熔融制样-X射线荧光光谱法测定菱镁矿中主次组分
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摘要
实验采用熔融法制样,以X射线荧光光谱法(XRF)实现了菱镁矿中MgO、Al2O3、SiO2、P2O5、CaO、TiO2、MnO、Fe2O3主次量组分的测定。选择白云岩、水镁石和石灰石国家一级标准物质及人工合成校准样品绘制校准曲线解决了高含量MgO和低含量CaO的测定问题。先测量样品灼烧减量,用灼烧后的样品进行熔片,以消去灼烧减量的含量与X射线荧光强度建立校准曲线,并进行基体校正,测出未知样灼烧后的含量后,再换算为样品实际含量。灼烧后样品与熔剂Li2B4O7的稀释比为1∶10,加入1滴LiBr溶液(1.0g/mL)作为脱模剂,在1 050℃熔融9min制备熔片。各组分校准曲线的相关系数在0.997 6~0.999 9之间;方法检出限在10~320μg/g之间。对一菱镁矿实际样品进行精密度考察,各组分测定结果的相对标准偏差(RSD,n=12)在0.25%~3.6%之间。所建方法应用于菱镁矿标准物质和实际样品的测定,结果与标准物质认定值或实际样品湿法值基本一致。
After the magnesite sample was prepared with fusion method,the content of MgO,Al_2O_3,SiO_2,P_2O_5,CaO,TiO_2,MnO and Fe_2O_3 in magnesite was determined by X-ray fluorescence spectrometry(XRF),realizing the simultaneous determination of major and minor components.The calibration curve was plotted with the national certified reference materials of dolomite,brucite and limestone and artificially synthetic calibration sample,solving the determination problems of high content MgO and low content CaO.The loss on ignition of sample was firstly measured.Then,the burned sample was prepared for fuse pieces.The calibration curve was established by the content after correction of loss on ignition and the corresponding X-ray fluorescence intensity,and the matrix correction was also conducted.Finally,the content in burned sample was determined to calculate the content in actual sample.The dilution ratio between the burned sample and flux(Li_2B_4O_7)was 1∶10.One drop of LiBr solution(1.0g/mL)was added and used as releasing agent.The fuse piece was prepared at 1 050 ℃for 9min.The correlation coefficients of calibration curves of components were between 0.997 6and 0.999 9.The detection limit of method was 10-320μg/g.One actual magnesite sample was used for precision test.The relative standard deviation(RSD,n=12)of components were between 0.25%and 3.6%.The proposed method was applied to the determination of certified reference material and actual samples of magnesite,and the results were basically consistent with the certified values and those obtained by wet method.
After the magnesite sample was prepared with fusion method,the content of MgO,Al_2O_3,SiO_2,P_2O_5,CaO,TiO_2,MnO and Fe_2O_3 in magnesite was determined by X-ray fluorescence spectrometry(XRF),realizing the simultaneous determination of major and minor components.The calibration curve was plotted with the national certified reference materials of dolomite,brucite and limestone and artificially synthetic calibration sample,solving the determination problems of high content MgO and low content CaO.The loss on ignition of sample was firstly measured.Then,the burned sample was prepared for fuse pieces.The calibration curve was established by the content after correction of loss on ignition and the corresponding X-ray fluorescence intensity,and the matrix correction was also conducted.Finally,the content in burned sample was determined to calculate the content in actual sample.The dilution ratio between the burned sample and flux(Li_2B_4O_7)was 1∶10.One drop of LiBr solution(1.0g/mL)was added and used as releasing agent.The fuse piece was prepared at 1 050 ℃for 9min.The correlation coefficients of calibration curves of components were between 0.997 6and 0.999 9.The detection limit of method was 10-320μg/g.One actual magnesite sample was used for precision test.The relative standard deviation(RSD,n=12)of components were between 0.25%and 3.6%.The proposed method was applied to the determination of certified reference material and actual samples of magnesite,and the results were basically consistent with the certified values and those obtained by wet method.
引文
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[6]朱俐,王金凤,尹利辉.X射线荧光光谱法在标准中的应用[J].理化检验:化学分册,2015,51(2):267-271.ZHU Li,WANG Jin-feng,YIN Li-hui.Application of Xray fluorescence spectrometry in standards[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2015,51(2):267-271.
[7]袁秀茹,余宇,赵峰,等.X射线荧光光谱法同时测定白云岩中氧化钙和氧化镁等主次量组分[J].岩矿测试,2009,28(4):376-378.YUAN Xiu-ru,YU Yu,ZHAO Feng,et al.Simultaneous determination of major and minor components in dolomite by X-ray fluorescence spectrometry[J].Rock and Mineral Analysis,2009,28(4):376-378.
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[9]孟德安,马慧侠.X射线荧光光谱法测定白云石中12种元素含量[J].理化检验:化学分册,2014,50(1):76-79.MENG De-an,MA Hui-xia.XRFS determination of 12elements in dolomite[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2014,50(1):76-79.
[10]吕善胜,徐金龙,田琼,等.X射线荧光光谱法测定石灰石中多组分含量[J].冶金分析,2014,34(9):39-42.LShan-sheng,XU Jin-long,TIAN Qiong,et al.Determination of muti-components in limestone by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2014,34(9):39-42.
[11]褚宁,李卫刚,蒋晓光,等.熔融制样-波长色散X射线荧光光谱法测定石灰石中主次成分[J].冶金分析,2014,34(10):37-41.CHU Ning,LI Wei-gang,JIANG Xiao-guang,et al.Determination of major and minor components in limestone by wavelength dispersive X-ray fluorescence spectrometry with fusion sample preparation[J].Metallurgical Analysis,2014,34(10):37-41.
[12]李小莉,安树清,徐铁民,等.超细粉末压片制样X射线荧光光谱测定碳酸岩中多种元素及CO2[J].光谱学与光谱分析,2015,35(6):1741-1745.LI Xiao-li,AN Shu-qing,XU Tie-min,et al.Ultra-fine pressed power pellet sample preparation XRF determination of multi-elements and carbon dioxide in carbonate[J].Spectroscopy and Spectral Analysis,2015,35(6):1741-1745.
[13]张鹏,曲月华,王一凌.X射线荧光光谱法测定镁砂、镁石及菱镁矿中主次成分[J].冶金分析,2010,30(9):28-31.ZHANG Peng,QU Yue-hua,WANG Yi-ling.Determination of major and minor elements in magnesia,humite and magnesite by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2010,30(9):28-31.
[14]赵恩好,岳明新,周国兴,等.X射线荧光光谱法测定镁质耐火材料及其原料中10种成分[J].冶金分析,2013,33(7):62-67.ZHAO En-hao,YUE Ming-xin,ZHOU Guo-xing,et al.Determination of ten components in magnesia refractory materials and raw materials by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2013,33(7):62-67.
[15]曲月华,王翠艳,王一凌,等.熔融制样-X射线荧光光谱法测定石灰石中5种组分[J].冶金分析,2013,33(12):29-33.QU Yue-hua,WANG Cui-yan,WANG Yi-ling,et al.Determination of five components in limestone by X-ray fluorescence spectrometry with fusion sample preparation[J].Metallurgical Analysis,2013,33(12):29-33.
[16]褚宁,李卫刚,蒋晓光,等.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[J].岩矿测试,2014,33(6):834-838.CHU Ning,LI Wei-gang,JIANG Xiao-guang,et al.Determination of calcium,magnesium,silicon,iron and aluminum in dolomite by wavelength dispersive X-ray fluorescence spectrometry with fusion sample preparation[J].Rock and Mineral Analysis,2014,33(6):834-838.
[17]Terrance Hettipathiran,Naomi Grey,Ravi Naidu.Elimination of analytical error due to the use of catch weights with loss-eliminated alphas in X-ray fluorescence spectrometric analysis of limestone using borate fusions[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2003,58(1):85-95.
[18]李国会,李小莉.X射线荧光光谱分析熔融法制样的系统研究[J].冶金分析,2015,35(7):1-9.LI Guo-hui,LI Xiao-li.Systematic study on the fusion sample preparation in X-ray fluorescence spectrometric analysis[J].Metallurgical Analysis,2015,35(7):1-9.
[19]LU Tian,Arash Tahmasebi,Jianglong Yu.An experimental study on thermal decomposition behavior of magnesite[J].Journal of Thermal Analysis and Calorimetry,2014,118(3):1577-1584.
[20]周旭良.菱镁矿热选机理研究[D].鞍山:辽宁科技大学,2007.
[21]Claisse F,Blanchette J S.硼酸盐熔融的物理与化学[M].卓尚军,译.上海:华东理工大学出版社,2006:38-39.
[2]丁建华,陈正海,杨国俊,等.中国菱镁矿成矿规律及资源潜力分析[J].中国地质,2013,40(6):1699-1711.DING Jian-hua,CHEN Zheng-hai,YANG Guo-jun,et al.Metallogeny and resource potential of magnesite deposits in China[J].Geology in China,2013,40(6):1699-1711.
[3]中华人民共和国国土资源部.DZ/T 0202—2002铝土矿、冶镁菱镁矿地质勘查规范[S].北京:地质出版社,2003.
[4]岩石矿物分析编委会.岩石矿物分析:第2分册[M].4版.北京:地质出版社,2011:176-179.
[5]靳芳,李青林,李文波.电感耦合等离子体发射光谱法测定菱镁矿中的铁[J].科技资讯,2012,26:93-96.JIN Fang,LI Qing-lin,LI Wen-bo.Determination of Fe in magnesite by inductively coupled plasma-atomic emission spectrometry[J].Science&Technology Information,2012,26:93-96.
[6]朱俐,王金凤,尹利辉.X射线荧光光谱法在标准中的应用[J].理化检验:化学分册,2015,51(2):267-271.ZHU Li,WANG Jin-feng,YIN Li-hui.Application of Xray fluorescence spectrometry in standards[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2015,51(2):267-271.
[7]袁秀茹,余宇,赵峰,等.X射线荧光光谱法同时测定白云岩中氧化钙和氧化镁等主次量组分[J].岩矿测试,2009,28(4):376-378.YUAN Xiu-ru,YU Yu,ZHAO Feng,et al.Simultaneous determination of major and minor components in dolomite by X-ray fluorescence spectrometry[J].Rock and Mineral Analysis,2009,28(4):376-378.
[8]乔蓉,郭刚.X射线荧光光谱法测定白云石、石灰石中氧化钙、氧化镁和二氧化硅[J].冶金分析,2014,34(1):75-78.QIAO Rong,GUO Gang.Determination of calcium oxide,magnesium oxide and silicon dioxide in dolomite and limestone by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2014,34(1):75-78.
[9]孟德安,马慧侠.X射线荧光光谱法测定白云石中12种元素含量[J].理化检验:化学分册,2014,50(1):76-79.MENG De-an,MA Hui-xia.XRFS determination of 12elements in dolomite[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2014,50(1):76-79.
[10]吕善胜,徐金龙,田琼,等.X射线荧光光谱法测定石灰石中多组分含量[J].冶金分析,2014,34(9):39-42.LShan-sheng,XU Jin-long,TIAN Qiong,et al.Determination of muti-components in limestone by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2014,34(9):39-42.
[11]褚宁,李卫刚,蒋晓光,等.熔融制样-波长色散X射线荧光光谱法测定石灰石中主次成分[J].冶金分析,2014,34(10):37-41.CHU Ning,LI Wei-gang,JIANG Xiao-guang,et al.Determination of major and minor components in limestone by wavelength dispersive X-ray fluorescence spectrometry with fusion sample preparation[J].Metallurgical Analysis,2014,34(10):37-41.
[12]李小莉,安树清,徐铁民,等.超细粉末压片制样X射线荧光光谱测定碳酸岩中多种元素及CO2[J].光谱学与光谱分析,2015,35(6):1741-1745.LI Xiao-li,AN Shu-qing,XU Tie-min,et al.Ultra-fine pressed power pellet sample preparation XRF determination of multi-elements and carbon dioxide in carbonate[J].Spectroscopy and Spectral Analysis,2015,35(6):1741-1745.
[13]张鹏,曲月华,王一凌.X射线荧光光谱法测定镁砂、镁石及菱镁矿中主次成分[J].冶金分析,2010,30(9):28-31.ZHANG Peng,QU Yue-hua,WANG Yi-ling.Determination of major and minor elements in magnesia,humite and magnesite by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2010,30(9):28-31.
[14]赵恩好,岳明新,周国兴,等.X射线荧光光谱法测定镁质耐火材料及其原料中10种成分[J].冶金分析,2013,33(7):62-67.ZHAO En-hao,YUE Ming-xin,ZHOU Guo-xing,et al.Determination of ten components in magnesia refractory materials and raw materials by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2013,33(7):62-67.
[15]曲月华,王翠艳,王一凌,等.熔融制样-X射线荧光光谱法测定石灰石中5种组分[J].冶金分析,2013,33(12):29-33.QU Yue-hua,WANG Cui-yan,WANG Yi-ling,et al.Determination of five components in limestone by X-ray fluorescence spectrometry with fusion sample preparation[J].Metallurgical Analysis,2013,33(12):29-33.
[16]褚宁,李卫刚,蒋晓光,等.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[J].岩矿测试,2014,33(6):834-838.CHU Ning,LI Wei-gang,JIANG Xiao-guang,et al.Determination of calcium,magnesium,silicon,iron and aluminum in dolomite by wavelength dispersive X-ray fluorescence spectrometry with fusion sample preparation[J].Rock and Mineral Analysis,2014,33(6):834-838.
[17]Terrance Hettipathiran,Naomi Grey,Ravi Naidu.Elimination of analytical error due to the use of catch weights with loss-eliminated alphas in X-ray fluorescence spectrometric analysis of limestone using borate fusions[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2003,58(1):85-95.
[18]李国会,李小莉.X射线荧光光谱分析熔融法制样的系统研究[J].冶金分析,2015,35(7):1-9.LI Guo-hui,LI Xiao-li.Systematic study on the fusion sample preparation in X-ray fluorescence spectrometric analysis[J].Metallurgical Analysis,2015,35(7):1-9.
[19]LU Tian,Arash Tahmasebi,Jianglong Yu.An experimental study on thermal decomposition behavior of magnesite[J].Journal of Thermal Analysis and Calorimetry,2014,118(3):1577-1584.
[20]周旭良.菱镁矿热选机理研究[D].鞍山:辽宁科技大学,2007.
[21]Claisse F,Blanchette J S.硼酸盐熔融的物理与化学[M].卓尚军,译.上海:华东理工大学出版社,2006:38-39.