Copper matrix-matched calibration samples were prepared by doping high purity copper powders (99.999%, 500–600 μm) with multi-element standard solutions with a total of 72 elements, and then the relative sensitivity factors (RSFs) of the 72 elements in both microsecond-pulsed and continuous direct current (dc) modes were determined by using Element GD type glow discharge mass spectrometry (GD-MS). The ability of pulsed and continuous dc-GD-MS to quantitatively determine trace elements in copper was demonstrated after calibration using the RSFs. The results showed that the uncertainty level of GD-MS analysis after calibration was comparable with that of ICP-MS and ICP-OES analysis. In order to standardize calibration sample preparation procedures, the doping concentration, pressed powder tablet compactness and tablet homogeneity were optimized. Good recovery (85% to 115%) was obtained. Good pressed powder tablet compactness and tablet homogeneity were obtained, which were expressed as relative standard deviations (<5%) of 6 times GD-MS analysis. Satisfactory repeatability of about 15% (RSD) for continuous and 10% (RSD) for pulsed dc-GD-MS was obtained by strictly controlling the intensity of the matrix to keep it stable when replacing graphite parts. Good reproducibility (RSD < 10%) was obtained after timely detector calibration, so the determined RSFs could remain constant and valid in an instrument for a long time. Under the optimized conditions mentioned above, the RSFs of the total 72 elements in both continuous and pulsed modes were determined and compared. The comparison of RSFs showed that the general trends of the two sets of RSFs were very similar; however, the RSFs in pulsed mode were 2–40% lower than those in continuous mode in most cases. Therefore, a dedicated RSF table for each mode is recommended to achieve accurate and quantitative analysis. The comparison of RSFs in this work with standard RSFs provided by the manufacturer of Element GD revealed that the accepted uncertainty of a factor of two was met for almost all investigated elements in both modes. The accuracy of the RSFs was validated by analyzing three Cu-matrix CRMs. The relative expanded uncertainties (U_rel, k = 2) of measured results by using pulsed dc-GD-MS, including the uncertainty of measurement repeatability and RSF, were less than 20%, which was much lower than those obtained by continuous dc-GD-MS (U_rel < 30%).

中文翻译：

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微秒脉冲连续直流辉光放电质谱法测定铜基质中元素的相对灵敏度因子

铜基体匹配的校准样品的制备方法是，将高纯度铜粉（99.999％，500–600μm）掺杂有总共72种元素的多元素标准溶液，然后在样品中掺杂72种元素的相对灵敏度因子（RSF）。微秒脉冲和连续直流（dc）模式都是通过使用GD型元素辉光放电质谱仪（GD-MS）确定的。使用RSF校准后，证明了脉冲和连续dc-GD-MS定量测定铜中痕量元素的能力。结果表明，校准后的GD-MS分析的不确定度与ICP-MS和ICP-OES分析的不确定度相当。为了标准化校准样品的制备程序，优化了掺杂浓度，压粉片剂的致密性和片剂的均一性。获得了良好的回收率（85％至115％）。获得了良好的压制粉片剂致密性和片剂均匀性，它们表示为GD-MS分析的6倍的相对标准偏差（<5％）。通过严格控制基体的强度以在更换石墨零件时保持稳定，可获得连续性约15％（RSD）的满意重复性和脉冲dc-GD-MS约10％（RSD）的令人满意的重复性。经过及时的检测器校准后，可获得良好的重现性（RSD <10％），因此，所测定的RSF可以在仪器中长期保持恒定并有效。在上述优化条件下，确定并比较了连续和脉冲模式下总共72个元素的RSF。RSF的比较表明，两组RSF的总体趋势非常相似。然而，在大多数情况下，脉冲模式下的RSF比连续模式下的RSF低2–40％。因此，建议为每种模式使用专用的RSF表以实现准确和定量的分析。这项工作中的RSF与Element GD制造商提供的标准RSF的比较表明，在两种模式下，几乎所有被调查的元素都满足了两倍的可接受不确定性。通过分析三种Cu-matrix CRM，验证了RSF的准确性。相对不确定性扩大（这项工作中的RSF与Element GD制造商提供的标准RSF的比较表明，在两种模式下，几乎所有被调查的元素都满足了两倍的可接受不确定性。通过分析三种Cu-matrix CRM，验证了RSF的准确性。相对扩大的不确定性（这项工作中的RSF与Element GD制造商提供的标准RSF的比较表明，在两种模式下，几乎所有被调查的元素都满足了两倍的可接受不确定性。通过分析三种Cu-matrix CRM，验证了RSF的准确性。相对不确定性扩大（脉冲dc-GD-MS的测量结果的U _rel（k = 2）包括测量重复性和RSF的不确定度均小于20％，远低于连续dc-GD-MS获得的测量结果（U_相对<30％）。