CN100510114C - Heat treating process for Fe-based big block amorphous alloy crystallization - Google Patents
Heat treating process for Fe-based big block amorphous alloy crystallization Download PDFInfo
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- CN100510114C CN100510114C CNB200710171695XA CN200710171695A CN100510114C CN 100510114 C CN100510114 C CN 100510114C CN B200710171695X A CNB200710171695X A CN B200710171695XA CN 200710171695 A CN200710171695 A CN 200710171695A CN 100510114 C CN100510114 C CN 100510114C
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Abstract
The invention discloses a thermal treatment process of the crystallization of the Fe-based large non-crystallized alloy and the process belongs to the thermal treatment process technology field for preparing the magnetic materials. The process is characterized by that a magnetic filed with an impulse magnetic filed strength of 2 to 8 T is added on the Fe-based large non-crystallized alloy under the crystallization temperature for vacuum annealing thermal treatment and the different patterns of the impulse magnetic field application and annealing are adopted, i.e. the temperature is kept until half of the annealing time passes and then the process of magnetization is implemented until 5 to 10 minutes of air cooling and then the process is stopped. By adopting the process of the invention, the remanence and coercive force of the Fe-based large non-crystallized alloy are obviously enhanced. The process of the invention provides a novel plan for preparing magnetic part with excellent magnetic permeability performance.
Description
Technical field
The present invention relates to a kind of thermal treatment process of Fe based big block amorphous alloy crystallization, belong to the thermal treatment process technology field of magneticsubstance.
Background technology
People launch research to the Fe base large amorphous alloy from nineteen nineties, taked a lot of means and method to understand the formation and the structure of amorphous and the reason that causes its characteristic, in addition, amorphous again the performance after the metastable state crystallization also become the focus of research gradually.Since Yoshizawa in 1988, to containing micro Cu, the iron-based non-crystalline alloy of Nb is carrying out short-cycle annealing a little more than its crystallization temperature, after having found the nanometer crystal alloy Finement of excellent soft magnetic performance, start the upsurge of research amorphous nanocrystalline soft magnetic material in the world wide, occurred the research method of multiple non-crystaline amorphous metal nano-crystallization in succession.Nineteen ninety, Lu Ke has proposed a kind of novel method of preparation nanocrystal---and amorphous complete crystallization method, this method have that technology is simple, grain fineness number is easy to control, interface cleanness and do not contain advantage such as micropore hole.This preparation method becomes one of 3 kinds of main preparation methods of current international nano material in the extensive approval that international nano material circle obtains going together.
So, the research of amorphous crystallization has been caused again adopting the exploration of which type of thermal treatment process in the amorphous alloy crystallization process.When adopting the conventional annealing crystallization, it is found that the magnetic field crystallization that adds of amorphous alloy is handled the average grain size of optimum performance magnet is diminished, thereby being gone up magnetic property, its macroscopic view produces favourable influence.The Yang and the Park of Korea S have studied Nd
2Fe
14B/Fe
3The B alloy is the variation of magnetic property after the anneal under high-intensity magnetic field, finds to add high-intensity magnetic field at home and abroad in annealing process, can crystal grain thinning, and uniform crystal particles is distributed, making that soft or hard magnetic is alternate has stronger exchange lotus root cooperation usefulness, thereby improves the remanent magnetism and the magnetic energy product of magnet.Wang Yan etc. think, at non-crystalline state Nd
8Fe
65Co
10B
17In the alloy crystallization process, magnetic field has suppressed metastable Nd
2Fe
23B
3Separate out, make it be decomposed into stable Nd
2Fe
14B and α-Fe are mutually.Reason is Nd
2Fe
23B
3From magnetic field, obtained energy, decomposed and cross potential barrier.Find also that simultaneously magnetic field makes crystal grain diminish, crystal grain distributes and becomes more even, and the amount of remaining amorphous phase is reduced, think that by thermomechanical analysis the existence in magnetic field has changed the free energy of system, thereby increased nucleation rate, make grain refining, and reduced the amount of amorphous phase.Research such as Zhu Jian high-intensity magnetic field finds that to the influence of Nd-Fe-Co-B amorphous alloy crystallization process high-intensity magnetic field has promoted the amorphous crystallization, has quickened Fe
3B, Nd
2Fe
23B
3To α-Fe, Nd
1.1Fe
4B
4And TbCu
7Type is Nd in opposite directions
2Fe
14B changes mutually.Simultaneously, the magnetic field crystal grain thinning makes even grain size, has strengthened the alternate exchange lotus root cooperation usefulness of soft or hard magnetic, has improved the magnetic property of magnet.Chao Yuesheng etc. are to non-crystaline amorphous metal Fe7
8Si
9B
13Carry out low frequency pulsed magnetic fields and handled the back discovery, as pulse-repetition 20-25Hz, magnetic field 16-32kAPm, action time≤2min, alloy generation nano-crystallization, nanophase α-Fe (Si) grain-size is 10nm.
Non-crystaline amorphous metal externally-applied magnetic field thermal treatment in the existing literature report, comprise pulsed magnetic field and high-intensity magnetic field, the general amorphous ribbon sample that is applied to more, by the crystallizing amorphous band of the thermal treatment process of externally-applied magnetic field, by the crystallizing amorphous band of the thermal treatment process in the magnetic field, thereby improve the soft magnetism or the hard magnetic of band.We are then preparing with suction casting method on the basis of Fe base large amorphous alloy, use applying pulse magnetic-field annealing technology crystallization large block amorphous, thereby improve magnetic property and soft or hard magnetic exchange-coupling interaction mutually after the block amorphous alloy crystallization.
Summary of the invention
The thermal treatment process that the purpose of this invention is to provide a kind of Fe based big block amorphous alloy crystallization, particularly a kind of Fe base large amorphous alloy is in the thermal treatment process that adds heating crystallization under the condition of pulsed magnetic field.Make bulk amorphous alloys after adding the magnetic field heating crystallization, improve its magnetic property.
The objective of the invention is to realize by following steps:
A kind of thermal treatment process of Fe based big block amorphous alloy crystallization, its processing step is as follows:
A. the Fe base large amorphous alloy is carried out the conventional subsequent annealing of one group of temperature, the sample after each annealing is measured magnetic hysteresis loop and the facies analysis of XRD crystallization, determine the crystallization temperature of this Fe base large amorphous alloy;
B. the Fe base large amorphous alloy is put into vacuum heat treatment furnace, extract furnace air and reach 3～5 * 10 up to vacuum tightness
-3Begin during Pa to heat up, be incubated after being warmed up to crystallization temperature, the annealing soaking time is 15～30min, and a half that is incubated the annealing soaking time begins to magnetize and stops behind cooling air-cooling 5～10min, the pulsed magnetic field frequency that magnetizes is 0.02～0.07Hz, and magneticstrength is 2～8T.
The material that technology of the present invention was suitable for is the Fe base large amorphous alloy that can form soft or hard magnetic phase after the crystallization, and this alloy has good amorphous formation ability, and at room temperature shows as soft magnetism.The step of design and preparation Fe base large amorphous alloy is as follows:
(1). in the composition design, must meet and can form soft or hard magnetic phase behind this big block amorphous alloy crystallization (for example α-Fe is mutually and Nd
2Fe
14The B phase) condition;
(2). by above-mentioned mentality of designing proportioning technical pure raw metal and master alloy, become alloy pig with the melting under argon shield of non-consumable electric arc, and with the mother alloy melt back;
(3). adopt copper mold negative pressure suction casting method to make bulk amorphous alloys, melting current density 100～220A/cm
2, obtain being of a size of the bulk amorphous alloys of 1mm * 10mm * 80mm.
Crystallization temperature is determined by following steps: the conventional subsequent annealing that earlier the Fe base large amorphous alloy is carried out one group of temperature range (as 3 temperature spots), subsequently the sample after each annealing is measured magnetic hysteresis loop and the facies analysis of XRD crystallization, determine when which annealing temperature point, to have formed soft or hard magnetic phase behind the big block amorphous alloy crystallization, and then determine its crystallization temperature and select this crystallization temperature as annealed temperature under pulsed magnetic field.
Technology characteristics of the present invention has: (1) has adopted the method for introducing pulsed magnetic field when the annealing crystallization is handled the Fe base large amorphous alloy, purpose is to guarantee to separate out in the process of soft or hard magnetic phase in large block amorphous crystallization, the applying pulse magnetic field energy plays crystal grain thinning, promotes the effect that soft or hard magnetic forms mutually and magnetic domain is rotated; (2) adopt pulsed magnetic field and the asynchronous mode of annealing of applying, a half that promptly is incubated the annealing soaking time begins to magnetize again and stops behind cooling air-cooling 5～10min, purpose is to promote after the crystallization in the alloy soft or hard magnetic phase exchange-coupling interaction and avoid in the process of cooling, before because the magnetic domain that the action of a magnetic field rotates is down recovered mixed and disorderly orientation because of the disappearance in magnetic field.
The present invention is the applying pulse thermomagnetic treatment technology that Fe base large amorphous alloy material is carried out, and adopts magnetic property such as the remanent magnetism and the coercive force of the Fe base large amorphous alloy after this technology crystallization, improves a lot.The Fe base large amorphous alloy remanent magnetism of conventional subsequent annealing is 36.1Am among Fig. 1
2Kg
-1, and the remanent magnetism of the Fe base large amorphous alloy by the pulsed magnetic field subsequent annealing is 41.9Am
2Kg
-1, improved 16.1%; The Fe base large amorphous alloy coercive force of conventional subsequent annealing is 497.9kAm among Fig. 2
-1And the coercive force of the Fe base large amorphous alloy by the pulsed magnetic field subsequent annealing is 610.1kAm
-1, improved 22.5%.Technology of the present invention provides a kind of new departure for the magnetics of preparation excellent magnetic energy.
Description of drawings
Fig. 1 is that nominal composition is Fe
68Nd
5Zr
2Y
4B
21Bulk amorphous alloys, with applying pulse magnetic-field annealing (technology of the present invention) with after not adding magnetic-field annealing (conventional thermal treatment crystallization process) and handling, at room temperature carry out the result of magnetism testing.
Fig. 2 is that nominal composition is Fe
66Nd
7Zr
2Y
4B
21Bulk amorphous alloys, with applying pulse magnetic-field annealing (technology of the present invention) with after not adding magnetic-field annealing (conventional thermal treatment crystallization process) and handling, at room temperature carry out the result of magnetism testing.
Embodiment
After now embodiments of the invention specifically being described in.
Embodiment 1
The concrete steps of present embodiment are as follows:
(1). the design nominal composition is Fe
68Nd
5Zr
2Y
4B
21And Fe
66Nd
7Zr
2Y
4B
21Two Fe base large amorphous alloys; according to formulation ratio technical pure raw metal and master alloy; become alloy pig with the melting under argon shield of non-consumable electric arc, adopt copper mold negative pressure suction casting method to prepare the bulk amorphous alloys that is of a size of 1mm * 10mm * 80mm.
(2). two Fe base large amorphous alloys are carried out conventional subsequent annealing in heat treatment furnace, be chosen in temperature range and be one group of 3 temperature spot of 650 ℃～750 ℃, by the sample after the annealing of each annealing temperature point being surveyed magnetic property and being done the XRD facies analysis, determine when annealing for 690 ℃ and 700 ℃, large block amorphous crystallization has formed soft or hard magnetic phase, and then the crystallization temperature of definite two non-crystaline amorphous metals is distinguished 690 ℃ and 700 ℃.
(3). two Fe base large amorphous alloys are put into vacuum heat treatment furnace respectively, extract furnace air and reach 4 * 10 until vacuum
-3Heat up behind the Pa, be warming up to 690 ℃ and 700 ℃ respectively after the insulation, the annealing soaking time is 30min, begin again to magnetize when being incubated and behind cooling air-cooling 5min, stop to 15min, the pulsed magnetic field frequency that is applied is 0.05Hz, and magneticstrength is 5T, and the time of magnetizing is 20min.
Characteristics in the embodiment of the invention are: the Fe base large amorphous alloy is being added employing crystallization temperature annealing thermal treatment under the pulsed magnetic field, impel in the bulk amorphous alloys soft or hard magnetic to separate out mutually, and magnetic domain is deflected, promote exchange-coupling interaction, thereby improve the remanent magnetism and the coercive force of non-crystaline amorphous metal, improve the magnetic property of alloy.
Prepared two Fe base large amorphous alloys in the present embodiment pass through conventional subsequent annealing and add two kinds of processing schemes of pulsed magnetic field subsequent annealing.At room temperature, the Fe base large amorphous alloy of two kinds of treatment process is carried out magnetic property measure, comparison diagram is seen accompanying drawing 1,2.Can find out the Fe based big block amorphous alloy crystallization of using technology of the present invention from accompanying drawing after, its magnetic property is significantly improved.Alloy Fe
68Nd
5Zr
2Y
4B
21Remanent magnetism by 36.1Am
2Kg
-1Bring up to 41.9Am
2Kg
-1, increase rate is 16.1%; Alloy Fe
66Nd
7Zr
2Y
4B
21Coercive force by 497.9kAm
-1Bring up to 610.1kAm
-1, increase rate is 22.5%.
Claims (1)
1. the thermal treatment process of a Fe based big block amorphous alloy crystallization, described Fe base large amorphous alloy is the Fe base large amorphous alloy that can form soft or hard magnetic phase after the crystallization, and this alloy has good amorphous formation ability, and at room temperature show as soft magnetism, it is characterized in that having following processing step:
A. the Fe base large amorphous alloy is carried out the conventional subsequent annealing of one group of temperature, the sample after each annealing is measured magnetic hysteresis loop and the facies analysis of XRD crystallization, determine the crystallization temperature of this Fe base large amorphous alloy;
B. the Fe base large amorphous alloy is put into vacuum heat treatment furnace, extract furnace air and reach 3～5 * 10 up to vacuum tightness
-3Begin during Pa to heat up, be incubated after being warmed up to crystallization temperature, the annealing soaking time is 15～30min, and a half that is incubated the annealing soaking time begins to magnetize and stops behind cooling air-cooling 5～10min, the pulsed magnetic field frequency that magnetizes is 0.02～0.07Hz, and magneticstrength is 2～8T.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101717901B (en) * | 2009-12-22 | 2011-07-20 | 上海大学 | Process and device for amorphous thin ribbon heat treatment under the action of pulsed magnetic field |
| CN101892376A (en) * | 2010-06-29 | 2010-11-24 | 上海大学 | Thermal treatment process for crystallizing nano-composite NdFeB permanent magnetic alloy |
| CN102565109B (en) * | 2012-01-06 | 2015-08-19 | 青岛云路新能源科技有限公司 | Phase Analysis |
| EP3050977B1 (en) * | 2013-09-27 | 2018-11-21 | Hitachi Metals, Ltd. | Method for producing fe-based nano-crystal alloy, and method for producing fe-based nano-crystal alloy magnetic core |
| CN109752397B (en) * | 2018-11-26 | 2021-09-10 | 湖南理工学院 | Method for detecting cluster type of amorphous alloy |
| CN110526298B (en) * | 2019-09-30 | 2022-07-15 | 北京无线电测量研究所 | Method for preparing ferrite at low temperature by magnetic field assisted glass crystallization method |
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Non-Patent Citations (6)
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| Fe78Si9B13非晶合金纳米晶化的低频脉冲磁场处理方法. 张艳辉等.东北大学学报（自然科学版），第24卷第10期. 2003 |
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