CN113215497B - Sintered neodymium-iron-boron permanent magnet material with high coercive force and high magnetic energy product and preparation method - Google Patents
Sintered neodymium-iron-boron permanent magnet material with high coercive force and high magnetic energy product and preparation method Download PDFInfo
- Publication number
- CN113215497B CN113215497B CN202110488544.7A CN202110488544A CN113215497B CN 113215497 B CN113215497 B CN 113215497B CN 202110488544 A CN202110488544 A CN 202110488544A CN 113215497 B CN113215497 B CN 113215497B
- Authority
- CN
- China
- Prior art keywords
- alloy
- main
- auxiliary
- hydrogen
- permanent magnet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 58
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 44
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 241
- 239000000956 alloy Substances 0.000 claims abstract description 241
- 238000000034 method Methods 0.000 claims abstract description 75
- 230000008569 process Effects 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 15
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 86
- 229910052739 hydrogen Inorganic materials 0.000 claims description 86
- 239000000843 powder Substances 0.000 claims description 79
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 77
- 239000000203 mixture Substances 0.000 claims description 46
- 238000013461 design Methods 0.000 claims description 33
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 150000002910 rare earth metals Chemical class 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 22
- 238000002074 melt spinning Methods 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 230000006698 induction Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000009694 cold isostatic pressing Methods 0.000 claims description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000654 additive Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 230000000996 additive effect Effects 0.000 description 18
- 230000008901 benefit Effects 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 230000002195 synergetic effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000000462 isostatic pressing Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001808 coupling effect Effects 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005347 demagnetization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910000583 Nd alloy Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/023—Hydrogen absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
-
- 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
- H01F1/0573—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 obtained by reduction or by hydrogen decrepitation or embrittlement
-
- 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
- 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
- H01F1/0577—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 sintered
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/20—Use of vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2202/00—Treatment under specific physical conditions
- B22F2202/05—Use of magnetic field
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention provides a sintered NdFeB permanent magnet material with high coercivity and high magnetic energy product and a preparation method thereof2(Fe,M)14B a main alloy of intermetallic compounds A and at least one RE biased toward high coercivity2(Fe,M)14B, a main alloy B of an intermetallic compound, wherein the auxiliary alloy is a grain boundary phase substance, the main alloy and the auxiliary alloy are mixed in a solid state, before the mixing, the main alloy is firstly made into an alloy sheet, and the auxiliary alloy is made into a sheet-shaped, block-shaped or larger granular alloy. The invention relates to a high-coercivity and high-magnetic-energy-product sintered neodymium-iron-boron permanent magnet material and a preparation method thereof, and provides process and technical support for batch production of high-coercivity and high-magnetic-energy-product double-height sintered neodymium-iron-boron permanent magnet materials.
Description
Technical Field
The invention relates to the technical field of sintered neodymium iron boron permanent magnet material manufacturing, in particular to a sintered neodymium iron boron permanent magnet material with high coercivity and high magnetic energy product and a preparation method thereof.
Background
The sintered Nd-Fe-B permanent magnet material is a strategic rare earth functional new material which is mainly developed in China, has the advantages of small volume, high magnetic energy density, strong demagnetization interference resistance and the like, is widely applied to various fields of new energy, electronic communication, artificial intelligence, rail traffic, aerospace, national defense war industry and the like, and continues to increase at the speed of 5-10% every year. In 2019, the actual national yield reaches about 17 ten thousand tons.
It is known from the application end that the neodymium iron boron magnet is designed by paying more attention to the size of magnetic flux, magnetic moment and surface magnetic induction intensity. However, it can be found from reading many professional works related to neodymium iron boron and from application practices that, in the main magnetic performance indexes of the permanent magnetic material, although the magnetic flux, the magnetic moment and the surface magnetic induction intensity have strong correlation with the remanence, the high remanence cannot necessarily obtain the high magnetic flux, the magnetic moment and the surface magnetic induction intensity, and under the condition of high coercive force and high magnetic energy product, the magnetic flux, the magnetic moment and the surface magnetic induction intensity can be higher. That is to say, the neodymium iron boron magnet with high coercivity and high magnetic energy product has more practical value.
At present, the sintered Nd-Fe-B permanent magnet material prepared in the industry generally adopts a powder metallurgy process, namely, the preparation of the material is completed through main procedures of rapid hardening and melt spinning, hydrogen crushing, airflow milling, magnetic field orientation molding, vacuum sintering, heat treatment and the like. Since the eighties of the last century till now, countless technical workers from scientific research institutions and enterprises have made a great deal of research and development work, and after decades of development and technical progress, the performance of the sintered neodymium iron boron permanent magnet material is much better than the performance of the sintered neodymium iron boron permanent magnet material in the past. However, how to realize the high-efficiency preparation of the 'double-high' sintered neodymium-iron-boron permanent magnet material with high coercivity and high magnetic energy product and the realization of the control of mass production is still a technical problem which is not well solved.
The invention patent (invention patent No. CN 111383808A) in China teaches a preparation method for preparing high remanence and high coercivity NdFeB magnet by adopting double alloy and grain boundary phase adding technology, but the invention focuses on solving the problems of remanence and coercivity of NdFeB permanent magnet material produced by mixed rare earth, which is only a small door in the whole NdFeB industry, and adopts a method of mixing three different alloys after respectively milling powder, namely NdFeB containing mixed rare earth, NdFeB not containing mixed rare earth and NdH2And (3) carrying, hydrogen crushing and pulverizing the + PrCu alloy, uniformly mixing, pressing and molding, sintering and aging to obtain the neodymium-iron-boron magnet. Due to the limitation that the scheme design must have two main component alloys of mixed rare earth neodymium iron boron and mixed rare earth neodymium iron boron, the method is not suitable for solving the performance problems of other types of neodymium iron boron except the door type. In addition, this method has the following problems: the three alloys are limited to be made into casting sheets by a melt-spun method, are not suitable for the alloys made by other methods, and cannot obtain the advantages of the alloys made by other methods; ② the auxiliary alloy is NdH only2+ PrCu can provide low-melting-point substances to a certain extent, so as to improve the structure of a grain boundary phase, but the capability of improving the coercive force is limited, and a magnet with low recovery magnetic permeability is difficult to obtain and is not suitable for preparing a magnet with high magnetic energy product; mixing in the powder stage, wherein the difficulty of uniform mixing is relatively high, and the industrial application needs to rely on better equipment to ensure that the powder is not oxidized and spontaneously combusted, so that potential safety hazards exist; and fourthly, no secondary proportioning design based on actual components is carried out, and the actual components may deviate.
Another method for improving the magnetic property of rare earth neodymium iron boron is disclosed in the Chinese invention patent (invention patent No. CN 109102976A). The method adopts a double-alloy method, namely rare earth neodymium iron boron main alloy and RTM crystal boundary auxiliary alloy cast pieces are respectively prepared by a strip-spinning method, and then are subjected to hydrogen crushing, powder preparation, molding, low-temperature long-time sintering and heat treatment together to obtain the neodymium iron boron magnet with higher performance. Problems with this approach are: the alloy is limited to be made into a cast sheet by a melt-spun method, so that the alloy is not suitable for the alloy made by other methods, and the advantage of making the alloy by other methods cannot be obtained; secondly, only one main alloy can not exert the synergistic advantage of the two main phases; r in RTM is only one or more of heavy rare earth elements, and the synergistic effect of light rare earth and heavy rare earth is not exerted; and fourthly, no secondary proportioning design based on actual components is carried out, and the actual components may deviate. The method can improve the performance of the neodymium iron boron magnet to a certain degree, but has no key effect on preparing the double-high neodymium iron boron permanent magnet material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-coercivity and high-magnetic-energy-product sintered neodymium-iron-boron permanent magnet material and a preparation method thereof, so that a process and a technical support are provided for batch production of a high-coercivity and high-magnetic-energy-product double-height sintered neodymium-iron-boron permanent magnet material.
(1) In order to achieve the purpose, the invention provides a high-coercivity and high-magnetic-energy-product sintered neodymium-iron-boron permanent magnet material which comprises a main alloy and at least one auxiliary alloy, wherein the main alloy comprises at least one RE biased to a high-magnetic-energy-product design2(Fe, M)14B a main alloy of intermetallic compounds A and at least one RE biased toward high coercivity2(Fe, M)14B, a main alloy B of an intermetallic compound, wherein the auxiliary alloy is a grain boundary phase substance; the main alloy and the auxiliary alloy are mixed in a solid state.
The innovation points of the invention are as follows: the invention is composed of at least two main alloys and at least one auxiliary alloy, and has at least two main phases and at least one grain boundary phase, wherein the main alloy A and the main alloy B both play the role of a main phase of a magnet, and the auxiliary alloy plays the role of strengthening and regulating the grain boundary phase for a grain boundary phase substance which is designed and added according to actual needs; the composition of the main alloy A and the main alloy B is not limited too much, so long as the difference of the design components of the two main alloys is increased as much as possible, and the proportion of the two main alloys in the total mass is emphasized according to the requirement of target performance, so that different main phases are formed after sintering to play the synergistic effect of the two main phases, for example, the main alloy A is mainly characterized by low total rare earth content, no or low heavy rare earth content, low return permeability and high magnetic energy product, and mainly plays the role of one of the main phases; the main alloy B is mainly characterized by lower total weight of heavy rare earth, relatively higher content of heavy rare earth, high intrinsic coercivity and high squareness, and mainly plays a role of the other main phase.
Preferably, before the main alloy and the secondary alloy are mixed in a solid state, the main alloy is firstly made into alloy flakes, and the secondary alloy is made into a flake-shaped, block-shaped or larger granular alloy; the alloy sheet of the main alloy is prepared by adopting a method of medium-frequency induction vacuum melting and rapid hardening melt-spinning, and the specific feeding steps in the manufacturing process of the alloy sheet are as follows:
(1) firstly, filling Fe, Co and B-Fe alloy into a medium-frequency induction vacuum melting furnace;
(2) adding rare earth raw materials when the previously added materials begin to melt;
(3) metallic Cu or metallic Ga is added to the previously added materials at the time of melting them completely.
Before a plurality of main alloys and auxiliary alloys are mixed, the main alloys are firstly made into alloy sheets, the auxiliary alloys are made into flaky, blocky or larger granular alloys, meanwhile, the main alloys adopt three times of feeding and different smelting rapid hardening melt-spinning process parameter settings, the difference of components and microstructure structures among different main alloys is maximized, and the main alloys are mixed in a solid state, so that elements and phases of the main alloys are not easily fused, a synergistic coupling effect is achieved among the main alloys, the performance of the different main alloys is exerted to the maximum, and the defect that the coercive force and the magnetic energy product cannot be obtained simultaneously or the performance of the coercive force and the magnetic energy product cannot achieve an ideal effect in the traditional method is overcome.
Preferably, when the alloy sheet is manufactured, the refining temperature of the main alloy A reaches 1550-; the refining temperature of the main alloy B reaches 1500-; in order to improve the dual high performance of the neodymium iron boron permanent magnet material, the difference between the components and the microstructure of the two main phases needs to be maximized as much as possible, so that the elements and the phases of the neodymium iron boron permanent magnet material are not easy to melt, and the neodymium iron boron permanent magnet material also has a synergistic coupling effect, and the performances of different main alloys are exerted to the maximum; one of the main alloy A and the main alloy B is different in composition component, so that the composition difference is formed, and the other is the microstructure difference.
Preferably, the main alloy and the auxiliary alloy are mixed in a solid state and then are made into coarse powder through two processes of hydrogen absorption and dehydrogenation; the two main alloys are made into coarse powder through two-wheel hydrogen absorption-dehydrogenation processes, the powder granularity and the apparent state of the two main alloys are different, the difference between the powder granularity and the apparent state is formed, and the difference between the composition components of the two main alloys and the difference between microstructure structures are combined, so that the uniform mixing, the high-orientation degree pressing, the sintering densification, the grain refinement and the continuous and uniform distribution of grain boundary phases of the powder are facilitated, and the synergistic effect between different main phases and between the main phase and the auxiliary phase is facilitated.
Preferably, the thickness of the alloy sheet is 0.2-0.4 mm; the thinner the alloy is, the faster the cooling rate is, and the more uniform the growth direction of the main phase grains and the better the penetrability from the roll surface to the free surface are, which contributes to the exertion of high coercive force and high magnetic energy product performance.
A preparation method of a sintered NdFeB permanent magnet material with high coercivity and high magnetic energy product comprises the following steps: (1) respectively adopting intermediate frequency induction vacuum melting and rapid hardening melt-spinning methods to prepare alloy sheets from at least two main alloys, equally dividing three times of feeding materials, namely firstly feeding Fe, Co and B-Fe alloys when the alloy sheets are fed into a furnace, secondly adding rare earth raw materials such as Pr-Nd alloy, Dy-Fe alloy and metal Tb when the front fed materials start to be melted, and finally adding metal Cu and metal Ga when the front fed materials are about to be completely melted, wherein the refining temperature of the main alloy A reaches 1550-; the refining temperature of the main alloy B reaches 1500-;
(2) mixing the obtained slices with at least one auxiliary alloy in solid state, and making into coarse powder by two-step hydrogen absorption-dehydrogenation process;
(3) after dehydrogenation and cooling, 0.01-0.3% of liquid or powder additive is added to mix the coarse powder for 1-5 h,
(4) controlling the average particle diameter SMD of the powder to be 2.0-4.0 μm by using an air flow mill,
(5) then adding 0.01-0.3% of liquid or powder additive to mix fine powder,
(6) orienting and pressing in a magnetic field of more than 1.8T,
(7) and preparing a green body by cold isostatic pressing, and obtaining the sintered neodymium iron boron permanent magnet material with high coercive force and high magnetic energy product by adopting vacuum sintering and heat treatment.
The innovation points of the invention are as follows:
(1) firstly, main alloys with different components are respectively made into slices by a vacuum melting rapid hardening melt-spinning method, the compound stability of the main alloys is strong after the slices are made, and the situation that elements and phases among different main alloys are mutually fused due to subsequent processing and mixing is avoided or rarely occurs; after the slice is made, the slice is mixed with the auxiliary alloy in the solid state (namely before hydrogen crushing), and each process of hydrogen crushing, coarse powder mixing, airflow milling and fine powder mixing of two subsequent rounds of hydrogen absorption-dehydrogenation can realize one-time mixing of the alloy with different components; secondly, the advantages of the various main alloys and at least one auxiliary alloy are exerted respectively and are cooperated with each other, so that the purpose of complementary advantages is achieved, and the defect that the coercive force and the magnetic energy product cannot be obtained simultaneously in the traditional method is overcome. Compared with the traditional method, the technical scheme provided by the invention saves the use amount of heavy rare earth under the condition of achieving the same performance; by adopting the traditional single alloy process with heavy rare earth and light rare earth elements, the heavy rare earth can easily enter the main phase to replace the light rare earth elements in the main phase, thereby reducing the saturation magnetic polarization strength of the material;
(2) in the hydrogen crushing process, under the hydrogen crushing process method of two rounds of hydrogen absorption-dehydrogenation, the effect of crushing single crystals can be approached by regulating and controlling pressure, temperature, time and other control parameters, and different alloys obtain different powder particle sizes, thereby being beneficial to the exertion of the synergistic effect among different main phases and between the main phase and the auxiliary phase; in the powder mixing process, liquid or powder additives can be added in a certain proportion to enhance the fluidity, the oxidation resistance and the like of the neodymium iron boron powder, and the neodymium iron boron powder is mixed for a certain time by powder mixing equipment to achieve a uniform mixing state; the powder process of the air current mill can be oxygenated or not according to the needs, and the technological and equipment parameters such as the oxygen addition amount, the gas medium, the pressure, the material level, the nozzle diameter, the nozzle angle and the like are regulated and controlled in a balanced manner, so that the powder particle size distribution is improved, the consistency of the material magnet is ensured, and the method is suitable for mass production.
Preferably, the two-round hydrogen absorption-dehydrogenation process in the step (2) is to firstly rotate and absorb hydrogen for 0.5-1h under the hydrogen partial pressure of 0.15MPa, keep the temperature at 580 ℃ and dehydrogenate to the vacuum degree of below 30Pa, fill hydrogen again, control the hydrogen partial pressure to 0.1MPa, rotate and absorb hydrogen to saturation, keep the temperature at 500 ℃ and dehydrogenate to the vacuum degree of below 1 Pa.
Preferably, the main alloy and the auxiliary alloy need to be designed through secondary proportioning before being mixed; different from the traditional proportioning design, because the invention is made of a plurality of main alloys and auxiliary alloys, in the initial stage of manufacture, firstly, the theoretical composition proportion of each element in each main alloy and each auxiliary alloy is independently designed, the different main alloys are respectively made into alloy sheets, the auxiliary alloys are made into flaky, blocky or larger granular alloys, after the actual composition component test analysis of each main alloy and each auxiliary alloy, the mass composition proportion between each main alloy and each auxiliary alloy is designed and calculated according to the analysis result; the secondary proportioning design and mixing must be carried out under the state of sheet or block alloy, which not only corrects the influence of element content change caused by the defects of raw materials and previous process operation (such as high impurity content of raw materials, large actual burning loss in the smelting melt-spinning process, and the like), but also eliminates the formation of magnetic body reverse magnetization nucleus caused by phase oxidation due to the mixture of powder state, the stability of process operation and actual composition of the magnetic body is good, the consistency of performance between products of different batches is better, and the product quality stability of mass production is facilitated; meanwhile, because the types and the number of the main alloys and the auxiliary alloys are not fixed, the secondary proportioning combination between the main alloys and the auxiliary alloys is not fixed, and the secondary proportioning combination can be the proportioning combination of two main alloys and one auxiliary alloy, the proportioning combination of two main alloys and a plurality of auxiliary alloys, and the proportioning combination of a plurality of main alloys and one or more auxiliary alloys.
Preferably, in the magnetic field orientation forming process, the preparation of the green body can be completed by the modes of magnetic field orientation, mechanical pressing and cold isostatic pressing, or by the modes of magnetic field orientation and direct mechanical pressing, or the green body can be further cut and processed into a smaller geometric shape and a smaller size under the protection of atmosphere; the magnetic field orientation forming mode is various and the application range is wide.
Preferably, the mass percent of the auxiliary alloy is 0.1% -3%; because the auxiliary alloy belongs to weak magnetic or non-magnetic materials, if the proportion is too large, the magnetic performance of the invention is influenced, and if the proportion is too small, the effect of a grain boundary phase cannot be exerted; meanwhile, the process control parameters of the subsequent process should be matched with the crystal grain boundary so that the crystal grain boundary is distributed as far as possible and does not enter the main phase.
The invention has the beneficial effects that: the method can effectively avoid the potential safety hazard of spontaneous combustion caused by oxidation in the powder mixing process, has better consistency of product performance in the same batch due to the mixing of different alloys in a solid state, does not need to depend on a high-cost atmosphere protection system, reduces the consumption of protective gases such as nitrogen, argon and the like, and enhances the reliability and the practicability of the technology; secondly, through secondary proportioning design before mixing, the product performance consistency can be effectively improved, the respective advantages of the main alloy and the auxiliary alloy are better exerted and are mutually cooperated at the same time, the purpose of advantage complementation is achieved, and the defect that coercive force and magnetic energy product cannot be obtained simultaneously in the traditional method is overcome; compared with the traditional method, the technical scheme provided by the invention saves the use amount of heavy rare earth under the condition of achieving the same performance.
The features and advantages of the present invention will be described in detail by embodiments in conjunction with the accompanying drawings.
Drawings
FIG. 1 is a process scheme of the present invention.
Fig. 2 is a conventional dual alloy process scheme.
Fig. 3 is a conventional dual main phase process scheme.
FIG. 4 is a comparative graph of remanence for example 1 and comparative examples 3, 4, 5.
Fig. 5 is a diagram showing comparison of the magnetic coercive force of example 1 with that of comparative examples 3, 4 and 5.
Fig. 6 is a schematic diagram comparing intrinsic coercive force of example 1 with those of comparative examples 3, 4 and 5.
FIG. 7 is a graph showing the comparison of the magnetic energy product of example 1 with that of comparative examples 3, 4 and 5.
Fig. 8 is a graph showing the comparison of the squareness of the demagnetization curves of example 1 and comparative examples 3, 4 and 5.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The main alloy A has the design component of (Pr)0.25Nd0.75)29Fe68.8Co1Cu0.1Ga0.2B0.9(mass ratio), the main alloy B is designed to be (Pr)0.25Nd0.75)29Dy1Fe67.75Co1Cu0.1Ga0.15B1(mass ratio), preparing alloy sheets with the thickness of 0.2-0.4mm by material preparation, vacuum melting and rapid hardening melt spinning; the secondary alloy C has the design component of (Pr)0.25Nd0.75)50Dy30Al10Zr3Nb7(mass ratio), and preparing alloy cast ingots through batching and vacuum melting. Sampling and testing three alloys respectively to analyze the components, mixing the three alloys according to the proportion of A: B: C =65:34:1 according to the analysis result, loading the three alloys into a hydrogen crushing furnace to absorb hydrogen, preparing coarse powder by adopting a two-wheel hydrogen absorption-dehydrogenation process, namely firstly rotationally absorbing hydrogen for 0.5-1h under the partial pressure of 0.15MPa hydrogen, preserving heat and dehydrogenating the mixture at 580 ℃ until the vacuum degree is below 30Pa, filling hydrogen again, controlling the partial pressure of the hydrogen to 0.1MPa rotationally absorbing hydrogen until the mixture is saturated, preserving heat and dehydrogenating the mixture at 500 ℃ until the vacuum degree is below 1Pa, adding 0.1% of liquid additive mixed coarse powder for 3h, controlling the particle size SMD to 3.0 mu m by using an air flow mill, adding 0.1% of liquid additive mixed fine powder for 2h, pressing and molding the mixture in a 1.8T magnetic field, placing the mixture into the furnace to sinter and thermally treat the mixture after isostatic pressing at 200 MPa: 1040 ℃ for 10h, 900 ℃ for 3h and 500 ℃ for 5h, and cooling and discharging to obtain the magnet.
Example 2
The main alloy A has the design component of (Pr)0.25Nd0.75)29Fe68.8Co1Cu0.1Ga0.2B0.9(mass ratio), the main alloy B is designed to be (Pr)0.25Nd0.75)29Dy1Fe67.75Co1Cu0.1Ga0.15B1(mass ratio), preparing alloy sheets with the thickness of 0.2-0.4mm by material preparation, vacuum melting and rapid hardening melt spinning; the secondary alloy C has the design component of (Pr)0.25Nd0.75)60Dy30Al10(mass ratio), the design component of the secondary alloy D is Zr30Nb70(mass ratio), preparing alloy ingots through proportioning and vacuum melting. Respectively sampling and testing four alloysAnalyzing the components, mixing the components according to the ratio of A: B: C: D =65:34:0.9:0.1, loading the mixture into a hydrogen crushing furnace for absorbing hydrogen, preparing coarse powder by adopting a two-wheel hydrogen absorption-dehydrogenation process, namely firstly rotationally absorbing hydrogen for 0.5-1h under the partial pressure of 0.15MPa hydrogen, preserving heat and dehydrogenating the mixture at 580 ℃ until the vacuum degree is below 30Pa, filling hydrogen again, controlling the partial pressure of the hydrogen to 0.1MPa for rotationally absorbing hydrogen until the mixture is saturated, preserving heat and dehydrogenating the mixture at 500 ℃ until the vacuum degree is below 1Pa, adding 0.1% of liquid additive mixed coarse powder for 3h, controlling the ground powder size SMD to 3.0 mu m by using an air flow mill, adding 0.1% of liquid additive mixed fine powder for 2h, pressing the mixture in a 1.8T magnetic field for forming, putting the mixture into the furnace for sintering and heat treatment after isostatic pressing at 200 MPa: 1040 ℃ for 10h, 900 ℃ for 3h and 500 ℃ for 5h, and cooling and discharging to obtain the magnet.
Example 3
The main alloy A comprises the following design components (Pr)0.25Nd0.75)29Fe68.8Co1Cu0.1Ga0.2B0.9(mass ratio), the main alloy B1 is designed to have the composition (Pr)0.25Nd0.75)29Dy0.7Fe68.05Co1Cu0.1Ga0.15B1(mass ratio), the main alloy B2 is designed to have the composition (Pr)0.25Nd0.75)29Dy1.5Fe67.25Co1Cu0.1Ga0.15B1(mass ratio), preparing alloy sheets with the thickness of 0.2-0.4mm by material preparation, vacuum melting and rapid hardening melt spinning; the secondary alloy C has the design component of (Pr)0.25Nd0.75)50Dy30Al10Zr3Nb7(mass ratio), and preparing alloy cast ingots through batching and vacuum melting. Respectively sampling and testing four alloys to analyze the components, mixing the four alloys according to the analysis result in the proportion of A: B1: B2: C =65:22:12:1, loading the four alloys into a hydrogen crushing furnace to absorb hydrogen, preparing coarse powder by adopting a two-wheel hydrogen absorption-dehydrogenation process, namely firstly rotationally absorbing hydrogen for 0.5-1h under the hydrogen partial pressure of 0.15MPa, preserving heat and dehydrogenating the mixture at 580 ℃ to the vacuum degree below 30Pa, filling hydrogen again, controlling the hydrogen partial pressure to be 0.1MPa, rotationally absorbing hydrogen to be saturated, preserving heat and dehydrogenating the mixture at 500 ℃ to the vacuum degree below 1Pa, adding 0.1% of liquid additive to mix the coarse powder for 3h, and milling SMD (surface mounted device) granularity by using a jet mill to control the particle sizeMaking into 3.0 μm, adding 0.1% liquid additive mixed fine powder for 2h, press-forming in 1.8T magnetic field, isostatic pressing at 200MPa, sintering in furnace and heat treating: 1040 ℃ for 10h, 900 ℃ for 3h and 500 ℃ for 5h, and cooling and discharging to obtain the magnet.
Comparative example 1
The main alloy is designed to have the composition (Pr)0.25Nd0.75)28.8Fe69Co1Cu0.1Ga0.2B0.9(mass ratio), preparing an alloy sheet with the thickness of 0.2-0.4mm by adopting industrial metal and alloy raw materials through batching, vacuum melting and rapid hardening melt spinning; the secondary alloy is designed to have the composition (Pr)0.25Nd0.75)55Dy30Al5Zr3Nb7(mass ratio), and preparing alloy cast ingots through batching and vacuum melting. Respectively putting the alloy powder into a furnace for hydrogen crushing, preparing coarse powder by adopting two-wheel hydrogen absorption-dehydrogenation processes, namely, firstly, rotationally absorbing hydrogen for 0.5-1h under the partial pressure of 0.15MPa hydrogen, preserving heat and dehydrogenating at 580 ℃ until the vacuum degree is below 30Pa, filling hydrogen again, controlling the partial pressure of the hydrogen to be 0.1MPa, rotationally absorbing the hydrogen until the hydrogen is saturated, preserving heat and dehydrogenating at 500 ℃ until the vacuum degree is below 1Pa, respectively adding 0.1% of liquid additive for mixing the coarse powder for 3h, controlling the powder size SMD of the main alloy to be 3.0 mu m through an air flow mill, controlling the powder size SMD of the auxiliary alloy to be 2.5 mu m, mixing the two alloy powders according to the proportion of the main alloy powder =98:2, adding 0.1% of liquid additive for mixing the fine powder for 2h, pressing and forming in a 1.8T magnetic field, putting the two alloy powders into the furnace for sintering and heat treatment after isostatic pressing at 200 MPa: 1050 ℃ for 10h, 900 ℃ for 3h and 500 ℃ for 5h, and cooling and discharging to obtain the magnet.
Comparative example 2
The main alloy A has the design composition of
(Pr0.25Nd0.75)29.2Dy0.6Fe67.79Co1Cu0.1Al0.11Zr0.03Nb0.07Ga0.18B0.92(mass ratio), the main alloy B is designed to be (Pr)0.25Nd0.75)29Dy1Fe67.8Co1Cu0.1Ga0.2B0.9(mass ratio), proportioning, vacuum smelting and rapid hardening and melt spinningRespectively preparing alloy sheets with the thickness of 0.2-0.4mm, respectively performing hydrogen crushing in a furnace,
two-wheel 'hydrogen absorption-dehydrogenation' process is adopted to prepare coarse powder, namely, firstly, rotary hydrogen absorption is carried out for 0.5-1h under 0.15MPa hydrogen partial pressure, heat preservation and dehydrogenation are carried out at 580 ℃ until the vacuum degree is below 30Pa, hydrogen is filled again, the hydrogen partial pressure is controlled to be 0.1MPa, rotary hydrogen absorption is carried out until the saturation, heat preservation and dehydrogenation are carried out at 500 ℃ until the vacuum degree is below 1Pa, 0.1% of liquid additive is respectively added for mixing the coarse powder for 3h, the milled powder size SMD of the main alloy A is controlled to be 3.0 mu m through an air flow mill, the milled powder size SMD of the main alloy B is controlled to be 2.5 mu m, the two alloy powders are mixed according to the proportion of A: B =95:5, 0.1% of liquid additive fine powder is added for mixing for 2h, the mixture is pressed and molded in a 1.8T magnetic field, and is put into a furnace for sintering and heat treatment after being isostatic pressed by 200 MPa: 1040 ℃ for 10h, 900 ℃ for 3h and 500 ℃ for 5h, and cooling and discharging to obtain the magnet.
Sintered Ru ferroboron permanent magnet materials are prepared according to the composition ratio and the preparation method of the examples 1-3 and the comparative examples 1-2, and the performance of each sintered Ru ferroboron permanent magnet material is tested, and the test results are shown in the following table 1:
TABLE 1
The above embodiment aims to maintain the final components to be basically consistent, and compares the advantages and disadvantages of different technical schemes under the condition that the subsequent processes are matched. Wherein, the embodiment 1, the embodiment 2 and the embodiment 3 all adopt the technical scheme of the invention, the difference is that the types, the quantity and the mixture ratio of the main alloy and the auxiliary alloy are different, and finally, the three implementation examples all obtain the double-high performance of high coercive force and high magnetic energy product, namely "H cJ+BH maxThe numerical values respectively reach 71.05, 70.68 and 71.31, and the high comprehensive magnetic performance of more than 70 is achieved. In contrast, comparative example 1 using the conventional double alloy process and comparative example 2 using the conventional double main phase process "H cJ+BH maxThe numerical values are only 67.70 and 67.16 respectively, and are obviously lower than the effect of the technical scheme of the invention. The main reason is that the technical proposal of the invention integrates double functionsThe advantages of both the alloy process and the double main phase process are that (1) the synergistic coupling effect among different main alloys and between the main alloy and the auxiliary alloy is exerted, and 1+1 is generated>2 "in the composition. Meanwhile, the technical scheme emphasizes that secondary proportioning design and mixing are carried out in a sheet or block alloy state, the influence of element content change caused by defects existing in raw materials and operation of a previous process is corrected, the formation of reverse magnetization nuclei of the magnet caused by phase oxidation due to mixing of powder states is avoided, the microstructure structure of the magnet is systematically optimized through matching control of process parameters of a subsequent process, the state of magnetic domain distribution when the magnet is subjected to technical magnetization and back-magnetization measurement is improved, and therefore the obtainment of high coercive force and high magnetic energy product is ensured, and the effect of the magnet especially aiming at low rare earth total amount is better.
The performance comparison is carried out on the mixing in the solid state before hydrogen crushing and the mixing in the traditional fine powder state, the secondary proportioning design based on the actual component test analysis result and the secondary proportioning design based on the original alloy design component in the scheme of the invention, and the two-round hydrogen absorption-dehydrogenation process and the conventional hydrogen crushing process in the scheme of the invention. Namely:
comparative example 3A Main alloy A has a design composition of (Pr)0.25Nd0.75)29Fe68.8Co1Cu0.1Ga0.2B0.9(mass ratio), the main alloy B is designed to be (Pr)0.25Nd0.75)29Dy1Fe67.75Co1Cu0.1Ga0.15B1(mass ratio), preparing alloy sheets with the thickness of 0.2-0.4mm by material preparation, vacuum melting and rapid hardening melt spinning; the secondary alloy C has the design component of (Pr 0).25Nd0.75)50Dy30Al10Zr3Nb7(mass ratio), and preparing alloy cast ingots through batching and vacuum melting. The three alloys are respectively put into a furnace to be hydrogen crushed and absorbed, and are all prepared into coarse powder by adopting a two-wheel hydrogen absorption-dehydrogenation process, namely, the coarse powder is firstly rotationally absorbed for 0.5 to 1 hour under the hydrogen partial pressure of 0.15MPa, is subjected to heat preservation and dehydrogenation at the temperature of 580 ℃ until the vacuum degree is below 30Pa, is filled with hydrogen again, and is rotationally absorbed until the hydrogen partial pressure is controlled to be 0.1MPaSaturating, preserving heat at 500 ℃ for dehydrogenation until the vacuum degree is below 1Pa, respectively adding 0.1% of liquid additive into the mixed coarse powder for 3h, preparing powder with the SMD granularity of 3.0 mu m by airflow milling, mixing according to the proportion of A: B: C =65:34:1, adding 0.1% of liquid additive into the mixed fine powder for 2h, pressing and molding in a 1.8T magnetic field, putting the mixture into a furnace for sintering and heat treatment after isostatic pressing at 200 MPa: 1040 ℃ x 10h, 900 ℃ x 3h and 500 ℃ x 5h, cooling and discharging to obtain a material blank, and machining into 30 axial magnets with the diameter of D10 x 10mm by a wire electric discharge machine.
Comparative example 4 the main alloy A had a design composition of (Pr)0.25Nd0.75)29Fe68.8Co1Cu0.1Ga0.2B0.9(mass ratio), the main alloy B is designed to be (Pr)0.25Nd0.75)29Dy1Fe67.75Co1Cu0.1Ga0.15B1(mass ratio), preparing alloy sheets with the thickness of 0.2-0.4mm by material preparation, vacuum melting and rapid hardening melt spinning; the secondary alloy C has the design component of (Pr)0.25Nd0.75)50Dy30Al10Zr3Nb7(mass ratio), and preparing alloy cast ingots through batching and vacuum melting. The three alloys are directly mixed according to the proportion of A: B: C =65:34:1, the mixture is put into a hydrogen crushing furnace to absorb hydrogen, two-wheel hydrogen absorption-dehydrogenation processes are adopted to prepare coarse powder, namely, the coarse powder is firstly rotationally absorbed for 0.5-1h under the partial pressure of 0.15MPa hydrogen, the temperature is kept and the dehydrogenation is carried out at 580 ℃ until the vacuum degree is below 30Pa, the hydrogen is filled again, the partial pressure of the hydrogen is controlled to be 0.1MPa, the rotational hydrogen absorption is carried out until the saturation, the temperature is kept and the dehydrogenation is carried out at 500 ℃ until the vacuum degree is below 1Pa, 0.1 percent of liquid additive mixed coarse powder is added for 3h, the ground powder size SMD is controlled to be 3.0 mu m through an air flow mill, 0.1 percent of liquid additive mixed fine powder is added for 2h, the mixture is pressed and molded in a 1.8T magnetic field, and the mixture is put into the furnace to be sintered and thermally treated after the isostatic pressure of 200 MPa: 1040 ℃ x 10h, 900 ℃ x 3h and 500 ℃ x 5h, cooling and discharging to obtain a material blank, and machining into 30 axial magnets with the diameter of D10 x 10mm by a wire electric discharge machine.
Comparative example 5 the main alloy A had a design composition of (Pr)0.25Nd0.75)29Fe68.8Co1Cu0.1Ga0.2B0.9(mass ratio), main ratioThe gold B design component is (Pr)0.25Nd0.75)29Dy1Fe67.75Co1Cu0.1Ga0.15B1(mass ratio), preparing alloy sheets with the thickness of 0.2-0.4mm by material preparation, vacuum melting and rapid hardening melt spinning; the secondary alloy C has the design component of (Pr)0.25Nd0.75)50Dy30Al10Zr3Nb7(mass ratio), and preparing alloy cast ingots through batching and vacuum melting. The three alloys are directly mixed according to the proportion of A: B: C =65:34:1, the mixture is put into a hydrogen crushing furnace to absorb hydrogen, the hydrogen pressure is controlled at 0.1MPa, the dehydrogenation temperature is 580 ℃, 0.1% of liquid additive mixed coarse powder is added for 3 hours, the ground powder size SMD is controlled to 3.0 mu m through an air flow mill, 0.1% of liquid additive mixed fine powder is added for 2 hours, the mixture is pressed and formed in a 1.8T magnetic field, and the mixture is put into the furnace to be sintered and thermally treated after being subjected to isostatic pressing at 200 MPa: 1040 ℃ x 10h, 900 ℃ x 3h and 500 ℃ x 5h, cooling and discharging to obtain a material blank, and machining into 30 axial magnets with the diameter of D10 x 10mm by a wire electric discharge machine.
The material blank of example 1 was machined into 30 pieces of D10X 10mm axial magnets by a wire electric discharge machine and a grinding machine.
Each of 30 magnets prepared according to example 1, comparative example 3, comparative example 4 and comparative example 5 was randomly divided into 3 groups, and performance parallel test comparisons were performed in 3 times, and the results are shown in table 2.
TABLE 2
As can be seen from table 2 and fig. 4 to 8, the performance and consistency of the magnet manufactured by the invention are significantly better than those of the magnet manufactured by the invention in the state of fine powder (comparative example 3), the magnet manufactured by the invention based on the design of the secondary proportion of the original alloy components (comparative example 4) and the conventional hydrogen absorption-dehydrogenation process (comparative example 5) under the same composition. The main reason why comparative example 3 is inferior to example 1 of the present invention is that the mixing uniformity in the fine powder state is inferior to that in the solid state (before hydrogen pulverization), and the powder oxidation easily occurs in the mixing in the fine powder state to form a reverse magnetization core, degrading the magnet performance. The main reason that the comparative example 4 is not the same as that of the example 1 of the present invention is that the secondary proportioning design based on the actual component test analysis result considers the influence of the ingredient segregation and impurity element enrichment of the raw material under the actual production condition (non-ideal state) and the operation aspects of the batching and smelting melt-spinning process, while the secondary proportioning design based on the original alloy design component only considers the ideal state, which causes the actual alloy proportioning of the final magnet to deviate; comparative example 5 is inferior to example 1 of the present invention in that the effect of crushing different alloys into single crystal powder particles of different particle diameters by the conventional hydrogen-absorption-dehydrogenation process is poor, which is disadvantageous in the formation of high coercive force, high magnetic energy product and improvement of performance uniformity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A sintered Nd-Fe-B permanent magnet material with high coercive force and high magnetic energy product is characterized in that: comprising a main alloy and at least one secondary alloy, the main alloy comprising at least one RE biased toward a high magnetic energy product design2(Fe, M)14B a main alloy of intermetallic compounds A and at least one RE biased toward high coercivity2(Fe, M)14B, a main alloy B of an intermetallic compound, wherein the auxiliary alloy is a grain boundary phase substance; mixing the main alloy and the auxiliary alloy in a solid state; before the main alloy and the auxiliary alloy are mixed in a solid state, firstly, the main alloy is made into an alloy sheet, and the auxiliary alloy is made into alloy in a sheet shape, a block shape or a larger particle shape; the alloy sheet of the main alloy is prepared by adopting a method of medium-frequency induction vacuum melting and rapid hardening melt-spinning, and the preparation method of the sintered neodymium iron boron permanent magnet material with high coercive force and high magnetic energy product comprises the following steps:
(1) respectively preparing alloy sheets from at least one main alloy A and at least one main alloy B by adopting a frequency induction vacuum melting and rapid hardening melt-spinning method, and uniformly dividing three times of feeding materials, namely firstly feeding Fe, Co and B-Fe alloys when the alloy sheets are fed into a furnace, secondly adding rare earth raw materials when the front fed materials start to be melted, and finally adding metal Cu or metal Ga when the front fed materials are about to be completely melted; (2) mixing the prepared alloy sheet and at least one auxiliary alloy in a solid state, then preparing coarse powder by two-wheel hydrogen absorption-dehydrogenation process, discharging, and then obtaining the sintered neodymium iron boron permanent magnet material with high coercivity and high magnetic energy product through coarse powder mixing, airflow milling, fine powder mixing, magnetic field orientation forming, vacuum sintering and vacuum heat treatment;
when the alloy sheet is manufactured, the refining temperature of the main alloy A reaches 1550-; the refining temperature of the main alloy B reaches 1500-;
the thickness of the alloy sheet is 0.2-0.4 mm;
the two-round process of hydrogen absorption and dehydrogenation in the step (2) is that firstly, the hydrogen is absorbed rotationally for 0.5 to 1 hour under the hydrogen partial pressure of 0.15MPa, the temperature is kept at 580 ℃ for dehydrogenation until the vacuum degree is below 30Pa, the hydrogen is filled again, the hydrogen partial pressure is controlled to be 0.1MPa, the hydrogen is absorbed rotationally until the saturation, and the temperature is kept at 500 ℃ for dehydrogenation until the vacuum degree is below 1 Pa;
the main alloy and the auxiliary alloy need to be designed through secondary proportioning before being mixed; the secondary proportioning design comprises the following steps:
(1) in the initial stage of manufacture, firstly, the theoretical composition proportion of each element in each main alloy and each auxiliary alloy is independently designed;
(2) respectively making different main alloys into alloy sheets, and making auxiliary alloys into sheet-shaped, block-shaped or larger granular alloys;
(3) testing and analyzing the respective actual composition components of the main alloy and the auxiliary alloy;
(4) designing and calculating the mass composition ratio of each main alloy and each auxiliary alloy according to the analysis result;
the mass percentage of the auxiliary alloy is 0.1% -3%.
2. The high coercivity, high magnetic energy product sintered nd-fe-b permanent magnet material of claim 1, wherein: the main alloy and the auxiliary alloy are mixed in a solid state and then are prepared into coarse powder through two processes of hydrogen absorption and dehydrogenation.
3. A method for preparing a sintered ndfeb permanent magnet material with high coercivity and high magnetic energy product according to claim 1, comprising the steps of: (1) respectively preparing alloy sheets from at least one main alloy A and at least one main alloy B by adopting a frequency induction vacuum melting and rapid hardening melt-spinning method, and uniformly dividing three times of feeding materials, namely firstly feeding Fe, Co and B-Fe alloys when the alloy sheets are fed into a furnace, secondly adding rare earth raw materials when the front fed materials start to be melted, and finally adding metal Cu or metal Ga when the front fed materials are about to be completely melted; (2) mixing the prepared alloy slice and at least one auxiliary alloy in a solid state, then preparing coarse powder by two-wheel hydrogen absorption-dehydrogenation process, discharging, and obtaining the sintered neodymium iron boron permanent magnet material with high coercivity and high magnetic energy product by coarse powder mixing, airflow milling, fine powder mixing, magnetic field orientation molding, vacuum sintering and vacuum heat treatment.
4. The method for preparing the sintered NdFeB permanent magnet material with high coercivity and high magnetic energy product as claimed in claim 3, wherein: in the magnetic field orientation forming process, the preparation of the green body can be finished by magnetic field orientation and mechanical pressing firstly and then cold isostatic pressing, or by magnetic field orientation and direct mechanical pressing, and the green body can be further cut and processed into a smaller geometric shape and a smaller size under the protection of atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110488544.7A CN113215497B (en) | 2021-05-06 | 2021-05-06 | Sintered neodymium-iron-boron permanent magnet material with high coercive force and high magnetic energy product and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110488544.7A CN113215497B (en) | 2021-05-06 | 2021-05-06 | Sintered neodymium-iron-boron permanent magnet material with high coercive force and high magnetic energy product and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113215497A CN113215497A (en) | 2021-08-06 |
| CN113215497B true CN113215497B (en) | 2022-06-07 |
Family
ID=77091127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110488544.7A Active CN113215497B (en) | 2021-05-06 | 2021-05-06 | Sintered neodymium-iron-boron permanent magnet material with high coercive force and high magnetic energy product and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113215497B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106298134B (en) * | 2015-06-12 | 2019-06-28 | 中国科学院物理研究所 | A kind of double main phase agglomeration permanent magnetic materials and preparation method and application |
| CN107146674B (en) * | 2017-05-27 | 2018-11-09 | 浙江大学 | From the cerium-rich rare earth permanent magnet and its production method of heat treatment |
-
2021
- 2021-05-06 CN CN202110488544.7A patent/CN113215497B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113215497A (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3196896B1 (en) | Heavy rare earth free sintered nd-fe-b magnets and manufacturing process thereof | |
| EP3827916A1 (en) | A manufacturing method of sintered nd-fe-b permanent magnet | |
| CN103779064B (en) | Amorphous state prepares the method for Nd-Fe-B magnet steel | |
| CN102903472A (en) | Sintered neodymium-iron-boron magnet and preparation method thereof | |
| CN110047636A (en) | A kind of preparation method of high-coercive force richness La/Ce sintered magnet | |
| CN110957090B (en) | A samarium cobalt 1: 5-type permanent magnet material and preparation method thereof | |
| WO2015149685A1 (en) | W-containing r-fe-b-cu sintered magnet and quenching alloy | |
| CN110323053B (en) | R-Fe-B sintered magnet and preparation method thereof | |
| KR102632991B1 (en) | Neodymium iron boron magnetic material, raw material composition, manufacturing method and application | |
| KR20140141509A (en) | METHOD FOR PREPARING R-Fe-B BASED SINTERED MAGNET | |
| CN104174857B (en) | A kind of air-flow Flour milling method of neodymium iron boron magnetic body | |
| CN108281246A (en) | A kind of performance Nd Fe B sintered magnet and preparation method thereof | |
| CN111341514A (en) | Low-cost neodymium iron boron magnet and preparation method thereof | |
| EP3845335A1 (en) | Method for preparing ndfeb magnet powder | |
| EP3819043B1 (en) | Method for improving performance of sintered ndfeb magnets | |
| CN113948263A (en) | Neodymium iron boron material and preparation method thereof | |
| CN103106993A (en) | Ndfeb magnetic material with light rare earth element and preparation method thereof | |
| JPS6181606A (en) | Preparation of rare earth magnet | |
| CN113215497B (en) | Sintered neodymium-iron-boron permanent magnet material with high coercive force and high magnetic energy product and preparation method | |
| JP6919788B2 (en) | Rare earth sintered magnet | |
| CN113921218B (en) | High-remanence neodymium-iron-boron magnet and preparation method and application thereof | |
| CN113096952B (en) | Preparation method of neodymium iron boron magnetic material | |
| CN105931780A (en) | Preparation method of samarium-cobalt permanent magnet material | |
| CN113223847A (en) | Preparation method of neodymium iron boron magnetic material and magnetic material prepared by adopting method | |
| CN113517126B (en) | SmCo5Samarium cobalt permanent magnet material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |