CN100365745C - Method for preparing rare-earth iron series biphase nanocrystalline composite permanent-magnet material - Google Patents
Method for preparing rare-earth iron series biphase nanocrystalline composite permanent-magnet material Download PDFInfo
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- CN100365745C CN100365745C CNB2005100871145A CN200510087114A CN100365745C CN 100365745 C CN100365745 C CN 100365745C CN B2005100871145 A CNB2005100871145 A CN B2005100871145A CN 200510087114 A CN200510087114 A CN 200510087114A CN 100365745 C CN100365745 C CN 100365745C
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Abstract
The present invention belongs to the field of magnetic materials. At present, most of permanent magnet materials are thin strips or powders, crystal grains can grow up caused by preparing block materials with the traditional sintering process, and accordingly, the magnetic property is obviously reduced. The present invention comprises following steps: the alloy of which the component is RxFeyBz is smelted into mother alloy in an alloy vacuum medium frequency induction furnace, wherein R is a rare earth element of Nd or Pr, x is from 4 to 10, y is from 78 to 88, and z is from 6 to 18, and then, quenched state alloy of the non-crystalline state, the nanometer crystalline state or mixed state of the non-crystalline state and the nanometer crystalline state can be prepared by using a fusant quick-quenching method, and the linear speed of fusant quick-quenching is 10 to 50 meters/second; under the protection of inert gas, the quenched state alloy is skived to alloy powders of which the granularity is less than 80 meshes; the powders are put in a mould to be prepressed and molded, and the range of the pressure is between 10MPa and 1000MPa; the processing of the discharge plasma sintering technology is carried out, the sintering temperature is between 550 DEG C and 700 DEG C, the pressure is between 30MPa and 1000MPa, the heating rate is between 50 and 500 DEG C/min, heat preservation time is between 0 and 10 minutes, and the cooling rate is between 50 and 200 DEG C/min. The present invention can obtain materials of which the density is high, crystal grain is smaller than 100 nanometers, the magnetic property is high, and the usage temperature is high.
Description
1. technical field
A kind of preparation method of full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material belongs to technical field of magnetic materials.
2. background technology
Nanocrystalline composite permanent magnetic RE material is a class new rare-earth permanent magnetic material.Be characterized in that exchange coupling under nano-scale becomes the two-phase composite permanent-magnetic material with high remanent magnetism, high-coercive force with the permanent magnetism with high-coercive force mutually with the soft magnetism of high saturation and magnetic intensity.Calculating shows that this class material has up to 1090kJ/m
3Theoretical maximum magnetic energy product (Skomski R, Coey JM D.Phys.Rev.B 1994,48:15812).People have adopted means such as melt-quenching method and mechanical alloying method to prepare Nd at present
2Fe
14B/Fe
3B (Kneller E F, Hawig R.IEEE Trans Magn, 1991,27:3588; International electric engineering association magnetics monograph), Nd
2Fe
14B/ α-Fe (Manaf A, Buckley R A, DavisH A.J Magn Magn Matef, 1993,128:302; Magnetics and magnetic material journal) etc. multiple nano composite permanent magnetic material.Yet, there is a difficult problem in this class permanent magnetic material in the practicability process, particularly, this class material of preparation mostly is strip or powder at present, adopt the fully dense block materials of conventional sintering prepared can cause material grains to grow up, thereby significantly reduce magnetic property, therefore can only be made into bonded permanent magnet, so just caused declining to a great extent of magnet magnetic property.
At the problems referred to above, the present invention adopts discharge plasma sintering technique (Spark PlasmaSintering is called for short the SPS technology) the full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material of preparation.The result shows that adopt the novel NdFeB permanent magnetic material of SPS technology preparation to have following advantage: (1) density reaches congruent alloy theory density more than 98%, has well solved the low density problem of bonded permanent magnet, and the magnet magnetic property is improved largely; (2) binder free in the magnet is compared with bonding class magnet, has higher serviceability temperature; (3)
The magnet microscopic structure is even, crystal grain is tiny, and crystallite dimension is less than 100 nanometers.
The SPS technology is a kind of pressure sintering method (the device schematic diagram as shown in Figure 1) of utilizing DC-pulse flow-thru electrode sintering.Its basic principle is to make inner each of sintered body evengranularly self produce Joule heat and make the particle surface activation by the plasma discharging that electrode is fed the instantaneous generation of dc pulse current, realizes sintering in pressurization.This technology has following characteristics: (1) sintering temperature is low, generally is lower than 200-300 ℃ of ordinary sinter temperature; (2) sintered heat insulating time weak point only needs 3-5 minute, only is about 1/100 of ordinary sinter temperature retention time; (3) sintering can be realized pressurization, reaches as high as 1000Mpa; (4) can obtain high compactedness material; (5) can obtain tiny, uniform grain structure.Therefore, adopt this sintering method when realizing the rare-earth iron series biphase nanocrystalline powder densification, effectively to suppress the grain growth phenomenon of material internal.Thereby guarantee that magnet obtains nanometer crystal microstructure and desirable magnetic property.This application for further this type of material of expansion is significant.
3. summary of the invention
The invention provides a kind of method of utilizing discharge plasma sintering technique to prepare full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material.Purpose is the Fe that acquisition has high-compactness, small grains tissue (crystal grain is less than 100 nanometers) and high magnetic characteristics and high serviceability temperature
3B/R
2Fe14B base system row and α-Fe/R
2Fe
14The B base system is listed as full compact block biphase nanocrystalline composite permanent-magnet alloy.
The preparation method of rare-earth iron series biphase nanocrystalline composite permanent-magnet material provided by the invention is characterized in that, may further comprise the steps:
Step 1: with composition is F
xFe
yB
zAlloy, wherein R is rare earth Nd or Pr element, x wherein, y, z are atomic percent, x:4-10, y:78-88, z:6-18 is master alloy melting in the alloy vacuum medium frequency induction furnace, makes the attitude alloy of quenching of amorphous state, crystalline state nanometer or amorphous and nanocrystalline mixed state afterwards with existing melt-quenching method, and the linear velocity of fast melt-quenching is the 10-50 meter per second;
Step 2: the attitude alloy of quenching of above-mentioned preparation is ground to granularity less than 80 purpose alloy powders under inert gas shielding;
Step 3: with the alloy powder of above-mentioned preparation pack into Talide mould or graphite jig and pre-molding, pressure limit 10-1000Mpa;
Step 4: utilize discharge plasma sintering technique to carry out sintering processes on above-mentioned alloy powder green compact through pre-molding, 550 ℃-700 ℃ of sintering temperatures, sintering pressure 30-1000Mpa, heating rate 50-500 ℃/min, temperature retention time 0-10min, rate of temperature fall 50-200 ℃/min, the magnet behind the sintering is full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material of the present invention.
In above-mentioned preparation method, can carry out crystallization and thermal treatment to the permanent magnetic material behind the sintering.
The rare earth permanent-magnetic material that utilizes the present invention to prepare, have the density height, magnet density reaches that congruent materials theory density (sees Table 1) more than 98%, the crystallite dimension of heterogeneity system magnet is all less than characteristics (seeing Table 1) such as 100 nanometers (seeing Fig. 2,3), magnetic property height.
4. description of drawings
Fig. 1: discharging plasma sintering equipment structure principle chart.
Fig. 2: the crystal grain micro-organization chart (high explanation transmission electron microscope photo) that adopts the full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material (embodiment 1) of discharge plasma sintering technique preparation.
Fig. 3: the crystal grain micro-organization chart (high explanation transmission electron microscope photo) that adopts the full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material (embodiment 2) of discharge plasma sintering technique preparation.
Fig. 4: the crystal grain micro-organization chart (high explanation transmission electron microscope photo) that adopts the full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material (embodiment 3) of discharge plasma sintering technique preparation.
Fig. 5: the crystal grain micro-organization chart (high explanation transmission electron microscope photo) that adopts the full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material (embodiment 4) of discharge plasma sintering technique preparation.
Fig. 6: the demagnetization curve figure that adopts the full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material (embodiment 1) of discharge plasma sintering technique preparation.
5. embodiment
Example 1, be Nd with composition
10Fe
84B
6Alloy carry out fast melt-quenching after adopting vacuum induction melting, the linear velocity of fast quenching is 50 meter per seconds.Fast quenched alloy is ground to granularity less than 80 purpose alloy powders under inert gas shielding.With above-mentioned alloy powder pack into graphite jig and pre-molding.Pressure 30MPa.Green compact utilization discharge Fast Sintering technology is sintered into block materials.Concrete sintering process parameter is: 700 ℃ of sintering temperatures, sintering pressure 30Mpa, 50 ℃/min of heating rate, temperature retention time 5min, 150 ℃/min of rate of temperature fall.
Example 2, be Nd with composition
8Fe
86B
6Alloy carry out fast melt-quenching after adopting vacuum induction melting, the linear velocity of fast quenching is 20 meter per seconds.Fast quenched alloy is ground to granularity less than 80 purpose alloy powders under inert gas shielding.With above-mentioned alloy powder pack into graphite jig and pre-molding.Pressure 300MPa.Green compact utilization discharge Fast Sintering technology is sintered into block materials.Concrete sintering process parameter is: 650 ℃ of sintering temperatures, sintering pressure 300Mpa, 100 ℃/min of heating rate, temperature retention time 0min, 200 ℃/min of rate of temperature fall.
Example 3, be Nd with composition
6Fe
88B
6Alloy carry out fast melt-quenching after adopting vacuum induction melting, the linear velocity of fast quenching is 22 meter per seconds.Fast quenched alloy is ground to granularity less than 80 purpose alloy powders under inert gas shielding.With above-mentioned alloy powder pack into graphite jig and pre-molding.Pressure 500MPa.Green compact utilization discharge Fast Sintering technology is sintered into block materials.Concrete sintering process parameter is: 600 ℃ of sintering temperatures, sintering pressure 500Mpa, 300 ℃/min of heating rate, temperature retention time 2min, 100 ℃/min of rate of temperature fall.
Example 4, be Pr with composition
4Fe
78B
18Alloy carry out fast melt-quenching after adopting vacuum induction melting, the linear velocity of fast quenching is 10 meter per seconds.Fast quenched alloy is ground to granularity less than 80 purpose alloy powders under inert gas shielding.With above-mentioned alloy powder pack into graphite jig and pre-molding.Pressure 1000MPa.Green compact utilization discharge Fast Sintering technology is sintered into block materials.Concrete sintering process parameter is: 550 ℃ of sintering temperatures, sintering pressure 1000Mpa, 200 ℃/min of heating rate, temperature retention time 5min, 50 ℃/min of rate of temperature fall.At last the magnet behind the sintering is carried out crystallization and thermal treatment, heat treatment temperature: 680 ℃, time 30min.
Table 1
Claims (1)
1. the preparation method of rare-earth iron series biphase nanocrystalline composite permanent-magnet material is characterized in that, may further comprise the steps:
Step 1: with composition is R
xFe
yB
zAlloy, wherein R is rare earth Nd or Pr element, x wherein, y, z are atomic percent, x:4-10, y:78-88, z:6-18 is master alloy melting in the alloy vacuum medium frequency induction furnace, makes the attitude alloy of quenching of amorphous state, crystalline state nanometer or amorphous and nanocrystalline mixed state afterwards with melt-quenching method, and the linear velocity of fast melt-quenching is the 10-50 meter per second;
Step 2: the attitude alloy of quenching of above-mentioned preparation is ground to granularity less than 80 purpose alloy powders under inert gas shielding;
Step 3: with the alloy powder of above-mentioned preparation pack into Talide mould or graphite jig and pre-molding, pressure limit 10-1000Mpa;
Step 4: utilize discharge plasma sintering technique to carry out sintering processes on above-mentioned alloy powder green compact through pre-molding, 550 ℃-700 ℃ of sintering temperatures, sintering pressure 30-1000Mpa, heating rate 50-500 ℃/min, temperature retention time 0-10min, rate of temperature fall 50-200 ℃/min, the magnet behind the sintering is full compact block rare-earth iron series biphase nanocrystalline composite permanent-magnet material.
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| CN100501883C (en) * | 2007-05-31 | 2009-06-17 | 钢铁研究总院 | High strong toughness iron-base rear earth permanent magnet and its preparation method |
| CN101425355B (en) * | 2008-07-31 | 2011-04-13 | 中国计量学院 | Pr/Nd based biphase composite permanent magnetic material and block body preparing method thereof |
| CN101620906B (en) * | 2009-06-10 | 2011-08-03 | 中国科学院上海硅酸盐研究所 | Block-shaped nanocrystalline magnetically soft alloy material and preparation method thereof |
| CN101894645A (en) * | 2010-06-29 | 2010-11-24 | 上海大学 | Nano-crystal composite NdFeB permanent magnet alloy and heating processing technology for improving magnetic performance thereof |
| CN102655050B (en) * | 2012-05-04 | 2013-12-11 | 江苏大学 | Method for preparing high-performance high-temperature-resisting nanometer composite permanent magnet |
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| CN103440949B (en) * | 2013-08-19 | 2015-10-14 | 南通万宝磁石制造有限公司 | A kind of nanocomposite rare earth permanent-magnetic material and surface-treated method thereof |
| CN103646777A (en) * | 2013-12-11 | 2014-03-19 | 江苏大学 | Method for preparing crystal boundary nano-composite intensified neodymium iron boron magnet |
| JP6393345B2 (en) | 2015-01-22 | 2018-09-19 | アルプス電気株式会社 | Dust core, method for producing the dust core, electric / electronic component including the dust core, and electric / electronic device on which the electric / electronic component is mounted |
| CN104911380A (en) * | 2015-06-09 | 2015-09-16 | 华南理工大学 | Preparation method of ultrafine-grain Ti-6Al-4V alloy |
| CN106856118A (en) * | 2015-12-08 | 2017-06-16 | 北京中科三环高技术股份有限公司 | The thinning method and bonded permanent magnet of nanocrystalline fast quenching rare-earth permanent-magnet material and its crystallite dimension |
| CN107946013B (en) * | 2017-11-27 | 2019-06-07 | 江民德 | A kind of production technology of neodymium iron boron composite magnetic |
| CN108913986B (en) * | 2018-05-18 | 2020-08-28 | 江西理工大学 | Nanocrystalline rare earth permanent magnet material with high corrosion resistance and preparation method thereof |
| CN109243797A (en) * | 2018-08-31 | 2019-01-18 | 江西理工大学 | A kind of preparation method of the nanocrystalline rare-earth permanent magnetic material containing Ce |
| JP2021127490A (en) * | 2020-02-13 | 2021-09-02 | 山陽特殊製鋼株式会社 | Sputtering target material and method for manufacturing the same |
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| CN1411007A (en) * | 2002-11-29 | 2003-04-16 | 北京工业大学 | Preparation method of rare earth-iron-boron permanent magnet material |
| CN1487535A (en) * | 2003-09-01 | 2004-04-07 | 北京科技大学 | Cryogenic treatment method of nano permanent magnetic RE crystal material |
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| CN1358595A (en) * | 2001-11-16 | 2002-07-17 | 清华大学 | Method for making rareearth permanent magnet material by discharge plasma sintering |
| CN1411007A (en) * | 2002-11-29 | 2003-04-16 | 北京工业大学 | Preparation method of rare earth-iron-boron permanent magnet material |
| CN1487535A (en) * | 2003-09-01 | 2004-04-07 | 北京科技大学 | Cryogenic treatment method of nano permanent magnetic RE crystal material |
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