稀土金屬脫除氧雜質的新技術及驅動機制研究進展

傅凱; 李栓; 姜曉靜; 韓麗輝; 田文懷; 李星國

doi:10.13374/j.issn2095-9389.2018.11.003

稀土金屬脫除氧雜質的新技術及驅動機制研究進展

doi: 10.13374/j.issn2095-9389.2018.11.003

傅凱^1,2,
李栓^1,2,
姜曉靜²,
韓麗輝³,
田文懷^1, ,,
李星國²

1) 北京科技大學材料科學與工程學院, 北京 100083;
2) 北京大學化學與分子工程學院, 北京 100871;
3) 北京科技大學冶金與生態工程學院, 北京 100083

基金項目:

北京市科學技術委員會資助項目(Z17110000091702)

國家自然科學基金資助項目(51431001,51771002,U1607126,21321001)

詳細信息

中圖分類號: TG146.45
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- 文章訪問數: 797
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- 被引次數: 0
出版歷程
- 收稿日期: 2017-11-15

Research progress on novel technology and mechanisms for the removal of oxygen impurities in rare-earth metals

1) School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China;
2) College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China;
3) School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China

摘要

摘要: 介紹了活潑金屬除氣法、等離子體熔煉法和固溶氫原子除氣法等稀土金屬脫除氧雜質的新方法,詳細歸納了將氧雜質含量限制在5×10^-5以下的工藝條件.重點介紹新方法中引入活潑金屬、氫等離子體、活性固溶氫原子等各種外部驅動因素的設計思想,提出提純新技術的同時探究了痕量雜質的遷移規律及去除機制,深化對雜質存在形式、行為規律及提純機理的認識.采用FAST-2D與Stefan數值模擬技術、¹⁸O₂示蹤同位素標記技術、CALPHAD相圖數據庫模擬計算技術對稀土金屬高純化的新工藝提供理論指導與評價,加深對提純驅動機制的理解.
- 稀土 /
- 高純化 /
- 氧含量 /
- 模擬計算 /
- 機理
Abstract: Rare-earth metals play a very important role in the development of high-tech industries and the research of functional materials. The demand for high-purity rare-earth metals has rapidly increased because of the development of modern society and the rare-earth industry. However, the purity of commercial rare-earth metal materials is the key factor limiting the rapid development of rare-earth industry. The major impurities in commercial rare-earth metal materials are gas impurities, especially oxygen. The removal of oxygen impurities is extremely challenging because of their strong affinity, which causes the problem of high oxygen concentrations of raw rare-earth metal materials. Therefore, effectively removing oxygen purities is the key to achieve ultra-high purity rare-earth metals. In recent years, several new and innovative strategies to remove oxygen impurities from rare earth metals have been proposed and investigated. To overcome the kinetic and thermodynamic barriers, various driving forces have been creatively introduced into the refining process. This article presented some novel purification methods to remove oxygen impurities, including active metal external getting method, hydrogen plasma arc melting method and hydrogen in-situ refining method. Experimental results show that the oxygen concentrations in rare-earth metals can be reduced effectively by introducing various driving forces. The optimum process conditions of these techniques were introduced in detail, with the final concentrations of oxygen being reduced to below 5×10^-5. The design concept and refining mechanism of the driving forces, including active metal, hydrogen plasma and dissolved active hydrogen atoms in rare-earth metal, were discussed systematically in this paper. The refining principle and migration mechanism of oxygen impurities were also discussed by combined experimental and calculated studies. The FAST-2D combined Stefan simulating method, ¹⁸O₂ isotope tracking method and CALPHAD method were used to study the purification mechanism. The study results provide theoretical basis for the removal of oxygen impurities in rare-earth metals. The methods demonstrated here may provide insight on the future research in rare-earth purification.
- rare earth /
- high purification /
- oxygen content /
- calculation /
- mechanism

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參考文獻(25)

[1]	Yamada Y, Miura M, Tajima K, et al. Film thickness change of switchable mirrors using Mg3Y alloy thin films due to hydrogenation and dehydrogenation.Solar Energy Mater Solar Cells, 2014, 126:237
[2]	Ngene P, Radeva T, Slaman M, et al.Seeing hydrogen in colors:low-cost and highly sensitive eye readable hydrogen detectors. Adv Funct Mater, 2014, 24(16):2374
[3]	Kalisvaart W P, Niessen R A H, Notten P H L. Electrochemical hydrogen storage in MgSc alloys:a comparative study between thin films and bulk materials.J Alloys Compd, 2006, 417(1-2):280
[4]	Chen J, Fu J, Fu K, et al. Combining catalysis and hydrogen storage in direct borohydride fuel cells:towards more efficient energy utilization.J Mater Chem A, 2017, 5:14310
[6]	Zhang H W, Zheng X Y, Wang T, et al.Significantly improved hydrogen desorption property of La₂Mg₁₇ alloy modified with Ni-Al nanocrystalline. Intermetallics, 2016, 70:29
[7]	Zheng Z G, Zhong X C, Su K P, et al. Magnetic properties and large magnetocaloric effects in amorphous Gd-Al-Fe alloys for magnetic refrigeration.Sci China Phys Mech Astron, 2011, 54(7):1267
[8]	Xu Z Y, Hui X, Wang E R, et al.Gd-Dy-Al-Co bulk metallic glasses with large magnetic entropy change and refrigeration capacity. J Alloys Compd, 2010, 504(Suppl 1):S146
[9]	Hirota K, Okabe T H, Saito F, et al. Electrochemical deoxidation of RE-O (RE=Gd, Tb, Dy, Er) solid solutions.J Alloys Compd, 1999, 282(1-2):101
[10]	Okabe T H, Hirota K, Kasai E, et al. Thermodynamic properties of oxygen in RE-O (RE=Gd, Tb, Dy, Er) solid solutions.J Alloys Compd, 1998, 279(2):184
[11]	Barin I.Thermochemical Data of Pure Substances. 3th Ed. Basel:VCH, Weinheim, 1993
[12]	Okabe T H, Deura T N, Oishi T, et al.Electrochemical deoxidation of yttrium-oxygen solid solutions. J Alloys Compd, 1996, 237(1-2):150
[13]	Okabe T H, Deura T N, Oishi T, et al.Thermodynamic properties of oxygen in yttrium-oxygen solid solutions. Metall Mater Trans B, 1996, 27(5):841
[14]	Volkov V T, Ionov A M, Nikiforova T V. Ultrapurification of yttrium metal from oxide to single crystal:results and perspectives.Vacuum, 1999, 53(1-2):105
[15]	Lee C K, Park J S, Yeon S H, et al. Modeling of solid-state electrotransport for purification of gadolinium.Met Mater Int, 2001, 7(4):343
[16]	Mimura K, Kornukai T, Isshiki M. Purification of chromium by hydrogen plasma-arc zone melting.Mater Sci Eng A, 2005, 403(1-2):11
[17]	Isshiki M. Purification of rare earth metals.Vacuum, 1996, 47(6-8):885
[18]	Li G L, Li L, Miao R Y, et al. Research on the removal of impurity elements during ultra-high purification process of terbium.Vacuum, 2016, 125:21
[19]	Li G L, Li L, Yang C, et al.Removal of gaseous impurities from terbium by hydrogen plasma arc melting. Int J Hydrogen Energy, 2015, 40(25):7943
[21]	Li G L, Guo H, Li L, et al. Purification of terbium by means of argon and hydrogen plasma arc melting. J Alloys Compd, 2016, 659:1
[22]	Li G L, Li L, Fu K, et al. Hydrogen in-situ refining method for preparing high purity gadolinium. J Alloys Compd, 2015, 648:29
[23]	Li G L, Li L, Hao J L, et al.Investigation of oxygen diffusion behavior in terbium using O-18(2) isotopic tracking by high resolution SIMS. Mater Lett, 2016, 176:253
[24]	Fu K, Li G L, Li J G, et al. Study on the thermodynamics of the gadolinium-hydrogen binary system (H/Gd=0.0-2.0) and implications to metallic gadolinium purification. J Alloys Compd, 2016, 673:131
[25]	Fu K, Li G L, Li J G, et al.Experimental study and thermodynamic assessment of the dysprosium-hydrogen binary system. J Alloys Compd, 2017, 696:60
[26]	Tian F, Li G L, Li L, et al.Advance in solid-state purification technology for metals. J Alloys Compd, 2014, 592:176
[27]	Li L, Li G L, Xu L, et al.A new process of manufacturing "oxygen-free" Gd. Rare Met Mater Eng, 2016, 45(10):2509