CN1053988C - Rare earth magnets and alloy powder for rare earth magnets and their manufacturing methods - Google Patents
Rare earth magnets and alloy powder for rare earth magnets and their manufacturing methods Download PDFInfo
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- CN1053988C CN1053988C CN92114394A CN92114394A CN1053988C CN 1053988 C CN1053988 C CN 1053988C CN 92114394 A CN92114394 A CN 92114394A CN 92114394 A CN92114394 A CN 92114394A CN 1053988 C CN1053988 C CN 1053988C
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- 239000000843 powder Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 31
- 150000002910 rare earth metals Chemical class 0.000 title claims description 21
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- 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 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 238000009689 gas atomisation Methods 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 238000007712 rapid solidification Methods 0.000 claims description 7
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 claims 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
- C22C1/0441—Alloys based on intermetallic compounds of the type rare earth - Co, Ni
-
- 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
-
- 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
- H01F1/0578—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 bonded together
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Provided is a manufacturing method to obtain the Fe3B type Fe-Co-B-R-M system high performance resin bonded magnet which possesses improved iHc and (BH)max and can be reliably mass produced. The alloy powder which contains the ferromagnetic phase, where the boron compound phase and the Nd2Fe14B type phase coexist, is combined with resin to produce the high performance resin bonded magnet with iHc>=3 kOe, Br>=5 kG, and (BH)max>=3 MGOe.
Description
The invention relates to alloy powder and manufacture method thereof that the resin bonded rare earth magnet is used, described rare-earth permanent magnet is suitable for magnetic roller, loud speaker, various instrument and meter, focuses on magnet, motor, magnet-sensitive element and the actuator of usefulness.By combination with molten method, spray method or these the two kinds of methods of quenching of swing roller, make fusion Fe-CO-B-R-M (M=Cu, Ca, Ag, Al, Si, Au) the alloy Quench of the specific composition composition that contains the lower content rare earth element, to obtain the amorphous microstructure structure.This amorphous microstructure structure obtains the alloy powder of thin druse through specific heat treatment, and (its main component is Fe, has cubic Fe by the boride phase for it
3The P type crystal structure) and Nd
2Fe
11The Type B crystal structure constitutes mutually.The powder that obtains with resin-bonded, is obtained residual magnetic flux density (Br) greater than 5KG, and this is that any ferrite hard magnetic body can not reach.The invention still further relates to the manufacture method of the isotropic resin bonded magnet of this Fe-B-R type.
Be used to produce the magnetic roller of static, the motor of electric equipment and the permanent magnetic material of actuator and mainly be limited to the ferrite hard magnetic material, this magnet is owing to suffering damage in the problems such as low temperature demagnetization characteristic that are lower than under the low temperature of iHc, and because the character of ceramic material, its mechanical strength is lower, might cause cracking and cracked, be difficult to form complicated shape.
At present, the direction of household electrical appliance and the miniaturization of office automation equipment forward develops, and employed magnetic material is also wanted miniaturization and lightweight.For energy-conservation, press for and alleviate automotive dead weight to improve the mileage that on average travels of 1 gallon of gasoline of the every consumption of automobile, therefore require car electrics miniaturization and weight reduction.
Therefore, people carrying out always various effort with the performance that reaches magnetic material the best and weight than this target.For example, in present motor designs, as magnetic material, the Br of 5-7KG is considered to optimum.
That is to say that in motor designs, if Br surpasses 8KG, will become the iron plate of magnetic flux path or the cross-sectional area of rotor and stator so just needs to increase at present, and this will cause weight to increase.In addition, owing to the miniaturization of magnetic roller and loud speaker, need have the magnet of high Br, but the residual magnetic flux density (Br) of common ferrite hard magnetic body can not reach more than the 5KG.
For example, though resin bonded Nd-Fe-B type magnet can satisfy desired magnetic property, it contains the Nd of 10-15% (atom), need carry out many processed separately and a large amount of production equipments separates, and purifies and reduces this metal.Compare with the ferrite hard magnetic body, it not only costs an arm and a leg, and nearly the magnetizing field of 20KOe just can make 90% magnet magnetization, therefore will realize that the multipole magnetized of the necessary complexity of magnet of magnetic roller or other purposes (for example stepping motor) usefulness is impossible.At present, people also do not find a kind of like this magnet, and it can be on a large scale, make economically, have the Br of 5-7KG and have good magnetization property.
The B that some purposes is had relatively high expectations, for example magnetic senser, loud speaker, actuator and stepping motor at present, are used for the material of these purposes, resin bonded Sm
2Co
17Anisotropy magnet is the highest magnet of performance, and resin bonded Nd-Fe-B isotropic magnet is the magnet that substitutes that cost hangs down some.But the cost of these magnets still is too high, need a kind of cost low, make and have the resin bonded magnetic material of high Br characteristic easily.
On the other hand, in the Nd-Fe-B series magnet, the someone has proposed a kind of magnetic material recently, Fe in this material
3The Type B compound is at Nd
4Fe
77B
18Near (atom %) main phase (see people such as R.Coehoorn, J.dephy.C8,1988, P669-670).This magnetic material is by heat treatment obtains to the amorphous state band, and Fe is contained in the metastable organization of generation
3B and Nd
2Fe
14The drusy structure of B.The Br of this metastable organization structure reaches 13KOe, but its iHc is not high enough, has only 2-3KOe.In addition, heat-treat condition is restricted, and is unpractical for industrial production.
In some research work of having reported, introduce some additional elements in the magnetropism material, make it to become multicomponent system, to improve its magnetic property.Wherein there is a research work except rare earth element nd, also to use Dy and Tb, purpose is to improve iHc, the problem of this practice is, these additional elements cost height, in addition, because the magnetic moment of these two kinds of rare earth elements and the magnetic moment antiparallel of Nd and Fe, thereby weakened magnetization (R Coehoon, J.Magn.Magn.Mat, 89 (1991), P228-230).
Also having a research work (Shen Bao-gen waits the people, J.Magn.Magn.Mat, 89 (1991) P335-340) is to replace part Fe with Co, and with raising Curie temperature and the temperature coefficient that improves iHc, but it exists the problem that reduces B along with the interpolation of Co.
The open CN 1051635A of Chinese invention patent application recently discloses a kind of biphase rare earth permanent-magnetic alloy material, its general formula is TMxMyRz, be Fe more than the 70 atom % among the TM wherein, the remainder of TM can be replaced with Co, and R is one or more rare earth element, x, y, z represent atomic percentage, 65%≤x≤80%, 18%≤y≤30%, 1.6%≤z≤4.8% wherein, this material is a double structure, and base is body-centered structure of the quartet Fe mutually
3B, less important is the R of tetragonal mutually
2Fe
14B.But the document only discloses by alloy melt and has made thick 35 microns crystallite strip through single roller rapid quenching, specifically openly which kind of technology to obtain body-centered structure of the quartet Fe by
3B and tetragonal R
2Fe
14The double structure of B.
Under any circumstance, Fe
3The magnet of Type B Nd-Fe-B system all is amorphous by making with the molten method of quenching of rotation roller, and it is heat-treated to obtain hard magnetic material.But resulting iHc is lower, and the heat-treat condition of in the past being mentioned is very harsh, causes magnetic energy product to reduce in order to improve the measure that iHc takes, and can not realize reliable suitability for industrialized production.Therefore, it can not replace ferrimagnet as a kind of substitute of economy.
The invention relates to and improved iHc and (BH) Fe of max
3Type B Fe-B-R series magnet (R=rare earth element) the objective of the invention is to set up and a kind ofly can reliablely and stablely carry out the manufacture method of suitability for industrialized production, and the resin bonded Fe of residual magnetic flux density (Br) greater than 5KG is provided
3Type B Fe-B-R series magnet is as the substitute of the economy of ferrite hard magnetic body.
In addition, in order to provide residual magnetic flux density (Br) greater than resin bonded Fe 5KG, economic and reliable
3Type B Fe-B-R magnet, the present invention also plans to provide the magnetic rare earth alloy powder and the manufacture method thereof of suitable this resin-bonded magnet.
The inventor is to providing iHc with improvement and (BH)
MaxFe
3The various manufacture methods of Type B Fe-B-R series magnet and the reliable suitability for industrialized production of this magnet are investigated.With regard to this alloy composite, usually, the amorphous microstructure structure is by obtaining with molten the quenching of rotation roller.But the particular alloy composition for wherein adding Co and other interpolation element adopts relatively low rotation roller peripheral speed scope (5-20m/s) just can obtain amorphous microstructure.We have found following situation by this fact, by from following method, selecting a kind of Quench and clotting method, finished the present invention: the gas atomization method of the molten method of quenching, generation and the molten identical cooling rate of method of quenching and the method that the molten alloy particle is sprayed to the rotation roller.
That is to say that by in order to the molten method of quenching than slow-speed of revolution live-rollers, the gas atomization method is after perhaps the combination of these Quench methods makes the molten alloy Quench with low content of rare earth and specific composition composition;
1) add a small amount of Co, the flowability of melt flow stream increases significantly, and the rate of recovery of Quench alloy is improved;
2) change mutually still imperfect tense when amorphous state,, make the boride phase (mainly constitute, have and Fe by Fe by carrying out suitable heat treatment
3The crystal structure that B is identical, i.e. body-centered tetragonal Fe
3The P type crystal structure) and have a Nd
2Fe
14The intermetallic compound of Type B crystal structure coexists as in the same powder particle mutually;
3) in addition, by adding additional elements M (M be a kind of among Al, Si, Cu, Ga, Ag and the Au or two kinds), when the alloy crystallization, the tiny and suitable compound of crystal diameter coexists as in the same powder particle mutually.
In addition, when average particulate diameter was in the 5nm-100nm scope, its intrinsic coercive force had reached more than the actual desired 2KG; When this alloy powder by resin-bonded when making given shape, this metastable crystal structure can be not cracked under near room temperature, can be used as the permanent magnet of useful form.
The present invention adopts the molten method of quenching to make basically amorphous structure greater than 90% by the Fe-Co-B-R-M molten alloy; After resulting alloy sheet or band heated up with 1-15 ℃ speed, and 550-730 ℃ of insulation with its heat treatment 5 minutes to 6 hours, forming average crystal diameter is the thin druse of 5nm-100nm, it is by having Nd
2Fe
14The ferromagnetic phase of Type B crystal structure and leading phase Fe
3The Type B compound constitutes mutually.Owing to limited programming rate, these ferromagnetic α-Fe that roll up mutually then reduce mutually.
In addition, the effect that comprises at least a element among Al, Si, Cu, Ga, Ag and the Au in the Fe-Co-B-R alloy is, do not reduce Br under the Co situation and can obtain iHc 〉=3KOe, Br 〉=8KG and (BH) adding
MaxThe magnetic property of 〉=8MGOe, and improve the rectangle degree of demagnetization curve.In addition,, make the alloyed powder of using for magnet, obtained being specially adapted to the alloyed powder of residual magnetic flux density (Br) greater than the resin bonded Fe-Co-B-R-M series magnet of 5KG by this alloy is ground.
In the present invention, employing effective gas spray method, is heat-treated it after molten alloy is made alloy powder by the Fe-Co-B-R-M of the specific composition that contains the low content rare earth element, obtains metastable system of compounds, and this system is by the Fe of rich Fe
3(it has the space group of belonging to 1 to Type B compound phase
4Body-centered tetragonal Fe
3The P type crystal structure) and Nd
2Fe
14The Type B crystal constitutes mutually.In the metastable process of deciding hybrid system of this acquisition, owing to contain the Co of ormal weight, at main phase Fe
3It is the thin druse of 5nm-100nm that the Type B compound has obtained average crystal diameter in mutually.Obtained dominant Fe
3Type B compound phase and Nd
2Fe
14Type B crystal phase is being used for the alloy powder of resin-bonded magnet, all has these ferromagnetic phases in each particle simultaneously.These alloy powders with resin-bonded, can be obtained having iHc 〉=3KOe, Br 〉=5KG and (BH)
MaxThe resin-bonded magnet of 〉=4MGOe magnetic property.
In the present invention, have only when rare-earth element R is restricted to one or both elements among Pr or the Nd and has the content of regulation, just can observe high magnetic property.If use other rare earth element, for example Ce and La, iHc can not surpass 2KOe.In addition, if use later medium wt rare earth element and the heavy rare earth element of Sm, will cause that magnetic property worsens, also will cause the cost of magnet to raise simultaneously, this is undesirable.
As R during less than 3% (atom), iHc can not reach more than the 2KOe, if but it surpasses 6% (atom), by Fe
3B does not grow mutually, causes non-ferromagnetic metastable phasing R
2Fe
23B
3Separate out, this will reduce iHc significantly, not meet the requirements, and therefore, its content range fixes on 3-5.5% (atom).
As B during less than 16% (atom) or greater than 22% (atom), iHc is no more than 2KOe, so its content range is decided to be 16-22% (atom).
Co can improve the rectangle degree of demagnetization curve effectively, but it is when surpassing 15% (atom), iHc significantly is reduced to is not more than 2KOe, so its content range is decided to be 0.05-15% (atom).
Al, Si, Cu, Ga, Ag and Au improve the rectangle degree and the raising (BH) of demagnetization curve by enlarging heat-treatment temperature range
MaxIn order to play this effect, need the addition of at least 0.1% (atom).But, if content surpasses 3% (atom), rectangle degree and (BH)
MaxThe capital reduces, so its content range fixes on 0.1-3% (atom).
Fe has constituted the remainder of above-mentioned constituent content.
The feature that constitutes the alloy powder of rare earth magnet of the present invention is: the boride Fe that contains the high saturation and magnetic intensity of 1.6T
3(wherein iron is essential element to the Type B phase, and has body-centered tetragonal Fe
3And contain the above Fe of 70% (volume) the P type crystal structure),
3Type B compound phase.This boride can replace Fe with Co
3A part of Fe among the B forms.This boride in certain scope can with have space group P
4The Nd of/mnm
2Fe
14The Nd of Type B crystal structure
2(Fe, Co)
14The ferromagnetic Asia mutually of B stably exists jointly.
In order to obtain high magnetic flux density and enough iHc, must exist this boride simultaneously mutually with mutually ferromagnetic.Even identical chemical composition is used casting method, formation be heat balance Fe with C16 type crystal structure
3B mutually with body-centred cubic α-Fe mutually rather than metastable phase.In this way, obtain the high magnetization, but iHc is reduced to below the 1KOe, can not be used as practical magnet.
In the present invention, rare earth magnet is made of following alloy powder, and this alloy powder is that (main component wherein is to have body-centered tetragonal Fe by the boride phase of common existence
3The Fe of P type crystal structure
3The Type B compound) form, and Nd
2Fe
14The Type B crystal exists mutually jointly as another kind of formation mutually.These are ferromagnetic mutually, but preceding a kind of itself be soft magnetism mutually, so it must just can have the iHc that needs with a kind of coexistence mutually in back.
But what only contain these coexistences also is not enough to obtain permanent magnet mutually.Unless the average crystalline particle diameter is in the 5nm-100nm scope, otherwise the rectangle characteristic of demagnetization curve will variation, and can not produce enough magnetic flux activating point.So the average crystalline particle diameter must fix on 5nm-100nm.
When utilizing the characteristic of resin bonded magnet to form complex-shaped thin magnet, require alloy powder to have enough little particle diameter, to finish high-precision moulding.But particle diameter surpasses 100 microns gas atomization powder owing to can not cool off fully, and most of crystallization becomes α-Fe phase.Even after Overheating Treatment, Fe
3Type B compound phase and Nd
2Fe
14The Type B compound can not separated out mutually yet, and therefore, it can not become hard magnetic material.
On the other hand, particle diameter because its surface area increases, needs a large amount of resins as binding agent less than 0.1 micron powder, and this will cause reducing bulk density, thereby not cater to the need.So the powder particle diameter dimension is defined as the 0.1-100 micron.
In the present invention, the method for quenching is melted in employing or atomization makes the molten alloy rapid solidification with afore mentioned rules composition, thereby makes major part wherein be transformed into amorphous structure.After in the temperature range of 500 ℃ or higher beginning, heating up, 550-730 ℃ of heat treatment 5 minutes to 6 hours with 1-15 ℃/minute speed.It is essential that thin druse has the metastable Fe of thermodynamics
3B compound phase, and the average crystalline particle diameter is 5-100nm.Make the method for molten alloy Quench that the combination of the molten method of quenching, atomization and these two kinds of methods that people know be arranged.Before above-mentioned heat treatment step, must have more than 90% in the alloy powder that rapid solidification obtains is amorphous state.
For example, in the molten method of quenching that adopts the Cu roller, the roller surface rotary speed of 5-50m/ second has produced the institutional framework that meets the requirements.That is to say that velocity of rotation during second, can not produce amorphous structure less than 5m/, the quantity that α-Fe is separated out mutually increases.If roller surface rotary speed surpasses 50m/ second, the alloy of Quench can not form continuous band and alloy sheet so.Because the rate of recovery of alloy and organic efficiency reduce, thereby do not meet the requirements.It in the alloy band of Quench, allows to exist the α-Fe phase of minute quantity, because can not reduce magnetic property significantly.
For example, in using the gas atomization method of Ar gas as refrigerating gas, for tissue and the granular size that obtains to suit, requiring injection pressure is 10-80kgf/cm
2
That is to say, if injection pressure is lower than 10kgf/cm
2, just can not obtain amorphous structure.Not only separating out of α-Fe phase can increase, and alloy deposition can not get sufficient cooling on the returnable surface, and powder forms group, piece, causes the rate of recovery of alloy lower.On the other hand, if injection pressure surpasses 80kgf/cm
2, particle diameter increases less than the volume ratio of 0.1 micron fine particle in the alloy powder, and this has not only reduced the rate of recovery and organic efficiency, but also has reduced pressed density, is undesirable therefore.
In addition, the Quench method that molten quench method and gas atomization are combined is suitable for producing in batches.In order to further specify this point, adopt the gas atomization method molten alloy to be sprayed to the roller of rotation with Sprayable.By selecting roller surface rotary speed and expulsion pressure, can obtain the alloy powder and the sheet of desired amorphous state particle diameter.
Heat treated condition
In the present invention, the method for quenching is melted in employing or atomization cools off the molten alloy of afore mentioned rules composition fast, and its major part is transformed into amorphous solid phase.The Technology for Heating Processing that produces high magnetic characteristics depends on that the structure of alloy forms.But when heat treatment temperature was lower than 550 ℃, amorphous state remained mutually, and can not obtain to be higher than the iHc of 2KOe; And when temperature surpasses 730 ℃, can generate the thermodynamical equilibrium phase, promptly α-Fe is mutually and Fe
2B or Nd
1.1Fe
4B
4Phase.Because being created in the equilibrium phase mixture of iHc can not taken place, so heat treatment temperature is restricted to 550-730 ℃.Inert gas, for example Ar gas is suitable as heat-treating atmosphere.
Heat treatment time can be shorter, if but be less than 5 minutes, microscopic structure growth fully just can not take place, and the rectangle degree of iHc and demagnetization curve can worsen; And,, then can not obtain the above iHc of 2KOe if surpass 6 hours.Therefore the heat treatment temperature retention time was defined as 5 minutes-6 hours.
A key character of the present invention is from 500 ℃ or higher temperature rising speed in heat treatment process.If temperature raises with the speed less than 1 ℃/minute, just can not obtain to be higher than the iHc of 2KOe, this is because Ne
2Fe
14B phase and Fe
3The crystal diameter of B phase is too big, and iHc is suffered damage.
And, if temperature rising speed surpasses 15 ℃/minute, then at the Nd that produces more than 500 ℃
2Fe
14B phase product just can fully not separated out, and α-Fe separates out increase mutually.The result reduces the magnetization that the second quadrant demagnetization curve is ordered near Br, has reduced (BH) in addition
Max, this is undesirable.But minute quantity α-Fe allows to exist.
In addition, in the heat treatment process before the temperature to 500 ℃, any programming rate comprises Fast Heating, all can allow.
Magnitizing method
For the present invention being used for the alloy powder magnetization of rare earth magnet, this alloy powder obtains in such a way, be that average crystal grain diameter is 5nm-100nm, by grinding the average powder diameter of alloy is dropped in the 0.1-100 micrometer range in case of necessity, when gas atomization and melt wire drawing are used in combination, so just need not adopt grinding.Subsequently, with this powder and habitual mixed with resin, make the resin bonded magnet, its residual magnetic flux density (Br) is higher than 5KG.
The resulting resin bonded magnet of the present invention is isotropic magnet, and it can adopt following any method manufacturing, for example compression moulding, injection moulding, extrusion modling, roll-forming and resin impregnation.
When adopting compression moulding, add thermoset plastics, coupling agent and lubricant in the magnetropism powder, and mix, compression moulding then, heating makes hardening of resin, obtains the resin bonded magnet.
When adopting injection moulding, extrusion modling and roll-forming, thermoplastic resin, coupling agent, lubricant are added in the Magnaglo, and mix, adopt a kind of forming method moulding in injection moulding, extrusion modling and the roll-forming then.
When adopting the resin impregnation method, after the Magnaglo compacting, if suitable, and heating, with the thermoset plastics dipping, heating makes this resin solidification then.In addition, the resin bonded magnet also can obtain by following method, i.e. compression moulding is if suitable (promptly when the powder of rapid solidification is directly suppressed) to its heat treatment, uses thermoplastic resin impregnated this Magnaglo then.
In the present invention, the part by weight of Magnaglo is distinguished to some extent according to above-mentioned manufacture method difference in the resin bonded magnet, generally is that 70-99.5% (weight) surplus is resin and other material of 0.5-30%.When adopting compression moulding, the part by weight of Magnaglo is 95-99.5% (weight); When adopting injection moulding, the filling rate of Magnaglo is 90-95% (weight); When adopting dip forming, the weight ratio of Magnaglo is 96-99.5%.
Synthetic resin as binding agent can be heat cured or thermoplastic, preferentially selects heat-staple resin for use.It can suitably be selected from following resin: polyamide, phenol resin, fluororesin, silicones and epoxy resin.
Embodiment 1
In order to obtain the chemical composition of No.1-13 in the table 1, use purity greater than 99.5% metal Fe, Co, B, Nd, Pr, Ag, Al, Si, Cu and Ga, total weight is 30g.These metals are put into silica crucible, and crucible bottom has the nozzle of a 0.8mm diameter.Under the Ar of 56cmHg atmosphere, adopt high-frequency induction heating that it is melted, after melt temperature reaches 1400 ℃, utilize the Ar atmospheric pressure that motlten metal is highly watered one at room temperature on the Cu roller outer surface with the high-speed rotation of 20m/ second by 0.7mm, obtain the molten metal tape of quenching of wide 2-3mm, thick 30-40 micron.
Carry out powder x-ray diffraction by the characteristic X-ray with Cu-K-α, the metal tape that confirms molten to quench has amorphous structure.
After in Ar atmosphere the above-mentioned molten metal tape of quenching being heated rapidly to 500 ℃, the speed shown in the table 1 of press heats up, and with the maintenance of the heat treatment temperature shown in the table 1 10 minutes, then temperature is rolled back room temperature.Make the sample of several wide 2-3mm, thick 30-40 micron, long 3-5mm by this metal tape, measure its magnetic property.The result who records shown in the table 2.
Result to these sample testings shows that main is to have cubic Fe mutually
3The Fe of P type crystal structure
3The B phase shows in addition, has simultaneously to comprise Nd
2Fe
14B phase and α-Fe heterogeneous structure mutually.The average crystal diameter of these crystal is less than 0.1 micron.In addition, these mutually in Co replaced part Fe, still, be difficult to analyze, because their addition is few and have a ultrafine crystal structure for Ag, Al, Si, Cu and Ga.
Comparative example 1
Prepare the molten metal tape of quenching of No.2 and No.7 composition among the embodiment 1 according to the condition identical, in Ar atmosphere, it is quickly heated up to 500 ℃, heat up in the speed with 11 ℃/minute more than 500 ℃, 620 ℃ of heat treatments 10 minutes with embodiment 1.After metal tape cooling, by with embodiment 1 in identical condition prepare sample (comparative example No.14 No.18), use VSM to measure its magnetic property, the results are shown in table 2.
The molten metal tape of quenching for preparing No.2 and No.7 composition among the embodiment 1 according to the condition identical with embodiment 1, in Ar atmosphere, it is quickly heated up to 500 ℃, to comparative example No.15 and No.19, heat-treated in 10 minutes 500 ℃ of insulations, to comparative example No.16 and No.20, heat up with 4 ℃/minute speed, heat-treated in 10 minutes 750 ℃ of insulations.After the cooling of each metal tape, prepare sample by the method identical with embodiment 1, measure its magnetic property with VSM, the results are shown in table 2.
Comparative example No.15 and No.19 demonstrate the amorphous state crystal structure, and comparative example No.16 and No.20 have shown the heterogeneous structure structure, and wherein coexistence has Fe simultaneously
2B mutually with α-Fe mutually.
Table 1
| Composition (atom %) | From 500 ℃ firing rates (℃/liter) | Heat treatment temperature | The retention time branch | ||||||||
| R | Fe | Co | B | M | |||||||
| The present invention | 1 | Pr2 Nd3 | 71.0 | 5.0 | 18.5 | Ga0.5 | 5 | 620 | 10 | ||
| 2 | Nd5 | 70.5 | 5.0 | 18.5 | Ga1.0 | 5 | 620 | 10 | |||
| 3 | Nd5 | 71.0 | 5.0 | 18.5 | Cu0.5 | 5 | 620 | 10 | |||
| 4 | Nd5 | 70.5 | 5.0 | 18.5 | Cu1.0 | 5 | 600 | 15 | |||
| 5 | Pr3 Nd2 | 71.0 | 5.0 | 18.5 | Cu0.25 Ga0.25 | 5 | 650 | 15 | |||
| 6 | Nd5 | 71.0 | 5.0 | 18.5 | Al0.5 | 5 | 670 | 10 | |||
| 7 | Nd5 | 70.5 | 5.0 | 18.5 | Al1.0 | 5 | 670 | 10 | |||
| 8 | Nd5 | 71.0 | 5.0 | 18.5 | Ag0.5 | 5 | 600 | 10 | |||
| 9 | Nd5 | 70.5 | 5.0 | 18.5 | Ag1.0 | 5 | 600 | 15 | |||
| 10 | Nd5 | 71.0 | 5.0 | 18.5 | Si0.5 | 5 | 680 | 15 | |||
| 11 | Nd5 | 70.5 | 5.0 | 18.5 | Si1.0 | 5 | 680 | 15 | |||
| 12 | Nd4 | 71.0 | 5.0 | 18.5 | Al0.5 Si1.0 | 5 | 670 | 15 | |||
| 13 | Pr3 Nd2 | 71.0 | 5.0 | 18.5 | Ag0.25 Al0.25 | 5 | 650 | 15 | |||
| Comparative example | 14 | Nd5 | 70.5 | 5.0 | 18.5 | Ga1.0 | 11 | 680 | 15 | ||
| 15 | Nd5 | 70.5 | 5.0 | 18.5 | Ga1.0 | - | 500 | 10 | |||
| 16 | Nd5 | 70.5 | 5.0 | 18.5 | Ga1.0 | 4 | 750 | 10 | |||
| 17 | Nd5 | 70.5 | 5.0 | 18.5 | 0 | 5 | 620 | 10 | |||
| 18 | Nd5 | 70.5 | 5.0 | 18.5 | Al1.0 | 11 | 680 | 15 | |||
| 19 | Nd5 | 70.5 | 5.0 | 18.5 | Al1.0 | - | 500 | 10 | |||
| 20 | Nd5 | 70.5 | 5.0 | 18.5 | Al1.0 | 4 | 750 | 10 | |||
Table 2
| Br (kG) | iHc (kOe) | (BH)max MGOe | ||
| The present invention | 1 | 10.0 | 4.2 | 10.5 |
| 2 | 10.6 | 4.3 | 13.2 | |
| 3 | 10.1 | 4.1 | 11.6 | |
| 4 | 9.7 | 4.2 | 11.5 | |
| 5 | 10.0 | 4.1 | 10.0 | |
| 6 | 10.0 | 4.2 | 10.5 | |
| 7 | 10.6 | 4.3 | 13.2 | |
| 8 | 10.1 | 4.1 | 11.6 | |
| 9 | 9.7 | 4.2 | 11.5 | |
| 10 | 10.7 | 3.8 | 12.6 | |
| 11 | 11.0 | 3.7 | 12.4 | |
| 12 | 10.5 | 3.7 | 11.7 | |
| 13 | 10.0 | 4.1 | 10.0 | |
| Comparative example | 14 | 9.5 | 3.4 | 7.2 |
| 15 | 9.8 | - | - | |
| 16 | 8.0 | 0.5 | 1.0 | |
| 17 | 9.3 | 4.1 | 9.5 | |
| 18 | 9.5 | 3.4 | 7.2 | |
| 19 | 9.8 | - | - | |
| 20 | 8.0 | 0.5 | 1.0 |
Embodiment 2
The molten metal tape of quenching that obtains among the embodiment 1, its composition is the No.4 and the No.9 of table 1, press table 1 with its heat treatment after, these metal tapes are milled to average particulate diameter less than 150 microns.Make binding agent with epoxy resin, mix with Magnaglo with the ratio of 3% (weight), making density is 5.8g/cm
3, size is the resin-bonded magnet of 15mm * 15mm * 7mm.
The magnetic property of this resin-bonded magnet is as follows:
No.4：iHc＝4.1KOe、B＝6.9KG、(BH)
max＝6.8MGOe。
No.9：iHc＝4.1KOe、B＝7.0KG、(BH)
max＝6.8MGOe。
Embodiment 3
In order to have the composition of No.30-36 in the table 3, weighing purity is greater than 99.5% metal Fe, Co, B, Nd, Pr, Al, Si, Cu, Ga, Ag and Au, making total weight is 1KG, put it in the alumina crucible, crucible bottom has the nozzle of a diameter 2.0mm, utilizes high-frequency induction heating to make it fusing in Ar atmosphere.When melt temperature reaches 1300 ℃, pull up the stopper that is inserted on the spout, with 40kgf/cm
2Pressure to spray purity by the gas nozzle be 99.9% Ar gas, make atomized molten alloy, obtain particle diameter and be several microns to 50 microns alloy powder.
Characteristic X-ray through Cu-K-α confirms that the structure of resulting like this alloy powder is an amorphous structure.
After in Ar atmosphere this alloy powder being quickly heated up to 500 ℃, heat up in the speed with 10 ℃/minute more than 500 ℃, the heat treatment holding temperature is as shown in table 3, and alloy powder is cooled to room temperature, takes out then.Get the 30g powder and mix, be heating and curing with paraffin.Measure the magnetic property of sample by VSM.The results are shown in table 4.
Test result shows, has heterogeneous structure, wherein has cubic Fe
3The Fe of P-structure
3B is main phase mutually, is mixed with Nd in addition
2Fe
14B and α-Fe are mutually.All mutually in, average crystal grain diameter is all less than 0.1 micron.In addition, every kind mutually in Co replaced the Fe of part, but with regard to Al, Si, Cu, Ga, Ag and Au,, therefore fail to detect because their addition is very little and crystal structure is very tiny.Table 3
Table 4
| No. | Composition (atom %) | Heat treatment temperature | |||||||||
| R | Fe | Co | B | Al | Si | Cu | Ga | Ag | Au | ||
| 21 | Nd5 | 71.5 | 5.0 | 18.5 | - | - | - | - | - | - | 620℃ |
| 22 | Nd5 | 71.0 | 5.0 | 18.5 | 0.5 | - | - | - | - | - | 620℃ |
| 23 | Nd4 | 71.5 | 5.0 | 18.5 | - | 1.0 | - | - | - | - | 670℃ |
| 24 | Nd3 Pr2 | 70.5 | 5.0 | 18.5 | - | - | 1.0 | - | - | - | 610℃ |
| 25 | Nd5 | 70.5 | 3.0 | 18.5 | - | - | - | 1.0 | - | - | 620℃ |
| 26 | Nd4.5 | 73.0 | 5.0 | 18.5 | - | - | 0.5 | - | 0.5 | - | 640℃ |
| 27 | Nd5 | 73.5 | 1.0 | 18.5 | - | - | 1.0 | - | - | 1.0 | 620℃ |
| Br(kG) | iHc(KOe) | (BH)max (MGOe) | |
| 21 | 8.4 | 4.1 | 8.0 |
| 22 | 9.0 | 4.2 | 9.1 |
| 23 | 9.6 | 3.7 | 9.3 |
| 24 | 8.7 | 4.2 | 8.7 |
| 25 | 9.5 | 4.3 | 9.8 |
| 26 | 10.0 | 4.1 | 10.1 |
| 27 | 9.3 | 4.2 | 9.4 |
Embodiment 4
By the No.37-42 elemental composition weighing purity in the table 5 is 99.5% metal Fe, Co, B, Nd, Pr, Cu, Ga, Ag, Au, Al and Si, and total weight is 30g, puts it in the silica crucible of the bottom nozzle that to have a diameter be 0.8mm.In the Ar of 56mmHg pressure atmosphere, make it fusing by high-frequency induction heating, the temperature of melt reaches 1400 ℃, on then melt liquid highly being sprayed onto Cu roller outer surface with the high rotating speed rotation of 20m/ second from 0.7mm, obtain the molten metal tape of quenching of wide 2-3mm, thick 30-40 micron.
Powder x-ray diffraction and electron scanning micrograph by the characteristic X-ray that adopts Cu-K-α can determine that its major part (more than 90% volume) is an amorphous state.
After this molten band of quenching is heated rapidly to 500 ℃, heat up, kept 10 minutes, treat behind the metal tape cool to room temperature its taking-up in heat treatment temperature shown in the table 1 with the speed shown in the table 1.
The institutional framework of sample is heterogeneous, and wherein coexistence simultaneously has Fe in the highest flight
3Type B phase, Nd
2Fe
14Type B mutually with α-Fe mutually, average crystal diameter is less than 0.1 micron.In addition, every kind mutually in Co replaced the Fe of part.
After this metal tape ground into the powder that the average particulate diameter scope is the 23-300 micron, the epoxy resin of getting the powder and 2% (weight) of 98% (weight) mixed, at 6 tons/centimetre
2Pressure under compression moulding, 150 ℃ of curing, obtain resin-bonded magnet.The density of this resin-bonded magnet is 5.6g/cm
3, its magnetic property has been shown in the table 6.
Comparative example 2
Make the molten metal tape of quenching of No.43 composition according to the condition identical with embodiment 4, in Ar atmosphere with its Fast Heating, speed with 11 ℃/minute more than 500 ℃ the time heats up, for No.44 comparative example sample 500 ℃ of heat treatments 10 minutes, and for No.45 comparative example sample with 4 ℃ of/minute intensifications, 750 ℃ of heat treatments 10 minutes.After treating these sample cool to room temperature, prepare sample, measure its magnetic property by the mode identical with embodiment 1.The results are shown in the table 6.
Comparative example No.44 shows it is amorphous structure, and No.45 is Fe
2The heterogeneous structure that B coexists mutually with α-Fe mutually.Table 5
| Composition (atom %) | Firing rate (℃/minute) | Heat treatment temperature | The retention time branch | ||||||
| R | Fe | Co | B | M | |||||
| The present invention | 28 | Nd5 | 70.5 | 5 | 18.5 | Cu1 | 5 | 600℃ | 15 |
| 29 | Nd5 | 70.5 | 5 | 18.5 | Gu1 | 5 | 620℃ | 10 | |
| 30 | Nd+Pr5 | 70.5 | 5 | 18.5 | Ag1 | 5 | 600℃ | 15 | |
| 31 | Nd4.5 | 73 | 3 | 18.5 | Al1 | 7 | 670℃ | 10 | |
| 32 | Nd4.5 | 73 | 3 | 18.5 | Si1 | 7 | 680℃ | 10 | |
| 33 | Nd5 | 70.5 | 5 | 18.5 | Au1 | 5 | 610℃ | 10 | |
| Comparative example | 34 | Nd4 | 77.4 | 0.1 | 18.5 | - | 11 | 680℃ | 15 |
| 35 | Nd5 | 71.5 | 5.0 | 18.5 | - | - | 500℃ | 10 | |
| 36 | Nd5 | 71.5 | 5.0 | 18.5 | - | 4 | 750℃ | 10 | |
Table 6
| Br k(G) | iHe (kOe) | (BH)max MGOe | ||
| The present invention | 28 | 5.8 | 4.0 | 5.5 |
| 29 | 6.4 | 4.1 | 6.2 | |
| 30 | 5.8 | 3.9 | 5.2 | |
| 31 | 6.9 | 3.6 | 6.7 | |
| 32 | 7.2 | 3.7 | 7.0 | |
| 33 | 5.8 | 4.1 | 5.5 | |
| Comparative example | 34 | 5.5 | 2.1 | 1.6 |
| 35 | 5.6 | - | - | |
| 36 | 4.9 | 0.4 | 0.6 |
The present invention adopts the combination of molten quench method or atomization or these two kinds of methods, make Fe-Co-B-R-M type molten alloy rapid solidification with predetermined component, make it major part and be transformed into the amorphous structure powder that average particulate diameter is the 0.1-100 micron, this amorphous alloy powder after heat treatment, obtain the magnetic alloy powder of thin druse, its average crystal diameter is 5-100nm.Making and can reliablely and stablely making a large amount of Fe-Co-B-R-M in this way is the alloy Magnaglo, and its magnetic property is: iHc 〉=3KOe, B 〉=8KG, (BH)
Max〉=8MGOe, residual magnetic flux density (Br) are particularly suitable for being used for making resin-bonded magnet greater than 5KG.
The resin-bonded magnet that adopts method of the present invention to obtain contains a spot of rare earth, and manufacture method is simple, therefore is fit to a large amount of production.Its residual magnetic flux density (Br) is greater than 5KG, and magnetic property has surpassed the ferrite hard magnetic body.Owing to adopt the unit formation of magnetic element and magnet, can shorten process for making.Resin-bonded magnet provided by the present invention, its performance and the ratio of cost have surpassed the ferrite hard magnetic body of sintering.
Claims (3)
1. manufacture method that is used for the alloy powder of rare earth magnet may further comprise the steps:
Have the molten alloy of following structural formula by the molten method rapid solidification of quenching,
Fe
100-x-y-zCo
xB
yR
zM
w
In the formula, R is one or both among Pr and the Nd, M is one or both among Al, Si, Cu, Ga, Ag and the Au, each expression of symbol x, y, z and w is by the composition range of atomic percentage, they satisfy 0.05≤x≤15 atom %, 16≤y≤22 atom %, 3≤z≤6 atom % and 0.1≤w≤3 atom % respectively
Obtain amorphous state and surpass 90% alloy powder,
With the alloy powder that obtains like this through following heat treatment:, and under temperature between 550 ℃ to 730 ℃, kept 5 to 360 minutes from 500 ℃ of intensifications with 1-15 ℃/minute heating rate, have body-centered tetragonal Fe thereby make to comprise
3The rich iron boride phase and the Nd of Type B crystal structure
2Fe
14The rare earth magnet of Type B crystal structure phase, this two-phase coexistent in same particle, described rare earth magnet by average crystal grain diameter be the crystallite aggregate of 5nm to 100nm form and
The crystallite aggregate that makes is like this ground, obtain the alloy powder that average particulate diameter is 0.1 to 100 μ m.
2. manufacture method that is used for the alloy powder of rare earth magnet may further comprise the steps:
Have the molten alloy of following structural formula by the gas atomization rapid solidification,
Fe
100-x-y-zCo
xB
yR
zM
w
In the formula, R is one or both among Pr and the Nd, M is one or both among Al, Si, Cu, Ga, Ag and the Au, each expression of symbol x, y, z and w is by the composition range of atomic percentage, they satisfy 0.05≤x≤15 atom %, 16≤y≤22 atom %, 3≤z≤6 atom % and 0.1≤w≤3 atom % respectively
Obtain amorphous state and surpass 90% alloy powder, this powder average particulate diameter is 0.1 μ m to 100 μ m,
With the alloy powder that obtains like this through following heat treatment:, and under temperature between 550 ℃ to 730 ℃, kept 5 to 360 minutes from 500 ℃ of intensifications with 1-15 ℃/minute heating rate, have body-centered tetragonal Fe thereby make to comprise
3The rich iron boride phase and the Nd of Type B crystal structure
2Fe
14The rare earth magnet of Type B crystal structure phase, this two-phase coexistent are in same particle, and described rare earth magnet is that the crystallite aggregate of 5nm to 100nm is formed by average crystal grain diameter.
3. manufacture method that is used for the alloy powder of rare earth magnet may further comprise the steps:
The Quench method rapid solidification that combines by molten quench method and gas atomization has the molten alloy of following structural formula,
Fe
100-x-y-zCo
xB
yR
zM
w
In the formula, R is one or both among Pr and the Nd, M is one or both among Al, Si, Cu, Ga, Ag and the Au, each expression of symbol x, y, z and w is by the composition range of atomic percentage, they satisfy 0.05≤x≤15 atom %, 16≤y≤22 atom %, 3≤z≤6 atom % and 0.1≤w≤3 atom % respectively
Obtain amorphous state and surpass 90% alloy powder, this powder average particulate diameter is 0.1 μ m to 100 μ m,
With the alloy powder that obtains like this through following heat treatment:, and under temperature between 550 ℃ to 730 ℃, kept 5 to 360 minutes from 500 ℃ of intensifications with 1-15 ℃/minute heating rate, have body-centered tetragonal Fe thereby make to comprise
3The rich iron boride phase and the Nd of Type B crystal structure
2Fe
14The rare earth magnet of Type B crystal structure phase, this two-phase coexistent are in same particle, and described rare earth magnet is that the crystallite aggregate of 5nm to 100nm is formed by average crystal grain diameter.
Applications Claiming Priority (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3323779A JP2966169B2 (en) | 1991-11-11 | 1991-11-11 | Rare earth magnet, alloy powder for rare earth magnet and method for producing the same |
| JP323779/91 | 1991-11-11 | ||
| JP323779/1991 | 1991-11-11 | ||
| JP9378092 | 1992-03-19 | ||
| JP93780/92 | 1992-03-19 | ||
| JP93780/1992 | 1992-03-19 | ||
| JP124180/1992 | 1992-04-16 | ||
| JP4124180A JP2986611B2 (en) | 1992-04-16 | 1992-04-16 | Fe-BR bonded magnet |
| JP124180/92 | 1992-04-16 | ||
| JP174767/92 | 1992-06-08 | ||
| JP17476792 | 1992-06-08 | ||
| JP176199/1992 | 1992-06-09 | ||
| JP17619992 | 1992-06-09 | ||
| JP176199/92 | 1992-06-09 | ||
| JP174767/1992 | 1993-06-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085007A CN1085007A (en) | 1994-04-06 |
| CN1053988C true CN1053988C (en) | 2000-06-28 |
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ID=27525665
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92114394A Expired - Lifetime CN1053988C (en) | 1991-11-11 | 1992-11-10 | Rare earth magnets and alloy powder for rare earth magnets and their manufacturing methods |
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| Country | Link |
|---|---|
| EP (1) | EP0542529B1 (en) |
| CN (1) | CN1053988C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0657899B1 (en) * | 1993-12-10 | 2000-03-08 | Sumitomo Special Metals Company Limited | Iron-based permanent magnet alloy powders for resin bonded magnets and magnets made therefrom |
| US6019859A (en) * | 1994-09-02 | 2000-02-01 | Sumitomo Special Metals Co., Ltd. | Iron-based permanent magnets and their fabrication as well as iron-based permanent magnet alloy powders for permanent bonded magnets and iron-based bonded magnets |
| DE19541948A1 (en) * | 1995-11-10 | 1997-05-15 | Schramberg Magnetfab | Magnetic material and permanent magnet of the NdFeB type |
| JPH10125518A (en) * | 1996-10-18 | 1998-05-15 | Sumitomo Special Metals Co Ltd | Thin sheet magnet with fine crystal structure |
| EP0959478B1 (en) * | 1997-02-06 | 2004-03-31 | Sumitomo Special Metals Company Limited | Method of manufacturing thin plate magnet having microcrystalline structure |
| WO1998036428A1 (en) * | 1997-02-14 | 1998-08-20 | Sumitomo Special Metals Co., Ltd. | Thin plate magnet having microcrystalline structure |
| EP0898287B1 (en) * | 1997-08-22 | 2003-05-21 | Alps Electric Co., Ltd. | Hard magnetic alloy having supercooled liquid region, sintered product thereof and applications |
| WO2000033325A1 (en) * | 1998-12-03 | 2000-06-08 | Institut für Festkörper- und Werkstofforschung Dresden e.V. | Hard magnetic alloy and casting mould produced therewith |
| US7195661B2 (en) | 1999-03-05 | 2007-03-27 | Pioneer Metals And Technology, Inc. | Magnetic material |
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| US6818041B2 (en) * | 2000-09-18 | 2004-11-16 | Neomax Co., Ltd | Magnetic alloy powder for permanent magnet and method for producing the same |
| CN101240398B (en) * | 2007-02-07 | 2010-12-29 | 罗阳 | Intermetallic compound anisotropy magnetic powder, preparation method and special device |
| CN101202143B (en) * | 2007-11-09 | 2012-01-11 | 钢铁研究总院 | Preparation method of high performance radial hot pressing magnet ring |
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| CN103871708B (en) * | 2014-03-04 | 2016-04-13 | 山西雷麦电子科技有限公司 | A kind of iron cobalt-based high magnetic intensity soft magnetic material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62208609A (en) * | 1986-03-07 | 1987-09-12 | Namiki Precision Jewel Co Ltd | Resin-bonded permanent magnet and manufacture of its magnetic powder |
| EP0264153A1 (en) * | 1986-10-10 | 1988-04-20 | Koninklijke Philips Electronics N.V. | Magnetic material comprising iron, boron and a rare earth metal |
| CN1051635A (en) * | 1989-12-31 | 1991-05-22 | 中国科学院三环新材料研究开发公司 | Biphase rare earth permanent-magnetic alloy material |
-
1992
- 1992-11-10 CN CN92114394A patent/CN1053988C/en not_active Expired - Lifetime
- 1992-11-11 DE DE1992612569 patent/DE69212569T2/en not_active Expired - Lifetime
- 1992-11-11 EP EP19920310299 patent/EP0542529B1/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62208609A (en) * | 1986-03-07 | 1987-09-12 | Namiki Precision Jewel Co Ltd | Resin-bonded permanent magnet and manufacture of its magnetic powder |
| EP0264153A1 (en) * | 1986-10-10 | 1988-04-20 | Koninklijke Philips Electronics N.V. | Magnetic material comprising iron, boron and a rare earth metal |
| CN1051635A (en) * | 1989-12-31 | 1991-05-22 | 中国科学院三环新材料研究开发公司 | Biphase rare earth permanent-magnetic alloy material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1085007A (en) | 1994-04-06 |
| DE69212569D1 (en) | 1996-09-05 |
| EP0542529B1 (en) | 1996-07-31 |
| EP0542529A1 (en) | 1993-05-19 |
| DE69212569T2 (en) | 1997-02-06 |
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