CN104021908A - R-T-B-M-A series rare-earth permanent magnet and manufacturing method thereof - Google Patents
R-T-B-M-A series rare-earth permanent magnet and manufacturing method thereof Download PDFInfo
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Abstract
The invention aims at reducing cost by controlling the appropriate values of nitrogen N and hydrogen H in an R-T-B-M-A series rare-earth permanent magnet. Meanwhile, the residual magnetism density performance Br is not reduced, and the coercivity performance Hcj is improved. Specifically, the R-T-B-M-A series rare-earth permanent magnet is mainly formed by R2T14B type compound. The weight percentage of R is 24%-34%, the weight percentage of T is 63%-74%, the weight percentage of B is 0.5%-1.5%, other ingredients are M and A, the microelement A is H smaller than 10ppm, and the M is smaller than 150ppm. In addition, the rare-earth type permanent magnet materials are easy to smash in the inert gas environment, and the average particle diameter is in a range from 2 mum to 5 mum.
Description
The application is be on 04 02nd, 2010, denomination of invention the applying date for the application number of " R-T-B-M-A based rare earth permanent magnet taking and manufacture method " be the divisional application of 201010142507.2 patent applications.
Technical field
The present invention relates to permanent magnetic material field.Concrete and say, its be rare-earth permanent magnetic material with and manufacture method, relate to the coercitive high-performance rare-earth class permanent magnetic material that do not reduce the residual flux density Br of magnet and greatly improve sintered body with and manufacture method.
Background technology
Follow the development of New Energy Industry and the progress of technology, the application of high performance R-T-B based rare earth permanent magnet (R is at least one in rare earth element, and T is at least one in transitional metallic element, and B is boron) expands worldwide.The new energy field development such as compressor electric motor, hybrid electric vehicle (HybridCar) motor and the generator from the pick-up of the voice coil motor (VCM) of the hard disk drive in existing electronic communication equipment field, CD/DVD, mobile phone, Medical Devices as NMR imaging device (MRI) to wind-driven generator, air-conditioning and the refrigerator in more efficient, energy-conservation dynamo-electric field.Therefore, constantly expand for the demand of high-performance R-T-B series permanent magnetic material, even if especially residual flux density in the situation that serviceability temperature the is high also high and coercive force also requirement of high rare-earth permanent magnetic material is improved.
The key technical indexes of the magnetic characteristic of R-T-B series permanent magnetic material is residual flux density and coercive force.Residual flux density is mainly determined by following factor, 1. forward farmland volume fraction, 2. principal phase (R
2t
14b) or the volume fraction of Magnetic Phase, the 3. degree of orientation of magnetocrystalline grain, the 4. actual density of sintered magnet and the ratio of solid density etc.
The residual flux density that is expressed from the next Br.
Ｂｒ＝Ａ（1－β）（ｄ／ｄ
0）ｃｏｓθ.Ｊｓ
Wherein, A: forward farmland volume fraction, 1-β: the volume fraction of principal phase, d: the actual density of sintered magnet, d
0: the solid density of sintered magnet, cos θ: the degree of orientation of crystal grain, Js:R
2t
14b monocrystal saturated pole intensity.
In addition, coercive force is mainly subject to the impact of quantity and distribution and the demagnetizing factor under the effect of reverse demagnetizing field of the heterogeneous microstructure (size, the shape etc. of such as grain size) of magnetocrystalline anisotropy field (Ha), sintered magnet, rich neodymium phase.
The coercivity H that is expressed from the next j.
Hcj=cHa-N
effMs
Wherein, Ha: magnetocrystalline anisotropy parameter, Ms: saturation magnetization, c: heterogeneous microstructure parameter, N
eff: demagnetizing factor.
Now, although not containing being agglomeration permanent magnetic material residual flux density Br higher (being generally 1.4T) as the Dy of heavy rare earth dvielement and the R-T-B of Tb, coercive force is lower, only has 960kA/m left and right.Therefore, only can in the low and stable environment of serviceability temperature, use, greatly limit the application of permanent magnetic material.And, for the coercive force that improves R-T-B based sintered magnet expands the scope of serviceability temperature, carry out the various improvements such as composition adjustment and crystal grain thinning.
As main the improving one's methods of prior art, adopt heavy rare earth dvielement Dy or the Tb that anisotropy field is higher to carry out partly to replace Nd, improve coercive force and serviceability temperature.For example, adopt the Dy of 5 quality % to carry out the method that part replaces Nd.Like this, although coercive force can be brought up to 1680(kA/m), residual flux density Br is but reduced to 1.28(T).
And, so as the Dy of heavy rare earth class and Tb because be that scarce resource price is high, the method is not suitable for a large amount of production.Especially in the wind-driven generator of the 1MW permanent magnet direct-drive as one of new energy field, the average quality of the permanent magnet of 1 use, for more than 1000kg, has formed very large restraining factors aspect cost.In addition, also have by adding the yttriums such as volume Ga, Nb, Mo and reduce grain size and optimize crystal boundary, thereby improve coercitive method, but this method also causes cost to improve.
In above-mentioned existing rare earth magnet composition distribution ratio, could not bring up to (temperature of environment for use is high) purposes of serviceability temperature condition harshness, for example electric automobile motor and hybrid vehicle motor, the necessary coercive force performance of generator.Aspect the magnet temperature of electric automobile or hybrid vehicle, if electric automobile, need resistance to firmly 150 DEG C, if hybrid vehicle, need resistance to firmly 200 DEG C, if from magnet coercive force aspect, need 1680(KA/m) above material, need in addition residual flux density at 1.28(T) more than.
If heavy rare earth dvielement Dy or Tb are added as additive, although can improve coercive force performance Hcj, but reduce residual flux density Br, this will cause the consequence that reduces motor and generator efficiency.
In addition, in order not reduce residual flux density, be necessary to add the yttriums such as Ga, Nb, Mo, but use owing to carrying out volume using the metallic element of high price as additive, therefore cost increases, want to be applied to electric automobile motor that demand is large and hybrid vehicle motor, generator, consider to implement more difficult from economic face.
Summary of the invention
The object of the invention is to solve these shortcomings, when significantly reduction becomes the Rare Metals Materials of high price of expensive main cause, affect residual flux density Br and the coercive force performance Hcj of motor, generator efficiency by raising, utilize cheaply abundant material and high performance rare earth magnet is provided.
In addition, according to the present invention, also how reduce the heavy rare earth dvielement Dy of high price or the use amount of Tb, can reduce costs.Product of the present invention can be used in the many-sides such as servo motor, linear motor, elevator motor.
The following describes the concrete effect while being applied to electric automobile motor and hybrid vehicle motor, generator.
The motor output characteristic of electric automobile motor or hybrid vehicle motor as shown in Figure 1, from basic rotary speed above, need to follow speed rising and torque reduce stabilized output characteristic.These motor mainly adopt the internal magnetic type permanent magnet synchronous motor (Interior Permanent Magnet type Synchronous Mot or, hereinafter to be referred as IPMSM) (with reference to Fig. 2) of described rare earth magnet uniformly-spaced being imbedded to the rotor core of motor on circumferentially.
As shown in Figure 3, be the current phase angle θ during as benchmark taking magnet magnetic flux axle (d axle) at transverse axis, when the longitudinal axis is torque T, the torque characteristics of this IPMSM is the synthetic torque of magnet torque: Tm and reluctance torque: Tr.
Represent each torque type below.
T＝Tm＋Tr
Tm=τ mcos θ (τ m: the maximum of magnet torque Tm)
Tr=τ rsin(2 θ) (τ r: magnet torque Tr maximum)
, there is magnetic flux and realized the stable output area of motor by reduce magnetic energy that described magnet has with armature flux in being characterized as of this motor.
From the IPMSM structure of Fig. 2, it is upper that described rare earth magnet is configured in magnet magnetic flux axle (d axle), and the magnetic permeability μ r ≒ 1.05 of the rare earth magnet taking R-T-B as principal component, is roughly identical with air magnetic permeability.Compared with the q axle inductance of the d axle inductance while therefore, observation from armature and the axle (q axle) perpendicular to this d axle, become following relation.
Lｄ＜Lq
In the output control of motor, in order to reduce magnetic flux, be certain value by the voltage control between the Terminal of motor of following speed rising and increase, preferably this d axle inductance is large.That is to say the thickness Lm of the magnet that is disposed in rotor core inside little of well.
In the design of motor, this magnet thickness Lm is by the serviceability temperature tm(environment for use temperature of the magnet using) time the field weakening energy Ata of coercive force performance Hcj, armature determine.Because field weakening energy Ata is determined by the output specification of motor, therefore depend on how in magnet serviceability temperature tm(environment for use temperature) the high magnet of the lower coercive force performance Hcj of use.That is to say, if coercive force performance Hcj is low, for resistance to live in the field weakening energy Ata(of armature in order not there is not demagnetize) be necessary to make magnet thickness Lm thickening.
But as mentioned above, if magnet thickness Lm thickening, above-mentioned d axle inductance diminishes, and in order to obtain regulation output characteristic, is necessary to make a lot of reactive currents to circulate in armature, this is by the efficiency characteristic of damaging significantly at the stable domain output of motor.That is to say, by using the high magnet of the present invention of coercive force performance Hcj, can make magnet thickness Lm thinner than existing magnet thickness, therefore can reduce the circulation of described reactive current in armature, and improve the efficiency of stablizing output area, obtain realizing energy-conservation very large effect.
The present invention compared with prior art approximately can improve 25% coercive force performance Hcj, can make the thin thickness 25% of magnet.Its result, owing to approximately can reducing 25% of described reactive current, therefore approximately can be reduced in 35% of the Joule heat loss that occurs in armature winding.
Feature of the present invention is in R-T-B-M-A based rare earth permanent magnetic material, most suitably to set the composition range of micro-A.
The present invention does not add described rare metal, improves the coercive force of magnet by the composition of micro-A being set in to most suitable scope on the basis of the granularity of refinement powder in pulverizing process.
First, the impact on oxygen " O " and the certainty of prescribed limit describe.
The granularity that is controlled so as to powder due to magnetic is very thin, and therefore in sintering process, abnormal growth easily occurs magnet crystal grain.Therefore, in pulverizing process, strictly control oxygen " O " content in magnet, prevent the abnormal growth of crystal grain at the surface of powder formation oxide-film.Therefore, be importantly only used to form oxygen " O " content of oxide-film, be necessary to set certain composition prescribed limit.If excessively put into oxygen, rich neodymium is mutually oxidized, causes coercive force to reduce.
Impact on hydrogen " H " and the certainty of prescribed limit describe.
If hydrogen " H " remains in magnet, in the time that sintering circuit is degassed, there is HDDR(Hydroge n-Disproportionation-Desorption-Recombination) reaction, produce the crystal grain of Nano grade, become the reason of abnormal grain growth in sintering circuit.In order to prevent this phenomenon, in hydrogen treatment process, carry out must strictly controlling vacuum degree after dehydrogenation, make remaining hydrogen " H " be no more than setting.
Below, the impact on nitrogen " N " and the certainty of prescribed limit describe.
If the granularity of magnetic is very thin, also grow of the activity of powder.If carry out powder process using common nitrogen as protection of the environment,, due to when the temperature rise, nitrogen and rare earth element react, and therefore the wetability of Grain-Boundary Phase are played to harmful effect, and coercive force is reduced.Therefore, first in order to make nitrogen " N " below setting, be necessary to implement powder process under the environment that inert gas is changed to argon or helium from nitrogen " N ", improve the coercive force of magnet.
Below, the impact on carbon " C " and the certainty of prescribed limit describe.
If the granularity of magnetic is very thin, powder is easily assembled, and it is difficult that the orientation of powder also becomes.In order to solve such problem, although be necessary to add a large amount of lubricants, powder is disperseed, lubricant is the one in methyl acetate, sad formicester, zinc stearate, lithium stearate, all lubricants are all the organic substances that comprises carbon " C ".Therefore likely increase carbon " C " content in magnet.
If carbon " C " increases, residual flux density Br reduces from certain value, and coercive force also sharply reduces.Therefore be necessary to make carbon " C " in certain prescribed limit.
The present invention is a kind of with R
2t
14type B compound is the R-T-B-M-A based rare earth permanent magnet of main composition, R is at least one in rare earth element, T is at least one in transitional metallic element, B is boron, M is at least one that select in the middle of the group who is made up of Ti, Mn, Ni, Cu, Zn, Al, Si, P, S, A is micro-first number, it is characterized by
R is 24 quality %～34 quality %,
T is 63 quality %～74 quality %,
B is 0.5 quality %～1.5 quality %,
All the other are made up of M and A,
A is by forming below,
The content of H is below 10ppm,
The content of N is below 150ppm,
And the mean particle diameter of pulverized permanent magnetic material is in 2～5 μ m scopes, and under argon or helium environment, pulverize described magnet material.
Brief description of the drawings
Fig. 1 is the motor output characteristic of electric automobile motor or hybrid vehicle motor.
Fig. 2 is the organigram of internal magnetic type permanent magnet synchronous motor (Interior Permanent Magnet type Synchro nous Motor).
Fig. 3 is the torque characteristics of above-mentioned IP MSM.
Fig. 4 is the correlation diagram of N content and residual flux density.
Fig. 5 is N content and coercitive correlation diagram.
Fig. 6 is the correlation diagram of sized particles diameter and residual flux density.
Fig. 7 is sized particles diameter and coercitive correlation diagram.
Fig. 8 is the correlation diagram of O content and residual flux density.
Fig. 9 is O content and coercitive correlation diagram.
Figure 10 is the correlation diagram of C content and residual flux density.
Figure 11 is C content and coercitive correlation diagram.
Figure 12 is the correlation diagram of H content and residual flux density.
Figure 13 is H content and coercitive correlation diagram.
Embodiment
Below, according to embodiment, embodiments of the present invention are described.
And quality status stamp is in the following embodiments represented by quality %, represents the mass ratio of each element in material.In addition, mean particle diameter is as the D50(50% particle diameter of median diameter) represent, each numerical value is the value of measuring by laser diffraction formula particle size distribution device.
Embodiment 1
The making of alloy
In ar gas environment, deposite metal or alloy raw material carry out refining.This alloy is in the constituting body of sintered body R-T-B-M-A,
R is
Nd:22.5 quality %,
Dy:3.5 quality %,
Pr:5.0 quality % forms,
T is
Fe:66.6 quality %,
Co:1.0 quality % forms,
B is
B:1.0 quality %,
M is
Al:0.3 quality %,
The alloy that Cu:0.1 quality % forms.By rapid hardening strip (SC) technique, make alloy molten metal cooled and solidified with water-cooled copper roller, obtain alloy sheet.
Pulverize
Described in coarse crushing after alloy, make hydrogen stove carry out dehydrogenation processing in vacuum state by hydrogenation treatment.Afterwards, use high pressure argon gas the alloy of described coarse crushing to be ground to form to the powder that mean particle diameter is 5.0 μ m left and right in airslide disintegrating mill.In order to prevent abnormal grain growth, in crushing process, pulverize with adding a certain amount of oxygen in inert gas at airslide disintegrating mill.Afterwards, in inert gas, preserve powder.
The interpolation of lubricant
In order to improve the orientation of powder, in powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under argon shield environment.
Moulding
Use the attritive powder of making by described method under inert gas environment, to carry out pressing under magnetic field.Afterwards, under the temperature environment more than 400 DEG C, by the formed body insulation certain hour by described method moulding, afterwards, carry out sintering by sintering circuit and obtain sintered body R-T-B-M-A.
Ageing Treatment
Carrying out, after sintering processes, magnet being carried out to Ageing Treatment.Afterwards, made the sample of the embodiment 1 of diameter 10mm, height 10mm size by machining.
Embodiment 2
Also made the sample of embodiment 2 simultaneously.Embodiment 2 is with the difference of embodiment 1, used helium pulverizing, in the interpolation of lubricant and molding procedure as protection of the environment.
Comparative example 1～3
In addition, in order to verify the effect of embodiment 1 and 2, also made the alloy of comparative example 1, comparative example 2 and comparative example 3.
The alloy manufacture method of comparative example
In nitrogen environment, deposite metal or alloy raw material carry out refining.This alloy is in the constituting body of sintered body R-T-B-M-A,
R is
Nd:21 quality %,
Dy:5.0 quality %,
Pr:5.0 quality % forms,
T is
Fe:66.6 quality %,
Co:1.0 quality % forms,
B is
B:1.0 quality %,
M is
Al:0.3 quality %,
The alloy that Cu:0.1 quality % forms.Make alloy molten metal cooled and solidified by rapid hardening strip technique with water-cooled copper roller, obtain alloy sheet.
Pulverize
Described in coarse crushing after alloy, make hydrogen stove carry out dehydrogenation processing in vacuum state by hydrogenation treatment.Afterwards, use high pressure nitrogen the alloy of described coarse crushing to be ground to form to the powder that mean particle diameter is 5.0 μ m left and right in airslide disintegrating mill.In order to prevent abnormal grain growth, in crushing process, pulverize with adding a certain amount of oxygen in nitrogen at airslide disintegrating mill.Afterwards, in nitrogen, preserve powder.
The interpolation of lubricant
In order to improve the orientation of powder, in powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under nitrogen protection environment.
Moulding
Use the attritive powder of making by described method under nitrogen environment, to carry out pressing under magnetic field.Afterwards, first under the temperature environment more than 400 DEG C, the formed body by described method moulding is incubated to certain hour, afterwards, carries out sintering by sintering circuit and obtain sintered body R-T-B-M-A.
Ageing Treatment
Carrying out, after sintering processes, magnet being carried out to Ageing Treatment.Afterwards, made the magnet of comparative example 1, comparative example 2 and the comparative example 3 of diameter 10mm, height 10mm size by machining.
Comparative example 1 to 3 is that the amount of clear and definite nitrogen N reduces the example exerting an influence to coercitive performance, and comparative example 1 is the nitrogen N=160ppm of " A ", and comparative example 2 is nitrogen N=160ppm, and comparative example 3 is nitrogen N=400ppm.
The analysis result of embodiment 1,2 and comparative example 1～3
The result contrast table of the measurement result of magnetic characteristic and analysis of components is shown in to following table 1 and Fig. 4, Fig. 5 (chart).
Fig. 4 is that the longitudinal axis represents both sides relation as residual flux density using transverse axis as nitrogen N content.Fig. 5 is that the longitudinal axis represents both sides relation as coercive force using transverse axis as nitrogen N content.Can confirm from these figure, be more than 1680kA/m in order to reach as the desired coercive force of high performance permanent magnetism, and need to make nitrogen N is below 150ppm, and now, residual flux density is more than 1.28T.
Table 1
Can obviously find out from table 1, although embodiments of the invention 1 have been cut down the addition of 30% rare rare earth metal Dy compared with comparative example 1, residual flux density there is no variation, and coercive force does not have large difference yet.That is to say, can cut down 30% the rare rare earth metal Dy of high price according to the present invention.
Embodiment 3～5
Alloy is made
Make alloy by the manufacturing process identical with embodiment 1.
Pulverize
The alloy described in coarse crushing by hydrogenation treatment, makes hydrogen stove carry out dehydrogenation processing in vacuum state.Afterwards, till using high pressure argon gas the alloy of described coarse crushing to be ground to mean particle diameter in airslide disintegrating mill to be 4.0,3.0,2.5 μ m left and right.
The mean particle diameter of embodiment 3 is 4.0 μ m, and the mean particle diameter of embodiment 4 is 3.0 μ m, and the mean particle diameter of embodiment 5 is 2.5 μ m.
In order to prevent abnormal grain growth, in crushing process, pulverize with adding a certain amount of oxygen in gas at airslide disintegrating mill, afterwards, in argon gas, preserve powder.
The interpolation of lubricant
In order to improve the orientation of powder, in powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under argon shield environment.Carry out the moulding identical with embodiment 1, sintering, Ageing Treatment and made sample.
Comparative example 4,5
Also made the sample of comparative example 4 and comparative example 5 simultaneously.The difference of comparative example 4 and comparative example 5 and embodiment 3～5 is the mean particle diameter of powder.The mean particle diameter of comparative example 4 is 6.0 μ m, and the mean particle diameter of comparative example 5 is 1.5 μ m.
The result contrast of the measurement result of magnetic characteristic and analysis of components is summarized in to following table 2 and Fig. 6, Fig. 7 (chart).
Fig. 6 is using transverse axis as mean particle diameter, and the longitudinal axis represents both sides relation as residual flux density.Fig. 7 is using transverse axis as mean particle diameter, and the longitudinal axis represents both sides relation as coercive force.Can confirm from these figure, be more than 1680kA/m in order to reach as the desired coercive force of high performance permanent magnetism, and need to make mean particle diameter is 2～5 μ m, and now, residual flux density is more than 1.28T.
Table 2
Can obviously find out from table 2, embodiment 3～5 is compared with ratio 4,5, although the addition of rare earth metal Dy is identical, coercive force has obviously improved.
Embodiment 6～8
Alloy is made
Make alloy by the manufacturing process identical with embodiment 1.
Pulverize
The alloy described in coarse crushing by hydrogenation treatment, makes hydrogen stove carry out dehydrogenation processing in vacuum state.Afterwards, till using high-pressure inert gas the alloy of described coarse crushing to be ground to mean particle diameter in airslide disintegrating mill to be 4.0 about μ m.In order to prevent abnormal grain growth, in crushing process, pulverize with adding a certain amount of oxygen in gas at airslide disintegrating mill, afterwards, in inert gas, preserve powder.
The interpolation of lubricant
In order to improve the orientation of powder, in powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under inert gas shielding environment.
Moulding, sintering, Ageing Treatment
Although adopt the method identical with embodiment 1 to make sample, be with the difference of embodiment 1, in pulverizing process, pulverize with adding a certain amount of oxygen in gas at airslide disintegrating mill, carry out the oxygen content in Control Assay.
Comparative example 6～8
The difference of comparative example 6,7,8 and embodiment 6 is, by the oxygen content control in pulverizing process outside lower limit and the upper limit.
The result contrast table of the measurement result of magnetic characteristic and analysis of components is shown in to following table 3 and Fig. 8, Fig. 9 (chart).
Fig. 8 is that the longitudinal axis represents both sides relation as residual flux density using transverse axis as oxygen O content.Fig. 9 is that the longitudinal axis represents both sides relation as coercive force using transverse axis as oxygen O content.Can confirm from these figure, be more than 1680kA/m in order to reach as the desired coercive force of high performance permanent magnetism, and it is more than 1300ppm need to making oxygen O, and below 2000ppm, now, residual flux density is more than 1.28T.
Table 3
Can obviously find out the square comparative example 6,7 that is better than of magnet of embodiment 6, embodiment 7, embodiment 8 from table 3.In addition, the magnet coercive force of embodiment 6, embodiment 7, embodiment 8 is difference high 182KA/m, 207KA/m, 194KA/m compared with comparative example 7, difference high 235KA/m, 260KA/m, 247KA/m compared with comparative example 8.Like this, fairly obvious, compared with comparative example 6 to 8, the coercive force performance 10%～20% of embodiment 6, embodiment 7, embodiment 8.
Embodiment 9
Alloy is made
Make alloy by the manufacturing process identical with embodiment 1.
Pulverize
Described in coarse crushing after alloy, make hydrogen stove carry out dehydrogenation processing in vacuum state by hydrogenation treatment.Afterwards, till using high pressure argon gas the alloy of described coarse crushing to be ground to mean particle diameter in airslide disintegrating mill to be 3.0 μ m left and right.In order to prevent abnormal grain growth, in crushing process, pulverize with adding a certain amount of oxygen in gas at airslide disintegrating mill, afterwards, in inert gas, preserve powder.
The interpolation of lubricant
In order to improve the orientation of powder, in powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under argon shield environment.
Moulding, sintering, Ageing Treatment
Made the sample of diameter 10mm, height 10mm size by the machining identical with embodiment 1.
Comparative example 9～11
Simultaneously also manufacture the sample of comparative example 9, comparative example 10, comparative example 11.The difference of comparative example 9,10,11 and embodiment 9 is the addition of lubricant.Although select in the one as lubricant from methyl acetate, sad formicester, zinc stearate, lithium stearate, these lubricants are the organic substances that comprise carbon " C ".Therefore, in sintered body, control the amount of this lubricant, make the content of carbon C different be exactly comparative example 9,10,11.
The result contrast of the measurement result of magnetic characteristic and analysis of components is summarized in to following table 4 and Figure 10, Figure 11 (chart).
Figure 10 is that the longitudinal axis represents both sides relation as residual flux density using transverse axis as carbon C content.Figure 11 is that the longitudinal axis represents both sides relation as coercive force using transverse axis as carbon C content.Can confirm from these figure, be more than 1680kA/m in order to reach as the desired coercive force of high performance permanent magnetism, and it is more than 1100ppm need to making carbon C, and below 2000ppm, now, residual flux density is more than 1.28T.
Table 4
Can obviously find out from table 4, embodiment 9 is compared with comparative example 9,10, and magnet residual flux density Br is high 0.08T, 0.07T respectively.In addition, compared with comparative example 11, the high 249KA/m of magnet coercive force.
Embodiment 10～12
Alloy is made
Make alloy by the manufacturing process identical with embodiment 1.
Pulverize
Described in coarse crushing after alloy, make hydrogen stove carry out dehydrogenation processing in vacuum state by hydrogenation treatment.Afterwards, till using high pressure argon gas the alloy of described coarse crushing to be crushed to mean particle diameter in airslide disintegrating mill to be 5.0 μ m left and right.In order to prevent abnormal grain growth, in crushing process, pulverize with adding a certain amount of oxygen in gas at airslide disintegrating mill, afterwards, in argon gas, preserve powder.
Lubricant adds
In order to improve the orientation of powder, in material powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under argon shield environment.
Moulding, sintering, Ageing Treatment
In common operation, make sample in the same manner with embodiment 1.
And the difference of embodiment 10, embodiment 11, embodiment 12 is hydrogen content, by regulating the vacuum degree after dehydrogenation to realize different hydrogen contents.
Comparative example 12
Although make in the same manner the sample of comparative example 12 with embodiment 10, its difference is hydrogen content, by regulating the vacuum degree after dehydrogenation to realize different hydrogen contents.
The result contrast of the measurement result of magnetic characteristic and analysis of components is summarized in to following table 5 and Figure 12, Figure 13 (chart).
Figure 12 is that the longitudinal axis represents both sides relation as residual flux density using transverse axis as hydrogen H content.Figure 13 is that the longitudinal axis represents both sides relation as coercive force using transverse axis as hydrogen H content.Can confirm from these figure, be more than 1680kA/m in order to reach as the desired coercive force of high performance permanent magnetism, and need to make hydrogen H is below 10ppm, and now, residual flux density is more than 1.28T.
Table 5
Can obviously find out from table 5, as shown in embodiment 10,11,12, follow and reduce hydrogen H content, coercive force has improved respectively 112KA/m, 88KA/m, 84KA/m with respect to comparative example 12.
Embodiment 13
Alloy is made
Make alloy by the manufacturing process identical with embodiment 1.
Pulverize
The alloy described in coarse crushing by hydrogenation treatment, makes hydrogen stove carry out dehydrogenation processing in vacuum state.Afterwards, till using high pressure argon gas the alloy of described coarse crushing to be crushed to mean particle diameter in airslide disintegrating mill to be 3.5 μ m left and right.In order to prevent abnormal grain growth, in pulverizing process, pulverize with adding a certain amount of oxygen in gas at airslide disintegrating mill, afterwards, in argon gas, preserve powder.
Lubricant adds
In order to improve the orientation of powder, in material powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under argon shield environment.
Moulding, sintering, Ageing Treatment
Made the sample of diameter 10mm, height 10mm size by the machining identical with embodiment 1.
Comparative example 13,14
Also make the sample of comparative example 13 and comparative example 14 simultaneously.
The alloy manufacture method of comparative example 13
In vacuum or inert gas (argon gas is most suitable) environment, deposite metal or alloy raw material carry out refining.This alloy in the constituting body of sintered body R-T-B-M-A,
R is
Nd:22.5 quality %,
Dy:3.5 quality %,
Pr:5.0 quality % forms,
T is
Fe:66.35 quality %,
Co:1.0 quality % forms,
B is
B:1.0 quality %,
M is
Al:0.3 quality %,
Cu:0.1 quality % forms,
Other be
Ga:0.15 quality %,
Nb:0.05 quality %,
The alloy that Mo:0.05 quality % forms.Make alloy molten metal cooled and solidified by rapid hardening strip technique with water-cooled copper roller, obtain alloy sheet.
Pulverize
Described in coarse crushing after alloy, make hydrogen stove carry out dehydrogenation processing in vacuum state by hydrogenation treatment.Afterwards, use high pressure nitrogen the alloy of described coarse crushing to be ground to form to the powder that mean particle diameter is 6.0 μ m left and right in airslide disintegrating mill.In order to prevent abnormal grain growth, in crushing process, pulverize with adding a certain amount of oxygen in inert gas at airslide disintegrating mill.Afterwards, in nitrogen, preserve powder.
The interpolation of lubricant
In order to improve the orientation of powder, in powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under argon shield environment.
Moulding, sintering, Ageing Treatment
Make the sample of diameter 10mm, height 10mm size by the machining identical with embodiment 1.
The alloy manufacture method of comparative example 14
In vacuum or inert gas (argon gas is most suitable) environment, deposite metal or alloy raw material carry out refining.This alloy in the constituting body of sintered body R-T-B-M-A,
R is
Nd:21.5 quality %,
Dy:4.5 quality %,
Pr:5.0 quality % forms,
T is
Fe:66.45 quality %,
Co:1.0 quality % forms,
B is
B:1.0 quality %,
M is
Al:0.3 quality %,
Cu:0.1 quality % forms,
Other be
Ga:0.05 quality %,
Nb:0.05 quality %,
The alloy that Mo:0.05 quality % forms.Make alloy molten metal cooled and solidified by rapid hardening strip technique with water-cooled copper rod, obtain alloy sheet.
Pulverize
Described in coarse crushing after alloy, make hydrogen stove carry out dehydrogenation processing in vacuum state by hydrogenation treatment.Afterwards, use high pressure nitrogen the alloy of described coarse crushing to be ground to form to the powder that mean particle diameter is 8.0 μ m left and right in airslide disintegrating mill.In order to prevent abnormal grain growth, in crushing process, pulverize with adding a certain amount of oxygen in inert gas at airslide disintegrating mill.Afterwards, in nitrogen, preserve powder.
The interpolation of lubricant
In order to improve the orientation of powder, in powder mixer, add a certain amount of lubricant.The process of sneaking into of lubricant is carried out under argon shield environment.
Moulding, sintering, Ageing Treatment
Make the sample of diameter 10mm, height 10mm size by the machining identical with embodiment 1.
The result contrast of the measurement result of magnetic characteristic and constituent analysis is summarized in to following table 6.
Table 6
Can obviously find out from table 6, reduce mean particle diameter and have and make the amount of Ga, Nb, Mo few, and also reduce the effect of metal Dy use amount.
The in the situation that of embodiment 13, although significantly reduce rare metal Ga, Nb, magnet coercive force has improved respectively 126KA/m, 88KA/m compared with comparative example 13 and comparative example 14, and residual flux density has improved 0.01T, 0.02T.
Effect of the present invention is arranged in table 7.
Table 7
As shown in table 7, the effect of the present embodiment is for having the following advantages,
About yttrium (Ga, Nb, Mo), with respect to comparative example, Ga can reduce to below 1/40～1/150, and Nb can reduce to below 1/50, and Mo can reduce to below 1/5.
About high price rare earth element Dy, there is the effect that reduces by 20% left and right.
The present invention can provide and not improve material cost, does not reduce again the residual flux density Br that affects motor, generator efficiency and the rare earth magnet that can improve coercive force performance Hcj.
In addition, the present invention is by making micro-A in the prescribed limit as shown in embodiment 1～13, can make the amount of the yttriums such as Ga, Nb, Mo few, do one's utmost to reduce the input amount of rare rare earth element, can significantly improve stable supplying and the cost of magnet.
Claims (2)
1. one kind with R
2t
14type B compound is the R-T-B-M-A based rare earth permanent magnet of main composition, R is at least one in rare earth element, T is at least one in transitional metallic element, B is boron, M is at least one that select in the middle of the group who is made up of Ti, Mn, Ni, Cu, Zn, Al, Si, P, S, A is micro-first number, it is characterized by
R is 24 quality %～34 quality %,
T is 63 quality %～74 quality %,
B is 0.5 quality %～1.5 quality %,
All the other are made up of M and A,
Described A's is composed as follows,
The content of H is below 10ppm,
The content of N is below 150ppm,
The mean particle diameter of described rare-earth permanent magnetic material powder is in 2～5 μ m scopes.
2. the manufacture method of rare-earth permanent magnet according to claim 1, is characterized by, and implements the pulverizing process of described rare-earth permanent magnetic material under argon gas or helium environment.
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