Method Research on Determination of Barium Sulfate in Barite by X-ray Fluorescence Spectrometry
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摘要: 应用XRF可快速测定重晶石中钡元素的总量，但当测定硫酸钡含量时，由于样品中的碳酸钡计入钡量造成硫酸钡的测定结果不准确，铜、铅、锌等有色金属元素对熔样坩埚会造成损害，需要进行酸处理除去碳酸钡、铅等干扰。而样品经酸处理后不同样品的剩余量不同，造成熔剂与样品的比例不确定，也不能准确测定硫酸钡的含量，因此保证熔剂与样品比例一致是解决该问题的关键。本文优化了样品前处理、熔片制样和仪器工作条件，将一定量样品以10%盐酸和10%硝酸溶解，过滤除去碳酸钡、硫酸钙及铜、铅、锌等有色金属元素，未溶解样品在700℃下灼烧后以氧化铝补充到原取样量，实现了熔剂与样品比例一致，再以硝酸铵作氧化剂，溴化锂和碘化铵作脱模剂，1075℃熔融制片，即可用XRF准确测定硫酸钡的含量。本方法的相对标准偏差（RSD）小于0.4%，检出限为72 μg/g，较ICP-OES等方法的检测周期短、干扰元素少，提高了测试效率和分析质量。Abstract: X-ray Fluorescence Spectrometry (XRF) can be used to rapidly determine the total content of barium in barite. However, the barium carbonate included in the total barium will result in inaccurate results of barium sulfate. Moreover, copper, lead, zinc and other non-ferrous metal elements can damage the sample melting pot. Acid treatment is required to remove interference such as barium carbonate and lead. The residue ratio of the different samples after the acid treatment is different to before and the ratio of the flux to sample is uncertain, and thus the content of barium sulfate cannot be accurately determined. Therefore, it is essential to ensure that the melting agent has the same proportion as the sample. The sample pretreatment conditions, melting conditions and equipment conditions were optimized and are described in this paper. 10% hydrochloric acid mixed with 10% nitric acid was used to dissolve the sample. The sample solution was filtered to remove barium carbonate, calcium sulfate and copper, lead, zinc and other non-ferrous metal elements. Alumina oxide was added to undissolved samples after 700℃ calcination to reach the original sample weight, which attains the same proportion of flux and sample. Ammonium nitrate was used as the oxidant, and lithium bromide and ammonium iodide were used as demoulding agents. Samples were melted at 1075℃, and barium sulfate content in the barite was determined by XRF. The relative standard deviation (RSD) of the method is less than 0.4% and the detection limit is 72 μg/g. This method needs less detection time and suffers from less interference elements than determination by Inductively Coupled Plasma-Optical Emission Spectrometry, improving the test efficiency and analysis quality.
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表 1 XRF仪器测量条件
Table 1. Measurement parameters of XRF instrument
元素 谱线 晶体 准直器
(μm)探测器 滤光片 管电压
(kV)管电流
(mA)2θ(°) 脉冲高度分析器 测量时间(s) 峰值 背景 LL PL 峰值 背景 Rh Kα-C LiF 200 150 Scint. Al(200 μm) 60 60 18.4386 - 26 78 20 10 Sr Kα LiF 200 300 Scint. Al(200 μm) 60 60 25.1190 0.6602 22 78 20 10 Ba Lα LiF 200 300 Flow None 40 90 87.1708 1.3070 33 66 20 10 S Kα Ge 111 300 Flow None 30 120 110.6960 1.6632 35 65 20 10 Ca Kα LiF 200 300 Flow None 30 120 113.1450 -1.0626 32 73 20 10 Fe Kα LiF 200 15 Flow None 60 60 57.5264 -0.9716 15 68 20 10 Ti Kα LiF 200 300 Flow None 40 90 8601904 -1.1912 28 71 20 10 
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表 2 样品前处理方法及铜铅锌的溶出率
Table 2. Sample pretreatment methods and dissolution rate of Cu, Pb, Zn
样品编号 前处理方法 溶出率(%) Pb Cu Zn GBW07816 10%盐酸10 mL 97.56 - 40.96 GSO-2 10%盐酸10 mL 99.08 40.95 41.78 GBW07816 10%盐酸10 mL+0.5 g氯化铵 99.76 - 67.82 GSO-2 10%盐酸10 mL+0.5 g氯化铵 100.0 41.9 40.14 GBW07816 10%盐酸10 mL+1 g氯化铵 99.76 - 86.17 GSO-2 10%盐酸10 mL+1 g氯化铵 99.96 29.52 46.01 GBW07816 10%盐酸10 mL+10%硝酸2 mL 99.94 - 96.01 GSO-2 10%盐酸10 mL+10%硝酸2 mL 100.0 89.52 95.31 GBW07816 10%盐酸10 mL+10%硝酸4 mL 99.92 - 99.73 GSO-2 10%盐酸10 mL+10%硝酸4 mL 100.0 91.43 98.84 注：“-”表示标准物质无标准值，未计算溶出率。
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表 3 不同补加成分的标准物质中硫酸钡的测定值
Table 3. Analytical results of BaSO4 in standards materials adding different ingredients
标准物质
编号补加剂 BaSO4含量 标准值
(%)测量值
(%)相对误差
(%)允许相对误差
(%)GBW07811 三氧化二铁+
氧化镁(70：30)42.32 42.23 -0.21 1.37 GBW07815 三氧化二铁+
氧化镁(70：30)67.04 66.83 -0.31 0.84 GBW07816 三氧化二铁+
氧化镁(70：30)18.87 18.66 -1.11 2.39 GBW07811 氧化铝 42.32 42.41 0.21 1.37 GBW07815 氧化铝 67.04 66.91 -0.19 0.84 GBW07816 氧化铝 18.87 19.02 0.79 2.39
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表 4 本方法与经典化学分析方法比较
Table 4. A comparison of analytical results by this method and traditional chemical methods
样品
编号重量法测定值
(%)本法测定值
(%)平均值
(%)相对偏差
(%)允许相对偏差
(%)1 11.40 11.21 11.31 0.84 4.38 2 59.12 58.97 59.05 0.13 1.39 3 34.58 35.64 35.11 -1.51 2.26 4 67.44 68.70 68.07 -0.93 1.16 5 71.16 71.52 71.34 -0.25 1.09 6 51.80 52.84 52.32 -0.99 1.59 7 5.52 5.69 5.61 -1.52 5.85 8 44.29 44.28 44.29 0.01 1.87 9 61.02 60.73 60.88 0.24 1.34 10 87.49 87.32 87.41 0.10 0.77
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