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    不同加热方式测定铝及铝合金中氢的差异性初步探讨

    Preliminary Discussion on Differences in Determination of Hydrogen in Aluminum and Aluminum Alloy by Different Heating Methods

    • 摘要: 脉冲惰气熔融法(以下简称脉冲法)测定铝及铝合金存在“二次氢”现象,即再次加热测试过的样品,仍旧有明显的氢释放,国内学者倾向于认为石墨坩埚释放氢引起的干扰,俄罗斯学者则倾向于认为加热时间过短时,氢不足以完全释放而引起的“二次氢”。针对上述不同观点,采用脉冲法及热脱附法进行铝及铝合金中氢测试的初步对比,结果如下:热脱附法测试脉冲法分析后的样品,仍旧有明显的氢释放,即“二次氢”现象,测试脉冲法参与定值的铝中氢标准物质GBW(E)020030认定值为(0.19±0.04) μg·g−1、GBW(E)020030a认定值(0.24±0.06) μg·g−1、GBW(E)020031a认定值(0.25±0.05) μg·g−1,结果分别为0.38,0.58,0.71 μg·g−1,前二者的释放峰值分别位于约450,380 ℃处;采用脉冲法、热脱附法同时测定不同批次的AlSi样品中氢的含量,脉冲法所得结果分别为0.13,0.16,0.16 μg·g−1,热脱附法所得结果分别为0.70,0.53,0.48 μg·g−1,前二者的释放峰值主要位于350,580 ℃处。上述结果表明,热脱附法测试结果普遍比脉冲法偏高。考虑到前者采用石英管加热,未涉及石墨坩埚,且慢速升温,分析时间以小时计,初步认为加热时间过短时,氢不足以完全释放而引起的“二次氢”的观点更有说服力。但鉴于国内普遍采用脉冲法测定铝合金中氢含量,仍需更详细比对验证,以期得到更有说服力的结论。

       

      Abstract: There was "secondary hydrogen" phenomenon in aluminum and aluminum alloy determination by pulse inert gas melting method (hereinafter referred to as the pulse method), which meant, there was still a significant hydrogen release after reheating the measured sample. Domestic scholars tended to believe that the interference caused by the release of hydrogen from graphite crucibles, while Russia scholars tended to believe that the heating time was too short to completely release hydrogen. In order to compare the different views, hydrogen in aluminum and aluminum alloy was determined by pulse method and thermal desorption method. The results were as follows: there was still obvious hydrogen released when the samples which were analyzed by pulse method were tested again by thermal desorption method, which meant "secondary hydrogen" phenomenon. The hydrogen in aluminum reference materials GBW (E) 020030certified value (0.19±0.04) μg·g−1 , GBW (E) 020030acertified value(0.24±0.06) μg·g−1 , and GBW (E) 020031a certified value (0.25±0.05) μg·g−1 which were certified by the pulse method, were tested by thermal desorption method, and the results were 0.38, 0.58, and 0.71 μg·g−1 , with the release peaks of the former two located at approximately 450, 380 ℃, respectively; The AlSi samples from different batches were simultaneously analyzed by pulse method and thermal desorption method, with results of 0.13, 0.16, 0.16 μg·g−1 for pulse method and 0.70, 0.53, 0.48 μg·g−1 for thermal desorption method, respectively. The release peaks of the former two were mainly located at 350 ℃ and 580 ℃. As shown by the above results, the testing results of thermal desorption method were generally higher than those of pulse method. Considering that the former used quartz tube heating, did not involve graphite crucible and slowly heated up, and the analysis time was measured in hours, it was preliminarily believed that the viewpoint that the heating time was too short to completely release hydrogen, was more convincing. However, considering the widespread use of pulse method for determination of hydrogen in aluminum alloys in China, more detailed comparison and verification were still needed in order to obtain more convincing conclusions.

       

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