CN1076115C - R-Fe-B permanent magnet materials and process of producing the same - Google Patents
R-Fe-B permanent magnet materials and process of producing the same Download PDFInfo
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- CN1076115C CN1076115C CN93115008A CN93115008A CN1076115C CN 1076115 C CN1076115 C CN 1076115C CN 93115008 A CN93115008 A CN 93115008A CN 93115008 A CN93115008 A CN 93115008A CN 1076115 C CN1076115 C CN 1076115C
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- 238000000034 method Methods 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 60
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- 230000005291 magnetic effect Effects 0.000 claims abstract description 136
- 239000000956 alloy Substances 0.000 claims abstract description 108
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 107
- 238000005266 casting Methods 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 238000003825 pressing Methods 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 209
- 239000002245 particle Substances 0.000 claims description 48
- 229910052742 iron Inorganic materials 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 229910052796 boron Inorganic materials 0.000 claims description 30
- 230000005347 demagnetization Effects 0.000 claims description 26
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 22
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 20
- 239000000696 magnetic material Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 15
- 229910000765 intermetallic Inorganic materials 0.000 claims description 15
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- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
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- 229920003023 plastic Polymers 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 claims 7
- 238000009749 continuous casting Methods 0.000 claims 5
- 238000000465 moulding Methods 0.000 claims 2
- 238000005096 rolling process Methods 0.000 claims 2
- 229910052718 tin Inorganic materials 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 18
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 238000010298 pulverizing process Methods 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 6
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- 125000004429 atom Chemical group 0.000 description 170
- 239000012071 phase Substances 0.000 description 132
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- 238000006253 efflorescence Methods 0.000 description 45
- 206010037844 rash Diseases 0.000 description 44
- 238000005245 sintering Methods 0.000 description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 28
- 239000001301 oxygen Substances 0.000 description 28
- 229910052760 oxygen Inorganic materials 0.000 description 28
- 229910052779 Neodymium Inorganic materials 0.000 description 20
- 229910052777 Praseodymium Inorganic materials 0.000 description 20
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- 239000007791 liquid phase Substances 0.000 description 17
- 229910000521 B alloy Inorganic materials 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 16
- 238000004453 electron probe microanalysis Methods 0.000 description 15
- 229910000859 α-Fe Inorganic materials 0.000 description 15
- 238000000137 annealing Methods 0.000 description 13
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- 229910001018 Cast iron Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
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- 239000010959 steel Substances 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000722 Didymium Inorganic materials 0.000 description 1
- 241000224487 Didymium Species 0.000 description 1
- 229910002548 FeFe Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0573—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes obtained by reduction or by hydrogen decrepitation or embrittlement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2202/00—Treatment under specific physical conditions
- B22F2202/05—Use of magnetic field
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Hard Magnetic Materials (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
It is an object of the present invention to provide R-Fe-B permanent magnet materials having a good oxidation resistance and magnetic characteristics, and a process of producing the same capable of pulverizing efficiently, whereby an R-Fe-B molten alloy having a specific composition is casted into a cast piece having a specific plate thickness and a structure, in which an R-rich phase is finely separated below 5 mu m, by a strip casting process, the cast piece is subjected to a Hydrogenation for spontaneous decay, and thereafter, an alloy powder is dehydrogenated and stabilized for pulverization so as to fractionize crystal grains of a main phase constituting an alloy ingot, thereby the powder having a uniform grain distribution can be produced at an efficiency of about twice as much as the conventional process, and the R-rich phase and an R2Fe14B phase are also fractionized at the time of pulverization, thus by magnetization by pressing after the orientation using a pulse magnetic field, a good oxidation resistance and magnetic characteristics can be obtained.
Description
The present invention relates to permanent magnetic material and this preparation methods mainly formed by R (wherein R contains the rare earth element of a kind of Y of containing at least), Fe and B, R-Fe-B permanent magnetic material that the invention particularly relates to and manufacture method thereof are the Strip casting methods that adopts such as single-roller method or double roller therapy and similar approach, are that the molten alloy of R, Fe and B obtains to have R wherein by main component
2Fe
14B mutually and rich R be the casting alloy of finely divided homogeneous texture mutually, or acquisition contains R
2Fe
14B is as the main-phase alloy and the R of principal phase
2Fe
17The adjustment alloy-steel casting of phase or R-Co intermetallic compound phase, utilize the hydrogenization of this alloy to make this casting alloy experience spontaneous decomposition, make this alloy dehydrogenation stabilisation again so that fully efflorescence, by single powder or the mixed-powder mold pressing and sintering of planting that will be orientated by added pulsed magnetic field, make to obtain the A+B total value (wherein A is maximum magnetic energy product (BH)
Max(MGOe) and B is coercive force iHc (KOe)) be 59 or square the degree { (Br of higher and demagnetization curve
2/ 4 (BH) max) be the high-performance R-Fe-B permanent magnet of 1.01-1.045.
Current, the principal phase that has ternary tetragonal crystal system compound for the R-Fe-B permanent magnet (Japanese Patent Application Publication No.Sho 59-46008) of typical high-performance permanent magnet because of structure makes it obtain high magnetic with rich R mutually, and it is used to the wide spectrum from general household electrical appliance to the mainframe computer external equipment, thereby has proposed to have the R-Fe-B permanent magnet of various structures so that bring into play different magnetic characteristics according to purposes.
Yet,, need have high performance cheap R-Fe-B permanent magnet in order to adapt to the strong needs of small-sized, the light-duty and multifunction of recent realization electrical equipment and electronic equipment.
Usually, equation (1) 1 expression that the residual magnetic flux density of R-Fe-B sintered magnet (Br) can be following.
Br
∞(Is β) f{p/po (1-α) }
2/3(1) wherein, Is: saturation magnetization
The temperature reliability of β: Is
F: the degree of orientation
P: sintered density
Po: solid density
α: crystal boundary phase volume percentage (non magnetic phase volume percentage)
Therefore, for the residual magnetic flux density (Br) that improves the R-Fe-B sintered magnet, 1) must improve R
2Fe
14The percentage by volume of B matrix phase, 2) magnet density must be increased to solid density, in addition, and 3) the necessary degree of orientation of strengthening the main phase grain on easy axis.
In other words, although being formed, magnet approaches above-mentioned R
2Fe
14The B stoichiometric composition realizes the 1st) bar is very important, but when when producing the R-Fe-B sintered magnet as starting material by the alloy pig that will make by above-mentioned alloy melting of forming and die casting, because α-Fe is at alloy pig intercrystalline and rich R phase spot segregation, be difficult to especially that just its efflorescence become smalls and during the oxidation efflorescence this composition to change.
Specifically, under the situation of mechanical efflorescence alloy pig after hydrogenation and the dehydrogenation (Japanese Patent Application Publication Nos.Sho60-63304 and Sho63-33505), α-the Fe of this alloy pig intercrystalline remains unchanged and hinders atomizing because of its ductility during efflorescence, and local ubiquitous rich R attenuates owing to hydrogenization mutually and generates hydride, but so when mechanical efflorescence or under with the situation of jet mill efflorescence accelerated oxidation, cause important composition difference because of disperseing to cause.
When with approaching R
2Fe
14The alloyed powder of the stoichiometric composition of B prepares sintered body and realizes the 1st) during bar, the rich Nd that is used to cause liquid-phase sintering in sintering process produces oxide and mutually by inevitably oxidation consumption, thereby hinders sintering, and since rich Nd mutually and rich B phase factor R
2Fe
14The increase of B phase and must reducing, it is more difficult that the generation of sintered body just becomes.In addition, degenerated as the coercive force (iHc) of one of the index that shows permanent magnetic material stability and important performance.
In addition, as for being generally used for preparing the 3rd in the R-Fe-B permanent magnet method) bar, in order to make the easy axis unanimity of main phase grain, adopt the mold pressing in magnetic field to handle.At that rate, we know, residual magnetic flux density (Br) value and degree the value { (Br of demagnetization curve pros
2/ 4 (BH) max) } apply direction and pressing direction according to magnetic field and become, or be subjected to the influence of added magnetic field intensity.
Recently, for preventing grain coarsening and for the remaining α-Fe of ingot casting comminuting method gained R-Fe-B alloyed powder defective and the generation of α-Fe segregation, a kind of production method has been proposed, wherein form foundry goods by the R-Fe-B molten alloy with specific thicknesses with the twin roller casting method, and according to common powder metallurgical technique bruisher, jaw crusher or similar fashion coarse crushing foundry goods, then pass through again such as using disc mill, ball mill, pulverizing mill, the mechanical crushing method of jet mill etc. is ground into the powder of particle mean size 3-5 μ m with it, after this in magnetic field, suppress again, sintering, and annealing (Japanese Patent Application Publication No.Sho 63-317643).
Yet, compare with the situation of the ingot casting comminuting method of habitually practising, this method can not obviously be improved the crush efficiency of pulverizing phase, in addition, and during pulverizing, because the intergranular fragmentation also takes place not only the crystal boundary fragmentation to take place, just can not improve magnetic characteristic greatly, and because rich R is not oxidation resistant stable RH2 phase mutually, or because rich R is mutually in small, broken bits and surface area is big, poor by non-oxidizability, therefore in this process oxidation is taking place and can not obtain high magnetic.
Recently, requiring to reduce the cost of R-Fe-B permanent magnetic material more and more consumingly, is very important so make the high-performance permanent magnet effectively.Therefore, must improve the processing conditions that causes limitting characteristic.
We have repeatedly carried out various researchs with regard to the method for effectively producing R-Fe-B permanent magnet and improvement magnetic characteristic.
By rising to the R of ferromagnetic phase
2Fe
14The content of B principal phase can be realized the reinforcement of R-Fe-B sintered magnet residual magnetic flux density (Br).In other words, importantly make the composition of this magnet approach R
2Fe
14The B stoichiometric composition.
Yet, when producing R by the alloy pig of making through melting above-mentioned alloy of forming and die casting
2Fe
14During the B cemented iron, as starting material, because the α-Fe of crystallization in alloy pig, the spy is the general local rich R phase that exists in addition, makes to pulverize to be difficult to carry out and cause the composition inequality.
And, when producing the alloyed powder of above-mentioned composition, the unreacted abrasive grit is arranged with direct reduction and diffusion method, and when when eliminating it and improve reduction temperature, then this abrasive grit sintering growth each other, in addition, add calcium as reducing agent, and its oxide is absorbed, thereby has increased impurity.
Therefore, according to improving the result of the multiple research of doing about these predicaments of producing alloy material, we find, use the Strip casting method to cool off and solidify molten alloy fast, can suppress α-Fe crystallization and can be made into fine grain and the uniform alloy-steel casting of composition.
The R-Fe-B sintered magnet is by liquid-phase sintering reaction institute sintering on the other hand.In other words, in magnet, except that being the R of principal phase
2Fe
14B mutually and ferromagnetic mutually outside, rich B phase exists with crystal boundary mutually with rich R, their reaction solution phases each other when sintering, thereby carrying out closeization reaction.
Therefore, rich B is mutually indispensable with rich R with respect to generating the R-Fe-B sintered magnet mutually.Certainly, in order to improve magnetic characteristic, must be with principal phase R
2Fe
14B improves mutually to greatest extent with ferromagnetic, and is that the key that reaches this purpose is how will approach R
2Fe
14Closeization of alloyed powder that the metering of B phase chemistry is formed.
One object of the present invention is to provide its A+B total value 〉=59{A to be (BH) max value (MGOe) }; B is iHc value (KOe) } and demagnetization curve { (Br
2/ 4)/(BH) max} pros degree is the high-performance R-Fe-B permanent magnetic material of 1.01-1.045, wherein solved a difficult problem of producing in the R-Fe-B materials process, atomizing is effectively carried out, the non-oxidizability height, reach high iHc by refinement magnet crystal grain, and improved the orientation of crystal grain easy magnetizing axis.
Another object of the present invention provides a kind of method of the R-Fe-B of production permanent magnetic material, wherein in liquid-phase sintering reaction, by with rich B mutually and be an impediment to the rich R phase reaction that improves the R-Fe-B magnetic property, generation principal phase R
2Fe
14Reduced mutually rich B mutually and rich R mutually, oxygen content reduces and is easy to and obtains to have the alloyed powder of forming upward corresponding to various magnetic characteristics with good productivity ratio in the alloyed powder.
A further object of the present invention provides a kind of method of the R-Fe-B of production permanent magnetic material, wherein makes to form to approach (R
2Fe
14The B phase) liquid-phase sintering of the alloyed powder of stoichiometric composition experience obtains high-performance R-Fe-B permanent magnet, and adds also blending can form liquid phase when sintering alloyed powder, thereby effectively obtains to have the alloyed powder of forming corresponding to various magnetic characteristics.
The invention reside in, by having the Strip casting R-Fe-B alloy hydride of specific composition and thickness, finely divided rich R has generated hydride mutually and has caused the volume expansion of alloy and final spontaneous decomposition, after this pulverizable constitutes the main phase grain of alloy and generates the powder of even particle size distribution, at this moment, rich R is finely divided and R mutually
2Fe
14B is mutually also by efflorescence, therefore when with dehydrogenation and stable alloyed powder efflorescence, because crush efficiency has improved more than the twice than conventional efficiency, just improved production efficiency greatly, and, just can obtain the R-Fe-B permanent magnet that obvious improvement of its Br, BH (max) and iHc value and demagnetization curve pros degree value show as 1.01-1.045 (make it maximum possible and approach theory state) by with pulsed magnetic field orientation and compacting.
The present invention also is, by accounting for total amount 60% or the Na that closes through the production of Strip casting method still less
2Fe
17The adjustment alloyed powder of phase adds and is blended into through what the Strip casting method was produced and closes R
2Fe
14In the R-Fe-B alloyed powder of B as principal phase, because this adjusts Nd in the alloyed powder
2Fe
17React alternate with rich Nb mutually with rich B in the R-Fe-B alloyed powder principal phase, can make the rich B of the permanent magnetic characteristic of infringement obtain mutually adjusting and reducing with rich Nd mutually, can improve the magnet performance of gained, in addition, can reduce the oxygen content in the alloyed powder, be convenient to obtain to have alloyed powder corresponding to the composition of various magnetic characteristics.
The present invention also comprises in addition, adds and is blended into through what the Strip casting method made and close R by accounting for total amount 60% or the adjustment alloyed powder that closes R-Co intermetallic compound phase that makes through the Strip casting method still less
2Fe
14In the R-Fe-B alloyed powder of B as principal phase, even when for want of liquid-phase sintering can not take place with R-Fe-B alloyed powder principal phase with rich B in rich R mutually mutually and only, the R-Co intermetallic compound of this adjustment alloyed powder is met and is melted the liquid phase that is provided for highly denseization, so can improve the magnet performance of gained, in addition, can reduce oxygen content in the alloyed powder and be easy to obtain to have alloyed powder corresponding to the composition of various magnetic characteristics.
Fig. 1 is the press schematic illustration, wherein can together apply pulsed magnetic field and common stabilizing magnetic field.
The figure that concerns between the magnetic field intensity of Fig. 2 for demonstration time and pulsed magnetic field.
We find, as in order to improve efflorescence efficient, non-oxidizability and R-Fe-B sintered magnet magnetic characteristic (particularly R-Fe-B alloy iHc) and the result of multiple research that grinding technology is carried out, in the R-Fe-B foundry goods of producing thin brilliant and homogeneous texture with the Strip casting method and efflorescence in the situation of the stable alloyed powder of dehydrogenation after the hydrogenation, efflorescence efficient than conventional efflorescence efficiency improvement 2 times more than, and by inciting somebody to action by the mold pressing of sintered magnet fine powder, sintering and the annealing of adding pulsed magnetic field orientation, (BH) the max value that obtains and the demonstration of the summation of iHc value are higher than 59, degree the value { (Br of demagnetization curve pros2/ 4 (BH) max) } be shown as 1.01-1.045, and the iHc of sintered magnet improves.
In other words, when make Strip casting and have thin disperse in its structure when the R-Fe-B alloy of the specific composition of the rich R phase of specific thicknesses and being in the hydrogenization of the generation hydride of the rich R phase of thin disperse and volume expansion, but this alloy Auto-decomposition consequently can will consist of the crystal grain efflorescence of alloy and can be made into the powder of even particle size distribution.
Particularly importantly, this moment, rich R wanted thin disperse and R mutually2Fe
14B is corresponding tiny. In addition, in adopting common die casting alloyage ingot process, when making alloy composition close to R2Fe
14During the stoichiometric composition of B phase, because of the formation of primary crystal iron inevitable so that the efflorescence efficient in the operation of back obviously worsens. And for this reason, although the measure of taking to heat-treat and eliminate α-Fe can make the alloy pig homogenising, because main phase grain chap and the segregation of rich R phase occurs, the iHc of sintered magnet just is difficult to improve.
Consistent or the degree of orientation of improving main phase grain of the direction of easy magnetizing axis also is absolutely necessary for the square degree that reaches high magnetization effect and improve demagnetization curve, therefore, has adopted the method for pressed powder in magnetic field.
Yet, act on the coil or the energy that are used for producing magnetic field on the common press (hydraulic press and punching machine), the magnetic field that only can produce at the most 10KOe-20KOe, and the degree { (Br of demagnetization curve pros2/ 4) (BH) max} also presents 1.05 or higher value, so be difficult to reach (BH) max theoretical value (in this case, the demagnetization curve { (Br that estimates according to the Br value2/ 4) (BH) the square degree of max} is 1). Therefore, attempt mold pressing in higher magnetic field, but for producing higher magnetic field, must increase the number of turn of coil and also must make the equipment that larger need are used high-energy source.
Relation when suppressing by analyzing between magnetic field intensity and sintered body Br, we find, it is higher that magnetic field intensity increases, the larger then demagnetization curve of magnetization pros degree just more improves, therefore by adopting the pulsed magnetic field in the strong magnetic field of the instantaneous generation of energy, just can reach higher magnetization effect and the demagnetization curve pros degree of Geng Gao.
Meanwhile we find, and are once very important with pulsed magnetic field moment orientation with in the technology of pulsed magnetic field, and can with etc. static pressure come the mold pressing powder, and, also can in magnetic field, carry out mold pressing by pulsed magnetic field being combined with magnetostatic field with electromagnet.
In other words, will consist of 12 atom %-16 atom %R (wherein R represents the rare earth element of at least a Y of containing), 4 atom %-8 atom %B, 5000ppm or O still less with the Strip casting method
2, Fe (part Fe can be replaced by one or both metals of Co and Ni) and unavoidable impurities molten alloy to cast principal phase be R
2Fe
14Behind the foundry goods of B, with this foundry goods container that can suck with air-out of packing into, the air H in the container
2Gas replaces, the alloyed powder dehydrogenation of the decomposition that will obtain by hydrogenation, after the dehydrogenation in noble gas stream efflorescence become the fine powder of particle mean size 1-10 μ m, with pack into mould and moment applies 10KOe or higher pulsed magnetic field makes its orientation of this fine powder, mold pressing then, sintering and timeliness are 59 or higher (A is iHc value (KOe) for (BH) max value (MGOe) B) and the degree { (Br of demagnetization curve pros thereby obtain A+B value sum
2/ 4) (BH) the max} value is 1.01-1.045 permanent magnetic material.
And the Nd in R-Fe alloy (such as the Nd-Fe alloy)
2Fe
17Curie point during near room temperature for when C has the intermetallic compound of direction of easy axis in mutually, when the amount of the B in the R-Fe-B sintered permanent magnet for example is lower than 6 atom % usually, generate Nd in the magnet
2Fe
17The weakening coercive force of meeting.
Yet we find according to various results of study, to the R that contains that has wherein added specified quantitative
2Fe
17Phase is (such as Nd
2Fe
17Phase) R-Fe alloyed powder and blending contain R
2Fe
14In the powder of the R-Fe-B alloyed powder of B principal phase, near rich Nd mutually in Nd and the crystal boundary Nd of middle R-Fe alloyed powder mutually
2Fe
17Under 690 ℃ the eutectic temperature of phase, taken place as Nd+Nd
2Fe
17The sintering of R-Fe-B alloyed powder has been quickened in the reaction of phase liquid phase by this eutectic master's liquid phase.
Simultaneously, contain Nd
2Fe
17The adjustment alloyed powder of phase with contain FeFe
14Following reaction takes place in the R-Fe-B alloyed powder of B principal phase during sintering, and plays increase principal phase R
2Fe
14The effect of B phase.
In other words, find, in above-mentioned reaction equation, owing to be by adjusting Nd in the alloyed powder
2Fe
17With the reaction that rich B is alternate with rich Nd mutually in the principal phase R-Fe-B alloyed powder newly-generated Nd
2Fe
14The B phase is so only containing R with conventional method
2Fe
14Rich B in the permanent magnet that the alloyed powder of B principal phase makes mutually and rich Nd mutually the amount of (it is for damaging one of magnetic characteristic factor) can be reduced at sintering reaction.
In addition, in fact from productive viewpoint, when producing the R-Fe-B magnet with powder metallurgic method, the alloy powder that acquisition is easy to efflorescence is greatly favourable, according to the various results of study that production R-Fe-B magnetic material method is done, we find, quick cooling that will be by the Strip casting method and solidify the main-phase alloy powder of the necessary amount that molten alloy makes and adjust alloyed powder and contain R
2Fe
14The main-phase alloy powder of B principal phase and contain R
2Fe
17The adjustment alloyed powder of phase mixes, and can obtain R-Fe-B permanent magnetic material powder.
In other words, the present invention is that by the reason that the alloy that adopts the Strip casting method to obtain prepares main-phase alloy powder and adjustment alloyed powder adopt the Strip casting method, concerning main-phase alloy powder, this main-phase alloy powder can derive from wherein R
2Ee
14The alloy-steel casting that the tiny and rich B of B principal phase and rich Nd fully disperse mutually, and suppressed the crystallization of primary crystal Fe, integrate bronze and exchange, this alloyed powder can derive from wherein R
2Fe
17The alloy-steel casting that is evenly distributed mutually.
Especially, R in the principal phase powder
2Fe
14The mutually tiny and rich B of B mutually and rich R mutually during even dispersion, the size reduction energy during production magnet significantly improves, and can obtain the powder of even particle distribution.And, when producing magnet,, can obtain high-coercive force because of crystal is tiny.
Simultaneously, contain R with the production of Strip casting method
2Fe
17The advantage of adjusting alloyed powder mutually is, because of this R when mixing with main-phase alloy powder
2Fe
17Tiny and the abundant disperse that can become is mutually evenly carried out reaction.In other words, concerning the common usefulness molten alloy method of mold, owing to α-Fe and other R-Fe (Co) compound phase are arranged at gained alloy pig intercrystalline, for obtaining stable alloy powder, the alloy pig heating must be homogenized, make the production cost of this alloyed powder improve and R
2Fe
17Growth mutually.And, producing under the adjustment alloy situation, run into such problem with directly reduction and diffusion method, promptly unreacted Fe crystal grain remain unchanged or each crystal grain composition differing from each other, and whole alloyed powders are homogenized is very difficult.
According to the result of study to above-mentioned supposition, we also find, specified quantitative contained the R-Co intermetallic compound (as Nd
3Co phase and NdCo
2Phase) the R-Co alloyed powder of principal phase adds and is blended into and contains R
2Fe
14In the R-Fe-B alloyed powder of B principal phase and in the powder that makes since near main-phase alloy powder Nd in the Nd of rich Nd phase and the R-Co alloyed powder
3Under 625 ℃ of the eutectic temperatures of Co eutectic reaction Nd+Nd is arranged
3Co phase=liquid phase, this low melting point liquid phase has been quickened the sintering of R-Fe-B alloy.
In other words, according to the present invention, can be provided for the necessary amount of liquid phase of sintering, the result can make the R that approaches that makes
2Fe
14The alloyed powder that the metering of B phase chemistry is formed carries out liquid-phase sintering, approaches R thereby can make magnet form
2Fe
14The stoichiometric composition of B phase.In other words, only with the R that contains of routine
2Fe
14B produces under the situation of magnet as the alloyed powder of principal phase, work the rich Nd that the effect of liquid phase source is provided and in this process, produce the Nd oxide because of inevitable material oxidation, thereby can not ensure the amount of liquid phase that sintering is required, the result just can not reach sufficiently high closeization effect, therefore must leave surplus ground in advance and determine this composition, certainly, this deviation can be calculated by the present invention.
Especially, the R in the principal phase powder
2Fe
14When mutually tiny the and rich B of B was uniformly dispersed mutually with rich Nb, the fragmentation powder when producing magnet significantly improved, and can produce the powder of even particle distribution.In addition, because crystal is tiny, just can obtain high coercive force when producing magnet.Particularly, even when alloyed powder is formed near R
2Fe
14During the stoichiometric composition of B phase, can exempt the crystallization of Fe primary crystal and obtain uniform structure.
In addition, the advantage of producing the adjustment alloyed powder that contains R-Co intermetallic compound phase with the Strip casting method is to solve some difficult problems like this, promptly in the common alloy melting method that adopts mold, Co (Fe) reaches the crystallization in the gained alloy pig of other R-Co (Fe) compound mutually, and these general mutually local existence, therefore for obtaining the alloyed powder of stabilizing material, must handle alloy pig heating and homogeneous, make the production cost of alloyed powder improve, in addition, when using directly reduction and diffusion method to produce the adjustment alloyed powder, unreacted Co and Fe grain remain or make each particle to form and differ from one another, so are difficult to whole alloyed powder homogenizing.
The magnetic characteristic of R-Fe-B permanent magnet of the present invention is, the total value of A+B is 59 or higher, wherein A is the ceiling capacity output value (BH) max (MGOe) and B is coercive force iHc (KOe), as (BH) when max is higher than 50MGOe, iHc is higher than 9KOe, as (BH) when max is higher than 45MGOe, iHc is higher than 14KOe, and square the degree { (Br of demagnetization curve
2/ 4) (BH) the max} value is 1.01-1.045, therefore by suitably selecting composition and working condition, can obtain required magnetic feature.
Among the present invention, has wherein R
2Fe
14B is to make by the molten alloy of Strip casting specific composition with single roller or double roller therapy for the ferromagnetic material foundry goods of specific composition and the mutually finely divided structure of rich R.The gained foundry goods is the sheet material of thickness 0.03mm-10mm, though suitably use single-roller method and double roller therapy according to desired casting thickness, generally preferably adopts double roller therapy when slab is thick, and preferably adopts single-roller method when slab is thin.
Casting thickness is limited in 0.03mm-10mm, and when this thickness was lower than 0.03mm, cooling effect increasing and crystallite dimension became and be lower than 1 μ m fast, so be easy to oxidation when efflorescence, magnetic characteristic are caused damage; And when this thickness was higher than 10mm, cooldown rate slowed down fast, and α-Fe is easy to crystallization, and grain size becomes big and goes back the rich Nd phase of ubiquity, and magnetic characteristic is worsened.
The section structure of the R-Fe-B alloy that has specific composition and obtained by the Strip casting method of the present invention is such, its principal phase R
2Fe
14The B crystal than the corresponding crystal in the conventional ingot that makes with die casting thin nearly ten/one or more (for example, crystalline size short-axis direction be 0.1 μ m-50 μ m and be 5 μ m-200 μ m at long axis direction), and rich R carefully looses around main phase grain mutually and distributes, even be prevalent in regional area, its size also is lower than 20 μ m.Has same character with Strip casting method main-phase alloy powder that obtains and the crystal grain of adjusting alloyed powder.
Make rich R finely divided,, evenly facilitate that cracked body is swollen to rise, so this main phase grain is through efflorescence and the cracked fine powder that obtains even particle size distribution by when this richness R generates hydride during hydrogenation treatment with the size that is lower than 5 μ m.
To tell about reason below to the composition qualification of R-Fe-B permanent magnet of the present invention and alloy pig.
Contained rare-earth element R comprises (Y) in the permanent magnet alloy ingot of the present invention, and is the rare earth element that comprises light rare earth and heavy rare earth.
As R, light rare earth element is just enough, and Nd and Pr are especially for well.Though common a kind of R is just enough, in fact, can use the mixture (mishmetal, didymium etc.) of two or more R, and Sm, Y, La, Ce, Gd etc. can be used to and other R (particularly Nd, Pr etc.) constitute mixture for the reason of availability.R is the pure rare earth element not necessarily, can use those to contain the rare earth R of unavoidable impurities on producing in the retrievable scope of industry.
R is the fixed indispensable a kind of element of alloy casting that is used for manufacturing the R-Fe-B permanent magnet, when being lower than 12 atom %, can not obtain high magnetic characteristic, especially can not obtain high-coercive force, and when it surpassed 16 atom %, residual magnetic flux density (Br) reduced and can not obtain the permanent magnet of first-class performance.Therefore, preferably in 12 atom %-16 atom % scopes, optimum range is 12.5 atom %-14 atom % to R.
B is the indispensable element of alloy cast ingot that is used for preparing the R-Fe-B permanent magnet, and it can not obtain high-coercive force (iHc) when being lower than 4 atom %, and it is when surpassing 8 atom %, and residual magnetic flux density reduces, and just can not obtain good permanent magnet.Therefore, B is preferably at 4 atom %-8 atom %, and optimum range is 5.8 atom %-7 atom %.
Concerning Fe, residual magnetic flux density (Br) reduces when being lower than 76 atom %, and when surpassing 84 atom %, can not get high-coercive force, so Fe is limited in 76-84 atom %.
In addition, though will replace a part of Fe with one or both of Co and Ni for reaching the effect of improving permanent magnet temperature characterisitic and corrosion resistance, when one or both of Co and Ni surpass 50% iron, can not obtain high-coercive force, can not obtain good permanent magnet.Therefore, Co and Ni on be limited to 50% of Fe.
With O
2Being limited in the reason that is lower than 5000ppm is, when it surpassed 5000ppm, rich R can not produce sufficient liquid phase during mutually oxidized and sintering, and the result has reduced density, just can not obtain high magnetic flux density and also make the weatherability variation, thereby, O
2Optimum range be 200-3000ppm.
When the apparent density of permanent magnetic material is lower than 7.45g/cm
3The time, can not obtain high magnetic flux density, and can not obtain its A+B (wherein A (MGOe) is (BH) max) value B (ROe) and be the iHc value) total value is higher than the magnetic material of 59 (these are characteristics of the present invention).
In addition, as initial powder of the present invention, except that the raw meal with the magnet composition, for R, B and the Fe that adjusts in the magnet composition measures, but also the blending use contains R
2Fe
14B is that principal phase and wherein contained R (hereinafter will illustrate) amount is the R-Fe-B alloyed powder of 11 atom %-20 atom % and contains R mutually
2Fe
17Mutually and wherein the R amount is lower than the R-Fe-B alloyed powder of 20 atom %.
As for containing B amount, can wherein to contain the B amount be 4 atom %-12 atom % or higher principal phase R-Fe-B alloyed powder and wherein contain B and measure the R that contains that is lower than 6 atom % by blending
2Fe
17The R-Fe-B of phase adjusts alloyed powder, or does not wherein contain the R that contains of B
2Fe
17The R-Fe of phase adjusts the composition that alloyed powder is adjusted magnet.
In addition, can contain R-Co intermetallic compound (Nd by blending
3-Co, Nd-Co
2Deng) R-Co (can Fe replace) adjust alloyed powder and adjust magnet and form.
Owing in alloy-steel casting of the present invention, allow to exist inevitable R, B and Fe impurity in addition in the industrial production, with total amount is that 4.0 atom % or at least a following material part still less replace the cost that B can improve productivity ratio and reduce magnet alloy, these materials are 4.0 atom % or C still less, 3.5 atom % or P still less, 2.5 atom % or S still less and 3.5 atom % or C still less.
Simultaneously, to containing R, B, Fe alloy or the R-Fe-B alloy (R that contains Co or blending
2Fe
14The B principal phase) in the alloyed powder, or to containing R
2Fe
17The adjustment alloyed powder of phase and contain and add at least a following material in the adjustment alloyed powder of R-Co intermetallic compound phase, just may make permanent-magnet alloy obtain high-coercive force, these materials are: 9.5 atom % or Al still less, 4.5 atom % or Ti still less, 9.5 atom % or V still less, 8.5 atom % or Cr still less, 8.0 atom or Mn still less, 5 atom % or Bi still less, 12.5 atom % or Nb still less, 10.5 atom % or Ta still less, 9.5 atom % or Mo still less, 9.5 atom % or W still less, 2.5 atom % or Sb still less, 7 atom % or Ge still less, 3.5 atom % or Sn still less, 5.5 atom % or Zr still less and 5.5 atom % or Hf still less.
In the R-Fe-B permanent magnet of the present invention, make the middle mutually principal phase R of crystal
2Fe
14B content is higher than 90%, and it is necessary preferably being higher than 94%.Present mass-produced R-Fe-B sintered magnet contains R
2Fe
14B is up to 90%, is lower than 90% and just can not obtains wherein A+B value of the present invention and be higher than 59 high magnetic.
The degree of orientation of magnet of the present invention is calculated according to aforementioned equation 1, the magnet degree of orientation is higher than 85% pair and keeps the A+B total value to be higher than 59 being absolutely necessary, and when this degree of orientation is lower than 85%, the square degree variation of demagnetization curve also reduces high residual magnetic flux density (Br), causes low (BH) max value.The degree of orientation preferably is higher than 92%.
Though demagnetization curve pros degree value shows as 1.00 in theory, because the above-mentioned degree of orientation is interfered inevitably in actual permanent magnetic material, even in the past through after repeatedly improving, this value also can only reach 1.05, and the demagnetization curve pros degree value of the permanent magnetic material of the present invention that obtains with above-mentioned ad hoc approach is 1.01-1.045.
Record and narrate restriction below and be used for the main-phase alloy of R-Fe-B permanent magnetic material and the reason of the composition of adjusting alloy.
To obtaining to contain R
2Fe
14B contains R as principal phase and to wherein adding to have mixed
2Fe
17The main-phase alloy powder of the adjustment alloyed powder of phase, when R was lower than 11 atom %, wherein the indiffusible residual iron of R and B increased, and when R surpasses 20 atom %, rich R increase mutually and during efflorescence oxygen content increase, so R is preferably 11 atom %-20 atom %, be more preferred from 13 atom %-16 atom %.
When B is lower than 4 atom %, can not obtain high-coercive force (iHc), and residual magnetic flux density (Br) can reduce when crossing 12 atom % because of B ultrasonic, can not obtain permanent magnet preferably, so B is preferably 4 atom %-12 atom %, is more preferred from 6 atom %-10 atom %.
Remaining Fe and the unavoidable impurities of consisting of, Fe is preferably in the 65 atom %-82 atom % scopes.When Fe was lower than 65 atom %, rare earth element was relative with B plentiful, and rich R increases mutually with rich B, and when Fe surpassed 82 atom %, rare earth element is relative with B to be reduced, and residual Fe increases, and makes alloyed powder inhomogeneous.Fe is preferably 74 atom %-81 atom %.
Because R
2Fe
14Fe in the B principal phase replace Co and Ni in the main-phase alloy powder one or both to reduce coercive force, Co is preferably lower than 10 atom % and Ni is preferably lower than 3 atom %.Yet when partly replacing Fe with above-mentioned Co or Ni, the Fe weight range is 55 atom %-72 atom %.
Preparation is contained R
2Fe
17The adjustment alloyed powder of phase, when R surpassed 20 atom %, rich R increased and causes oxidation mutually when producing alloyed powder, so R is preferably 5-15 atom %.When B is lower than 6 atom %, owing to only there is R
2Fe
14The B phase just can be adjusted the B amount in the main-phase alloy powder, so B is preferably lower than 6 atom %.
At this moment, remaining Fe and the unavoidable impurities of consisting of, Fe is preferably 85 atom %-95 atom %.
Preparation is contained R
2Fe
14B principal phase and mixed the alloyed powder that the R-Fe that contains R-Co intermetallic compound phase adjusts alloyed powder to wherein adding, because, when R is lower than 11 atom %, residual Fe increases when R and B indiffusion, and when R surpasses 15 atom %, rich R increase mutually and during efflorescence oxygen content can increase, so R is preferably 11 atom %-15 atom %, and be more preferred from 12 atom %-14 atom %.
Because B can not get high coercive force (iHc) when being lower than 4 atom %, and be lower than the reduction of 12 atom % residual magnetic flux densities (Br), all can not obtain good permanent magnet,, be more preferred from 6 atom %-10 atom % so B is preferably 4 atom %-12 atom %.
At this moment, remaining consists of Fe and the spiral of inevitably mixing, and Fe is preferably 73 atom %-85 atom %.When Fe is lower than 73 atom %, rare earth element and B become relative plentiful and make rich R mutually and rich B increase mutually, when Fe surpasses 85 atom %, the relative minimizing of rare earth element and residual Fe increase with B, produce uneven alloyed powder, so Fe is more preferred from 76 atom %-82 atom %.
Because one or both of Co in the main-phase alloy powder and Ni and R
2Fe
14Fe in the B principal phase replaces making the coercive force variation, and Ni is lower than 3 atom % so preferably make Co be lower than 10 atom %.Yet, partly replacing under the Fe situation with above-mentioned Co and Ni, Fe is preferably 63 atom %-82 atom %.
Concerning preparation contained the adjustment alloyed powder of R-Co intermetallic compound phase, when R surpassed 45 atom %, rich R increased mutually, caused oxidation when producing alloyed powder, so R is preferably 10-20 atom %.
At this moment, remaining Co and the unavoidable impurities of consisting of, Co is preferably 55 atom %-95 atom %.
One or both that replace to adjust Fe and Ni in the alloyed powder with Co be because, when the Fe amount increases, adjust the non-oxidizability variation of alloyed powder, and when the increase of Ni amount, the decline of the coercive force of magnet, Ni is lower than 10 atom % so preferably make Fe be lower than 50 atom %.Yet with Fe or Ni instead of part Co the time, Co is preferably 5 atom %-45 atom %.
Magnet component alloyed powder among the present invention, contain R
2Fe
14The main-phase alloy powder of B principal phase, and contain R
2Fe
17The adjustment alloyed powder of phase or R-Co intermetallic compound phase is for example to adopt the known Strip casting method that single roller is handled or two roller is handled to make.
Hydrogenation treatment is, for example, is that the foundry goods of 0.03mm-10mm inserts a magazine with being cut into preliminary dimension and thickness, covers this box and with its sealable container of packing into, with this container airtight after, it is fully vacuumized, after this, introduce 200Torr-50Kg/cm
2The H of pressure
2Gas is so that this foundry goods is inhaled hydrogen.
Because hydrogenation is exothermic reaction, is infeeding H with predetermined pressure and certain hour
2To have in the time of gas around the temperature rise in the pipeline confession cooling water inhibition container of this container, absorb H
2The foundry goods of gas is spontaneous to carry out the decomposition efflorescence.At this moment, this broken alloy is cooled and dehydrogenation in vacuum.
Owing to produce minute crack in the alloyed powder particle of handling, just available ball mill, jet mill etc. are its efflorescence, and can obtain to have the alloyed powder of the desired particle size of 1 μ m-80 μ m.
Among the present invention, the air in this container handling can replace with inert gas in advance, and subsequently again with H
2Replace this inert gas.
Foundry goods to cut size more little, hydrogen-pressure is low more, although even and under vacuum foundry goods absorb pulverizable behind the hydrogen, pressure exceeds ambient pressure and gets over Gao Zeyue and be easy to efflorescence.But, H
2Efflorescence deleterious when being lower than 200Torr is although consider that from hydrogenation and efflorescence pressure surpasses 50Kg/cm in addition
2Be preferably, but slave unit and security consideration are then really not so, so Hydrogen Vapor Pressure is preferably 200Torr-50Kg/cm
2Consider from output, be preferably 2Kg/cm
2-10Kg/cm
2
Among the present invention, though the efflorescence time of hydrogenation become with the different of closed container size, casting dimension and Hydrogen Vapor Pressure, be more than 5 minutes.
Make the cracked alloyed powder of hydrogenation in vacuum, carry out first dehydrogenation after the cooling.At this moment, when the alloy of fragmentation is heated to 100 ℃-750 ℃ in vacuum or argon gas, and experienced 0.5 hour or the longer time the secondary dehydrogenation after, hydrogen in the fragmentation alloy can be removed fully, and can prevent the oxidation that powder or mold pressing piece cause because of long term storage, thereby can prevent the degeneration of gained permanent magnet magnetic.
Handle good dehydrogenation effect arranged because the present invention heating reaches 100 ℃ or higher dehydrogenation, just can remove above-mentioned first vacuum dehydrogenation process from, and also can make the powder that resolves under vacuum or argon atmospher in 100 ℃ or higher temperature direct dehydrogenation.
In other words, in aforesaid hydrogenation container, carry out hydrogenation and decomposition reaction after, the decomposed powder that can make gained then carries out dehydrogenation under 100 ℃ or higher temperature in container atmosphere handles.Or after vacuum dehydrogenation, the powder that decomposes is taken out efflorescence from this container, then, the dehydrogenation of the present invention that can be heated to 100 ℃ or higher temperature in this container is again handled.
When above-mentioned certain embodiments heating-up temperature is lower than 100 ℃, need long-time the removal to remain in the H that decomposes in the alloyed powder
2So, be unfavorable for high yield.When temperature surpasses 750 ℃, generate liquid phase and powder curing, make to be difficult to efflorescence and to make mouldability variation when suppressing, so this is for producing sintered magnet and inadvisable.
Consider the agglutinating property of sintered magnet, this desorption temperature is preferably 200-600 ℃.Though should become in the processing time, need 0.5 hour or longer with treating capacity.
When next carrying out efflorescence, available jet mill at inert gas (as N
2, Ar) in carry out.Needless to say, also the mode of ball mill of (as benzene, toluene or the like) and grinder pulverizing is with an organic solvent carried out.
The particle mean size of powder is preferably 1 μ m-10 μ m during pulverizing.When being lower than 1 μ m, it is oxidized greatly and easily that the powder activity of pulverizing becomes, thereby be easy to touch combustion.When surpassing 10 μ m, the coarse grain of efflorescence does not remain unchanged and makes the coercive force variation and the sintering velocity that slows down, and causes low-density.So the particle mean size of fine powder is more preferred from 2-4 μ m.
As follows for the compacting proposition method that adopts magnetic field to carry out.
Under inert atmosphere, the powder of efflorescence is adorned mould.Except that with nonmagnetic metal and the oxide, the also available organic compound such as plastics, rubber etc. of this mould is made.
The density that fills of powder (fills density 1.4g/cm for the apparent density from static powder
3) (fill density 3.0g/cm to the knot density range that is preferably after the depanning
3).That is, this fills limitations in density in 1.4-3.0g/cm
3
The pulsed magnetic field and the capacitor energy of using air core coil make the powder orientation.During orientation, can repeatedly apply pulsed magnetic field, simultaneously with upper punch and following punching press system.Pulsed magnetic field intensity is the bigger the better, and need be higher than 10KOe at least, is preferably 30KOe-80KOe.
As show that the pulsed magnetic field time is preferably 1 μ sec-10sec as shown in Fig. 2 of time and magnetic field intensity relation, and used field frequency is preferably 1-10 times, is more preferred from 1-5 times.
Can adopt the powder compact of hydrostatic method with orientation.Using under the plastics mould situation, adopt this moment so hydrostatic be useful.Adopt the pressure of hydrostatic method to be preferably 0.5ton/cm
2-5ton/cm
2, be more preferred from 1ton/cm
2-3ton/cm
2
In order to carry out magnetic field orientating and compacting continuously, can come mold pressing with a common field pressing at the coil embedding pressing mold that will produce pulsed magnetic field and after with this magnetic field orientating.Adopt the pressure of magnetic field pressing to be preferably 0.5ton/cm
2-5ton/cm
2, be more preferred from 1ton/cm
2-3ton/cm
2
Embodiment
Embodiment 1
Use comprises two roll shape strip casters of two 200mm diameter copper rollers, will in high frequency melting furnace, melt the molten alloy that consists of Nd13.0-B6.0-Fe81 make the slab foundry goods of the about 1mm of thickness.The crystal grain of foundry goods is 0.5 μ m-15 μ m and be 5 μ m-80 μ m at long axis direction at short-axis direction, and finely divided rich R to about 3 μ m exists around principal phase mutually.Oxygen content is 300ppm.
To be cut into 50 * 50mm
2Or littler foundry goods 1000Kg packs into and can suck and the closed container of discharged air, charges into N to this container
230 minutes, and after using air instead, infeeding pressure to this container is 3Kg/cm
2H
2Reach 2 hours to make the spontaneous decomposition of this foundry goods by hydrogenation, came dehydrogenation in 5 hours in vacuum and 500 ℃ of following maintenances then, after this be cooled to room temperature and gains are milled to 100 orders.
Then, in jet mill, the efflorescence of 800g meal is got the alloyed powder that average particle size particle size is 3.5 μ m.Pack into the pulsed magnetic field of rubber pattern and the instantaneous 60KOe of applying of gained alloyed powder is orientated, after this carries out 2.5ton/cm with hydrostatic method
2Hydrostatic compacting.
The mold pressing piece that will take out from mould obtains permanent magnet in 600 ℃ of annealing after 1 hour 1090 ℃ of following sintering 3 hours.Table 1 has been listed magnetic characteristic and density, grain size, the degree of orientation, demagnetization curve pros degree, principal phase amount and oxygen content.
Embodiment 2
Carrying out Strip casting to forming the molten alloy identical with embodiment 1, must thickness of slab be the slab foundry goods of about 0.5 μ m.
The crystallite dimension of this foundry goods is 0.3 μ m-12 μ m and be 5 μ m-70 μ m at long axis direction at short-axis direction, and finely divided rich R to about 3 μ m exists around principal phase mutually.With jet mill efflorescence foundry goods, obtain the alloyed powder that particle mean size is about 3.4 μ m with the condition identical with embodiment 1.Make this powder at first in the pulsed magnetic field of about 30KOe, in the magnetic field of about 12KOe, use the press mold pressing after the orientation again, press as shown in Figure 1, wherein, magnetostatic field coil 3,4 is around last low punch 1,2 configurations, and pulsed magnetic field coil 6 is arranged in the pressing mold 5, thereby makes pulsed magnetic field and general magnetic field acting in conjunction in material powder 7.After this, make mold pressing piece sintering and annealing with the condition identical with embodiment 1.
The magnetic characteristic of gained permanent magnet and density, grain size, the degree of orientation, demagnetization curve pros degree, principal phase amount and O
2Content is shown in table 1.
Embodiment 3
Identical with embodiment 1, Strip casting alloy Nd13.5-Dy0.5-B6.5-Co1.0-Fe78.5 gets the slab foundry goods.Make by the hydrogenation process identical and to be cut into 50 * 50mm with embodiment 1
2Or the littler spontaneous decomposition of foundry goods 100g, and dehydrogenation 6 hours in vacuum.Then, after the corase grind, efflorescence in jet mill, the powder of particle mean size 3.5 μ m.
With embodiment 1 the gained powder is orientated in pulsed magnetic field, and the mold pressing piece that is pressed into hydrostatic method is carried out similar sintering.Magnetic characteristic and density, grain size, the degree of orientation, demagnetization curve pros degree, principal phase amount and O
2Content is shown in table 1.Comparative Examples 1
Will dry state compression moulding in the magnetic field of powder that obtains under the condition identical with the general magnetic field press at about 12KOe with embodiment 1, then with condition sintering and the annealing identical with embodiment 1.Yet, oxidation appears during compacting, so the density of the extremely abundant sintering of impossible closeization, feasible not energy measurement magnetic characteristic has only been measured density and O
2Content.Comparative Examples 2
To do the ball mill efflorescence of solvent through using toluene with the meal that embodiment 1 the same terms obtains down, get the fine powder of particle mean size 3.5 μ m, with it with general magnetic field press hygrometric state compression moulding under the magnetic field of about 12KOe, then with the condition sintering identical and anneal with embodiment 1.
The magnetic characteristic of gained permanent magnet and density, grain size, the degree of orientation, demagnetization curve pros degree, principal phase amount and O
2Amount is shown in table 1.Comparative Examples 3
The molten alloy that the consists of Nd14-B6.0-Fe80 die casting in swage that in high frequency melting furnace, melt and get.When observation post gets the alloy pig structure, can see the crystallization of Fe primary crystal, carry out the homogeneous processing in 10 hours so will heat down at 1050 ℃.
The crystallite dimension of gained ingot casting is 30-150 μ m at short-axis direction, and is 100 μ m-numbers millimeter at long axis direction, and rich R is with the size spot segregation of about 150 μ m.
After the alloy pig coarse crushing, use the method identical to obtain corase meal by hydrogenation and dehydrogenation with embodiment 1.In addition, under the condition identical, pulverize this corase meal with aeropulverizer with embodiment 1, and the alloy powder of about 3.7 μ m average particle size particle size that will obtain in about 1212KOe magnetic field compression moulding with the same terms of embodiment 1 under carry out sintering and heat treatment.The square degree of the magnetic characteristic of gained permanent magnet and density, crystal grain size, the degree of orientation, demagnetization curve, principal phase amount and O
2Content is shown in table 1.Comparative example 4
After the made-up belt foundry goods meal that will have composition identical with embodiment 1 and thickness is broken into 50mm or littler size, in stamping mill, the 1000g corase meal was ground one hour, without oxidation and deoxidation treatment, then in aeropulverizer efflorescence to obtain the alloy powder of 3.8 μ m average particle size particle size.
This alloyed powder is suppressed in about 12KOe magnetic field, and sintering and annealing are to obtain permanent magnet.The magnetic domestic animal feature of gained permanent magnet and density, crystal grain size, the degree of orientation, demagnetization curve pros degree, principal phase amount and oxygen content are shown in table 1.Comparative example 5
Consist of a kind of alloy of N13.5-Dy0.5-B6.5-Co1.0-Fe78.5 with the method casting identical with comparative example 3.Because crystallization goes out the Fe primary crystal in the alloy pig that obtains, and it is stood 1050 ° of following heat treatments 6 hours.After with this alloy pig coarse crushing, just it carries out the oxidation identical with embodiment 1, deoxidation in a vacuum then.In aeropulverizer, roughly grind and this corase meal of efflorescence, obtain the powder of 3.7 μ m average particle size particle size.
In about 12KOe magnetic field with this powder compaction, then with embodiment 1 the same terms under sintering and heating.The square degree of the magnetic characteristic of gained permanent magnet and density, the degree of orientation, demagnetization curve, principal phase amount and oxygen content are shown in table 1.Comparative example 6
The alloy that will consist of Nd16.5-B7-Fe76.5 is cast as the ingot identical with ratio 3 without liquefaction after, with this ingot coarse crushing, and as in proportion 4, in stamping mill, roughly grind, efflorescence in the aeropulverizer then obtains the fine powder of 3.7 μ m average particle size particle size.
In addition, in about 12KOe magnetic field with the compacting of this fine powder, sintering and annealing under the condition identical then with executing solid yardage case 1.The square degree of the magnetic characteristic of gained permanent magnet and density, crystallite dimension, the degree of orientation, demagnetization curve, principal phase amount and O
2Content is shown in table 1.
Table 1-1
| Br (KG) | Hc (KOe) | (BH) (MGOe) | iHC (KOe) | |
| Embodiment 1 | 14.8 | 10.50 | 53.1 | 10.58 |
| Embodiment 2 | 14.5 | 11.0 | 50.8 | 11.50 |
| Embodiment 3 | 13.8 | 12.9 | 45.9 | 15.00 |
| Comparative example 1 | - | - | - | - |
| Comparative example 2 | 13.3 | 9.9 | 42.0 | 9.98 |
| Comparative example 3 | 13.4 | 10.3 | 42.7 | 10.70 |
| Comparative example 4 | 13.1 | 10.0 | 40.5 | 10.30 |
| Comparative example 5 | 12.9 | 11.3 | 39.3 | 13.50 |
| Comparative example 6 | 12.2 | 10.5 | 34.4 | 11.50 |
Table 1-2
Embodiment 4
| Density p (g/cm 2) | Crystallite dimension (μ m) | Degree of orientation f (%) | Angled { (Br 2/4) /(BH)max} | Principal phase amount (1-α) (%) | Oxygen content (ppm) | |
| Embodiment 1 | 7.55 | Average 6 | 96 | 1.031 | 96.5 | 1500 |
| Embodiment 2 | 7.57 | Average 6 | 95.5 | 1.035 | 94.0 | 2500 |
| Embodiment 3 | 7.59 | Average 6 | 93.2 | 1.038 | 92.7 | 2000 |
| Comparative example 1 | 6.8 | - | - | - | - | 6500 |
| Comparative example 2 | 7.40 | Average 11 | 87.5 | 1.053 | 96.5 | 4200 |
| Comparative example 3 | 7.44 | Average 15 | 88.4 | 1.052 | 95.5 | 5000 |
| Comparative example 4 | 7.43 | Average 12 | 86.5 | 1.060 | 95.5 | 5500 |
| Comparative example 5 | 7.44 | Average 14 | 87.2 | 1.058 | 92.7 | 5000 |
| Comparative example 6 | 7.50 | Average 15 | 85.8 | 1.081 | 86.0 | 6500 |
The electrolytic iron that uses the metal Dy of metal Hb, the 8g purity 99% of 340g purity 99%, Fe-B alloy that 65.5g contains 20%B and 600g purity 99% is as the material that obtains the main-phase alloy powder with Strip casting technology, and it is melted in Ar atmosphere to obtain closing the alloy of predetermined component, the Strip casting cast by using the copper roller is to obtain the foundry goods of the about 2mm of thickness of slab then.Make this foundry goods coarse crushing by oxidation processes, and in jaw crusher, disc grinder and similar grinding machine, pulverize, obtain the powder of the about 10 μ m average grains of 800g cun chi.
Observe the powder that obtains consisting of 14.9 atom %Nd, 0.1 atom %Pr, 0.3 atom %Dy, 8.0 atom %B and Fe by X-ray diffraction EPMA, the result confirms that oxygen content is about 800ppm.The result that casting structure EPMA is observed is R
2Fe
14The B principal phase is about 5 μ m on short-axis direction, and is 20-80 μ m on long axis direction, and rich R is with finely divided around the principal phase form.
Using 250g purity is that 99% metal Nd, 11g purity are that 99% metal Dy, 730g purity are that the Fe-B alloy that 99% electrolytic iron and 20g contain 20.0%B contains R as obtaining with Strip casting technology
2Fe
17The material of the adjustment alloy powder of phase obtains the foundry goods of the thickness of slab about 2mm identical with main-phase alloy.And, use the method powder process identical with main-phase alloy.The gained powder consist of 0.8 atom %Nd, 0.1 atom %Pr, 0.4 atom %Dy, 2,4 atom % and Fe.
To the result that casting structure EPMA observes, its R
2Fe
17Phase, part R
2Fe
14B and rich Nd phase composition do not confirm to have α-Fe.Oxygen content is 850ppm.
Use above-mentioned two kinds of material powders, adjust alloyed powder with 30% and mix with main-phase alloy powder.The material powder is infeeded grinder, as jet mill etc. with efflorescence to about 3 μ m, the fine powder that obtains is filled into rubber pattern, and after applying the instantaneous orientation of 60KOe pulsed magnetic field, makes it at 2.5T/cm with hydrostatic machine
2Under stand hydrostatic pressure compacting, obtain the mold pressing piece of 8mm * 15mm * 10mm thus.
With this mold pressing piece in Ar atmosphere in 1100 ℃ of sintering 3 hours, and in 550 ℃ of annealing 1 hour down, the magnetic characteristic of gained magnet is shown in table 2.Comparative example 7
Using 340g purity is that 99% metal Nd, 8g purity are 99% metal Dy, the 600g purity Fe-B alloy that to be 99% electrolytic iron contain 20%B with 65.5g as the raw material of the main-phase alloy powder identical with embodiment 4, it is melted in Ar atmosphere and casts in the cast iron casting mould.With the powder that the alloy pig efflorescence that obtains is become 10 μ m average particle size particle size as the same procedure of enforcement scheme 1.The result of component analysis, it is made up of 14.9 atom %Nd, 0,1 atom %Pr, 0.3 atom %Dy, 8.0 atom %B and Fe.The about 900ppm of oxygen content.
According to the result that alloy pig structure EPMA is observed, R
2Fe
14The B principal phase on the short-axis direction for about 50 μ m be about 500 μ m on special direction of principal axis, the part is with 50 μ m ubiquities mutually for rich R, in addition, can be observed α-Fe in principal phase is 5-10 μ m.
Use 200g Nd
2O
3(purity 99%), 12g Dy
2O
3It is that 99% iron powder is as containing R that (purity 99%), 65g contain the Fe-B alloy of 20%B and 600g purity
2Fe
17The adjustment material of phase is 99% metal Ca and the anhydrous CaCl of 25g to wherein being mixed into 150g purity
2, and in the rustless steel container of packing into, in Ar atmosphere, obtained adjusting alloyed powder in 8 hours in direct reduction of 950 ℃ of processes and DIFFUSION TREATMENT.To the constituent analysis result of gained alloyed powder, it is made up of 10.8 atom %Nd, 0.1 atom %Pr, 0,4 atom %Dy, 2,4 atom %B and Fe.Oxygen content is 1500ppm.Use above-mentioned two kinds of material powders, adjust with 30% that alloyed powder and main-phase alloy powder are mixed to be incorporated in such as efflorescence in the grinder of aeropulverizer etc. into about 3 μ m.In about 10KOe magnetic field, make gained fine powder orientation, and at the be about 1.5T/cm vertical with magnetic field
2Pressure under mold pressing, obtain the mold pressing piece of 8mm * 15mm * 10mm.
In Ar atmosphere under 1100 ℃ with this mold pressing piece sintering 3 hours, and in 550 ℃ of annealing 1 hour, the magnetic characteristic of gained magnet was shown in table 2.Comparative example 8
Use the main-phase alloy powder of comparative example 1, and use 250g purity be 99% metal Nd, 11g purity be 99% metal Dy, 730g purity be 99% electrolytic iron and 20g contain 20%B the Fe-B alloy as the raw material of adjusting alloy powder, it dissolved in Ar atmosphere and in the cast iron casting mould, cast.Observed result to gained alloy pig structure confirms that crystallization goes out a large amount of α-Fe, so that will carry out homogeneous and handle 12 hours under 1000 ℃.
The result of the constituent analysis of carrying out with the method identical with embodiment 4 is that it is made up of 10.8 atom %Nd, 0.1 atom %Pr, 0.4 atom %Dy, 2.4 atom %B and Fe.
Use above-mentioned two kinds of material powder, adjust alloyed powder and main-phase alloy powder mixing to obtain the magnet identical with comparative example 7 with 30%.The magnetic characteristic of gained magnet is shown in table 2.Comparative example 9
Using 315g purity is that 99% metal Nd, 8.59 purity are 99% metal Dy, 52g closes 20%B Fe-B alloy and 636g purity are that 99% electrolytic iron is as raw material, fusing obtains the foundry goods of the about 2mm of thickness of slab then so that obtain having the alloy of predetermined composition through the Strip casting technology of using the copper roller in Ar atmosphere.In addition, make this foundry goods coarse crushing by oxidation processes, efflorescence in jaw crusher, disc mill and similar grinding machine then obtains the powder of 800g 10 μ m average particle size particle size.
According to the EPMA observed result to the gained powder, it is made up of 13.8 atom %Nd, 0.1 atom %Pr, 0.3 atom %Dy, 6.3 atom %B and Fe.Oxygen content is about 800ppm.According to the EPMA observed result of again casting structure being carried out, R
2Fe
14The B principal phase is 20-80 μ m on long axis direction being about 6 μ m on the short-axis direction, and rich R is to exist around the principal phase form is in small, broken bits.
The alloyed powder that use makes through Strip casting technology is manufactured magnet as comparative example 7.The magnetic characteristic of gained magnet is shown in table 2.
Table 2-1
| Form | Magnetic characteristic | ||||
| Br | Hc | (BH)max | iHc | ||
| Embodiment 4 | 13.8Nd-0.1Pr-0.3Dy-6.3B-Fe surplus | 14.0 | 12.5 | 47.5 | 13.5 |
| Comparative example 7 | 13.8Nd-0.1Pr-0.3Dy-6.3B-Fe surplus | 13.2 | 12.0 | 40.7 | 12.5 |
| Comparative example 8 | 13.8Nd-0.1Pr-0.3Dy-6.3B-Fe surplus | 13.2 | 11.9 | 40.8 | 12.0 |
| Comparative example 9 | 13.8Nd-0.1Pr-0.3Dy-6.3B-Fe surplus | 13.3 | 12.3 | 42.3 | 12.9 |
Table 2-2
Embodiment 5
| Density p (g/cm) | Crystallite dimension (μ m) | Degree of orientation f (%) | Angled { Br 2/4)/ (BH)max} | Principal phase amount (1-α) (%) | Oxygen content (ppm) | |
| Embodiment 4 | 7.56 | Average 8 | 94.5 | 1.32 | 92.8 | 3000 |
| Comparative example 7 | 7.53 | Average 15 | 89.2 | 1.07 | 92.8 | 5000 |
| Comparative example 8 | 7.53 | Average 16 | 89.2 | 1.068 | 92.8 | 5500 |
| Comparative example 9 | 7.54 | Average 8 | 89.9 | 1.053 | 92.8 | 4000 |
Obtain the main-phase alloy powder that 800g forms the 10 μ m average particle size particle size different with embodiment 4 with the method identical with embodiment 4.The gained powder is made up of 14 atom %Nd, 0.1 atom %Pr, 0.5 atom %Dy, 8 atom %B and Fe.With the result that X-ray diffraction EPMA observes, it mainly is R
2Fe
14The B phase.The about 80ppm of oxygen content.To the EPMA observed result of casting structure, R
2Fe
14The B principal phase is 5-90 μ m on long axis direction being about 0.5-15 μ m on the short-axis direction, rich R is with finely divided around the principal phase form.
The metal Dy of metal Nd, the 5g purity 9g% of use 125g purity 99% and the electrolytic iron of 275g purity 99% are as containing R
2Fe
17Adjust the raw material of alloyed powder mutually, and obtain the foundry goods of the about 2mm of thickness of slab by the Strip casting technology identical with main-phase alloy.In addition, adopt the treatment process powder process identical with main-phase alloy.The gained powder consist of 11.0 atom %Nd, 0.05 atom %Pr, 0.4 atom %Dy and Fe.
According to the EPMA observed result to casting structure, it is by R
2Fe
17Phase, part R
2Fe
14α-Fe is not observed in B and rich R phase composition.Oxygen content during 10 μ m average particle size particle size is 700ppm.
Use above-mentioned two kinds of material powders, adjust alloyed powder with 25% and mix with main-phase alloy powder.To expect the powder grinding machine of packing into, as aeropulverizer with efflorescence to about 3 μ m, be filled in the rubber pattern then, and after applying the instantaneous orientation of 60KOe pulsed magnetic field with isostatic pressing machine with the gained fine powder at 2.5T/cm
2Stand hydrostatic compacting under the pressure to get the mold pressing piece of 8mm * 15mm * 10mm.
In Ar atmosphere under 1100 ℃ with this mold pressing piece sintering 3 hours, and 550 ℃ of annealing 1 hour.The magnetic characteristic of gained magnet is shown in table 3.Comparative example 10
In the cast iron casting mould, cast with embodiment 5 with the method identical and to form identical alloy, obtain the powder of about 10 μ m average particle size particle size with embodiment 4.As main-phase alloy powder.This consists of 14 atom %Nd, 0.1 atom %Pr, 0.5 atom %Dy, 8 atom %B and Fe.The about 900ppm of oxygen content.The result is about 50 μ m and is about 500 μ m at long axis direction at short-axis direction, and rich R is local mutually with 50 μ m ubiquities.Simultaneously, part 5-10 μ m α-Fe is present in the principal phase.
With direct reduction and the diffusion technology identical, use 280gNd with comparative example 7
2O
3(purity 9 8%), 12gDy
2O
3(purity 99%) and 750g iron powder (purity 99%) make and contain R
2Fe
17The adjustment alloyed powder of phase.Component is 11.0 atom %Nd, 0.05 atom %Pr, 0.9 atom %Dy and Fe, and oxygen content is 1500ppm.
Act on above-mentioned two kinds of material powder, adjust alloyed powder with 25% and mix with main-phase alloy powder, and in pack into aeropulverizer and its similar grinding machine, to be crushed to about 3 μ m.In about 10 KOe magnetic fields, make gained fine powder orientation, and at the about 1.5T/cm vertical with this magnetic field
2Mold pressing under the pressure obtains the mold pressing piece of 8mm * 15mm * 10mm.
In Ar atmosphere in 1100 ℃ with this mold pressing piece sintering 3 hours, and in 550 ℃ of annealing 1 hour.The magnetic characteristic of gained magnet also is shown in table 3 comparative example 11
Use the main-phase alloy powder of comparative example 10, make the adjustment alloyed powder by the electrolytic iron that in Ar atmosphere, melts 350g metal Nd, 10g metal Dy and 750g purity 99%, and in the cast iron casting mould, cast.See according to the result that the gained alloy pig is observed, because a large amount of α-Fe crystallization was handled 12 hours so will carry out homogeneous at 1000 ℃.According to the result of constituent analysis, it is made up of 11.0 atom %Nd, 0.05 atom %Pr, 0.4 atom %Dy and Fe.
Use above-mentioned two kinds of material powder, adjust alloyed powder with 25% and mix as comparative example 10, obtain magnet with main-phase alloy powder.The magnetic characteristic of gained magnet also is shown in table 3.Comparative example 12
Use 300g metal Nd, 13g metal Dy, 50g to contain the electrolytic iron of the Fe-B alloy of 20%B and 645g purity 99% as raw material, and fusing obtains the foundry goods of the about 2mm of thickness of slab then so that obtain having the alloy of predetermined composition through the Strip casting technology of using the copper roller in Ar atmosphere.In addition, this foundry goods is pulverized, obtained the powder of the about 10 μ m average particle size particle size of 800g by oxidation, jaw crusher, disc mill and similar grinding machine.
The powder of gained is made up of 13.3 atom %Nd, 0.1 atom %Pr, 0.5 atom %Dy, 6 atom %B and Fe.The about 800ppm of oxygen content.According to the EPMA observed result to this casting structure, R
2Fe
14The B principal phase is about 0.3-15mm and at the about 5-90 μ of long axis direction m at short-axis direction, and rich R is to exist around the principal phase form is finely divided.
Use makes the magnet identical with comparative example 10 through the alloyed powder of Strip casting technology gained.The magnetic characteristic of gained magnet shows in table 3.
Table 3-1
| Component | Magnetic characteristic | ||||
| Br | Hc | (BH)max | iHc | ||
| Embodiment 5 | 13.3Nd-0.1Pr-0.5Dy-6B-Fe surplus | 14.2 | 12.8 | 48.5 | 14.5 |
| Comparative example 10 | 13.3Nd-0.1Py-0.5Dy-6B-Fe surplus | 13.3 | 11.5 | 41.5 | 13.5 |
| Comparative example 11 | 13.3Nd-0.1Pr-0.5Dy-6B-Fe surplus | 13.3 | 11.8 | 41.7 | 13.6 |
| Comparative example 12 | 13.3Nd-0.1Pr-0.5Dy-6B-Fe surplus | 13.4 | 11.6 | 42.6 | 14.0 |
Table 3-2
Embodiment 6
| Density p (g/cm) | Crystalline size (μ m) | Degree of orientation f (%) | Angled { (Br 2/4 /(BH)max} | Principal phase amount (1-α) (%) | Oxygen content (ppm) | |
| Embodiment 5 | 7.57 | Average 6 | 95.9 | 1.039 | 94.0 | 2000 |
| Comparative example 10 | 7.56 | Average 14 | 89.8 | 1.066 | 94.0 | 5000 |
| Comparative example 11 | 7.55 | Average 15 | 89.8 | 1.060 | 94.0 | 5500 |
| Comparative example 12 | 7.56 | Average 8 | 90.5 | 1.054 | 94.0 | 3800 |
Use metal Dy, the 68.5g of metal Nd, the 23g purity 99% of 260g purity 99% to close the electrolytic iron of 20% Fe-B alloy and 655g purity 99% as raw material with Strip casting technology system main-phase alloy powder, and it is melted in Ar atmosphere so that obtain having the alloy of predetermined composition, the Strip casting cast through using the copper roller obtains the foundry goods of the about 2mm of thickness of slab then.Make this foundry goods coarse crushing by hydrogenation treatment, and pulverize, obtain the powder of the about 10 μ m average particle size particle size of 800g by jaw crusher, disc mill and similar grinding machine.
Must contain the powder of 11 atom %Nd, 0.1 atom %Pr, 1.0 atom Dy, 8 atom %B and Fe by X-ray diffraction EPMA observation post, the result confirms that this powder mainly is by R
2Fe
14The B phase composition.The about 800ppm of oxygen content.According to the EPMA observed result to casting structure, R
2Fe
14The B principal phase is 5-90 μ m for about 0.5-1.5 μ m at long axis direction at short-axis direction, and rich R is finely divided around principal phase mutually.
The Co that uses 490g metal Nd, 2.6 metal Dy and 500g purity 99% obtains the foundry goods of the thickness of slab about 2mm identical with main-phase alloy as obtain the raw material that contains R-Co intermetallic compound adjustment alloyed powder mutually with Strip casting technology.Simultaneously, by the treatment process powder process identical with main-phase alloy.The gained powder consist of 27.0 atom %Nd, 0.5 atom %Pr, 1.3 atom %Dy and Co.
According to the EPMA observed result to casting structure, it is by R
3Co phase and part R
2Co
17Phase composition, and R
3Co is finely divided mutually.Oxygen content is 700ppm in the powder of 10 μ m average particle size particle size.
Use above-mentioned two kinds of powders, adjust alloyed powder with 20% and mix with main-phase alloy powder.With this powder grinder of packing into, as efflorescence such as aeropulverizers to about 3 μ m, be packed in the rubber pattern then and after applying the instantaneous orientation of 60KOe pulsed magnetic field with hydrostatic machine at 2.5T/cm
2Under make it stand hydrostatic compacting, thereby obtain the mold pressing piece of 8mm * 15mm * 10mm.
In Ar atmosphere in 1100 ℃ with this mold pressing piece sintering 3 hours, and 550 ℃ of annealing 1 hour.The magnetic characteristic of gained magnet is shown in table 4.Revolve scheme 7 in fact
By with 10% adjust alloyed powder and embodiment 1 made main-phase alloy powder mix, and magnetize by the technology identical with embodiment 6, the magnetic characteristic that obtains magnet is shown in table 4.Comparative example 13
For main-phase alloy powder, use the metal Nd of 260g purity 99%, the metal Dy of 26g purity 99%, the electrolytic iron of 665g purity 99% and the Fe-B alloy that 68.5g contains 20.0%B in the same manner with embodiment 6, in Ar atmosphere the fusing and in the cast iron casting mould, cast.By the method identical the gained alloy pig is pulverized powder into about 10 μ m average particle size particle size with embodiment 1.According to the result of constituent analysis, this powder is made up of 11 atom %Nd, 0.1 atom %Pr, 1.0 atom %Dy, 8 atom %B and iron, the about 90ppm of oxygen content.
According to the EPMA observed result to the alloy pig structure, R
2Fe
14The B principal phase is about 50 μ m and is about 500 μ m at long axis direction at short-axis direction, and rich R is local mutually with 50 μ m ubiquities.α-Fe of part 5-10 μ m is present in the principal phase.
Use 550Nd
2O
3(purity 99%), 29gDy
2O
3The Co powder work of (purity 99%) and 500g purity 99% obtains as diffusion technology as direct reduction and contains R-Co intermetallic compound adjustment material mutually, to metal Ca that wherein is mixed into 350g purity 99% and the anhydrous CaCl of 60g
2, and with in its rustless steel container of packing into, in Ar atmosphere, obtained alloy powder through 8 hours in 750 ℃.According to the result of constituent analysis, the gained alloy powder is made up of 27.0 atom %Nd, 0.6 atom %Pr, 1.3 atom %Dy and Co, and oxygen content is 1500ppm.
Use above-mentioned two kinds of powders, adjust alloyed powder with 20% and mix, and the grinder of packing into, be crushed to 3 μ m as aeropulverizer etc. with main-phase alloy powder.In about 10KOe magnetic field, make gained fine powder orientation, and with the about 1.5T/cm vertical with this magnetic field
2The pressure mold pressing obtains the mold pressing piece of 8mm * 15mm * 10mm.
In Ar atmosphere in 1100 ℃ with this mold pressing piece sintering 3 hours, and 550 ℃ of annealing 1 hour down.The magnetic characteristic of gained magnet also is shown in table 4.Comparative example 14
Use the main-phase alloy of embodiment 13, make the adjustment alloy powder by the Co that in Ar atmosphere, melts 490g metal Nd, 26g metal Dy and 500g purity 99%, and in the cast iron casting mould, cast.According to the observed result to gained alloy pig structure, crystallization goes out a large amount of Co, so that will carry out homogeneous at 800 ℃ and handle 12 hours.According to the constituent analysis result, it is made up of 11.0 atom %Nd, 0.6 atom %Pr, 1.3 atom %Dy and Co.
Use above-mentioned two kinds of powders, hand over 20% alloyed powder to mix, obtain the magnet identical with comparative example 13 with main-phase alloy powder.The magnetic characteristic of gained magnet also is shown in table 4.Comparative example 15
Use 305g metal Nd, 26g metal Dy, 55g to contain the electrolytic iron of the Co of Fe-B alloy, 100g purity 99% of 20%B and 525g purity 99% as raw material, fusing to be obtaining having the alloy of predetermined composition in Ar atmosphere, and the Strip casting technology through using the copper roller obtains the foundry goods of the about 2mm of thickness of slab.Make this foundry goods coarse crushing and, obtain the powder of the about 10 μ m particle sizes of 800g by hydrogenation treatment by jaw crusher, disc mill and the pulverizing of similar grinding machine.
The gained powder is made up of 13.5 atom %Nd, 0.1 atom %Pr, 1.0 atom %Dy, 6.7%B, 11.3 atom %Co and Fe.The about 800ppm of oxygen content.According to the EPMA observed result to casting structure, R
2(Fe, Co)
14B is about 0.3-1.5 μ m at short-axis direction, and long axis direction for about 5-90 μ m and rich R and R-Co mutually around the carefully diffusing existence of main-phase alloy.
As comparative example 3, use the alloyed powder that makes with Strip casting technology to manufacture magnet.The magnetic characteristic of gained magnet also is shown in table 4.
Table 4-1
| Form | Magnetic characteristic | Density g/cm 2 | ||||
| Br | Hc | (BH)max | iHc | |||
| Embodiment 6 | 13.5Nd-0.1Pr-1.0Dy-6.7B-6.5Co-Fe surplus | 13.3 | 12.4 | 42.5 | 17.0 | 7.62 |
| Alternative 7 | 12.3Nd-0.1Py-1.0Dy-7.3B-11.3Co-Fe surplus | 13.5 | 12.5 | 44.0 | 16.8 | 7.61 |
| Comparative example 13 | 13.5Nd-0.1Pr-1.0Dy-6.7B-11.3Co-Fe surplus | 12.0 | 11.0 | 34.0 | 15.8 | 7.56 |
| Comparative example 14 | 13.5Nd0.1Pr-1.0Dy-6.7B-11.3Co-Fe surplus | 12.2 | 11.1 | 35.0 | 15.5 | 7.55 |
| Comparative example 15 | 13.5Nd-0.1Pr-1.0Dy-6.7B-11.3Co-Fe surplus | 12.2 | 11.2 | 35.2 | 16.5 | 7.58 |
Table 4-2
| Density p (g/cm 2) | Crystallite dimension (μ m) | Degree of orientation f (%) | Angled { Br 2/4/ (BH)max} | Principal phase amount (1-α) (%) | Oxygen content (ppm) | |
| Embodiment 6 | 7.62 | Average 5 | 94 | 1.04 | 91 | 2800 |
| Embodiment 7 | 7.61 | Average 6 | 95.5 | 1.036 | 94 | 2200 |
| Comparative example 13 | 7.56 | Average 14 | 85.7 | 1.056 | 91 | 4800 |
| Comparative example 14 | 7.55 | Average 16 | 87.1 | 1.063 | 91 | 5000 |
| Comparative example 15 | 7.58 | Average 6 | 87.1 | 1.057 | 91 | 3500 |
Claims (39)
Applications Claiming Priority (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19288693A JP3415208B2 (en) | 1993-07-06 | 1993-07-06 | Method for producing R-Fe-B permanent magnet material |
| JP192886/93 | 1993-07-06 | ||
| JP192886/1993 | 1993-07-06 | ||
| JP20719093A JP3151087B2 (en) | 1993-07-28 | 1993-07-28 | Method for producing raw material powder for R-Fe-B-based permanent magnet and alloy powder for adjusting raw material powder |
| JP207191/93 | 1993-07-28 | ||
| JP5207192A JPH0745412A (en) | 1993-07-28 | 1993-07-28 | R-fe-b permanent magnet material |
| JP207191/1993 | 1993-07-28 | ||
| JP207190/1993 | 1993-07-28 | ||
| JP207192/1993 | 1993-07-28 | ||
| JP207192/93 | 1993-07-28 | ||
| JP207190/93 | 1993-07-28 | ||
| JP20719193A JP3151088B2 (en) | 1993-07-28 | 1993-07-28 | Method for producing raw material powder for R-Fe-B-based permanent magnet and alloy powder for adjusting raw material powder |
| JP21217193A JP3299000B2 (en) | 1993-08-03 | 1993-08-03 | Method for producing raw material powder for R-Fe-B-based permanent magnet and alloy powder for adjusting raw material powder |
| JP212171/1993 | 1993-08-03 | ||
| JP212171/93 | 1993-08-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1114779A CN1114779A (en) | 1996-01-10 |
| CN1076115C true CN1076115C (en) | 2001-12-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93115008A Expired - Lifetime CN1076115C (en) | 1993-07-06 | 1993-10-15 | R-Fe-B permanent magnet materials and process of producing the same |
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| Country | Link |
|---|---|
| EP (1) | EP0633581B1 (en) |
| KR (1) | KR0131060B1 (en) |
| CN (1) | CN1076115C (en) |
| AT (1) | ATE165477T1 (en) |
| DE (1) | DE69318147T2 (en) |
| RU (1) | RU2113742C1 (en) |
| TW (1) | TW272293B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320565C (en) * | 2003-11-18 | 2007-06-06 | Tdk株式会社 | Method for making sintered magnet and alloy for sintering magnet |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5666635A (en) * | 1994-10-07 | 1997-09-09 | Sumitomo Special Metals Co., Ltd. | Fabrication methods for R-Fe-B permanent magnets |
| US5858123A (en) * | 1995-07-12 | 1999-01-12 | Hitachi Metals, Ltd. | Rare earth permanent magnet and method for producing the same |
| US6319335B1 (en) | 1999-02-15 | 2001-11-20 | Shin-Etsu Chemical Co., Ltd. | Quenched thin ribbon of rare earth/iron/boron-based magnet alloy |
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| JP7409285B2 (en) * | 2020-10-22 | 2024-01-09 | トヨタ自動車株式会社 | Rare earth magnet and its manufacturing method |
| CN115747611B (en) * | 2022-10-13 | 2023-10-20 | 包头金山磁材有限公司 | Auxiliary alloy cast sheet, high-remanence high-coercivity neodymium-iron-boron permanent magnet and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0101552A2 (en) * | 1982-08-21 | 1984-02-29 | Sumitomo Special Metals Co., Ltd. | Magnetic materials, permanent magnets and methods of making those |
| CN1057922A (en) * | 1986-08-04 | 1992-01-15 | 住友特殊金属株式会社 | Rare-earth permanent magnet with excellent corrosion resistance |
| EP0517179A1 (en) * | 1991-06-04 | 1992-12-09 | Shin-Etsu Chemical Co., Ltd. | Method of making two phase Rare Earth permanent magnets |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62291901A (en) * | 1986-06-12 | 1987-12-18 | Toshiba Corp | Permanent magnet |
| GB2201426B (en) * | 1987-02-27 | 1990-05-30 | Philips Electronic Associated | Improved method for the manufacture of rare earth transition metal alloy magnets |
| DE3850001T2 (en) * | 1987-08-19 | 1994-11-03 | Mitsubishi Materials Corp | Magnetic rare earth iron boron powder and its manufacturing process. |
| JPH01119001A (en) * | 1987-10-30 | 1989-05-11 | Kubota Ltd | Method for manufacturing rare earth-containing permanent magnet powder |
| JPH0529117A (en) * | 1990-10-22 | 1993-02-05 | Kawasaki Steel Corp | Method for producing rare earth-transition metal anisotropic magnetic powder |
| SU1760563A1 (en) * | 1990-12-14 | 1992-09-07 | Центральный научно-исследовательский институт черной металлургии им.И.П.Бардина | Method of producing permanent magnet billets |
| JP2782024B2 (en) * | 1992-01-29 | 1998-07-30 | 住友特殊金属株式会社 | Method for producing raw material powder for R-Fe-B-based permanent magnet |
-
1993
- 1993-10-14 EP EP93308184A patent/EP0633581B1/en not_active Expired - Lifetime
- 1993-10-14 DE DE69318147T patent/DE69318147T2/en not_active Expired - Lifetime
- 1993-10-14 AT AT93308184T patent/ATE165477T1/en active
- 1993-10-14 RU RU93049098A patent/RU2113742C1/en active
- 1993-10-15 TW TW082108554A patent/TW272293B/zh not_active IP Right Cessation
- 1993-10-15 CN CN93115008A patent/CN1076115C/en not_active Expired - Lifetime
- 1993-10-15 KR KR93021615A patent/KR0131060B1/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0101552A2 (en) * | 1982-08-21 | 1984-02-29 | Sumitomo Special Metals Co., Ltd. | Magnetic materials, permanent magnets and methods of making those |
| CN1057922A (en) * | 1986-08-04 | 1992-01-15 | 住友特殊金属株式会社 | Rare-earth permanent magnet with excellent corrosion resistance |
| EP0517179A1 (en) * | 1991-06-04 | 1992-12-09 | Shin-Etsu Chemical Co., Ltd. | Method of making two phase Rare Earth permanent magnets |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320565C (en) * | 2003-11-18 | 2007-06-06 | Tdk株式会社 | Method for making sintered magnet and alloy for sintering magnet |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69318147D1 (en) | 1998-05-28 |
| KR950004295A (en) | 1995-02-17 |
| EP0633581B1 (en) | 1998-04-22 |
| ATE165477T1 (en) | 1998-05-15 |
| KR0131060B1 (en) | 1998-04-24 |
| DE69318147T2 (en) | 1998-11-12 |
| TW272293B (en) | 1996-03-11 |
| CN1114779A (en) | 1996-01-10 |
| RU2113742C1 (en) | 1998-06-20 |
| EP0633581A1 (en) | 1995-01-11 |
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