analysis,2017,37(2):646-650.
[21] LIANG M S,LIU H T. Single reaction chamber microwave digestion coupled with ICP-MS for the determination of ultra-trace mercury in rocks[J]. Anal Methods,2024,16(35):6049-6056.
[22]冯慧林，刘金龙.电感耦合等离子体质谱（ICP-MS）法测定钒钛磁铁矿中稀土元素[J].中国无机分析化学，2024,14(12):1656-1666.FENG Huilin,LIU Jinlong. Determination of rare earth elements in vanadium titanomagnetite by inductively coupled plasma mass spectrometry(ICP-MS)[J].Chinese Journal of Inorganic Analytical Chemistry,2024,14(12):1656-1666.
[23]丁洋，王顺祥，龚仓，等.电感耦合等离子体质谱仪测定地质样品中15种稀土元素-3种前处理方法的比较[J].辽宁化工，2021,50(8):1261-1264,1272.DING Yang,WANG Shunxiang,GONG Cang,et al.Comparison of three different pretreatment methods in determinationof 15 rare earth elements in geological samples by inductively coupled plasma mass spectrometry[J]. Liaoning Chemical Industry,2021,50(8):1261-1264,1272.
[24] MENG R,DU J H,LIU Y H,et al. Exploration of digestion method for determination of heavy metal elements in soil by ICP-MS[J]. Spectroscopy and Spectral Analysis,2021,41(7):2122-2128.
[25]张杰，田秀梅，刘冬杰，等.炼钢用钼铁中五害元素测定方法研究[J].鞍钢技术，2021(5):34-38.ZHANG Jie,TIAN Xiumei,LIU Dongjie,et al. Study on determination method for five harmful elements in ferromolybdenum for steel making[J]. Angang Technology,2021(5):34-38.
[26]王崴，韩丽华，于晟.电感耦合等离子体质谱仪ICPMS测定低合金钢中Pb、Sn、As、Sb、Bi[J].天津冶金，2014(2):79-81.WANG Wei,HAN Lihua,YU Sheng. Measurement of Pb,Sn,As,Sb and Bi in low alloy steel with ICPMS[J]. Tianjin Metallurgy,2014(2):79-81.
[27]刘跃，王记鲁，李静，等.高压密闭消解-电感耦合等离子体质谱（ICP-MS）法测定土壤背景点样品中的29种元素[J].中国无机分析化学，2023,23(2):136-142.LIU Yue,WANG Jilu,LI Jing,et al. Determination of29 elements in soil background site samples by inductively coupled plasma mass spectrometry with high-pressure closed digestion[J]. Chinese Journal of Inorganic Analytical Chemistry,2023,13(2):136-142.
[28]李冰，陆文伟. ATC017电感耦合等离子体质谱分析技术[M].北京：中国质检出版社，中国标准出版社，2017:117-118.LI Bing,LU Wenwei. ATC017 Inductively coupled plasma mass spectrometry[M]. Beijing:China Quality Inspection Press,Stand Press of China,2017:117-118.
[29]孙娟，庞振兴，顾红琴，等. ICP-MS法测定管线钢中痕量砷、铅、锡、锑、铋[C]//中国金属学会.第十届中国钢铁年会暨第六届宝钢学术年会论文集Ⅱ.北京：冶金工业出版社，2015:1323-1328.SUN Juan,PANG Zhenxing,GU Hongqin,et al.Determination of trace As,Pb,As,Sb,Bi in pipe line steel by inductively coupled plasma mass spectrometry[C]//China Society for Metals. ProceedingsⅡof the 10th China Iron and Steel Congress&the 6th Baosteel Academic Annual Conference. Beijing:Metallurgical Industry Press,2015:1323-1328.
[30]庞振兴，王贵玉，金伟，等.电感耦合等离子体质谱法测定硅铁中痕量铌、砷、锑[J].中国测试，2018,44(5):49-52.PANG Zhenxing,WANG Guiyu,JIN Wei,et al.Determination of trace niobium,arsenic and stibonium in ferrosilicon by ICP-MS[J]. China Measurement&Test,2018,44(5):49-52.
基本信息:
DOI：10.20236/j.CJIAC.2025.12.001
中图分类号:O657.63;TG115.33
引用信息:
[1]王莉娜,李丽丽,庞振兴,等.敞开酸溶-电感耦合等离子体质谱(ICP-MS)法测定锰铁合金中砷、铅、锡、锑、铋[J].中国无机分析化学,2025,15(12):1901-1908.DOI:10.20236/j.CJIAC.2025.12.001.
基金信息:
国家自然科学基金资助项目（22306051）; 河北省自然科学基金资助项目（B2022201080）