CN1060178A - The preparation method and the equipment thereof of anisotropy crystallite rare earth permanent-magnetic material - Google Patents
The preparation method and the equipment thereof of anisotropy crystallite rare earth permanent-magnetic material Download PDFInfo
- Publication number
- CN1060178A CN1060178A CN 90107845 CN90107845A CN1060178A CN 1060178 A CN1060178 A CN 1060178A CN 90107845 CN90107845 CN 90107845 CN 90107845 A CN90107845 A CN 90107845A CN 1060178 A CN1060178 A CN 1060178A
- Authority
- CN
- China
- Prior art keywords
- quenching
- spray
- working chamber
- chamber
- anisotropy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Hard Magnetic Materials (AREA)
- Continuous Casting (AREA)
Abstract
The present invention relates to ferrous alloy and permanent magnetic material field, particularly rare earth permanent-magnetic material.The invention provides a kind of rare-earth-iron-boron alloy thin band preparation methods and special equipment thereof for preparing magnetic anisotropy.The inventive method is that the rare-earth-iron-boron alloy is smelted in the working chamber, and quench on the single roller of water-cooled in the spray indoor spray of quenching, working chamber and the spray chamber of quenching is separated from each other and is only linked to each other by nozzle, when the alloy spray is quenched, the working chamber is 50～150 millimetress of mercury with the pressure reduction that sprays the chamber of quenching, and single roller roller speed is 16.5～21.5 meter per seconds.It is with low cost to use the inventive method and equipment to obtain, the anisotropy crystallite permanent magnetic material that magnetic energy product is high, method and apparatus simple and feasible.
Description
The present invention relates to ferrous alloy and hard magnetic material field.
The development of permanent magnetic material has been experienced three milestones so far from earlier 1900s, and they are that improvement with maximum magnetic energy product and HCJ is as dividing sign.From the high-carbon steel of the beginning of this century is the phase I of permanent magnetic material development to aluminium nickel cobalt; The ferrite of the '30s exploitation is second milestone; The Rare-Earth Magnetic that the sixties come out then is the 3rd milestone.The rare permanent magnetism of going up of the third generation replaces rare expensive samarium (Sm) with the abundant neodymium (Nd) of reserves, replaces cobalt with iron, and contains boron.The R that contains the about 12at% of rare earth element
2Fe
14B base rare earth magnet is the representative of third generation rare earth permanent magnet.
Aspect the manufacturing process of Nd-Fe-B magnetic material, mainly contain powder metallurgic method, melt spinning method method and reduction-diffusion process.The melt spinning method method is that the alloy with fusion is injected on the metal rolls of a high speed rotating, alloy liquation cooled and solidified at a terrific speed becomes strip, the thickness of this book band is generally 35～50 microns, widely be several millimeters, its institutional framework and roller speed or the speed of quenching are closely related, speed is slow excessively if quench, and then demonstrates thick crystal grain on the strip section, about 3～10 microns of its diameter.The excessive then whole fractography of speed is an amorphous state if quench.There is tangible temperature gradient in the alloy thin band that conventional rapid quenching technique is made on its section in the fast quenching process, the cooling rate that roller rest is taken turns a side is higher than Free Surface, thereby causes the significant difference of institutional framework on the band section; If roller rest is taken turns a side when being crystallite, then the crystal grain of Free Surface is thick; If when Free Surface was crystallite, then the strip of roll surface one side was noncrystalline state.For overcoming inhomogeneities by the excessive institutional framework that causes of temperature gradient, often be forced to be prepared into earlier amorphous ribbon, increase special crystallization treatment process then and obtain micro rare earth permanent magnetic material.Because nucleation site is random distribution in material volume during crystallization, the orientation of crystallite crystal grain is at random, so dusty material is isotropism.From as seen above, only in the narrower fast scope of quenching, just form microstructure uniformly, crystal grain on average is about 0.1 micron.Because the restriction of apparatus and process condition, generally can only produce thickness is 35～50 microns strip, thereby also can only produce isotropic magnetic.Be directly to quench the granulation degree evenly and the consistent crystallite strip of orientation, the temperature gradient in the system process that must reduce to quench on the strip section, the i.e. thickness of strip that attenuate is quenched.But under the common process condition, be limited to jet size, technological factor basic fixed such as melt deadweight can't make the further attenuate of strip.
Practice shows, roller speed, when promptly the superficial velocity of roller was about 22 meter per seconds, the coercive force of gained strip can reach maximum, necessary strict control roll speed in common process, make crystallite crystallite dimension optimization, just can make the coercive force maximum, roller speed has some deviations slightly, then coercive force reduces bigger, therefore, strip revolve the process conditions strictness of quenching, be difficult for obtaining the crystallite magnetic of high-coercive force.
In the characteristic of magnetic material, maximum magnetic energy product is the important parameter of comprehensive characterization material magnetic property, and it had both depended on the HCJ of material, also depended on the remanent magnetism of material.It all is isotropic that prior art prepares rare earth permanent-magnetic material with the melt spinning method technology, though they have high HCJ, but remanent magnetism is not high, thereby limited the application of this kind material, the outstanding magnetic characteristic that yet is them is not given full play of as yet, therefore, the remanent magnetism that further improves micro rare earth permanent magnetic material just becomes one of key factor that enlarges its range of application.
As everyone knows, the institutional framework of the performance of permanent magnetic material and material and composition are closely related.The Nd-Fe-B alloy does not use valuable samarium and metallic cobalt, and can obtain the material with excellent permanent magnetism performance be made up of crystallite crystal grain by the melt spinning method method.Obviously, all be isotropic with generally revolving the permanent magnetic material that method obtained of quenching.For example the spy opens clear 60-162750(1985) a kind of terres rares permanent magnetism disclosed, also use the melt spinning method technology, revolve quench after, noncrystalline is more than microcrystalline structure, so improve coercive force and remanent magnetism with annealing in process subsequently, obtain the isotropism powder after the strip of gained is pulverized like this.
And for example the spy opens clear 60-89546 and discloses a kind of rare-earth permanent magnetic material, has used various quick cooling methods, and cooling back gained permanent magnetism strip or required form can directly use or pulverize the back and use.In the embodiment 1 of this document, the X-radioscopy has been done on the surface of the strip shred that pair roller speed 1000rpm is cooled off, and shows to have C-axle anisotropy.This inventor thinks that he not only obtains isotropism but also obtains anisotropic permanent-magnetic material.In fact, on strip, only there is superficial layer as thin as a wafer to have the anisotropic structure of C-axle, but says, be still isotropic structure from material monolithic.
The object of the invention is: a kind of preparation method and used improved equipment thereof for preparing the complete golden thin-band material of rare-earth-iron-boron magnetic anisotropy, that magnetic energy product is higher and inexpensive is provided.
Purpose of the present invention has reached fully by taking following technical measures: neodymium-iron-rare earth alloy of selecting optimum content, by improved melt spinning method technology and relevant device thereof, thereby change the institutional framework of revolving the strip of quenching, obtain anisotropy high energy product rare earth permanent magnet microcrystalline powder at last.
The present invention is described in detail below in conjunction with accompanying drawing.
Accompanying drawing 1 is that improved vacuum is revolved the equipment schematic diagram of quenching; Accompanying drawing 2 be with the made rare earth permanent magnet microcrystalline powder of the inventive method through or without the corresponding demagnetization curve of pressing under magnetic field gained magnet; Accompanying drawing 3 is the coercive force of the made permanent magnetism strip of melt spinning method method and the relation of roller speed.
The present invention relates to prepare the used melt spinning method method of anisotropy rare-earth permanent magnetic material and equipment. The remanent magnetism Br=6 of the made isotropism powder of tradition melt spinning method method～7.5 kilogauss, and the remanent magnetism Br=9.5 of the prepared anisotropic powder of the inventive method～12 kilogauss, also be that the inventive method can improve average 3～4 kilogauss of rare earth permanent-magnet powder, thereby correspondingly significantly improve the maximum magnetic energy product of rare-earth-iron-boron permanent magnetism material.
The rare-earth permanent magnetic material of selecting in the methods of the invention is NdxFeyBz, wherein, and x=10～25at%, y=70～84at%, z=3～10at%. Certainly also can utilize the inventive method to make anisotropic powder with other permanent magnetism composition.
The inventive method is achieved in that the common melt spinning method equipment that adopts, in this equipment, there are melting equipment such as high frequency to smelt stove, vaccum-pumping equipment, water casting machine and the water-cooled roller that rotates at a high speed, it is characterized in that: the melting operation in the vacuum quick quenching device and the spray operation of quenching is divided into two Room, namely in quenching the chamber, melting chamber and spray carry out respectively, between two Room, only be communicated with by nozzle, when spray is quenched, the melt isolation that nozzle is injected into, two Room namely are cut off, device by the indoor adjustable pressure of melting leads to into inert gas argon gas for example again, makes the indoor residue pressure of melting greater than the spray indoor pressure of quenching. Like this, when spray was quenched, alloy liquid also overcame the resistance of the thin seam surface tension force of spout, and sprays smoothly evenly except deadweight by means of the differential pressure action between two Room. Therefore, its thin seam is littler than common user, and the alloy amount of ejection is also less, can obtain thickness less than 20 microns strip, thereby makes the permanent magnetism material of anisotropic structure. And common equipment can only spray the strip of 35～50 micron thickness of quenching, so thick strip, and its thermograde is obvious, bigger to section structure and uniformity impact, like this, perhaps obtain the different tissues structure, perhaps obtain carrying out annealing in process after the amorphous state, the permanent magnetism material of gained all is isotropic again. The present invention is revolved in the technology of quenching, and is 50～150 millimeters mercury in melting chamber and the pressure reduction quenched between the chamber of spray.
Crystal structure with the prepared permanent magnetic material radical change fast quenching thin strap of the inventive method, the thickness of the rare-earth-iron-boron permanent magnetism thin-band material of the content of mentioned component and composition has only below 20 microns, its section temperature gradient only is equivalent to usually 1/4 of thick 35 microns strips, therefore, the section temperature gradient greatly reduces the institutional framework and the inhomogeneity influence of strip section, but required columnar crystal structure is enough to grow, rare-earth-iron-boron permanent magnetism strip of the present invention the has been characterised in that radical change crystal structure of fast quenching thin strap, all rapid quenching techniques can only prepare isotropic micro crystal material before this, and the present invention can provide the fast quenching thin strap of magnetocrystalline anisotropy, its section structure is the column crystal that runs through section, it is consistent with temperature gradient direction on the section that it generates direction, promptly perpendicular to the strip surface, easy magnetizing axis then is parallel to this strip plane.The column crystal diameter has anisotropy less than 1 micron.The principal phase of the made rare earth permanent-magnetic material of the inventive method is the Nd of tetragonal
2Fe
14B has rich neodymium phase at grain boundary, and a little boron-rich phase is arranged on the crystal boundary crosspoint.For example gained crystallite strip is measured with the magnetic vibrating specimen magnetometer, obtains: Br=9.2KG, iHc=11.8KOe, (BH) max=16.4MGOe.
The permanent magnetism melt spinning method improved device of the inventive method special use is seen accompanying drawing 1, the melting operation of original melt spinning method device and the spray operation of quenching is quenched with spray in working chamber 1 respectively and carried out in the chamber 2, quench with spray in working chamber 1 and to communicate by nozzle 6 between the chamber 2, earthenware field 4 is by high frequency coil 5 heating as usual, nozzle 6 places at tundish 3 are heated by high frequency coil 7, the alloy liquid of ejection is sprayed onto on the single roller 8 of water-cooled, and arrow is the direction of cold water turnover.Feed argon gas by air intake valve 9 when regulating the pressure in the working chamber 1, evacuating valve 10 is to working chamber's usefulness of bleeding.The roller speed of the single roller 8 of water-cooled is 16.5～21.5 meter per seconds.
With the inventive method and equipment, can obtain the strip of thickness below 20 microns, its section structure is the column crystal that runs through section, and this column crystal is less than 1 micron.With the flakey powder of this strip preparation, in magnetic field and do not add the magnetic field internal shaping, the curve of gained bonded permanent magnet is shown in accompanying drawing 2 respectively, and wherein, a is a magnetic forming, and b is not for adding magnetic forming.Be not difficult to find out: the advantage of anisotropic permanent-magnetic material is that remanent magnetism significantly improves, and with the bonded permanent magnet that it is made, its magnetic energy product can reach more than the 16MGOe.
The inventive method has significantly been improved the change curve of coercivity H with roller speed, the quench peak value in speed district of the best is shifted to low regime, and peak height increases the peak width expansion.In other words, significantly broaden corresponding to the quench scope in speed district of the best of high-coercive force.For example, get Hc=14KOe, common process has only strict control roll speed, makes the V=22.25 meter per second, and Shi Caineng reaches.Roller speed has some deviations slightly, as has only ± 1 meter per second (being equivalent to 4.5%), and then Hc reduces by 18%, i.e. 2.5KOe.When adopting improvement technology of the present invention, roller speed in the scope of 16.5～21.5 meter per seconds, the coercivity H 〉=14KOe of fast quenching thin strap, that is to say that roller speed changes ± 13% near 19 meter per seconds, promptly ± 2.5 meter per second all can, see accompanying drawing 3, this point is most important for producing.Because the best fast scope of quenching is big, produce that going up to quench earlier and make amorphous alloy and carry out crystallization again and handle, but the direct best fast anisotropy crystallite rare earth permanent-magnetic material that meets performance requirement of just can producing of quenching of control.
It is with low cost to utilize the inventive method to make, the permanent-magnet alloy of magnetic excellence, and the preparation method and the device simple of rare-earth-iron-permanent magnetic material of the present invention are feasible, have initiative.
Embodiment 1
Adopting purity is 99.8(weight) Nd, the 99.8(weight of %) Fe, the 16(weight of %) the B-Fe alloy of % is as raw material, before the effect through the processing of derusting.The master alloy ingot arc melting of 50 grams.For the composition that guarantees master alloy ingot meets design mix substantially, must give special concern to the waste of rare earth element in fusion process.For making the foundry alloy composition even, each spindle remelting 4 times.The content of the rare earth of foundry alloy, Fe, B is all measured with chemical analysis.The result shows, alloy cast ingot middle rare earth content and design load deviation＜5%; The deviation of Fe, B content＜3%.
It is Nd that the atom of the alloy pig composition that this is routine has proportion by subtraction
14.5Fe
80B
5.5Alloy is prepared into thick 20 microns crystallite strip with the single roller rapid quenching technology under argon shield.
Working chamber and the spray constant pressure difference of quenching is 80 millimetress of mercury.
Gained crystallite strip is measured with the magnetic vibrating specimen magnetometer, and its result is as follows:
Br＝8.9KG，iHc＝14.3KOe，（HB）max＝14.6MGOe。
Embodiment 2
This example is raw materials used, smelting, analysis, method of testing such as embodiment 1.The atomic percent of alloying component is Nd
13.5Fe
81.5B
5The pressure reduction that working chamber and spray are quenched between the chamber is 120 millimetress of mercury, and the measurement result of gained crystallite strip is: Br=9.2KG, iHc=11.8KOe, (HB) max=16.4MGOe.
Claims (2)
1, the preparation method of anisotropy crystallite rare earth permanent-magnetic material, use the alloy that contain neodymium, iron and boron of atomic ratio as X=10～25at%, y=70～84at%, z=3～10at%:
Nd
xFe
xB
zIt is characterized in that: melting in the working chamber of melt spinning method equipment, and quench on the single roller of water-cooled in the spray indoor spray of quenching, said working chamber and the spray chamber of quenching is linked to each other by nozzle, melt separates said working chamber and the spray chamber of quenching when alloy spray is quenched, advance product by argon gas immediately and send into argon gas, regulate the pressure of working chamber, making working chamber and the pressure reduction that sprays the chamber of quenching is 50～150 millimetress of mercury, alloy liquid is sprayed onto on the single roller of water-cooled that roller speed is 16.5～21.5 meter per seconds smoothly by the nozzle finedraw, is less than 20 microns thereby make thickness, have the column microstructure of the column crystal direction of growth perpendicular to the strip face, the direction of easy axis of crystal is parallel to the anisotropy rare earth permanent magnet thin-band material of zone face.
2, the device of preparation anisotropy crystallite rare earth permanent magnet strip, said device comprises crucible 4, single roller 8, the valve 9 of supplying gas, the valve 10 of finding time, the single roller 8 of water-cooled, crucible heater coil 5, the nozzle heater coil 7 that rotate, it is characterized in that: working chamber 1 and spray chamber 2 setting that is separated from each other of quenching is only linked to each other by nozzle 6 therebetween.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107845 CN1021607C (en) | 1990-09-22 | 1990-09-22 | Producing method and apparatus of anisotropic micro rare earth permanent magnetic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107845 CN1021607C (en) | 1990-09-22 | 1990-09-22 | Producing method and apparatus of anisotropic micro rare earth permanent magnetic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1060178A true CN1060178A (en) | 1992-04-08 |
| CN1021607C CN1021607C (en) | 1993-07-14 |
Family
ID=4880734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90107845 Expired - Fee Related CN1021607C (en) | 1990-09-22 | 1990-09-22 | Producing method and apparatus of anisotropic micro rare earth permanent magnetic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1021607C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101160634B (en) * | 2005-03-17 | 2012-01-18 | 美蓓亚株式会社 | Permanent magnet magnetization device |
| CN104347215A (en) * | 2013-07-23 | 2015-02-11 | 有研稀土新材料股份有限公司 | Method for preparing rare-earth permanent magnet powder |
| CN107377907A (en) * | 2017-08-04 | 2017-11-24 | 芜湖君华材料有限公司 | A kind of ultra-thin Fe-based amorphous alloy magnetic band preparation method |
-
1990
- 1990-09-22 CN CN 90107845 patent/CN1021607C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101160634B (en) * | 2005-03-17 | 2012-01-18 | 美蓓亚株式会社 | Permanent magnet magnetization device |
| CN104347215A (en) * | 2013-07-23 | 2015-02-11 | 有研稀土新材料股份有限公司 | Method for preparing rare-earth permanent magnet powder |
| CN107377907A (en) * | 2017-08-04 | 2017-11-24 | 芜湖君华材料有限公司 | A kind of ultra-thin Fe-based amorphous alloy magnetic band preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1021607C (en) | 1993-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7431070B2 (en) | Rare earth magnet alloy ingot, manufacturing method for the same, R-T-B type magnet alloy ingot, R-T-B type magnet, R-T-B type bonded magnet, R-T-B type exchange spring magnet alloy ingot, R-T-B type exchange spring magnet, and R-T-B type exchange spring bonded magnet | |
| KR102096958B1 (en) | Highly thermostable rare-earth permanent magnetic material, preparation method thereof and magnet containing the same | |
| CN104700973B (en) | A kind of rare-earth permanent magnet being made up of the common association raw ore mischmetal of Bayan Obo and preparation method thereof | |
| KR101687981B1 (en) | Rare-earth permanent magnetic powders, bonded magnet comprising same, and device using bonded magnet | |
| EP0886284A1 (en) | Cast alloy used for production of rare earth magnet and method for producing cast alloy and magnet | |
| CN105989983B (en) | Permanent magnet | |
| JPH01704A (en) | Rare earth-iron permanent magnet | |
| JP2022516380A (en) | Rare earth diffusing magnet manufacturing method and rare earth diffusing magnet | |
| CN113674945B (en) | Low-cost high-coercivity LaCe-rich neodymium-iron-boron permanent magnet and preparation method and application thereof | |
| EP1154445A2 (en) | Alloy for high-performance rare earth permanent magnet and manufacturing method thereof | |
| JPH03153006A (en) | Permanent magnet and raw material therefor | |
| CN1570155A (en) | Sintered Nd Iron boron permanent magnet tempering process | |
| JPH05209210A (en) | Production of magnet alloy particle | |
| Yang et al. | Combination strategy for high-performance Sm (CoFeCuZr) z sintered permanent magnet: Synergistic improvement of the preparation process | |
| CN1021607C (en) | Producing method and apparatus of anisotropic micro rare earth permanent magnetic material | |
| WO2003020993A1 (en) | Rare earth magnet alloy ingot, manufacturing method for the same, r-t-b type magnet alloy ingot, r-t-b type magnet, r-t-b type bonded magnet, r-t-b type exchange spring magnet alloy ingot, r-t-b type exchange spring magnet, and r-t-b type exchange spring bonded magnet | |
| TWI608500B (en) | Rare earth permanent magnetic powder, bonded magnet, and device using the bonded magnet | |
| JP5982567B2 (en) | Rare earth permanent magnet powder, bonded magnet and device using the bonded magnet | |
| JP2003334643A (en) | Method for manufacturing rare earth alloy, alloy lump for r-t-b magnet, r-t-b magnet, r-t-b bonded magnet, alloy lump for r-t-b exchangeable spring magnet, r-t-b exchangeable spring magnet and r-t-b exchangeable spring bonded magnet | |
| JP2857824B2 (en) | Rare earth-iron permanent magnet manufacturing method | |
| CN114012096B (en) | Preparation method of anisotropic Sm-Fe-N magnetic powder | |
| JPH0323256B2 (en) | ||
| CN1061460C (en) | Carbide permanent magnet and its prepn. method | |
| CN112885550A (en) | Preparation method of high-density cerium-based hot-pressed rare earth magnetic steel | |
| CN117133522A (en) | MnBi permanent magnet alloy powder with high magnetic energy product and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |