基于惰气熔融-红外法的镍助熔剂法和锡浴法测定钛及钛合金中氢的方法对比  

Comparison of nickel flux method and tin bath method based on inert gas fusion-infrared method for the determination of hydrogen in titanium and titanium alloy

作　　者：张毅[1] 刘攀[1] 孟秋达 张欣耀[1] ZHANG Yi;LIU Pan;MENG Qiuda;ZHANG Xinyao(Luoyang Ship Material Research Institute,Luoyang 471023,China)

机构地区：[1]中国船舶重工集团公司第七二五研究所(洛阳船舶材料研究所),河南洛阳471023

出　　处：《冶金分析》2022年第2期70-75,共6页Metallurgical Analysis

摘　　要：氢含量对钛及钛合金的组织形貌与物理机械性能有显著影响。分别采用镍(简称镍助熔剂法)与锡(简称锡浴法)为助熔剂,用惰气熔融-红外法对钛及钛合金中氢含量进行测定,从氢释放率、空白值、校准方式、检出限、定量限、精密度、正确度等方面对这两种方法进行了对比。结果表明,锡浴法相对于镍助熔剂法氢释放率高且空白值低,两种方法在测定过程中不能使用同一校准曲线。锡浴法在3.8μg/g≤w(H)≤200μg/g范围内有良好的线性关系,相关系数大于0.999;镍助熔剂法宜采取分段校准方式,在8.2μg/g≤w(H)<90μg/g和90μg/g≤w(H)≤200μg/g分析范围内分别建立校准曲线,各分段校准曲线的相关系数均不小于0.999。锡浴法测定氢的检出限和定量限(分别为1.2μg/g和3.8μg/g)相对镍助熔剂法均较低(分别为2.5μg/g和8.2μg/g)。采用镍助熔剂法和锡浴法对钛合金标准样品中氢含量平行测定6次,结果表明,两种方法测定结果与认定值均保持一致。将这两种方法应用于样品分析,镍助熔剂法测定结果的相对标准偏差(RSD,n=6)为1.9%~8.6%,锡浴法为1.6%~4.3%。采用镍助熔剂法和锡浴法对多种牌号的钛及钛合金中氢含量分别进行单次测量,用其中一种分析方法精密度参数中的重复性限r和再现性限R检验两种分析方法测量结果的一致性,结果表明,镍助熔剂法的测定结果与锡浴法具有良好的一致性。锡浴法的氢释放率、空白值、检出限、定量限、精密度均优于镍助熔剂法,适用于单独测定钛及钛合金中氢含量,常作为标准方法使用。因镍助熔剂法测定条件可用于测定氧和氮,适用于钛及钛合金中氧、氮、氢的同时测定。The hydrogen content has a significant effect on the structure morphology and physical and mechanical properties of titanium and titanium alloys.The contents of hydrogen in titanium and titanium alloys were determined by inert gas fusion-infrared method using nickel(abbreviated as nickel flux method)and tin(abbreviated as tin bath method)as the flux,respectively.Two methods were compared in terms of hydrogen release rate,blank value,calibration method,limit of detection,limit of quantification,precision and trueness.The results showed that the tin bath method had higher hydrogen release rate and lower blank value compared to the nickel flux method.Same calibration curve could not be used for two methods in the measurement process.The tin bath method exhibited a good linear relationship in the range of 3.8μg/g≤w(H)≤200μg/g,and the correlation coefficient was greater than 0.999.For the nickel flux method,a segmented calibration mode should be used.The calibration curves were established in the analytical range of 8.2μg/g≤w(H)<90μg/g and 90μg/g≤w(H)≤200μg/g,respectively.The correlation coefficients of two calibration curves were both greater than 0.999.The limit of detection and limit of quantification for the determination of hydrogen in tin bath method was 1.2μg/g and 3.8μg/g,respectively,which was lower than that of nickel flux method,i.e.,2.5μg/g and 8.2μg/g.The content of hydrogen in certified reference materials of titanium alloy was determined for six times by both nickel flux method and tin bath method.It was found that the found results of two methods were both consistent with the certified values.Two proposed methods were applied for the analysis of actual samples.The relative standard deviations(RSD,n=6)of the determination results in nickel flux method and tin bath method were 1.9%-8.6%and 1.6%-4.3%,respectively.The proposed nickel flux method and tin bath method were applied for the single measurement of hydrogen content in titanium and titanium alloys with various brands.The repeata

关 键 词：惰气熔融 红外吸收法 钛合金 氢 镍 锡 释放率 

分 类 号：O659.2[理学—分析化学] TF823[理学—化学]