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高基体进样-电感耦合等离子体串联质谱法在高纯难熔金属痕量元素分析中的应用

Application of high matrix introduction-inductively coupled plasma tandem mass spectrometry in trace element analysis of high-purity refractory metals

  • 摘要: 电感耦合等离子体串联质谱(ICP-MS/MS)在高纯难熔金属痕量、超痕量杂质元素分析方面具有极大的优势。本文以高纯难熔金属中特定干扰元素为分析对象,对高纯Nb中痕量元素Ag、高纯Hf中痕量元素Pt和高纯Ta中痕量元素Au,采用了高基体进样(HMI)-ICP-MS/MS进行分析。所建立方法通过优化高基体进样参数,选择载气流速0.45 L/min,稀释气体流速0.65 L/min,无需基体匹配的校准曲线即可测量。研究了串接四极杆质谱(MS/MS)模式下的O2/NH3反应模式和作用机理,消除基体对待测元素的质谱干扰。以O2质量原位模式分析Ag(一级质量过滤器Q1=107,二级质量过滤器Q2=107),流速0.50 mL/min;以NH3质量转移模式分析Pt (Q1=194,Q2=228;Q1=195,Q2=229)、Au(Q1=197,Q2=231),流速分别为0.75 mL/min和0.50 mL/min。Ag、Pt、Au的线性范围均为0.10~50.0 ng/mL,线性相关系数均大于0.999,检出限为0.001~0.035μg/g。在高纯Nb、Hf、Ta基体中,分别加入已知浓度的Ag、Pt、Au标准溶液进行加标回收试验,并对测定结果进行精密度考察。实验结果显示,Ag、Pt、Au的加标回收率为83.0%~113.0%,测定结果的相对标准偏差(RSD,n=6)为3.0%~7.9%。采用实验方法对3种高纯难熔金属进行分析,同时采用辉光放电质谱法(GDMS)进行比对,两种分析方法测定结果基本一致。

     

    Abstract: Inductively coupled plasma tandem mass spectrometry(ICP-MS/MS) has great advantages in the analysis of trace and ultra-trace impurity elements in high-purity refractory metals. In this study, the high matrix introduction(HMI) ICP-MS/MS method was employed to analyze specific interfering elements in high-purity refractory metals, such as trace silver(Ag) in high-purity niobium(Nb), trace platinum(Pt) in high-purity hafnium(Hf), and trace gold(Au) in high-purity tantalum(Ta). The HMI parameters were optimized: the carrier gas flow was 0.45 L/min, and the dilution gas flow was 0.65 L/min, enabling direct quantification using calibration curves without matrix matching.The reaction mode and action mechanism of O2/NH3 in tandem quadrupole mass spectrometer(MS/MS) mode was investigated to eliminate the mass spectral interference of matrix on tested elements. Ag was analyzed in the O2 on-mass mode(primary mass filter Q1=107, secondary mass filter Q2=107) with the flow rate of 0.50 mL/min. Pt and Au were analyzed in the NH3 mass shift mode(Pt: Q1=194, Q2=228; Q1=195, Q2=229. Au: Q1=197, Q2=231) with the flow rate of 0.75 mL/min and 0.50 mL/min, respectively. The linear ranges of Ag, Pt, and Au were 0.10-50.0 ng/mL,with correlation coefficients(r) all greater than 0.999.The limits of detection were in range of 0.001-0.035 μg/g. The standard solution of Ag, Pt, and Au with known concentration was added into high-purity Nb, Hf and Ta matrixes for the standard addition recovery tests. Moreover, the precision investigations of measurement results were also conducted. The experimental results showed that the spiked recoveries of Ag, Pt, and Au were between 83.0% and 113.0%. The relative standard deviations(RSD, n=6) of determination results were between 3.0% and 7.9%. The proposed method was applied for the analysis of three high-purity refractory metals, and the results were compared with those obtained by glow discharge mass spectrometry(GDMS). It was found that the determination results of two analysis methods were basically consistent.

     

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