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高Cr鎳基合金脫氮反應(yīng)熱力學(xué)與動力學(xué)研究
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中國科學(xué)院金屬研究所

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國家自然科學(xué)基金項目(面上項目,重點項目,重大項目)


Thermodynamic and Kinetic Study on the Nitrogen-Removing Process of High Cr Content Nickel Based Alloy
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Institute of Metal Research, Chinese Academy of Sciences

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    摘要:

    Cr作為抗熱腐蝕性元素鉻在高溫合金中廣泛添加,因其可增大氮元素溶解度,故高鉻合金的冶金脫氮難度較大。合金氮含量升高可引發(fā)氮化物析出進而影響材料組織質(zhì)量與力學(xué)性能,因此,非常必要澄清高Cr合金的脫氮行為與規(guī)律。本文以高Cr鎳基合金為實驗對象,對其在真空感應(yīng)熔煉脫氮過程的熱力學(xué)與動力學(xué)進行研究。結(jié)果表明,氮在高Cr鎳基合金中的熱力學(xué)平衡溶解度較高且主要受真空壓力控制,為實現(xiàn)[N]≤10 ppm的純凈度指標(biāo),合金冶煉真空壓力不可高于0.1Pa。脫氮反應(yīng)初期氮含量迅速下降,但反應(yīng)中后期需較長時間才可接近氮平衡溶解度,提高精煉溫度有助于縮短脫氮平衡反應(yīng)時間。動力學(xué)分析表明高Cr鎳基合金脫氮符合二級反應(yīng)規(guī)律,受界面化學(xué)反應(yīng)過程控制,1500℃、1550℃和1600℃條件下的脫氮表觀速率常數(shù)分別為0.0184m?s-1、0.0233 m?s-1和0.0397 m?s-1,表觀活化能為211.4 kJ?mol-1。

    Abstract:

    Nitrogen is one of the undesirable impurity elements of superalloys and it can induce the precipitation of nitrides and the formation of microporosity to worsen the mechanical properties of material. With the increasingly high demands in superalloy component quality, nowadays the nitrogen content in superalloy has been recommended to be no higher than 10×10-6 wt.%. Chromium is an important beneficial alloying element widely employed in superalloys (with an addition up to 20 wt.%) for it can enhance the anti-corrosion performance of alloys at elevated temperature. However, chromium has a high affinity to nitrogen that it could be very hard to achieve a low nitrogen content in high-Cr alloys. Therefore, it is necessary to study the features of the nitrogen-removing process of high-Cr alloys. In this work, the nitrogen-removing process during the vacuum induction melting of a high-Cr nickel based alloy was investigated through thermodynamic calculation and kinetic experiments. Results show that high-Cr nickel based alloy had a high thermodynamic equilibrium solubility of nitrogen, and it was mainly dominated by the vacuum pressure. In order to achieve the goal of [N]≤10 ppm, the melting vacuum pressure should be no higher than 0.1 Pa. To study the kinetic characteristics of nitrogen-removing process, the melted metal was held at 1500, 1550 and 1600 ℃, and sampled at 0, 30, 60, 120, 180 and 240 min at 0.1 Pa after the complete melting of alloy, respectively. Results indicate that nitrogen content dramatically decreased at the beginning of melt holding, but in the medium and later stage it took a much longer period of time to get close to the equilibrium solubility of nitrogen. Kinetic data analysis shows that the nitrogen-removing process of high-Cr nickel based alloy can be classified as the second-order reaction, which reflects that the process was controlled by the chemical reaction on melt surface. The apparent rate constants of nitrogen-removing process at 1500, 1550 and 1600 ℃ were calculated to be 0.0184, 0.0233 and 0.0397 m?s-1 , respectively, and the apparent activation energy was determined to be 211.4 kJ?mol-1.

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引用本文

王旻,張龍,楊亞倩,丁磊磊,馬穎澈,劉奎.高Cr鎳基合金脫氮反應(yīng)熱力學(xué)與動力學(xué)研究[J].稀有金屬材料與工程,2020,49(11):3803~3808.[Wang Min, Zhang Long, Yang Yaqian, Ding Leilei, Ma Yingche, Liu Kui. Thermodynamic and Kinetic Study on the Nitrogen-Removing Process of High Cr Content Nickel Based Alloy[J]. Rare Metal Materials and Engineering,2020,49(11):3803~3808.]
DOI:10.12442/j. issn.1002-185X.20190984

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  • 收稿日期:2019-11-25
  • 最后修改日期:2019-12-27
  • 錄用日期:2020-01-03
  • 在線發(fā)布日期: 2020-12-09
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