钕铁硼永磁体室温熔盐电镀铝研究
摘要
钕铁硼稀土永磁材料是80年代初发展起来的第三代稀土永磁材料，它具有优异的磁性能，较高的性价比，并且资源储备丰富，一经问世，在短短几年时间内，迅速进入工业化生产，并很快渗透到各个工业领域。但由于稀土元素钕性质非常活泼，导致钕铁硼永磁体的耐蚀性能很差。因此，如何提高钕铁硼永磁体的表面防护质量是其产品总体质量与性能长期稳定的关键。
本文以提高钕铁硼稀土永磁材料的表面防护质量为目的，合成了一种AlCl_3—MEIC室温熔盐电解质，利用这种熔盐电解质，开展了钕铁硼稀土永磁材料电沉积铝的电镀工艺研究，在国内，首次在钕铁硼永磁材料表面电沉积出了一层附着力较好，耐蚀性能优良的高纯铝镀层。并在此基础上，提出了一种完全无水的镀前处理工艺，为以后的产业化实验打下了坚实的基础。
本文的研究成果体现在以下方面：
(1)根据实验的需要，设计并制作了真空手套箱。
(2)应用正交实验法确定了合成1—甲基—3—乙基氯化咪唑(MEIC)这种有机盐的最佳反应条件，并成功地合成了这种有机盐。
(3)将无水AlCl_3和MEIC混合，制备出了性质独特的AlCl_3—MEIC室温熔盐电解质，在配制过程中，对控制体系温度的方法，去除重金属杂质和水分的方法作了详细阐述。
(4)研究了AlCl_3和MEIC的摩尔比、芳香化合物及除水剂对室温熔盐电镀的影响，制备了AlCl_3-MEIC室温熔盐电沉积铝溶液，并从该溶液中电镀出了具有银白色金属光泽、致密光滑的铝镀层。
(5)利用室温熔盐电解质作活化液对钕铁硼磁体进行电活化处理，可以提高基体和镀层的结合力，并提出如F电镀工艺流程：
烘烤除油→喷砂除锈→干燥→电活化→电镀→溶剂洗→水洗→干燥
NdFeB permanent magnetic material is the third generation of rare earth magnetic material developed at the beginning of the eighties, it can have excellent magnetic performance, higher performance -cost ratio and abundant resources reserve. Since it was discoveried, NdFeB magnetic material have been produced rapidly within a short period , and permeate through each industrial field quickly. But because of the Nd element is vivaciously active, the anti-corrosion performance of NdFeB permanent magnet is very bad. So how to improve surface protection of NdFeB magnet is the key of improving product quality and long steady of performance.
The text is to improve surface protection of NdFeB magnetic material as the purpose of this text, a kind of AlCla-MEIC room temperature molten salt electrolyte is synthesized, the craft of electroplating of the aluminium is studied. At home , layer of pure aluminium is deposited on surface of NdFeB magnet for the first time, and it has better adhesive force and excellent anti-corrosion. And on this basis, the craft of pretreatement anhydrously was study , which have laid a solid foundation for the experiment of industrialization on the future.
Main innovations and results are described as below:
(1) According to the needs of experiment, the glove case of vacuum is designed and made.
(2) AlCl3-MEIC was prepared by reacting 1-methylimidazolium and ethyl chloride ,and the best situation of synthesis was confirmed.
(3) Ambient temperature chloraluminate ionic liquids are formed from mixture ofl- methyl-3-ethylimidazolium chloride and aluminum chloride,in the course mix,method of controlling system temperature and removing impuritys such as heavy metal and water was provided.
(4) By studying the effects of mole rate of AlCl3-MEIC and fragrant chemical compound and dewater agent, electroplating aluminium bath of AlCl3-MEIC room temperature melt salt was prepared, and silvery white metallic luster , pre-pressing smooth aluminium layer is electroplated on NdFeB magnet from this solution.
(5) In electroplating aluminum on NdFeB magnet with use of AlCl3-MEIC room temperature melt salt bath,said magnet is activated to improve deposit adhesion by carrying out.before plating,electrolysis on said magnet.and plating process was described as below:
Toasting and degreasing ?Sand blasting Drying Electricity activating
?ElectroplatingSolvent washing Water washing Drying
本文以提高钕铁硼稀土永磁材料的表面防护质量为目的，合成了一种AlCl_3—MEIC室温熔盐电解质，利用这种熔盐电解质，开展了钕铁硼稀土永磁材料电沉积铝的电镀工艺研究，在国内，首次在钕铁硼永磁材料表面电沉积出了一层附着力较好，耐蚀性能优良的高纯铝镀层。并在此基础上，提出了一种完全无水的镀前处理工艺，为以后的产业化实验打下了坚实的基础。
本文的研究成果体现在以下方面：
(1)根据实验的需要，设计并制作了真空手套箱。
(2)应用正交实验法确定了合成1—甲基—3—乙基氯化咪唑(MEIC)这种有机盐的最佳反应条件，并成功地合成了这种有机盐。
(3)将无水AlCl_3和MEIC混合，制备出了性质独特的AlCl_3—MEIC室温熔盐电解质，在配制过程中，对控制体系温度的方法，去除重金属杂质和水分的方法作了详细阐述。
(4)研究了AlCl_3和MEIC的摩尔比、芳香化合物及除水剂对室温熔盐电镀的影响，制备了AlCl_3-MEIC室温熔盐电沉积铝溶液，并从该溶液中电镀出了具有银白色金属光泽、致密光滑的铝镀层。
(5)利用室温熔盐电解质作活化液对钕铁硼磁体进行电活化处理，可以提高基体和镀层的结合力，并提出如F电镀工艺流程：
烘烤除油→喷砂除锈→干燥→电活化→电镀→溶剂洗→水洗→干燥
NdFeB permanent magnetic material is the third generation of rare earth magnetic material developed at the beginning of the eighties, it can have excellent magnetic performance, higher performance -cost ratio and abundant resources reserve. Since it was discoveried, NdFeB magnetic material have been produced rapidly within a short period , and permeate through each industrial field quickly. But because of the Nd element is vivaciously active, the anti-corrosion performance of NdFeB permanent magnet is very bad. So how to improve surface protection of NdFeB magnet is the key of improving product quality and long steady of performance.
The text is to improve surface protection of NdFeB magnetic material as the purpose of this text, a kind of AlCla-MEIC room temperature molten salt electrolyte is synthesized, the craft of electroplating of the aluminium is studied. At home , layer of pure aluminium is deposited on surface of NdFeB magnet for the first time, and it has better adhesive force and excellent anti-corrosion. And on this basis, the craft of pretreatement anhydrously was study , which have laid a solid foundation for the experiment of industrialization on the future.
Main innovations and results are described as below:
(1) According to the needs of experiment, the glove case of vacuum is designed and made.
(2) AlCl3-MEIC was prepared by reacting 1-methylimidazolium and ethyl chloride ,and the best situation of synthesis was confirmed.
(3) Ambient temperature chloraluminate ionic liquids are formed from mixture ofl- methyl-3-ethylimidazolium chloride and aluminum chloride,in the course mix,method of controlling system temperature and removing impuritys such as heavy metal and water was provided.
(4) By studying the effects of mole rate of AlCl3-MEIC and fragrant chemical compound and dewater agent, electroplating aluminium bath of AlCl3-MEIC room temperature melt salt was prepared, and silvery white metallic luster , pre-pressing smooth aluminium layer is electroplated on NdFeB magnet from this solution.
(5) In electroplating aluminum on NdFeB magnet with use of AlCl3-MEIC room temperature melt salt bath,said magnet is activated to improve deposit adhesion by carrying out.before plating,electrolysis on said magnet.and plating process was described as below:
Toasting and degreasing ?Sand blasting Drying Electricity activating
?ElectroplatingSolvent washing Water washing Drying
引文
[1]杨遇春 稀土漫谈化学工业出版社 北京 1999 94
[2]耿文范 神奇的现代新材料 兵器工业出版社 北京 1991 30
[3]周向阳 李庆余 NdFeB永磁体电镀新工艺 电镀与环保 2000(1)：16
[4]周寿增 稀土永磁材料及其应用 北京 冶金工业出版社 1990 1～5
[5]张世崇 钕铁硼合金滚镀锌、镍工艺 电镀与精饰 1997(1)：37
[6]谢锐兵 张立茗 钕铁硼材料电镀镍技术研究 技术鉴定资料 1997
[7]Steyaert S. Le Breton J. M. TeilletJ. J. physD: Appl phys1998 31:1534-1547
[8]Kim AS. CampFE. J Appl phys, 1996.79(8):5035～5039
[9]特开昭 63—110708
[10]M. GALOVA. Electrodeposition of Aluminium from Orgnic Aprotic Solvents Surface and Coating Technology 34 (1988) 358～359
[11]D. E. couch and A. Brenner. J. Electrochem. soc 99(1952)2321
[12]U S patent 2651608(1953) to A. Brenner and D. E couch
[13]Yoshio I et al. Electrochimica Acta 1972. (17):1343
[14]岱如 电镀铝 腐蚀与防护 1998(2)：147
[15]Capuano GA. J. Electrochem. Soc (2) :484
[16]曾华梁等 电镀工艺手册 北京 机械工业出版社 2002第二版 689～690
[17]Peled E. Gileadi E.J. Electrochem. Soc. 1976.123:15
[18]Roggendorf W. Galvanotechnik 1965. (56):158
[19]Fendia RJ et a] U S Patent 4894125.1990
[20]Corilium Corp U S .3414492.1968
[21]Grips VKW et al U S. 5019223 1991
[22]Hurley F H. Wier. TP.J. Electrochem. soc1951(98):203
[23]Robsinson J. Osteryoung J.A.J. Am. Chem. Soc 1997(102): 323
[24]WilkesJ. S. LecviskyJA. Wilson RA.Hussey cl. Inorg. Chem. 1982.21: 1263
[25]Johns. WilkesandMichael. hirandwater Stable 1-Ethyl-3-methylim
idazolium Based Ionic liquids J. Chem. Soc. 1992.965～967
[26]Carmichael AJ. Hardaere C. Holbery JD. Structure and Bonding in Ionic Liquids .Extended Abstracts of the 196th Meeting of the Electrochemical Society. Inc. Hawaii U.S.A. Oct 17-22.1999. No 2259
[27]杨绮琴 方北龙 常温熔盐体系 化学通报 1993(5)：17
[28]R.J. Gale. B.G. Ibert and R.A. osteryoung. Inorg. Chem. 17(1979)2728
[29]J. cyvin. P. klaobe. E. RyterangH. A. oye. J. chem. phys. 52(1970)2776
[30]E. Rytter and H.A. oye. J. Inorg Nucl. chem. lett. 35(1973)1185
[31]L.G. Boxal. H.L. Jones and R.A. osteryoung. J. Electrochem. soc. 1973 120.223
[32]Z.J. Karpinski and R.A. osteryoung. Inorg. chem. 1985.24.2259
[33]R.J. Carlin and R.A. osteryoung. J. Electrochem. soc. 1989. (136) 1409
[34]周少雄 2003年国际稀土永磁材料产业发展论坛
[35]Thomas Welton. Cbem. Rev[J].1999.99:2071-2083
[36]Jairton Dupont. Crestina S. Consorti and John Spener. J. Braz. soc [J] 2000. 11(4):337-344
[37]李述文 范如霖编译 实用有机化学手册 上海科学技术出版社 1981
[38]中国现场统计研究会三次设计组编著 正交法和三次设计 科学出版社 1985
[39]李德和 李长太编译 实验有机化学 山东科学技术出版社 1980
[40]J. Robison and R.A. osteryoung. An Electrochemical and SpectroscoPic Study of some Aromatic Hydrocarbons in the Room Temperature Molten Salt System Aluminium Chloride-n-butylpyridinium Chloride. J. American Chemical Society 1997(4):323
[41]Xiao-Hong Xu and Charles L. Hussey. The Electrochemstry of Mercury at Glassy Carbon and Tungsten Electrodes in the Aluminium Chloridel-Methyl-3-Ethylimidazolium Chloride Molten Salt. J. ElectrochemSoc. Vol. 140. No. 5. May. 1993
[42]Takahashi et al Electrochemistry 54. (3):257
[43]Shoichrio Mori. Kazuhikolda.U S. Patent 5135825 1992
[44]徐寿昌 有机化学 高等教育出版社 第二版
[45]上海轻工业专科学校 电镀原理 上海科技出版社 1982
[46]黄子勋 吴纯素 电镀原理 中国农业机械出版社 1982
[47]Kawahara et al U S Patent 5543522 1996
[48]李青 熔融盐电沉积金属及合金 电镀与精饰 1998(2)：26
[49]方景礼 多元络和物电镀 国防工业出版社 1983
[50]全国金属与非金属覆盖层标准化技术委员会编著 覆盖层标准应用手册(上) 中国标准出版社 1999
[51]卢燕平 金属表面防蚀处理 冶金工业出版社 1995
[2]耿文范 神奇的现代新材料 兵器工业出版社 北京 1991 30
[3]周向阳 李庆余 NdFeB永磁体电镀新工艺 电镀与环保 2000(1)：16
[4]周寿增 稀土永磁材料及其应用 北京 冶金工业出版社 1990 1～5
[5]张世崇 钕铁硼合金滚镀锌、镍工艺 电镀与精饰 1997(1)：37
[6]谢锐兵 张立茗 钕铁硼材料电镀镍技术研究 技术鉴定资料 1997
[7]Steyaert S. Le Breton J. M. TeilletJ. J. physD: Appl phys1998 31:1534-1547
[8]Kim AS. CampFE. J Appl phys, 1996.79(8):5035～5039
[9]特开昭 63—110708
[10]M. GALOVA. Electrodeposition of Aluminium from Orgnic Aprotic Solvents Surface and Coating Technology 34 (1988) 358～359
[11]D. E. couch and A. Brenner. J. Electrochem. soc 99(1952)2321
[12]U S patent 2651608(1953) to A. Brenner and D. E couch
[13]Yoshio I et al. Electrochimica Acta 1972. (17):1343
[14]岱如 电镀铝 腐蚀与防护 1998(2)：147
[15]Capuano GA. J. Electrochem. Soc (2) :484
[16]曾华梁等 电镀工艺手册 北京 机械工业出版社 2002第二版 689～690
[17]Peled E. Gileadi E.J. Electrochem. Soc. 1976.123:15
[18]Roggendorf W. Galvanotechnik 1965. (56):158
[19]Fendia RJ et a] U S Patent 4894125.1990
[20]Corilium Corp U S .3414492.1968
[21]Grips VKW et al U S. 5019223 1991
[22]Hurley F H. Wier. TP.J. Electrochem. soc1951(98):203
[23]Robsinson J. Osteryoung J.A.J. Am. Chem. Soc 1997(102): 323
[24]WilkesJ. S. LecviskyJA. Wilson RA.Hussey cl. Inorg. Chem. 1982.21: 1263
[25]Johns. WilkesandMichael. hirandwater Stable 1-Ethyl-3-methylim
idazolium Based Ionic liquids J. Chem. Soc. 1992.965～967
[26]Carmichael AJ. Hardaere C. Holbery JD. Structure and Bonding in Ionic Liquids .Extended Abstracts of the 196th Meeting of the Electrochemical Society. Inc. Hawaii U.S.A. Oct 17-22.1999. No 2259
[27]杨绮琴 方北龙 常温熔盐体系 化学通报 1993(5)：17
[28]R.J. Gale. B.G. Ibert and R.A. osteryoung. Inorg. Chem. 17(1979)2728
[29]J. cyvin. P. klaobe. E. RyterangH. A. oye. J. chem. phys. 52(1970)2776
[30]E. Rytter and H.A. oye. J. Inorg Nucl. chem. lett. 35(1973)1185
[31]L.G. Boxal. H.L. Jones and R.A. osteryoung. J. Electrochem. soc. 1973 120.223
[32]Z.J. Karpinski and R.A. osteryoung. Inorg. chem. 1985.24.2259
[33]R.J. Carlin and R.A. osteryoung. J. Electrochem. soc. 1989. (136) 1409
[34]周少雄 2003年国际稀土永磁材料产业发展论坛
[35]Thomas Welton. Cbem. Rev[J].1999.99:2071-2083
[36]Jairton Dupont. Crestina S. Consorti and John Spener. J. Braz. soc [J] 2000. 11(4):337-344
[37]李述文 范如霖编译 实用有机化学手册 上海科学技术出版社 1981
[38]中国现场统计研究会三次设计组编著 正交法和三次设计 科学出版社 1985
[39]李德和 李长太编译 实验有机化学 山东科学技术出版社 1980
[40]J. Robison and R.A. osteryoung. An Electrochemical and SpectroscoPic Study of some Aromatic Hydrocarbons in the Room Temperature Molten Salt System Aluminium Chloride-n-butylpyridinium Chloride. J. American Chemical Society 1997(4):323
[41]Xiao-Hong Xu and Charles L. Hussey. The Electrochemstry of Mercury at Glassy Carbon and Tungsten Electrodes in the Aluminium Chloridel-Methyl-3-Ethylimidazolium Chloride Molten Salt. J. ElectrochemSoc. Vol. 140. No. 5. May. 1993
[42]Takahashi et al Electrochemistry 54. (3):257
[43]Shoichrio Mori. Kazuhikolda.U S. Patent 5135825 1992
[44]徐寿昌 有机化学 高等教育出版社 第二版
[45]上海轻工业专科学校 电镀原理 上海科技出版社 1982
[46]黄子勋 吴纯素 电镀原理 中国农业机械出版社 1982
[47]Kawahara et al U S Patent 5543522 1996
[48]李青 熔融盐电沉积金属及合金 电镀与精饰 1998(2)：26
[49]方景礼 多元络和物电镀 国防工业出版社 1983
[50]全国金属与非金属覆盖层标准化技术委员会编著 覆盖层标准应用手册(上) 中国标准出版社 1999
[51]卢燕平 金属表面防蚀处理 冶金工业出版社 1995