CN106298133A - Permanent magnet material based on the primary norium of common association and its preparation method and application - Google Patents
Permanent magnet material based on the primary norium of common association and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of double principal phase permanent magnet materials based on the primary norium of common association and its preparation method and application, consisting of: (RMaFe100-a-b-cMbBc)1-x{[(Pr1-yNdy)1-zRz]dFe100-d-e-fMeBf}x, described permanent magnet material includes RMaFe100-a-b-cMbBc[(Pr1-yNdy)1-zRz]dFe100-d-e-fMeBfTwo kinds of principal phases, wherein, RMFor the primary norium of common association, its quality composition includes: 20%～32%La, 48%～58%Ce, 4%～6%Pr and 15%～17%Nd；M is one or more in Mn, Co, Ni, Zr, Ti, Cu, Zn, Al, Ga, In, Sn, Ge and Si；R is one or more in Y, La, Ce, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.Owing to the permanent magnet of the present invention is cheap, and comprehensive permanent magnetism excellent performance, therefore there is using value widely.
Description
Technical field
The present invention relates to a kind of permanent magnet material based on the primary norium of common association and preparation thereof
Methods and applications.
Background technology
Neodymium iron boron has high remanent magnetism B as third generation rare earth permanent-magnetic materialr, high-coercive force Hcj, high magnetic energy
Long-pending (BH)mFeature, be applied to the high-tech sectors such as Aero-Space, information and the energy, be
One of important foundation material of modern industry.But it is as being continuously increased of whole world neodymium iron boron demand, rare earth
The use of element neodymium is also greatly increased, thus cause neodymium metal account for the 90% of the neodymium iron boron cost of raw material with
On.The biggest pressure is caused to magnetic materials production producer and user.And owing to rare earth is intergrowth mineral,
Therefore on the one hand cause La, Ce, Y contour rich the demand of the narrow resources such as Pr, Nd, Tb, Dy
The a large amount of of degree rare earth overstock, and cause the waste of rare earth resources.On the other hand, dilute from the primary mixing of common association
Earth metal extracts and separates single high pure rare earth metals complex process, not only consume the substantial amounts of energy and money
Source, and serious increase carrying capacity of environment.
If can directly use the primary norium of common association substitute separated single Pr, Nd,
The high pure rare earth metals such as Tb, Dy prepare permanent magnet, then the rare earth being possible not only to significantly reduce or remit complexity carries
Pure procedure, the reduction energy and the consumption of resource, reduction cost, and China's rare earth money can be substantially solved
The balanced use problem in source, alleviates carrying capacity of environment, has very important using value and strategic importance.
At present, much to reduce cost, research without heavy rare earth or few neodymium metal have been obtained for attention
(CN102436892A, CN102800454A, CN102969112A, CN103137314A, CN
103035350A).In conjunction with the feature of China's rare earth resources, with Ce and the LaCe alloy that reserves are the abundantest
Or mischmetal (LaCePrNd) substitutes single Nd and becomes the focus of at present research, but due to
La2Fe14B and Ce2Fe14B has far below Nd2Fe14The anisotropy field of B, and it is difficult to into phase.
Therefore, in actual production, the replacement of Rare-Earth Ce or La all can cause the decline of permanent magnet performance,
Particularly when the replacement amount of La or Ce is more than 60%, and magnet cost performance is extremely low, without practical value
(JOURNAL OF APPLIED PHYSICS 115,113912(2014)。
Although using melt spinning technology (belt-rejecting technology) that the permanent magnet material that performance is slightly higher can be obtained
(JOURNAL OF APPLIED PHYSICS 111,07A718 (2012)), but the most this
Magnetism of material can be the lowest, and on the other hand, this magnet is a kind of thin slice (shape is fixed), no
Can widespread adoption.Therefore, how to prepare high performance association primary norium base altogether to sinter forever
Magnet is still problem the most in the urgent need to address.
2007 Nian Zhong section three rings (CN 101471165B) use the mode of dual alloy to be prepared for having height
The permanent magnet that coercivity and remanent magnetism decline hardly, allows it is seen that the advantage of dual alloy.2012
Iron and Steel Research Geueral Inst (CN 102800454A, CN 103187133A, CN 103714939A) is again
Disclose double principal phase or many principal phases magnet and manufacture method thereof respectively, and foretell by method made above
The permanent magnet of excellent combination property can be prepared.
Typically, why double (many) principal phase magnet combination properties are higher than single principal phase magnet, except
Outside " mixing " effect that it shows, the coupling between magnet is an important reason, therefore makes
The single principal phase magnet performance substituting the preparations such as Nd by high abundance rare earth or mischmetal part is the highest,
The effect of 1+1 ＞ 2 can not be realized.Although and using double principal phase magnet can obtain the raising (CN of performance
102800454A), but to be an up effect the most inconspicuous.Currently used high abundance rare earth or mix dilute
In double principal phase magnets of soil preparation, be all need by the other rare earth element of interpolation by high abundance rare earth or
Mischmetal is first prepared as single principal phase magnet, is prepared as double principal phase magnet the most again with another principal phase, and
The most directly use La, Ce or mischmetal (MM) iron boron magnet as the principal phase of one of them.
Although this method be conducive to magnet preparation process realization (preparation process that can be new, directly
Continue to use the preparation method of single principal phase), but reduce this pair of principal phase magnet the most to a certain extent
Coupling advantage, is unfavorable for the lifting of magnet combination property and effective utilization of rare earth resources.
Summary of the invention
In order to overcome prior art not enough, the present invention provides a kind of association primary norium base altogether
Double principal phase permanent magnet materials and preparation method thereof, this permanent magnet material is with common association primary mischmetal gold
Belong to and prepare permanent magnet for base, the most cheap, the beneficially balance profit of environmental conservation and rare earth resources
With, and one of them principal phase comprises only the primary norium of common association and without other rare earth
Element, is conducive to improving the coupling advantage of double principal phase magnet and the raising of magnet comprehensive magnetic energy.
For the ease of describing, following title or term are defined and illustrate:
1, preparation raw material: use ball blast, the mode of polishing to remove the oxide layer on raw material surface,
And weigh raw material in proportion.
2, preparation rapid-hardening flake: after the raw material mixing that will weigh up in proportion, put into ZGSN-0.003 type
Crucible in vacuum induction rapid hardening furnace, is heated to all raw material under argon shield and melts, then drop
Temperature keeps it in 1200～1600 DEG C, finally by water-cooled that solution-cast to linear velocity is 1～5 meter per seconds
On copper roller, it is prepared as the rapid-hardening flake that thickness is 0.1～0.5mm.
3, hydrogen crushes: rapid-hardening flake is put into hydrogen broken furnace, is first evacuated down to below 5Pa, then fills
Enter the H of about 0.2Mpa2, supplement H at any time2, make H2Pressure substantially remains in the pressure of 0.2Mpa
Under, at room temperature inhale hydrogen 1～2 hours, be then evacuated down to below 5Pa, 200～600 DEG C of dehydrogenations
1～2 hour, obtain hydrogen and break powder.
4, airflow milling: raw material to be ground (generally hydrogen breaks powder) is put into QLM-100T type air-flow
Grinding machine, under the oxygen content content less than 0.1ppm, carries out airflow milling, by regulation selecting crude drugs with winnower wheel speed
Degree obtains the air-flow pulverizing that particle mean size is 1～5 μm.
In order to realize goal of the invention, the technical scheme is that
A kind of double principal phase permanent magnet materials based on the primary norium of common association, its elemental composition presses matter
Amount ratio is (RMaFe100-a-b-cMbBc)1-x{[(Pr1-yNdy)1-zRz]dFe100-d-e-fMeBf}x, described permanent magnet material bag
Include RMaFe100-a-b-cMbBc[(Pr1-yNdy)1-zRz]dFe100-d-e-fMeBfTwo kinds of principal phases, wherein, RMIt is common
The primary norium of association, its quality composition includes: 20～32%La, 48～58%Ce, 4～6%Pr
With 15～17%Nd；M is Mn, Co, Ni, Zr, Ti, Cu, Zn, Al, Ga, In, Sn, Ge
With one or more in Si；R is Y, La, Ce, Eu, Gd, Tb, Dy, Ho, Er, Tm,
One or more in Yb and Lu, and 27≤a≤33,0≤b≤5,0.9≤c≤1.3,0.1≤x≤0.9,0≤y≤1,
0≤z≤0.1,28≤d≤32,0≤e≤5,0.9≤f≤1.2.
Preferably, in described double principal phase permanent magnet materials, the span of x is: 0.4≤x≤0.9, more excellent
Elect 0.6≤x≤0.9 as.
The double principal phase permanent magnet materials provided according to the present invention, wherein, described " the primary mischmetal of association altogether
Metal " refer to from the primary Rare Earth Mine of common association extract without Rare Earth Elements Determination separate, rare earth is joined
Divide the norium keeping consistent with raw ore.The primary norium of common association for the present invention
It can be the primary norium of common association from baiyuneboite.
In the described altogether primary norium of association, it is also possible to include following component: Sm < 0.5%,
Fe < 0.04%, Si < 0.02%, Mg < 0.06%, Zn < 0.01%, W < 0.01%, Mo < 0.01%,
Cu < 0.01%, Ti < 0.01%, Ca < 0.01%, Pb < 0.01%, Cr < 0.01%, C < 0.01%.
Preferably, described double principal phase permanent magnet materials can be the one in following material:
(RM32Fe63Zr3Al0.9B1.1)30((Pr0.4Nd0.6)30Fe67Al2B1)70；
(RM32Fe66Al1B1)10((Nd0.97Dy0.03)30Fe69B1)90；
(RM31Fe63Zr2Al1Si2B1)40((Pr0.2Nd0.8)31Fe67Co1B1)60；
(RM33Fe62Zr1Al1.8Si1B1.2)60((Pr0.2Nd0.8)32Fe66Ga0.8Sn0.2B1)40。
The present invention also provides for the preparation method of above-mentioned permanent magnet material, and described method comprises the steps:
(1) R is prepared respectivelyMaFe100-a-b-cMbBcAnd ((Pr1-yNdy)1-zRz)dFe100-d-e-fMeBfTwo kinds of masters
Phase alloy, and make the rapid-hardening flake that thickness is 0.1～0.5mm, then crush through hydrogen and obtain 1～3mm
Hydrogen breaks powder (width is 1～3mm, and thickness is the flap-type powder of 0.1～0.5mm)；
(2) by RMaFe100-a-b-cMbBcHydrogen breaks powder and ((Pr1-yNdy)1-zRz)dFe100-d-e-fMeBfHydrogen breaks powder
According to the ratio mix homogeneously that mass ratio is 10:90～90:10, put into airflow milling and make particle mean size and be
The air-flow pulverizing of 1～5 μm；
(3) by air-flow pulverizing under the protection of noble gas, oriented moulding in the magnetic field of 0.5～2T；
(4) magnet being orientated is put into hot isostatic press, under the isostatic pressure of 50～400MPa,
At a temperature of the isostatic pressed of 400 DEG C～1100 DEG C, suppress 0.01～4h.
The preparation method provided according to the present invention, it is preferable that in step (1), RMaFe100-a-b-cMbBc:
((Pr1-yNdy)1-zRz)dFe100-d-e-fMeBfMass component be 10:90～60:40 than scope.
The preparation method provided according to the present invention, it is preferable that the high temperature insostatic pressing (HIP) power in step (4) is
50～200Mpa；Preferably, hip temperature is 650～1040 DEG C；Preferably, during high temperature insostatic pressing (HIP)
Between be 0.5～2h.
The preparation method provided according to the present invention, wherein, described preparation method can also include step (5):
Magnet after compressing for step (4) is put into the sintering at 800～1060 DEG C in the sintering furnace of fine vacuum
At a temperature of sinter 0.01～2 hour.
The preparation method provided according to the present invention, wherein, described preparation method can also include step (6):
Sintered body step (5) obtained is tempered 0.01～2h at a temperature of 200～500 DEG C.
Present invention also offers above-mentioned pair of principal phase permanent magnet material or the double masters prepared according to the inventive method
Phase permanent magnet material is at instrument and meter, household electrical appliances, motor, wind-power electricity generation, Aero-Space, mobile phone, logical
Application in letter equipment, rotating machinery, magnetotherapy appliance and sports goods.
Compared to La, Ce or MM base sintered rare-earth permanent magnetic material of preparation at present, the present invention uses not
Permanent magnet is prepared, therefore raw material process through the common association primary norium raw material of rare earth purification processes
Simply, few to the energy and resource consumption, cheap, and beneficially environmental conservation and rare earth resources
Balanced use.Further, since one of them principal phase in double principal phase magnets of preparing of the present invention comprises only altogether
The primary norium of association and without other rare earth element, therefore improve the coupling of double principal phase magnet
Conjunction advantage, thus add the comprehensive magnetic energy of magnet.Again, use due to the preparation method of the present invention
Be conducive to the special hot isostatic pressing of double principal phase magnets, not only simplify preparation process, Er Qiejin
One step improves magnetic property.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further described in detail, the enforcement be given
Example is only for illustrating the present invention rather than in order to limit the scope of the present invention.
The mischmetal R used in following exampleMBuy from Suzhou Kang Ming Chemical Co., Ltd., its
Chemical composition is about in mass ratio: 27.8%La, 51.9%Ce, 5.1%Pr and 15.1%Nd, remaining
For impurity such as Sm, Fe, Si, Al, C.
Embodiment 1
(1) two kinds of master alloying R of preparationM32Fe63Zr3Al0.9B1.1(Pr0.4Nd0.6)30Fe67Al2B1, two kinds
Master alloying gross mass is 2.5Kg, is prepared as the rapid-hardening flake that thickness is 0.3mm respectively.
(2) above two master alloying is crushed respectively through hydrogen, obtain granularity and be evenly distributed about 1～3mm
Granule, airflow milling powder the most respectively, obtain particle mean size and be about the granule of 2 μm.
(3) R in mass ratioM32Fe63Zr3Al0.9B1.1: (Pr0.4Nd0.6)30Fe67Al2B1For 30:70's
Ratio mixes above air-flow pulverizing, and weighs wherein 10g, puts into the magnetic field orientating of argon shield after sealing
In mould, oriented moulding (pressure is about 20MPa) under the magnetic field of 1.5T.
(4) magnet after molding is put into hot isostatic press under the isostatic pressure of 150MPa, at 700 DEG C
At a temperature of, suppress 0.5 hour, then quickly cooled down by built-in cooler.
(5) magnet after hip moulding is put in the sintering furnace of fine vacuum and sinter, sintering temperature
1000 DEG C, sinter 0.5 hour, air-cooled to room temperature.
(6) magnet after sintering is tempered latter 2 hours at 490 DEG C, i.e. obtains double principal phases of the present embodiment
Permanent magnet material.
The materials processing prepared is become the small column of Φ 10mm × 10mm, and at NIM-2000HF
(measurement temperature is room temperature to the permanent magnetism performance of the permanent magnetism B-H hysteresiscope measurement magnet of type, about
20～22 DEG C, following example are identical).Test result is listed in table 1.
As seen from Table 1, double principal phase magnet performances that the present embodiment prepares are excellent, altogether
In the case of the primary content of rare earth of association 30%, magnet coercivity is more than 10kOe, and magnetic energy product is more than 40
MGOe, it is already possible to realize reality application.
Comparative example 1
According to the double principal phase magnet of step preparation same as in Example 1, difference is, does not carry out reality
Execute the step (4) described in example 1, and step (4) is changed into: implement cold under the pressure of 150Mpa
Isostatic pressed processes.The test result of the material that this comparative example prepares is also found in table 1.
By carrying out contrasting with embodiment 1 it can be seen that the high temperature insostatic pressing (HIP) step in embodiment 1 is replaced
After the isostatic cool pressing step of this comparative example, the magnetic property of material declines to a great extent.
Comparative example 2
According to the double principal phase magnet of step preparation same as in Example 1, difference is, step (4)
For: under the pressure of 150Mpa, implement isostatic cool pressing process；And step (5) is: by step (4)
Magnet after process is put in the sintering furnace of fine vacuum and is sintered, and sintering temperature 1000 DEG C sinters 8 hours,
Air-cooled to room temperature.The test result of the material that this comparative example prepares is also found in table 1.
By carrying out contrasting with embodiment 1 it can be seen that the high temperature insostatic pressing (HIP) step in embodiment 1 is replaced
After the isostatic cool pressing step of this comparative example, even if increasing sintering time, the magnetic property of material still can be big
Width declines.
Comparative example 3
According to the double principal phase magnet of step preparation same as in Example 1, difference is, step (4)
For: under the pressure of 150Mpa, implement isostatic cool pressing process；And step (5) is: by step (4)
Magnet after process is put in the sintering furnace of fine vacuum and is sintered, and sintering temperature 1040 DEG C sinters 2 hours,
Air-cooled to room temperature.The test result of the material that this comparative example prepares is also found in table 1.
By carrying out contrasting with embodiment 1 it can be seen that the high temperature insostatic pressing (HIP) step in embodiment 1 is replaced
After the isostatic cool pressing step of this comparative example, by regulation sintering temperature, sintering time also can reach preferable
Magnetic property, but compared to embodiment 1 result, its magnetic property is the most relatively low.
Comparative example 4
Preparing magnet according to step same as in Example 1, difference is, step (1) is for joining
Make single main-phase alloy (RM32Fe63Zr3Al0.9B1.1)30[(Pr0.4Nd0.6)30Fe67Al2B1]70Rather than separately
The alloy of two kinds of principal phases of preparation；And step (2) is for by this single main-phase alloy hydrogen is broken and air-flow grinds
Powder obtains the granule that particle mean size is 2 μm.The test result of the material that this comparative example prepares is also found in table 1.
By carrying out contrasting with embodiment 1 it can be seen that do not use double principal phase magnet, but pass through element
The mode substituted is prepared as single principal phase, even if using hot isostatic pressing technique, increasing its magnetic property (can be referring to
Comparative example 5), its magnetic property is also much lower than double principal phase magnet performances.
Comparative example 5
Preparing magnet according to step same as in Example 1, difference is, step (1) is for joining
Make single main-phase alloy (RM32Fe63Zr3Al0.9B1.1)30[(Pr0.4Nd0.6)30Fe67Al2B1]70Rather than separately
The alloy of two kinds of principal phases of preparation；Step (2) is for by this single main-phase alloy hydrogen is broken and airflow milling powder obtains
To the granule that particle mean size is 2 μm；Step (4) is: implement cold etc. quiet under the pressure of 150Mpa
Pressure processes；And step (5) is: the magnet after step (4) being processed puts into the sintering furnace of fine vacuum
Middle sintering, sintering temperature 1040 DEG C, sinter 2 hours, air-cooled to room temperature.The material that this comparative example prepares
Test result be also found in table 1.
By carrying out contrasting with embodiment 1 and comparative example 4 it can be seen that even for single principal phase magnet,
Hip treatment replacing with isostatic cool pressing process, its magnetic property also can decrease, and this also illustrates heat
Isostatic pressing technology is also applied for single principal phase magnet.But compared to double principal phase magnets, this replacement is to magnetic
The impact of energy is smaller.
Comparative example 6
(1) two kinds of master alloying R of preparation the most in mass ratioM16Pr16Fe63Zr3Al0.9B1.1And
(RM0.22Pr0.18Nd0.6)30Fe67Al2B1, the gross mass of two kinds of master alloyinies is 2.5Kg, then distinguishes
It is prepared as the rapid-hardening flake that thickness is 0.3mm；
(2) rapid-hardening flake of step (1) is crushed respectively through hydrogen, obtain particle mean size and be about 1～3mm
Granule, airflow milling powder the most respectively, obtain particle mean size and be about the granule of 2 μm.
(3) R in mass ratioM16Pr16Fe63Zr3Al0.9B1.1: (RM0.22Pr0.18Nd0.6)30Fe67Al2B1
Ratio for 30:70 mixes above air-flow pulverizing, and weighs wherein 10g, puts into argon and protect after sealing
In the magnetic field orientating mould protected, oriented moulding (pressure is about 20MPa) under the magnetic field of 1.5T.
(4) magnet after molding is put into hot isostatic press under the isostatic pressure of 150MPa,
At a temperature of 700 DEG C, suppress 0.5 hour, then quickly cooled down by built-in cooler.
(5) magnet after hip moulding is put in the sintering furnace of fine vacuum and sinter, sintering temperature
Spend 1000 DEG C, sinter 0.5 hour, air-cooled to room temperature.
(6) magnet after sintering is tempered the rear magnet just obtaining this comparative example for 2 hours at 490 DEG C.
The above-mentioned sintered magnet prepared is processed into Φ 10mm × 10mm small column exist
(measure temperature is the permanent magnetism performance of the permanent magnetism B-H hysteresiscope measurement magnet of NIM-2000HF type
Room temperature, about 20～22 DEG C).Test result is also found in table 1.
By the contrast with embodiment 1, by the data in table 1 it can be seen that use Pr part to replace
For RM, coupling can be weakened in the case of identical content of rare earth and interact, ultimately cause magnet
The decline of energy.
Embodiment 2
According to the double principal phase magnet of step preparation same as in Example 1, difference is, step (4)
For: the magnet after molding is put into hot isostatic press under the isostatic pressure of 120MPa, at 900 DEG C
At a temperature of, suppress 0.5 hour, then quickly cooled down by built-in cooler；And do not carry out step (5)
(6).Test result is listed in table 1.
As long as by the data in table 1 it can be seen that the temperature implemented of high temperature insostatic pressing (HIP), time are suitable, without
Later the sintering of phase, tempering, and directly prepare magnet and be not result in being remarkably decreased of magnetic property.This for
It is very favorable for reducing preparation time.
Embodiment 3
(1) two kinds of master alloying R of preparationM32Fe66Al1B1(Nd0.97Dy0.03)30Fe69B1, two kinds of master alloyinies
Gross mass is 2.5Kg, is respectively prepared the rapid-hardening flake of 0.3mm.
(2) above two master alloying is crushed respectively through hydrogen, obtain average particle size distribution and be about 1～3mm
Granule, airflow milling powder the most respectively, obtain particle mean size and be respectively 1.5 μm and the air-flow of 3 μm
Abrasive particle.
(3) R in mass ratioM32Fe66Al1B1: (Nd0.97Dy0.03)30Fe69B1Ratio for 10:90 is mixed
Close above air-flow pulverizing, and weigh wherein 10g, put in the magnetic field orientating mould of argon shield after sealing,
Oriented moulding (pressure is about 20MPa) under the magnetic field of 1.5T.
(4) magnet after molding is put into hot isostatic press under the isostatic pressure of 100MPa,
At a temperature of 1040 DEG C, suppress 0.5 hour, then quickly cooled down by built-in cooler.
The above-mentioned magnet prepared is processed into Φ 10mm × 10mm small column in BH loop instrument
Testing, test result is listed in table 1.
Embodiment 4
(1) two kinds of master alloying R of preparationM31Fe63Zr2Al1Si2B1(Pr0.2Nd0.8)31Fe67Co1B1, two kinds
Master alloying gross mass is 2.5Kg, is respectively prepared the rapid-hardening flake of 0.3mm.
(2) above two master alloying is crushed respectively through hydrogen, obtain average particle size distribution and be about 1～3mm
Granule, airflow milling powder the most respectively, obtain particle mean size and be respectively 2 μm and the airflow milling of 3 μm
Granule.
(3) R in mass ratioM31Fe63Zr2Al1Si2B1: (Pr0.2Nd0.8)31Fe67Co1B1For 40:60's
Ratio mixes above air-flow pulverizing, and weighs wherein 10g, puts into the magnetic field orientating of argon shield after sealing
In mould, oriented moulding (pressure is about 20MPa) under the magnetic field of 1.5T.
(4) magnet after molding is put into hot isostatic press under the isostatic pressure of 200MPa, at 970 DEG C
At a temperature of, suppress 0.8 hour, then quickly cooled down by built-in cooler.
The above-mentioned magnet prepared is processed into Φ 10mm × 10mm small column in BH loop instrument
Testing, test result is listed in table 1.
Embodiment 5
(1) preparation RM33Fe62Zr1Al1.8Si1B1.2(Pr0.2Nd0.8)32Fe65Ga0.8Sn0.2Co1B1Two kinds of masters
Alloy, gross mass is 2.5Kg, is respectively prepared the rapid-hardening flake of 0.3mm.
(2) above two master alloying is crushed respectively through hydrogen, obtain average particle size distribution and be about 1～3mm
Granule, airflow milling powder the most respectively, obtain particle mean size and be respectively 2 μm and the airflow milling of 3 μm
Granule.
(3) R in mass ratioM33Fe62Zr1Al1.8Si1B1.2: (Pr0.2Nd0.8)32Fe65Ga0.8Sn0.2Co1B1For
The ratio of 60:40 mixes above air-flow pulverizing, and weighs wherein 10g, puts into argon shield after sealing
In magnetic field orientating mould, oriented moulding (pressure is about 20MPa) under the magnetic field of 2T.
(4) magnet after molding is put into hot isostatic press under the isostatic pressure of 50MPa, at 650 DEG C
At a temperature of, suppress 2 hours, then quickly cooled down by built-in cooler.
The above-mentioned magnet prepared is processed into Φ 10mm × 10mm small column in BH loop instrument
Testing, test result is listed in table 1.
Table 1
As long as by the result of embodiment 3-5 it can be seen that keep two kinds of principal phases, and in one of them principal phase
Rare earth element comprises only RM, can be transferred through regulating preparation process and obtain the sintered magnet of excellent performance, as
Fruit can be in conjunction with hot isostatic pressing, and its magnetic property can improve further.
Technical scheme has been described in detail by embodiment described above, it should be understood that with
The upper described specific embodiment being only the present invention, is not limited to the present invention, every of the present invention
Meet the technical scheme of condition of the present invention, the present invention, embodiment numerous to list herein can be realized；All
Any amendment made in spirit of the present invention, supplementary or similar replacement, should be included in the present invention
Protection domain within.
Claims (9)
1. a double principal phase permanent magnet material based on the primary norium of common association, its composition is by matter
Amount ratio is: (RMaFe100-a-b-cMbBc)1-x{[(Pr1-yNdy)1-zRz]dFe100-d-e-fMeBf}x, described permanent magnet material
Including RMaFe100-a-b-cMbBc[(Pr1-yNdy)1-zRz]dFe100-d-e-fMeBfTwo kinds of principal phases, wherein, RM
For the primary norium of common association, its quality composition includes: 20%～32%La, 48%～58%Ce,
4%～6%Pr and 15%～17%Nd；M is Mn, Co, Ni, Zr, Ti, Cu, Zn, Al, Ga,
One or more in In, Sn, Ge and Si；R is Y, La, Ce, Eu, Gd, Tb, Dy,
One or more in Ho, Er, Tm, Yb and Lu, and 27≤a≤33,0≤b≤5,0.9≤c≤1.3,
0.1≤x≤0.9,0≤y≤1,0≤z≤0.1,28≤d≤32,0≤e≤5,0.9≤f≤1.2.
The most according to claim 1 pair of principal phase permanent magnet material, wherein, the span of x is:
0.4≤x≤0.9, preferably 0.6≤x≤0.9.
The most according to claim 1 and 2 pair of principal phase permanent magnet material, wherein, described double principal phases
Permanent magnet material can be the one in following material:
(RM32Fe63Zr3Al0.9B1.1)30((Pr0.4Nd0.6)30Fe67Al2B1)70；
(RM32Fe66Al1B1)10((Nd0.97Dy0.03)30Fe69B1)90；
(RM31Fe63Zr2Al1Si2B1)40((Pr0.2Nd0.8)31Fe67Co1B1)60；
(RM33Fe62Zr1Al1.8Si1B1.2)60((Pr0.2Nd0.8)32Fe66Ga0.8Sn0.2B1)40。
4. the preparation method of double principal phase permanent magnet materials, described system according to any one of claims 1 to 3
Preparation Method comprises the following steps:
(1) R is prepared respectivelyMaFe100-a-b-cMbBcAnd ((Pr1-yNdy)1-zRz)dFe100-d-e-fMeBfTwo kinds of masters
Phase alloy, and make the rapid-hardening flake that thickness is 0.1～0.5mm, then obtain particle mean size and be through hydrogen is broken
The hydrogen of 1～3mm breaks powder；
(2) by RMaFe100-a-b-cMbBcHydrogen breaks powder and ((Pr1-yNdy)1-zRz)dFe100-d-e-fMeBfHydrogen breaks powder
According to the ratio mix homogeneously that mass ratio is 10:90～90:10, put into airflow milling and make particle mean size and be
The air-flow pulverizing of 1～5 μm；
(3) by air-flow pulverizing under the protection of noble gas, oriented moulding in the magnetic field of 0.5～2T；
(4) magnet being orientated is put into hot isostatic press, under the isostatic pressure of 50～400MPa,
At a temperature of the isostatic pressed of 400 DEG C～1100 DEG C, suppress 0.01～4h.
Preparation method the most according to claim 4, wherein, airflow milling described in step (2)
Powder Particle Size is 1～3 μm.
Preparation method the most according to claim 4, wherein, the high temperature insostatic pressing (HIP) in step (4)
Power is 50～200Mpa；Preferably, hip temperature is 650～1040 DEG C；Preferably, heat etc.
The static pressure time is 0.5～2h.
7. according to the preparation method according to any one of claim 4 to 6, wherein, described preparation side
Method also includes step (5): put into by the blank after compressing for step (4) in the sintering furnace of fine vacuum
0.01～2h is sintered under the sintering temperature of 800～1060 DEG C.
Preparation method the most according to claim 7, wherein, described preparation method also includes step
(6): sintered body step (5) obtained is tempered 0.01～2h at a temperature of 200～500 DEG C.
9. double principal phase permanent magnet materials according to any one of claims 1 to 3 or according to claim
Method according to any one of 4 to 8 prepare double principal phase permanent magnet materials instrument and meter, household electrical appliances, motor,
Wind-power electricity generation, Aero-Space, mobile phone, communication equipment, rotating machinery, magnetotherapy appliance and physical culture are used
Application in product.
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