熔盐电化学法制备Fe-6.5wt%Si合金的研究
|
摘要
利用正交法研究了不同熔盐的摩尔配比、电流密度、电流的占空比和脉冲周期对硅沉积层的厚度与质量的影响规律,得到了最佳的电沉积工艺参数:熔盐的摩尔比1:1:3:0.3,电流密度60mA/cm2,占空比20%,脉冲周期1000μs。SEM表明:电流密度、电流占空比和脉冲周期对镀层质量具有重要影响。此外,施加反向电流对镀层质量也有一定的影响。
对沉积层的硅含量分布曲线研究表明:沉积过程中,硅的扩散符合恒定源扩散规律;对沉积后试样的扩散退火研究发现:沉积50min的试样均匀化扩散退火需60min,退火后的硅含量为3.3%。
采用GDA750型辉光放电光谱仪测量硅含量沿镀层厚度方向的分布曲线,然后利用ORIGIN软件求其积分的方法,来计算沉积层中总的含硅量。此方法计算出的试样退火后的理论硅含量与实验得到硅含量误差在10%内。
对基体电沉积80min,在1200℃和94.4%Ar+5.6%H2的还原气氛下扩散退火110 min,成功制备出了硅含量为6.5%的铁硅合金。
在FClNaK-SiO2体系中熔盐电沉积硅,采用脉冲电流比普通直流电源具有更好的镀层质量。FClNaK-SiO2体系中,采用电沉积法制备Fe-6.5wt%Si合金是切实可行的,且有更低的制作成本。该方法有工艺简单、操作方便和有利于环保的优点,将具有较好的应用前景。
The molar ratio of molten salt, the current density, current duty ratio and the influence of the pulse interval on the thickness and the quality of the silicon deposition layer have been studied by orthogonal method, electro-deposition process parameter was obtained: the molar ratio of molten salt is 1:1:3:0.3, current density is 60 mA/cm2, duty ratio is 20%, the pulse interval is 1000μs. The SEM of deposit indicated that: the coating quality is obvious influenced by current density, duty ratio and the pulse interval, the deposit quality is also influenced by back current.
The result of the distribution curve of silicon content in the silicon deposition indicates that the diffusion of silicon in deposition matches constant current diffusion rule in the process of deposition. The research of diffusion annealing on post-depositional specimen shows that: 60 minutes are needed to homogenization diffusion anneal for depositing the 50min test specimen homogenization diffusion annealing, and the silicon content approximately is about 3.3% after annealing.
Survey the silicon content distribution curve by glow discharge spectrometer in this article and associate with integral method to calculate the content of silicon in deposition, the error is in 10%.
After 80 minutes electro-deposition on the base, and diffusion annealing 110 minutes under 94.4%Ar+5.6%H2 reducing atmosphere at 1200℃,the ferro-silicium which the silicon content is 6.5% was made out.
In the FClNaK-SiO2 system, the coating is influenced by the impulse current which is better than the ordinary direct constant source electric current treatment. In the FClNaK-SiO2 system, it is a feasible method to make Fe-6.5wt%Si alloy by electro-deposition process, and the cost of electro-deposition silicon in molten salt is low. This method will have good prospect because of simple, handing convenience and environmental protection.
对沉积层的硅含量分布曲线研究表明:沉积过程中,硅的扩散符合恒定源扩散规律;对沉积后试样的扩散退火研究发现:沉积50min的试样均匀化扩散退火需60min,退火后的硅含量为3.3%。
采用GDA750型辉光放电光谱仪测量硅含量沿镀层厚度方向的分布曲线,然后利用ORIGIN软件求其积分的方法,来计算沉积层中总的含硅量。此方法计算出的试样退火后的理论硅含量与实验得到硅含量误差在10%内。
对基体电沉积80min,在1200℃和94.4%Ar+5.6%H2的还原气氛下扩散退火110 min,成功制备出了硅含量为6.5%的铁硅合金。
在FClNaK-SiO2体系中熔盐电沉积硅,采用脉冲电流比普通直流电源具有更好的镀层质量。FClNaK-SiO2体系中,采用电沉积法制备Fe-6.5wt%Si合金是切实可行的,且有更低的制作成本。该方法有工艺简单、操作方便和有利于环保的优点,将具有较好的应用前景。
The molar ratio of molten salt, the current density, current duty ratio and the influence of the pulse interval on the thickness and the quality of the silicon deposition layer have been studied by orthogonal method, electro-deposition process parameter was obtained: the molar ratio of molten salt is 1:1:3:0.3, current density is 60 mA/cm2, duty ratio is 20%, the pulse interval is 1000μs. The SEM of deposit indicated that: the coating quality is obvious influenced by current density, duty ratio and the pulse interval, the deposit quality is also influenced by back current.
The result of the distribution curve of silicon content in the silicon deposition indicates that the diffusion of silicon in deposition matches constant current diffusion rule in the process of deposition. The research of diffusion annealing on post-depositional specimen shows that: 60 minutes are needed to homogenization diffusion anneal for depositing the 50min test specimen homogenization diffusion annealing, and the silicon content approximately is about 3.3% after annealing.
Survey the silicon content distribution curve by glow discharge spectrometer in this article and associate with integral method to calculate the content of silicon in deposition, the error is in 10%.
After 80 minutes electro-deposition on the base, and diffusion annealing 110 minutes under 94.4%Ar+5.6%H2 reducing atmosphere at 1200℃,the ferro-silicium which the silicon content is 6.5% was made out.
In the FClNaK-SiO2 system, the coating is influenced by the impulse current which is better than the ordinary direct constant source electric current treatment. In the FClNaK-SiO2 system, it is a feasible method to make Fe-6.5wt%Si alloy by electro-deposition process, and the cost of electro-deposition silicon in molten salt is low. This method will have good prospect because of simple, handing convenience and environmental protection.
引文
[1]王东.高硅电工钢的特性及应用[J].电工材料,2001(3):25-28.
[2]胡广勇.Fe-6.5%Si与Fe-3%Si薄板、薄带的制备、织构及晶界特征分布的研究[D].沈阳:东北大学,1998.
[3]小昭光晴.等离子体成膜基础[M].北京:国防工业出版社,1994.
[4] TAKACLA Y. Silicon steel sheet made by chemical vapor deposition [J]. Adv Mater & Proc, 1995(6):9-12.
[5]何忠治.电工钢[M].北京:冶金工业出版社,1997,28-38.
[6]张译中.国外晶粒取向硅钢技术的进展[J].上海金属,2002(5):31-38.
[7]张泽玮.电源技术中应用的软磁材料发展回顾和分析[J].金属功能材料,2001,5(8):1-7.
[8]胡长征.粉末冶金方法制备高硅铁硅合金的探索性研究[D].武汉:武汉理工大学,2004.
[9] MATUSUMURA S, TANAKA Y, KOGA Y, et al. Concurrent ordering and phase separation in the vicinity of the meta stable critical point of order-disorder transition in Fe-Si alloys[J]. Mater. Sci. Eng A, 2001,312(1-2):284-292.
[10] SWANN P R, DAVID J. Development and applications of a 300 keV ultrahigh-vacuum high-resolution electron microscope [J]. Ultra-microscopy, 2005,49(1-4):26-36.
[11] VIALA B, FERRARA E, FIORILLO F, et al. Study of the brittle behavior of annealed Fe-6.5wt%Si ribbons produced by planar flow casting[J].Materials Science and Engineering A, 1996,212(1):62-68.
[12] NARITA K, ENOKIZINO M, TESHIMA N. Magnetic properties of 6.5% silicon-iron ribbon produced by splat-cooling technique [J]. Journal of Magnetism and Magnetic Materials, 1980,19(1-3):143-144.
[13] HAIJI H, OKADA K, ABE M, et al. Magnetic properties and workability of 6.5%Si steel [J]. J Mag. Mater. 1996(160):109-114.
[14] SHIN J S, BAE J S, KIM H J, et al. Ordering-disordering phenomena and micro-hardness characteristics of B2 phase in Fe-(5-6.5%) Si alloys [J]. Materials Science and Engineering A, 2005(407):282-290.
[15] SHIN J S, LEE Z H, LEE T D, et al. The effect of heat treatments and Si contents on B2 ordering reaction in high-silicon steel [J]. Materials Science and Engineering A, 2001,307(1-2):29-34.
[16] ISHIZAKA T, YAMABE K, TAKAHASHI T. Magnetic properties of rapidly quenched Fe-6.5%Si alloy [J].日本金属学会杂志,1996(30):552-556.
[17]刘海明,彭长平,李玉国.Fe-6.5%Si快速凝固极薄带[J].钢铁,1993,7(28):55-59.
[18]胡广勇.沉积—扩散法制取Fe-6.5%Si薄板的织构研究[J].金属学报,1998,34(5):506-510.
[19]蔡宗英,张莉霞,李运刚.电化学还原法制备Fe-6.5%Si薄板[J].湿法冶金,2005,24(2):83-86.
[20] KASAMA A H, BOLFARINI C, KIMINAMI C. Magnetic properties evaluation of spray formed and rolled Fe-6.5wt%Si-1.0wt%Al alloy [J]. Materials Science and Engineering A, 2007,449-451(3):375-377.
[21]员文杰,沈强,张联盟.粉末轧制法制备Fe-6.5%Si硅钢片的研究[J].粉末冶金技术,2007,25(1):32-34.
[22]林均品.Fe-6.5wt%Si高硅钢冷轧薄板制备工艺、结构和性能[J].前沿科学,2007,2:13-26.
[23]吴耀明,苏明忠.熔融盐研究进展[J].化工进展,1995,5:25-30.
[24]杨绮琴,段淑贞.熔盐电化学的新进展[J].电化学,2001,7(1):10-15.
[25]冯秋元,丁志敏.熔融盐电镀铝的研究进展[J].电镀与环保,2003,(9):1-4.
[26]段淑贞,乔芝郁.熔盐化学—原理和应用[M].北京:冶金工艺出版社,1990:201-236.
[27] FELLNER P, MATIASOVSKY K. Electrolytic silicon coating in fused salts[J]. Electro-deposition and Surface Treatment, 1975(3):235-244.
[28] GOPALAKRISHNA, RAO M. Electro-winning of silicon from K2SiF6-Molten fluoride systems[J]. Electrochemical Science and Technology, 1980,127(9):1900-1944.
[29]程东骥.双辊机连铸1毫米厚6%硅薄带钢产品缺陷讨论[J].世界钢铁,1993,(1):41-45.
[30] KOGIKU F, YUKUMOTO M, SHIBUYA K, et al. Rapidly Solidified Alloys and Their Mechanical and Magnetic Properties [J]. Materials Research Society, 1985(12):2-4.
[31]刘海明.全国第六届和冶金部第三届非晶态材料研讨会文集[C].桂林,1991:462-463.
[32]潘纯久.二十辊轧机及高精度冷轧钢带生产[M].北京:冶金工业出版社,2003:320-321.
[33]丘利,胡玉和.X射线衍射技术及设备[M].北京:冶金工业出版社,1995:77-91.
[34]梁精龙.熔盐法沉积Si及制备Fe-6.5wt%Si薄板的研究[D].唐山:河北理工大学,2005.
[35]杨德.试验设计与分析[M].北京:中国农业出版社,2002:171-186.
[36]谢刚.熔融盐理论与应用[M].北京:冶金工业出版社,1998:197-215.
[37]李正伟,徐强.串联电脉冲沉积Co-Cr弥散Y2O3合金化微晶涂层[J].中国稀土学报,2002,20(4):22-25.
[38]翁海峰,陈秋龙,鲍明东,等.脉冲占空比对纯铝微弧氧化膜的影响[J].表面技术,2005,34(5):12-15.
[39]刘国华,谢刚,陈书荣,等.熔融盐电镀金属钛的讨论[J].电镀与涂饰,1999(6):25-30.
[40]顾学范,段淑贞.第四届全国熔盐电化学及化学会议论文集[C].郑州,1987.
[41]顾学范,段淑贞.KCL-NACL熔盐体系中电镀钛的基础研究[J].稀有金属,1992,16(2):30-32.
[42]刘智恩.材料科学基础[M].西安:西北工业大学出版社,2003:199-208.
[43]蔡宗英.熔盐电沉积法制备Fe-6.5wt%Si薄板研究[D].唐山:河北理工学院.
[44]潘应君.铁与硅粉及硅铁粉复合电镀工艺的研究[J].电镀与精饰,2004,26(6):13-15.
[2]胡广勇.Fe-6.5%Si与Fe-3%Si薄板、薄带的制备、织构及晶界特征分布的研究[D].沈阳:东北大学,1998.
[3]小昭光晴.等离子体成膜基础[M].北京:国防工业出版社,1994.
[4] TAKACLA Y. Silicon steel sheet made by chemical vapor deposition [J]. Adv Mater & Proc, 1995(6):9-12.
[5]何忠治.电工钢[M].北京:冶金工业出版社,1997,28-38.
[6]张译中.国外晶粒取向硅钢技术的进展[J].上海金属,2002(5):31-38.
[7]张泽玮.电源技术中应用的软磁材料发展回顾和分析[J].金属功能材料,2001,5(8):1-7.
[8]胡长征.粉末冶金方法制备高硅铁硅合金的探索性研究[D].武汉:武汉理工大学,2004.
[9] MATUSUMURA S, TANAKA Y, KOGA Y, et al. Concurrent ordering and phase separation in the vicinity of the meta stable critical point of order-disorder transition in Fe-Si alloys[J]. Mater. Sci. Eng A, 2001,312(1-2):284-292.
[10] SWANN P R, DAVID J. Development and applications of a 300 keV ultrahigh-vacuum high-resolution electron microscope [J]. Ultra-microscopy, 2005,49(1-4):26-36.
[11] VIALA B, FERRARA E, FIORILLO F, et al. Study of the brittle behavior of annealed Fe-6.5wt%Si ribbons produced by planar flow casting[J].Materials Science and Engineering A, 1996,212(1):62-68.
[12] NARITA K, ENOKIZINO M, TESHIMA N. Magnetic properties of 6.5% silicon-iron ribbon produced by splat-cooling technique [J]. Journal of Magnetism and Magnetic Materials, 1980,19(1-3):143-144.
[13] HAIJI H, OKADA K, ABE M, et al. Magnetic properties and workability of 6.5%Si steel [J]. J Mag. Mater. 1996(160):109-114.
[14] SHIN J S, BAE J S, KIM H J, et al. Ordering-disordering phenomena and micro-hardness characteristics of B2 phase in Fe-(5-6.5%) Si alloys [J]. Materials Science and Engineering A, 2005(407):282-290.
[15] SHIN J S, LEE Z H, LEE T D, et al. The effect of heat treatments and Si contents on B2 ordering reaction in high-silicon steel [J]. Materials Science and Engineering A, 2001,307(1-2):29-34.
[16] ISHIZAKA T, YAMABE K, TAKAHASHI T. Magnetic properties of rapidly quenched Fe-6.5%Si alloy [J].日本金属学会杂志,1996(30):552-556.
[17]刘海明,彭长平,李玉国.Fe-6.5%Si快速凝固极薄带[J].钢铁,1993,7(28):55-59.
[18]胡广勇.沉积—扩散法制取Fe-6.5%Si薄板的织构研究[J].金属学报,1998,34(5):506-510.
[19]蔡宗英,张莉霞,李运刚.电化学还原法制备Fe-6.5%Si薄板[J].湿法冶金,2005,24(2):83-86.
[20] KASAMA A H, BOLFARINI C, KIMINAMI C. Magnetic properties evaluation of spray formed and rolled Fe-6.5wt%Si-1.0wt%Al alloy [J]. Materials Science and Engineering A, 2007,449-451(3):375-377.
[21]员文杰,沈强,张联盟.粉末轧制法制备Fe-6.5%Si硅钢片的研究[J].粉末冶金技术,2007,25(1):32-34.
[22]林均品.Fe-6.5wt%Si高硅钢冷轧薄板制备工艺、结构和性能[J].前沿科学,2007,2:13-26.
[23]吴耀明,苏明忠.熔融盐研究进展[J].化工进展,1995,5:25-30.
[24]杨绮琴,段淑贞.熔盐电化学的新进展[J].电化学,2001,7(1):10-15.
[25]冯秋元,丁志敏.熔融盐电镀铝的研究进展[J].电镀与环保,2003,(9):1-4.
[26]段淑贞,乔芝郁.熔盐化学—原理和应用[M].北京:冶金工艺出版社,1990:201-236.
[27] FELLNER P, MATIASOVSKY K. Electrolytic silicon coating in fused salts[J]. Electro-deposition and Surface Treatment, 1975(3):235-244.
[28] GOPALAKRISHNA, RAO M. Electro-winning of silicon from K2SiF6-Molten fluoride systems[J]. Electrochemical Science and Technology, 1980,127(9):1900-1944.
[29]程东骥.双辊机连铸1毫米厚6%硅薄带钢产品缺陷讨论[J].世界钢铁,1993,(1):41-45.
[30] KOGIKU F, YUKUMOTO M, SHIBUYA K, et al. Rapidly Solidified Alloys and Their Mechanical and Magnetic Properties [J]. Materials Research Society, 1985(12):2-4.
[31]刘海明.全国第六届和冶金部第三届非晶态材料研讨会文集[C].桂林,1991:462-463.
[32]潘纯久.二十辊轧机及高精度冷轧钢带生产[M].北京:冶金工业出版社,2003:320-321.
[33]丘利,胡玉和.X射线衍射技术及设备[M].北京:冶金工业出版社,1995:77-91.
[34]梁精龙.熔盐法沉积Si及制备Fe-6.5wt%Si薄板的研究[D].唐山:河北理工大学,2005.
[35]杨德.试验设计与分析[M].北京:中国农业出版社,2002:171-186.
[36]谢刚.熔融盐理论与应用[M].北京:冶金工业出版社,1998:197-215.
[37]李正伟,徐强.串联电脉冲沉积Co-Cr弥散Y2O3合金化微晶涂层[J].中国稀土学报,2002,20(4):22-25.
[38]翁海峰,陈秋龙,鲍明东,等.脉冲占空比对纯铝微弧氧化膜的影响[J].表面技术,2005,34(5):12-15.
[39]刘国华,谢刚,陈书荣,等.熔融盐电镀金属钛的讨论[J].电镀与涂饰,1999(6):25-30.
[40]顾学范,段淑贞.第四届全国熔盐电化学及化学会议论文集[C].郑州,1987.
[41]顾学范,段淑贞.KCL-NACL熔盐体系中电镀钛的基础研究[J].稀有金属,1992,16(2):30-32.
[42]刘智恩.材料科学基础[M].西安:西北工业大学出版社,2003:199-208.
[43]蔡宗英.熔盐电沉积法制备Fe-6.5wt%Si薄板研究[D].唐山:河北理工学院.
[44]潘应君.铁与硅粉及硅铁粉复合电镀工艺的研究[J].电镀与精饰,2004,26(6):13-15.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |