CN105118595B - A kind of compound rare-earth magnet containing Gd and Mn - Google Patents
A kind of compound rare-earth magnet containing Gd and Mn Download PDFInfo
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- CN105118595B CN105118595B CN201510540034.4A CN201510540034A CN105118595B CN 105118595 B CN105118595 B CN 105118595B CN 201510540034 A CN201510540034 A CN 201510540034A CN 105118595 B CN105118595 B CN 105118595B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 45
- 229910052688 Gadolinium Inorganic materials 0.000 title claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 26
- -1 compound rare-earth Chemical class 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 57
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 21
- 239000007789 gas Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000013078 crystal Substances 0.000 description 16
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
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- 230000001590 oxidative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000007499 fusion processing Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000013021 overheating Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 3
- 229940063655 aluminum stearate Drugs 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
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- 230000005347 demagnetization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052789 astatine Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a kind of compound rare-earth magnet containing Gd and Mn, the rare-earth magnet contains R2Fe14Type B principal phase, it includes following material composition：R：28wt%~33wt%, R are the rare earth element including at least Nd and Gd, wherein, Gd contents are 0.3wt%~5wt%, B：0.8wt%~1.3wt%, Mn：0.02wt%~0.4wt%, and surplus are T and inevitable impurity, and the T is the main element for including Fe and below 18wt% Co.This kind of rare-earth magnet Gd high by adding the De Rena factors (De Gennes), overcome because Mn enters principal phase, the defects of causing Curie temperature and magnetic anisotropy to reduce, for low oxygen content, microscopic grains magnet for, can preferably play technique effect caused by addition Mn.
Description
Technical field
The present invention relates to the manufacturing technology field of magnet, more particularly to it is a kind of it is compound it is containing Gd and Mn, tool is high square
The very-high performance rare-earth magnet of degree and high-fire resistance.
Background technology
In in general thinks, a certain amount of Mn is added, can be with acceleration of sintering for the manufacturing process of sintered magnet
Reaction, is sintered in low temperature or in the short time, and because sintering structure becomes homogeneity, the squareness of demagnetizing curve has carried
It is high.But as known as road, Mn is ferrous materials, same with P, S-phase, easily it is segregated to crystal grain boundary, specific to Nd-
Fe-B magnet, by the situation that segregations of the Mn to crystal boundary causes magnet coercivity drastically to decline also is recognized by everybody.In addition, Mn
Addition the problem of also magnet curie point, anisotropy field etc. being brought to decline.Therefore, manufactured in conventional conventional magnet
In engineering, Mn addition is unwelcome.
In recent years, as the index for investigating the stable heat resistance of magnet, to the squareness of coercivity, particularly demagnetizing curve
Requirement gradually step up, thus, done it is many reduction oxygen contents effort, high performance magnet of the oxygen content in below 2000ppm
Volume production be possibly realized.In the relatively low magnet of oxygen content, the situation of Mn cyrystal boundary segregations is not easy to occur, that is to say, that Mn
It is main toward spreading in principal phase.But if Mn is diffused into principal phase, Curie temperature can reduce, and cause heat resistance, heat to subtract magnetic
Degradation.
The content of the invention
It is an object of the invention to overcome the deficiency of prior art, there is provided a kind of compound rare-earth magnet containing Gd and Mn.
By the compound addition De Rena factors in the feed high Gd and Mn, due to Mn presence, Gd can pole be evenly distributed in magnetic
In iron, cause Curie temperature and magnetic anisotropy while the defects of reduce so as to overcome Mn to enter principal phase, raising Curie temperature
(Tc), coercivity and heat resistance, the squareness of demagnetizing curve also increase.
Technical approach provided by the invention is as follows：
A kind of compound rare-earth magnet containing Gd and Mn, the rare-earth magnet contain R2Fe14Type B principal phase, and including as follows
Material composition：
R：28wt%~33wt%, R be including at least Nd and Gd rare earth element, wherein, Gd contents be 0.3wt%~
5wt%,
B：0.8wt%~1.3wt%,
Mn：0.02wt%~0.4wt%,
And surplus is T and inevitable impurity, the T is the main Co including Fe and below 18wt% element；
The oxygen content of the rare-earth magnet is in below 2000ppm.
The rare earth element referred in the present invention is including yttrium.
The present invention is by the compound addition De Rena factors in the feed high Gd and Mn, and due to Mn presence, Gd can pole
It is evenly distributed in magnet, causes Curie temperature and magnetic anisotropy while the defects of reduce so as to overcome Mn to enter principal phase,
Curie temperature (Tc), coercivity and heat resistance, the squareness of demagnetizing curve is improved also to increase.That is, it can so fill
Distribution shoots addition Mn potential ability.
It should be noted that in the present invention, R：28wt%~33wt%, B：0.8wt%~1.3wt% content range is
The conventional selection of the industry.
In the embodiment of recommendation, the oxygen content of the rare-earth magnet is in below 1000ppm.In oxygen content 1000ppm
In following magnet, Mn is easier to spread into principal phase, causes heat resistance, heat to subtract magnetic property variation.
In the embodiment of recommendation, T include below 2.0wt% selected from Zr, V, Mo, Zn, Ga, Nb, Sn, Sb, Hf,
At least one of Bi, Ni, Ti, Cr, Si, S or P element, below 0.8wt% Cu, below 0.8wt% Al and surplus
Fe。
In the embodiment of recommendation, the rare-earth magnet is made by the steps：By the rare-earth magnet raw material into
The process that the fused solution divided is prepared into rare-earth magnet alloy；Crushing of Ultrafine will be passed through again after the rare-earth magnet alloy coarse crushing
The process of fine powder is made；By the fine powder with magnetic forming method obtain formed body, and in vacuum or inert gas to it is described into
Body is sintered, and obtains process of the oxygen content in below 2000ppm sintering rare-earth magnet.
By adding Mn and then the further compound addition De Rena factors (De into nearest low oxygen content magnet
Gennes) high Gd, can overcome because Mn enters principal phase, what is caused Curie temperature and the side of magnetic anisotropy two while reduce lacks
Fall into, obtain the high-performance magnet with high-fire resistance.
In low oxygen content magnet of the oxygen content less than 2000ppm, Mn preferentially spreads into principal phase, but has micro Mn still
Spread into crystal boundary.As a result, can prevent the crystal grain of grain boundaries from growing, the unmagnetize and noncrystalline of grain boundaries,
So as to obtain most suitable crystal boundary phase structure for magnet.That is, by micro Mn cyrystal boundary segregation result, make coercivity
Upwards, squareness improves, and heat resistance also has improvement.
In the embodiment of recommendation, the rare-earth magnet with alloy be by raw alloy fused solution band casting method,
With 102More than DEG C/sec, 104Cooling velocity below DEG C/sec cools down what is obtained.
In the embodiment of recommendation, the coarse crushing is that the rare-earth magnet is crushed with absorption hydrogen, obtains coarse powder
Process, the Crushing of Ultrafine are the process to the coarse powder air-flow crushing.
By above-mentioned process, Mn can be evenly distributed, sintering structure becomes homogeneity, improves the side of demagnetizing curve
Shape degree.
In the embodiment of recommendation, described rare-earth magnet is Nd-Fe-B systems sintered magnet.
In the embodiment of recommendation, Nd-Fe-B systems sintered magnet is with 2~8 microns of average crystallite particle diameter
Nd systems sintered magnet.
Degraded performance caused by Mn segregations in crystal grain boundary, for the small magnet of more than crystal grain boundary, crystallization particle diameter
Apparently more sensitive, this is the inevitable problem points of the Nd systems sintered magnet with core generation type coercivity generating mechanism.
The crystal grain boundary phase of magnet with microscopic grains is more, is easily influenceed by segregation element, that is to say, that the segregated zone of Mn elements
What the coercivity (heat resistance) come declined has a great influence.
As a rule, the less powder of particle diameter can be selected to be made magnet, crystal grain-growth during sintering, according to sintering condition and
Fusion degree, the crystallization particle diameter of common sintered magnet is 10~20 microns.
It is extremely difficult to make the sintered magnet with the discontented 2 microns fine tissue of average crystallite particle diameter, this is because, system
Make the fine powder particle diameter of Nd systems sintered magnet below 2 microns, easily formed and reunited, powder forming is poor, causes the degree of orientation and Br
Drastically reduce.Further, since not improving pressure embryo density fully, it can also drastically reduce magnetic flux density, so can not make heat-resisting
The good magnet of property.And the crystal grain boundary amount with sintered magnet of the average crystallite more than 8 microns is seldom, Gd, Mn compound addition
Afterwards, lifted coercivity, heat resistance effect also and unobvious, the difference ratio that coercivity caused by this is due to Mn segregations reduces
It is less, so the effect of the present invention is less.For the Nd systems sintered magnet of the average crystallite particle diameter with 2~8 microns, lead to
Gd, Mn compound addition are crossed, reduces Mn segregation, while Curie temperature (Tc), magnetic anisotropy, Hcj is improved, is improved resistance to
Hot property and magnet squareness.
In the embodiment of recommendation, T includes 0.1wt%~0.8wt% Cu, and appropriate Cu improves Mn in principal phase and crystal boundary
Distribution coefficient, reduce distributions of the Mn in principal phase, increase the distribution in crystal boundary, giving full play to Mn improves sintering structure
Effectiveness.
In the embodiment of recommendation, T includes 0.1wt%~0.8wt% Al, and appropriate Al can strengthen the even of sintering structure
Matter, improve coercivity and squareness.
In the embodiment of recommendation, T include 0.3wt%~2.0wt% selected from Zr, V, Mo, Zn, Ga, Nb, Sn, Sb,
At least one of Hf, Bi, Ni, Ti, Cr, Si, S or P addition element.
In the embodiment of recommendation, B content is preferably 0.8wt%~0.92wt%.B content 0.92wt% with
When lower, the crystalline structure of quick cooling alloy piece is easier to make, and is also easier to be fabricated to fine powder, however, the content in B is less than
When 0.8wt%, the crystalline structure of quick cooling alloy piece can become meticulous, and be mixed into amorphous phase, cause magnetic flux density Br reductions.
Brief description of the drawings
Fig. 1 is the EPMA detection figures of embodiment 3 in embodiment one.
Embodiment
The present invention is described in further detail with reference to embodiments.
The sintered magnet that following examples are obtained is determined using following detection mode.
Magnetic property evaluation procedure：Sintered magnet is lossless using the NIM-10000H type BH block rare earth permanent magnetism of metering institute of China
Measuring system carries out magnetic property detection.
The measure of flux decay rate：Sintered magnet is placed in 120 DEG C of environment and is incubated 30min, and then natural cooling cools again
To room temperature, then magnetic flux is measured, the measurement data before the result of measurement and heating compares, and is declined before calculating heating with the magnetic flux after heating
Lapse rate.
Magnet crystallization average grain diameter test：Magnet is placed on big 2000 times of laser metallographic microscope decentralization and shot, and shoots
When detection faces it is parallel below with visual field.During measurement, the straight line that a length is 146.5 μm is drawn in field of view center position, by counting
Number is crystallized by the principal phase of straight line, calculates the average crystallite average grain diameter of magnet.
Embodiment one
In raw material process for preparation：Prepare the Nd of the purity 99.5%, Gd of purity 99.9%, industrial Fe-B, industrial pure
Fe and purity 99.99% Mn, prepared with percentage by weight wt%.
The content of each element is as shown in table 1：
The proportioning of each element of table 1
Each sequence number group is prepared according to element composition in table 1, weighs, prepared 10Kg raw material respectively.
Fusion process：1 part of raw material prepared is taken to be put into the crucible of oxidation aluminum every time, in vacuum induction melting furnace
10-2Vacuum melting is carried out with less than 1500 DEG C of temperature in Pa vacuum.
Casting process：After Ar gases are passed through in smelting furnace after vacuum melting air pressure is reached 5.0 ten thousand Pa, single roller is used
Chilling method is cast, with 102DEG C/sec~104DEG C/sec cooling velocity obtain quick cooling alloy.
Hydrogen crushing process：The broken stove evacuation of hydrogen of quick cooling alloy will be placed at room temperature, and in the broken stove of backward hydrogen
Hydrogen that purity is 99.5% is passed through to pressure 0.095MPa, after placing 2 hours, is heated up when vacuumizing, in 500 DEG C of temperature
Under vacuumize 2 hours, cooled down afterwards, take out hydrogen crushing after powder.
Crushing of Ultrafine process：Under atmosphere below oxidizing gas content 100ppm, the pressure that chamber pressure is 0.45Mpa is being crushed
Airflow milling crushing is carried out to the sample after hydrogen crushing under power, obtains fine powder, the average grain diameter of fine powder is 1.8 μm (Fei Shi methods).
Oxidizing gas refers to oxygen or moisture.
Methyl caprylate is added in powder after airflow milling crushing, the addition of methyl caprylate is powder weight after mixing
0.18%, then be sufficiently mixed with V-type batch mixer.
Magnetic forming process：Using the pressing under magnetic field machine of right angle orientation type, in 1.8T alignment magnetic field, in 0.2ton/
cm2Briquetting pressure under, by the above-mentioned powder that with the addition of methyl caprylate it is once-forming into the length of side be 25mm cube, once into
Demagnetized after shape.
For make it is once-forming after formed body be not exposed to air, sealed, reuse secondary forming machine and (wait quiet
Pressing formation machine) carry out it is secondary forming.
Sintering process：Each formed body is removed to sintering furnace and is sintered, is sintered in 10-3Under Pa vacuum, at 200 DEG C and
After respectively being kept for 2 hours at a temperature of 600 DEG C, sintered 1 hour with 980 DEG C of temperature, being passed through Ar gases afterwards reaches air pressure
After 0.05Mpa, room temperature is cooled to.
Heat treatment process：Sintered body after carrying out heat treatment in 1 hour with 600 DEG C of temperature, is cooled to room in high-purity Ar gas
Taken out after temperature.
Process：Sintered body through Overheating Treatment is processed into φ 15mm, thickness 5mm magnet, and 5mm directions take for magnetic field
To direction.
The evaluation result of the magnet of embodiment and comparative example is as shown in table 2：
The magnetic property of the embodiment of table 2 and comparative example evaluates situation
In whole implementation process, the O content of comparative example magnet and embodiment magnet is controlled in below 1000ppm.
Testing result and conclusion：The magnet of embodiment and comparative example was through neutral salt spray test 48 hours, only in comparative example 1
Magnet observes the situation got rusty, and remaining embodiment has no the situation got rusty.It can be seen that by adding Gd in the feed, overcome
The problem of magnet gets rusty easily.
Mn addition makes sintering structure become homogeneity, is integrally improved the squareness of demagnetizing curve.
It can see from comparative example and embodiment, when Gd content is less than 0.3wt%, because the De Rena factors are high
Gd contents are very few, it is difficult to play a role, magnet heat resistance is low.
It will be noted from fig. 1 that after adding Mn and Gd (0.3wt%~5wt%) in the feed, due to Mn homogeneous work
With Gd poles are evenly distributed in magnet, and part Gd forms (Nd, Gd) further into principal phase2Fe14B, due to (Nd, Gd)2Fe14B's
Anisotropy field has positive temperature coefficient at 200 DEG C, and the heat resistance of magnet is improved, so as to overcome Mn to enter principal phase
The defects of causing Curie temperature to reduce, improve Curie temperature (Tc) and heat resistance.
And when Gd content is more than 5wt%, (Nd, Gd)2Fe14B amount is too high, and due to (Nd, Gd)2Fe14B
Anisotropy field be inferior to Nd2Fe14B anisotropy field, cause magnet hydraulic performance decline.
Embodiment two
In raw material process for preparation：Prepare the Nd of purity 99.5%, the PrNd of purity 99.5%, the Gd of purity 99.9%, work
Industry Fe-B, industrial pure Fe and purity 99.99% Mn, prepared with percentage by weight.
The content of each element is as shown in table 3：
The proportioning of each element of table 3
Each sequence number group is prepared according to element composition in table 3, weighs, prepared 10Kg raw material respectively.
Fusion process：1 part of raw material prepared is taken to be put into the crucible of oxidation aluminum every time, in vacuum induction melting furnace
10-1Vacuum melting is carried out with less than 1520 DEG C of temperature in Pa vacuum.
Casting process：After Ar gases are passed through in smelting furnace after vacuum melting air pressure is reached 5.2 ten thousand Pa, single roller is used
Chilling method is cast, with 102DEG C/sec~104DEG C/sec cooling velocity obtain quick cooling alloy.
Hydrogen crushing process：The broken stove evacuation of hydrogen of quick cooling alloy will be placed at room temperature, and in the broken stove of backward hydrogen
Hydrogen that purity is 99.5% is passed through to pressure 0.2MPa, places, after fully inhaling hydrogen, is heated up when vacuumizing, in 520 DEG C of temperature
Vacuumize under degree 2 hours, cooled down afterwards, take out the powder after hydrogen crushing.
Crushing of Ultrafine process：Under atmosphere below oxidizing gas content 300ppm, the pressure that chamber pressure is 0.5MPa is being crushed
Airflow milling crushing is carried out to the sample after hydrogen crushing under power, obtains fine powder, the average grain diameter of fine powder is 3.8 μm (Fei Shi methods).
Oxidizing gas refers to oxygen or moisture.
Aluminum stearate is added in powder after airflow milling crushing, the addition of aluminum stearate is powder weight after sieving
0.05%, then be sufficiently mixed with V-type batch mixer.
Magnetic forming process：Using the pressing under magnetic field machine of right angle orientation type, in 1.8T alignment magnetic field, in 0.2ton/
cm2Briquetting pressure under, by the above-mentioned powder that with the addition of aluminum stearate it is once-forming into the length of side be 25mm cube, once into
Demagnetized after shape, formed body is taken out from space, then apply another magnetic field to formed body, the magnetic for being attached to formed body surface is entered
Second of demagnetization of row is handled.
For make it is once-forming after formed body be not exposed to air, sealed, reuse secondary forming machine and (wait quiet
Pressing formation machine) carry out it is secondary forming.
Sintering process：Each formed body is removed to sintering furnace and is sintered, is sintered in 10-4Under Pa vacuum, at 300 DEG C and
After respectively being kept for 2 hours at a temperature of 500 DEG C, sintered with 1020 DEG C of temperature, being passed through Ar gases afterwards makes air pressure reach 0.08MPa
Afterwards, it is cooled to room temperature.
Heat treatment process：Sintered body is in high-purity Ar gas, after being heat-treated with 550 DEG C of temperature, after being cooled to room temperature
Take out.
Process：Sintered body through Overheating Treatment is processed into φ 15mm, thickness 5mm magnet, and 5mm directions take for magnetic field
To direction.
The evaluation result of the magnet of embodiment and comparative example is as shown in table 4：
The magnetic property of the embodiment of table 4 and comparative example evaluates situation
In whole implementation process, the O content of comparative example magnet and embodiment magnet is controlled in below 1000ppm.
Testing result and conclusion：The magnet of embodiment and comparative example was showed no what is got rusty through neutral salt spray test 48 hours
Situation.It can be seen that by adding appropriate Gd in the feed, the problem of magnet gets rusty easily is overcome.
It can see from comparative example and embodiment, when Mn content is less than 0.02wt%, Mn homogeneity effect has
Limit, Gd can not be evenly distributed with pole to be formd (Nd, Gd)2Fe14B, magnet squareness decline.
Mn addition when 0.02wt%~0.4wt%, sintering structure can be made to become homogeneity, be integrally improved
The squareness of demagnetizing curve, simultaneously as Mn homogeneous effect, Gd poles are evenly distributed in magnet, part Gd is further into master
Mutually form (Nd, Gd)2Fe14B, due to (Nd, Gd)2Fe14B anisotropy field has positive temperature coefficient, magnet at 200 DEG C
Heat resistance be improved, so as to overcome Mn to enter the defects of principal phase causes Curie temperature to reduce, while improve Curie temperature
And heat resistance (Tc).
And when Mn content is more than 0.4wt%, because Mn too high levels cause to reduce Tc, Mn is produced to the different of crystal boundary
Often segregation, magnet coercivity drastically decline, and magnet heat resistance drastically reduces simultaneously.
Embodiment three
In raw material process for preparation：Prepare the Nd of the purity 99.5%, Gd of purity 99.9%, industrial Fe-B, industrial pure
Fe, the Mn of purity 99.99%, the Cu of the Zr of purity 99.99% and purity 99.5%, prepared with percentage by weight.
The content of each element is as shown in table 5：
The proportioning of each element of table 5
Each sequence number group is prepared according to element composition in table 5, weighs, prepared 10Kg raw material respectively.
Fusion process：1 part of raw material prepared is taken to be put into the crucible of oxidation aluminum every time, in vacuum induction melting furnace
10-2Vacuum melting is carried out in Pa vacuum.
Casting process：After Ar gases are passed through in smelting furnace after vacuum melting air pressure is reached 4.8 ten thousand Pa, single roller is used
Chilling method is cast, with 102DEG C/sec~104DEG C/sec cooling velocity obtain quick cooling alloy.
Hydrogen crushing process：The broken stove evacuation of hydrogen of quick cooling alloy will be placed at room temperature, and in the broken stove of backward hydrogen
Hydrogen that purity is 99.5% is passed through to pressure 0.05MPa, places, after fully inhaling hydrogen, is heated up when vacuumizing, at 500 DEG C
At a temperature of vacuumize, cooled down afterwards, take out hydrogen crushing after powder.
Crushing of Ultrafine process：Under atmosphere below oxidizing gas content 5ppm, the pressure that chamber pressure is 0.4MPa is being crushed
Under to after hydrogen crushing sample carry out airflow milling crushing, obtain fine powder, the average grain diameter of fine powder is 3.0 μm (Fei Shi methods).Oxygen
Change gas and refer to oxygen or moisture.
Magnetic forming process：Using the pressing under magnetic field machine of right angle orientation type, with 0.25ton/cm2Briquetting pressure, taking
It is into magnetic field that the above-mentioned powder that with the addition of methyl caprylate is once-forming into the cube that the length of side is 25mm, once-forming retrogressing
Magnetic, formed body is taken out from space, then apply another magnetic field to formed body, second is carried out to the magnetic for being attached to formed body surface
Secondary demagnetization processing.
For make it is once-forming after formed body be not exposed to air, sealed, reuse secondary forming machine and (wait quiet
Pressing formation machine) carry out it is secondary forming.
Sintering process：Each formed body is removed to sintering furnace and is sintered, is sintered in 10-3Under Pa vacuum, at 250 DEG C and
After respectively being kept for 1 hour at a temperature of 800 DEG C, sintered 2 hours with 980 DEG C of temperature, being passed through Ar gases afterwards reaches air pressure
After 0.09MPa, room temperature is cooled to.
Heat treatment process：Sintered body is in high-purity Ar gas, after being heat-treated with 500 DEG C of temperature, after being cooled to room temperature
Take out.
Process：Sintered body through Overheating Treatment is processed into φ 15mm, thickness 5mm magnet, and 5mm directions take for magnetic field
To direction.
The evaluation result of the magnet of embodiment and comparative example is as shown in table 6：
The magnetic property of the embodiment of table 6 and comparative example evaluates situation
In whole implementation process, the O content of comparative example magnet and embodiment magnet is controlled in below 1000ppm.
Testing result and conclusion：The magnet of embodiment and comparative example was showed no what is got rusty through neutral salt spray test 48 hours
Situation.It can be seen that by adding Gd in the feed, the problem of magnet gets rusty easily is overcome.
It can see from comparative example and embodiment, when Cu content is less than 0.1wt%, distributions of the Cu in crystal boundary is not
Foot, it is difficult to play its effect, magnet squareness is low.
0.1wt%~0.8wt% Cu can improve Mn in principal phase and the distribution coefficient of crystal boundary, make distributions of the Mn in principal phase
Reduce, while increase the distribution in crystal boundary, giving full play to Mn improves sintering and promote (Nd, Gd)2Fe14B's is equally distributed
Effectiveness.
And when Cu content is more than 0.8wt%, because Cu is nonmagnetic elements, its too high levels can cause magnet B r
Reduced with squareness.
Example IV
In raw material process for preparation：Prepare the Nd of the purity 99.5%, Gd of purity 99.9%, industrial Fe-B, industrial pure
Fe, the Al of purity 99.5%, the Mn of the Ga of purity 99.99% and purity 99.99%, prepared with percentage by weight.
The content of each element is as shown in table 7：
The proportioning of each element of table 7
Each sequence number group is prepared according to element composition in table 7, weighs, prepared 10Kg raw material respectively.
Fusion process：1 part of raw material prepared is taken to be put into crucible every time, 10 in vacuum induction melting furnace-2Pa's
Vacuum melting is carried out in vacuum.
Casting process：After being passed through Ar gases in smelting furnace after vacuum melting and air pressure is reached 60,000 Pa, use single roller anxious
Cold process is cast, with 102DEG C/sec~104DEG C/sec cooling velocity obtain quick cooling alloy, by quick cooling alloy 700 DEG C carry out 5
The insulation heat treatment of hour, is then cooled to room temperature.
Hydrogen crushing process：The broken stove evacuation of hydrogen of quick cooling alloy will be placed at room temperature, and in the broken stove of backward hydrogen
Hydrogen that purity is 99.5% is passed through to pressure 0.12MPa, places, after fully inhaling hydrogen, is heated up when vacuumizing, at 540 DEG C
At a temperature of vacuumize, cooled down afterwards, take out hydrogen crushing after powder.
Crushing of Ultrafine process：Under atmosphere below oxidizing gas content 500ppm, the pressure that chamber pressure is 0.5MPa is being crushed
Airflow milling crushing is carried out to the sample after hydrogen crushing under power, obtains fine powder, the average grain diameter of fine powder is 5.8 μm (Fei Shi methods).
Oxidizing gas refers to oxygen or moisture.
Methyl caprylate is added in powder after airflow milling crushing, the addition of methyl caprylate is powder weight after sieving
0.15%, then be sufficiently mixed with V-type batch mixer.
Magnetic forming process：Using the pressing under magnetic field machine of right angle orientation type, in 1.8T alignment magnetic field, in 0.2ton/
cm2Briquetting pressure under, by the above-mentioned powder that with the addition of methyl caprylate it is once-forming into the length of side be 25mm cube, once into
Demagnetized after shape, formed body is taken out from space, then apply another magnetic field to formed body, the magnetic for being attached to formed body surface is entered
Second of demagnetization of row is handled.
For make it is once-forming after formed body be not exposed to air, sealed, reuse secondary forming machine and (wait quiet
Pressing formation machine) carry out it is secondary forming.
Sintering process：Each formed body is removed to sintering furnace and is sintered, is sintered in 10-3Under Pa vacuum, at 300 DEG C and
After respectively being kept for 2 hours at a temperature of 700 DEG C, sintered with 1020 DEG C of temperature, being passed through Ar gases afterwards makes air pressure reach 0.08MPa
Afterwards, it is cooled to room temperature.
Heat treatment process：Sintered body is in high-purity Ar gas, after being heat-treated with 500 DEG C of temperature, after being cooled to room temperature
Take out.
Process：Sintered body through Overheating Treatment is processed into φ 15mm, thickness 5mm magnet, and 5mm directions take for magnetic field
To direction.
The evaluation result of the magnet of embodiment and comparative example is as shown in table 8：
The magnetic property of the embodiment of table 8 and comparative example evaluates situation
In whole implementation process, the O content of comparative example magnet and embodiment magnet is controlled in below 1000ppm.
Testing result and conclusion：The magnet of embodiment and comparative example was showed no what is got rusty through neutral salt spray test 48 hours
Situation.It can be seen that by adding Gd in the feed, the problem of magnet gets rusty easily is overcome.
It can see from comparative example and embodiment, when Al content is less than 0.1wt%, because Al content is very few,
It is difficult to play its effect, magnet squareness is low.
0.1wt%~0.8wt% Al can cooperate with the homogeneity of enhancing sintering structure with Mn, and promote (Nd, Gd)2Fe14B
Be uniformly distributed, improve sintered magnet squareness.
And when Al content is more than 0.8wt%, excessive Al can cause magnet B r and squareness dramatic decrease.
Above-described embodiment is only used for further illustrating several specific embodiments of the present invention, but the present invention does not limit to
In embodiment, any simply modification, the equivalent variations that every technical spirit according to the present invention is made to above example are with repairing
Decorations, each fall within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of compound rare-earth magnet containing Gd and Mn, the rare-earth magnet contain R2Fe14Type B principal phase, it is characterised in that bag
Include following material composition：
R：28wt%~33wt%, R are the rare earth element including at least Nd and Gd, wherein, Gd contents are 0.3wt%~5wt%,
B：0.8wt%~1.3wt%,
Mn：0.02wt%~0.2wt%,
And surplus is T and inevitable impurity, the T is the main element for including Fe and below 18wt% Co；
The rare-earth magnet is made by the steps：The fused solution of the rare-earth magnet material composition is prepared into rare-earth magnet
With the process of alloy；By the rare-earth magnet with the process that fine powder is made up after alloy coarse crushing of Crushing of Ultrafine again；Will be described thin
Powder obtains formed body with magnetic forming method, and the formed body is sintered in vacuum or inert gas, obtains oxygen content
In the process of below 2000ppm sintering rare-earth magnet；
The coarse crushing, which is that the rare-earth magnet absorption hydrogen is broken, obtains the process of coarse powder, after fully inhaling hydrogen, fully inhales hydrogen
Afterwards, heated up when vacuumizing；The Crushing of Ultrafine is the process that air-flow crushing is carried out to the coarse powder；
The oxygen content of the rare-earth magnet is in below 2000ppm.
A kind of 2. compound rare-earth magnet containing Gd and Mn according to claim 1, it is characterised in that：The rare-earth magnet
Oxygen content in below 1000ppm.
A kind of 3. compound rare-earth magnet containing Gd and Mn according to claim 2, it is characterised in that：T includes 2.0wt%
It is following selected from least one of Zr, V, Mo, Zn, Ga, Nb, Sn, Sb, Hf, Bi, Ni, Ti, Cr, Si, S or P addition element,
Below 0.8wt% Cu, below 0.8wt% Al and surplus Fe.
A kind of 4. compound rare-earth magnet containing Gd and Mn according to claim 3, it is characterised in that：The rare-earth magnet
It is by raw alloy fused solution band casting method, with 10 with alloy2More than DEG C/sec, 104Cooling velocity cooling below DEG C/sec
Obtain.
A kind of 5. compound rare-earth magnet containing Gd and Mn according to claim 1 or 2 or 3 or 4, it is characterised in that：
Described rare-earth magnet is Nd-Fe-B systems sintered magnet.
A kind of 6. compound rare-earth magnet containing Gd and Mn according to claim 5, it is characterised in that：The Nd-Fe-B
It is that sintered magnet is the Nd systems sintered magnet with 2~8 microns of average crystallite particle diameter.
A kind of 7. compound rare-earth magnet containing Gd and Mn according to claim 5, it is characterised in that：T includes 0.1wt%
~0.8wt% Cu.
A kind of 8. compound rare-earth magnet containing Gd and Mn according to claim 5, it is characterised in that：T includes 0.1wt%
~0.8wt% Al.
A kind of 9. compound rare-earth magnet containing Gd and Mn according to claim 5, it is characterised in that：T includes 0.3wt%
~2.0wt%'s adds selected from least one of Zr, V, Mo, Zn, Ga, Nb, Sn, Sb, Hf, Bi, Ni, Ti, Cr, Si, S or P
Element.
A kind of 10. compound rare-earth magnet containing Gd and Mn according to claim 5, it is characterised in that：B content is
0.8wt%~0.92wt%.
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| CN101552060A (en) * | 2008-04-03 | 2009-10-07 | 有研稀土新材料股份有限公司 | Rare earth permanent magnetic powder and preparation method thereof |
| CN102290182A (en) * | 2011-04-29 | 2011-12-21 | 天津天和磁材技术有限公司 | Sintered neodymium iron boron material with low oxygen content and ultrahigh performance and production method thereof |
| JP5405634B2 (en) * | 2012-09-13 | 2014-02-05 | 株式会社ソフテム | Permanent magnet anticorrosion method |
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|---|---|---|---|---|
| CN101552060A (en) * | 2008-04-03 | 2009-10-07 | 有研稀土新材料股份有限公司 | Rare earth permanent magnetic powder and preparation method thereof |
| CN102290182A (en) * | 2011-04-29 | 2011-12-21 | 天津天和磁材技术有限公司 | Sintered neodymium iron boron material with low oxygen content and ultrahigh performance and production method thereof |
| JP5405634B2 (en) * | 2012-09-13 | 2014-02-05 | 株式会社ソフテム | Permanent magnet anticorrosion method |
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