金属中超低氢的分析研究  

Research on analysis of ultralow content hydrogen in metals

作　　者：谢君[1] 张琳[1] 朱瑛才[1] 侯桂臣[1] 周亦胄[1] 朱跃进[1] XIE Jun;ZHANG Lin;ZHU Yingcai;HOU Guichen;ZHOU Yizhou;ZHU Yuejin(Institute of Metal Research,Chinese Academy of Sciences,Shenyang 110016,China)

机构地区：[1]中国科学院金属研究所,辽宁沈阳110016

出　　处：《冶金分析》2021年第5期1-8,共8页Metallurgical Analysis

基　　金：国家自然科学基金(51701212);辽宁省自然基金项目(2019-MS-336)。

摘　　要：探讨了钢、铜、铝、高温合金等金属材料中超低氢(w(H)<1.0μg/g)的测定方法及相关问题。钢中超低氢长期未被重视,直至"零峰值"问题的出现和解决,开启通往准确测定"钢中超低氢"的通道。应用基于2种不同加热提气原理的3台仪器,对已知含量的4种钢中超低氢标样进行测定,结果显示:基于高频-热抽取原理的氢分析仪的4组分析数据与标样认定值一致,成功率为100%;而基于脉冲-熔融法的分析结果成功率仅为50%,其中一组数值严重超差。应用基于脉冲-熔融法原理的仪器,测定钢中超低氢实际样品的成功率很难达到100%,以测定"共同样"钢样为例:钢中超低氢10点测定结果为(0.16±0.19)μg/g,标准偏差值大于平均值,检测失败。相反,基于高频-热抽取法的10点测定结果为(0.13±0.02)μg/g,数据可靠可信;基于管式炉-热抽取法测定结果为(0.13±0.04)μg/g,数据可靠可信。铜中超低氢分析容易受到表面氧化层的干扰,使释放的氢被反应吸收而不能全部到达检测器,用洁净表面的样品完成铜中超低氢测定,可将氧化层干扰降至最低。铝中超低氢分析相对成熟,已形成国家标准。按国标方法检测后的铝样品中可测出"残留氢",即第2次投样后,可见与第1次投样相同数量级的氢峰,因此,二次样氢峰问题成为困扰国标实施的关键问题。在此注重于解决"二次样的问题",实验表明:该问题由石墨坩埚引起,如果使用石英坩埚第2次投样,测定结果完全归零(0.0μg/g),二次样氢峰为石墨坩埚引起的干扰峰而非"残留氢"峰,这表明该问题未能干扰到国标的实施。高温合金中超低氢分析的主要干扰来自石墨坩埚,排除坩埚因素后仍然遇见"非超低氢"现象。通过对高温合金进行横向和纵向解剖、取样和分析,观察的氢分布,结果表明,高温合金显现超高氢突发现象由取样部位引起;横向截面中心有"非超低氢"点;纵向分布�The determination method and related issues of ultralow hydrogen(w(H)<1.0μg/g)in metal materials such as steel,copper,aluminum and superalloy were discussed.Ultralow hydrogen in steel had been neglected for a long time,until the emergence and resolution of "zero peak" problem,which opened a channel for the accurate determination of " ultralow hydrogen in steel".Three instruments based on two types of heating and gas extraction principles were used to measure four standard samples of ultralow hydrogen in steel with known contents.The results showed that the analysis data of four groups of hydrogen analyzer based on the principle of high-frequency and heat extraction were consistent with the certified values of the standard sample,and the success rate was 100%.However,the success rate of analytical results based on impulse-fusion method was only 50%,and one set of data was seriously out of tolerance.When the instrument based on impulse-fusion method was employed,the success rate of the actual sample of ultralow hydrogen in steel was difficult to reach 100%.Taking the "common sample" as an example:the 10-point measurement result of ultralow hydrogen in steel was(0.16±0.19)μg/g;the standard deviation value was greater than the average value,and the analysis failed.On the contrary,the 10-point detection result based on high-frequency and heat extraction method was(0.13±0.02)μg/g,and the data were reliable and credible;the measurement result based on tubular furnace and heat extraction method was(0.13±0.04)μg/g,which was also reliable and credible.The analysis of ultralow hydrogen in copper was easily interfered by the surface oxide layer,so that the released hydrogen was absorbed by the reaction and could not reach the detector completely.The determination of ultralow hydrogen in copper samples with clean surface could reduce the interference of oxide layer to the minimum.The analysis of ultralow hydrogen in aluminum was relatively mature and a national standard method had been formed.The "residual hydrogen" in

关 键 词：超低氢 钢 铜 铝 高温合金 热抽取法 脉冲熔融法 

分 类 号：O659.2[理学—分析化学]