摘要
高纯钨具有高熔点、高密度和耐腐蚀等优点,是军事国防、核工业、半导体等领域不可或缺的材料,但其物理化学性能受杂质元素含量的影响较大。电感耦合等离子体质谱(ICP-MS)是一种检出限低、可进行多元素同时快速测定的无机质谱分析技术,但一些元素在测定时会遇到较为严重的基体复合离子质谱干扰问题。采用ICP-MS法测定高纯钨中Nb和Re时,Nb和Re分别受到基体钨的双电荷和氢化物离子干扰,这两种干扰难以通过反应池等技术进行消除。通过乙酸铅沉淀法分离溶液中钨基体从而消除质谱干扰,主要考察了钨基体对Nb和Re元素的干扰强度和内标元素对残留基体及仪器信号漂移的校正效果,探讨了溶样试剂、沉淀剂用量、酸度、沉淀温度和陈化时间等条件对基体分离的影响。实验结果表明,1 mg·mL^(-1)质量浓度钨基体溶液对Nb和Re的测定均有显著的正干扰作用,其干扰强度随着钨质量浓度的增大而增强;当溶液中钨的质量浓度含量小于2μg·mL^(-1)时,由钨基体引起的质谱干扰可以忽略(考虑测定下限0.10μg·g^(-1)的要求)。通过各项试验,优化选择的条件为:硝酸-氢氟酸混酸溶样,加入600μL氨水(1+1)和1.0 mL乙酸-乙酸铵缓冲溶液,在250℃条件下滴加2.7 mL 10 g·L^(-1)醋酸铅溶液并陈化5 min,整个分离周期约10 min;基体分离后样品溶液以Cs作为内标进行测定。该方法简单快速,Nb和Re的检出限分别为0.007和0.036μg·g^(-1),相对标准偏差分别为12%和4.8%,加标回收率分别为108%和105%,可以满足实际高纯钨样品的测定需求。
High purity tungsten is an indispensable material in military defense,nuclear industry,semiconductors and other fields for its high melting point,high density and corrosion resistance.Its physical and chemical properties are greatly affected by the content of impurity elements.With the rapid development of new material research,the manufacturing of some key components puts forward higher requirements on the purity of tungsten,and this demand corresponds to strict detection of types and contents of trace impurity elements in high purity tungsten.Inductively coupled plasma mass spectrometry(ICP-MS)is an inorganic mass spectrometry technique with a low detection limit and rapid determination of multiple elements.However,some elements encounter serious mass spectrometry interference problems.Nb and Re in high purity tungsten determined by ICP-MS are interfered with by the doubly charged ions and hydride ions respectively,which are difficult to be eliminated by reaction cells and other techniques.In this paper,the tungsten matrix was separated from the solution by precipitation method using lead acetate as a precipitator to eliminate mass spectral interference.The interference intensity of tungsten matrix on Nb and Re,and the correction effect of standard internal elements on residual matrix and signal drift were mainly investigated.The experimental conditions,including sample dissolution solvents,the dosage of precipitator,acidity,temperature and aging time,were also discussed.The results showed that tungsten matrix solution with a concentration of 1 mg·mL^(-1)had a significant positive interference effect on the determination of Nb and Re,and interference intensity enhanced with the increase of tungsten mass concentration.When tungsten concentration in solution was less than 2μg·mL^(-1)the mass spectral interferences produced by tungsten could be ignored(considering the requirement for a determination limit of 0.10μg·g^(-1)).Through various condition tests,the final conditions were as follows:sample was dissolved by mixed acid of nitric acid and hydrochloric acid,600μL ammonia(1+1)and 1.0 mL acetic acid-ammonium acetate buffer solution were added,2.7 mL lead acetate solution with a concentration of 10 g·L^(-1)was dripped at 250℃,and then the solution was heated for 5 min,and entire separation process was about 10 min;Cs was chosen as the standard internal element.The detection limit of Nb and Re was 0.007 and 0.036μg·g^(-1),the relative standard deviation was 12%and 4.8%,and the spiked recovery rate was 108%and 105%,respectively.This method is simple and fast,and the precision and accuracy of results meet actual requirements for the analysis of high purity tungsten.
作者
张璇
王长华
胡芳菲
墨淑敏
李继东
ZHANG Xuan;WANG Chang-hua;HU Fang-fei;MO Shu-min;LI Ji-dong(National Analysis and Testing Center of Nonferrous Metals and Electronic Materials,Beijing 100088,China;China United Test&Certification Co.,Ltd.,Beijing 101400,China;General Research Institute for Nonferrous Metals,Beijing 100088,China)
出处
《光谱学与光谱分析》
SCIE
EI
CAS
CSCD
北大核心
2022年第7期2169-2174,共6页
Spectroscopy and Spectral Analysis
基金
国家新材料测试评价平台建设项目(TC170A5SU)资助。
关键词
电感耦合等离子体质谱
基体分离
高纯钨
铌
铼
Inductively coupled plasma mass spectrometry
Matrix separation
High purity tungsten
Niobium
Rhenium
