CN1866417A - Method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material - Google Patents
Method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material Download PDFInfo
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- CN1866417A CN1866417A CN 200610018869 CN200610018869A CN1866417A CN 1866417 A CN1866417 A CN 1866417A CN 200610018869 CN200610018869 CN 200610018869 CN 200610018869 A CN200610018869 A CN 200610018869A CN 1866417 A CN1866417 A CN 1866417A
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Abstract
The invention discloses a permanent magnet regenerating method of degenerated rare earth permanent magnet material, which comprises the following steps: grinding mechanically; removing impurity; dewetting in the vacuum; proceeding hydrogen disposal or hydrogen disproportionating reaction; adding high-magnetocrystalline anisotropic element and auxiliary texture forming element or alloy; moulding through sintering or adhering to produce anisotropic regenerated permanent magnet. The technology is reasonable with little oxide reaction, which can explore new path for degenerated rare earth permanent magnet.
Description
Affiliated technical field
The present invention relates to adopt degenerated rare earth permanent magnetic material sintering or bonding to prepare the method for the permanent magnet of regenerating.Specifically be meant the method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material.
Technical background
China is rare earth resources big country, accounts for 80% of world saving.The rare earth permanent magnet that with NdFeB is representative has high magnetic energy density.Therefore, efficiently with the place of machinery and the mutual conversion of electric energy, it all is first-selected or indispensable material to any needs.Such as: the computer hard drive motor, NMR imaging instrument, the magnetic suspension compartment, the modern household automobile, magneto-optic data driver etc. all adopts this kind material in a large number.Although rare earth permanent-magnetic material has superior magnetic property, but it also has serious weakness, one of them is that corrosion resistance is very poor, the electrochemical corrosion potential of its rich Nd phase of rare-earth permanent magnet is extremely low, oxidation easily, inhale the hydrogen hydrolysis, thereby rare-earth permanent magnet can degenerate rapidly under certain environment, lose its magnetic property fully.The magnetic field intensity that rare earth permanent-magnetic material had of corrosion degradation only is equivalent to the 5-40% of original material generally speaking, has not had industrial use value, but if it is abandoned, then can cause the waste of rare earth resources.Therefore, be necessary to carry out the research of degenerated rare earth permanent magnetic material regeneration.Chinese patent notification number: CN 1150076C, the day for announcing: on May 19th, 2004, denomination of invention: " a kind of method for preparing hydrogenation-disproportionation-dehydrogenation-recombinant rare earthy permanent magnetism powder ", the method that has proposed to utilize waste material that rare-earth permanent magnet produced in sintering, processing, production process and offal to prepare disproportionation (HDDR) anisotropic magnet powder has realized the utilization to permanent magnet waste material and offal.But this process is had relatively high expectations to the magnetic property and the homogeneity of ingredients of rare earth permanent magnet spent material, the offal that is adopted there is no substantive difference with the casting alloy that common manufacturing rare earth permanent magnet technology is adopted at composition and tissue, and prepared magnetic particle capability index is lower, is difficult to recover its magnetic property for the relatively poor degenerated rare earth material of magnetic property comprehensively.Particularly some is because of rare-earth permanent magnet or its discarded permanent magnet product of corrosion and oxidation serious degradation, such degenerated rare earth permanent magnet oxide impurity is more, also often leave corrosion resistant metal or nonmetallic coating at the permanent magnet outer surface, it makes and the impurity component variation of degenerated rare earth permanent magnetic material causes the difficulty of its recycling to increase.
Summary of the invention
The objective of the invention is existing rare-earth permanent magnet regeneration recombinant technique is improved, overcome its defective and deficiency, particularly, provide the method for the simple regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material of a kind of technology at rare-earth permanent magnet because of corrosion and oxidation serious degradation.Its production cost is lower, and the regeneration permanent magnet magnetic performance of preparation is higher.
Technical solution of the present invention is: the method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material may further comprise the steps:
(1) to the degenerated rare earth permanent magnetic material mechanical crushing of same family, removes impurity, and place (10
-2-10
-9Bar) dried under the vacuum 0.5-3 hour;
(2) the degenerated rare earth permanent magnetic material after will drying places vacuum degree: 10
-2-10
-9Bar, temperature: under room temperature or 0-100 ℃ the environment, import pure hydrogen (H
2), hydrogen pressure: 0.5-30bar carried out hydrogen quick-fried (HD) 0.5-2 hour, the degenerated rare earth permanent magnetic material becomes hydrogen quick-fried (HD) micro mist, under the protective atmosphere of nitrogen or argon gas, its hydrogen quick-fried (HD) micro mist is carried out ball milling or airflow milling, its granularity is ground to the 1-20 micron, perhaps;
(3) the degenerated rare earth permanent magnetic material after will drying places vacuum degree: 10
-2-10
-9Bar under temperature: 700-880 ℃ the environment, imports pure hydrogen (H
2), hydrogen pressure: 0.5-30bar carried out disproportionated reaction (HDDR) 0.5-2.5 hour, and the degenerated rare earth permanent magnetic material becomes disproportionation (HDDR) micro mist;
(4) it is identical and can to make this be element or the alloy that rare earth permanent-magnetic material constitutes the Hard Magnetic phase structure to sneak into particle diameter at quick-fried (HD) micro mist of hydrogen after grinding or disproportionation (HDDR) micro mist under the protective atmosphere of nitrogen or argon gas, and mix is even;
(5) becoming anisotropic regeneration permanent magnet after to hydrogen quick-fried (HD) the micro mist magnetization moulding after mixing powder, sintering, heat treatment under the protection environment of vacuum or nitrogen or argon gas, perhaps;
(6) in disproportionation (HDDR) micro mist after mixing powder under the protection environment of vacuum or nitrogen or argon gas, add the permanent magnet adhesive, adopt the heat rejector extrusion molding, obtain anisotropic regeneration permanent magnet.
The present invention can also be the degenerated rare earth permanent magnetic material for R-Fe-B in step (4), and R=Nd or Pr, element that is added or alloy are Dy, Sm, Co, Cu, Zr, B, Fe, Dy
3Co, Dy
3Co
2, Dy
1.5Nd
1.5Co
2, Nd
3Co, Nd
xPr
yIn one or more mixture, R
xFe
yB
zX=10-18at% in the degenerated rare earth permanent magnetic material, y=66-88at%, z=4-12at%, wherein:
The ratio that element Dy, Co, Cu, Zr, B, Fe add is: RDy
VCo
XCu
yZr
WB
ZFe
Bal, x=0-4.2at%, y=0-0.5at%, z=4-8at%, v=0.1-6at%, w=0-1.0at%, bal are contained Fe aequum,
Alloy Dy
3Co, Dy
3Co
2, Dy
1.5Nd
1.5Co
2The ratio that adds is:
Add Dy
3Co accounts for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Dy
3Co
2Account for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Dy
1.5Nd
1.5Co
2Account for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Nd
3Co accounts for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-5wt%,
Add Nd
xPr
yAccount for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-5wt%,
For Sm-Co is the degenerated rare earth permanent magnetic material,
SmCo
5In the element that added be one or both mixture among Sm, the Co, the ratio of its adding is: Sm=0.01-0.8at%, Co=0.01-2.0at%,
Sm
2(Co
BalFe
bCu
cZr
d)
17In the element that added be one or more mixture among Co, Cu, Zr, the Fe, the ratio of its adding is: b=0.01-0.42at%, c=0.01-1.8at%, d=0.01-1.6at%, bal are contained Co aequum.
The present invention can also be in step (1), the particle diameter of mechanical crushing degenerated rare earth permanent magnetic material is the 2-10 millimeter, removing impurity is that the degenerated rare earth permanent magnetic material after its pulverizing is carried out magnetic separation, rare-earth separating permanent magnet and anti-corrosion coated layer, nonmagnetic corrosion thing and oxide.
The present invention can also be in step (5), hydrogen quick-fried (HD) micro mist behind the mixed powder is packaged in the rubber die, adopt the reverse magnetic vibration of little frequency alternation to handle, the frequency of little frequency magnetic vibration is 3-10 time/minute, time is 2-5 minute, magnetic field intensity is 1-6Tesla, adopts static pressure or warm compaction moldings such as normal temperature again.
The present invention can also be in step (5), is R for mixing behind the powder
xCu
yCo
zFe
uB
v(R=Nd or Pr, x=10-18at%, y=0.01-0.48at%, Co=0-10at%, u=73-79at%, v=5-9at%) rare earth permanent-magnetic material, after the compression moulding temperature 1010-1080 ℃ of following sintering 1 hour, 500 ℃ of heat treatments after 1 hour under vacuum then, cold soon (air-cooled under the vacuum) becomes anisotropic regeneration permanent magnet to room temperature; Perhaps temperature 1010-1080 ℃ of following sintering 1 hour, 630 ℃ of heat treatment 1 hour under vacuum then; Cold soon (air-cooled under the vacuum) becomes anisotropic regeneration permanent magnet to room temperature.
The permanent magnet adhesive that the present invention can also be added in step (6) is epoxy resin or polytetrafluoroethylene.
Degenerated rare earth permanent magnetic material of the present invention is meant and is corroded, the rare earth permanent-magnetic material or the rare earth permanent magnet product of basic forfeiture magnetic property after the hydrolysis, suction hydrogen, oxidation, and its included composition range is as follows:
R-Fe-B is and comprises that the R-Fe-B that wherein adds other elements or alloy is the degenerated rare earth permanent magnetic material.Wherein R represents rare earth element nd or Pr, add element or alloying component is: Co, Dy, Cu, Tb, Zr, Al, Dy
3Co, DyTe, PrDy, Dy
1.5Nd
1.5Co
2
Sm-Co system comprises 1:5, and 2:17 type and the Sm-Co that wherein adds other elements or alloy are the degenerated rare earth permanent magnetic material, add elemental composition and be: Sm, Co, Zr, Cu, Fe.
Compared with prior art the invention has the beneficial effects as follows:
1. it is wide to handle the raw material scope, not only can handle the be corroded rare earth permanent-magnetic material of the basic forfeiture in back magnetic property of rare earth permanent-magnetic material product, also can be used for the waste material that rare-earth industry is produced and the processing of offal.
2. technology is reasonable.Hydrogen quick-fried (HD) and disproportionation (HDDR) are handled, process conditions are easy, and its vacuum-sintering moulding and heat rejector extrusion modling are easy to operate, constant product quality, production cost is lower, has avoided original wet processing to cause the further degeneration of rare earth permanent-magnetic material composition and performance because of pickling.Simultaneously, adopt H
2Reducing atmosphere, this makes entire process process cleaning, no further oxidation take place; The oxide that the part of having reduced simultaneously produces because of degeneration.Given this method, the rare-earth permanent magnet that reclaims and make has higher magnetic property.
3. the permanent magnet magnetic performance of regenerating height.Degenerated rare earth permanent magnetic material magnetic property recovers better, add high magnetocrystalline anisotropy field element or alloy after, its regeneration permanent magnet has the texture orientation of height, grasps coercive force in it and obviously improves, industrial utilization is worth.And, in the vacuum-sintering forming process after hydrogen quick-fried (HD) micro mist mixes powder, adopt reverse magnetic vibration of little frequency alternation and normal temperature isostatic compaction, can obviously improve the performance of regeneration permanent magnet.
4. add the wide material sources of element or alloy, the range of choice broad.Its additional proportion is easy to calculate and control, and is easier to the magnetic property control of regeneration permanent magnet.
5. the impurity in the removal permanent magnet, nonmagnetic corrosion thing and oxide.To the permanent magnet that reclaims pulverize, mechanical oscillation and magnetic separation, adopt magnetic field to separate broken back degeneration rare-earth permanent magnet and anti-corrosion coated layer, effectively removed oxide and non-magnetic impurity, make the recycling process of degenerated rare earth permanent magnetic material easy, regeneration effect is better.For new efficient approach has been opened up in the high efficiente callback utilization and the large-scale industrialization production of degenerated rare earth permanent magnet.
6. removal process is cleaning manufacturing fully.Grind the superfine rare-earth micro mist again to making permanent magnet from drying to of degenerated rare earth material, whole technology is all carried out under the protection environment of hydrogen and nitrogen or argon gas or vacuum, make the oxidation reaction of rare earth material in the course of processing reduce to minimum, prepared micro mist has higher magnetic dependence structural parameters, helps making the higher permanent magnet of magnetic energy product; Simultaneously, adopt processing method of the present invention can not produce any pollution, make that magnetic degeneration waste material is reclaimed fully environment.
Description of drawings
Fig. 1 is Nd in the embodiment of the invention 2
16Fe
76B
8+ 0.25at%Cu, two kinds of Technologies for Heating Processing of its A, B and normal sintering are handled the demagnetization curve figure of resulting restored permanent magnet
Embodiment
The present invention is described in further detail below in conjunction with description of drawings and embodiment:
Degenerated rare earth permanent magnetic material of the present invention mainly is meant in natural environment has lost magnetic property discarded rare earth permanent magnet product components and parts or material because of reasons such as burn into oxidations.The degenerated rare earth permanent magnetic material is divided and can be divided into from raw-material composition: Nd-Fe-B system, Pr-Fe-B system and Sm-Co are three major types, and also can be divided into R-Fe-B system and Sm-Co is two big classes.When it is carried out Regeneration Treatment, should be earlier the degenerated rare earth permanent magnetic material of its recovery be sorted classification, the degenerated rare earth permanent magnetic material of same family is put together.Though R-Fe-B system has comprised the degenerated rare earth permanent magnetic material of Nd-Fe-B system and Pr-Fe-B system, and can be used as a family and reclaim classification, had better be by Nd-Fe-B, Pr-Fe-B system separately sorts out, and is convenient to control the addition of interpolation element like this.On the degenerated rare earth permanent magnetic material outer surface that reclaims, corrosion resistant metal coating is arranged more, as chromium plating, copper facing, zinc-plated, nickel plating, aluminize or its MULTILAYER COMPOSITE coating or nonmetallic coating etc., therefore tackle such material and pulverize and remove the impurity processing.Degenerated rare earth permanent magnetic material mechanical crushing to particle diameter to same family is the 2-10 millimeter, the particle diameter of mechanical crushing is if cause degenerated rare earth permanent magnetic material accelerated oxidation less than 2 millimeters meetings, if greater than 10 millimeters, be unfavorable for that then coated metal separates from rare-earth permanent magnet.And to remove impurity can be artificial or other modes to the letter sorting removal of impurities of anti-corrosion coated layer, nonmagnetic corrosion thing and oxide, but the mode that preferably adopts the degenerated rare earth permanent magnetic material after it is pulverized to carry out magnetic separation.Magnetic separation be with the oxide in the degenerated rare earth permanent magnetic material and namagnetic substance as: Cr, Ni, Cu, Al, Zn and rare earth permanent magnet in use interact with environmental factor and the corrosion thing that produces as Nd
2O
3, Nd (OH)
3, Fe (OH)
2, Fe (OH)
3Deng separating out.Before magnetic separation, can also carry out earlier mechanical oscillation 10-60 minute, separate with its corrosion thing, oxide, coating and coated metal to promote the degenerated rare earth permanent magnetic material.
Temperature in hydrogen among the present invention quick-fried (HD) processing procedure can be a normal temperature, but in order to improve the effect that material is pulverized, its temperature can be increased to 100 degree.The vacuum degree that hydrogen quick-fried (HD) is handled: 10
-2-10
-9Bar, temperature: under room temperature or 0-100 ℃ the environment, import pure hydrogen (H
2); hydrogen pressure: 0.5-30bar; carried out hydrogen quick-fried (HD) 0.5-2 hour; after hydrogen quick-fried (HD) is handled; under the protective atmosphere of nitrogen or argon gas, its hydrogen quick-fried (HD) micro mist is carried out ball milling or airflow milling; its granularity is ground to the 1-20 micron, and it is identical and can to make this be element or the alloy that rare earth permanent-magnetic material constitutes the Hard Magnetic phase structure to add particle diameter at hydrogen quick-fried (HD) micro mist after grinding under the protective atmosphere of nitrogen or argon gas then, and mix is even.
Under vacuum environment, after mixing hydrogen quick-fried (HD) micro mist magnetization moulding behind the powder, sintering, heat treatment, become anisotropic regeneration permanent magnet.Wherein to mixing hydrogen quick-fried (HD) the micro mist magnetization forming process behind the powder, can take under the axial magnetic field or under the radial magnetic field with micro mist by required magnetic direction distribution compression moulding; But preferably obtaining micro mist envelope is hit in the rubber flexible die, adopt little frequency alternation backing field method for oscillating (AlternateMagnetic Pulsing) to handle, arrange to reach the high magnetic aligning of magnetic to its micro mist.The frequency of little frequency vibration is 3-10 time/minute, and the time is 2-5 minute, and magnetic field intensity is 1-6Tesla.After adopting this little frequency magnetic vibration to handle, its remanent magnetism can improve 5-10%.Adopt static pressure or warm compaction moldings such as normal temperature subsequently, this moulding process can be made regular and irregular shape magnet, to satisfy the concrete function demand.
Wherein, be R for mixing behind the powder
xCu
yCo
zFe
uB
v(R=Nd or Pr, x=10-18at%, y=0.01-0.48at%, Co=0-10at%, u=73-79at%, rare earth permanent-magnetic material v=5-9at%) is after the compression moulding, temperature 1010-1080 ℃ of following sintering 1 hour, 500 ℃ of heat treatments are after 1 hour under vacuum then, and cold soon (air-cooled under the vacuum) becomes anisotropic regeneration permanent magnet to room temperature; Perhaps temperature 1010-1080 ℃ of following sintering 1 hour, 630 ℃ of heat treatment 1 hour under vacuum then, cold soon (air-cooled under the vacuum) becomes anisotropic regeneration permanent magnet to room temperature.Through this processing, generate a series of crystal boundary phases thus, the most significant is Nd
3(Co Fe) mixes looks and rich Cu mutually with 5%Cu.This type of generates mutually and helps its coercitive raising.
The vacuum degree that disproportionation among the present invention (HDDR) is handled: 10
-2-10
-9Bar under temperature: 700-880 ℃ the environment, imports pure hydrogen (H
2), hydrogen pressure: 0.5-30bar carried out disproportionated reaction (HDDR) 0.5-2.5 hour, and the degenerated rare earth permanent magnetic material becomes disproportionation (HDDR) micro mist.The fineness of disproportionation (HDDR) micro mist is about 500 microns, and such particle diameter can directly be made the rare-earth permanent magnet of adhesion type.It is identical and can to make this be high magnetocrystalline anisotropy field element or the alloy that rare ± permanent magnetic material constitutes the Hard Magnetic phase structure to add particle diameter to disproportionation (HDDR) micro mist under the protection environment of vacuum or nitrogen or argon gas; mix is even; and adding permanent magnet adhesive such as epoxy resin or polytetrafluoroethylene or its combination adhesive; adopt the heat rejector extrusion molding, then can obtain anisotropic regeneration permanent magnet.
According to the composition difference of degenerated rare earth permanent magnetic material, high magnetocrystalline anisotropy field element that is added or auxiliary texture forming element and alloy are also different.For R-Fe-B is degenerated rare earth permanent magnetic material (wherein R represents rare earth element nd or Pr),, element that is added or alloy are Dy, Sm, Co, Cu, Zr, B, Fe, Dy
3Co, Dy
3Co
2, Dy
1.5Nd
1.5Co
2, Nd
3Co, Nd
xPr
yIn one or more mixture, R
xFe
yB
zX=10-18at% in the degenerated rare earth permanent magnetic material, y=66-88at%, z=4-12at%, wherein:
The ratio that element Dy, Co, Cu, Zr, B, Fe add is: RDy
VCo
XCu
yZr
WB
ZFe
Bal, x=0-4.2at%, y=0-0.5at%, z=4-8at%, v=0.1-6at%, w=0-1.0at%, bal are contained Fe aequum,
Alloy Dy
3Co, Dy
3Co
2, Dy
1.5Nd
1.5Co
2The ratio that adds is:
Add Dy
3Co accounts for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Dy
3Co
2Account for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Dy
1.5Nd
1.5Co
2Account for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Nd
3Co accounts for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-5wt%,
Add Nd
XPr
yAccount for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-5wt%,
For Sm-Co is the degenerated rare earth permanent magnetic material,
SmCo
5In the element that added be one or both mixture among Sm, the Co, the ratio of its adding is: Sm=0.01-0.8at%, Co=0.01-2.0at% is with compensation SmCo
5Material is loss of active ingredients in degenerative process.
Sm
2(Co
BalFe
bCu
cZr
d)
17In the element that added be one or more mixture among Co, Cu, Zr, the Fe, the ratio of its adding is: b=0.01-0.42at%, c=0.01-1.8at%, d=0.01-1.6at%, bal are contained Co aequum.
The inventive method begins until the processing procedure that obtains the regeneration permanent magnet from the vacuum drying step, all needs under anti-oxidation state, to carry out to its degenerated rare earth permanent magnetic material and to the treatment step that adds element or alloy, such as: (N under vacuum, the protective atmosphere
2Or Ar
2).To prevent and to avoid the generation of any oxidative phenomena.
Embodiment 1: get degeneration Nd
16Fe
76B
8Be rare-earth permanent magnet 1000 grams, mechanical crushing to material footpath is 3 millimeters, adopts electromagnet to magneticly elect degenerated rare earth permanent magnetic material 930 grams, is placed on 10
-5Dried under-bar the vacuum 1.5 hours; In vacuum degree: 10
-6Bar, temperature: under 70 ℃ the environment, import pure hydrogen (H
2), hydrogen pressure: 10bar carried out hydrogen quick-fried (HD) 2 hours, and the degenerated rare earth permanent magnetic material becomes hydrogen quick-fried (HD) micro mist; Under the atmosphere of nitrogen protection, its hydrogen quick-fried (HD) micro mist is carried out airflow milling, its granularity is ground to the 3-6 micron; Than evenly sneaking into Cu and the Co micro mist that particle diameter is the 3-6 micron, wherein Cu content keeps 0.25at% constant by the atomic wts that calculates, and Co content changes from 3.5at% to 10at%, sees the following form 1:
Table 1
| Co(at％) | Cu(at％) | Nd(at％) | Fe(at％) | B(at％) |
| 3.5 | 0.25 | 15.40 | 73.15 | 7.7 |
| 5.0 | 0.25 | 15.15 | 72.00 | 7.6 |
| 7.0 | 0.25 | 14.84 | 70.49 | 7.42 |
| 10.0 | 0.25 | 14.36 | 68.21 | 7.18 |
In anti-oxidation case and under the argon shield; hydrogen quick-fried (HD) micro mist behind the mixed powder is packaged in the rubber flexible die, adopts reverse little frequency vibration of magnetic field alternation and normal temperature isostatic compaction, the frequency of little frequency vibration is 7 times/minute; time is 3 minutes, and magnetic field intensity is 5Tesla.Handling by universal standard heat treatment step then, is R for mixing behind the powder
xCu
yCo
zFe
uB
v, (R=Nd or Pr, x=10-18at%, y=0.01-0.48at%, Co=0-10at%, u=73-79at%, rare earth permanent-magnetic material v=5-9at%), after compression moulding, temperature 1010-1080 ℃ of following sintering 1 hour, at this moment, one can be under vacuum 500 ℃ of heat treatments after 1 hour, cold soon (air-cooled under the vacuum) becomes anisotropic regeneration permanent magnet to room temperature; It two can be temperature 1010-1080 ℃ of following sintering 1 hour, 630 ℃ of heat treatment 1 hour under vacuum then, and cold soon (air-cooled under the vacuum) becomes anisotropic regeneration permanent magnet to room temperature.These two kinds of operations can generate a series of crystal boundary phases, and the most significant is Nd
3(Co Fe) mixes looks and rich Cu mutually with 5%Cu.This type of generates mutually and helps its coercitive raising.
Two kinds of heat treatment processes beyond the above standard heat treatment step are as follows:
500 ℃ of heat treatment is 1 hour under vacuum, and chilling (cooled with liquid nitrogen under the vacuum) is to room temperature.
630 ℃ of heat treatment is 1 hour under vacuum, and cold soon (air-cooled under the vacuum) is to room temperature.Promptly obtain the anisotropy sintered permanent magnet.The rare earth permanent-magnetic material that uses this method to reclaim, its magnetic property index is recovered substantially.Adopt 0.25at%Cu and 0-10at%Co to unite to mix powder to add and handle degeneration NdFeB rare-earth permanent magnet, behind 1 hour+chilling of 500 ℃ of heat treatment, its magnetic property and Curie temperature thereof can recover to reach parameter referring to table 2:
Table 2
| Cobalt +0.25Cu (at％) | B r ±20 (mT) | iH c ±10 (kA/m) | bH c ±10 (kA/m) | (BH)max ±15 (kJ/m 3) | Square-ne ss ％ | Curie temperature ± 3 |
| 0 | 1244 | 854 | 803 | 295 | 0.88 | 313 |
| 3.5 | 1277 | 765 | 718 | 308 | 0.90 | 356 |
| 5.0 | 1270 | 685 | 646 | 302 | 0.89 | 366 |
| 7.0 | 1299 | 546 | 524 | 302 | 0.89 | 386 |
| 10.0 | 1307 | 548 | 538 | 315 | 0.94 | 420 |
Adopt 0.25at%Cu and 0-10at%Co to unite to mix powder to add and handle degeneration NdFeB rare-earth permanent magnet, through after 630 ℃ of heat treatments 1 hour+fast cold, its magnetic property recovers the parameter that reaches referring to table 3:
Table 3
| Cobalt +0.25Cu (at％) | B r ±20 (mT) | iH c ±10 (kA/m) | bH c ±10 (kA/m) | (BH)max ±15 (kJ/m 3) | Square- |
| 0 | 1263 | 813 | 776 | 303 | 0.91 |
| 3.5 | 1226 | 693 | 671 | 281 | 0.95 |
| 5.0 | 1313 | 605 | 595 | 320 | 0.92 |
| 7.0 | 1295 | 459 | 438 | 268 | 0.81 |
| 10.0 | 1278 | 460 | 454 | 275 | 0.92 |
Embodiment 2: get degeneration Nd
16Fe
76B
8Rare-earth permanent magnet 1000 grams, mechanical crushing to particle diameter is 5 millimeters, adopts electromagnet to magneticly elect degenerated rare earth permanent magnetic material 940 grams, is placed on 10
-5Dried under-bar the vacuum 2 hours; Adopt hydrogen quick-fried (HD) method and add the mixed powder of element Cu, micro mist to mix powder under radial magnetic field after is by required magnetic direction distribution compression moulding, adopt other two kinds of heat treatment mode: A respectively after conventional sintering, the heat treatment, chilling (cooled with liquid nitrogen under the vacuum) back is 500 ℃ of heat treatment 1 hour and B under vacuum, two groups of anisotropic regeneration permanent magnets are made in the 630 ℃ of heat treatment 1 hour under vacuum of cold soon (air-cooled under the vacuum) back.Its magnetic property all can return to the level of original performance parameter 100%, has recycled the Nd that degenerates because of corrosion effectively
16Fe
76B
8Rare-earth permanent magnet.
Nd
16Fe
76B
8Mixing powder adds its magnetic property of Cu element and recovers parameter referring to table 4:
Table 4
| Cu mixes powder content (at%) | Density (gcm -2) | Heat treatment A/B | B r ±20 (mT) | iH c ±10 (kA/m) | bH c ±10 (kA/m) | (BH)max ±15 (kJ/m 3) | Square- |
| 0 | 7.46 | A | 1244 | 771 | 690 | 290 | 0.75 |
| B | 1240 | 854 | 777 | 291 | 0.85 | ||
| 0.05 | 7.47 | A | 1248 | 670 | 628 | 295 | 0.87 |
| B | 1249 | 845 | 713 | 296 | 0.81 | ||
| 0.10 | 7.47 | A | 1267 | 628 | 601 | 305 | 0.91 |
| B | 1261 | 835 | 783 | 302 | 0.90 | ||
| 0.15 | 7.46 | A | 1255 | 613 | 605 | 298 | 0.94 |
| B | 1232 | 759 | 718 | 286 | 0.88 | ||
| 0.20 | 7.46 | A | 1237 | 839 | 796 | 291 | 0.93 |
| B | 1211 | 803 | 758 | 277 | 0.90 | ||
| 0.25 | 7.46 | A | 1244 | 854 | 803 | 295 | 0.88 |
| B | 1263 | 813 | 776 | 303 | 0.91 | ||
| 0.30 | 7.45 | A | 1251 | 844 | 791 | 298 | 0.87 |
| B | 1233 | 805 | 759 | 287 | 0.91 | ||
| 0.35 | 7.45 | A | 1241 | 837 | 780 | 292 | 0.92 |
| B | 1248 | 782 | 711 | 293 | 0.86 | ||
| 0.40 | 7.43 | A | 1231 | 843 | 784 | 287 | 0.88 |
| B | 1226 | 785 | 752 | 283 | 0.82 | ||
| 0.45 | 7.38 | A | 1225 | 791 | 761 | 281 | 0.89 |
| B | 1229 | 755 | 674 | 282 | 0.83 | ||
| 0.50 | 7.32 | A | 1205 | 738 | 679 | 265 | 0.85 |
| B | 1219 | 715 | 686 | 274 | 0.80 |
(A) 500 ℃ of heat treatment is 1 hour, behind the chilling (cooled with liquid nitrogen under the vacuum)
(B) 630 ℃ of heat treatment is 1 hour, after cold soon (air-cooled under the vacuum)
EDX observes and contains the mixed powder Nd of 0.25at% Cu
16Fe
76B
8Recovering the magnet phase constituent distributes referring to table 5:
Table 5
| Sample | Phase | Nd(at％) | Fe(at％) | Cu(at％) |
| Recover sintered magnet | Hard Magnetic phase matrix Boride is rich, and Nd contains the Cu phase mutually | 14 24 97 80 | 86 76 3 14 | 0 0 0 6 |
| After the heat treatment | Rich Nd contains the Cu phase mutually | 98 30 | 2 52 | 18 |
In the table 4, Nd
16Fe
76B
8The demagnetization curve that+0.25at%Cu, two kinds of Technologies for Heating Processing of its A, B and normal sintering handle resulting restored permanent magnet is referring to Fig. 1:
Embodiment 3: get degeneration Nd
16Fe
76B
8Rare-earth permanent magnet 1000 gram, pulverize and the step of drying identical with embodiment 1, adopt disproportionated reaction (HDDR) recycling degenerated rare earth permanent magnet, the degenerated rare earth permanent magnetic material after drying is placed vacuum 10
-6Bar under the temperature 700-880 ℃ of environment, imports pure hydrogen (H
2), hydrogen pressure is 15bar, handle degenerated rare earth permanent magnetic material generation disproportionated reaction: HydrogenationDisproportionation Desorption Recombination (HDDR), 2 hours time, the degenerated rare earth permanent magnetic material becomes anisotropic magnetic, and the fineness of its magnetic is about 500 microns.Further add high magnetocrystalline anisotropy field element Dy, the addition of Dy is 2at%, perhaps adds alloy Dy
3Co, addition is 5wt%, mixes thoroughly.Consumption adds epoxy resin routinely, adopts the heat rejector extrusion molding, promptly obtains anisotropic Nd
16Fe
76B
8The regeneration rare-earth permanent magnet, its magnetic property returns to the level of original performance parameter 100%.
The inventive method goes for the recycling that Sm-Co is the degenerated rare earth permanent magnetic material equally, and its magnetic property can return to the level of original performance parameter 100% equally.
Claims (6)
1. the method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material is characterized in that may further comprise the steps:
(1) to the degenerated rare earth permanent magnetic material mechanical crushing of same family, removes impurity, remove impurity and comprise that magnetic separation separates.And place (10
-2-10
-9Bar) dried under the vacuum 0.5-3 hour;
(2) the degenerated rare earth permanent magnetic material after will drying places vacuum degree: 10
-2-10
-9Bar, temperature: under room temperature or 0-100 ℃ the environment, import pure hydrogen (H
2), hydrogen pressure: 0.5-30bar carried out hydrogen quick-fried (HD) 0.5-2 hour, the degenerated rare earth permanent magnetic material becomes hydrogen quick-fried (HD) micro mist, under the protective atmosphere of nitrogen or argon gas, its hydrogen quick-fried (HD) micro mist is carried out ball milling or airflow milling, its granularity is ground to the 1-20 micron, perhaps;
(3) the degenerated rare earth permanent magnetic material after will drying places vacuum degree: 10
-2-10
-9Bar under temperature: 700-880 ℃ the environment, imports pure hydrogen (H
2), hydrogen pressure: 0.5-30bar carried out disproportionated reaction (HDDR) 0.5-2.5 hour, and the degenerated rare earth permanent magnetic material becomes disproportionation (HDDR) micro mist;
(4) it is identical and can to make this be high magnetocrystalline anisotropy field element or the alloy that rare earth permanent-magnetic material constitutes the Hard Magnetic phase structure to sneak into particle diameter at quick-fried (HD) micro mist of hydrogen after grinding or disproportionation (HDDR) micro mist under the protective atmosphere of nitrogen or argon gas, and mix is even;
(5) becoming anisotropic regeneration permanent magnet after to hydrogen quick-fried (HD) the micro mist magnetization moulding after mixing powder, sintering, heat treatment under the protection environment of vacuum or nitrogen or argon gas, perhaps;
(6) in disproportionation (HDDR) micro mist after mixing powder under the protection environment of vacuum or nitrogen or argon gas, add the permanent magnet adhesive, adopt the heat rejector extrusion molding, obtain anisotropic regeneration permanent magnet.
2. the method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material according to claim 1, it is characterized in that: in step (4), for R-Fe-B is the degenerated rare earth permanent magnetic material, and R=Nd or Pr, element that is added or alloy are Dy, Sm, Co, Cu, Zr, B, Fe, Dy
3Co, Dy
3Co
2, Dy
1.5Nd
1.5Co
2, Nd
3Co, Nd
xPr
yIn one or more mixture, R
xFe
yB
zX=10-18at% in the degenerated rare earth permanent magnetic material, y=66-88at%, z=4-12at%, wherein:
The ratio that element Dy, Co, Cu, Zr, B, Fe add is: RDy
vCo
xCu
yZr
wB
zFe
Bal, x=0-4.2at%, y=0-0.5at%, z=4-8at%, v=0.1-6at%, w=0-1.0at%, bal are contained Fe aequum,
Alloy Dy
3Co, Dy
3Co
2, Dy
1.5Nd
1.5Co
2The ratio that adds is:
Add Dy
3Co accounts for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Dy
3Co
2Account for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Dy
1.5Nd
1.5Co
2Account for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-15wt%,
Add Nd
3Co accounts for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-5wt%,
Add Nd
xPr
yAccount for R
xFe
yB
zDegenerated rare earth permanent magnetic material 0.1-5wt%,
For Sm-Co is the degenerated rare earth permanent magnetic material,
SmCo
5In the element that added be one or both mixture among Sm, the Co, the ratio of its adding is: Sm=0.01-0.8at%, Co=0.01-2.0at%,
Sm
2(Co
BalFe
bCu
cZr
d)
17In the element that added be one or more mixture among Co, Cu, Zr, the Fe, the ratio of its adding is: b=0.01-0.42at%, c=0.01-1.8at%, d=0.01-1.6at%, bal are contained Co aequum.
3. the method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material according to claim 1, it is characterized in that: in step (1), the degenerated rare earth permanent magnetic material particle diameter of mechanical crushing is the 2-10 millimeter, removing impurity is that the degenerated rare earth permanent magnetic material after its pulverizing is carried out magnetic separation, rare-earth separating permanent magnet and anti-corrosion coated layer, nonmagnetic corrosion thing and oxide.
4. the method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material according to claim 1, it is characterized in that: in step (5), hydrogen quick-fried (HD) micro mist behind the mixed powder is packaged in the rubber die, adopt little frequency alternation backing field vibration processing, the frequency of little frequency magnetic vibration is 3-10 time/minute, time is 2-5 minute, and magnetic field intensity is 1-6Tesla, adopts static pressure or warm compaction moldings such as normal temperature again.
5. the method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material according to claim 1 is characterized in that: in step (5), be R for composition behind the mixed powder
xCu
yCo
zFe
uB
v(R=Nd or Pr, x=10-18at%, y=0.01-0.48at%, Co=0-10at%, u=73-79at%, rare earth permanent-magnetic material v=5-9at%) is after the compression moulding, temperature 1010-1080 ℃ of following sintering 1 hour, 500 ℃ of heat treatments are after 1 hour under vacuum then, and cold soon (air-cooled under the vacuum) becomes anisotropic regeneration permanent magnet to room temperature; Perhaps temperature 1010-1080 ℃ of following sintering 1 hour, 630 ℃ of heat treatment 1 hour under vacuum then, cold soon (air-cooled under the vacuum) becomes anisotropic regeneration permanent magnet to room temperature.
6. the method for regenerating high-performance permanent magnet by degenerated rare earth permanent magnet material according to claim 1, it is characterized in that: the permanent magnet adhesive that is added in step (6) is epoxy resin or polytetrafluoroethylene.
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