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摘要: 铌钽精矿标准物质在监控选冶样品分析的过程起到重要作用，在选厂及冶金系统有很大的需求，国内外的文献检索均未发现铌钽精矿标准物质的报道；而铌钽矿物的性质决定了铌钽精矿的粉碎粒度及均匀性对铌钽精矿标准物质的研制提出了更高的要求。本文阐述了4个铌钽精矿标准物质的研制过程，铌钽精矿采集于宜春及尼日利亚铌钽选厂，样品经气流粉碎和高铝球磨两次细碎及机械混匀后，随机抽取包装好的样品进行均匀性和稳定性检验及定值。采用电感耦合等离子体发射光谱法与质谱法（ICP-OES/MS）进行均匀性和稳定性检验，结果表明样品的均匀性和稳定性良好。采用多个实验室协同测试的定值方式，利用不同原理的分析方法对此样品的铌钽等12个元素进行定值，给出了各定值元素的认定值和不确定度。4个铌钽精矿标准物质Ta（Nb）2O5的含量为9.89%、20.55%、40.79%、53.69%，形成一个从粗精矿到精矿较为完整的含量体系，可以满足选冶试验各阶段流程样品分析对标准物质的需求。Abstract:
BACKGROUNDNiobium-tantalum concentrate reference materials play an important role in monitoring mineral smelting and sample analysis. There is a great demand of niobium-tantalum concentrate reference materials in the dressing plant and metallurgical system, but no domestic and foreign literature has reported these materials. The nature of niobium-tantalum mineral determines the crushed grain size and homogeneity of the niobium-tantalum concentrate and puts forward higher requirements for the development of a niobium-tantalum concentrate standard substance. OBJECTIVESTo develop the four standard materials of niobium-tantalum concentrate with different contents. METHODSThe preparation process of niobium-tantalum concentrate reference materials is introduced. Niobium-tantalum concentrate samples collected from the Yichun and Nigeria selection plant were finely milled and mechanically mixed by air milling and high-alumina ball milling. The packaged samples were randomly selected for homogeneity and stability testing and determined values. The homogeneity and stability of the samples were tested by Inductively Coupled Plasma-Optical Emission Spectrometry/Mass Spectrometry (ICP-OES/MS). RESULTSTwelve elements of different samples are detected by the different analytical methods, with a calibration method for collaborative testing in multiple laboratories, the certified value and uncertainty of each element are given. The samples have good uniformity and stability. CONCLUSIONSThe contents of Ta(Nb)2O5 in the four antimony concentrates are 9.89%, 20.55%, 40.79% and 53.69%, respectively, forming a complete system from crude concentrates to concentrates, which meets the sample requirements for reference materials in the stages of metallurgical tests. -
Key words:
- niobium-tantalum concentrate /
- reference materials /
- standard values /
- uncertainty /
- uniformity /
- stability /
- certified values
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表 1 采集铌钽精矿候选物的基本特征
Table 1. Basic characteristics of niobium-tantalum concentrate candidates
样品编号 Ta2O5含量(×10-2) Nb2O5含量(×10-2) 采样地及采样量 主要矿物组成 NTJK-1 5.72 4.17 江西宜春，80 kg 长石30%，黄玉35%，钽铌锰矿15%，石英10%，锡石3%，萤石2% NTJK-2 12.07 8.48 江西宜春，80 kg 黄玉20%，钽铌锰矿30%~35%，锡石5%，细晶石6%~8%，磁铁矿1%，长石10%，石英2% NTJK-3 21.02 19.77 江西宜春，80 kg (钽铌+铌钽+锡钽)锰矿60%，黄玉10%，细晶石15%，锡石10%，磁铁矿1% NTJK-4 5.81 47.88 尼日利亚，80 kg 铌钽铁矿75%，钛铁矿+铁金红石15%，赤铁矿5%，锡石3%，角闪石3%，钍石2% 
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表 2 候选物均匀性检验结果
Table 2. Homogeneity tests of niobium-tantalum concentrate candidates
元素 NTJK-1 NTJK-2 NTJK-3 NTJK-4 含量测定平均值 RSD(%) F 含量测定平均值 RSD(%) F 含量测定平均值 RSD(%) F 含量测定平均值 RSD(%) F Nb2O5 4.07 1.15 1.43 8.54 1.85 1.41 20.94 3.74 1.58 49.01 1.60 1.46 Ta2O5 5.39 1.52 1.41 10.80 1.51 0.79 19.58 2.92 1.46 5.45 1.37 1.51 SiO2 26.75 1.37 1.49 20.61 0.41 0.48 10.81 0.93 0.99 2.03 3.67 1.12 Fe2O3 3.47 1.73 1.32 4.47 1.39 1.00 5.81 1.18 1.23 23.89 1.60 1.36 TiO2 0.068 6.12 1.49 0.12 4.01 0.85 1.43 1.17 0.92 10.41 0.97 1.24 MnO 1.94 1.15 0.83 3.55 3.08 0.91 5.63 2.12 1.03 2.46 3.27 0.87 P2O5 0.37 1.51 1.50 0.26 5.05 0.26 0.26 4.61 1.27 0.090 1.56 0.98 Zr* 897.75 3.55 1.47 1549.44 1.52 1.14 1812.26 1.46 0.77 2733.70 1.75 0.32 Hf* 159.72 3.16 0.43 303.87 5.11 1.50 294.38 2.62 1.52 238.87 4.06 1.41 U* 957.05 3.42 1.52 2168.39 4.76 1.54 2955.06 2.95 1.51 340.01 4.19 1.59 Th* 98.94 0.69 1.55 192.83 2.91 0.94 377.83 3.50 1.18 1357.67 2.33 0.78 W* 532.68 4.20 1.59 1127.25 4.91 1.49 2283.44 2.89 1.39 2445.83 3.30 0.66 注：表中带“*”成分的测定平均值单位为10-6，其他成分的测定平均值单位为10-2。
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表 3 ICP-OES法测定Nb2O5和Ta2O5短期稳定性的结果
Table 3. Short-term stability test results of Nb2O5 and Ta2O5 by ICP-OES
样品编号 检验方式 取样部位 Nb2O5 Ta2O5 T临界值 平均测定值(×10-2) T检测值 平均测定值(×10-2) T检测值 NTJK-1 机器振荡 上部 4.11 0.9 5.47 0.7 2.3 下部 4.13 5.46 正常存放 上部 4.22 1.0 5.40 0.8 下部 4.21 5.36 NTJK-2 机器振荡 上部 8.52 2.0 11.28 1.1 2.3 下部 8.62 11.41 正常存放 上部 8.82 1.9 11.37 1.3 下部 8.83 11.36 NTJK-3 机器振荡 上部 21.04 1.2 19.26 1.2 2.3 下部 20.98 19.56 正常存放 上部 21.38 1.5 20.30 1.3 下部 21.33 20.31 NTJK-4 机器振荡 上部 48.92 1.3 5.45 1.0 2.3 下部 49.15 5.47 正常存放 上部 54.14 1.2 5.71 0.7 下部 54.12 5.72
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表 4 样品各定值元素的分析方法
Table 4. Analytical methods of certified value elements in samples
定值元素 分析方法 Nb2O5和Ta2O5 碱熔-纸上层析重量法；混合酸溶ICP-OES测定；混合碱熔ICP-OES测定 Fe2O3 磺基水杨酸比色法；混合酸溶ICP-OES测定 TiO2 二氨替比林甲烷比色法；混合酸溶ICP-OES测定 WO3 硫氰酸盐比色法；混合酸溶ICP-OES测定；混合碱熔ICP-OES测定 SiO2 动物胶凝聚重量法；硅钼蓝比色法；混合碱熔ICP-OES测定 U3O8 钒酸铵容量法；混合酸溶ICP-OES测定
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表 5 铌钽精矿标准物质的认定值及不确定度
Table 5. Certified values and expanded uncertainty of niobium-tantalum concentrates reference materials
定值元素 认定值与扩展不确定度 NTJK-1 NTJK-2 NTJK-3 NTJK-4 MnO(×10-2) 1.84±0.065 3.59±0.094 5.82±0.158 2.47±0.124 P2O5(×10-6) 3785±414.33 2839±455.71 2189±183.94 1002±114.49 SiO2(×10-2) 27.88±0.542 21.60±0.586 10.99±0.7 2.12±0.282 Fe2O3(×10-2) 3.67±0.307 4.75±0.254 6.34±0.473 24.51±0.343 TiO2(×10-2) 0.075±0.013 0.13±0.016 1.45±0.041 11.28±0.485 Ta2O5(×10-2) 5.72±0.05 12.07±0.10 21.02±0.16 5.81±0.08 Nb2O5(×10-2) 4.17±0.225 8.48±0.267 19.77±0.550 47.88±0.968 W(×10-6) 742±19.62 1540±101.34 2899±107.37 2997±97.46 Th(×10-6) 103±16.10 170±12.11 383±26.91 1520±129.01 U(×10-6) 984±42.50 2084±118.444 3322±290.60 334±12.48 Zr(×10-6) 971±64.30 1624±88.53 1900±110.73 2898±189.44 Hf(×10-6) 171±17.28 283±14.26 295±25.38 166±19.03
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表 6 实际样品应用分析结果对照
Table 6. Comparison of analytical results of actual samples
样品编号 Nb2O5分析结果(×10-2) Ta2O5分析结果(×10-2) 宜春选厂 洛阳钼业 参考值 宜春选厂 洛阳钼业 参考值 NTJK-1 4.23 4.19 4.17 5.64 5.74 5.72 NTJK-2 8.49 8.36 8.48 12.25 12.04 12.07 NTJK-3 20.06 19.96 19.77 20.87 20.93 21.02 NTJK-4 48.09 47.97 47.88 5.72 5.87 5.81 注：参考值为8家实验室测定数据统计分析后的算术平均值。
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