电感耦合等离子体质谱法测定镍基合金中痕量砷、铅、锡、锑

罗凤焱; 李文强; 张庆宇; 王国华; 郭晋轩

doi:10.13832/j.jnpe.2023.S2.0211

电感耦合等离子体质谱法测定镍基合金中痕量砷、铅、锡、锑

doi: 10.13832/j.jnpe.2023.S2.0211

中国核动力研究设计院反应堆燃料及材料重点实验室，成都，610213

详细信息

作者简介:
罗凤焱（1993—），女，助理研究员，现主要从事核燃料及材料分析检测，Email：fengyanluo1211@163.com

中图分类号: TL34;O657.63;O655.1
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出版历程
- 收稿日期: 2023-07-11
- 修回日期: 2023-09-26
- 刊出日期: 2023-12-30

Determination of Trace Arsenic, Plumbum, Stannum and Stibium in Nickel-Based Alloys by Inductively Coupled Plasma Mass Spectrometry

Science and Technology on Reactor Fuel and Mateerials Laboratory, Nuclear Power Institute of China, Chengdu, 610213, China

摘要

摘要: 为准确测定镍基合金（NBS）中痕量砷、铅、锡、锑，采用电感耦合等离子体质谱法（ICP-MS），于HNO₃-HCl体系密闭溶解镍基合金，同位素质量数分别选择75、208、120、121，以动能歧视（KED）模式克服质谱干扰，内标⁸⁹Y在线监测仪器稳定性和基体效应，建立了NBS中砷、铅、锡、锑的测定方法。在优化条件下，各元素的信号强度与对应质量浓度呈良好的线性关系，线性相关系数大于0.9999，当称样量为0.1 g时，4种元素的检测范围为10.0 ~100.0 μg/g，各元素检测下限均优于0.15 ng/mL，加标回收率在85%~120%之间，加标样品的相对标准偏差（n=6）为2.8%~5.6%。该方法的灵敏度、精密度和准确度良好，可用于NBS中痕量As、Pb、Sn、Sb的测定。
- 镍基合金(NBS) /
- 动能歧视(KED) /
- 电感耦合等离子体质谱法(ICP-MS) /
- 基体效应
Abstract: In order to accurately determine trace arsenic, plumbum, stannum and stibium in the nickel-based alloy (NBS), inductively coupled plasma mass spectrometry (ICP-MS) was used. The HNO₃-HCl system was used for airtight digestion of NBS, and the isotope mass numbers were selected as 75, 208, 120, and 121 respectively. The kinetic energy discrimination (KED) mode was used to overcome the mass spectral interference, and the internal standard element ⁸⁹Y was used to monitor the stability of the instrument and the matrix effect online. A method for the determination of arsenic, plumbum, stannum and stibium in nickel-based alloy was established. Under the optimized conditions, the signal intensities of each element had a good linear relationship with the corresponding mass concentrations, and the linear correlation coefficient was greater than 0.9999. When the sample weight was 0.1 g, the detection range of of the four elements was 10.0-200.0 μg/g. The detection limit of each element was better than 0.15 ng/mL, and the recovery rate of standard addition was between 85%-120%. The relative standard deviation (n=6) of the spiked sample was 2.8%-5.6%. This method has good sensitity, precision and accuracy, and can be used for the determination of arsenic, plumbum, stannum and stibium in NBS.
- NBS /
- KED /
- ICP-MS /
- Matrix effect

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图 1 不同He流量下I/I₁₀

Figure 1. I/I₁₀ under Different He Flow Rates

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表 1 ICP-MS优化参数

Table 1. Optimization Parameters of ICP-MS

参数	参数值
雾化器流量（STD标准模式）/(L·min⁻¹)	0.92
辅助气流量 /(L·min⁻¹)	1.20
等离子气流量/(L·min⁻¹)	16.00
He流量（KED模式) /(mL·min⁻¹)	4.00
偏转电压/V	−12.50
ICP RF 功率/W	1150.00
模拟阶段电压/V	−2087.00
脉冲电压/V	1300.00
四级杆进/出电压/V	−11.00

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表 2 NBS样品中As的受到的主要质谱干扰

Table 2. Main Mass Spectral Interference of Arsenic in NBS Sample

同位素	丰度/%	主要质谱干扰	干扰情况
⁷⁵As	100	⁴⁰Ar_{（99.6003%）}³⁵Cl_（75.78%）、 ³⁸Ar_{（0.0632%）}³⁷Cl_（24.22%）	HCl体系时，干扰严重
		⁵⁶Fe_{（91.754%）}¹⁹F_（100.0%）	HF体系时，干扰严重
		⁵⁷Fe_（2.119%）¹⁸O_{（0.2050%）}、 ⁵⁸Fe_（0.282%）¹⁷O_（0.038%）	干扰元素丰度低，干扰小
		¹⁵⁰Sm++_（7.38%）、 ¹⁵⁰Nd++_（5.6%）、 ¹⁵¹Eu++_（47.81%）	干扰元素含量高时，干扰严重

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表 3 线性相关系数（R²）与方法检出限

Table 3. Linear Correlation Coefficients (R²) and Method Detection Limits

元素	标准曲线	R²	检出限/（ng·mL⁻¹）
As	y=36.00x+13.53	1.0000	0.149
Pb	y=861.09x+154.46	0.9999	0.020
Sn	y=250.39x+146.77	1.0000	0.019
Sb	y=94.27x+10.10	0.9999	0.014

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表 4 精密度与回收率实验

Table 4. Precision and Recovery Tests

元素	测定平均值/（ng·mL⁻¹）	加标量/（ng·mL⁻¹）	测得总量/（ng·mL⁻¹）	回收率/%	RSD（n=6）/%
As	7.13	10.0	17.77, 18.69, 18.92, 18.65, 19.00, 17.96	106.4, 115.6, 117.9, 115.2, 118.7, 108.3	2.8
		20.0	28.98, 28.05	109.3, 104.6	/
		50.0	62.21, 63.50	110.2, 112.7	/
Pb	1.82	10.0	10.33, 10.91, 11.22, 11.61, 12.20, 11.24	85.1, 90.9, 94.0, 97.9, 103.8, 94.2	5.6
		20.0	20.11, 20.19	91.5, 91.6	/
		50.0	49.13, 49.65	94.6, 95.7	/
Sn	4.74	10.0	14.30, 16.29, 16.25, 15.59, 16.18, 15.73	95.6, 115.5, 115.1, 108.5, 114.4, 109.9	4.8
		20.0	23.09, 29.93	91.8, 106.0	/
		50.0	55.12, 56.96	100.8, 104.44	/
Sb	1.22	10.0	10.65, 11.04, 11.05, 10.42, 11.98, 10.53	94.3, 98.2, 98.3, 92.0, 107.6, 93.1	5.2
		20.0	20.60, 20.00	96.9, 93.9	/
		50.0	51.11, 50.72	99.78, 99.0	/

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