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
ZHANG Yi, LIU Pan*, MENG Qiuda, ZHANG Xinyao
Luoyang Ship Material Research Institute, Luoyang 471023, China
Abstract：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 3.8 μg/g≤w(H)≤200 μg/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 8.2 μg/g≤w(H)<90 μg/g and 90 μg/g≤w(H)≤200 μg/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 1.2 μg/g and 3.8 μg/g, respectively, which was lower than that of nickel flux method, i.e., 2.5 μg/g and 8.2 μg/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 repeatability limit (r) and reproducibility limit (R) in precision parameters of one method were used to verify the consistency of measurement results of two methods. The results showed that the nickel flux method and tin bath method had good consistency. The hydrogen release rate, blank value, limit of detection, limit of quantification and precision of tin bath method were all better than those of nickel flux method. Therefore, the tin bath method was applicable for the single determination of hydrogen content in titanium and titanium alloys, and it could be used as standard method. The measurement conditions of nickel flux method were available for the determination of oxygen and nitrogen, so it was appliable for the simultaneous determination of oxygen, nitrogen and hydrogen in titanium and titanium alloys.
张毅, 刘攀, 孟秋达, 张欣耀. 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[J]. 冶金分析, 2022, 42(2): 70-75.
ZHANG Yi, LIU Pan, MENG Qiuda, ZHANG Xinyao. 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. , 2022, 42(2): 70-75.
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