CN108735413A - One kind high-coercivity magnet of high-performance containing Tb and preparation method thereof - Google Patents
One kind high-coercivity magnet of high-performance containing Tb and preparation method thereof Download PDFInfo
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- 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
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- 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
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- 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 high-coercivity magnet of high-performance containing Tb and preparation method thereof, the magnet is RE-Fe-B magnets, and the main phase grain of the RE-Fe-B magnets is " core-shell structure copolymer " structure, and the core is (RE, Tb)2Fe14B phases or RE2Fe14B phases, the shell are (RE, Tb)2Fe14B phases；Preparation method includes the following steps：Step S1：According at configuration main-phase alloy and Tb alloys is grouped as, by melting, rapid hardening to main-phase alloy slab and Tb alloy casting pieces；Step S2：The main-phase alloy slab and the Tb alloy casting pieces are crushed, are milled to obtain magnetic powder；Step S3：The magnetic powder is pressed to obtain green compact；Step S4：The green compact are subjected to low-temperature sintering and multiple tempering handles to obtain magnet.It the advantage is that, magnet is the RE-Fe-B magnets with " core-shell structure copolymer " structure, and core is the RE without or with a small amount of heavy rare earth Tb2Fe14B phases, shell contain a large amount of heavy rare earth Tb (RE, Tb)2Fe14B phases, the Tb in magnet main phase grain are distributed on crystal boundary, preferably repair defect existing for former grain surface, keep crystal boundary distribution continuous.
Description
Technical field
The present invention relates to rareearth magnetic material preparing technical fields, more particularly to a kind of high-coercivity magnet of high-performance containing Tb
And preparation method thereof.
Background technology
Sintered Nd-Fe-B has many advantages, such as that abundant raw materials, magnetic property are high, is widely used in communication, electronics, medical treatment and vapour
The various fields such as garage's industry.The Nd-Fe-B alloys permanent-magnet material best as comprehensive performance, in the period of considerably long from now in,
Still it can not be substituted.With constantly being expanded by the new opplication field of representative of power motor, the requirement to its magnetic property is also got over
Come higher, improves the magnetic property especially coercivity of magnet, it has also become an important directions of Nd-Fe-B investigations of materials.
Currently, it is adding for addition heavy rare earth element Dy or Tb, Dy or Tb to improve the universal measure of sintered Nd-Fe-B magnetic property
There are two types of add modes, and one is raw material additions, and heavy rare earth Dy or Tb are exactly directly added in neodymium iron boron master alloy, and part replaces
Nd2Fe14Nd in B compounds forms (Nd, Dy)2Fe14B or (Nd, Tb)2Fe14B, although this method is so that coercivity obtains
It improves, but since Dy and Tb and Fe are antiferromagnetic couplings, the saturation magnetization of neodymium iron boron can be reduced, and be easy to cause weight
The waste of rare earth.Another is that Japanese researchers propose " grain boundary decision " concept several years ago, they use special work
Skill makes Dy or Tb pass through diffusion to exist only in crystal boundary such as being deposited diffusion, magnetron sputtering, surface coating, transgranular without entering.
In this way, not only increasing the performance of NdFeB material, and greatly reduce the total amount of heavy rare earth element, reduces the cost of material.
But these grain boundary diffusion process will especially change existing neodymium iron the problem is that complex process, the production cost increases
Boron production procedure, therefore promote and apply relatively difficult.
Invention content
The purpose of the present invention is being directed to deficiency in the prior art, a kind of high-coercivity magnet of high-performance containing Tb is provided.
To achieve the above object, the technical solution adopted by the present invention is that：
A kind of high-coercivity magnet of high-performance containing Tb, the magnet are RE-Fe-B magnets, the master of the RE-Fe-B magnets
Phase crystal grain is " core-shell structure copolymer " structure, and the core is (RE, Tb)2Fe14B phases or RE2Fe14B phases, the shell are (RE, Tb)2Fe14B phases.
Preferably, the Tb contents in the core are less than the Tb contents in the shell.
Preferably, the thickness of the shell is 0.5 μm~3 μm.
Preferably, the RE-Fe-B magnets contain transition metal.
Preferably, the content of the transition metal is 1wt%~20wt%.
Preferably, in the RE-Fe-B magnets, the RE is the combination of one or more of Nd, Pr, Dy.
Preferably, in the RE-Fe-B magnets, the content of the B meets following atomic ratio relational expression：
-5≤14[B]-[Fe]≤2；
-4≤2[B]-[R]≤1；
Wherein, [B] is the B amounts indicated with atom %, and [Fe] is the Fe amounts indicated with atom %, and [R] is with atom % tables
The total amount of rare earth shown.
The second object of the present invention is to provide a kind of preparation method of the high-coercivity magnet of high-performance containing Tb.
A kind of preparation method of the high-coercivity magnet of high-performance containing Tb, is used to prepare the high-coercivity magnet of high-performance containing Tb,
Include the following steps：
Step S1：According at being grouped as configuration main-phase alloy and Tb alloys, by melting, rapid hardening to main-phase alloy slab and
Tb alloy casting pieces；
Step S2：The main-phase alloy slab and the Tb alloy casting pieces are crushed, are milled to obtain magnetic powder；
Step S3：The magnetic powder is pressed to obtain green compact；
Step S4：The green compact are subjected to low-temperature sintering and multiple tempering handles to obtain magnet；
Wherein, the main-phase alloy is RE-Fe-B alloys, and the Tb alloys are Tb-K alloys.
Preferably, the step S2 includes：
Step S21a：The Tb alloy casting pieces are added in the main-phase alloy slab and obtain hybrid alloys slab, it is right
The hybrid alloys slab is crushed to obtain hybrid alloys coarse powder；
Step S22a：The hybrid alloys coarse powder is milled to obtain magnetic powder.
Preferably, the step S2 includes：
Step S21b：Respectively the main-phase alloy slab and the Tb alloy casting pieces are crushed to obtain main-phase alloy thick
Powder and Tb alloy coarse powder；
Step S22b：The Tb alloys coarse powder is added in the main-phase alloy coarse powder and obtains hybrid alloys coarse powder, it is right
The hybrid alloys coarse powder is milled to obtain magnetic powder.
Preferably, the step S2 includes：
Step S21c：Respectively the main-phase alloy slab and the Tb alloy casting pieces are crushed to obtain main-phase alloy thick
Powder and Tb alloy coarse powder；
Step S22c：Respectively the main-phase alloy coarse powder and the Tb alloys coarse powder are milled to obtain main-phase alloy thin
The main-phase alloy fine powder and the Tb alloys fine powder are mixed to get magnetic powder by powder and Tb alloy fine powders.
Preferably, described to be broken for coarse crushing, the broken method is that Mechanical Crushing or hydrogen are broken.
Preferably, the method for the compression moulding is the combination of parallel compression moulding and isostatic pressed compacting densification.
Preferably, the method for the compression moulding is the combination of vertical compression moulding and isostatic pressed compacting densification.
Preferably, the Tb contents in the magnet are less than 5wt%.
Preferably, the mass percent of the Tb alloys is 0.2wt%~5wt%；
The mass percent of the main-phase alloy is 95wt%~99.8wt%.
Preferably, the K is the combination of one or more of Fe, Cu, Al, Ga, and the content of the K is less than 50wt%.
Preferably, the group of the main-phase alloy is divided into (PrNd)x-(Fe1-a,Ma)bal-By1, wherein 29.5wt%≤x≤
31.5wt%, 0.5wt%≤a≤3wt%, 0.9wt%≤y1≤1.5wt%.
Preferably, the group of the Tb alloys is divided into Tby2K1-y2, wherein 70wt%≤y2≤90wt%.
Preferably, the method for the melting is to carry out under protection of argon gas, and smelting temperature is 1200 DEG C~1500 DEG C, melting
Soaking time is 30min~60min.
Preferably, the broken method be using hydrogen breaking method, slab is put into hydrogen broken furnace carry out inhale hydrogen be crushed,
10 are evacuated in hydrogen broken furnace-1Pa is heated to carry out dehydrogenation reaction within the scope of 400 DEG C~600 DEG C, after vacuum degree is less than 10Pa
Terminate.
Preferably, the granularity of the broken magnetic powder is 100 μm~300 μm.
Preferably, the grinding pressure of the milling is 0.3MPa~0.9MPa.
Preferably, the granularity of the magnetic powder after the milling is 2.7 μm~3 μm.
Preferably, the method for the compression moulding is the combination of vertical compression moulding and isostatic pressed compacting densification, is orientated magnetic
It is 2T~5T, briquetting pressure is 18MPa~50MPa, and the pressure of isostatic pressed compacting is 160MPa~240MPa, and the dwell time is
20s~50s.
Preferably, the low sintering method is：
Respectively in 200 DEG C~400 DEG C, 500 DEG C~600 DEG C, 750 DEG C~900 DEG C, 1000 DEG C~1020 DEG C range inside holdings
30min~120min；
1030 DEG C~1050 DEG C are warming up to, 3h~6h is kept the temperature, vacuum degree is 10 in stove-2Pa。
Preferably, the multiple tempering processing includes level-one temper and second annealing processing；
The level-one temper is：In 750 DEG C~950 DEG C range inside holding 1h~4h of temperature；
The second annealing is handled：In 400 DEG C~600 DEG C range inside holding 2h~6h of temperature.
The present invention is had the following technical effect that compared with prior art using above technical scheme：
One kind high-coercivity magnet of high-performance containing Tb and preparation method thereof of the present invention, magnet are with " core-shell structure copolymer " structure
RE-Fe-B magnets, core be without or with a small amount of heavy rare earth Tb RE2Fe14B phases, shell contain a large amount of heavy rare earth Tb
(RE,Tb)2Fe14B phases, the Tb in magnet main phase grain are distributed on crystal boundary mostly, are preferably repaired existing for former grain surface
Defect, and keep crystal boundary distribution continuous；Compared with raw material adding technology, the coercivity of magnet is increased substantially, and remanent magnetism will not
Reducing can even increase；Compared with grain boundary diffusion process, the preparation process of magnet is simple, and production cost is low.
Description of the drawings
Fig. 1 is the Nd-Fe-B magnet preparation technology flow charts of the embodiment of the present invention 2.
Fig. 2 is the scanning electron microscope schematic diagram of the magnet of embodiment 2.
Fig. 3 is the Nd-Fe-B magnet preparation technology flow charts of the embodiment of the present invention 3.
Fig. 4 is the scanning electron microscope schematic diagram of the magnet of embodiment 3.
Fig. 5 is the Nd-Fe-B magnet preparation technology flow charts of the embodiment of the present invention 4.
Fig. 6 is the scanning electron microscope schematic diagram of the magnet of embodiment 4.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of not making creative work it is all its
His embodiment, shall fall within the protection scope of the present invention.
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
The invention will be further described in the following with reference to the drawings and specific embodiments, but not as limiting to the invention.
Embodiment 1
A kind of preparation method of high-coercivity magnet of high-performance containing Tb of the present invention, includes the following steps：
Step S1：According at being grouped as configuration main-phase alloy and Tb alloys, by melting, rapid hardening to main-phase alloy slab and
Tb alloy casting pieces；
Step S2：The main-phase alloy slab and the Tb alloy casting pieces are crushed, are milled to obtain magnetic powder；
Step S3：The magnetic powder is pressed to obtain green compact；
Step S4：Low-temperature sintering is carried out to the green compact and multiple tempering handles to obtain magnet.
What above-mentioned steps were obtains the basic steps of the high-coercivity magnet of high-performance containing Tb.
Main-phase alloy is RE-Fe-B alloys, Tb alloys are Tb-K alloys, and wherein RE is one or more of Nd, Pr, Dy
Combination, the combination of one or more of M Co, Cu, Al, Ga, Nb, the group of one or more of K Fe, Cu, Al, Ga
It closes.
Further, the group of main-phase alloy is divided into (PrNd)x-(Fe1-a,Ma)bal-By1, wherein 29.5wt%≤x≤
31.5wt%, 0.5wt%≤a≤3wt%, 0.9wt%≤y1≤1.5wt%.
Further, the group of Tb alloys is divided into Tby2K1-y2, wherein 50wt%≤y2≤100wt%.Preferably, 70wt%
≤ y2≤90wt%.
Optimize by many experiments, preferred steps are further obtained on the basis of the technical solution of basic steps.
In step sl, the method for melting is：Using argon gas as protection gas, smelting temperature is 1200 DEG C~1500 DEG C,
Melting soaking time is 30min~60min.
In step s 2, there are three types of selection process is available.
Technique one：
Step S21a：The Tb alloy casting pieces that step S1 is obtained are added to main-phase alloy slab and obtain hybrid alloys slab,
Hybrid alloys slab is crushed to obtain hybrid alloys coarse powder；
Step S22a：Hybrid alloys coarse powder is subjected to further milling and obtains magnetic powder.
Technique two：
Step S21b：Main-phase alloy slab and Tb alloy casting pieces that step S1 is obtained are crushed respectively to obtain main phase conjunction
Golden coarse powder and Tb alloy coarse powder；
Step S22b：Tb alloy coarse powder is added in main-phase alloy coarse powder and obtains hybrid alloys coarse powder, to hybrid alloys
Coarse powder carries out further milling and obtains magnetic powder.
Technique three：
Step S21c：Main-phase alloy slab and Tb alloy casting pieces that step S1 is obtained are crushed respectively to obtain main phase conjunction
Golden coarse powder and Tb alloy coarse powder；
Step S22c：Further milling is carried out to main-phase alloy coarse powder and Tb alloy coarse powder respectively and obtains main-phase alloy fine powder
With Tb alloy fine powders, carry out main-phase alloy fine powder and Tb alloys fine powder to be mixed to get magnetic powder.
By above-mentioned three kinds of technique, the magnetic powder that particle is uniform, granularity is small can be obtained.
When being mixed, the mass percent of Tb alloys is 0.2wt%~5wt%；The mass percent of main-phase alloy
For 95wt%~99.8wt%.
In step s 2, a variety of crumbling methods may be used to be crushed, as Mechanical Crushing or hydrogen are broken.In the present invention
In, preferred crumbling method is broken for hydrogen.
The broken method of hydrogen is：Slab is put into hydrogen broken furnace carry out inhale hydrogen be crushed, 10 are evacuated in hydrogen broken furnace-1Pa,
It is heated to carry out dehydrogenation reaction within the scope of 400 DEG C~600 DEG C, terminate after vacuum degree is less than 10Pa.
Use the granularity of the broken obtained magnetic powder (coarse powder) of hydrogen for 100 μm~300 μm.
The grinding pressure of milling is 0.3MPa~0.9MPa.
The granularity for the magnetic powder (fine powder) that milling obtains is 2.7 μm~3 μm.
In step s3, compression moulding is there are two types of method, and a kind of method is that parallel compression moulding and isostatic pressed compacting are fine and close
Combination, another method is vertical compression moulding and the fine and close combination of isostatic pressed compacting.In the present invention, it is preferred to be pressed into
Type method is the combination of vertical compression moulding and isostatic pressed compacting densification.
Vertical compression moulding and isostatic pressed suppress fine and close method：Alignment magnetic field is 2T~5T, briquetting pressure 18MPa
The pressure of~50MPa, isostatic pressed compacting are 160MPa~240MPa, and the dwell time is 20s~50s.
In step s 4, low sintering method is：Respectively 200 DEG C~400 DEG C, 500 DEG C~600 DEG C, 750 DEG C~
900 DEG C, 1000 DEG C~1020 DEG C range inside holding 30min~120min；1030 DEG C~1050 DEG C are warming up to, 3h~6h is kept the temperature,
Vacuum degree is 10 in stove-2Pa。
In step s 4, multiple tempering processing includes level-one temper and second annealing processing, wherein at level-one tempering
The method of reason is, in 750 DEG C~950 DEG C range inside holding 1h~4h of temperature；The method of second annealing processing is, in temperature 400
DEG C~600 DEG C of range inside holding 2h~6h.
By using above-mentioned Optimization Steps, available can the more high-coercivity magnet of high-performance containing Tb.
The high-coercivity magnet of high-performance containing Tb prepared using above-mentioned preparation method is RE-Fe-B magnets, main phase grain
For " core-shell structure copolymer " structure, core is (RE, Tb) containing small amount Tb2Fe14B phases or RE without containing Tb2Fe14B phases, shell be containing
(RE, the Tb) of higher amount Tb2Fe14B phases.
When core and shell contain Tb, the Tb contents in core are less than the Tb contents in shell.
The thickness of the shell of the main phase grain of RE-Fe-B magnets is 0.5 μm~3 μm.
Since main-phase alloy and Tb alloys contain transition metal, the RE-Fe-B magnets also contain corresponding transition gold
Belong to, and the combination that transition metal is one or more of Co, Cu, Al, Ga, Nb, and the mass percent of transition metal is
1wt%~20wt% of gross mass.
B content in RE-Fe-B magnets meets following atomic ratio relational expression：
-5≤14[B]-[Fe]≤2；
-4≤2[B]-[R]≤1；
Wherein, [B] is the B amounts indicated with atom %, and [Fe] is the Fe amounts indicated with atom %, and [R] is with atom % tables
The total amount of rare earth shown.
Embodiment 2
Preparation method is as shown in Figure 1 in the present embodiment, wherein in step s 2, using one side of technique in embodiment 1
Case.
In step sl, the main-phase alloy slab group obtained by melting, rapid hardening is divided into (PrNd)30.3Nb0.4Cu0.2Al0.2Fe67.88B1.02, Tb alloy casting piece groups are divided into Tb85Cu15, wherein the mass percent of Tb is in Tb alloys
85%.
In step s 2, the Tb alloy casting pieces that mass percent is 2.8% are mixed into main-phase alloy slab, it is broken by hydrogen
Broken method is crushed, and the coarse powder that average particle size is 220 μm is obtained；After being ground to coarse powder, it is 2.92 μ to obtain average particle size
The magnetic powder of m.Wherein in milling process, oxygen-adding amount 30ppm.Granularity Detection is measured using laser particle size analyzer.
In step s3, magnetic powder is handled and is given birth to using vertical compression moulding and isostatic pressed compacting method for densifying
Base.
In step s 4, low sintering sintering temperature is 1040 DEG C, and 6h is kept the temperature under sintering temperature；Level-one temper
Temperature is 780 DEG C, soaking time 2.5h；The temperature of second annealing processing is 490 DEG C, soaking time 3.5h.
Structural analysis is carried out to RE-Fe-B magnets made from above-mentioned steps using scanning electron microscope, as shown in Fig. 2, from figure
As can be seen that RE-Fe-B magnets have apparent " core-shell structure copolymer " structure, center RE2Fe14B phases, shell are (RE, Tb)2Fe14B
Phase, and crystal boundary distribution is continuous.
RE-Fe-B magnets made from above-mentioned steps test its magnetic property using magnetic property automatic measuring instrument,
Its control group 1 is the heavy rare earth Tb that phase homogenous quantities are added directly in master alloy, is prepared using identical sintering and aging technique
Magnet, test result are shown in Table 1.
Table 1
The above results show, for Nd-Fe-B permanent magnet prepared by this method compared with prepared by traditional handicraft, coercivity can be with
4.33KOe is improved, remanent magnetism can improve 0.06KGs, and magnetic energy product can also improve 0.88MGOe.Coercivity raising is primarily due to：
Heavy rare earth Tb enters in master alloying, and a part of Tb is used for master alloying grain surface defect repair, and remaining Tb, which will diffuse into, to become owner of
2 in alloy:14:The surface of 1 phase crystal grain is formed (Pr, Nd, Dy, the Tb) of richness Tb2Fe14B phases, this boundary layer have high magnetic
Anisotropic crystalline field prevents the movement of magnetic reversal domain wall, to improve coercivity.
Embodiment 3
Preparation method is as shown in Figure 3 in the present embodiment, wherein in step s 2, using two side of technique in embodiment 1
Case.
In step sl, the main-phase alloy slab group obtained by melting, rapid hardening is divided into (PrNd)28.01Dy1.89Zr0.17Co1Cu0.12Al0.1Ga0.25Fe67.56B0.91, Tb alloy casting piece groups are divided into (PrNd)15Tb72Cu3Fe10, wherein
The mass percent of Tb is 72% in Tb alloys.
Main-phase alloy slab and Tb alloy casting pieces are crushed respectively by hydrogen breaking method, it is 180 μm to obtain average particle size
Coarse powder；The Tb alloy coarse powder that mass percent is 4% is mixed into main-phase alloy coarse powder；Hybrid alloys coarse powder is ground
Afterwards, the magnetic powder that average particle size is 2.79 μm is obtained.Wherein in milling process, oxygen-adding amount 35ppm.Granularity Detection uses laser grain
Degree analyzer measures.
In step s3, magnetic powder is handled and is given birth to using vertical compression moulding and isostatic pressed compacting method for densifying
Base.
In step s 4, low sintering sintering temperature is 1040 DEG C, and 4.5h is kept the temperature under sintering temperature；Level-one temper
Temperature be 800 DEG C, soaking time 3h；The temperature of second annealing processing is 500 DEG C, soaking time 5h.
Structural analysis is carried out to RE-Fe-B magnets made from above-mentioned steps using scanning electron microscope, as shown in figure 4, from figure
As can be seen that RE-Fe-B magnets have apparent " core-shell structure copolymer " structure, center RE2Fe14B phases, shell are (RE, Tb)2Fe14B
Phase, and crystal boundary distribution is continuous.
RE-Fe-B magnets made from above-mentioned steps test its magnetic property using magnetic property automatic measuring instrument,
Its control group 2 is the heavy rare earth Tb that phase homogenous quantities are added directly in master alloy, is prepared using identical sintering and aging technique
Magnet, test result are shown in Table 2.
Table 2
The above results show, for Nd-Fe-B permanent magnet prepared by this method compared with prepared by traditional handicraft, coercivity can be with
3.01KOe is improved, remanent magnetism can improve 0.05KGs, and magnetic energy product can also improve 0.74GOe.Coercivity raising is primarily due to：Weight
Rare earth Tb enters in master alloying, and a part of Tb is used for master alloying grain surface defect repair, and remaining Tb, which will diffuse into, becomes owner of conjunction
2 in gold:14:The surface of 1 phase crystal grain is formed (Pr, Nd, Dy, the Tb) of richness Tb2Fe14B phases, this boundary layer have high magnetocrystalline
Anisotropy field prevents the movement of magnetic reversal domain wall, to improve coercivity.
Embodiment 4
Preparation method is as shown in Figure 5 in the present embodiment, wherein in step s 2, using the technique tripartite in embodiment 1
Case.
In step sl, the main-phase alloy slab group obtained by melting, rapid hardening is divided into (PrNd)31Dy0.6Co1Cu0.2Al0.2Ga0.2Fe65.9B0.9, Tb alloy casting piece groups are divided into (PrNd)7Tb80Cu3Fe10, wherein Tb in Tb alloys
Mass percent be 80%.
Main-phase alloy slab and Tb alloy casting pieces are crushed respectively by hydrogen breaking method, it is 200 μm to obtain average particle size
Coarse powder；After being ground respectively to main-phase alloy coarse powder and Tb alloy coarse powder, the fine powder that average particle size is 2.82 μm is obtained；To
The Tb alloy fine powders that mass percent is 1% are mixed in main-phase alloy fine powder.Wherein in milling process, oxygen-adding amount 25ppm.Grain
Degree detection is measured using laser particle size analyzer.
In step s3, magnetic powder is handled and is given birth to using vertical compression moulding and isostatic pressed compacting method for densifying
Base.
In step s 4, low sintering sintering temperature is 1035 DEG C, and 4.5h is kept the temperature under sintering temperature；Level-one temper
Temperature be 900 DEG C, soaking time 2h；The temperature of second annealing processing is 485 DEG C, soaking time 4h.
Structural analysis is carried out to RE-Fe-B magnets made from above-mentioned steps using scanning electron microscope, as shown in fig. 6, from figure
As can be seen that RE-Fe-B magnets have apparent " core-shell structure copolymer " structure, center RE2Fe14B phases, shell are (RE, Tb)2Fe14B
Phase, and crystal boundary distribution is continuous.
RE-Fe-B magnets made from above-mentioned steps test its magnetic property using magnetic property automatic measuring instrument,
Its control group 3 is the heavy rare earth Tb that phase homogenous quantities are added directly in master alloy, is prepared using identical sintering and aging technique
Magnet, test result are shown in Table 3.
Table 3
The above results show, for Nd-Fe-B permanent magnet prepared by this method compared with prepared by traditional handicraft, coercivity can be with
3.16KOe is improved, remanent magnetism can improve 0.12KGs, and magnetic energy product can also improve 0.17MGOe.Coercivity raising is primarily due to：
Heavy rare earth Tb enters in master alloying, and a part of Tb is used for master alloying grain surface defect repair, and remaining Tb, which will diffuse into, to become owner of
2 in alloy:14:The surface of 1 phase crystal grain is formed (Pr, Nd, Dy, the Tb) of richness Tb2Fe14B phases, this boundary layer have high magnetic
Anisotropic crystalline field prevents the movement of magnetic reversal domain wall, to improve coercivity.
From the result of 2~embodiment of embodiment 4 it is found that compared with traditional handicraft, even if the Tb of addition identical weight, this hair
The coercivity of bright middle neodymium iron boron magnetic body will improve more, this Tb being primarily due in the magnet main phase grain of the present invention divides mostly
Cloth preferably repairs defect existing for former grain surface on crystal boundary, while keeping crystal boundary distribution continuous.
The foregoing is merely preferred embodiments of the present invention, are not intended to limit embodiments of the present invention and protection model
It encloses, to those skilled in the art, should can appreciate that all with made by description of the invention and diagramatic content
Equivalent replacement and obviously change obtained scheme, should all be included within the scope of the present invention.
Claims (15)
1. a kind of high-coercivity magnet of high-performance containing Tb, which is characterized in that the magnet is RE-Fe-B magnets, the RE-Fe-B
The main phase grain of magnet is " core-shell structure copolymer " structure, and the core is (RE, Tb)2Fe14B phases or RE2Fe14B phases, the shell be (RE,
Tb)2Fe14B phases.
2. the high-coercivity magnet of high-performance containing Tb according to claim 1, which is characterized in that the Tb contents in the core are small
Tb contents in the shell.
3. the high-coercivity magnet of high-performance containing Tb according to claim 1, which is characterized in that the thickness of the shell is 0.5 μ
M~3 μm.
4. the high-coercivity magnet of high-performance containing Tb according to claim 1, which is characterized in that the RE-Fe-B magnets contain
There is transition metal.
5. the high-coercivity magnet of high-performance containing Tb according to claim 4, which is characterized in that the content of the transition metal
For 1wt%~20wt%.
6. the high-coercivity magnet of high-performance containing Tb according to claim 1, which is characterized in that in the RE-Fe-B magnets,
The RE is the combination of one or more of Nd, Pr, Dy.
7. the high-coercivity magnet of high-performance containing Tb according to claim 1, which is characterized in that in the RE-Fe-B magnets,
The content of the B meets following atomic ratio relational expression：
-5≤14[B]-[Fe]≤2；
-4≤2[B]-[R]≤1；
Wherein, [B] is the B amounts indicated with atom %, and [Fe] is the Fe amounts indicated with atom %, and [R] is indicated with atom %
Total amount of rare earth.
8. a kind of preparation method of the high-coercivity magnet of high-performance containing Tb is used to prepare and contains Tb high as described in claim 1~7
Performance high-coercivity magnet, which is characterized in that include the following steps：
Step S1：According at configuration main-phase alloy and Tb alloys is grouped as, closed by melting, rapid hardening to main-phase alloy slab and Tb
Golden slab；
Step S2：The main-phase alloy slab and the Tb alloy casting pieces are crushed, are milled to obtain magnetic powder；
Step S3：The magnetic powder is pressed to obtain green compact；
Step S4：Low-temperature sintering is carried out to the green compact and multiple tempering handles to obtain magnet；
Wherein, the main-phase alloy is RE-Fe-B alloys, and the Tb alloys are Tb-K alloys.
9. the preparation method of the high-coercivity magnet of high-performance containing Tb according to claim 8, which is characterized in that the step S2
Including：
Step S21a：The Tb alloy casting pieces are added in the main-phase alloy slab and obtain hybrid alloys slab, to described
Hybrid alloys slab is crushed to obtain hybrid alloys coarse powder；
Step S22a：The hybrid alloys coarse powder is milled to obtain magnetic powder；
Or,
Step S21b：Respectively to the main-phase alloy slab and the Tb alloy casting pieces be crushed to obtain main-phase alloy coarse powder and
Tb alloy coarse powder；
Step S22b：The Tb alloys coarse powder is added in the main-phase alloy coarse powder and obtains hybrid alloys coarse powder, to described
Hybrid alloys coarse powder is milled to obtain magnetic powder；
Or,
Step S21c：Respectively to the main-phase alloy slab and the Tb alloy casting pieces be crushed to obtain main-phase alloy coarse powder and
Tb alloy coarse powder；
Step S22c：Respectively to the main-phase alloy coarse powder and the Tb alloys coarse powder be milled to obtain main-phase alloy fine powder and
The main-phase alloy fine powder and the Tb alloys fine powder are mixed to get magnetic powder by Tb alloy fine powders.
10. the preparation method of the high-coercivity magnet of high-performance containing Tb according to claim 8, which is characterized in that the pressure
It is that parallel compression moulding and the fine and close combination of isostatic pressed compacting or vertical compression moulding and isostatic pressed compacting cause to make molding method
Close combination.
11. the preparation method of the high-coercivity magnet of high-performance containing Tb according to claim 8, which is characterized in that the magnetic
Tb contents in body are less than 5wt%.
12. the preparation method of the high-coercivity magnet of high-performance containing Tb according to claim 8, which is characterized in that the Tb
The mass percent of alloy is 0.2wt%~5wt%；
The mass percent of the main-phase alloy is 95wt%~99.8wt%.
13. the preparation method of the high-coercivity magnet of high-performance containing Tb according to claim 8, which is characterized in that the K is
The content of the combination of one or more of Fe, Cu, Al, Ga, the K is less than 50wt%.
14. the preparation method of the high-coercivity magnet of high-performance containing Tb according to claim 8, which is characterized in that the master
The group of phase alloy is divided into (PrNd)x-(Fe1-a,Ma)bal-By1, wherein 29.5wt%≤x≤31.5wt%, 0.5wt%≤a≤
3wt%, 0.9wt%≤y1≤1.5wt%.
15. the preparation method of the high-coercivity magnet of high-performance containing Tb according to claim 8, which is characterized in that the step
In rapid S4, the low sintering method is：
Respectively in 200 DEG C~400 DEG C, 500 DEG C~600 DEG C, 750 DEG C~900 DEG C, 1000 DEG C~1020 DEG C range inside holdings
30min~120min；
1030 DEG C~1050 DEG C are warming up to, 3h~6h is kept the temperature, vacuum degree is 10 in stove-2Pa。
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| CN110853856A (en) * | 2019-11-22 | 2020-02-28 | 安泰科技股份有限公司 | High-coercivity cerium-containing magnet and preparation method thereof |
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