·1308. 工程科学学报，第40卷，第11期 于稀土金属高纯化研究，可以成功实现超低氧含量 of RE-O RE =Gd,Tb,Dy,Er)solid solutions.J Alloys Compd, 稀土金属的制备.最优工艺条件可以将稀土金属的 1999,282(1-2):101 气态杂质质量分数限制在5×10-以下 [10]Okabe T H,Hirota K,Kasai E,et al.Thermodynamic properties of oxygen in RE-O (RE Gd,Tb,Dy,Er)solid solutions.JAl (2)102示踪同位素标记技术表明金属的表面 loys Compd,1998,279(2):184 氧化层并不能阻碍氧在稀土金属中的迁移，因此活 [11]Barin I.Thermochemical Data of Pure Substances.3th Ed.Basel 性金属除气法过程中，氧杂质可以从稀土金属内部 VCH,Weinheim,1993 [12]Okabe T H,Deura T N,Oishi T,et al.Electrochemical deoxida- 顺利到迁移表面，并进一步扩散到表面的活性金属 tion of yttrium-oxygen solid solutions.J Alloys Compd,1996, 镀层中，达到除氧效果 237(1-2):150 (3)氢等离子体电弧产生的特殊温度梯度除了 [13]Okabe T H,Deura T N,Oishi T,et al.Thermodynamic proper- 熔融金属样品，破坏表层氧化膜，还能导致熔体内的 ties of oxygen in yttrium-oxygen solid solutions.Metall Mater 液相对流.这种流体场不断将金属内部的氧杂质携 Trans B,1996,27(5):841 [14]Volkov V T,lonov A M,Nikiforova T V.Ultrapurification of yt- 带至气液相界层，与冲击表面的强还原性氢等离子 trium metal from oxide to single crystal:results and perspectives. 体反应，实现氧杂质的高效脱除 Vacm,1999,53(1-2):105 (4)CALPHAD相图数据库表明，当活性固溶氢 [15]Lee C K,Park J S,Yeon S H,et al.Modeling of solid-state 原子除氧反应的吉布斯自由能为负，将普通氢气还 electrotransport for purification of gadolinium.Met Mater Int, 2001,7(4):343 原的热力学禁阻状态改变为活性固溶氢原子还原的 [16]Mimura K,Kornukai T,Isshiki M.Purification of chromium by 热力学可行状态.由于吉布斯自由能的变化.提纯 hydrogen plasma-are zone melting.Mater Sci Eng A,2005,403 工艺中采用大于8×10-4的固溶氢质量分数会取得 (1-2):11 更佳的提纯效果，这一预测与实验结果一致 [17]Isshiki M.Purification of rare earth metals.Vacuum,1996,47 (6-8):885 参考文献 [18]Li G L,Li L,Miao R Y,et al.Research on the removal of im- [1]Yamada Y,Miura M,Tajima K,et al.Film thickness change of purity elements during ultra-high purification process of terbium. switchable mirrors using Mg3Y alloy thin films due to hydrogena- Vacuum,2016,125:21 tion and dehydrogenation.Solar Energy Mater Solar Cells,2014, [19]Li G L,Li L,Yang C,et al.Removal of gaseous impurities from 126:237 terbium by hydrogen plasma arc melting.Int J Hydrogen Energy, [2]Ngene P.Radeva T.Slaman M,et al.Seeing hydrogen in colors: 2015,40(25):7943 low-cost and highly sensitive eye readable hydrogen detectors.Ad [20]Li G L,Tian F,Li L,et al.Application of hydrogen plasma arc Funct Mater,2014,24(16):2374 melting technique on refining refractory metals.Rare Met Mater [3]Kalisvaart W P,Niessen R A H,Notten P H L.Electrochemical Eng,2015,44(3):775 hydrogen storage in MgSe alloys:a comparative study between thin (李国玲，田丰，李里，等.氢等离子体电弧熔炼技术在难熔金 films and bulk materials.J Alloys Compd,2006,417(1-2):280 属提纯中的应用.稀有金属材料与工程，2015,44(3)：75) [4]Chen J,Fu J,Fu K,et al.Combining catalysis and hydrogen [21]Li G L,Guo H,Li L,et al.Purification of terbium by means of storage in direct borohydride fuel cells:towards more efficient en- argon and hydrogen plasma arc melting.J Alloys Compd,2016 ergy utilization.J Mater Chem A,2017,5:14310 659:1 [5]Zhang H W,Zheng X Y,Liu Y,et al.Application and develop- [22]Li G L,Li L,Fu K,et al.Hydrogen in-situ refining method for pre- ment of rare earth-based hydrogen storage materials.J Chin Soc paring high purity gadolinium.J Alloys Compd,2015,648:29 Rare Earths,2016,34(1):1 [23]Li G L,Li L,Hao J L,et al.Investigation of oxygen diffusion be- (张怀伟，郑鑫遥，刘洋，等.稀土元素在储氢材料中的应用 havior in terbium using 0-18(2)isotopic tracking by high resolu- 进展.中国稀土学报，2016,34(1)：1) tion SIMS.Mater Lett,2016,176:253 [6]Zhang H W,Zheng X Y,Wang T,et al.Significantly improved [24]Fu K,Li G L,Li J G,et al.Study on the thermodynamics of the hydrogen desorption property of La2 Mg alloy modified with Ni-Al gadolinium-hydrogen binary system H/Gd =0.0-2.0)and im- nanocrystalline.Intermetallics,2016,70:29 plications to metallic gadolinium purification.J Alloys Compd [7]Zheng Z G.Zhong X C.Su K P,et al.Magnetic properties and 2016,673:131 large magnetocaloric effects in amorphous Gd-Al-Fe alloys for [25]Fu K,Li G L,Li J G,et al.Experimental study and thermody- magnetic refrigeration.Sci China Phys Mech Astron,2011,54 namic assessment of the dysprosium-hydrogen binary system. (7):1267 Alloys Compd,2017,696:60 [8]Xu Z Y,Hui X,Wang E R,et al.Gd-Dy-Al-Co bulk metallic [26]Tian F,Li G L,Li L,et al.Advance in solid-state purification glasses with large magnetic entropy change and refrigeration capac- technology for metals.J Alloys Compd,2014,592:176 ity.J Alloys Compd,2010,504(Suppl 1):S146 [27]Li L,Li G L,Xu L,et al.A new process of manufacturing "oxy- [9]Hirota K,Okabe T H,Saito F,et al.Electrochemical deoxidation gen-free"Gd.Rare Met Mater Eng,2016,45(10):2509工程科学学报,第 40 卷,第 11 期 于稀土金属高纯化研究,可以成功实现超低氧含量 稀土金属的制备. 最优工艺条件可以将稀土金属的 气态杂质质量分数限制在 5 伊 10 - 5以下. (2) 18O2 示踪同位素标记技术表明金属的表面 氧化层并不能阻碍氧在稀土金属中的迁移,因此活 性金属除气法过程中,氧杂质可以从稀土金属内部 顺利到迁移表面,并进一步扩散到表面的活性金属 镀层中,达到除氧效果. (3)氢等离子体电弧产生的特殊温度梯度除了 熔融金属样品,破坏表层氧化膜,还能导致熔体内的 液相对流. 这种流体场不断将金属内部的氧杂质携 带至气液相界层,与冲击表面的强还原性氢等离子 体反应,实现氧杂质的高效脱除. (4)CALPHAD 相图数据库表明,当活性固溶氢 原子除氧反应的吉布斯自由能为负,将普通氢气还 原的热力学禁阻状态改变为活性固溶氢原子还原的 热力学可行状态. 由于吉布斯自由能的变化. 提纯 工艺中采用大于 8 伊 10 - 4的固溶氢质量分数会取得 更佳的提纯效果,这一预测与实验结果一致. 参 考 文 献 [1] Yamada Y, Miura M, Tajima K, et al. 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J Alloys Compd, 2016, 673: 131 [25] Fu K, Li G L, Li J G, et al. Experimental study and thermody鄄 namic assessment of the dysprosium鄄hydrogen binary system. J Alloys Compd, 2017, 696: 60 [26] Tian F, Li G L, Li L, et al. Advance in solid鄄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 “oxy鄄 gen鄄free冶 Gd. Rare Met Mater Eng, 2016, 45(10): 2509 ·1308·