Quantitative Analysis of Mineral Composition of Kyanite by X-ray Diffraction with Rietveld Refinement Method
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摘要: 蓝晶石矿物定量分析通常采用的化学物相法分析流程繁琐，易受同质异象矿物和难熔矿物的干扰；采用X射线衍射内标法需要提纯矿物绘制标准曲线，但矿物包体的存在使得获取纯净单矿物成为难题；由于不同矿区蓝晶石矿物成分之间存在着差异性，以上两种方法都仅仅适用于同一矿区样品的矿物定量分析。为简化分析流程，提高测试效率，本文采用X射线衍射（XRD）全谱拟合法对蓝晶石国家二级标准物质和野外样品进行分析，并与RIR法、绝热法和K值法等衍射定量方法及化学分析结果进行了比较验证方法的可靠性。结果表明：全谱拟合法无需采用标准物质，也不用引入内标物，一次扫谱分析能获得样品中所有成分的信息，操作简单，能有效降低择优取向对衍射定量结果的影响；对于含量大于5%的矿物，组分分析结果的绝对误差小于1%，显著低于绝对误差允许限；采用Highscore和Jade两种衍射数据处理软件获得的定量结果吻合度高，目标矿物蓝晶石分析结果的双差均小于0.8%，相对偏差小于2.5%；蓝晶石的加标回收率在95.3%~101.0%之间，能实现不同矿区蓝晶石矿的快速定量分析。Abstract:
BACKGROUNDThe content of minerals in kyanite can be analyzed by chemical phase method, but the analytical process is very tedious. Moreover, the existence of heteromorphism and refractory minerals can affect the accuracy of analysis results. An internal standard method by X-ray diffraction (XRD) for direct determination of kyanite requires the use of pure mineral to draw a standard curve, but it is extremely challenging to purify minerals due to the inclusion. The differences between the mineral components of kyanite in different mining areas makes the above two methods applicable only to the quantitative analysis of minerals in the same mining area. OBJECTIVESTo simplify analysis the process of mineral composition of kyanite and improve efficiency. METHODSThe content of minerals in kyanite was studied by X-ray diffraction. The X-ray diffraction Rietveld refinement method was used to analyze the secondary standard materials and field samples of kyanite, and the results were compared with the diffraction quantitative method and chemical analysis results including RIR method, adiabatic method and K-value method. RESULTSRietveld refinement method was simple and effective in correcting the diffraction intensity error caused by the preferred orientation. Accurate results can be obtained by Rietveld refinement method more than other methods of X-ray quantitative phase analysis, such as RIR method, adiabatic method, K-value method. The analytic absolute error of minerals with content greater than 5% was less 1%, and significantly lower than the allowable error. The results obtained by Highscore agree well with results measured by Jade, and the double difference of results was less than 0.8%. The relative standard deviation was less than 2.5%. The spiked recoveries of kyanite were 95.3%-101.0%. CONCLUSIONSX-ray diffraction with Rietveld refinement method is simple, and can be used to determine the content of all minerals in kyanite from different mining areas. -
Key words:
- kyanite /
- phase composition /
- X-ray diffraction /
- Rietveld refinement method /
- preferred orientation
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表 1 样品全谱拟合分析结果和晶体结构参数
Table 1. Phase analysis results and crystallographic parameters obtained by Rietveld refinement of X-ray diffraction
样品编号 判定因子 卡片号 矿物名称 矿物含量(%) 比重(g/cm3) 晶胞体积(nm3) 晶体结构参数 a(nm) b(nm) c(nm) α(°) β(°) γ(°) 样品1 Rp=6.86%
Rwp=9.19%98-004-0799 石英 69.6 2.65 0.1130 0.4913 0.4913 0.5404 90.00 90.00 120.00 98-000-5699 蓝晶石 22.6 3.67 0.2932 0.5573 0.7119 0.7847 73.99 89.95 78.87 98-001-7444 叶腊石 3.9 2.73 0.2175 0.5286 0.5194 0.9341 79.49 85.41 59.61 98-002-8230 高岭石 0.6 2.56 0.1651 0.5143 0.5172 0.7403 84.14 75.20 60.15 98-004-5732 长石 0.5 2.59 0.3572 0.7181 0.7595 0.7899 113.23 103.90 103.54 98-006-1852 白云母 1.5 2.87 0.9307 0.5170 0.8946 2.0210 90.00 95.36 90.00 98-007-6735 金红石 1.2 4.25 0.0624 0.4592 0.4592 0.2961 90.00 90.00 90.00 样品2 Rp=5.67%
Rwp=8.03%98-004-5584 蓝晶石 60.6 3.67 0.2932 0.5573 0.7119 0.7847 73.99 89.96 78.89 98-005-3283 刚玉 29.6 3.99 0.2548 0.4759 0.4759 1.2990 90.00 90.00 120.00 98-002-3352 硬水铝石 5.6 3.32 0.1180 0.9423 0.2845 0.4402 90.00 90.00 90.00 98-001-1963 云母 0.5 2.83 0.7015 0.5171 0.5171 3.0291 90.00 90.00 120.00 98-001-7624 绿脆云母 1 3.25 0.4574 0.5232 0.9036 0.9842 90.00 100.55 90.00 98-001-7216 地开石 0.9 2.57 0.6564 0.5150 0.8899 1.4393 90.00 95.66 90.00 98-005-0903 重晶石 1.7 4.49 0.3451 0.8875 0.5475 0.7102 90.00 90.00 90.00 样品3 Rp=7.17%
Rwp=9.72%98-005-6873 石英 58.1 2.65 0.1129 0.4913 0.4913 0.5404 90.00 90.00 120.00 98-006-1891 蓝晶石 27.7 3.67 0.2931 0.5574 0.7115 0.7845 74.09 90.02 78.87 98-003-8360 铁铝榴石 1.8 4.31 1.5337 1.1532 1.1532 1.1532 90.00 90.00 90.00 98-007-7906 黑云母 3.4 3.06 0.4993 0.5361 0.9249 1.0246 90.00 100.64 90.00 98-001-1963 白云母 0.5 2.84 0.6998 0.5199 0.5199 2.9892 90.00 90.00 120.00 98-002-8573 透辉石 2.5 3.33 0.4366 0.9768 0.8908 0.5220 90.00 106.006 90.00 98-005-6870 长石 4.3 2.60 0.3353 0.7038 0.7648 0.7916 120.09 104.98 98.74 98-003-7562 磷灰石 1.7 3.40 0.5243 0.9380 0.9380 0.6882 90.00 90.00 120.00 样品4 Rp=7.61%
Rwp=10.45%98-004-5584 蓝晶石 95.0 3.67 0.2932 0.5574 0.7118 0.7846 73.99 89.96 78.89 98-004-0799 石英 2.0 2.64 0.1135 0.4912 0.4912 0.5431 90.00 90.00 120.00 98-004-5786 白云母 3.0 2.91 0.9054 0.5196 0.8610 2.0307 90.00 94.74 90.00 
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表 2 方法回收率
Table 2. Recovery tests of the method
样品编号 加入量(g) 回收量(g) 回收率(%) 样品1 0.9502 0.9505 100.0 样品3 0.9502 0.9355 98.4 样品2 0.9502 0.9058 95.3 样品4 0.9502 0.9608 101.0
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表 3 Highscore和Jade衍射数据处理软件分析结果对比
Table 3. Comparison of analytical results determined by Highscore and Jade diffraction data treatment software
样品编号 Highscore软件 Jade软件 双差(%) 相对偏差(%) 成分 含量(%) 成分 含量(%) 样品1 低温石英 69.6 石英 69.7 0.1 0.19 蓝晶石 22.6 蓝晶石 23.1 0.5 2.32 叶腊石 3.9 叶腊石 2.4 1.5 46.4 高岭石 0.6 高岭石 1.0 0.4 42.9 长石 0.5 长石 0.8 0.3 53.1 云母 1.5 白云母 1.7 0.2 7.50 金红石 1.2 金红石 1.2 0 0.80 样品2 蓝晶石 60.6 蓝晶石 59.8 0.8 1.33 刚玉 29.6 刚玉 28.5 1.1 3.68 硬水铝石 5.6 硬水铝石 5.4 0.2 4.37 云母 0.5 1M型云母 1.6 - - 绿脆云母 1.0 2M型云母 2.5 - - 地开石 0.9 高岭石 1.2 - - 重晶石 1.7 重晶石 0.9 0.8 59.2 样品3 石英 58.1 石英 57.4 0.77 1.33 蓝晶石 27.7 蓝晶石 28.0 0.3 1.08 铁铝榴石 1.8 铁铝榴石 0.5 1.3 117 黑云母 3.4 黑云母 0.8 2.6 124 白云母 0.5 白云母 4.9 4.4 164 透辉石 2.5 透辉石 1.3 1.2 66.0 长石 4.3 长石 5.7 1.4 29.6 磷灰石 1.7 羟基磷灰石 1.4 0.3 17.5 样品4 蓝晶石 95.0 蓝晶石 95.4 0.4 0.37 石英 2.0 石英 1.9 0.1 2.05 白云母 3.0 白云母 2.7 0.3 10.5
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表 4 样品化学成分分析误差统计
Table 4. Statistics of analytical error for the chemical components in samples
样品编号 参数 SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O TiO2 P2O5 MnO 样品1 含量(%) 78.76 14.69 2.41 0.29 0.05 0.26 0.06 1.24 0.25 0.01 偏差(%) 3.13 1.51 -2.36 - -0.05 -0.01 -0.06 0.01 - - 相对偏差(%) 3.98 10.25 -97.85 - -91.45 -4.41 -88.73 0.81 - - 样品2 含量(%) 23.29 71.53 0.2 0.32 - 0.16 0.16 0.064 0.22 - 偏差(%) -0.01 2.00 -0.19 0.05 - -0.10 - - - - 相对偏差(%) -0.03 2.79 -95.25 14.43 - -61.09 - - - - 样品3 含量(%) 74.56 18.46 2.42 1.19 0.32 1 0.2 0.22 0.82 0.038 偏差(%) 0.35 0.61 -0.68 0.24 0.57 -0.59 0.33 -0.14 -0.17 -0.01 相对偏差(%) 0.47 3.31 -28.14 19.76 178.84 -59.32 164.00 -63.65 -20.51 -37.70 样品4 含量(%) 37.9 59.73 0.48 0.03 < 0.24 < 0.04 0.03 0 偏差(%) 0.71 1.17 - - - 0.11 - - - - 相对偏差(%) 1.86 1.96 - - - 47.77 - - - -
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