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  

Determination of manganese,silicon and phosphorus in ferromanganese and manganese metal by X-ray fluorescence spectrometry with fusion sample preparation

作　　者：陈德 朱文军 谌亚 刘媛 熊维蓉 CHEN De;ZHU Wenjun;CHEN Ya;LIU Yuan;XIONG Weirong(Testing and Metrology Center,Xichang Steel&Vanadium Co.,Ltd.,Xichang 615000,China)

机构地区：[1]西昌钢钒有限公司检测计量中心,四川西昌615000

出　　处：《冶金分析》2024年第3期15-22,共8页Metallurgical Analysis

摘　　要：锰铁合金和金属锰是炼钢过程加入的重要原料,锰、硅、磷含量的准确检测对商务结算及生产控制具有重要意义。以四硼酸锂、偏硼酸锂、过氧化钡、钴粉与试样按一定质量比例混合包球,先在石墨垫底的瓷坩埚中通过马弗炉低温加热熔融,再置于盛有四硼酸锂的铂-金坩埚熔制成片,解决了合金中单质元素腐蚀铂-金坩埚的问题;用钴内标对锰进行校正克服了因烧失量及元素价态变化导致的样片质量波动对主量元素锰测定结果的影响,硅、磷的测定结果无需内标校正,实现了熔融制样-X射线荧光光谱法对锰铁合金和金属锰中锰、硅、磷的测定。选用各元素含量呈一定梯度的锰铁合金、金属锰等标准样品绘制校准曲线,采用ZSX Primus分析软件自带数学校正功能校正元素间吸收增强效应,校准曲线的相关系数不小于0.9994,硅的方法检出限为0.0008%,磷检出限为0.0003%。分别选取高碳锰铁、中碳锰铁、金属锰试样,按实验方法进行10次平行试验,锰、硅、磷测定结果的相对标准偏差(n=10)在0.06%~4.1%之间。将实验方法应用于锰铁和金属锰标准样品中锰、硅、磷的测定,测定值与标准值的误差分别满足GB/T 5686.1、GB/T 5686.2、GB/T 5686.4标准方法的允许差要求。随即抽取锰铁、金属锰试样共8件,采用实验方法和GB/T 5686系列标准方法进行方法比对,结果表明,实验方法与GB/T 5686.1中高氯酸氧化滴定法测定锰、GB/T 5686.2中高氯酸重量法测定硅、GB/T 5686.4中钼蓝光度法测定磷的结果基本一致。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 0.9994.The limits of detection for silicon and phosphorus were 0.0008%and 0.0003%,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 fer

关 键 词：X射线荧光光谱法(XRF) 熔融制样 钴内标 锰铁 金属锰 锰 硅 磷 

分 类 号：O657.34[理学—分析化学] TF031[理学—化学]