熔盐电解法制备铝钪中间合金研究进展
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摘要
在铝合金中加入微量钪,能显著提高铝合金的强度、硬度以及焊接性能。铝钪合金有望成为新一代的航天、航空、舰船工业用轻质结构材料。钪的熔点为1 541℃,与铝的熔点(660℃)相差太大,因此钪必须以中间合金的形式加入到铝合金中。本文总结了铝钪中间合金的制备方法,整理分析了对掺法、金属热还原法、熔盐电解法的特点,分析了金属热还原法制备铝钪中间合金的热力学,重点综述了熔盐电解法制备铝钪中间合金的研究进展,并展望了铝钪中间合金的研究发展方向。
It can significantly improve the strength,hardness and welding performance of aluminum alloy by adding trace amounts of scandium in aluminum alloy.Al-Sc alloy is expected to be a new generation of lightweight structural materials for aerospace,aviation and naval industry.The melting point of scandium is 1541℃,which is much higher than that of the aluminum(660℃).Thus,scandium must be added to the aluminum alloy in the form of an intermediate alloy.The preparation method of Al-Sc master alloy is summarized,the characteristics of the direct mixing,metallothermic reduction and molten salt electrolytic methods are sorted out and analyzed.The thermodynamic of Al-Sc master alloy prepared by metallothermic reduction is analysed.The research progress in the molten salt electrolysis preparation of the Al-Sc master alloy is reviewed and the prospects of the related research works are discussed.
It can significantly improve the strength,hardness and welding performance of aluminum alloy by adding trace amounts of scandium in aluminum alloy.Al-Sc alloy is expected to be a new generation of lightweight structural materials for aerospace,aviation and naval industry.The melting point of scandium is 1541℃,which is much higher than that of the aluminum(660℃).Thus,scandium must be added to the aluminum alloy in the form of an intermediate alloy.The preparation method of Al-Sc master alloy is summarized,the characteristics of the direct mixing,metallothermic reduction and molten salt electrolytic methods are sorted out and analyzed.The thermodynamic of Al-Sc master alloy prepared by metallothermic reduction is analysed.The research progress in the molten salt electrolysis preparation of the Al-Sc master alloy is reviewed and the prospects of the related research works are discussed.
引文
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31 Liu Q,Xue J,Zhu J,et al.Preparing aluminium-scandium inter-alloys during reduction process in KF-AlF3-Sc2O3 melts[J].Light Metals,2012:685.
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37 Zaikov Y,Tkacheva O,Suzdaltsev A,et al.Lab Scale synthesis of Al-Sc Alloys in NaF-AlF3-Al2O3-Sc2O3 Melt[J].Advanced Materials Research,2015,1088:213.
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2 Harrell T J,Topping T D,Wen H,et al.Microstructure and strengthening mechanisms in an ultrafine grained Al-Mg-Sc alloy produced by powder metallurgy[J].Metallurgical and Materials Transactions A,2014,45(13):6239.
3 Asta M,Ozolins V.Structural,vibrational,and thermodynamic properties of Al-Sc alloys and intermetallic compounds[J].Physical Review B,2001,64(9):115.
4 Fujii H,Akiyama H,Kaneko J,et al.Al-Sc master alloy prepared by mechanical alloying of aluminum with addition of Sc2O3[J].Materials Transactions,2005,44(5):1049.
5 Liao X J,Xie H W,Zhai Y C.Progress in research of preparation processes and prospect of Al-Sc master alloy compounds[J].Materials Review,2009,23(z1):443(in Chinese).廖先杰,谢宏伟,翟玉春.Al-Sc中间合金生产研发现状及展望[J].材料导报,2009,23(z1):443.
6 林河成.铝钪合金材料的发展现状及前景[J].稀土,2010,31(3):97.
7 Huang Y F,Dang J Z.The present situation and the development prospect of aluminum ally with scandium contained[J].Heavy Casting and Forging,2006(4):45(in Chinese).黄玉凤,党惊知.含钪铝合金的现状与开发前景[J].大型铸锻件,2006(4):45.
8 孙全喜,黄瑞芬.新型含钪铝合金的应用研究与发展前景[J].内蒙古科技与经济,2007(10):107.
9 Jiang F,Yin Z M,Li H G.Preparation methods of scandium-bearing master alloy[J].Chinese Rare Earths,2001,22(1):41(in Chinese).姜锋,尹志民,李汉广.铝钪中间合金的制备方法[J].稀土,2001,22(1):41.
10 尹志民,潘清林,姜锋.钪和含钪合金[M].长沙:中南大学出版社,2007.
11 Harata M,Nakamura T,Yakushiji H,et al.Production of scandium and Al-Sc alloy by metallothermic reduction[J].Mineral Processing and Extractive Metallurgy,2008,117(2):95.
12 Liu Q C,Xue J L,Zhu J.Study on aluminum thermos-reduction in K3AlF6-Sc2O3system[J].Nonferrous Metals(Extractive Metallurgy),2013(3):24(in Chinese).刘翘楚,薛济来,朱骏.钾冰晶石-氧化钪体系中铝热还原反应过程的研究[J].有色金属(冶炼部分),2013(3):24.
13 Gan P Y,He H J,Xie Y B,et al.Preparation of Al-Sc master alloy by aluminothermic reduction of Sc2O3in NaF-NaCl-KCl-ScF3molten salt system[J].Rare Metals and Cemented Carbides,2016,44(6):49(in Chinese).甘培原,何航军,谢营邦,等.NaF-NaCl-KCl-ScF3熔盐体系中铝热还原Sc2O3制备Al-Sc中间合金[J].稀有金属与硬质合金,2016,44(6):49.
14 Gan P Y,Zhang J F,Liu D M,et al.Preparation of Al-Sc alloys by aluminum thermite reaction in NaF-NaCl-KCl melt[J].Chinese Rare Earths,2017,38(1):49(in Chinese).甘培原,张建飞,刘东梅,等.NaF-NaCl-KCl熔盐体系中铝热还原法制备Al-Sc合金[J].稀土,2017,38(1):49.
15 Lu G M,Liu X S.Preparation of Al-Sc master alloy by alumionthermy in nNaF·AlF3 molten salt[J].The Chinese Journal of Nonferrous Metals,1999,9(1):171(in Chinese).路贵民,刘学山.冰晶石熔体中Al热还原法制备Al-Sc合金[J].中国有色金属学报,1999,9(1):171.
16 Yang Q S,Chen J J,Chen W P.Preparation of Al-Sc intermediate alloy by alumino-thermic reduction of Sc2O3[J].Rare Metals and Cemented Carbides,2007,35(2):5(in Chinese).杨庆山,陈建军,陈卫平.铝热还原Sc2O3制备Al-Sc中间合金[J].稀有金属与硬质合金,2007,35(2):5.
17 Tang C C,Chang H Q,Bao X G,et al.Preparation of Al-Sc intermediate alloy by alumino-thermic reduction of Sc2O3[J].Journal of the Chinese Rare Earth Society,2012,30(6):680(in Chinese).唐冲冲,常化强,包晓刚,等.铝锶热还原Sc2O3制备铝钪中间合金[J].中国稀土学报,2012,30(6):680.
18 Lu G,Liu X.Dissolution of Sc2O3in fluoride molten salt[J].The Chinese Journal of Nonferrous Metals,1999,9(3):624(in Chinese).路贵民,刘学山.氧化钪在nNaF·AlF3-ScF3熔盐体系中的溶解[J].中国有色金属学报,1999,9(3):624.
19 Lu Q T,Ni F S,Chen Y C.Advance in application of scandium and its extractive metallurgy[J].Shanghai Nonferrous Metals,1995,16(3):160(in Chinese).陆庆桃,倪福生,陈寅初.钪的应用及其提取冶金的进展[J].上海有色金属,1995,16(3):160.
20 Guo T,Wang S,Ye X,et al.Research progress in the preparation of rare earth alloys by molten salt electrolysis method[J].Scientia Sinica(Chimica),2012,42(9):1328(in Chinese).郭探,王世栋,叶秀深,等.熔盐电解法制备稀土合金研究进展[J].中国科学:化学,2012,42(9):1328.
21 Liu Q,Xue J,Zhu J,et al.Processing Al-Sc alloys at liquid aluminum cathode in KF-AlF3 molten salt[J].ECS Transactions,2013,50(11):483.
22 Castrillejo Y,Hernández P,Rodriguez J A,et al.Electrochemistry of scandium in the eutectic LiCl-KCl[J].Electrochimica Acta,2012,71:166.
23 Castrillejo Y,Vega A,Vega M,et al.Electrochemical formation of Sc-Al intermetallic compounds in the eutectic LiCl-KCl.Determination of thermodynamic properties[J].Electrochimica Acta,2014,118:58.
24 Tian Y,Sun B,Zhai Y.Preparation of Al-Sc alloy in chloride system with molten salt electrolysis[J].Transactions of Nonferrous Metals Society of China,1998,8(4):626.
25 Teng G C,Zhai X J,Li J F,et al.Study on preparation of Al-Sc alloys by molten electrolysis[J].Non-Ferrous Mining and Metallurgy,2009,25(1):26(in Chinese).縢国春,翟秀静,李俊福,等.铝钪合金的熔盐电解法制备研究[J].有色矿冶,2009,25(1):26.
26 Harata M,Yasuda K,Yakushiji H,et al.Electrochemical production of Al-Sc alloy in CaCl2-Sc2O3 molten salt[J].Journal of Alloys and Compounds,2009,474:124.
27 Han Y U,Koh J W,Lee B P,et al.The dissolution mechanism of Sc2O3in CaO-CaCl2flux for the calciothermic production of Al-Sc alloy[J].Journal of Alloys and Compounds,2016,658:595.
28 Chen T,Lv Z J,Zhai X J,et al.Preparation of Al-Sc alloys investigated in the systems of CaCl2-LiF[J].Journal of Materials and Metallurgy,2010,9(1):39(in Chinese).程涛,吕子剑,翟秀静,等.CaCl2-LiF体系制备铝钪合金[J].材料与冶金学报,2010,9(1):39.
29 Liao X,Xie H,Zhai Y,et al.Preparation of Al3Sc intermetallic compound by FFC method[J].Journal of Materials Science and Technology,2009,25(5):717.
30 Shtefanyuk Y,Mann V,Pingin V,et al.Production of Al-Sc alloy by electrolysis of cryolite-scandium oxide melts[J].Light Metals,2015:589.
31 Liu Q,Xue J,Zhu J,et al.Preparing aluminium-scandium inter-alloys during reduction process in KF-AlF3-Sc2O3 melts[J].Light Metals,2012:685.
32 Guo R,Cao W L,Zhai X J,et al.Al-Sc alloys prepared by molten salt electrolysis the physical and chemical properties research[J].Non-Ferrous Mining and Metallurgy,2008,24(6):40(in Chinese).郭瑞,曹文亮,翟秀静,等.电解法制备铝钪合金的物理化学性质研究[J].有色矿冶,2008,24(6):40.
33 Sun B L,Zhai Y C,Tian Y W.Preparation of Al-Sc alloy in fluoride molten salts with molten salt electrolysis[J].Chinese Journal of Rare Metals,1998,22(3):191(in Chinese).孙本良,翟玉春,田彦文.氟盐体系中电解制取铝钪合金的研究[J].稀有金属,1998,22(3):191.
34 Guo R,Cao W L,Zhai X J,et al.Preparation of Al-Sc application alloys by molten salt electrolysis method[J].Chinese Journal of Rare Metals,2008,32(5):645(in Chinese).郭瑞,曹文亮,翟秀静,等.熔盐电解法制备Al-Sc应用合金的工艺研究[J].稀有金属,2008,32(5):645.
35 Yang S.The research on direct electrolytic Al-Sc alloys in molten salt[D].Zhengzhou:Zhengzhou University,2003(in Chinese).杨昇.电解法生产铝钪合金的研究[D].郑州:郑州大学,2003.
36 Yang S,Li Q,Gu S.Solubility of Sc2O3in nNaF·AlF3-Al2O3melts[J].Chinese Journal of Rare Metals,2003,27(3):418.杨昇,李强,顾松青.氧化钪在冰晶石氧化铝体系中的溶解性能研究[J].稀有金属,2003,27(3):418.
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