熔融制样波长色散X射线荧光光谱法测定白云石中钙镁硅铁铝

褚宁; 李卫刚; 蒋晓光; 张彦甫; 毕孝瑞

熔融制样波长色散X射线荧光光谱法测定白云石中钙镁硅铁铝

鲅鱼圈出入境检验检疫局, 辽宁营口 115007

基金项目: 出入境检验检疫行业标准计划项目(2012B072);辽宁检验检疫局科研项目(LK15-2008)

详细信息

作者简介: 褚宁, 博士, 工程师, 主要从事矿产品检测及方法研究.E-mail: n_chu2009@sina.com

中图分类号: O657.34;P619.234

收稿日期: 2014-03-14

修回日期: 2014-11-02

录用日期: 2014-11-12

刊出日期: 2014-06-25

Determination of Calcium, Magnesium, Silicon, Iron and Aluminum in Dolomite by Wavelength Dispersive X-ray Fluorescence Spectrometry with Fusion Sample Preparation

Bayuquan Entry-Exit Inspection & Quarantine Bureau, Yingkou 115007, China

Received Date: 14 March 2014

Revised Date: 02 November 2014

Accepted Date: 12 November 2014

Publish Date: 25 June 2014

摘要

摘要:
白云石属碳酸盐矿物, 应用熔融制样X射线荧光光谱法测定其中主次量组分钙、镁、硅、铁、铝时, 由于白云石灼烧减量大, 在试料片制备过程中, 如果以干基试料制备试料片, 除灼烧减量外还有少量其他组分被分解出的大量CO₂带走, 导致试料损失, 测定结果偏低; 如果以灼烧基试料制备试料片, 由于灼烧后的试料极易吸收空气中的水分和CO₂, 同样使测定结果偏低。基于质量守恒原理, 本文直接以灼烧减量测量后的灼烧基试料质量作为试料量(即灼烧减量测定所称量的干基试料量扣除灼烧减量的量), 以四硼酸锂为熔剂, 5%碘化铵溶液为脱模剂, 试料与熔剂的稀释比为1:10, 于1050℃熔融15 min以上制备的试料片透彻、玻璃化程度高。以白云石标准物质和标准样品作为标准试料, 制作各组分的标准曲线的相关系数在0.9940~0.9994之间; 方法检出限为0.011%~0.48%;标准物质和标准样品的测定值与认定值基本一致, 各组分的相对标准偏差(RSD, n=11) 在0.5%~1.7%之间, 方法具有较好的重现性。本方法以1050℃灼烧后的试样作为试料制备XRF分析样片, 最大限度地降低了灼烧减量因素(空气中的水分和CO₂)对测定结果的影响, 适用于白云石及其煅烧物中钙、镁、硅、铁、铝等组分的同时测定。
- 白云石 /
- 主次量成分 /
- 熔融制样 /
- 波长色散X射线荧光光谱法 /
- 样品基态 /
- 灼烧减量
Abstract:
A method has been developed for the determination of calcium, magnesium, silica, iron and aluminum in dolomite by Wavelength Dispersive X-ray Fluorescence Spectrometry. Dolomite is a carbonate mineral with a large portion of loss on ignition. In the process of test glass disc preparation, if dry-base sample powder is used, a small amount of test components evaporates with the large amount of carbon dioxide, and causes lower determination results; if the ignited test portion is used, because of moisture and carbon dioxide in air being easily absorbed by the ignited sample powder, the determination results are also be low. To avoid these influences, the mass of the ignited test portion was directly used as the amount of test portion, and fused under 1050℃ with fusion agent lithium tetraborate for glass disc preparation. 5% ammonium iodide solution was used as the releasing agent, and the dilution proportion of test portion and fusion agent was 1:10. Dolomite reference standard materials and samples were used for calibration. The related coefficients of all components were in the range of 0.9940-0.9994, and the limits of detection were in the range of 0.011%-0.48%. Accuracy and repeatability of the proposed method were good, the results of determination were in good agreement with certified values and the relative standard deviation (RSD, n=11) was in the range of 0.5%-1.7%. This method is suitable for simultaneous determination of calcium, magnesium, silica, iron and aluminum in dolomite and its ignited residue.
- dolomite /
- primary and secondary content of components /
- fusion sample preparation /
- Wavelength Dispersive X-ray Fluorescence Spectrometry /
- basic state of sample /
- loss on ignition

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表 1 仪器测量条件

Table 1. Measurement conditions of the XRF instrument

分析项目	分析谱线	晶体	准直器 (°)	峰位 (°)	电流 (mA)	电压 (kV)	测量时间 (s)
CaO	Ca Kα₁	LiF200	0.23	113.091	10	50	20
MgO	Mg Kα₁	XS-55	0.46	20.787	111	27	20
SiO₂	Si Kα₁	PET	0.46	109.023	111	27	20
Fe₂O₃	Fe Kα₁	LiF200	0.46	57.529	50	60	20
Al₂O₃	Al Kα₁	PET	0.23	144.650	111	27	12

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表 2 不同基态样品的灼烧减量

Table 2. Loss on ignition of the different basic states of samples

灼烧减量 (%)	YSBC28724-93		BH191-4		YSBC11703-95
灼烧减量 (%)	干基	1050℃灼烧基	干基	1050℃灼烧基	干基	1050℃灼烧基
认定值	43.02	0	43.95	0	46.46	0
测量值	44.05	0.17	45.00	0.18	47.55	0.22
偏差	1.03	0.17	1.05	0.18	1.09	0.22

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表 3 稀释比试验结果

Table 3. Experimental results of the dilution proportion

试料与熔剂 (四硼酸锂)的稀释比	熔融效果
1:5	流动性差，玻璃化程度差
1:8	流动性较好，玻璃化程度一般
1:10	流动性和玻璃化程度好
1:12	流动性和玻璃化程度好，低量组分测量误差大
1:15	流动性和玻璃化程度好，低量组分测量误差大

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表 4 白云石标准试料中各成分含量

Table 4. Components content of dolomite standard test portion

标准试料片编号	含量(%)
标准试料片编号	CaO	MgO	SiO₂	Fe₂O₃	Al₂O₃	灼烧减量
YSBC28721-93	34.80	17.75	1.51	0.185	0.31	44.70
YSBC28722-93	29.80	21.06	2.09	0.209	0.285	45.80
YSBC28724-93	29.10	20.78	5.47	0.21	0.31	43.02
YSBC11703-95	30.45	21.51	1.12	0.165	0.105	46.46
BH191-4	28.57	19.84	5.01	0.56	1.05	43.95
BH0119-2Wa	37.59	15.38	0.25	0.459	0.11	45.88
GBW 07217	30.60	20.73	0.96	0.376	0.295	46.30
GBW 07217a	32.11	20.37	0.021	0.224	0.017	46.89
GBW 07216	36.55	16.59	0.092	0.226	0.027	46.23
GBW 07216a	35.02	17.88	0.049	0.495	0.024	46.32

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表 5 白云石标准曲线相关系数、标准偏差和检出限

Table 5. The related coefficients of dolomite standard curves, standard deviations and detection limits

分析项目	测量范围(%)		曲线回归方程	相关系数	标准偏差 (%)	检出限 (%)
分析项目	干基含量	灼烧基含量	曲线回归方程	相关系数	标准偏差 (%)	检出限 (%)
CaO	28.57~36.55	50.97~69.46	y=4.605x+2.219	0.9940	0.51	0.45
MgO	15.38~21.51	28.42~40.18	y=0.2839x+0.1705	0.9994	0.09	0.48
SiO₂	0.25~5.47	0.46~9.60	y=1.059x+0.3118	0.9986	0.14	0.051
Fe₂O₃	0.17~0.56	0.31~1.00	y=0.1682x+0.0006	0.9986	0.10	0.015
Al₂O₃	0.10~1.05	0.19~1.87	y=1.145x+0.1033	0.9976	0.03	0.011

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表 6 方法精密度分析结果

Table 6. Analytical results of precision tests of the proposed method

分析项目	QD10-111标准样品				BH191-4标准样品
分析项目	认定值	本法测定平均值(%)	标准偏差 (%)	RSD (%)	认定值	本法测定平均值(%)	标准偏差 (%)	RSD (%)
CaO	30.80	30.69	0.15	0.5	28.57	28.79	0.17	0.6
MgO	20.79	20.69	0.16	0.8	19.84	19.97	0.12	0.6
SiO₂	0.99	0.96	0.017	1.7	5.01	5.09	0.035	0.7
Fe₂O₃	0.32	0.32	0.0050	1.2	0.56	0.54	0.0070	1.3
Al₂O₃	0.23	0.22	0.0038	1.7	1.05	1.03	0.013	1.3

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表 7 方法准确度分析结果

Table 7. Analytical results of accuracy test of the proposed method

分析项目	QD10-113样品			QD10-114样品
分析项目	认定值 (%)	本法测定平均值(%)	相对偏差 (%)	认定值 (%)	本法测定平均值(%)	相对偏差 (%)
CaO	30.79	30.55	0.78	34.74	34.39	1.01
MgO	20.73	20.50	1.11	17.16	16.96	1.17
SiO₂	2.12	2.05	3.30	1.45	1.38	4.83
Fe₂O₃	0.275	0.272	1.09	0.404	0.398	1.49
Al₂O₃	0.203	0.199	1.97	0.296	0.290	2.03

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参考文献(15)

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熔融制样波长色散X射线荧光光谱法测定白云石中钙镁硅铁铝

鲅鱼圈出入境检验检疫局, 辽宁 营口 115007

作者简介: 褚宁, 博士, 工程师, 主要从事矿产品检测及方法研究.E-mail: n_chu2009@sina.com

Determination of Calcium, Magnesium, Silicon, Iron and Aluminum in Dolomite by Wavelength Dispersive X-ray Fluorescence Spectrometry with Fusion Sample Preparation

Bayuquan Entry-Exit Inspection & Quarantine Bureau, Yingkou 115007, China

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鲅鱼圈出入境检验检疫局, 辽宁营口 115007