CN106548843A - Rare earth permanent-magnetic material and preparation method thereof - Google Patents
Rare earth permanent-magnetic material and preparation method thereof Download PDFInfo
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- CN106548843A CN106548843A CN201610901288.9A CN201610901288A CN106548843A CN 106548843 A CN106548843 A CN 106548843A CN 201610901288 A CN201610901288 A CN 201610901288A CN 106548843 A CN106548843 A CN 106548843A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 121
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 115
- 239000000696 magnetic material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 81
- 239000006247 magnetic powder Substances 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 27
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 19
- 238000003856 thermoforming Methods 0.000 claims abstract description 18
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 14
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 12
- 229910001122 Mischmetal Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 32
- 238000007731 hot pressing Methods 0.000 claims description 14
- 238000005496 tempering Methods 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000007499 fusion processing Methods 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000010891 electric arc Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims 1
- 239000012071 phase Substances 0.000 description 35
- 239000013078 crystal Substances 0.000 description 29
- 239000002994 raw material Substances 0.000 description 29
- 230000005389 magnetism Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000280 densification Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910001172 neodymium magnet Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000583 Nd alloy Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RKLPWYXSIBFAJB-UHFFFAOYSA-N [Nd].[Pr] Chemical compound [Nd].[Pr] RKLPWYXSIBFAJB-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 praseodymium Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
Abstract
The present invention relates to a kind of preparation method of rare earth permanent-magnetic material, which comprises the following steps：(1) Re Fe B quenched powders and R are provided respectivelyMFe B quenched powders, wherein the RMThe chemical formula of Fe B quenched powders is RMdFe100‑d‑e‑fMeBf, RMIt is by the common association mischmetal of Rare Earth Mine exploitation, RMIncluding each element of following mass fraction：20%～30%La, 48%～58%Ce, 4%～7%Pr and 15%～20%Nd；(2) by the Re Fe B quenched powders and the RMFe B quenched powder mix homogeneously obtains mixing magnetic powder, wherein, the R described in the mixing magnetic powderMMass percent shared by Fe B quenched powders is 10%～90%；(3) the mixing magnetic powder is carried out into hot-forming, thermoforming and temper successively, obtain rare earth permanent-magnetic material, the rare earth permanent-magnetic material is many principal phase structures, the rare earth permanent-magnetic material is mainly made up of nano-grade crystalline substance.The present invention also provides a kind of rare earth permanent-magnetic material obtained using above-mentioned preparation method.
Description
Technical field
The present invention relates to a kind of rare earth permanent-magnetic material and preparation method thereof.
Background technology
Rare earth permanent-magnetic material is based on the intermetallic compound formed with thulium and magnesium-yttrium-transition metal
Permanent magnet material.Nd-Fe-B permanent magnet material (also referred to as Nd-Fe-B permanent magnet materials), with excellent magnetic characteristic, is widely used to society
The fields such as production, life and national defence and space flight, become the critical function material for supporting social progress.In Nd-Fe-B permanent magnetism materials
In material, the cost of rare earth Nd accounts for more than the 90% of the cost of raw material.With industrial expansion and the progress of society, Nd-Fe-B
The usage amount of permanent magnet material increases year by year, production cost also more and more higher.And, in Nd-Fe-B permanent magnet materials, Jing often adds
Rare earth element have praseodymium (Pr), dysprosium (Dy), terbium (Tb), but, these rare earth metals be particularly heavy rare earth institute in rare earth resources
Accounting example is few, and resource shortage is expensive.Therefore, much without heavy rare earth or less with heavy rare earth with the research of reduces cost
Become the research emphasis of current area.
In the recovery process of Rare Earth Mine, primary Rare Earth Mine obtains norium (Misch through chemical treatment
Metal), mischmetal goes out lanthanum (La), cerium (Ce) and the praseodymium (Pr) containing cerium, neodymium (Nd) enriched substance through extract and separate, then passes through
Extract and separate obtains Pr and Nd.While Pr, Nd metal smelting, these lanthanums (La), cerium (Ce) metal are also refined simultaneously, are produced
Amount is very high, but its price is but far below metals such as praseodymium, neodymiums.And the extensive application of praseodymium neodymium alloy causes the big of the metals such as lanthanum, cerium
Amount overstocks.If be not used, the pollution of environment is also brought while the wasting of resources is caused.
However, due to La2Fe14B and Ce2Fe14The saturation magnetization of B is below Nd with anisotropy field2Fe14B phases, because
And RM- Fe-B compound (RMIt is the common association mischmetal exploited by Rare Earth Mine, containing abundant La, Ce) it is difficult to while having
Standby high remanent magnetism and HCJ.
Someone is broken by rapid hardening, hydrogen, air-flow grinding process prepares Pr-Nd-Fe-B and RMSinter after the mixing of-Fe-B magnetic powders, by
In sintering process, the element such as La, Ce is difficult to uniform diffusion, and magnet is with RMThe increase of content, coercivity drastically decline,
Remanent magnetism also declines simultaneously, RMThere is CeFe in the high magnet of content2Phase, destroys principal phase structure, while oxygen content is higher, destroys micro-
Structure is seen, comprehensive magnetic can be poor.Magnet cost performance is extremely low, almost without practical value.
The content of the invention
In view of this, it is necessory to provide, a kind of cost is relatively low and the preferable rare earth permanent-magnetic material of magnetic property and its preparation side
Method.
The present invention provides a kind of preparation method of rare earth permanent-magnetic material, and which comprises the following steps：
(1) Re-Fe-B quenched powders and R are provided respectivelyM- Fe-B quenched powders, wherein the RMThe chemical formula of-Fe-B quenched powders
For RMdFe100-d-e-fMeBf, RMIt is by the common association mischmetal of Rare Earth Mine exploitation, RMIncluding each element of following mass fraction：
20%～30%La, 48%～58%Ce, 4%～7%Pr and 15%～20%Nd, the quality percentage of d, e and f for corresponding element
Content, and 25%≤d≤35%, 0%≤e≤3%, 0.6%≤f ＜ 1.1%；
(2) by the Re-Fe-B quenched powders and the RM- Fe-B quenched powder mix homogeneously obtains mixing magnetic powder, wherein,
R described in the mixing magnetic powderMMass percent shared by-Fe-B quenched powders is 10%～90%；
(3) the mixing magnetic powder is carried out into hot-forming, thermoforming and temper successively, obtain rare earth permanent magnet
Material, the rare earth permanent-magnetic material are many principal phase structures, and the rare earth permanent-magnetic material is mainly made up of nano-grade crystalline substance.
Wherein, the chemical formula of the Re-Fe-B quenched powders is ReaFe100-a-b-cMbBc, wherein Re be Nd, Pr, Y, La, Ce,
One or more in Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, M be Mn, Co, Ni, Zr, Ti, Cu, Zn, Al, Ga, In,
One or more in Sn, Ge and Si, weight/mass percentage compositions of a～c for corresponding element, and 25%≤a≤35%, 0%≤b≤
3%, 0.6%≤c ＜ 1.1%.
Wherein, the R described in the mixing magnetic powderMMass percent shared by-Fe-B quenched powders is 10%～50%.
Wherein, step (1) described in RMThe preparation method of-Fe-B quenched powders is as follows：
First, using the method melting R of electric arc or induction meltingMdFe100-d-e-fMeBfFoundry alloy, the fusion process exist
Carry out under inert atmosphere；
Then, in an inert atmosphere by molten state RMdFe100-d-e-fMeBfFoundry alloy is sprayed to water-cooled running roller carries out fast quenching,
Obtain RM- Fe-B rapid tempering belts, wherein roll surface speed are 10m/s～50m/s, and fast quenching temperature is 1000 DEG C～1500 DEG C, injection pressure
Power is 0.01MPa～0.1MPa；
Finally, by the RM- Fe-B rapid tempering belts carry out Mechanical Crushing, form the R that particle diameter is 50 microns～300 micronsM-Fe-
B quenched powders.
Wherein, step (3) described in hot-forming process be specially：Mixing magnetic powder is put in the first mould, true
Carry out being heated to the first temperature to mixing magnetic powder in Altitude, and first pressure is applied to the first mould, obtain hot-pressed magnets, its
In, first temperature is 550 DEG C～750 DEG C, and the first pressure is 50MPa～250MPa, and the vacuum environment is true
Reciprocal of duty cycle is not less than 5 × 10-2Pa。
Wherein, step (3) described in the process of thermoforming be specially：The hot-pressed magnets are put into into the second mould
In, in an inert atmosphere the hot-pressed magnets are carried out being heated to second temperature, then second is applied to the hot pressing blank after deformation
Pressure, makes the hot pressing blank carry out the deformation that degree of deformation is 30%～95%, obtains heat distortion magnet, wherein described second is warm
Spend for 700 DEG C～900 DEG C, the second pressure is 30MPa～150MPa.
Wherein, step (3) described in the process of temper be specially：By the heat distortion magnet in vacuum environment
It is heated to the 3rd temperature and is incubated, and the chilling that quenches after insulation terminates, wherein the 3rd temperature is 500 DEG C～900 DEG C, during insulation
Between be 0.5 hour～10 hours, during heating heating rate be 5 DEG C/min～20 DEG C/min.
The present invention also provides a kind of rare earth permanent-magnetic material obtained using above-mentioned preparation method, and the rare earth permanent-magnetic material is
Many principal phase structures, wherein principal phase are (Re, La, Ce)2(Fe,M)14B, the rare earth permanent-magnetic material is mainly by nano-grade crystalline substance group
Into.
Wherein, the brilliant length of the nano-grade is 200nm～1000nm, and thickness is 50nm～100nm.
(Re, R are prepared with traditional sintering techniquesM)-Fe-B permanent magnet materials compare, raw materials used process is simple of the invention,
It is few to the energy and resource consumption, cheap, common association mischmetal is taken full advantage of, material cost can be substantially reduced, while
Alleviate environmental pollution, promote rare earth element balance and efficient utilization.
It is difficult to uniformly spread relative to La, Ce in existing sintering process etc., and the rare earth permanent-magnetic material that the present invention is provided
Preparation method in, during hot-forming and thermoforming, La, Ce and Pr, Nd can occur uniform counterdiffusion, be formed into
Point, the high performance magnet of even structure.
It is column crystal with respect to existing sintered magnet, crystal grain larger (micron order), grain surface defect is more, it is heat treated
Cheng Zhong, rich rare earth liquid phase are relatively poor to wettability of the surface, cause coercivity not high；Conjunction is made by hot-forming in the application
Golden densification, obtains hot pressing blank, in thermal deformation process, hot-pressed magnets setting temperature and pressure effect under, nanometer etc.
Axialite forms the nano-grade crystalline substance being consistently oriented along easy magnetizing axis, crystal grain stacking side by dissolving-mass transfer-recrystallization process
To for pressure at right angle direction, preferable texture is formed, therefore obtains the magnet of high anisotropy, the magnet has higher remanent magnetism.And
As hot pressing and thermoforming temperature are low, temperature retention time is short, therefore crystal grain is tiny, and coercivity is high.
Relative to working as R in existing sintering processMWhen content is high, in sintered magnet, easily there is CeFe2Phase, destruction principal phase knot
Structure, while oxidizable cause oxygen content higher, destroys microstructure, so comprehensive magnetic can be poor.And in the application due to
Low temperature moulding is adopted in hot pressing and thermoforming, it is ensured that La, Ce etc. are not oxidized, also inhibits and lead because La, Ce exist
The principal phase of cause easily decomposes Phase-change Problems, and obtained from, rare earth permanent-magnetic material crystal grain is tiny, and densification degree is higher, and the degree of orientation is more
It is good, and there is no CeFe2Deng dephasign, with more excellent organizational structure, so the rare earth permanent-magnetic material has higher coercivity
And remanent magnetism, magnetic property is excellent.
Herein described rare earth permanent-magnetic material is many principal phase structures, and which is mainly made up of nano-grade crystalline substance, corrosion resistance
By force, with preferable practicality.
Further, the R can be also precisely adjusted as neededMThe mixing of-Fe-B quenched powders and the Re-Fe-B quenched powders
Ratio, and then adjust R in the rare earth materialMContent adjusting its magnetic characteristic, to meet the need of magnetic property in different product
Will.
The preparation method is easily achieved newly net forming, and material recovery rate is high, and process is simple is adapted to industrialized production.
Description of the drawings
Fig. 1 is R of the present invention using different quality containingMEach rare earth permanent-magnetic material that-Fe-B quenched powders are prepared
X-ray diffraction (XRD) figure, wherein, RMThe mass fraction of-Fe-B quenched powders refers in preparation method the (2) step mixing magnetic powder
Middle RMMass percent shared by-Fe-B quenched powders (0% is comparative example, 20% correspondence embodiment 1,30% correspondence embodiment 3,
40% correspondence embodiment 5,50% correspondence embodiment is 6).
Fig. 2 to Fig. 4 be the present invention adopt mass fraction for 30% RMThe rare earth permanent magnet material that-Fe-B quenched powders are prepared
Scanning electron microscope (SEM) photo of material.
Fig. 5 be the present invention adopt mass fraction for 50% RMThe rare earth permanent-magnetic material that-Fe-B quenched powders are prepared
SEM photograph.
Specific examples below will further illustrate the present invention with reference to above-mentioned accompanying drawing.
Specific embodiment
Rare earth permanent-magnetic material provided to the present invention below with reference to accompanying drawing and preparation method thereof is described further.
The present invention provides a kind of preparation method of rare earth permanent-magnetic material, and which includes following step：
S1, provides Re-Fe-B quenched powders and R respectivelyM- Fe-B quenched powders, wherein the RMThe chemistry of-Fe-B quenched powders
Formula is RMdFe100-d-e-fMeBf, RMIt is by the common association mischmetal of Rare Earth Mine exploitation, RMIncluding each unit of following mass fraction
Element：20%～30%La, 48%～58%Ce, 4%～7%Pr and 15%～20%Nd, the quality of d, e and f for corresponding element
Percentage composition, and 25%≤d≤35%, 0%≤e≤3%, 0.6%≤f ＜ 1.1%；
S2, by the Re-Fe-B quenched powders and the RM- Fe-B quenched powder mix homogeneously obtains mixing magnetic powder, wherein,
R described in the mixing magnetic powderMMass percent shared by-Fe-B quenched powders is 10%～90%；And
The mixing magnetic powder is carried out hot-forming, thermoforming and temper, obtains rare earth permanent magnet material by S3 successively
Material, the rare earth permanent-magnetic material are many principal phase structures, and the rare earth permanent-magnetic material is mainly made up of nano-grade crystalline substance.
In step sl, the RMThe preparation method of-Fe-B quenched powders is specific as follows：
S111, using the method melting R of electric arc or induction meltingMdFe100-d-e-fMeBfFoundry alloy, the fusion process exist
Carry out under inert atmosphere；
S112, in an inert atmosphere by molten state RMdFe100-d-e-fMeBfFoundry alloy is sprayed to water-cooled running roller carries out fast quenching,
Obtain RM- Fe-B rapid tempering belts, wherein roll surface speed are 10m/s～50m/s, and fast quenching temperature is 1000 DEG C～1500 DEG C, injection pressure
Power is 0.01MPa～0.1MPa；
S113, by the RM- Fe-B rapid tempering belts carry out Mechanical Crushing, form the R that particle diameter is 50 microns～300 micronsM-Fe-
B quenched powders.
In step S111, first according to RMThe proportioning preparation raw material of each element in-Fe-B quenched powders, then carry out melting and obtain
Molten state RMdFe100-d-e-fMeBfFoundry alloy.The inert atmosphere refers to the atmosphere such as nitrogen, argon, neon, Krypton.
In step S112, by fast quenching, amorphous state or the nanocrystalline R coexisted with amorphous are obtainedM- Fe-B rapid tempering belts, with
It is easy to prepare the rare earth material with high magnetic characteristics.
In step S113, the RM- Fe-B rapid tempering belts form R by Mechanical CrushingM- Fe-B quenched powders, in order to rear
It is continuous it is hot-forming in formed with Re-Fe-B quenched powders and preferably contact.
Preferably, RMIncluding each element of following mass fraction：23%～28%La, 50%～55%Ce, 4%～6%
Pr and 15%～17%Nd, d, e and f are the weight/mass percentage composition of corresponding element, the reasons why preferred are：Each element selection range is more
Each element ratio in the nearly packet header baiyuneboite mischmetal of adjunction, directly shortens Rare Earth Mine separating step using mischmetal,
It is cost-effective.Preferably, 28%≤d≤33%, the reasons why preferred be：On the one hand, correspondence is total to association mixed rare-earth elements RM's
Content d can not be too small, because higher than the R for just dividing ratioMIt is the essential condition for producing rich rare earth Grain-Boundary Phase, rich rare earth Grain-Boundary Phase is favourable
In magnet densification, while promoting crystal grain that the preferential growth under pressure or rotation occur, good texture, and non magnetic richness are obtained
Rare earth Grain-Boundary Phase realizes that crystal grain isolation obtains higher coercivity；On the other hand, d can not be too high, when rich rare earth crystal boundary phase content too
Height, magnetic principal phase ratio are reduced, then cause magnet remanent magnetism to reduce with magnetic energy product, while the content of d is too high also producing into raising
This.
The chemical formula of the Re-Fe-B quenched powders is ReaFe100-a-b-cMbBc, wherein Re be Nd, Pr, Y, La, Ce, Eu,
One or more in Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, M are Mn, Co, Ni, Zr, Ti, Cu, Zn, Al, Ga, In, Sn, Ge
With one or more in Si, weight/mass percentage compositions of a～c for corresponding element, and 25%≤a≤35%, 0%≤b≤3%,
0.6%≤c ＜ 1.1%.Preferably, 28%≤a≤33%, the reasons why preferred be：On the one hand, content a of rare earth element Re is not
Can be too small, because higher than the Re for just dividing ratio being the essential condition for producing rich rare earth Grain-Boundary Phase, rich rare earth Grain-Boundary Phase is conducive to magnet
Densification, while promoting crystal grain that the preferential growth under pressure or rotation occur, obtains good texture, and non magnetic rich rare earth is brilliant
Mutually realize that crystal grain isolation obtains higher coercivity in boundary；On the other hand, a can not be too high, when rich rare earth crystal boundary phase content it is too high, magnetic
Principal phase ratio is reduced, then cause magnet remanent magnetism to reduce with magnetic energy product, while the content of a is too high will also to improve production cost.
The Re-Fe-B quenched powders can refer to above-mentioned RMThe preparation method of-Fe-B quenched powders is prepared, also can directly from
Market is buied, and will not be described here.
In step s 2, by by the RM- Fe-B quenched powders are mixed with the Re-Fe-B quenched powders so that the RM-
Fe-B quenched powders are uniformly distributed in the Re-Fe-B quenched powders.The mixing can be carried out in three-dimensional material mixer.Described mixed
Close R described in magnetic powderMMass ratio shared by-Fe-B quenched powders is 10%～90%.The R described in the mixing magnetic powderM-Fe-
Mass ratio shared by B quenched powders is preferably 10%～50%.
In step s3, by described hot-forming dilute with thermoforming technique is prepared into lamellar crystal structure many principal phases
Native permanent magnet material.Specially：It is hot-forming to make alloy densification, obtain hot-pressed magnets；In thermal deformation process, hot-pressed magnets exist
Under high moderate pressure effect, (Nd, Ce)2(Fe,Co)14B phases crystal grain is formed along easy magnetization by dissolving-mass transfer-recrystallization process
The flake crystalline that axle c-axis are consistently oriented, therefore heat distortion magnet has higher remanent magnetism；As forming temperature is low, temperature retention time is short, therefore
Crystal grain is tiny, and coercivity is high.
The hot-forming process is specially：Mixing magnetic powder is put in the first mould, to mixing in vacuum environment
Magnetic powder carries out being heated to the first temperature, and applies first pressure to the first mould, obtains hot-pressed magnets.Wherein, described first is warm
Spend for 550 DEG C～750 DEG C, the first pressure be 50MPa～250MPa and the vacuum of the vacuum environment be not less than 5 ×
10-2Pa.Preferably, first temperature is 650 DEG C～700 DEG C, the reasons why preferred is：First temperature is too low, is unfavorable for magnet
Densification, magnet density is relatively low, and magnet is present compared with multiple hole between inside；When the first temperature is raised, during more than 710 DEG C, magnetic
The crystal grain of body is grown up rapidly, causes coercivity to decrease, further, since the first temperature is higher, the grain boundary liquid phase of rich rare earth is obtained
Obtain compared with large fluidity, magnet is easily extruded under first pressure effect.Preferably, the first pressure be 170MPa～
220MPa, the reasons why preferred be：First pressure is too small, and in hot pressing, to be caused magnet fine and close hot pressing temperature is just too high,
Cause crystal grain to be grown up, rich rare earth liquid phase flows out, reduce coercivity.
The process of the thermoforming is specially：The hot-pressed magnets are put in the second mould, in an inert atmosphere
The hot-pressed magnets are carried out being heated to second temperature, then second pressure is applied to the hot pressing blank after deformation, make the hot pressing
Magnet carries out the deformation that degree of deformation is 30%～95%, obtains heat distortion magnet.Wherein described second temperature is 700 DEG C～900
DEG C, the second pressure is 30MPa～150MPa.Preferably, the second temperature is 780 DEG C～860 DEG C, the reasons why preferred
For：Low temperature is unfavorable for magnet effective deformation, because the internal equi-axed crystal for larger crackle occur and not having to deform under low temperature,
Magnet deformation is insufficient, and texture intensity is weak, and remanent magnetism is relatively low；When deformation temperature rises, and reaches 870 DEG C, crystal grain occurs abnormal long
Greatly, coercivity is on the one hand caused to reduce, another aspect coarse grain is difficult to produce deformation, and texture intensity suffers a certain degree of broken
It is bad, so remanent magnetism is also reduced.Preferably, the second pressure is 30MPa～70MPa, the reasons why preferred is：In thermal deformation process
Average deformation drag of the flow stress for elastic and plastic deformation process, is to ensure being smoothed out for thermal deformation process, forms preferable
Crystal grain orientation texture, needs higher deformation temperature and relatively low rate of deformation, and this is accomplished by appropriate Reducing distortion drag, and presses
Power is excessive, the too fast formation for being unfavorable for that crystal grain is consistently oriented of rate of deformation.
The process of the temper is specially：The heat distortion magnet is heated to into the 3rd temperature simultaneously in vacuum environment
Insulation, and the chilling that quenches after insulation terminates.3rd temperature is 500 DEG C～900 DEG C, and temperature retention time is 0.5 hour～10
Hour, during heating, heating rate is 5 DEG C/min～20 DEG C/min.Preferably, the 3rd temperature is 600 DEG C～700 DEG C, insulation
Time is 2 hours～5 hours, and during heating, heating rate is 8 DEG C/min～15 DEG C/min, the reasons why preferred is：Nd-rich phase turns
Become about 620 DEG C of temperature during liquid phase, therefore heat treatment temperature effectively facilitates the flowing of liquid phase, promotes respectively by being close to the temperature
Atoms permeating, continuing to rise a high-temperature then easily makes crystal grain grow up reduction coercivity；Temperature retention time is too short to be unfavorable for spreading, long, prolongs
Long production time and cost, experiment prove that insulation can just reach good effect in 2.5 hours.It should be noted that thermal deformation magnetic
Through temper, by atoms permeating, composition is mutually and crystal grain occurs a certain degree of change into branch for body, but grain morphology and
Size is not changed in substantially.
The present invention also provides a kind of rare earth permanent-magnetic material, and the rare earth permanent-magnetic material is prepared by said method.Institute
It is many principal phase structures to state rare earth permanent-magnetic material, and wherein principal phase is (Re, La, Ce)2(Fe,M)14B.The rare earth permanent-magnetic material is main
It is made up of nano-grade crystalline substance.The brilliant length of the nano-grade is 200nm～1000nm, and thickness is 50nm～100nm.
(Re, R are prepared with traditional sintering techniquesM)-Fe-B permanent magnet materials compare, raw materials used process is simple of the invention,
It is few to the energy and resource consumption, cheap, common association mischmetal is taken full advantage of, material cost can be substantially reduced, while
Alleviate environmental pollution, promote rare earth element balance and efficient utilization.
(Re, R are prepared with traditional sintering techniquesM)-Fe-B permanent magnet materials compare, raw materials used process is simple of the invention,
It is few to the energy and resource consumption, cheap, common association mischmetal is taken full advantage of, material cost can be substantially reduced, while
Alleviate environmental pollution, promote rare earth element balance and efficient utilization.
It is difficult to uniformly spread relative to La, Ce in existing sintering process etc., and the rare earth permanent-magnetic material that the present invention is provided
Preparation method in, during hot-forming and thermoforming, La, Ce and Pr, Nd can occur uniform counterdiffusion, be formed into
Point, the high performance magnet of even structure.
It is column crystal with respect to existing sintered magnet, crystal grain larger (micron order), grain surface defect is more, heat treatment
When, rich rare earth liquid phase is relatively poor to wettability of the surface, causes coercivity not high；Alloy is made by hot-forming in the application
Densification, obtains hot pressing blank, and in thermal deformation process, under the temperature and pressure effect of setting, equiax crystal leads to hot-pressed magnets
Dissolving-mass transfer-recrystallization process is crossed, the nano-grade crystalline substance being consistently oriented along easy magnetizing axis is formed, crystal grain stacking direction is vertical
Vertical compression force direction, forms preferable texture, therefore obtains the magnet of high anisotropy, and the magnet has higher remanent magnetism.And due to heat
Pressure and thermoforming temperature are low, and temperature retention time is short, therefore crystal grain is tiny, and coercivity is high.
Relative to working as R in existing sintering processMWhen content is high, in sintered magnet, easily there is CeFe2Phase, destruction principal phase knot
Structure, while oxygen content is higher, destroys microstructure, so comprehensive magnetic can be poor.And due to becoming in hot pressing and heat in the application
In formation type adopt low temperature moulding, it is ensured that La, Ce etc. are not oxidized, also inhibits because La, Ce exist and caused principal phase is easy
Decompose Phase-change Problems, rare earth permanent-magnetic material crystal grain is tiny obtained from, and densification degree is higher, the degree of orientation more preferably, and is not deposited
In CeFe2Deng dephasign, with more excellent organizational structure, so the rare earth permanent-magnetic material has higher coercivity and remanent magnetism, magnetic
Excellent performance.
Herein described rare earth permanent-magnetic material is many principal phase structures, and which is mainly made up of nano-grade crystalline substance, corrosion resistance
By force, with preferable practicality.
Further, the R can be also precisely adjusted as neededMThe mixing of-Fe-B quenched powders and the Re-Fe-B quenched powders
Ratio, and then adjust R in the rare earth materialMContent adjusting its magnetic characteristic, to meet the need of magnetic property in different product
Will.
The preparation method is easily achieved newly net forming, and material recovery rate is high, and process is simple is adapted to industrialized production.
Hereinafter, will further illustrate in conjunction with specific embodiments.
Embodiment (1)
According to RM- Fe-B quenched powder (MM29.6Fe69.5B0.9) in each element dispensing accurate in scale, Jing electric arcs or induction furnace
Melting is prepared into MM29.6Fe69.5B0.9Foundry alloy, fusion process are carried out under argon protection.Will in argon gas atmosphere
MM29.6Fe69.5B0.9Foundry alloy remelting, fill-before-fire to water-cooled copper roller carry out fast quenching, obtain MM29.6Fe69.5B0.9Rapid tempering belt, wherein
Roll surface speed is 35m/s, and fast quenching temperature is 1350 DEG C, and injection pressure is 0.02MPa.By MM29.6Fe69.5B0.9Rapid tempering belt is broken into
Particle diameter is the MM of 50 microns～300u microns29.6Fe69.5B0.9Quenched powder.
After magnetic separation, by MM29.6Fe69.5B0.9(composition is Nd to quenched powder with MQU-F powder29.8Pr0.4Ga0.46Co4Fe64.41B0.93)
The mixing in three-dimensional material mixer obtains mixing magnetic powder for 3 hours.Wherein MM29.6Fe69.5B0.9Quenched powder accounts for mixing magnetic powder gross mass
20%.
Mixing magnetic powder is put in the first mould, the sensing heating in vacuum environment, when temperature is upgraded to 200 DEG C, is started
First pressure is applied to the first mould, and maximum temperature is controlled to 670 DEG C, obtains hot-pressed magnets.Wherein highest is raised to from room temperature
The time of temperature is 5 minutes～6 minutes, and first pressure is 150MPa, and in hot pressing, vacuum is not less than 5 × 10-2Pa。
Hot-pressed magnets are put in the second mould being relatively large in diameter, in argon gas atmosphere hot-pressed magnets are carried out with sensing and is added
Heat, makes the hot-pressed magnets carry out the deformation that degree of deformation is 70%.1 minute is incubated after temperature reaches 790 DEG C of the highest temperature, then
Apply second pressure, obtain rare earth permanent-magnetic material.Wherein, the time for being raised to maximum temperature from room temperature is 6 minutes～7 minutes, the
Two pressure are about 50MPa.
For the composition for more preferably analyzing the rare earth permanent-magnetic material for obtaining, XRD (see Fig. 1) point is also carried out to rare earth permanent-magnetic material
Analysis.
Obtained rare earth permanent-magnetic material is tested at room temperature using the permanent magnetism B-H hysteresiscopes of NIM-500C types
Magnetic property, test result are shown in Table 1.Wherein, BrRemanent magnetism is represented, unit is kGs；HcjCoercivity is represented, unit is kOe；(BH)mTable
Show magnetic energy product, unit is MGOe.
The magnetic property of rare earth permanent-magnetic material obtained in 1 embodiment 1 to 10 of table
Embodiment (2)
The process that embodiment (2) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in heat
Deformation molding after, also including one in vacuum environment, 650 DEG C tempering 2 hours the step of.
Obtained rare earth permanent-magnetic material is carried out test magnetic property at room temperature, test result is shown in Table 1.
Embodiment (3)
The process that embodiment (3) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic powder, wherein MM29.6Fe69.5B0.9Quenched powder accounts for the 30% of mixing magnetic powder gross mass；Highest in thermoforming
Temperature is 830 DEG C.
Obtained rare earth permanent-magnetic material is carried out test magnetic property at room temperature, test result is shown in Table 1.
More preferably to analyze the composition and microscopic pattern of the rare earth permanent-magnetic material, also the rare earth permanent-magnetic material is carried out
XRD (see Fig. 1), SEM (see Fig. 2, Fig. 3, Fig. 4) and X-ray energy spectrum (EDS) (being shown in Table 2) analysis.
The EDS results of rare earth permanent-magnetic material prepared by 2 embodiment of table 3
Embodiment (4)
The process that embodiment (4) prepares rare earth permanent-magnetic material is essentially identical with embodiment (3), and difference is that heat becomes
After formation type, also including one in vacuum environment, 650 DEG C tempering 2 hours the step of.
Obtained rare earth permanent-magnetic material is carried out test magnetic property at room temperature, test result is shown in Table 1.
Embodiment (5)
The process that embodiment (5) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic powder, wherein MM29.6Fe69.5B0.9Quenched powder accounts for the 40% of mixing magnetic powder gross mass；Highest in thermoforming
Temperature is 830 DEG C.
The rare earth permanent-magnetic material for obtaining is carried out into XRD analysis (see Fig. 1).
Obtained rare earth permanent-magnetic material is carried out test magnetic property at room temperature, test result is shown in Table 1.
Embodiment (6)
The process that embodiment (6) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic powder, wherein MM29.6Fe69.5B0.9Quenched powder accounts for the 50% of mixing magnetic powder gross mass；Highest in thermoforming
Temperature is 850 DEG C.
Obtained rare earth permanent-magnetic material is carried out test magnetic property at room temperature, test result is shown in Table 1.
More preferably to analyze the composition and microscopic pattern of the rare earth permanent-magnetic material, also the rare earth permanent-magnetic material is carried out
XRD (see Fig. 1), SEM (see Fig. 5) and X-ray energy spectrum (EDS) (being shown in Table 3) analysis.
The EDS results of rare earth permanent-magnetic material prepared by 3 embodiment of table 6
Embodiment (7)
The process that embodiment (7) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic powder, by MM29.6Fe69.5B0.9(composition is for quenched powder and MQU-G powder
Nd25.5Pr0.5Dy3.5Co6.05Ga0.58Fe62.97B0.9) in three-dimensional material mixer mixing obtain within 3 hours mix magnetic powder, wherein
MM29.6Fe69.5B0.9Quenched powder accounts for the 50% of mixing magnetic powder gross mass；Maximum temperature in thermoforming is 830 DEG C.
The magnetic property of the rare earth permanent-magnetic material for obtaining is tested, 1 is the results are shown in Table.
Embodiment (8)
The process that embodiment (8) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic powder, by MM29.6Fe69.5B0.9Quenched powder and Nd22.79Pr6.67Co3.53Ga0.48Al0.2Fe65.44B0.89Quenched powder exists
Mixing in three-dimensional material mixer obtains mixing magnetic powder, wherein MM for 3 hours29.6Fe69.5B0.9Quenched powder accounts for mixing magnetic powder gross mass
30%；Maximum temperature in thermoforming is 830 DEG C.
The magnetic property of the rare earth permanent-magnetic material for obtaining is tested, 1 is the results are shown in Table.
Embodiment (9)
The process that embodiment (9) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic powder, by MM29.6Fe69.5B0.9(composition is Nd for quenched powder, MQU-G powder and two-phase powder17.7Pr5.7Fe75.7B0.9) press
Mass percent is 30：30：40 ratio mix in three-dimensional material mixer obtain within 3 hours mix magnetic powder；In thermoforming
Maximum temperature is 830 DEG C.
The magnetic property of the rare earth permanent-magnetic material for obtaining is tested, 1 is the results are shown in Table.
Embodiment (10)
The process that embodiment (10) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic powder, by MM29.6Fe69.5B0.9Quenched powder, MQU-G powder and Nd22.79Pr6.67Co3.53Ga0.48Al0.2Fe65.44B0.89
Quenched powder is 30 by mass percentage：30：40 ratio mix in three-dimensional material mixer obtain within 3 hours mix magnetic powder；Thermal deformation
Maximum temperature in molding is 830 DEG C.
The magnetic property of the rare earth permanent-magnetic material for obtaining is tested, 1 is the results are shown in Table.
Comparative example
The process that comparative example prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is to be added without
RM- Fe-B quenched powders, only prepare rare earth permanent-magnetic material with Re-Fe-B quenched powders.
The rare earth permanent-magnetic material for obtaining is carried out into XRD tests, Fig. 1 is as a result seen.
From table 1, with RMThe increase of-Fe-B quenched powder additions, heat distortion magnet coercivity decline, and remanent magnetism declines not
Substantially.Using MQU-F powder and RMWhen-Fe-B quenched powders mix, work as RMThe proportion of-Fe-B rapidly quenched magnetic powders is less than or equal to
When 20%, its remanent magnetism Br>=13.5kGs, coercivity Hcj>=12kOe, maximum magnetic energy product (BH)max≥44MGOe；Work as proportion
During less than or equal to 30%, its remanent magnetism Br>=13.4kGs, coercivity Hcj>=10kOe, maximum magnetic energy product (BH)max≥43MGOe；
When proportion is less than or equal to 40%, its remanent magnetism Br>=13.2kGs, coercivity Hcj>=8kOe, maximum magnetic energy product (BH)max
≥39MGOe；When proportion is less than or equal to 40%, its remanent magnetism Br>=13.2kGs, coercivity Hcj>=8kOe, maximum magnetic energy
Product (BH)max≥39MGOe.When proportion is less than or equal to 50%, its remanent magnetism Br>=13kGs, coercivity Hcj>=6kOe, most
Big magnetic energy product (BH)max≥32MGOe.The rare earth permanent-magnetic material for obtaining all has very high magnetic property.Also, pass through embodiment 1
The contrast of contrast, embodiment 3 and embodiment 4 with embodiment 2, it is seen that magnetic can further be improved by low-temperature tempering heat treatment
Performance.
As seen from Figure 1, the principal phase of the rare earth permanent-magnetic material is (Nd/Pr, La, Ce)2(Fe,Co)14B phases.And
With RMThere is not CeFe in the increase of-Fe-B quenched powder additions, heat distortion magnet2Deng dephasign；Heat distortion magnet has higher orientation
Degree, keeps preferable texture, so higher remanent magnetism can be kept.
From Fig. 2 to Fig. 5, table 2 and table 3, rare earth permanent-magnetic material is made up of many principal phases, and main phase grain mostly is lamellar
Crystalline substance, there is also the equiax crystal that part does not deform, wherein the length of the flake crystalline is 600nm～800nm, thickness is about
100nm。
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improve and modification is also fallen in the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope for causing.
Claims (9)
1. a kind of preparation method of rare earth permanent-magnetic material, which comprises the following steps：
(1) Re-Fe-B quenched powders and R are provided respectivelyM- Fe-B quenched powders, wherein the RMThe chemical formula of-Fe-B quenched powders is
RMdFe100-d-e-fMeBf, RMIt is by the common association mischmetal of Rare Earth Mine exploitation, RMIncluding each element of following mass fraction：
20%～30%La, 48%～58%Ce, 4%～7%Pr and 15%～20%Nd, the quality percentage of d, e and f for corresponding element
Content, and 25%≤d≤35%, 0%≤e≤3%, 0.6%≤f ＜ 1.1%；
(2) by the Re-Fe-B quenched powders and the RM- Fe-B quenched powder mix homogeneously obtains mixing magnetic powder, wherein, described mixed
Close R described in magnetic powderMMass percent shared by-Fe-B quenched powders is 10%～90%；
(3) the mixing magnetic powder is carried out into hot-forming, thermoforming and temper successively, obtains rare earth permanent-magnetic material,
The rare earth permanent-magnetic material is many principal phase structures, and the rare earth permanent-magnetic material is mainly made up of nano-grade crystalline substance.
2. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, it is characterised in that the Re-Fe-B quenched powders
Chemical formula is ReaFe100-a-b-cMbBc, during wherein Re is Nd, Pr, Y, La, Ce, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
One or more, M is one or more in Mn, Co, Ni, Zr, Ti, Cu, Zn, Al, Ga, In, Sn, Ge and Si, and a～c is right
Answer the weight/mass percentage composition of element, and 25%≤a≤35%, 0%≤b≤3%, 0.6%≤c ＜ 1.1%.
3. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, it is characterised in that described in the mixing magnetic powder
RMMass percent shared by-Fe-B quenched powders is 10%～50%.
4. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, it is characterised in that step (1) described in RM-Fe-B
The preparation method of quenched powder is as follows：
First, using the method melting R of electric arc or induction meltingMdFe100-d-e-fMeBfFoundry alloy, the fusion process is in indifferent gas
Carry out under atmosphere；
Then, in an inert atmosphere by molten state RMdFe100-d-e-fMeBfFoundry alloy is sprayed to water-cooled running roller carries out fast quenching, obtains
RM- Fe-B rapid tempering belts, wherein roll surface speed are 10m/s～50m/s, and fast quenching temperature is 1000 DEG C～1500 DEG C, and injection pressure is
0.01MPa～0.1MPa；
Finally, by the RM- Fe-B rapid tempering belts carry out Mechanical Crushing, form the R that particle diameter is 50 microns～300 micronsM- Fe-B is fast
Quench powder.
5. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, it is characterised in that step (3) described in be hot pressed into
The process of type is specially：Mixing magnetic powder is put in the first mould, carries out being heated to first to mixing magnetic powder in vacuum environment
Temperature, and first pressure is applied to the first mould, hot-pressed magnets are obtained, wherein, first temperature is 550 DEG C～750 DEG C, institute
It is 50MPa～250MPa to state first pressure, and the vacuum of the vacuum environment is not less than 5 × 10-2Pa。
6. the preparation method of rare earth permanent-magnetic material as claimed in claim 5, it is characterised in that step (3) described in thermal deformation
The process of molding is specially：The hot-pressed magnets are put in the second mould, in an inert atmosphere the hot-pressed magnets are carried out
Be heated to second temperature and second pressure is applied to the hot pressing blank after deformation again, make the hot pressing blank degree of deformation be carried out for 30%
～95% deformation, heat distortion magnet is obtained, wherein the second temperature is 700 DEG C～900 DEG C, the second pressure is
30MPa～150MPa.
7. the preparation method of rare earth permanent-magnetic material as claimed in claim 6, it is characterised in that step (3) described at tempering
The process of reason is specially：The heat distortion magnet is heated to into the 3rd temperature in vacuum environment and is incubated, and terminated in insulation
After quench chilling, wherein the 3rd temperature is 500 DEG C～900 DEG C, temperature retention time is 0.5 hour～10 hours, and heat up during heating speed
Rate is 5 DEG C/min～20 DEG C/min.
8. the rare earth permanent-magnetic material that a kind of employing preparation method as described in claim 1 to 7 is obtained, it is characterised in that described dilute
Native permanent magnet material is many principal phase structures, and wherein principal phase is (Re, La, Ce)2(Fe,M)14B, the rare earth permanent-magnetic material is mainly by receiving
Meter level flake crystalline is constituted.
9. rare earth permanent-magnetic material as claimed in claim 8, it is characterised in that the brilliant length of the nano-grade is 200nm
～1000nm, thickness are 50nm～100nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108515177A (en) * | 2018-05-18 | 2018-09-11 | 江西理工大学 | A kind of nanocomposite rare earth permanent-magnetic material and its preparation with more main phase structures |
| CN108766703A (en) * | 2018-06-08 | 2018-11-06 | 江西理工大学 | A kind of more main phase high abundance rare earth permanent-magnetic materials of high temperature resistant and preparation method thereof |
| CN109300680A (en) * | 2018-08-24 | 2019-02-01 | 中国科学院宁波材料技术与工程研究所 | The screening technique of rare earth permanent-magnetic material |
| CN111161949A (en) * | 2019-12-31 | 2020-05-15 | 浙江大学 | YCe co-doped nanocrystalline rare earth permanent magnet and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3626406A1 (en) * | 1985-08-13 | 1987-02-26 | Seiko Epson Corp | METHOD FOR PRODUCING PERMANENT MAGNETS BASED ON RARE EARTH METALS |
| CN104599802A (en) * | 2014-12-03 | 2015-05-06 | 中国科学院宁波材料技术与工程研究所 | Rare earth permanent magnetic material and preparation method thereof |
| CN104637643A (en) * | 2015-03-05 | 2015-05-20 | 内蒙古科技大学 | Rare-earth permanent magnet material mixed with bayan obo co-existence and associated crude ores and method for manufacturing rare-earth permanent magnet material |
-
2016
- 2016-10-17 CN CN201610901288.9A patent/CN106548843A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3626406A1 (en) * | 1985-08-13 | 1987-02-26 | Seiko Epson Corp | METHOD FOR PRODUCING PERMANENT MAGNETS BASED ON RARE EARTH METALS |
| CN104599802A (en) * | 2014-12-03 | 2015-05-06 | 中国科学院宁波材料技术与工程研究所 | Rare earth permanent magnetic material and preparation method thereof |
| CN104637643A (en) * | 2015-03-05 | 2015-05-20 | 内蒙古科技大学 | Rare-earth permanent magnet material mixed with bayan obo co-existence and associated crude ores and method for manufacturing rare-earth permanent magnet material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108515177A (en) * | 2018-05-18 | 2018-09-11 | 江西理工大学 | A kind of nanocomposite rare earth permanent-magnetic material and its preparation with more main phase structures |
| CN108515177B (en) * | 2018-05-18 | 2020-09-01 | 江西理工大学 | Nanocrystalline composite rare earth permanent magnet material with multi-main-phase structure and preparation thereof |
| CN108766703A (en) * | 2018-06-08 | 2018-11-06 | 江西理工大学 | A kind of more main phase high abundance rare earth permanent-magnetic materials of high temperature resistant and preparation method thereof |
| CN109300680A (en) * | 2018-08-24 | 2019-02-01 | 中国科学院宁波材料技术与工程研究所 | The screening technique of rare earth permanent-magnetic material |
| CN109300680B (en) * | 2018-08-24 | 2023-08-29 | 中国科学院宁波材料技术与工程研究所 | Screening method of rare earth permanent magnet material |
| CN111161949A (en) * | 2019-12-31 | 2020-05-15 | 浙江大学 | YCe co-doped nanocrystalline rare earth permanent magnet and preparation method thereof |
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