CN110021466A - A kind of R-Fe-B-Cu-Al system sintered magnet and preparation method thereof - Google Patents
A kind of R-Fe-B-Cu-Al system sintered magnet and preparation method thereof Download PDFInfo
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- CN110021466A CN110021466A CN201711464349.0A CN201711464349A CN110021466A CN 110021466 A CN110021466 A CN 110021466A CN 201711464349 A CN201711464349 A CN 201711464349A CN 110021466 A CN110021466 A CN 110021466A
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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
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Abstract
The invention discloses a kind of R-Fe-B-Cu-Al system sintered magnets and preparation method thereof, and the sintered magnet contains R2Fe14Type B main phase, the R is at least one rare earth element for including Nd, the sintered magnet includes following ingredient: R:31.0wt%-34.5wt%, B:1.08wt%-1.20wt%, Al:0.42wt%-0.50wt%, Cu:0.30wt%-0.50wt%, X:5.0wt% or less, X is selected from Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Hf, at least one kind of element in Ta or W, it include Nb in X, when at least one of Zr or Cr, Nb, the total content of Zr and Cr is in 0.20wt% or less, surplus is Co, Fe and and inevitably it is miscellaneous Matter, and the content of the Co is 0wt%-10wt%.The sintered magnet is by the way that by TRE (total rare earth content) control, in 31.0wt%-34.5wt%, and low-melting-point metal Cu, Al of compound addition high level overcome the problems, such as brought by high B content magnet, and obtain significant improvement.
Description
Technical field
The present invention relates to the manufacturing technology fields of magnet, more particularly to a kind of R-Fe-B-Cu-Al system sintered magnet.
Background technique
R-T-B based sintered magnet (R refers to that rare earth element, T refer to that transition metal element, B refer to boron element) is due to its excellent magnetic
Characteristic and be widely used in wind power generation field, electric car field and convertible frequency air-conditioner field etc., demand is growing, and
Requirement of each business men for magnet performance also steps up.
The component of strict control Nd-Fe-B magnet is to obtain high performance necessary condition.Sintered nd-fe-b magnet mainly by
Four phase compositions: Nd2Fe14B main phase, rich-Nd phase, richness B phase and Nd oxide.
It is the atomic radius of 0.126nm, Nd is 0.182nm that the atomic radius of B, which is the atomic radius of 0.092nm, Fe,.Existing
In some cognitions, increase the B element content of small atomic radius in right amount, improve the effect of amorphous forming ability, can refine
Nd2Fe14The crystal grain of B main phase.What B mainly influenced is the quick cooling alloy preparation section of magnet.This is because, improving amorphous nuclear energy
The increase of the B of power causes original grain nucleation ability in fast quenching thin strap to reduce, so that the precipitation of crystal grain is more uniform, changes
Kind microstructure, improves magnet magnetic property.And more B then will appear rich B phase (Nd1.1Fe4B4), rich B phase is introduced for
Guarantee that boron content is slightly above the inevitable outcome of normal composition, rich B phase is paramagnetism phase, in general, appearance will lead to magnetic
The decline of body magnetic property, belongs to the phase that should keep minimum content.Rich B phase changes less in entire alloy different conditions, this knot
Structure has been formed in the quick cooling alloy that molten liquid obtains, small-sized, only a few micrometers, is generally existed with the particle of disperse
In crystal boundary or part Nd2Fe14In B main phase grain.
And for the sintering character of magnet, due to being added to low-melting-point metal Cu, Al in low oxygen content magnet, meeting
Cause low melting point liquid phase in sintering process to increase, while sintering character significantly improves, it is significant to be easy to happen squareness (SQ)
The shortcomings that reduction.
Summary of the invention
It is an object of the invention to overcome the deficiency of the prior art, provides a kind of R-Fe-B-Cu-Al system sintered magnet, should
Sintered magnet is by controlling TRE (total rare earth content) in 31.0wt%-34.5wt%, and the eutectic of compound addition high level
Ni metal, Al are put to overcome the problems, such as brought by high B content magnet, and obtains significant improvement.
Technical solution provided by the invention is as follows:
A kind of R-Fe-B-Cu-Al system sintered magnet, the sintered magnet contain R2Fe14Type B main phase, the R are to include
At least one rare earth element of Nd, which is characterized in that the sintered magnet includes following ingredient:
R:31.0wt%-34.5wt%,
B:1.08wt%-1.20wt%,
Al:0.42wt%-0.50wt%,
Cu:0.30wt%-0.50wt%,
X:5.0wt% or less, X be selected from Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd,
At least one kind of element in Sn, Sb, Hf, Ta or W, when X includes at least one of Nb, Zr or Cr, Nb, Zr and Cr's is total
Content in 0.20wt% hereinafter,
Surplus be Co, Fe and and inevitable impurity, and the content of the Co be 0wt%-10wt%.
Heretofore described wt% is weight percentage.
R mentioned by the present invention is selected from Nd, Pr, Dy, Tb, Ho, La, Ce, Pm, Sm, Eu, Gd, Er, Tm, Yb, Lu or yttrium member
At least one of element.
In existing cognition, temperature coefficient can be improved by individually increasing B content, but the comprehensive performance of sintered magnet can drop
It is low.Individually addition Al can then significantly improve coercivity, but the temperature coefficient of sintered magnet can significantly reduce.Individually addition Cu then can
Improve the sintering character of magnet.
The present invention increases B amount by appropriateness, and TRE (total rare earth content) is controlled in 31.0wt%-34.5wt%, and
It is compound addition high level low-melting-point metal Al, Cu, can improve simultaneously due to B amount increase caused by magnetic property reduce and
The problem of temperature coefficient caused by Al amount increases reduces, the comprehensive temperature coefficient and magnet performance for promoting sintered magnet.By
It is unknown in the mechanism of action for obtaining above-mentioned technical effect, thus it is speculated that may be (the R for foring high-temperature stable2(Fe,Cu,Al)17Bx
Phase) so that the temperature coefficient of sintered magnet and magnet performance are significantly improved.
Another object of the present invention is to provide a kind of preparation methods of R-Fe-B-Cu-Al system sintered magnet.
A kind of preparation method of R-Fe-B-Cu-Al system sintered magnet, the sintered magnet contain R2Fe14Type B main phase, institute
The R stated is at least one rare earth element for including Nd, which is characterized in that the sintered magnet includes following ingredient:
R:31.0wt%-34.5wt%,
B:1.08wt%-1.20wt%,
Al:0.42wt%-0.50wt%,
Cu:0.30wt%-0.50wt%,
X:5.0wt% or less, X be selected from Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd,
At least one kind of element in Sn, Sb, Hf, Ta or W, when X includes at least one of Nb, Zr or Cr, Nb, Zr and Cr's is total
Content in 0.20wt% hereinafter,
Surplus be Co, Fe and and inevitable impurity, and the content of the Co be 0wt%-10wt%,
And following mode is used to be made: by sintered magnet material composition molten liquid with 102DEG C/sec -104DEG C/sec cooling
The process that speed is prepared into sintered magnet alloy；It will be made up carefully of Crushing of Ultrafine again after sintered magnet alloy coarse crushing
The process of powder；With magnetic forming method obtain formed body, and in vacuum or inert gas with 900 DEG C -1100 DEG C of temperature to institute
It states after formed body is sintered and obtains.
It should be noted that in the present invention, X:5.0at% or less, Co content be the content model of 0wt%-10wt% etc.
The conventional selection for the industry is enclosed, therefore, in embodiment, the content range of X and Co is not tested and is verified.
In addition, the inevitable impurity referred in the present invention further includes that can not keep away in the feed or in the fabrication process
Exempt from mixed a small amount of C, N, S, P and other impurities, therefore, in the present invention sintered magnet that refers in the production process, most
It is good C content is controlled in 1at% hereinafter, more preferably in 0.4at% hereinafter, N content then control in 0.5at% hereinafter, S content then
Control is in 0.1at% hereinafter, P content is then controlled in 0.1at% or less.
The digital scope announced in the present invention includes all point values of this range.
Detailed description of the invention
Fig. 1 is Dy, Nd, B, Al, Cu distribution situation in magnet in embodiment 3.
Fig. 2 is Dy, Nd, B, Al, Cu distribution situation in magnet in embodiment 3a.
Specific embodiment
Invention is further described in detail with reference to embodiments.
The definition that BHH, magnetic property evaluation procedure, composition measurement, the coercive force temperature coefficient referred in each embodiment measures
It is as follows:
BHH is the summation of (BH) max and Hcj, is one of the evaluation criterion of magnet comprehensive performance.
Magnetic property evaluation procedure: sintered magnet is lossless using the NIM-10000H type BH block rare earth permanent magnetism of metering institute, China
Measuring system carries out magnetic property detection.
Composition measurement: each ingredient is surveyed using high-frequency inductive coupling plasma body ICP Atomic Emission Spectrophotometer method (ICP-OES)
It is fixed.In addition, O (oxygen amount) based on gas melting-infrared absorption gas analyzing apparatus using being measured, N (nitrogen quantity) makes
With melted based on gas-gas analyzing apparatus of thermally conductive method is measured, C (carbon amounts) is using being based on burning-infrared absorption
Gas analyzing apparatus be measured.
Coercive force temperature coefficient (20 DEG C~100 DEG C): the β=Δ H/ Δ unit of T × 100%: %/DEG C
The detection of the FE-EPMA detection referred in each embodiment is limited to 100ppm or so, FE-EPMA equipment highest resolution
Reach 3nm.
In the embodiment of recommendation, the impurity includes O, and the O content of the sintered magnet is 0.5wt% or less.
For low oxygen content magnet (5000ppm or less), although having good magnetic property, it is easy when being sintered at relatively high temperatures
The agglomeration of crystal grain occurs, therefore, addition of microstructure and low melting material Al, Cu etc. for quick cooling alloy etc. produces
Come into force fruit response it is more sensitive.
It should be noted that since the hypoxemia manufacturing process of magnet has been the prior art, and all embodiments of the invention
All using hypoxemia manufacture, no longer it is described in detail herein.
In the embodiment of recommendation, the sintered magnet is made by following step: sintered magnet material composition is melted
Melt liquid with 102DEG C/sec -104DEG C/sec the cooling velocity process that is prepared into sintered magnet alloy；The sintered magnet is closed
The process that fine powder is made by Crushing of Ultrafine again after golden coarse crushing；Formed body is obtained with magnetic forming method or hot pressing thermal deformation, and
It is obtained after being sintered with 900 DEG C -1100 DEG C of temperature to the formed body in vacuum or inert gas.Cooling velocity uses
102DEG C/sec -104DEG C/sec, sintering temperature uses 900 DEG C -1100 DEG C of temperature for the conventional selection of the industry, therefore, is implementing
In example, the range of sintering temperature is not tested and verified.
In the embodiment of recommendation, the coarse crushing is the process that sintered magnet was crushed with absorption hydrogen, obtained coarse powder,
The Crushing of Ultrafine is the process of coarse powder air-flow crushing.By above-mentioned mode, the dispersion degree of B is further increased, magnet is improved
Heat resistance.
It further include that 1.0 μm of partial size below at least one are removed from the powder after Crushing of Ultrafine in the embodiment of recommendation
Part reduces 1.0 μm of powder volumes below of partial size to 10% process below of all powder volumes.
It include Pr in the R in the embodiment of recommendation, the content of the Pr is 0.2wt% or less.It needs Pr's
Content control it is below in 0.2wt% the reason is that, Pr-Fe-B alloy hydride Pr-Fe-B-Hx (x is natural number)
Easy magnetizing axis C axis changes, and misplaces in magnetic aligning, causes Br (remanent magnetism), and SQ (squareness) is reduced, therefore, for
For the lower sintered magnet of Pr content, the content for adjusting B, Cu, Al is more significant to the improvement of its magnetic property.
It include Mn in the X, and the content of the Mn is 0.035wt% or less in the embodiment of recommendation.It is studying
Middle discovery, for sintered magnet lower for Mn content, the content for adjusting R, B, Cu, Al is more aobvious to the improvement of its magnetic property
It writes.
In the embodiment of recommendation, the total content of Nb, Zr and Cr are 0.With in the past into raw material add more amount Zr,
Refractory metals such as Cr, Nb (more being limited to 0.25wt% or so) refine quick cooling alloy crystal grain, lead to obtained quick cooling alloy
In can generate amorphous phase and isotropism chilling phase, make crystalline orientation degree variation, Br, the significantly reduced trend of (BH) max not
Together, the present invention refines quick cooling alloy crystal grain by addition B and Cu, to reduce the use of Nb, Zr and Cr.
It further include that the sintered magnet is subjected to RH (heavy rare earth element) metal or RH alloy in the embodiment of recommendation
The process of grain boundary decision processing, the RH are selected from least one of Dy or Tb.Crystal boundary expansion is being implemented to above-mentioned sintered magnet
When dissipating, due to the comprehensive function of R, Cu, Al and Cu, the wellability of crystal grain boundary is more preferable, accelerates the diffusion velocity of RH, and obtain non-
Often high performance, obtains tremendous raising.
Grain boundary decision generally 700 DEG C~1050 DEG C at a temperature of carry out, this temperature range is the conventional choosing of the industry
It selects, therefore, in embodiment, above-mentioned temperature range is not tested and verified.
Embodiment one
Raw material process for preparation: prepare Nd, Dy, Pr of purity 99.5%, industrial Fe-B, industrial pure Fe, purity
99.9% Co, Mn, Si, Nb, Cr, Zr, Cu, Al of purity 99.5%, with mass percent wt% preparation.
Fusion process: take prepared raw material be put into oxidation aluminum crucible in, in high-frequency vacuum induction melting furnace
10-2Vacuum melting is carried out in the vacuum of Pa with 1500 DEG C of temperature below.
Casting process: it is passed through in the smelting furnace after vacuum melting after Ar gas makes air pressure reach 50,000 Pa, uses single roller anxious
Cold process is cast, with 102DEG C/sec~104DEG C/sec cooling velocity obtain quick cooling alloy, by quick cooling alloy 600 DEG C carry out
Heat preservation heat treatment in 60 minutes, is then cooled to room temperature.
Hydrogen crushing process: the broken stove evacuation of hydrogen that quick cooling alloy will be placed at room temperature, and in the broken furnace of backward hydrogen
The hydrogen that purity is 99.5% is passed through to pressure 0.1MPa, after placing 2 hours, is heated up when vacuumizing, 500 DEG C at a temperature of
It vacuumizes, is cooled down later, the powder after taking out hydrogen crushing.
Crushing of Ultrafine process: being 0.4MPa crushing chamber pressure under oxidizing gas content 100ppm nitrogen atmosphere below
Pressure under to after hydrogen crushing powder carry out 2 hours airflow milling crush, obtain fine powder.Oxidizing gas refers to oxygen or water
Point.
The fine powder (accounting for fine powder total weight 30%) after the Crushing of Ultrafine of part is classified using clasfficiator, remove 1.0 μm of partial size with
Under powder, then the fine powder after classification is mixed with remaining unassorted fine powder.In mixed fine powder, 1.0 μm of partial size or less
Powder volume reduce to 10% or less all powder volumes.
Methyl caprylate is added in the smashed powder of airflow milling, the additive amount of methyl caprylate is powder weight after mixing
0.2%, then be sufficiently mixed with V-type batch mixer.
Magnetic forming process: using the pressing under magnetic field machine of right angle orientation type, in the alignment magnetic field of 1.8T, in 0.4ton/
cm2Briquetting pressure under, by the above-mentioned powder for being added to methyl caprylate it is once-forming at side length be 25mm cube, once at
It demagnetizes in the magnetic field of 0.2T after shape.
For make it is once-forming after formed body be not exposed to air, be sealed, reuse secondary forming machine and (wait quiet
Pressing formation machine) in 1.4ton/cm2Pressure under carry out it is secondary forming.
Sintering process: each formed body being removed to sintering furnace and is sintered, and is sintered 10-3Under the vacuum of Pa, at 200 DEG C and
After respectively keeping 2 hours at a temperature of 800 DEG C, it is sintered 2 hours with 1030 DEG C of temperature, being passed through Ar gas later reaches air pressure
After 0.1MPa, it is cooled to room temperature.
Heat treatment process: sintered body after carrying out heat treatment in 1 hour with 460 DEG C of temperature, is cooled to room in high-purity Ar gas
It is taken out after temperature.
Process: the sintered body through Overheating Treatment is processed into the magnet of diameter 15mm, thickness 5mm, and the direction 5mm is magnetic field
Differently- oriented directivity obtains sintered magnet.
Magnet made of the sintered body of each embodiment and each comparative example directly carries out magnetic property detection, evaluates its magnetic characteristic.
The ingredient and evaluation result of each embodiment and each comparative example magnet are as shown in table 1, table 2:
The proportion (wt%) of 1 each element of table
The magnetic property of 2 embodiment of table evaluates situation
As conclusion we it follows that
When R content is less than 31.0wt% in magnet, since R content is very few, the collaboration of B, Al, Cu are added, to sintering
The temperature coefficient of magnet and the promotion of magnet performance are unobvious, relatively, when R content is more than 34.5wt%, due to R content
Excessively, B, Al, Cu in claim 1 range cooperate with addition, equally mentioning to the temperature coefficient of sintered magnet and magnet performance
It rises unobvious.For TRE (total rare earth content) is in 31.0wt%-34.5wt%, B, Al, Cu in claim 1 range
Collaboration addition, the promotion of temperature coefficient and magnet performance to sintered magnet become apparent.
When the content of B is less than 1.08wt% in magnet, since B content is very few, R, Al in claim 1 range,
The collaboration of Cu is added, and cannot preferably be promoted to the temperature coefficient improvement of magnet, relatively, be more than in B content
When 1.20wt%, the B of too excessive starts the deterioration for causing magnet performance, the collaboration of R, Al, Cu in claim 1 range again
Addition, it is equally unobvious to the promotion of the temperature coefficient of sintered magnet and magnet performance.And for B in 1.08wt%-
For 1.20wt%, the collaboration of R, Al, Cu in claim 1 range are added, to the temperature coefficient and magnet of sintered magnet
The promotion of energy becomes apparent.
When the content of Al is less than 0.42wt% in magnet, since Al content is very few, not sufficiently effective, magnetic is moistened in invading for crystal boundary
Body ag(e)ing process cannot preferably play crystal boundary repairing effect, the collaboration addition of R, B, Cu in claim 1 range, magnet
Energy promotion is unobvious, relatively, when Al content is more than 0.50wt%, since Al is excessive, although magnet Hcj gets a promotion,
But it will lead to the Tc decline of magnet, the temperature coefficient for influencing magnet is promoted, and the collaboration of R, B, Cu in claim 1 range add
Add, the promotion of temperature coefficient and magnet performance to sintered magnet is unobvious.For Al is in 0.42wt%-0.50wt%,
The collaboration of R, B, Cu in claim 1 range are added, and the promotion of temperature coefficient and magnet performance to sintered magnet is more bright
It is aobvious.
When the content of Cu is less than 0.30wt% in magnet, since Cu content is very few, R, B in claim 1 range,
The collaboration of Al is added, and sintering process Cu inhibits magnet abnormal grain growth and the effect of raising Tc that cannot well play, phase
Over the ground, when Cu content is more than 0.50wt%, excessive Cu can deteriorate magnet performance, R, B, Al in claim 1 range
Collaboration addition, the promotion of temperature coefficient and magnet performance to sintered magnet is unobvious.For Cu in 0.30wt%-
For 0.50wt%, the collaboration of R, B, Al in claim 1 range are added, temperature coefficient and magnet performance to sintered magnet
Promotion become apparent.
The ingredients such as Nd, Cu, Al, Co and B of sintered magnet are made to embodiment 3 and carry out FE-EPMA (field emission electron probe
Microscopic analysis) [Jeol Ltd. (JEOL), 8530F] detection, as a result as shown in fig. 1, it is observed that
Distribution of the B of 1.11wt% in entire magnet (including crystal boundary and crystal grain) is extremely uniform, and the Al of 0.45wt% is in entire magnet
Distribution be also greatly improved, and then improve due to B amount increase caused by magnetic property reduce and Al amount increase
The problem of caused temperature coefficient reduces, the mechanism of action of above-mentioned technical effect is unknown, thus it is speculated that may be to form high-temperature stable
(R2(Fe,Cu,Al)17BxPhase) so that the temperature coefficient of sintered magnet and magnet performance are significantly improved.
Similarly, other each embodiments are detected, it is observed that B and Al is uniformly distributed with higher dispersion degree
In entire magnet, reduced and temperature caused by the increase of Al amount so as to improve since B amount increases caused magnetic property
The problem of coefficient reduces.
Embodiment two
Raw material process for preparation: Nd, Pr of preparation purity 99.5%, industrial Fe-B, industrial pure Fe, purity 99.9%
Co, Mn, Nb, Cr, Zr, Cu, Al of purity 99.5%, with mass percent wt% preparation.
Fusion process: take prepared raw material be put into oxidation aluminum crucible in, in high-frequency vacuum induction melting furnace
10-3Vacuum melting is carried out in the vacuum of Pa with 1500 DEG C of temperature below.
Casting process: it is passed through in the smelting furnace after vacuum melting after Ar gas makes air pressure reach 30,000 Pa, uses chilling method
It is cast, with 102DEG C/sec~104DEG C/sec cooling velocity obtain quick cooling alloy, by quick cooling alloy 550 DEG C carry out 120 points
The heat preservation of clock is heat-treated, and is then cooled to room temperature.
Hydrogen crushing process: the broken stove evacuation of hydrogen that quick cooling alloy will be placed at room temperature, and in the broken furnace of backward hydrogen
The hydrogen that purity is 99.5% is passed through to pressure 0.08MPa, after sufficiently inhaling hydrogen, is heated up when vacuumizing, 650 DEG C at a temperature of
It vacuumizes 1 hour, is cooled down later, the powder after taking out hydrogen crushing.
Crushing of Ultrafine process: in oxidizing gas content 100ppm-1000ppm, (embodiment 20 is 100ppm, and embodiment 21 is
500ppm, embodiment 22 are 800ppm, and embodiment 23 is 1000ppm, and comparative example 24 is 1500ppm, remaining each embodiment and each
Comparative example is 100ppm) atmosphere under, crush chamber pressure be 0.42MPa pressure under to after hydrogen crushing powder carry out 3
Hour airflow milling crushes, and obtains fine powder.Oxidizing gas refers to oxygen or moisture.
Methyl caprylate is added in the smashed powder of airflow milling, the additive amount of methyl caprylate is powder weight after mixing
0.25%, then be sufficiently mixed with V-type batch mixer.
Magnetic forming process: using the pressing under magnetic field machine of right angle orientation type, in the alignment magnetic field of 1.8T, in 0.3ton/
cm2Briquetting pressure under, by the above-mentioned powder for being added to methyl caprylate it is once-forming at side length be 25mm cube, once at
It demagnetizes in the magnetic field of 0.2T after shape.
For make it is once-forming after formed body be not exposed to air, be sealed, reuse secondary forming machine and (wait quiet
Pressing formation machine) in 1.0ton/cm2Pressure under carry out it is secondary forming.
Sintering process: each formed body being removed to sintering furnace and is sintered, and is sintered 10-2Under the vacuum of Pa, at 300 DEG C and
After respectively keeping 3 hours at a temperature of 600 DEG C, it is sintered with 1020 DEG C of temperature, being passed through Ar gas later makes air pressure reach 0.1MPa
Afterwards, it is cooled to room temperature.
Heat treatment process: sintered body after carrying out heat treatment in 1 hour with 620 DEG C of temperature, is cooled to room in high-purity Ar gas
It is taken out after temperature.
Process: the sintered body through Overheating Treatment is processed into the magnet of diameter 10mm, thickness 5mm, and the direction 5mm is magnetic field
Differently- oriented directivity obtains sintered magnet.
Magnet made of the sintered body of each embodiment and each comparative example directly carries out magnetic property detection, evaluates its magnetic characteristic.
The ingredient of each embodiment and each comparative example magnet and magnetic evaluation result are as Table 3 and Table 4:
The proportion (wt%) of 3 each element of table
The magnetic property of 4 embodiment of table evaluates situation
As conclusion we it follows that
The collaboration of R, B, Cu, Al in claim 1 range are added, and are more than the sintered magnet of 0.25wt% for O content
For, it makes moderate progress to magnet performance and temperature coefficient.And for O content is in 0.25wt% magnet below, to magnet
Performance and temperature coefficient improve more significant.
The collaboration of R, B, Cu, Al in claim 1 range are added, and are more than the sintered magnet of 0.2wt% for Pr content
For, it makes moderate progress to magnet performance and temperature coefficient.And for Pr content is in 0.2wt% magnet below, to magnet
Performance and temperature coefficient improve more significant.
The collaboration of R, B, Cu, Al in claim 1 range are added, and are more than the sintering magnetic of 0.035wt% for Mn content
For iron, make moderate progress to magnet performance and temperature coefficient.And for Mn content is in 0.035wt% magnet below, it is right
Magnet performance and temperature coefficient improve more significant.
The collaboration of R, B, Cu, Al in claim 1 range are added, right for the sintered magnet containing Nb, Zr, Cr
Magnet performance and temperature coefficient make moderate progress.And for the magnet without containing Nb, Zr, Cr, magnet performance and temperature coefficient are changed
It is apt to more significant.
Similarly, each embodiment is detected, it is observed that B and Al be evenly distributed on higher dispersion degree it is whole
In a magnet, reduced and temperature coefficient caused by the increase of Al amount so as to improve since B amount increases caused magnetic property
The problem of reduction.
Embodiment three
The sintered magnet of Example 1-19 and comparative example 1-17 (is processed into the magnet of diameter 15mm, thickness 5mm, the side 5mm
To for magnetic field orientating direction).
Grain boundary decision treatment process: the magnet that each group sintered magnet is processed into is cleaned, and after clean surface, uses metal
The diffusion source material of Dy preparation, by way of vapor deposition, with temperature diffusion heat treatments 24 hours of 850 DEG C.
Magnetic property evaluation procedure: sintered magnet is lossless using the NIM-10000H type BH block rare earth permanent magnetism of metering institute, China
Measuring system carries out magnetic property detection.As a result as shown in table 5:
The coercivity of 5 embodiment of table evaluates situation
The number of each comparative example and each embodiment respectively corresponds each comparative example in Tables 1 and 2 and each embodiment in table 5
Number.
It can be seen that, sintered magnet produced by the present invention has good crystal boundary wellability from table 5, will not hinder Dy,
The diffusion of Tb, diffusion velocity are very fast.Magnet of the invention passes through the grain boundary decision of Dy, Tb, can obtain very high property
Energy.
Dy, Nd, B, Al, Cu distribution situation in magnet are as shown in Figure 2 in embodiment 3a.
Above-described embodiment is only used to further illustrate several specific embodiments of the invention, but the present invention does not limit to
In embodiment, any simple modification to the above embodiments, equivalent variations and repair according to the technical essence of the invention
Decorations, fall within the scope of protection of technical solution of the present invention.
Claims (10)
1. a kind of R-Fe-B-Cu-Al system sintered magnet, the sintered magnet contain R2Fe14Type B main phase, the R be include Nd
At least one rare earth element, which is characterized in that the sintered magnet includes following ingredient:
R:31.0wt%-34.5wt%,
B:1.08wt%-1.20wt%,
Al:0.42wt%-0.50wt%,
Cu:0.30wt%-0.50wt%,
X:5.0wt% or less, X be selected from Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn,
At least one kind of element in Sb, Hf, Ta or W, when X includes at least one of Nb, Zr or Cr, the total content of Nb, Zr and Cr
In 0.20wt% hereinafter,
Surplus be Co, Fe and and inevitable impurity, and the content of the Co be 0wt%-10wt%.
2. a kind of R-Fe-B-Cu-Al system sintered magnet according to claim 1, it is characterised in that: described inevitable
Impurity include O, and the O content of the sintered magnet is 0.5wt% or less.
3. a kind of R-Fe-B-Cu-Al system sintered magnet according to claim 2, which is characterized in that by following step
It is made: by sintered magnet material composition molten liquid with 102DEG C/sec -104DEG C/sec cooling velocity be prepared into sintered magnet alloy
Process；The process that fine powder will be made by Crushing of Ultrafine again after sintered magnet alloy coarse crushing；With magnetic forming method or
Hot pressing thermal deformation obtains formed body, and is carried out with 900 DEG C -1100 DEG C of temperature to the formed body in vacuum or inert gas
It is obtained after sintering.
4. a kind of R-Fe-B-Cu-Al system sintered magnet according to claim 3, it is characterised in that: the coarse crushing is to burn
The process that knot magnet was crushed with absorption hydrogen, obtained coarse powder, the Crushing of Ultrafine are the process of coarse powder air-flow crushing.
5. a kind of R-Fe-B-Cu-Al system sintered magnet according to claim 4, it is characterised in that: further include from Crushing of Ultrafine
1.0 μm of at least part below of partial size are removed in powder afterwards, reduce 1.0 μm of powder volumes below of partial size to complete
The process below of the 10% of body powder volume.
6. a kind of R-Fe-B-Cu-Al system sintered magnet described according to claim 1 or 2 or 3 or 4 or 5, it is characterised in that:
It include Pr in the R, the content of the Pr is 0.2wt% or less.
7. a kind of R-Fe-B-Cu-Al system sintered magnet described according to claim 1 or 2 or 3 or 4 or 5, it is characterised in that:
It include Mn in the X, and the content of the Mn is 0.035wt% or less.
8. a kind of R-Fe-B-Cu-Al system sintered magnet described according to claim 1 or 2 or 3 or 4 or 5, it is characterised in that:
The total content of Nb, Zr and Cr are 0.
9. a kind of R-Fe-B-Cu-Al system sintered magnet described according to claim 1 or 2 or 3 or 4 or 5, it is characterised in that:
It further include the process that the sintered magnet is carried out to RH metal or the processing of RH alloy grain boundary decision, the RH is in Dy or Tb
At least one.
10. a kind of preparation method of R-Fe-B-Cu-Al system sintered magnet, the sintered magnet contains R2Fe14B type main phase, institute
The R stated is at least one rare earth element for including Nd, which is characterized in that the sintered magnet includes following ingredient:
R:31.0wt%-34.5wt%,
B:1.08wt%-1.20wt%,
Al:0.42wt%-0.50wt%,
Cu:0.30wt%-0.50wt%,
X:5.0wt% or less, X be selected from Zn, In, Si, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn,
At least one kind of element in Sb, Hf, Ta or W, when X includes at least one of Nb, Zr or Cr, the total content of Nb, Zr and Cr
In 0.20wt% hereinafter,
Surplus be Co, Fe and and inevitable impurity, and the content of the Co be 0wt%-10wt%,
And following mode is used to be made: by sintered magnet material composition molten liquid with 102DEG C/sec -104DEG C/sec cooling velocity
The process for being prepared into sintered magnet alloy；Fine powder will be made by Crushing of Ultrafine again after sintered magnet alloy coarse crushing
Process；With magnetic forming method obtain formed body, and in vacuum or inert gas with 900 DEG C -1100 DEG C of temperature to it is described at
Body obtains after being sintered.
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| CN110853855A (en) * | 2019-11-21 | 2020-02-28 | 厦门钨业股份有限公司 | R-T-B series permanent magnetic material and preparation method and application thereof |
| CN110993233A (en) * | 2019-12-09 | 2020-04-10 | 厦门钨业股份有限公司 | R-T-B series permanent magnetic material, raw material composition, preparation method and application |
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| US12119150B2 (en) | 2019-09-26 | 2024-10-15 | Lg Chem, Ltd. | Method for producing sintered magnet and sintered magnet |
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