CN101265529A - Method for preparing block-shaped nano-crystal SmCo series permanent magnetic material - Google Patents

Method for preparing block-shaped nano-crystal SmCo series permanent magnetic material Download PDF

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CN101265529A
CN101265529A CNA200810106137XA CN200810106137A CN101265529A CN 101265529 A CN101265529 A CN 101265529A CN A200810106137X A CNA200810106137X A CN A200810106137XA CN 200810106137 A CN200810106137 A CN 200810106137A CN 101265529 A CN101265529 A CN 101265529A
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smco
sintering
magnetic material
crystal
permanent magnetic
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张东涛
岳明
刘卫强
许刚
杨建军
张久兴
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Beijing University of Technology
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Beijing University of Technology
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Abstract

The invention relates to a method for preparing bulk nanometer crystal SmCo permanent magnetic material, and belongs to the technology field of magnetic materials. The prior art can only prepare powdered sample, and can not prepare nanometer crystal SmCo permanent magnet. The inventive method comprises smelting SmCo5, Sm2CO17 and Sm(Co, Cu, Fe, Zr)7.5 alloy into mother alloy, and rapidly quenching at a speed of 40-50 m/s to obtain nanometer crystal thin band; and ball milling for 5-10 hours to obtain amorphous powder, charging into a mould, pre-pressing and forming under pressure of 10-30 Mpa, and sintering with SPS technique to obtain permanent magnetic material, wherein the sintering temperature is 650-750 DEG C, the sintering pressure is 300-1,000 Mpa, the heating rate is 50-200 DEG C/min, and the temperature holding time is 0-10 min. The obtained permanent magnetic material in the invention has the advantages of good density, high coercitive force and good high-temperature magnetic characteristics; and the crystal grain size is less than 100 nm.

Description

The preparation method of block-shaped nano-crystal SmCo series permanent magnetic material
Technical field
The invention belongs to technical field of magnetic materials, be specifically related to a kind of preparation method of full compact block SmCo system nano-crystal permanent magnet material.
Background technology
SmCo system (1: 5 and 2: 17 being) rare earth permanent magnet has excellent high-temperature magnetic energy, is mainly used in high temperature permanent magnetism fields such as Aeronautics and Astronautics and military project.The preparation technology of this class material is comparatively strict and complicated, as SmCo 5Need first slow cooling behind the high temperature sintering, coldly just can obtain high-coercive force soon again, processing condition are relatively harsher, and it is not high to handle bad then coercive force; The Sm of binary 2Co 17Coercive force very low (about 2KOe) obtains cell structure by adding after elements such as Fe, Cu, Zr are handled through complicated precipitation hardening, just make Sm (Co, Cu, Fe, Zr) zAlloy obtains high-coercive force.And present discovering, when grain-size during near single-domain particle material have maximum coercive force.Therefore, as long as make the material microstructure nanometer, do not need complicated technology, material just obtains high-coercive force easily.People have adopted means such as melt-quenching method and mechanical alloying method to prepare nanocrystalline Nd 2Fe 14B permanent magnetism (Kneller EF, et al.IEEE.Trans.Magn., 1991,27:3588; International electric engineering association magnetics monograph) and coercive force up to the nanocrystalline SmCo of 5T 5(J.Ding, et al.J.Alloys Compd., 1993, multiple nano crystal permanent magnetic material such as 191:197).Yet, this class material of preparation mostly is strip or powder at present, can cause grain growth when adopting conventional sintering prepared compact block, coercive force seriously descends, thereby significantly reduce magnetic property, therefore can only be made into bonded permanent magnet, this is the difficult problem that this type of permanent magnet material exists in the practicability process.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, and a kind of method of utilizing discharge plasma sintering technique to prepare the high block SmCo system nano-crystal permanent magnet material of high-compactness, grain structure tiny (crystal grain is less than 100 nanometers), high-coercive force and use temperature is provided.
The preparation method of block SmCo system nano-crystal permanent magnet material provided by the invention may further comprise the steps:
1) be SmCo with composition 5, Sm 2Co 17And Sm (Co, Cu, Fe, Zr) 7.5Alloy in electric arc furnace, be smelted into mother alloy, with melt-quenching method mother alloy is made the fast quenching thin strap of crystalline state nanometer again, the linear velocity of melt-spun is the 40-50 meter per second;
2) with the fast quenching thin strap for preparing in the step 1), under protection of inert gas, high-energy ball milling 5-10h, ratio of grinding media to material is 15: 1, obtains amorphous powder;
3) with step 2) amorphous powder pack into the WC sintered-carbide die and the pre-molding of preparation, pressure range 10-30MPa;
4) utilize discharge plasma sintering technique to obtain block-shaped nano-crystal SmCo series permanent magnetic material with carrying out sintering through the amorphous powder of pre-molding in the step 3); Wherein, sintering temperature is 650-750 ℃, and sintering pressure is 300-1000MPa, and temperature rise rate is 50-200 ℃/min, and soaking time is 0-10min.
Block-shaped nano-crystal SmCo series permanent magnetic material described in the step 4) is SmCo 5, Sm 2Co 17And Sm (Co, Cu, Fe, Zr) 7.5
Discharge plasma sintering technique (Spark Plasma Sintering is called for short the SPS technology) is a kind of DC-pulse flow-thru electrode agglomerating pressure sintering method (the device synoptic diagram as shown in Figure 1) of utilizing.Its ultimate principle is to feed dc pulse current by counter electrode, and the plasma discharging of instantaneous generation makes inner each of sintered compact evengranularly self produce joule heating and make the particle surface activation, realizes sintering in pressurization.This technology has following characteristics: (1) sintering temperature is low, generally than low 200-300 ℃ of ordinary sinter temperature; (2) sintered heat insulating time weak point only needs 3-10 minute; (3) can plus-pressure during sintering, reach as high as 1000MPa; (4) can obtain high compactedness material; (5) can obtain tiny, uniform grain structure.Therefore, adopt the SPS sintering method when realizing that SmCo is powder densification, effectively to suppress the grain growth of material internal, thereby guarantee that magnet obtains nanometer crystal microstructure and ideal magnetic property.This Application Areas for further this type of material of expansion is significant.
Compared with prior art, the present invention has following beneficial effect:
1) the prepared permanent magnet material density of the inventive method 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) the prepared permanent magnet material of the inventive method has high-coercive force (seeing Table 1) and good high-temperature magnetic property;
3) the prepared permanent magnet material microstructure of the inventive method is even, crystal grain is tiny, and grain-size is less than 100 nanometers (seeing Fig. 2,3,4).
Description of drawings
Fig. 1, discharging plasma sintering equipment structural representation.
The block-shaped nano-crystal SmCo of Fig. 2, embodiment 1 preparation 5The transmission electron microscope of permanent magnet material and selected diffraction photo.
The brilliant Sm of the lumpy nanometer of Fig. 3, embodiment 3 preparations 2Co 17The transmission electron microscope of permanent magnet material and selected diffraction photo.
The brilliant Sm of the lumpy nanometer of Fig. 4, embodiment 5 preparations (Co, Cu, Fe, Zr) 7.5The transmission electron microscope of permanent magnet material and selected diffraction photo.
The block-shaped nano-crystal SmCo of Fig. 5, embodiment 1 preparation 5Demagnetizing curve (b) figure under magnetic hysteresis loop of permanent magnet material (a) and the differing temps.
The brilliant Sm of the lumpy nanometer of Fig. 6, embodiment 3 preparations 2Co 17The magnetic hysteresis loop figure of permanent magnet material.
The brilliant Sm of the lumpy nanometer of Fig. 7, embodiment 5 preparations (Co, Cu, Fe, Zr) 7.5The magnetic hysteresis loop figure of permanent magnet material.
Wherein, among Fig. 5 to 7: μ 0H (T): the size of externally-applied magnetic field, unit is tesla (T); μ 0Hc (T): the coercitive size of material, unit is tesla (T); 4 π M (T): the size of the material specific magnetising moment, unit is tesla (T); 4 π Ms (T): the size of material saturation magnetization, unit is tesla (T); 4 π Mr (T): the size of material residual magnetization, unit is tesla (T).
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
Embodiment 1
1) be SmCo with composition 5Alloy carry out melt-spun after adopting arc melting, the linear velocity of fast quenching is 50 meter per seconds;
2) with fast quenched alloy high-energy ball milling 5h under protection of inert gas, obtain amorphous powder, ratio of grinding media to material is 15: 1;
3) amorphous powder is packed into WC sintered-carbide die and pre-molding, pressure is 10MPa;
4) the amorphous powder utilization discharge Fast Sintering technology with pre-molding is sintered into SmCo 5Block materials (performance sees Table 1), concrete sintering process is: under sintering pressure 1000MPa, be warming up to 650 ℃ from room temperature with the temperature rise rate of 50 ℃/min after, insulation 0min.
Embodiment 2
1) be SmCo with composition 5Alloy carry out melt-spun after adopting arc melting, the linear velocity of fast quenching is 50 meter per seconds;
2) with fast quenched alloy high-energy ball milling 5h under protection of inert gas, obtain amorphous powder, ratio of grinding media to material is 15: 1;
3) amorphous powder is packed into WC sintered-carbide die and pre-molding, pressure is 10MPa;
4) the amorphous powder utilization discharge Fast Sintering technology with pre-molding is sintered into SmCo 5Block materials (performance sees Table 1), concrete sintering process is: under sintering pressure 500MPa, be warming up to 700 ℃ from room temperature with the temperature rise rate of 50 ℃/min after, insulation 3min.
Embodiment 3
1) be Sm with composition 2Co 17Alloy carry out melt-spun after adopting arc melting, the linear velocity of fast quenching is 40 meter per seconds;
2) with fast quenched alloy high-energy ball milling 8h under protection of inert gas, obtain amorphous powder, ratio of grinding media to material is 15: 1;
3) amorphous powder is packed into WC sintered-carbide die and pre-molding, pressure 20MPa;
4) the amorphous powder utilization discharge Fast Sintering technology with pre-molding is sintered into Sm 2Co 17Block materials (performance sees Table 1), concrete sintering process is: under sintering pressure 800MPa, be warming up to 700 ℃ from room temperature with the temperature rise rate of 100 ℃/min after, insulation 10min.
Embodiment 4
1) be Sm with composition 2Co 17Alloy carry out melt-spun after adopting arc melting, the linear velocity of fast quenching is 40 meter per seconds;
2) with fast quenched alloy high-energy ball milling 8h under protection of inert gas, obtain amorphous powder, ratio of grinding media to material is 15: 1;
3) amorphous powder is packed into WC sintered-carbide die and pre-molding, pressure 20MPa;
4) the amorphous powder utilization discharge Fast Sintering technology with pre-molding is sintered into Sm 2Co 17Block materials (performance sees Table 1), concrete sintering process is: under sintering pressure 500MPa, be warming up to 750 ℃ from room temperature with the temperature rise rate of 100 ℃/min after, insulation 5min.
Embodiment 5
1) with composition be Sm (Co, Cu, Fe, Zr) 7.5Alloy carry out melt-spun after adopting arc melting, the linear velocity of fast quenching is 45 meter per seconds;
2) with fast quenched alloy high-energy ball milling 10h under protection of inert gas, obtain amorphous powder, ratio of grinding media to material is 15: 1;
3) amorphous powder is packed into WC sintered-carbide die and pre-molding, pressure 30MPa;
4) the amorphous powder utilization of pre-molding discharge Fast Sintering technology is sintered into Sm (Co, Cu, Fe, Zr) 7.5Block materials (performance sees Table 1), concrete sintering process is: under sintering pressure 300MPa, be warming up to 750 ℃ from room temperature with the temperature rise rate of 200 ℃/min after, insulation 5min.
Figure A20081010613700081
The performance of the block-shaped nano-crystal SmCo series permanent magnetic material that table 1 the present invention is prepared

Claims (2)

1, a kind of preparation method of block-shaped nano-crystal SmCo series permanent magnetic material is characterized in that, may further comprise the steps:
1) be SmCo with composition 5, Sm 2Co 17And Sm (Co, Cu, Fe, Zr) 7.5Alloy in electric arc furnace, be smelted into mother alloy, with melt-quenching method mother alloy is made the fast quenching thin strap of crystalline state nanometer again, the linear velocity of melt-spun is the 40-50 meter per second;
2) with the fast quenching thin strap for preparing in the step 1), under protection of inert gas, high-energy ball milling 5-10h, ratio of grinding media to material is 15: 1, obtains amorphous powder;
3) with step 2) amorphous powder pack into the WC sintered-carbide die and the pre-molding of preparation, pressure range 10-30MPa;
4) utilize discharge plasma sintering technique to obtain block-shaped nano-crystal SmCo series permanent magnetic material with carrying out sintering through the amorphous powder of pre-molding in the step 3); Wherein, sintering temperature is 650-750 ℃, and sintering pressure is 300-1000MPa, and temperature rise rate is 50-200 ℃/min, and soaking time is 0-10min.
2, method according to claim 1 is characterized in that, the block-shaped nano-crystal SmCo series permanent magnetic material described in the step 4) is SmCo 5, Sm 2Co 17Or Sm (Co, Cu, Fe, Zr) 7.5
CNA200810106137XA 2008-05-09 2008-05-09 Method for preparing block-shaped nano-crystal SmCo series permanent magnetic material Pending CN101265529A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101476055B (en) * 2009-01-16 2011-02-02 北京工业大学 Preparation of fully dense massive anisotropic nanocrystalline SmCo5 magnet
CN101962722A (en) * 2010-10-15 2011-02-02 北京工业大学 Method for preparing single-phase SmCo7 nanocrystalline alloy block material without doping elements
CN102240810A (en) * 2011-06-24 2011-11-16 北京工业大学 Method for preparing high-coercivity manganese bismuth magnetic powder
CN102543418A (en) * 2012-01-12 2012-07-04 北京工业大学 Method for preparing high-magnetic energy product samarium-cobalt-based permanent magnet by modifying hydrogenated samarium nano powder
CN102568807A (en) * 2012-01-16 2012-07-11 北京工业大学 Method for preparing high-coercivity SmCoFeCuZr (samarium-cobalt-ferrum-copper-zirconium) high-temperature permanent magnet by doping nano-Cu powder
CN103343250A (en) * 2013-07-09 2013-10-09 北京工业大学 Method for improving coercive force of Sm5Co19 alloy through step-by-step doping
CN109148139A (en) * 2018-09-12 2019-01-04 北矿磁材（阜阳）有限公司 A kind of preparation method of high-performance SmCo sintered permanent magnet superelevation autoclaving
CN110024056A (en) * 2016-11-30 2019-07-16 Tdk株式会社 Rare-earth sintered magnet
CN115938771A (en) * 2021-11-05 2023-04-07 燕山大学 SmFe x M 12-x Method for preparing nanocrystalline permanent magnetic material

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101476055B (en) * 2009-01-16 2011-02-02 北京工业大学 Preparation of fully dense massive anisotropic nanocrystalline SmCo5 magnet
CN101962722A (en) * 2010-10-15 2011-02-02 北京工业大学 Method for preparing single-phase SmCo7 nanocrystalline alloy block material without doping elements
CN102240810B (en) * 2011-06-24 2013-07-10 北京工业大学 Method for preparing high-coercivity manganese bismuth magnetic powder
CN102240810A (en) * 2011-06-24 2011-11-16 北京工业大学 Method for preparing high-coercivity manganese bismuth magnetic powder
WO2013104264A1 (en) * 2012-01-12 2013-07-18 北京工业大学 Method for fabricating samarium-cobalt based magnet with high magnetic energy product by modification of samaric hydride nanometer powder
CN102543418A (en) * 2012-01-12 2012-07-04 北京工业大学 Method for preparing high-magnetic energy product samarium-cobalt-based permanent magnet by modifying hydrogenated samarium nano powder
CN102568807A (en) * 2012-01-16 2012-07-11 北京工业大学 Method for preparing high-coercivity SmCoFeCuZr (samarium-cobalt-ferrum-copper-zirconium) high-temperature permanent magnet by doping nano-Cu powder
CN102568807B (en) * 2012-01-16 2013-07-24 北京工业大学 Method for preparing high-coercivity SmCoFeCuZr (samarium-cobalt-ferrum-copper-zirconium) high-temperature permanent magnet by doping nano-Cu powder
WO2013107274A1 (en) * 2012-01-16 2013-07-25 北京工业大学 Method for preparing high-coercivity smcofecuzr high-temperature permanent magnet by doping nano cu powder
CN103343250A (en) * 2013-07-09 2013-10-09 北京工业大学 Method for improving coercive force of Sm5Co19 alloy through step-by-step doping
CN110024056A (en) * 2016-11-30 2019-07-16 Tdk株式会社 Rare-earth sintered magnet
CN109148139A (en) * 2018-09-12 2019-01-04 北矿磁材（阜阳）有限公司 A kind of preparation method of high-performance SmCo sintered permanent magnet superelevation autoclaving
CN115938771A (en) * 2021-11-05 2023-04-07 燕山大学 SmFe x M 12-x Method for preparing nanocrystalline permanent magnetic material
CN115938771B (en) * 2021-11-05 2024-04-12 燕山大学 SmFe (zinc oxide) x M 12-x Preparation method of nanocrystalline permanent magnet material

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