强磁场下非晶软磁合金NiCoFeSi的弛豫和晶化研究
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摘要
非晶合金作为一种亚稳相，随着温度的升高，其组织结构发生变化，最终形成稳定晶化相。非晶合金在低于T_g温度以下退火会发生结构弛豫，对后续晶化过程产生影响。非晶合金的晶化受热处理过程、时间以及其它条件的影响。非晶软磁合金以及新近发展起来的纳米晶软磁合金是一种性能非常优异的功能材料，很多研究者对非晶材料的结构弛豫和晶化行为进行了研究。均恒强磁场能够将高强度的能量无接触地传递到物质的原子尺度，改变原子的排列、匹配和迁移等行为，从而对材料的组织和性能产生影响。
强磁场是研究材料的一种很好的工具。本文在强磁场存在的情况下，考察非晶软磁合金NiCoFeSi薄带在R_g温度以下的弛豫处理，分析不同退火条件对晶化行为的影响。实验结果表明，该非晶合金晶化分两个阶段进行，弛豫处理提高了后续晶化阶段的相变激活能，使晶化开始温度降低；强磁场下的弛豫处理促进了某种有序原子团簇的析出，进一步提高了相变激活能，使结晶开始温度更低。XRD分析以及电阻率ρ和矫顽力H_c的测量结果表明，外加强磁场促进了FeNi_3晶化相的析出，使电阻率下降，矫顽力升高；同时造成晶化相的晶格畸变，影响了合金的原子有序排列。
As a kind of metastable phase, amorphous alloy will change towards to crystalline phase when heated. And structure relaxation will take place if an amorphous alloy is annealed under the temperature Tg, which can influence the latter crystallization. The crystallization is related with the heat treatment condition, time and other conditions. The amorphous soft magnetic alloy and nanometer soft magnetic alloy developed recently are a kind of new good function material, and a lot of research works have been carried on structure relaxation and crystallization of the amorphous material. The high magnetic field can change the microstructure and have important influence on the structure and performance of material.
The high magnetic field is a kind of very good tool for studying the material. Based on this, here the relaxation of the amorphous soft magnetic alloy NiCoFeSi under temperature Tg and the influence of anneal conditions have been investigated at the presence of high magnetic field. The results show that this kind of alloy has two stages during crystallization process. The pre-relaxation enhances the crystallization activation energy and makes the crystallization take place earlier. The high magnetic field has more influence on this and accelerates the precipitating of one cluster. The analysis of XRD, resistivity p and coercive
force Hc has the same conclusion. The high magnetic field brings out FeNi3 phase to appear earlier, makes the resistivity drop and coercive force rise. And the high magnetic field cause the aberrance of crystal lattice of the crystallization phase, influence the atom order arrange of the alloy.
强磁场是研究材料的一种很好的工具。本文在强磁场存在的情况下，考察非晶软磁合金NiCoFeSi薄带在R_g温度以下的弛豫处理，分析不同退火条件对晶化行为的影响。实验结果表明，该非晶合金晶化分两个阶段进行，弛豫处理提高了后续晶化阶段的相变激活能，使晶化开始温度降低；强磁场下的弛豫处理促进了某种有序原子团簇的析出，进一步提高了相变激活能，使结晶开始温度更低。XRD分析以及电阻率ρ和矫顽力H_c的测量结果表明，外加强磁场促进了FeNi_3晶化相的析出，使电阻率下降，矫顽力升高；同时造成晶化相的晶格畸变，影响了合金的原子有序排列。
As a kind of metastable phase, amorphous alloy will change towards to crystalline phase when heated. And structure relaxation will take place if an amorphous alloy is annealed under the temperature Tg, which can influence the latter crystallization. The crystallization is related with the heat treatment condition, time and other conditions. The amorphous soft magnetic alloy and nanometer soft magnetic alloy developed recently are a kind of new good function material, and a lot of research works have been carried on structure relaxation and crystallization of the amorphous material. The high magnetic field can change the microstructure and have important influence on the structure and performance of material.
The high magnetic field is a kind of very good tool for studying the material. Based on this, here the relaxation of the amorphous soft magnetic alloy NiCoFeSi under temperature Tg and the influence of anneal conditions have been investigated at the presence of high magnetic field. The results show that this kind of alloy has two stages during crystallization process. The pre-relaxation enhances the crystallization activation energy and makes the crystallization take place earlier. The high magnetic field has more influence on this and accelerates the precipitating of one cluster. The analysis of XRD, resistivity p and coercive
force Hc has the same conclusion. The high magnetic field brings out FeNi3 phase to appear earlier, makes the resistivity drop and coercive force rise. And the high magnetic field cause the aberrance of crystal lattice of the crystallization phase, influence the atom order arrange of the alloy.
引文
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2. J. Kramer. Annin Phys., 1934, 19:37
3. Brenner A., Couch D. E. and Williams E.K.J.Res.Natn.Bur. 1950, 44:109
4．卢博斯基主编，柯成等译．非晶态金属合金．北京：冶金工业出版，1989
5. Duwez P., Willens R.H. and Klement W. Appl. Phy. Lett. 1960, 31:1136
6. Pond R. and Maddin R.. TMS-AIME, 245(1969):2475
7．J．扎奇斯基．玻璃与非晶态材料．科学出版社，2001，9：77～80
8. Luborsky F. E., Walter J. L. Stability of Amorphous Metallic Alloys. J. Appl. Phys., 1976, 47(8): 1276～1281,3648～3650
9. Luborsky F. E., Becker, Joseph J., Cary M. C., Richard O.. Magnetic Annealing of Amorphous Alloys. IEEE Transactions on Magnetics. 1975, 11 (6): 1644～1649
10. Simpson A. W.,. Clemets W. G. Magnetostriction in Some Amorphous Fe-Co-Ni-P Alloys. IEEE Transaction on Magnetics., 1975, 11(5):1338～1340
11. Inoue A.. Bulk Amorphous Alloys with Soft and Hard Magnetic Properties. Mater. Sci. and Eng., 1997, A226-228:357-363
12. Chen H.S.. Glassy Metals. Rep. Prog. Phys., 1980, 43:353-432
13. Perepezko.J.H.and Smith.J.S.. J.Non-Cryst.Solids, 1981,44:65
14. Inoue A., Kohinata M., Ohtera K., Tsai A.P. and Masumoto T.. Mg-Ni-La Amorphous Alloys with a Wide Supercooled Liquid Region. Mater. Trans., JIM, 1989, 30:378-381
15. Kim S. G., Inoue A. and Mosumoto T.. High Mechanical Strengths of Mg-Ni-Y and Mg-Cu-Y Amorphous Alloys with Significant Supercooled Liquid Region. Mater. Trans., 1990, JIM, 31:929-934
16. Inoue. A, Zhang, T and Mosumoto. T.. AI-La-Ni Amorphous Alloys with a Wide Supercooled Liquid Region. Mater. Trans., JIM, 1989, 30:965-972
17. Inoue A., Kita K., Zhang T. and Mosumoto T.. An Amorphous La_(55)Al_(25)Ni_(20) Alloy Prepared by Water Quenching. Mater. Trans., JIM, 1989, 30:722-725
18. Inoue A., Yamaguchi H., Zhang T. and Mosumoto T.. Al-La-Cu Amorphous Alloys with a Wide supercooled Liquid Region. Mater. Trans., JIM, 1990, 31:104-109
19. Inoue A., Zhang T. and Mosumoto T.. Zr-Al-Ni Amorpuous Alloys with High Glass Transition Temperature and Significant Supercooled Liquid Region. Mater. Trans., JIM, 1990, 31:177-183
20. Inoue A., Nishiyama N. and Matsuda T.. Preparation of Bulk Glassy Pd_(40)Ni_(10)Cu_(30)P_(20) Alloy of 40 mm in Diameter by Water Quenching. Mater. Trans., JIM, 1996, 37:181-184
21. Inoue A., Zhang T., Zhang W. and Takeuchi.. A Bulk Nd-Fe-Al Amorphous Alloys with Hard Megnetic Properties. Mater. Trans., JIM, 1996, 37:99-108
22. Zhang T. and Inoue A.. Density.Thermal Stability and Mechanical Properties of Zr-Ti-Al-Cu-Ni Bulk Amorphous Alloys with High Al Plus Ti Concentrations. Mater. Trans., JIM, 1998, 39:857-862
23. Peker A. , Johnson W. L.. A Highly Processable Metallic Glass: Zr_(41.2)Ti_(13.8)Cu_(12.5)Ni_(10.0)Be_(22.5). Appl. Phys. Lett., 1993,63:2342-2344
24. Nishyama N., Inoue A.. Glass-Forming Ability of Bulk Pd_(40)Ni_(10)Cu_(30)P_(20) Alloy. Mater. Trans., JIM, 1996, 37:1531～1539
25. Wang Limin, Ma Liquan, Kimura. H, Inoue A.. Amorphous Forming Ability and Mechanical Properties of Rapidly Solidified AI-Zr-LTM (LTM=Fe, Co, Ni and Cu) Alloys. Materials Letters, 2002, 52(1-2):47-52
26. Das S. K., Perepezko J. H., Wu R. H., Wilde G.. Undercooling and Glass Formation in Al-based Alloys. Mater. Sci. and Eng., 2001, A304-306:159～165
27. Zhong Z. C., Jiang X. Y., Greer A. L. Microstructure and Hardening of Al-based Nanophase Composites. Mater. Sci. and Eng., 1997, A226-228:531～535
28. Bee D. H., Kim H. K., Kim S. H., Kim W. T. Mechanical Behavior of a Bulk Cu-Ti-Zr-Ni-Si-Sn Metallic Glass Forming Nano-crystal aggregate Bands during Deformation in the Supercooled Liquid region. Acta. Mater., 2002, 50(7):1749～1759
29. Janik-Czachor M., Szummer A., Bukowska J., Molnar A., Mack P., Filipek S. M., Kedzierzawski P. Modification of Surface Activity of Cu-based Amorphous Alloys by Chemical Process of Metal Degradation. Applied Catalysis A: General. 2002, 235(1-2):157-170
30. Kawashima A., Habazaki H., Hashimoto K. Highly Corrosion-Resistant Ni-based Bulk Amorphous Alloys. Mater. Sci. and Eng., 2001, A304-306:753～757
31. Zhang. T, Inoue. A. Ti-based Amorphous Alloys with a Large Supercooled Liquid Region. Mater. Sci. Eng. 2001, A304-306:771～774
32. Kim K. B., Kim. S. H, Kim. W. T, Kim. D. H. Structural Evolution of the Ti_(70)Ni_(15)Al_(15) Powders Prepared by Mechanical Alloying. Mater. Sci. and Eng., 2001, A300 (1-2):148～152
33. Gebert A., Wolff U., John A., Eckert J., Schultz L. Stability of the Bulk Glass-forming Mg65Y10Cu25 Alloy in Aqueous Electrolytles. Mater. Sci. and Eng., 2001, A299:125～135
34. Yim Choi, Haein, Conner, Robert D., Johnson W. L. Processing, Microstructure and Properties of Bulk Metallic Glass Composites. 2002, 27(5):113～118
35. Haein, Yim Chio, Robert D., Conner, Frigyes Szuecs, Johnson W. L. Quasistatic and Dynamic Deformation of Tungstern Reinforced Zr_(57)Nb_5Al_(10)Cu_(15.4)N_(12.6)Bulk Metallic Glass Matrix Composites. Scripta Mate., 2001, 45:1039～1045
36. Yokoyama, Yoshihiko. Ductility Improvement of Zr-Cu-Ni-Al Glass Alloy. J. Non-Cryst. Solids, 2003, 316(1):104～113
37. F. Beuche, J. Chem. Phys., 21(1953): 1850; 24(1953): 418; 30(1959):748
38．张海峰，丁炳哲，胡壮麒．块状金属玻璃研究进展．金属学报．2001，37(11)：1132～1141
39. Kawamura Y., Shibata T., Inoue A., and Masumoto T. Workability of the Supercooled Liquid in the Zr_(65)Al_(10)Ni_(10)Cu_(15)Bulk Metallic Glass. Acta Meta., 1998, 46:253-263
40. Inoue A., Zhang T., Nishiyama N., Ohba K. and Masumoto T. Preparation of 16 mm Diameter Rod of Amorphous Zr_(65)Al_(7.5)Ni_(10)Cu_(17.5) Alloys. Mater. Trans., JIM, 1993, 34:1234-1237
41. Inoue A. and Zhang T. Fabrication of Bulky Zr-based Glassy Alloys by Suction Casting into Copper Mold. Mater. Trans., JIM, 1995, 36:1184～1187
42. Inoue A. and Zhang T. Fabrication of Bulk Glassy Zr_(55)Al_(10)Ni_5Cu_(30) Alloys of 30mm in Diameter by a Suction Casting Method. Mater. Trans., JIM, 1996, 37:185～187
43. Inoue A., Yokoyama Y,, Shinohara Y., Masumoto T. Preparation of Bulky Zr-based Amorphous Alloys by a Zone Melting Method. Mater. Trans., JIM, 1994, 35:923～926
44. Kang H. G., Park E. S., Kim W. T., g Kim D. H. and Cho H. K. Fabrication of Bulk Mg-Cu-Ag-Y Glassy Alloy by Squeeze Casting. Mater. Trans., JIM, 2000, 40:846～849
45．张海峰，丁炳哲，王爱民，李宏，胡壮麒．中国发明专利．01128043．2，2001
46. Egami T..Mater.Res.Bull., 1978, 13:557
47. Cost J.R.,Stanley J.T.,Thijsse B.J..Structural Relaxation in Pd-Ge metallic glass,Mater.Sci.Eng. 1988,97:523-7
48. Van den Beukel A..In rapidly quenched matetial,edited by P.W.Lee and S.Carbonara(ASM,Ohio), 1986:193-203
49. Takahara Yo and Matsuda H..Reversible structural relaxation in Fe-B-Si amorphous alloys,Mater, Sci.Eng., 1994,A 179/180:279-82
50. Van Den Beukel A. and Radelaar S..On the kinetic of structural relaxation in metallic gtasses,Acta Metall. 1983,31:419-27
51. H.S. Chen.In Rapidly Quenched Metals Ⅳ. ed. By T. Masumoto and K. Suzuki, Vol.1:495
52. J. M. Ziman, Phil. Mag., 6(1961):1031
53. Kelton K.F.,Spaepen F., Kinetics of structural relaxation in several metallic glasses observed by changes in electronic resistivity. Phys.Rev.B, 1984,30:5516-24
54. Kissinger H.E..Reaction kinetics in diferential thermal analysis. Anal. Chem.,1957, 29:1702-6
55. Ghosh G..Chandrasekaran M., and Delaey L.,Isothermal crystallization kinetics of Ni24Zr76 and Ni24(Zr-X)76 amorphous alloys. Acta Metaall. Mater.,1991, 39:925-936
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