Determination of manganese,silicon and phosphorus in ferromanganese and manganese metal by X-ray fluorescence spectrometry with fusion sample preparation
CHEN De, ZHU Wenjun, CHEN Ya, LIU Yuan, XIONG Weirong
Testing and Metrology Center,Xichang Steel ＆ Vanadium Co.,Ltd.,Xichang 615000,China
Abstract：Ferromanganese and manganese metal are important raw materials as the additives in the steelmaking process. It is of great significance to determine accurately the contents of manganese, silicon and phosphorus for business settlement and production control. Lithium tetraborate, lithium metaborate, barium peroxide and cobalt powder were mixed with the sample in a certain mass ratio to wrap the balls. The mixture was fused in porcelain crucible with graphite base by low temperature heating in muffle furnace, and it was transferred into platinum crucible containing lithium tetraborate to prepare the pellet, solving the corrosion problem of platinum crucible by elemental substance in alloy. Cobalt was selected as the internal standard for the correction of manganese, which could eliminate the influence of sample mass change (caused by ignition loss and element valence change) on the determination results of major element of manganese. The determination results of silicon and phosphorus do not need to be corrected by internal standard. Therefore, the determination of manganese, silicon and phosphorus in ferromanganese and manganese metal was realized by X-ray fluorescence spectrometry with fusion sample preparation. The calibration curves were drawn with reference materials such as ferromanganese and manganese metal with a certain gradient of each element content. The absorption enhancement effect among elements was corrected by the ZSX Primus analysis software with mathematical correction function. The correlation coefficients of calibration curves were not less than 0.999 4. The limits of detection for silicon and phosphorus were 0.000 8% and 0.000 3%, respectively. The samples of high carbon ferromanganese, mid-carbon ferromanganese and manganese metal were determined according to the proposed method. The relative standard deviations (RSD, n=10) of determination results of manganese, silicon and phosphorus were between 0.06% and 4.1%. The proposed method was applied for determination of manganese, silicon and phosphorus in reference materials of ferromanganese and manganese metal. The errors between the results and standard values could meet the requirements of allowable deviation specified in GB/T 5686.1, GB/T 5686.2 and GB/T 5686.4. 8 samples of ferromanganese and manganese metal were randomly selected and determined according to the proposed method as well as the standard methods in GB/T 5686 series. It was found that the determination results of proposed method were basically consistent with those obtained by the standard methods, i.e., perchloric acid oxidation titration in GB/T 5686.1 for determination of manganese, perchloric acid gravimetry in GB/T 5686.2 for determination of silicon, and molybdenum blue photometry in GB/T 5686.4 for determination of phosphorus.
陈德, 朱文军, 谌亚, 刘媛, 熊维蓉. 熔融制样-X射线荧光光谱法测定锰铁合金和金属锰中锰硅磷[J]. 冶金分析, 2024, 44(3): 15-22.
CHEN De, ZHU Wenjun, CHEN Ya, LIU Yuan, XIONG Weirong. Determination of manganese,silicon and phosphorus in ferromanganese and manganese metal by X-ray fluorescence spectrometry with fusion sample preparation. , 2024, 44(3): 15-22.
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