低铌铁基纳米晶合金的研究
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摘要
Finemet合金是目前具有优异软磁性能的软磁材料之一,但是合金中含有昂贵的Nb,使得Finemet具有很高的成本。为了降低合金的成本,本文利用Mo和V两种元素替代了合金中的Nb元素,制备了Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3)和Fe73.5Si13.5B9Cu1Nb3-xVx(x=1, 2, 3)两种纳米晶非晶合金,通过X射线衍射仪(XRD)、热综合分析仪(DSC)、震动样品磁强计(VSM)等实验手段,研究了V和Mo两种元素对非晶合金热稳定性、晶化机制和磁性能的影响。得出了如下结论:
(1)Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3)和Fe73.5Si13.5B9Cu1Nb3-xVx(x=1, 2)非晶合金的晶化过程出现两个晶化峰,其析出相分别为α-Fe(Si)相和Fe-B相。添加元素V和Mo后合金的热稳定性降低,并且三者的热稳定性为:Nb>V>Mo。
(2)由Avrami指数n值可知,Fe73.5Si13.5B9Cu1Nb1Mo2和Fe73.5Si13.5B9Cu1Nb1V2非晶合金中α-Fe(Si)软磁相在晶化初期为扩散控制的二维和三维形核和晶粒生长的整体晶化,形核率逐渐减小,在晶化后期为一维形核和生长的表面晶化,形核率近似为零。
(3)退火后的非晶样品的磁性能较退火前有极大的改善。Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3)和Fe73.5Si13.5B9Cu1Nb3-xVx(x=1, 2)两种非晶合金在不同温度下真空退火后的析出晶粒大小为13nm-21nm和4nm-12nm之间,抑制晶粒长大能力为:V>Nb>Mo。选定合适的退火温度以获得合适的纳米晶相与非晶相配比和抑制析出纳米晶粒大小,是保证非晶合金获得优异磁性能的关键。
At persent,the FINEMET alloys is one of materials with excellent soft magnetic properties,but the Nb increased the cost of the alloys.In order to reduce the cost of the FINMET alloys.This article studied influence of substitute element V and Mo,different heating temperature,different heating rate to the process of alloy crystallization and magnetic properties by many measure methods.such as XRD、DSC and VSM.The results as follow:
(1)Two peaks can be observed during crystallization of Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3) and Fe73.5Si13.5B9Cu1Nb3-xVx(x=1, 2) amorphous alloys,the two crystallization stages are related to the appearance ofα-Fe(Si) phase and Fe-B phase,separately.The thermostability of the alloy was deteriorated as a consequence of Nb substituted by Mo and V,and thermostability rank order was Nb>V>Mo.
(2) Due to the average value of Avrami exponent n, in the initial stage,the crystallization mechanism of the Fe73.5Si13.5B9Cu1Nb3-xMox(x=1,2,3) and Fe73.5Si13.5B9Cu1Nb1V2 alloys two and three dimensional nucleation and grain growth controlled by diffusion at decreasing nuckeation rate,in the next stage was one dimensional nucleation and grain growth at a near-zero nucleation rate are responsible for surface crystallization.
(3)Magnetic properities were improved after annealing.With vacuum annealing at different temperature,the grain size of Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3) and Fe73.5Si13.5B9Cu1Nb3-xVx( x=1, 2) amorphous alloys were between 13nm-21nm and 4nm-12nm separately,the ability of restrain the growth of grains rank order was V>Nb>Mo,restraining grain size and controlling crystrallization fraction with changing annealing temperature was the key of getting excellent magnetic properities.
(1)Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3)和Fe73.5Si13.5B9Cu1Nb3-xVx(x=1, 2)非晶合金的晶化过程出现两个晶化峰,其析出相分别为α-Fe(Si)相和Fe-B相。添加元素V和Mo后合金的热稳定性降低,并且三者的热稳定性为:Nb>V>Mo。
(2)由Avrami指数n值可知,Fe73.5Si13.5B9Cu1Nb1Mo2和Fe73.5Si13.5B9Cu1Nb1V2非晶合金中α-Fe(Si)软磁相在晶化初期为扩散控制的二维和三维形核和晶粒生长的整体晶化,形核率逐渐减小,在晶化后期为一维形核和生长的表面晶化,形核率近似为零。
(3)退火后的非晶样品的磁性能较退火前有极大的改善。Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3)和Fe73.5Si13.5B9Cu1Nb3-xVx(x=1, 2)两种非晶合金在不同温度下真空退火后的析出晶粒大小为13nm-21nm和4nm-12nm之间,抑制晶粒长大能力为:V>Nb>Mo。选定合适的退火温度以获得合适的纳米晶相与非晶相配比和抑制析出纳米晶粒大小,是保证非晶合金获得优异磁性能的关键。
At persent,the FINEMET alloys is one of materials with excellent soft magnetic properties,but the Nb increased the cost of the alloys.In order to reduce the cost of the FINMET alloys.This article studied influence of substitute element V and Mo,different heating temperature,different heating rate to the process of alloy crystallization and magnetic properties by many measure methods.such as XRD、DSC and VSM.The results as follow:
(1)Two peaks can be observed during crystallization of Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3) and Fe73.5Si13.5B9Cu1Nb3-xVx(x=1, 2) amorphous alloys,the two crystallization stages are related to the appearance ofα-Fe(Si) phase and Fe-B phase,separately.The thermostability of the alloy was deteriorated as a consequence of Nb substituted by Mo and V,and thermostability rank order was Nb>V>Mo.
(2) Due to the average value of Avrami exponent n, in the initial stage,the crystallization mechanism of the Fe73.5Si13.5B9Cu1Nb3-xMox(x=1,2,3) and Fe73.5Si13.5B9Cu1Nb1V2 alloys two and three dimensional nucleation and grain growth controlled by diffusion at decreasing nuckeation rate,in the next stage was one dimensional nucleation and grain growth at a near-zero nucleation rate are responsible for surface crystallization.
(3)Magnetic properities were improved after annealing.With vacuum annealing at different temperature,the grain size of Fe73.5Si13.5B9Cu1Nb3-xMox(x=1, 2, 3) and Fe73.5Si13.5B9Cu1Nb3-xVx( x=1, 2) amorphous alloys were between 13nm-21nm and 4nm-12nm separately,the ability of restrain the growth of grains rank order was V>Nb>Mo,restraining grain size and controlling crystrallization fraction with changing annealing temperature was the key of getting excellent magnetic properities.
引文
[1]戴道生，韩汝琪等.非晶态物理[M].第1版.北京:电子工业 版社，1989.
[2] F.E.Luborsky非晶态金属合金[M]，第1版北京:冶金工业出版社，1989.
[3] H.S.Chen,D.Tumbull.Formation,Stabilityand Structure of Palladium-silicon Based AlloyGlasses[J].Acta Metallurgica,1969,17:1021-1031.
[4] J.扎齐斯基主编，玻璃与非晶态材料[M].北京:科学出版社第九卷,2001.
[5]卢志超，李德仁，周少雄.非晶、纳米晶合金国内外反战概况及应用展望[J].新材料产业.2002年第3期，20-23.
[6]陈国钧，涂国超，桑灿，Finemet型FeCuNbSiB系纳米软磁合金的发展和产业化[J].磁性材料及器件.2004年4月35：9-13.
[7]朱凤霞，易健宏，李丽娅.铁基纳米晶软磁合金的研究现状[J].磁性材料及器件.2008年4月1-6
[8] Giselher Herzer.Soft magnetic nanocrystalline materials[J]. Scripta Metallurgica etMaterialia.1995, 33 (10-11): 1741-1756
[9]张世远。新型纳米晶软磁合金及其应用（一）[J].磁性材料及器件.2004年4月.1-5
[10]李健靓，卢志超，李德仁.非品态合金及其在配电变压器中的应用进展[J].材料导报.2007年.第25卷.第20期71-76
[11]纪松，钱坤明，张延松，非晶／纳米晶软磁材料及其应用，兵器材料科学与工程，第28卷2005丘第5期1月51-55
[12]易健宏李丽娅彭元东.微波场作用下非晶合金Fe73.5Cu1Nb3Si13.5B9的纳米晶化[J].材料研究学报. 2007年12月第21卷第6期.632-636
[13] Q.Z. Zhi，B.S. Donga，W.Z. Chenb，K.Y. He.Elevated temperature initial permeabilitystudy of Fe73.5Cu1Nb3Si13.5B9 alloy[J]. Materials Science and Engineering.2007A448:249-252
[14] L.A. Valenzuela，J.G.S. Duque，C.T. Meneses. Structural and magnetic properties ofnanocrystalline particles in an amorphous Fe73.5Nb3CuSi13.5B9 matrix. [J].Journal ofNon-Crystalline Solids.2008.11.1 Volume 35 44871-4873.
[15]周飞何开元隋曼龄.Cu和Nb对非晶态Fe-Si-B合金等温晶化过程的影响[J].材料研究学报. l994年6月第8卷第3期218-222
[16]傅明喜，甘俊旗，张纪波.Nb对铁基非晶合金的晶化影响[J].金属功能材料.2007年4月.第14卷第2期.5-9.
[17] P. Marin，M. Vkquez，A.O. Olofinjana. Influence of Cu and Nb on relaxation andcrystallization of amorphous FeSiB(CuNb) wires[J]. Nanostructured Materials，Vol. 10. No. 2.pp. 299-310.1998.
[18] M.H. Phan，H.X. PengS.C. Yu.Nanocrystallization kinetics, structure and magneticproperties of FINEMET-type ribbons with Cu substitution by Ag. Article in press. 22 May2006.1-7.
[19] F.Shahri，A.Beitollahi，S.G. Shabestari.Structural characterization and magnetoimpedanceeffect in amorphous and nanocrystalline AlGe-substituted FeSiBNbCu ribbons. Journal ofMagnetism and Magnetic Materials. Volume 312, Issue 1, May 2007, Pages 35-42.
[20] Muraca D, Cremaschia V J, Sirkin H. Effect of the addition of Ge to the FINEMET alloy[J]. J Magn Magn Mater, 2007, 311: 618-622.
[21]张延忠.纳米晶Fe72.5Cu1Nb1.5Si13.5Mo1.5V1B9合金的磁性能[J].上海钢研.火2000年第二期.3-7
[22]张延忠.新纳米晶合金Fe72Cu1Nb2V2Si14B9和Fe72Cu1Nb1Mo1V2Si14B9的磁性能及应用[J].上海钢研1997年第5期.1-5
[23]唐人剑，严彪，张延忠.纳米晶Fe72.8Cu1Nb1.7V1.5Mn0.5Si13.5B9软磁合金的磁性能[J].金属功能材料.第10卷第4期2003年8月.9-11
[24]严彪1，2，唐人剑1，2，张延忠.高导磁纳米晶Fe72.8Cu1Nb1.7V1.5Mn0.5Si13.5B9合金的磁性能[J].同济大学学报.第31卷第4期2003年4月.30-32.
[25]张延忠.低Ｂｒ纳米晶Fe73.5Cu1Nb2V1Si13.5B9合金的低频损耗行为[J].第8卷第2期2001年4月.23-27.
[26]王晓军，陈学定，夏天东.非晶合金应用现状[J].材料导报.2006年10月第20卷第10期75-79.
[27]马广斌，朱正吼，黄渝鸿.非晶FeCuNbSiB带材压磁性能的特点[J].稀有金属材料与工程. 2008年2月第37卷第2期286-288.
[28]李传福，张川江，辛学祥.非晶态合金的制备与应用进展山.东轻工业学院学报第2 2卷第1期2008年3月.50-53.
[29]惠希东、陈国良.块体非晶合金.化学工业出版社.2007年1月第一版.43-44.
[30] G.A. Stergioudis,G. Vourlias, H. Morawiecb.Instabilities in crystallization and magneticbehavior of Fe–Si–B amorphous alloys. Materials Research Bulletin.2004.39:231–236
[31] N. Mattern，A.Danzig，M.Mi.iller Effect of Cu and Nb on crystallization and magneticproperties of amorphous Fe77.5Si15.5B7 alloys Materials Science and Engineering 1995.A194: 77-85
[32]钟满福，温鸣.非晶纳米晶软磁材料的制备与应用.精细化工.2004年10月第21卷增刊.59-63
[33] Lu W, Yan B, Huang W H. Complex primary crystallization kinetics of amorphousFinemet alloy.[J]. Journal of Non-Crystalline Solids, 2005, 351:3320-3324.
[34]黎阳，陆伟，严彪. FINEMET合金晶化行为的DSC研究[J].材料科学与工程学报，2006, 24(1): 132–134
[35] L.A.Valenzuela,J.G.S.Duque,C.T.Meneses,et al. Structural and magnetic properties ofnanocrystalline particles in an amorphous Fe73.5Nb3Cu1Si13.5B9 matrix.[J] Journal ofNon-Crystalline Solids, 2008,354:4871-4873.
[36] Bayri N, Izgi T, Gencer H, et al. Crystallization kinetics of Fe73.5-xMnxCu1Nb3Si13.5B9(x =0,1,3,5,7)amorphous alloys [J]. Journal of Non-Crystalline Solids, 2009, 355(1): 12-16.
[37] Jiri Malek.The applicability of Johnson-Mehl-Avrami model in the thermal analysis of thecrystallization kinetics of glasses[J]. Thermochimica Acta.1995,267:61-73.
[38] A.S.Aronin;G.E. Abrosimova, A.F. Gurov.Nanocrystallization of bulk Zr–Cu–Ti metallicglass. Materials Science and Engineering. 2001. 304–306：375–379
[39] J.W.Zhang,X.Y.Zhang,F.R.Xiao.et al. Influence of additive elements Nb and Mo on thecrystallization process of amorphous alloy Fe76.5 Cu 1 Si13.5 B 9 [J]. MaterialsLetters.1998,36:223-228.
[40]张志,李建中,郭金柱.FeCuNbSiB非晶合金的纳米晶化及其软磁性能.铸造技术.2009年3月.30（3）:333-336
[41] M.Ohnuma,K.Hono,J.S.Pedersen,ect.Cu Clustering stage before the crystallization inFe-Si-B-Nb-Cu amorphous alloys.Nanostructured Material.1999.12:693-696
[42] J.M.Silveyra，Emilia Illekova，Petersvec.et.Phase transformation in Mo-dopeFINEMETs.Physia B.(2010),doi;10.1016/j.physb.2010.03.061
[43] Liang Gongying,，Huang Yi kun,G.Friedman.Effects of Mo substituted Nb on magneticproperties of Finemet alloy. Trans.Nonferrous.Met.Soc.China,2002,12(2):189-192.
[44] Liang Gongying，Huang Yikun,G.friedaman.Effects of Mo substituded Nb on magnetics ofFinemet alloy.Trans.Noferrous Met.Soc.China.2002.Apr.12(2):189-19243
[2] F.E.Luborsky非晶态金属合金[M]，第1版北京:冶金工业出版社，1989.
[3] H.S.Chen,D.Tumbull.Formation,Stabilityand Structure of Palladium-silicon Based AlloyGlasses[J].Acta Metallurgica,1969,17:1021-1031.
[4] J.扎齐斯基主编，玻璃与非晶态材料[M].北京:科学出版社第九卷,2001.
[5]卢志超，李德仁，周少雄.非晶、纳米晶合金国内外反战概况及应用展望[J].新材料产业.2002年第3期，20-23.
[6]陈国钧，涂国超，桑灿，Finemet型FeCuNbSiB系纳米软磁合金的发展和产业化[J].磁性材料及器件.2004年4月35：9-13.
[7]朱凤霞，易健宏，李丽娅.铁基纳米晶软磁合金的研究现状[J].磁性材料及器件.2008年4月1-6
[8] Giselher Herzer.Soft magnetic nanocrystalline materials[J]. Scripta Metallurgica etMaterialia.1995, 33 (10-11): 1741-1756
[9]张世远。新型纳米晶软磁合金及其应用（一）[J].磁性材料及器件.2004年4月.1-5
[10]李健靓，卢志超，李德仁.非品态合金及其在配电变压器中的应用进展[J].材料导报.2007年.第25卷.第20期71-76
[11]纪松，钱坤明，张延松，非晶／纳米晶软磁材料及其应用，兵器材料科学与工程，第28卷2005丘第5期1月51-55
[12]易健宏李丽娅彭元东.微波场作用下非晶合金Fe73.5Cu1Nb3Si13.5B9的纳米晶化[J].材料研究学报. 2007年12月第21卷第6期.632-636
[13] Q.Z. Zhi，B.S. Donga，W.Z. Chenb，K.Y. He.Elevated temperature initial permeabilitystudy of Fe73.5Cu1Nb3Si13.5B9 alloy[J]. Materials Science and Engineering.2007A448:249-252
[14] L.A. Valenzuela，J.G.S. Duque，C.T. Meneses. Structural and magnetic properties ofnanocrystalline particles in an amorphous Fe73.5Nb3CuSi13.5B9 matrix. [J].Journal ofNon-Crystalline Solids.2008.11.1 Volume 35 44871-4873.
[15]周飞何开元隋曼龄.Cu和Nb对非晶态Fe-Si-B合金等温晶化过程的影响[J].材料研究学报. l994年6月第8卷第3期218-222
[16]傅明喜，甘俊旗，张纪波.Nb对铁基非晶合金的晶化影响[J].金属功能材料.2007年4月.第14卷第2期.5-9.
[17] P. Marin，M. Vkquez，A.O. Olofinjana. Influence of Cu and Nb on relaxation andcrystallization of amorphous FeSiB(CuNb) wires[J]. Nanostructured Materials，Vol. 10. No. 2.pp. 299-310.1998.
[18] M.H. Phan，H.X. PengS.C. Yu.Nanocrystallization kinetics, structure and magneticproperties of FINEMET-type ribbons with Cu substitution by Ag. Article in press. 22 May2006.1-7.
[19] F.Shahri，A.Beitollahi，S.G. Shabestari.Structural characterization and magnetoimpedanceeffect in amorphous and nanocrystalline AlGe-substituted FeSiBNbCu ribbons. Journal ofMagnetism and Magnetic Materials. Volume 312, Issue 1, May 2007, Pages 35-42.
[20] Muraca D, Cremaschia V J, Sirkin H. Effect of the addition of Ge to the FINEMET alloy[J]. J Magn Magn Mater, 2007, 311: 618-622.
[21]张延忠.纳米晶Fe72.5Cu1Nb1.5Si13.5Mo1.5V1B9合金的磁性能[J].上海钢研.火2000年第二期.3-7
[22]张延忠.新纳米晶合金Fe72Cu1Nb2V2Si14B9和Fe72Cu1Nb1Mo1V2Si14B9的磁性能及应用[J].上海钢研1997年第5期.1-5
[23]唐人剑，严彪，张延忠.纳米晶Fe72.8Cu1Nb1.7V1.5Mn0.5Si13.5B9软磁合金的磁性能[J].金属功能材料.第10卷第4期2003年8月.9-11
[24]严彪1，2，唐人剑1，2，张延忠.高导磁纳米晶Fe72.8Cu1Nb1.7V1.5Mn0.5Si13.5B9合金的磁性能[J].同济大学学报.第31卷第4期2003年4月.30-32.
[25]张延忠.低Ｂｒ纳米晶Fe73.5Cu1Nb2V1Si13.5B9合金的低频损耗行为[J].第8卷第2期2001年4月.23-27.
[26]王晓军，陈学定，夏天东.非晶合金应用现状[J].材料导报.2006年10月第20卷第10期75-79.
[27]马广斌，朱正吼，黄渝鸿.非晶FeCuNbSiB带材压磁性能的特点[J].稀有金属材料与工程. 2008年2月第37卷第2期286-288.
[28]李传福，张川江，辛学祥.非晶态合金的制备与应用进展山.东轻工业学院学报第2 2卷第1期2008年3月.50-53.
[29]惠希东、陈国良.块体非晶合金.化学工业出版社.2007年1月第一版.43-44.
[30] G.A. Stergioudis,G. Vourlias, H. Morawiecb.Instabilities in crystallization and magneticbehavior of Fe–Si–B amorphous alloys. Materials Research Bulletin.2004.39:231–236
[31] N. Mattern，A.Danzig，M.Mi.iller Effect of Cu and Nb on crystallization and magneticproperties of amorphous Fe77.5Si15.5B7 alloys Materials Science and Engineering 1995.A194: 77-85
[32]钟满福，温鸣.非晶纳米晶软磁材料的制备与应用.精细化工.2004年10月第21卷增刊.59-63
[33] Lu W, Yan B, Huang W H. Complex primary crystallization kinetics of amorphousFinemet alloy.[J]. Journal of Non-Crystalline Solids, 2005, 351:3320-3324.
[34]黎阳，陆伟，严彪. FINEMET合金晶化行为的DSC研究[J].材料科学与工程学报，2006, 24(1): 132–134
[35] L.A.Valenzuela,J.G.S.Duque,C.T.Meneses,et al. Structural and magnetic properties ofnanocrystalline particles in an amorphous Fe73.5Nb3Cu1Si13.5B9 matrix.[J] Journal ofNon-Crystalline Solids, 2008,354:4871-4873.
[36] Bayri N, Izgi T, Gencer H, et al. Crystallization kinetics of Fe73.5-xMnxCu1Nb3Si13.5B9(x =0,1,3,5,7)amorphous alloys [J]. Journal of Non-Crystalline Solids, 2009, 355(1): 12-16.
[37] Jiri Malek.The applicability of Johnson-Mehl-Avrami model in the thermal analysis of thecrystallization kinetics of glasses[J]. Thermochimica Acta.1995,267:61-73.
[38] A.S.Aronin;G.E. Abrosimova, A.F. Gurov.Nanocrystallization of bulk Zr–Cu–Ti metallicglass. Materials Science and Engineering. 2001. 304–306：375–379
[39] J.W.Zhang,X.Y.Zhang,F.R.Xiao.et al. Influence of additive elements Nb and Mo on thecrystallization process of amorphous alloy Fe76.5 Cu 1 Si13.5 B 9 [J]. MaterialsLetters.1998,36:223-228.
[40]张志,李建中,郭金柱.FeCuNbSiB非晶合金的纳米晶化及其软磁性能.铸造技术.2009年3月.30（3）:333-336
[41] M.Ohnuma,K.Hono,J.S.Pedersen,ect.Cu Clustering stage before the crystallization inFe-Si-B-Nb-Cu amorphous alloys.Nanostructured Material.1999.12:693-696
[42] J.M.Silveyra，Emilia Illekova，Petersvec.et.Phase transformation in Mo-dopeFINEMETs.Physia B.(2010),doi;10.1016/j.physb.2010.03.061
[43] Liang Gongying,，Huang Yi kun,G.Friedman.Effects of Mo substituted Nb on magneticproperties of Finemet alloy. Trans.Nonferrous.Met.Soc.China,2002,12(2):189-192.
[44] Liang Gongying，Huang Yikun,G.friedaman.Effects of Mo substituded Nb on magnetics ofFinemet alloy.Trans.Noferrous Met.Soc.China.2002.Apr.12(2):189-19243