液态Sc腐蚀W坩埚的机理与防护
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摘要
采用粉冶法制备W坩埚2件,其中1件使用原位合成法制备成表面有WC层的WC/W复合结构W坩埚。在等同工艺条件下,将2件W坩埚用于真空蒸馏提纯Sc的寿命对比实验。通过金相、SEM/EDS、硬度和密度测试等分析手段,研究了液态Sc对W的腐蚀机理和复合结构W坩埚的防护效果。研究结果表明:高温下Sc与W会在晶界上发生共晶反应,共晶液体沿晶界快速扩散导致W坩埚盛装物料功能失效。复合结构W坩埚的WC层耐Sc液腐蚀效果显著,但长时间高温服役后,Sc在WC阻挡层前聚集、形核、晶粒长大,最终破坏WC层。
Two kinds of tungsten crucibles are prepared by powder metallurgy technology, and one of them is prepared into WC/W composite structure tungsten with WC layer on the surface by in-situ synthesis. The life comparison experiment for vacuum distillation to purify the crucible has been done under the equivalent process conditions. Hardness, density,metallographic and SEM/EDS analysis methods are used to systematically study the corrosion mechanism of liquid scandium on tungsten and the protective effect of composite structure tungsten crucible. The results show that at high temperature,scandium and tungsten will undergo eutectic reaction at the grain boundary, and the eutectic liquid will rapidly diffuse along the grain boundary, which will cause the function of tungsten crucible to fail. The WC layer of composite tungsten crucible has remarkable blocking effect on scandium liquid. The failure mechanism is that after a long time of high temperature service, the scandium gathers, nucleates and crystallizes,which will cuase the destruction of WC layer.
Two kinds of tungsten crucibles are prepared by powder metallurgy technology, and one of them is prepared into WC/W composite structure tungsten with WC layer on the surface by in-situ synthesis. The life comparison experiment for vacuum distillation to purify the crucible has been done under the equivalent process conditions. Hardness, density,metallographic and SEM/EDS analysis methods are used to systematically study the corrosion mechanism of liquid scandium on tungsten and the protective effect of composite structure tungsten crucible. The results show that at high temperature,scandium and tungsten will undergo eutectic reaction at the grain boundary, and the eutectic liquid will rapidly diffuse along the grain boundary, which will cause the function of tungsten crucible to fail. The WC layer of composite tungsten crucible has remarkable blocking effect on scandium liquid. The failure mechanism is that after a long time of high temperature service, the scandium gathers, nucleates and crystallizes,which will cuase the destruction of WC layer.
引文
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[2]武红磊,郑瑞生,孙秀明.坩埚形状对氮化铝晶体生长的影响[C].全国晶体生长与材料学术会议(论文集),福州:2006:79.Wu Honglei, Zheng Ruisheng, Sun Xiuming. Effect of crucible shape on crystal growth of aluminum nitride[C]. National Conference on Crystal Growth and Materials, Fuzhou:2006:79.
[3]廖彬彬,魏修宇.钨钼材料在蓝宝石单晶炉中的应用[J].硬质合金,2018,35(02):134-141.Liao Binbin, Wei Xiuyu. The application of tungsten and molybdenum materials in sapphire single crystal furnace[J]. Cemented Carbide, 2018,35(02):134-141.
[4]付学成,权雪玲,刘民,王凤丹,王英.钨坩埚蒸镀金膜表面黑色颗粒的控制研究[J].真空科学与技术学报,2018,38(02):113-116.Fu Xuecheng, Quan Xueling, Liu Min, et al. Study on the control of black particles on the surface of tungsten crucible steam gilt film[J].Chinese Journal of Vacuum Science and Technology, 2018, 38(02):113-116.
[5]吴志盈,窦永庆.稀土用钨坩埚的研制[J].稀有金属快报,2001,1:21-22.Wu Zhiying, Dou Yongqing. Development of tungsten crucible for rare earth[J]. Rare Metals Letters, 2001,1:21-22.
[6]刘燚,陈海清,魏威,苏莎.高纯金属钪的制备[J].湖南有色金属,2016,32(05):41-44.Liu Yan, Chen Haiqing, Wei wei, et al. Preparation of high purity scandium metal[J]. Hunan Nonferrous Metals, 2016, 32(05):41-44.
[7]庞思明,王志强,周林,等.稀土超磁致伸缩材料用高纯金属铽、镝的制备工艺研究[J].稀土,2008,29(06):31-35.Pang Siming, Wang Zhiqiang, Zhou Lin, et al. Study on preparation of high purified terbium and dysprosium metals used for rare earth giant magnetostrictive materials[J]. Chinese Rare Earths, 2008, 29(06):31-35.
[8]郝占忠,许林成.金属钆中钨的演化迁移行为与调控[J].有色金属(冶炼部分),2018, 04:65-70.Hao Zhanzhong, Xu Lincheng. Evolution mirgration behavior and regulation of tungsten in metallica gadolinium[J]. Nonferrous Metals(Extractive Metallurgy), 2018, 04:65-70.
[9]杨庆山,陈建军,谢建秋,朱剑军.金属镝中杂质钨控制的研究[J].湖南冶金,2006, 04:19-21.Yang Qingshan, Chen Jianjun, Xie Jianqiu, et al. Study on controlling impurity tungsten in metal dysprosium. Hunan Metallurgy, 2006, 34(04):19-21.
[10]张小琴,姜银举,代清.真空蒸馏法制备高纯金属钆[J].包钢科技,2007, 33(03):17-20.Zhang Xiaoqin, Jiang Yinju, Dai Qing. Preparation of highpurity matallic gadolinium by the vacuum distillation method[J]. Science&Technology of Baotou Steel(Group)Corporation, 2007,33(03):17-20.
[11]杨银,闫晓东.一种高纯钨表面生成WC方法.中国:CN106591772A[P], 2017-04-26.Yang Yin, Yan Xiaodong. The invention relates to a method for producing WC on the surface of high purity tungsten[P]. China:CN106591772A. 2017-04-26.
[12]黄广华,盛银梅,王德志.原位合成WC/W表面复合材料组织和性能研究[J].硬质合金,2018,35(06):420-426.Huang Guanghua, Sheng Yinmei, Wang Dezhi. Study on microstructure and properties of in-situ synthesised WC-W composite[J], Cemented Carbide, 2018, 35(06):420-426.
[13]Okamoto H. Sc-W(scandium-tungsten)[J]. Journal of Phase Equilibria, 2000, 21(6):574.
[14]Argyropoulos SA, Guthrie RIL. The dissolution of titanium in liquid steel[J]. Metallurgical Transactions B, 1984, 15(1):47-58.