CN1085007A - Alloy powder that rare earth magnet and rare earth magnet are used and manufacture method thereof - Google Patents

Alloy powder that rare earth magnet and rare earth magnet are used and manufacture method thereof Download PDF

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CN1085007A
CN1085007A CN 92114394 CN92114394A CN1085007A CN 1085007 A CN1085007 A CN 1085007A CN 92114394 CN92114394 CN 92114394 CN 92114394 A CN92114394 A CN 92114394A CN 1085007 A CN1085007 A CN 1085007A
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magnet
alloy powder
rare earth
rare
alloy
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CN1053988C (en
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広泽哲
金清裕和
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Hitachi Metals Ltd
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Sumitomo Special Metals Co Ltd
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Priority claimed from JP4124180A external-priority patent/JP2986611B2/en
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    • 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

Abstract

A kind of manufacturing resin bonded Fe is provided 3The method of Type B Fe-Co-B-R-M series high-performance magnet, described magnet have improved iHc and (BH) Max, batch process that can be reliable and stable.This alloy powder contains ferromagnetic phase, wherein has boride phase and Nd simultaneously 2Fe 14The Type B phase.With itself and mixed with resin, obtain the high performance resin bonded permanent magnet, its iHc 〉=3KOe, Br 〉=5KG, (BH) Max〉=3MGOe.

Description

Alloy powder that rare earth magnet and rare earth magnet are used and manufacture method thereof
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, the Au of the specific composition composition that contains the lower content rare earth element) the alloy Quench, 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 14The 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 10-15%(atom) Nd, need carry out many processed separately and a large amount of production equipments separates, purify and reduce 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 19Near (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 has a research work (Shen Bao-gen, Deng the people, J.Magn.Magn.Mat, 89(1991) P335-340) be to replace part Fe with Co, 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.
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) MaxFe 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, be a kind of among Al, Si, Cu, Ga, Ag and the Au or two kinds by adding additional elements M(M), 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.
When R less than the 3%(atom) time, iHc can not reach more than the 2KOe, if but it surpasses the 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 the 3-5.5%(atom).
When B less than the 16%(atom) or greater than the 22%(atom) time, iHc is no more than 2KOe, so its content range is decided to be the 16-22%(atom).
Co can improve the rectangle degree of demagnetization curve effectively, but it surpasses the 15%(atom) time, iHc significantly is reduced to is not more than 2KOe, so its content range is decided to be the 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 0.1%(atom at least) addition.But, if content surpasses the 3%(atom), rectangle degree and (BH) MaxThe capital reduces, so its content range fixes on the 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 3The P type crystal structure), and contain the 70%(volume) above Fe 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 0.1-500 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 different and difference to some extent according to above-mentioned manufacture method of the part by weight of Magnaglo generally is a 70-99.5%(weight in the resin bonded magnet) surplus is resin and other material of 0.5-30%.When adopting compression moulding, the part by weight of Magnaglo is a 95-99.5%(weight); When adopting injection moulding, the filling rate of Magnaglo is a 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
Figure 92114394X_IMG1
Table 2
Figure 92114394X_IMG2
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, with 3%(weight) ratio mix with Magnaglo, 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
Figure 92114394X_IMG3
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, get 98%(weight) powder and 2%(weight) epoxy resin mix, 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
Figure 92114394X_IMG4
Table 6
Figure 92114394X_IMG5
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 (23)

1, a kind of rare earth magnet, its structural formula is:
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, symbol x, y, z and w respectively represent composition range, they satisfy 0.05≤x≤15 atom %, 16≤y≤22 atom %, 3≤z≤6 atom % and 0.1≤w≤3 atom % respectively, and described rare earth magnet comprises and has body-centered tetragonal Fe 3The boride phase and the Nd of the rich iron of P type crystal structure 2Fe 14The phase of Type B crystal structure, this rare earth magnet is to be formed by aggregates of crystallites, its average crystalline particle diameter is 5nm to 100nm.
2, the rare earth magnet of claim 1, wherein said rare earth magnet has magnetic property: iHc 〉=3KOe, Br 〉=9KG and (BH) Max〉=10MGOe.
3, the rare earth magnet of claim 1, wherein said rare earth magnet are the magnets of bonding.
4, a kind of alloy powder that is used for rare earth magnet, its average particulate diameter is 0.1-500 μ m, the structural formula of described rare earth magnet is:
In the formula, R is one or both among Pr and the Nd, M is that Al, Si, Cu, Ga, Ag and Au neutralize one or both, symbol x, y, z and w represent composition range separately, they satisfy 0.05≤x≤15 atom %, 16≤y≤22 atom %, 3≤z≤6 atom % and 0.1≤w≤3 atom % respectively, and described rare earth magnet contains and has body-centered tetragonal Fe 3The boride phase and the Nd of the rich iron of P type crystal structure 2Fe 14The phase of Type B crystal structure, this rare earth magnet are that the crystallite aggregate of 5nm-100nm forms by the average crystalline particle diameter.
5, the described alloy powder that is used for rare earth magnet of claim 4, wherein, alloy powder is to grind by the alloy band that will melt the formation of quenching to obtain.
6, the described alloy powder that is used for rare earth magnet of claim 4, wherein, alloy powder obtains by the gas atomization method.
7, the described alloy powder that is used for rare earth magnet of claim 4, wherein, the magnetic property that this rare earth magnet has is: iHc 〉=3KOe, Br 〉=8KG and (BH) Max〉=8MGOe.
8, a kind of manufacture method that is used for the alloy powder of rare earth magnet comprises step: make the molten alloy rapid solidification by the molten method of quenching, make the molten alloy more than 90% become amorphous state;
With the alloy heat treatment of this rapid solidification, produce the crystallite aggregate, it comprises and has body-centered tetragonal Fe 3The boride phase and the Nd of the rich iron of P type crystal structure 2Fe 14The phase of Type B crystal structure, the average crystalline particle diameter of described crystallite aggregate is 5nm-100nm;
Such crystallite aggregate that produces is ground, obtain alloy powder.
9, a kind of manufacture method that is used for the alloy powder of rare earth magnet comprises step:
Make the molten alloy rapid solidification by gas atomization, what make this molten alloy becomes amorphous state more than 90%;
Alloy to this rapid solidification is heat-treated, and produces the crystallite condensate, and it comprises and has body-centered tetragonal Fe 3The boride phase and the Nd of the rich iron of P type crystal structure 2Fe 14The phase of Type B crystal structure, the average crystalline particle diameter of described crystallite aggregate is 5nm-100nm;
The crystallite aggregate that is produced is ground, and obtaining particle diameter is the alloy powder of 0.1 μ m-100 μ m.
10, a kind of manufacture method that is used for the alloy powder of rare earth magnet comprises step:
Make the molten alloy rapid solidification by the gas atomization that carries out on the roller in rotation, thus make this molten alloy become amorphous state more than 90%;
Alloy to this rapid solidification is heat-treated, and produces the crystallite aggregate, and it comprises and has body-centered tetragonal Fe 3The boride phase and the Nd of the rich iron of P type crystal structure 2Fe 14The phase of Type B crystal structure, the average crystalline particle diameter of described crystallite aggregate is 5nm-100nm;
The crystallite aggregate that forms is like this ground, obtain alloy powder.
11, each described manufacture method that is used for the alloy powder of rare earth magnet in the claim 8,9 and 10, wherein molten alloy has structural formula:
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, and symbol x, y, z and w represent composition range separately, and they satisfy respectively: 0.05≤x≤15 atom %, 16≤y≤22 atom %, 3≤z≤6 atom % and 0.1≤w≤3 atom %.
12, each described manufacture method that is used for the alloy powder of rare earth magnet in the claim 8,9 and 10, wherein, heat treatment is undertaken by following mode, promptly heats up from 500 ℃ of firing rates with 1-15 ℃/minute, keeps 5 minutes to 360 minutes 550-730 ℃ of temperature.
13, a kind of with the described alloy powder that is used for rare earth magnet of claim 3 with the resin-bonded rare-earth bond magnet that forms.
14, the described rare-earth bond magnet of claim 13, wherein, the magnetic property of this rare-earth bond magnet is: iHc 〉=3KOe, Br 〉=5KG and (BH) Max〉=4MGOe.
15, the described rare-earth bond magnet of claim 13 wherein, is resin-bondedly undertaken by any method in compression moulding, injection moulding, extrusion modling, roll-forming or the resin impregnation.
16, the described rare-earth bond magnet of claim 13, wherein, the quantity of the contained alloy powder of rare-earth bond magnet is 70-99.5%(weight).
17, the described rare-earth bond magnet of claim 13, wherein, the quantity of the contained alloy powder of rare-earth bond magnet is 95-99.5%(weight).
18, the described rare-earth bond magnet of claim 13, wherein, the quantity of the contained alloy powder of rare-earth bond magnet is 90-99.5%(weight)
19, the described rare-earth bond magnet of claim 13, wherein, the quantity of the contained alloy powder of magnet of rare-earth bound is 96-99.5%(weight).
20, the manufacture method of the described rare-earth bond magnet of claim 13 comprises with the described processing step that is used for the alloy powder of rare earth magnet of resin-bonded claim 8.
21, the manufacture method of the described rare-earth bond magnet of claim 13 comprises with the described processing step that is used for the alloy powder of rare earth magnet of resin-bonded claim 9.
22, the manufacture method of the described rare-earth bond magnet of claim 13 comprises with the described processing step that is used for the alloy powder of rare earth magnet of resin-bonded claim 10.
23, each described rare-earth bond magnet manufacture method in the claim 20,21 and 22 wherein, is resin-bondedly finished by any method in compression moulding, injection moulding, extrusion modling, roll-forming or the resin impregnation.
CN92114394A 1991-11-11 1992-11-10 Rare earth magnets and alloy powder for rare earth magnets and their manufacturing methods Expired - Lifetime CN1053988C (en)

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