Finemet型纳米晶软磁合金的双团簇特征与成分优化
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摘要
基于Finemet合金的成分及其非晶前驱体的晶化特征,提出了Finemet型合金的"双团簇"结构模型和团簇式成分,即Finemet合金的非晶前驱体可看作由2类团簇结构构成:一种为基于a-Fe(Si)有序固溶体(例如Fe_3Si相)的[Si-Fe_(14)](Cu_(1/13)Si_(12/13))_3弱稳定团簇结构;另一种为对应于Fe-B-Si-Nb系块体非晶合金的[(Si,B)-B_2(Fe,Nb)_8]Fe强稳定团簇结构。将2种团簇成分式按等比例混合,设计并制备了多个新成分合金。热分析和磁性测量结果表明,所有成分的非晶样品均显示多峰晶化特征,其中,[(Si_(0.8)B_(0.2))-B_2Fe_(7.2)Nb_(0.8)]Fe+[Si-Fe_(14)](Cu_(1/13)Si_(12/13))_3(即Fe_(74)B_(7.33)Si_(15.23)Nb_(2.67)Cu_(0.77))非晶两晶化峰的峰间距(ΔT_p=T_(p2)-T_(p1))最大,约为192 K。该非晶样品在813 K等温退火60 min后获得典型的纳米晶/非晶复相结构,其饱和磁化强度B_s约为1.26 T,矫顽力H_c约为0.5 A/m,1 k Hz下的有效磁导率m_e约为8.5×10~5。新成分纳米晶合金的综合软磁性能均优于典型成分为Fe_(73.5)Si_(13.5)B_9Cu_1Nb_3的已有Finemet纳米晶合金。
The development of nanocrystalline Fe-Si-B-Nb-Cu alloys, commercially known as Finemet, has established a new approach to obtain soft-magnetic materials with high magnetic flux density. The material consists of a-Fe(Si) nanocrystals embedded in an amorphous matrix, which is made by means of partial crystallization. The composition and local structure of the precursor amorphous alloys are crucial for the formation of the unique nanocrystalline structure. The present study is devoted to understanding the composition characteristics and developing new compositions of Finemet alloys. Using the"cluster-plus-glue-atom"model and noticing the crystallization characteristic of Finemet alloy, a"dualcluster"amorphous structure model is proposed. In this model, the precursor amorphous structure of Finemet alloy is considered to contain a mixture of the [(Si, B)-B_2(Fe, Nb)_8]Fe cluster derived from the FeB-Si-Nb bulk glassy alloys, and the [Si-Fe_(14)](Cu_(1/13)Si_(12/13))_3 cluster from Fe_3Si phase. A series of new Finemet nanocrystalline alloy compositions are designed by mixing [(Si, B)-B_2(Fe, Nb)_8]Fe and [Si-Fe_(14)](Cu_(1/13)Si_(12/13))_3 cluster formulas with a ratio of 1∶1. Thermal analysis results show that [(Si_(0.8)B_(0.2))-B_2Fe_(7.2)Nb_(0.8)]Fe+[Si-Fe_(14)](Cu_(1/13)Si_(12/13))_3(alloy composition: Fe_(74)B_(7.33)Si_(15.23)Nb_(2.67)Cu_(0.77)) amorphous alloy exhibits a maximal temperature interval of about 192 K between the first and second crystallization peaks. Magnetic measurement results show that the Fe_(74)B_(7.33)Si_(15.23)Nb_(2.67)Cu_(0.77) nanocrystalline alloy exhibits optimal soft magnetic properties with a saturation magnetization Bsabout 1.26 T, a coercive force Hcabout 0.5 A/m and an effective permeability meabout 8.5 × 105 at 1 k Hz after isothermal annealing at 813 K for 60 min. The soft magnetic properties of the new composition nanocrystalline alloys are better than that of the typical Finemet nanocrystalline alloy(Fe_(73.5)Si_(13.5)B_9Cu_1Nb_3).
The development of nanocrystalline Fe-Si-B-Nb-Cu alloys, commercially known as Finemet, has established a new approach to obtain soft-magnetic materials with high magnetic flux density. The material consists of a-Fe(Si) nanocrystals embedded in an amorphous matrix, which is made by means of partial crystallization. The composition and local structure of the precursor amorphous alloys are crucial for the formation of the unique nanocrystalline structure. The present study is devoted to understanding the composition characteristics and developing new compositions of Finemet alloys. Using the"cluster-plus-glue-atom"model and noticing the crystallization characteristic of Finemet alloy, a"dualcluster"amorphous structure model is proposed. In this model, the precursor amorphous structure of Finemet alloy is considered to contain a mixture of the [(Si, B)-B_2(Fe, Nb)_8]Fe cluster derived from the FeB-Si-Nb bulk glassy alloys, and the [Si-Fe_(14)](Cu_(1/13)Si_(12/13))_3 cluster from Fe_3Si phase. A series of new Finemet nanocrystalline alloy compositions are designed by mixing [(Si, B)-B_2(Fe, Nb)_8]Fe and [Si-Fe_(14)](Cu_(1/13)Si_(12/13))_3 cluster formulas with a ratio of 1∶1. Thermal analysis results show that [(Si_(0.8)B_(0.2))-B_2Fe_(7.2)Nb_(0.8)]Fe+[Si-Fe_(14)](Cu_(1/13)Si_(12/13))_3(alloy composition: Fe_(74)B_(7.33)Si_(15.23)Nb_(2.67)Cu_(0.77)) amorphous alloy exhibits a maximal temperature interval of about 192 K between the first and second crystallization peaks. Magnetic measurement results show that the Fe_(74)B_(7.33)Si_(15.23)Nb_(2.67)Cu_(0.77) nanocrystalline alloy exhibits optimal soft magnetic properties with a saturation magnetization Bsabout 1.26 T, a coercive force Hcabout 0.5 A/m and an effective permeability meabout 8.5 × 105 at 1 k Hz after isothermal annealing at 813 K for 60 min. The soft magnetic properties of the new composition nanocrystalline alloys are better than that of the typical Finemet nanocrystalline alloy(Fe_(73.5)Si_(13.5)B_9Cu_1Nb_3).
引文
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[2]Yoshizawa Y,Oguma S,Yamauchi K.New Fe-based soft magnetic alloys composed of ultrafine grain structure[J].J.Appl.Phys.,1988,64:6044
[3]Chen G J,Wang X J.Recent advance in Finemet type nanocrystaline soft magnetie alloys[J].Met.Funct.Mater.,2003,10(4):28(陈国钧,王旭军.Finemet型Fe Cu Nb Si B系纳米软磁合金的新进展[J].金属功能材料,2003,10(4):28)
[4]Yoshizawa Y,Yamauchi K.Fe-based soft magnetic alloys composed of ultrafine grain structure[J].Mater.Trans.JIM,1990,31:307
[5]Ayers J D,Harris V G,Sprague J A,et al.On the formation of nanocrystals in the soft magnetic alloy Fe73.5Nb3Cu1Si13.5B9[J].Acta Mater.,1998,46:1861
[6]Hono K,Ping D H,Ohnuma M,et al.Cu clustering and Si partitioning in the early crystallization stage of an Fe73.5Si13.5B9Nb3Cu1amorphous alloy[J].Acta Mater.,1999,47:997
[7]Wang Z R,Qiang J B,Wang Y M,et al.Composition design procedures of Ti-based bulk metallic glasses using the cluster-plus-glueatom model[J].Acta Mater.,2016,111:366
[8]Han G,Qiang J B,Li F W,et al.The e/a values of ideal metallic glasses in relation to cluster formulae[J].Acta Mater.,2011,59:5917
[9]Luo L J,Chen H,Wang Y M,et al.24 electron cluster formulas as the‘molecular’units of ideal metallic glasses[J].Philos.Mag.,2014,94:2520
[10]Geng Y X,Wang Y M,Qiang J B,et al.Composition formulas of Fe-B binary amorphous alloys[J].J.Non-Cryst.Solids,2016,432:453
[11]Geng Y X,Zhang Z J,Wang Z R,et al.Magnetic properties and a structure model for high Fe content Fe-B-Si-Zr bulk glassy alloys[J].J.Non-Cryst.Solids,2016,450:1
[12]Geng Y X,Zhang Z J,Wang Y M,et al.Structure-property correlation of high Fe-content Fe-B-Si-Hf bulk glassy alloys[J].Acta Metall.Sin.,2017,53:369(耿遥祥,张志杰,王英敏等.高Fe含量Fe-B-Si-Hf块体非晶合金的结构-性能关联[J].金属学报,2017,53:369)
[13]Pang C,Jiang B B,Shi Y,et al.Cluster-plus-glue-atom model and universal composition formulas[cluster](glue atom)xfor BCC solid solution alloys[J].J.Alloys Compd.,2015,652:63
[14]Geng Y X,Wang Y M,Qiang J B,et al.Fe-B-Si-Zr soft magnetic bulk glassy alloys[J].Intermetallics,2015,67:138
[15]Geng Y X.Composition design and properties investigation for FeB-Si based amorphous and nanocrystalline alloys[D].Dalian:Dalian University of Technology,2016(耿遥祥.Fe-B-Si系非晶/纳米晶合金的成分设计及性能研究[D].大连:大连理工大学,2016)
[16]Wang Q,Zha Q F,Liu E X,et al.,Composition design of highstrength martensitic precipitation hardening stainless steels based on a cluster model[J].Acta Metall.Sin.,2012,48:1201(王清,查钱锋,刘恩雪等.基于团簇模型的高强度马氏体沉淀硬化不锈钢成分设计[J].金属学报,2012,48:1201)
[17]Geng Y X,Wang Y M,Qiang J B,et al.Composition design and optimization of Fe-B-Si-Nb bulk amorphous alloys[J].Acta Metall.Sin.,2016,52:1459(耿遥祥,王英敏,羌建兵等.Fe-B-Si-Nb块体非晶合金的成分设计与优化[J].金属学报,2016,52:1459)
[18]Ma Y P,Dong D D,Dong C,et al.Composition formulas of binary eutectics[J].Sci.Rep.,2015,5:17880
[19]Mondal K,Murty B S.On the parameters to assess the glass forming ability of liquids[J].J.Non-Cryst.Solids,2005,351:1366
[20]Makino A,Men H,Kubota T,et al.New Fe-metalloids based nanocrystalline alloys with high Bsof 1.9 T and excellent magnetic softness[J].J.Appl.Phys.,2009,105:07A308
[21]Mc Henry M E,Willard M A,Laughlin D E.Amorphous and nanocrystalline materials for applications as soft magnets[J].Prog.Mater.Sci.,1999,44:291
[22]Patterson A L.The Scherrer formula for X-ray particle size determination[J].Phys.Rev.,1939,56:978
[23]Herzer G.Grain structure and magnetism of nanocrystalline ferromagnets[J].IEEE Trans.Magn.,1989,25:3327
[24]Herzer G.Grain size dependence of coercivity and permeability in nanocrystalline ferromagnets[J].IEEE Trans.Magn.,1990,26:1397