CN108962524A - A kind of sintering orientation magnet infiltration composition for treating, purposes and method - Google Patents
A kind of sintering orientation magnet infiltration composition for treating, purposes and method Download PDFInfo
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- CN108962524A CN108962524A CN201810589832.XA CN201810589832A CN108962524A CN 108962524 A CN108962524 A CN 108962524A CN 201810589832 A CN201810589832 A CN 201810589832A CN 108962524 A CN108962524 A CN 108962524A
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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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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5029—Magnesia
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5031—Alumina
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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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
- H01F41/0293—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 diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets
Abstract
The invention discloses a kind of sintered magnet infiltration compositions, including 30-99.9wt% penetrant and 0.1-70wt% permeable masses；The penetrant is that aluminium oxide, magnesia, zirconium oxide, titanium oxide are any one or more of, the permeable masses contain 29.8 DEG C of fusing point of metal Ga, the composition solve in the prior art infiltration raw material when lower melting-point osmoticum is added in infiltration in there are a large amount of losses, the higher osmoticum of viscosity be added because poor fluidity is difficult to be diffused the industry problem of reaction.The invention also discloses a kind of methods for being sintered orientation magnet processing using the composition, it is handled in infiltration, magnet and the infiltration macroscopical displacement movement remained in addition to atomic migration campaign between composition, the processing method can stablize coercivity, the thermal stability for improving sintered magnet.
Description
Technical field
The invention belongs to penetration material preparation fields, and in particular to a kind of sintering orientation magnet infiltration composition for treating and
Method.
Technical background
Third generation rare-earth Nd-Fe-B permanent magnetic material is due to high saturation magnetization, coercivity and magnetic energy product (BH)
Max, the price of good machining characteristics and relative moderate are widely used in many fields, but perishable, brittleness
Greatly, it is the major defect for restricting sintered NdFeB and further developing and apply that operating temperature is relatively low.
Studies have shown that the continuous uniform of high-orientation, the uniform crystal grain of refinement and relatively thin rich rare earth Grain-Boundary Phase is distributed, is smooth
Flawless phase interface etc. is the key factor for preparing performance Nd Fe B sintered magnet.Vapor deposition or coating film are generallyd use at present
Layer, reheats the mode of processing to magnet internal penetration heavy rare earth element, to improve the magnetic property of Sintered NdFeB magnet, but this
A little methods are very low to the utilization rate of infiltration element, and material loss is high for infiltration, can not be recycled, and cause processing cost high, no
It is able to satisfy the production of industrialized scale metaplasia, and limited penetration depth, infiltration capacity is not easy to control, to magnetic behavior, heat resistance, corrosion-resistant
Property improvement it is unstable, be easy to make the magnet degree of orientation reduce, yield rate it is lower.
Summary of the invention
In order to make up for the deficiencies of the prior art, the present invention provides a kind of sintered magnet infiltration compositions, including 30-
99.5wt% penetrant and 0.5-70wt% permeable masses, the penetrant are aluminium oxide, in magnesia, zirconium oxide
It is any one or more；Preferably, the permeable masses contain 29.8 DEG C of fusing point of metal Ga.
The permeable masses include can penetrate into magnet 2:14:1 type main phase element include La, Ce, Pr, Nd, Pm,
Sm, Eu, Gd, Tb, Dy, any one or more elements of Ho, Er, Tm, Yb, Lu, Y, Sc and any of Fe, Co, Ni, B or
Multiple element；Preferably, the element for infiltrating through Grain-Boundary Phase and/or crystal boundary corner phase include Ga, Nb, Cu, Al, Zr, Ti, O,
F, C, N are any one or more of.Preferably, the compound includes the simple substance, oxide, fluoride, carbonization of above-mentioned element
Object, nitride, hydride, alloy, and/or solid solution.
Preferably, the infiltration composition include: 55-99.9wt% selected from zirconium oxide or magnesia or aluminium oxide or
Any one or more of titanium oxide, the gallium of 0.1-5wt%, 0-35% fluorination terbium, 0-2wt% carbonyl cobalt powder, 0-
3wt% niobium powder or zirconium powder；It or include: 30-98.5wt% in zirconium oxide or magnesia or aluminium oxide or titanium oxide
The carbonyl for being fluorinated terbium, 0.5-20% dysprosium fluoride, 0.2-10wt% of any one or more, 0.1-5wt% gallium, 0.2-25%
Base cobalt powder, 0.5-10wt% niobium powder or zirconium powder or titanium valve.
Preferably, the sintered magnet group as following general formula indicate: RaTbMcBdXe, in which: R be selected from include Y and
At least one of rare earth element of Sc element, T be one or both of Fe and Co, M be selected from Al, Ti, Ni, Cu, Ga,
At least one of Zr, Nb element, B are boron, at least one of X O, F, N, C, H element；A, b, e, d, e indicate weight hundred
Divide ratio, 28≤a≤34,0.1≤c≤4,0.95≤d≤1.15,0≤e≤0.5, surplus b.
Preferably, the sintered magnet is orientation sintered magnet, including parallel-oriented magnet and radiation orientation magnet, including
It is sintered magnet ring, magnetic shoe, magnetic sheet.
The present invention also provides a kind of methods for being sintered magnet infiltration using the composition, it is characterised in that: seeps
During thoroughly, the atom diffusive migration between magnet and infiltration composition in addition to penetrative composition element relative to magnet is moved
In addition, the macro position of penetrative composition and magnet is not relatively-stationary, there is macroscopical relative motion, the macroface pair
Movement does not include that ball milling moves.
It is all to be spread to the internal method for penetrating into certain element of magnet (including magnet ring, magnetic shoe, magnetic sheet etc.) all using atom
Mechanism based on solid phase reaction, i.e., under the high temperature conditions, when the solid contact containing various concentration element together when, member
Element can be low to concentration from highly concentrated solid solid diffusion, i.e., generation atomic migration diffusion motion, this be also infiltration or diffusion
The mechanism of reaction.
In particular, the movement is the rotary motion in process of osmosis between magnet and infiltration composition；Alternatively, the fortune
Dynamic is the stirring movement in process of osmosis between magnet and infiltration composition.
The speed of the rotary motion is 0.01rpm-6000rpm, preferably 1-500rpm, the more preferable 1-100rpm present invention
Additionally provide it is a kind of using aforementioned composition be sintered magnet infiltration method, successively the following steps are included:
A, it is surface-treated: removing the surface contaminant, rusty stain and oxide layer of magnet；
B, infiltration composition is prepared；Each material powder of infiltration composition is proportionally mixed, is obtained pre-
Mixed infiltration composition；
C, movement infiltration processing: by the infiltration group of the premixing of magnet and step B configuration by step A surface treatment
Close object according to the volume ratio of 1:1-1:100 be packed into batches container carry out movement infiltration processing, in process of osmosis, the magnet with
There is macroscopical relative motion always between the infiltration composition；Vacuum or inert gas atmosphere are kept in movement infiltration；
D, movement infiltration after treatment, magnet is separated with infiltration with composition substance, carries out tempering；
E, after tempering, product is obtained.
In the step B, 1050 DEG C or more of high-temperature baking is carried out to zirconium oxide or magnesia or alumina powder, then will
The metal simple-substance or compound of low melting point, which are added in the powder toasted, forms premix, will toast by 100 DEG C or more
Other raw materials be added in the premix.
In the step C infiltration, infiltration is used to use slow rate to heat up and be segmented keeping temperature rule: with 3-8 DEG C/min's
The rate of heat addition is warming up to 650-800 DEG C, keeps the temperature 0.5-5h, is then warming up to 800-1050 DEG C with the rate of 0.5-2 DEG C/min, protects
Warm 2-45h is quickly cooled down or naturally cools to later 40-80 DEG C, and wherein first segment heating rate is greater than second segment heating rate.
Preferably, in step D, tempering temperature is 400-600 DEG C, time 1-12h.
Preferably, before step A, also have and rough machined step is carried out to orientation magnet surfaces externally and internally.
The present invention also provides a kind of preparation methods of radiation orientation sintered magnet, it is characterised in that: including orientation magnet
Forming step and sintering step, wherein in molding, there are relative rotary motions between alignment magnetic field and mold.
The forming step includes: that magnetic powder to be formed is filled in (1) die cavity, mold cavity one internal magnetic pole of setting, outside die cavity
An outer magnetic pole is arranged in portion；(2) outer magnetic pole is rotated relative to die cavity or die cavity is rotated relative to outer magnetic pole, generates one between inside and outside magnetic pole
Alignment magnetic field, there are relative rotation between the alignment magnetic field and magnetic powder, are magnetized to magnetic powder and are orientated；(3) rotation is same
When, apply the pressure gradually increased and the magnetic powder is pressed, orientation magnet green body is obtained, by the green body in 1000-
1100 DEG C of progress vacuum-sinterings must arrive magnet before processing.
Alternatively, the forming step includes: filling magnetic powder to be formed in (1) die cavity, a magnetic core, die cavity is arranged in mold cavity
Multiple outer magnetic poles are arranged in outer symmetrical；(2) multiple outer magnetic poles are simultaneously relative to the relatively described outer magnetic pole rotation of die cavity rotation or die cavity
Turn, multiple alignment magnetic fields is generated between magnetic core and multiple outer magnetic poles, there are relative rotation between the alignment magnetic field and magnetic powder, right
Magnetic powder is magnetized and is orientated；(3) while rotation, apply the pressure being stepped up and the magnetic powder is pressed, obtain
To orientation magnet green body, which must be arrived into the preceding magnet of processing in 1000-1100 DEG C of progress vacuum-sintering.
The alignment magnetic field is stationary magnetic field, regular changing magnetic field or irregular magnetic field.
The present invention have it is following prominent the utility model has the advantages that
(1) containing selected from any one of aluminium oxide, magnesia, zirconium oxide or titanium oxide in present invention infiltration composition
Or a variety of penetrants solves infiltration raw material in the prior art once adding especially containing 29.8 DEG C of fusing point of metal Ga
Occur the problem of a large amount of loss when entering lower melting-point osmoticum in diffusion reaction, be added the higher osmoticum of viscosity because
Poor fluidity is difficult to be diffused the industry problem of reaction, and is made by the collaboration of each material composition of infiltration composition and proportion
With, solve the problems, such as in the prior art infiltration stock dispersion it is poor, wellability is bad, permeability-thickness is limited；
(2) infiltration composition of the invention and magnet keep opposite macroscopic motion, the high rigidity in infiltration composition
Particle, such as aluminium oxide, zirconium oxide etc. have friction cleaning action to magnet surfaces externally and internally, as magnet constantly exposes fresh table
Face, target infiltration element are constantly permeated, are spread, promoted the lasting progress of permeable reactive, solve in industrial production and seep
The technical problem that transflection answers low efficiency, object element limited penetration depth, infiltration capacity uncontrollable.
(3) the methods of currently used sputtering, coating, powder covering are compared, and target infiltration element of the invention enters magnetic
The infiltration capacity in internal portion is easily controllable, infiltration is uniform, is no longer limited by fusing point, the physical property, state of infiltration raw material, the selection of raw material
Range is wide, at low cost, and osmotic effect is good, can stablize coercivity, the thermal stability for improving sintered magnet.
(4) target of the invention infiltration element is not lost substantially, and the object element for participating in infiltration with magnet contact is direct
It diffuses into inside magnet, the object element for not being diffused or permeating still is retained in infiltration source with original state, next time
It can continue to use；And coating in the prior art, plated film, powder covering etc. techniques there is permeable reactive after do not join
With or fail the film permeated completely, powder or other residues, all become waste residue；Therefore compared with traditional penetration technique,
The present invention permeate element utilization rate it is high, it is basic without loss, it is at low cost, be suitable for industrialized production.
(5) present invention is heated up and is segmented using variable Rate keeping temperature rule in infiltration processing, effectively avoid because of magnet
Uneven heating is even to lead to cracking, deformation, and make infiltration uniformly, permeable reactive it is high-efficient, improve industrial scale
Handle the quality and yield rate of magnet.
(6) the method for the present invention can steadily improve the magnetic property of sintered magnet, and wherein coercivity improves before relatively handling
40%, remanent magnetism declines then less than 3%, and thermal stability significantly improves.
Specific embodiment
The present invention is described in further details With reference to embodiment, but protection scope of the present invention and unlimited
In this.
Embodiment 1
A kind of sintering orientation magnet infiltration composition, ingredient include: 55-99.9wt% selected from zirconium oxide or oxidation
Magnesium or any one or more of aluminium oxide or titanium oxide, the gallium of 0.1-5wt%, the fluorination terbium of 0-35%, 0-2wt%
Carbonyl cobalt powder, 0-3wt% niobium powder or zirconium powder.
A method of magnet is sintered using composition described in embodiment 1 and is permeated, including following preparation step:
A, prepare magnetic powder, oriented moulding and then sintering to be formed by set composition and ratio and obtain orientation sintered magnet, at
There are relative rotation between alignment magnetic field and magnetic powder described in type；The composition and ratio of the magnetic powder are (weight percent): dilute
Native PrNd content 28-31%, Dy+Tb+Ho content 2-5%, Co content 0.2-0.8%, B content 0.95-1.15%, Nb content
0.2-1%, Cu content≤0.20%, Al content 0.2-1.0%, surplus are Fe and inevitable impurity；
B, it pre-processes: removing the pollutant, rusty stain and oxide layer of magnet surface, it is preferable that first to magnet before pretreatment
Surfaces externally and internally carries out roughing, advantageously to magnet internal organizational structure to be repaired；
C, the infiltration composition is prepared: according to the ratio of above-mentioned composition, in advance to selected from zirconium oxide or magnesia
Or any one or more of aluminium oxide or titanium oxide raw material carry out 1050 DEG C or more of high-temperature baking, then gallium is heated and is melted
Change is added in the powder toasted, then successively by the fluorination terbium, carbonyl cobalt powder, niobium powder (or zirconium powder) by 120 DEG C of bakings
It is added in aforementioned premix, after mixing, obtains infiltration composition；
D, rotation infiltration processing: rotatable, vacuum-pumping infiltration will be added to by pretreated orientation sintered magnet
In processing unit, by the infiltration composition substance prepared by the pretreated magnet of step B and step C according to 1:1-1:100
Volume ratio be fitted into a vacuum-pumping, carry out infiltration processing in rotatable and heatable container；In process of osmosis, magnet with
Always there is rotary motion, rotation speed 0.01rpm-6000rpm, preferably 0.5- between infiltration composition substance
1000rpm, more preferable 0.5-500rpm or 1-100rpm；First 6Pa is vacuumized hereinafter, preferably smaller than 6x10 in movement infiltration- 2Pa continues to keep vacuum later or is filled with inert gas, and inert gas is specially nitrogen or argon gas；To avoid magnet heated not
The problems such as uniformly causing deformation, cracking permeates keeping temperature rule using variable Rate heating and multistage；With the heating speed of 3-8 DEG C/min
Rate is warming up to 700 DEG C, keeps the temperature 1.5h, is then warming up to 870 DEG C with the rate of 1-3 DEG C/min, keeps the temperature 3-10h, then again with
The rate of 0.5-2 DEG C/min, which is warming up at 880-950 DEG C, keeps the temperature 15-40h, is quickly cooled down or naturally cools to 40-80 DEG C later,
Vacuum or inert gas shielding atmosphere are kept in cooling, and magnet continues that the relative rotation relative to infiltration composition is kept to transport
It is dynamic；
D, movement infiltration after treatment, magnet is separated with infiltration with composition substance, at 450-550 DEG C, 3-8h
Carry out tempering；
After F tempering, product is obtained.
Magnetism testing shows: Exemplary magnetic energy, the thermal stability of orientation sintered magnet are as follows before the present embodiment processing: surplus
Magnetic Br=13.01kGs, coercivity H j=18.27kOe, magnetic energy product (BH) max=40.6MGO, magnet are heated to 120 from room temperature
DEG C return room temperature, magnetic flux heat fade -11.9%.
Exemplary magnetic energy, the thermal stability that sintered magnet is orientated after the present embodiment processing are as follows: remanent magnetism Br=12.70kGs,
Coercivity H j=25.70kOe, magnetic energy product (BH) max=38.21MGOe, magnet are heated to 120 DEG C from room temperature and return room temperature,
Magnetic flux heat fade drops to less than 3%.
As it can be seen that nearly 40% is steadily improved after the present embodiment processing before the relatively processing of the coercivity of sintered magnet, under remanent magnetism
Less than 3%, magnet is heated to the magnetic flux heat fade that 120 DEG C return room temperature from room temperature and drops to less than 3% drop, is sintered after processing
Magnetic property, the thermal stability of magnet significantly improve.
Orientation sintered magnet in the embodiment can be specially orientation sintering magnet ring, magnetic shoe, magnetic sheet etc..
Embodiment 2
A kind of sintering orientation magnet infiltration composition, comprising: 30-98.5wt%'s is selected from zirconium oxide or magnesia or oxygen
Change aluminium or titanium oxide is any one or more of, gallium of 0.1-5wt%, the fluorination terbium of 0.2-25%, 0.5-20% fluorination
Dysprosium, the carbonyl cobalt powder of 0.2-10wt%, 0.5-10wt% niobium powder or zirconium powder or titanium valve；
A method of magnet is sintered using composition as described in example 2 and is permeated, including following preparation step:
A, prepare magnetic powder, oriented moulding and then sintering to be formed by set composition and ratio and obtain orientation sintered magnet, at
There are relative rotation between alignment magnetic field and magnetic powder described in type；The composition and ratio of the magnetic powder are (weight percent): dilute
Native PrNd content 28-30%, Tb+Dy content 2-3%, Ho content 0.5-2.0%, Co content 0.1-0.5%, B content 0.95-
1.1%, Nb+Zr content 0.5-2.0%, Cu content 0.05-1.0%, Al content 0.05-1.0%, Ti content 0.02-1.0%,
Surplus is Fe and inevitable impurity；；
B, it pre-processes: removing the pollutant, rusty stain and oxide layer of magnet surface, it is preferable that first to magnet before pretreatment
Surfaces externally and internally carries out roughing, advantageously to magnet internal organizational structure to be repaired；
C, prepare infiltration composition: 1050 DEG C being carried out to zirconium oxide or magnesia or aluminium oxide or raw titanium oxide material in advance
Above high-temperature baking, then by gallium heating fusing be added in Zirconium oxide powder, will by 120 DEG C baking fluorination terbiums,
Dysprosium fluoride, carbonyl cobalt powder, niobium powder or zirconium powder or titanium valve are added sequentially to gallium and zirconium oxide (or magnesia or aluminium oxide)
In premix, after mixing, infiltration composition substance is obtained；
D, rotation infiltration processing: rotatable, vacuum-pumping infiltration will be added to by pretreated orientation sintered magnet
In processing unit, by the infiltration composition substance prepared by the pretreated magnet of step B and step C according to 1:1-1:100
Volume ratio be fitted into a vacuum-pumping in batches, carry out infiltration processing in rotatable and heatable container；In process of osmosis, magnetic
Always there is rotary motion, rotation speed 0.01rpm-6000rpm, preferably 0.5- between body and infiltration composition substance
1000rpm, more preferable 0.5-500rpm or 1-100rpm；First 6Pa is vacuumized hereinafter, preferably smaller than 6x10 in movement infiltration- 2Pa is filled with inert gas, specially nitrogen or argon gas later；To avoid magnet uneven heating is even deformation, cracking etc. is caused to be asked
Topic permeates keeping temperature rule using variable Rate heating and multistage；It is warming up to 650-800 DEG C with the rate of heat addition of 3-8 DEG C/min, heat preservation
Then 2h is warming up to 850-1050 DEG C with the rate of 0.5-3 DEG C/min, keep the temperature 2-20h, and wherein first segment heating rate is greater than the
Two sections of heating rates are quickly cooled down or naturally cool to later 40-60 DEG C, and inert gas shielding atmosphere, and magnetic are kept in cooling
Body continues to keep the relative rotary motion relative to infiltration composition；
D, movement infiltration after treatment, magnet is taken out, the tempering 4h at 550-600 DEG C.
Magnetism testing shows: Exemplary magnetic energy, the thermal stability of orientation sintered magnet are as follows before the present embodiment processing: surplus
Magnetic Br=13.31kGs, coercivity H j=18.83kOe, magnetic energy product (BH) max=40.26MGO, magnet are heated to from room temperature
120 DEG C return room temperature, magnetic flux heat fade -10.4%.
Exemplary magnetic energy, the thermal stability that sintered magnet is orientated after the present embodiment processing are as follows: remanent magnetism Br=12.8kGs,
Coercivity H j=24.71kOe, magnetic energy product (BH) max=38.4MGOe, magnet are heated to 120 DEG C from room temperature and return room temperature,
Magnetic flux heat fade drops to -2.9%.
As it can be seen that the coercivity of sintered magnet steadily improves 30% after the present embodiment processing before relatively handling, remanent magnetism decline
Less than 4%, magnet is heated to the magnetic flux heat fade that 120 DEG C return room temperature from room temperature and sharply declines from -10.4% before processing
To -2.9%, the magnetic property of sintered magnet, thermal stability are significantly improved after processing.
Further analysis shows, pass through the composition proportion of each element, step in the infiltration composition for preparing in rate-determining steps C
Rotation speed, the highest of rapid D permeates temperature and time, is adjusted, controls above-mentioned element and enter the amount of main phase, into Grain-Boundary Phase
Amount and the amount for entering crystal boundary corner phase.
Orientation sintered magnet in the embodiment can be specially orientation sintering magnet ring, magnetic shoe, magnetic sheet etc..
Above embodiments are only the preferred embodiment of the present invention, can not be interpreted as the limitation of the scope of the present invention.
It should be pointed out that for those of ordinary skill in the art, without departing from the inventive concept of the premise, if can also make
Dry deformation, substitution and improvement, these are all belonged to the scope of protection of the present invention.
Claims (10)
1. a kind of orientation sintered magnet infiltration composition, it is characterised in that: including 30-99.9wt% penetrant and 0.1-
70wt% permeable masses；The penetrant is that aluminium oxide, magnesia, zirconium oxide, titanium oxide are any one or more of, institute
It states permeable masses and contains simple substance and/or compound that fusing point is lower than 400 DEG C；Preferably, containing 29.8 DEG C of fusing point of metal Ga.
2. composition according to claim 1, it is characterised in that: the permeable masses include that can penetrate into magnet 2:
The element of 14:1 type main phase, including La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, any of Ho, Er, Tm, Yb, Lu, Y, Sc
Kind or multiple element and Fe, Co, Ni, B any one or more elements, and infiltrate through Grain-Boundary Phase and/or crystal boundary corner phase
Element, including Ga, Nb, Cu, Al, Zr, Ti, O, F, C, N are any one or more of；Preferably, the permeable masses include
Simple substance, oxide, fluoride, carbide, nitride, hydride, alloy, and/or the solid solution of above-mentioned element.
3. composition according to claim 1, it is characterised in that: be selected from zirconium oxide or oxidation including 55-99.9wt%
Magnesium or any one or more of aluminium oxide or titanium oxide, the gallium of 0.1-5wt%, the fluorination terbium of 0-35%, 0-2wt%
Carbonyl cobalt powder, 0-3wt% niobium powder or zirconium powder；Alternatively, including 30-98.5wt% selected from zirconium oxide or magnesia or aluminium oxide or
Titanium oxide is any one or more of, 0.1-5wt% gallium, the fluorination terbium of 0.2-25%, 0.5-20% dysprosium fluoride, 0.2-
Carbonyl cobalt powder, 0.5-10wt% niobium powder or the zirconium powder or titanium valve of 10wt%.
4. composition according to claim 1 to 3, it is characterised in that: the orientation sintered magnet be it is parallel-oriented or
Radiation orientation sintered magnet, including sintering magnet ring, magnetic shoe, magnetic sheet；Preferably, magnet composition is expressed by the following formula:
RaTbMcBdXe, in which: R is selected from least one of the rare earth element for including Y and Sc element, and T is one in Fe and Co
Kind or two kinds, M is selected from least one of Al, Ti, Ni, Cu, Ga, Zr, Nb element, and B is boron, in X O, F, N, C, H extremely
A kind of few element；A, b, e, d, e expression weight percent, 28≤a≤34,0.1≤c≤4,0.95≤d≤1.15,0≤e≤
0.5, surplus b.
5. a kind of method for being sintered orientation magnet infiltration using any composition of claim 1-4, feature exist
In: in process of osmosis, the atom diffusion between magnet and infiltration composition in addition to penetrative composition element relative to magnet is moved
Other than shifting movement, the macro position of penetrative composition and magnet is not relatively-stationary, there is macroscopical relative motion, this is macro
Seeing relative motion does not include ball milling movement；In particular, the macroscopic view relative motion be in process of osmosis magnet with permeate with combining
Rotary motion or stirring movement between object；It is furthermore preferred that the speed of the rotary motion is 0.01rpm-6000rpm, preferably
For 1-500rpm, more preferably 1-100rpm.
6. a kind of method for being sintered orientation magnet infiltration using any composition of claim 1-4, successively includes
Following steps:
A, it is surface-treated: surface contaminant, rusty stain and the oxide layer of removal sintering orientation magnet；
B, with infiltration composition；Preferably, each material powder of infiltration composition is proportionally mixed, configuration is seeped
Composition is used thoroughly；It is furthermore preferred that first carrying out 1050 DEG C or more of height to zirconium oxide or magnesia or aluminium oxide or titanium dioxide powder
Temperature baking, then simple substance by fusing point lower than 400 DEG C and/or compound metal simple substance or compound are added in the powder toasted
Premix is formed, other raw materials toasted by 100 DEG C or more are added in the premix；
C, movement infiltration processing: it is preferred, by the infiltration of the premixing of magnet and step B configuration by step A surface treatment
With composition according to 1:1-1:100 volume ratio be packed into container carry out movement infiltration processing, in process of osmosis, the magnet with
There is macroscopical relative motion always between the infiltration composition, but does not include ball milling movement；Vacuum is kept in movement infiltration
Or inert gas atmosphere；
D, movement infiltration after treatment, magnet is separated with infiltration with composition, carries out tempering；Preferably, tempering temperature
Degree is 400-600 DEG C, time 1-12h；
E, after tempering, product is obtained.
7. according to the method described in claim 6, it is characterized by: infiltration is heated up and is segmented heat preservation using variable Rate in step C
System: it is slowly warming up to 650-800 DEG C with the rate of heat addition of 3-8 DEG C/min, 0.5-5h is kept the temperature, then with 0.5-2 DEG C/min's
Rate is warming up to 800-1050 DEG C, keeps the temperature 2-45h, is quickly cooled down or naturally cools to later 40-80 DEG C, and wherein first segment heats up
Rate is greater than second segment heating rate.
8. a kind of preparation method of any orientation sintered magnet of claim 1-7, it is characterised in that: including orientation magnet
Forming step and sintering step, wherein in molding, there are relative rotary motions between alignment magnetic field and mold.
9. according to the method described in claim 8, it is characterized by: oriented moulding step includes: that the interior filling of (1) die cavity is to be formed
Magnetic powder, mold cavity are arranged an internal magnetic pole, an outer magnetic pole are arranged outside die cavity；(2) outer magnetic pole is relative to die cavity rotation or die cavity phase
Outer magnetic pole is rotated, generates an alignment magnetic field between inside and outside magnetic pole, there are relative rotation between the alignment magnetic field and magnetic powder,
Magnetic powder is magnetized and is orientated；(3) while rotation, apply the pressure gradually increased and the magnetic powder be pressed,
Orientation magnet green body is obtained, by the green body in 1000-1100 DEG C of progress vacuum-sintering, obtains handling preceding magnet；Alternatively, being orientated to
Type step includes: filling magnetic powder to be formed in (1) die cavity, and a magnetic core is arranged in mold cavity, and the setting of die cavity outer symmetrical is multiple outer
Magnetic pole；(2) multiple outer magnetic poles are rotated relative to die cavity rotation or die cavity relative to the outer magnetic pole simultaneously, magnetic core and multiple outer magnetic poles
Between generate multiple alignment magnetic fields, there are relative rotation between the alignment magnetic field and magnetic powder, are magnetized to magnetic powder and are orientated；
(3) while rotation, apply the pressure being stepped up and the magnetic powder is pressed, orientation magnet green body is obtained, by this
Green body obtains handling preceding magnet in 1000-1100 DEG C of progress vacuum-sintering.
10. according to the method described in claim 8, it is characterized by: the magnetic field is the magnetic of stationary magnetic field, regular variation
Field or irregular magnetic field.
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| CN201810589832.XA CN108962524B (en) | 2018-06-08 | 2018-06-08 | Composition for sintering oriented magnet permeation treatment, application and method |
| US16/401,655 US20190378651A1 (en) | 2018-06-08 | 2019-05-02 | Permeating treatment method for radially oriented sintered magnet, magnet, and composition for magnet permeation |
| US18/501,659 US20240071683A1 (en) | 2018-06-08 | 2023-11-03 | Permeating treatment Method for Radially Oriented Sintered Magnet, Magnet, and Composition for Magnet Permeation |
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| CN111243807A (en) * | 2020-02-26 | 2020-06-05 | 厦门钨业股份有限公司 | Neodymium-iron-boron magnet material, raw material composition, preparation method and application |
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