CN107408438A - MnBi based magnetic powders and its manufacture method and bonded permanent magnet mixture, bonded permanent magnet and metallic magnet - Google Patents
MnBi based magnetic powders and its manufacture method and bonded permanent magnet mixture, bonded permanent magnet and metallic magnet Download PDFInfo
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- CN107408438A CN107408438A CN201680013880.3A CN201680013880A CN107408438A CN 107408438 A CN107408438 A CN 107408438A CN 201680013880 A CN201680013880 A CN 201680013880A CN 107408438 A CN107408438 A CN 107408438A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
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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
- H01F1/06—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 in the form of particles, e.g. powder
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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
- H01F1/06—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 in the form of particles, e.g. powder
- H01F1/08—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 in the form of particles, e.g. powder pressed, sintered, or bound together
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F7/00—Magnets
- H01F7/02—Permanent magnets [PM]
Abstract
The present invention, which provides, contains hexagonal crystal MnBi magnetic phases, and the content of the Zn in hexagonal crystal MnBi magnetic phases is 0.5~8 mass % MnBi based magnetic powders.Further it is provided that the bonded permanent magnet comprising the MnBi based magnetic powders and resinoid bond.And then, there is provided containing the hexagonal crystal MnBi magnetic phases comprising Zn, metallic magnet in hexagonal crystal MnBi magnetic phases, that amounted to relative to Mn, Bi and Zn, Zn contents are 0.5~8 mass %.
Description
Technical field
The present invention relates to MnBi based magnetic powders and its manufacture method and, bonded permanent magnet mixture, bonding magnetic
Body and metallic magnet.
Background technology
MnBi magnet powders have higher saturation magnetization and big crystal magnetic anisotropy, it is therefore contemplated that in work
It is used as various engine magnets etc. in industry.However, existing, oxidative resistance is low, the rapidly oxygen particularly in the atmosphere comprising water
Change corrosion, the shortcomings that reducing saturation magnetization.Therefore, in order to eliminate the shortcomings that such, trial covered with binding resin or
Use the method for antirust agent.
As other methods, the method for attempting to add other metallic elements.For example, in patent document 1, six are replaced with Ni
A prismatic crystal MnBi Mn part.Thus, propose to stabilize crystal structure in electrochemistry, prevent point under corrosive environment
Solution.It is proposed to add the alkaline-earth metal such as Sr in MnBi Magnaglos in patent document 2, so as to improve corrosion resistance.
It is proposed to make living comprising the cation system activating agent of nitrogen-atoms or both sexes for amine, acid amides, acid imide etc. in patent document 3
Property agent absorption prevent oxidation Decomposition in MnBi Magnaglos, suppress the reduction of saturation magnetization.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 9-139304 publications
Patent document 2：Japanese Unexamined Patent Publication 2001-257110 publications
Patent document 3：Japanese Unexamined Patent Publication 9-7163 publications
The content of the invention
Problems to be solved by the invention
However, in conventional technology, the corrosion resistance of MnBi based magnetic powders is insufficient, particularly under hot and humid,
Saturation magnetization is greatly reduced.Therefore, it is also not up to practical as magnet material.Therefore, in the side of the present invention
In, its object is to, there is provided even if carrying out keeping for a long time under hot and humid environment, high saturation and magnetic intensity can also be maintained
MnBi based magnetic powders and manufacture as MnBi based magnetic powders method.
In addition, it is of the invention in another side, its object is to, there is provided even if being carried out for a long time under hot and humid environment
Keeping, the bonded permanent magnet of high saturation and magnetic intensity can also be maintained and the bonded permanent magnet of such bonded permanent magnet can be manufactured
Use mixture.The present invention in other sides, its object is to, there is provided even if under hot and humid environment carry out long-time guarantor
Pipe, the metallic magnet of high saturation and magnetic intensity can also be maintained.
The solution used to solve the problem
Up to now when MnBi Magnaglos carry out keeping under hot and humid environment, oxide etch is quickly carried out, its
To cause the factor that saturation magnetization reduces.Understand that this is primarily due to contained hexagonal crystal MnBi in MnBi Magnaglos
The reduction of the oxidative resistance of magnetic phase.Therefore, the present inventor etc. enter to improve the oxidative resistance of hexagonal crystal MnBi magnetic phases
Row further investigation.As a result, understand that the Zn containing regulation content is effective in hexagonal crystal MnBi magnetic phases.The present invention is base
Formed in such opinion, in a side, there is provided containing hexagonal crystal MnBi magnetic phases, in hexagonal crystal MnBi magnetic phases
Zn contents are 0.5~8 mass % MnBi based magnetic powders.
For above-mentioned MnBi based magnetic powders, contain 0.5~8 matter in the low hexagonal crystal MnBi magnetic phases of oxidative resistance
Measure % Zn.Thus, the oxidative resistance for estimating the hexagonal crystal MnBi magnetic phases under hot and humid environment improves.As a result,
Even if MnBi based magnetic powders carry out keeping for a long time under hot and humid environment, high saturation and magnetic intensity can also be maintained.
The present invention is in other sides, there is provided Zn contents in hexagonal crystal MnBi magnetic phases be 0.5~8 mass %,
The manufacture method of MnBi based magnetic powders, it has following process：Mix MnBi alloy powders and Zn powder, in a vacuum or
In the non-active gas atmosphere under decompression, it is heat-treated, is obtained containing six sides comprising Zn at 280~380 DEG C
The MnBi based magnetic powders of brilliant MnBi magnetic phase.
In the manufacture method of above-mentioned MnBi based magnetic powders, in a vacuum or in the nonactive gas under decompression
The mixture of MnBi alloy powders and Zn powder is heated to 280~380 DEG C in body atmosphere.Thus, Zn gasifies, and Zn diffuses to six
The inside of prismatic crystal MnBi magnetic phases, obtain the hexagonal crystal MnBi magnetic phases that Zn contents are 0.5~8 mass %.Presumption so operation
Mutually the oxidative resistance under hot and humid environment improves resulting hexagonal crystal MnBi magnetic.As a result, pass through above-mentioned manufacturer
Even if MnBi based magnetic powders obtained from method carry out keeping for a long time under hot and humid environment, high saturation magnetic can also be maintained
Change intensity.
The present invention is in another side, there is provided Zn contents in hexagonal crystal MnBi magnetic phases be 0.5~8 mass %,
The manufacture method of MnBi based magnetic powders, it has following process：Implementation is carried out to MnBiZn alloys obtained from melting quenching
The heat treatment and crushing of strip are quenched, obtains the MnBi based magnetic powders containing the hexagonal crystal MnBi magnetic phases comprising Zn.
In the manufacture method of above-mentioned MnBi based magnetic powders, after carrying out melting quenching, it is heat-treated and powder
It is broken, so as to obtain the MnBi based magnetic powders that the Zn contents in hexagonal crystal MnBi magnetic phases are 0.5~8 mass %.It is such
Even if MnBi based magnetic powders carry out keeping for a long time under hot and humid environment can also maintain high saturation and magnetic intensity.Need
Illustrate, which is heat-treated and crushed and first carries out.Heat treatment is preferably in non-active gas atmosphere, 280~380
Implement at DEG C.
The present invention is in other sides, there is provided by the mixture for including above-mentioned MnBi based magnetic powders and resinoid bond
The bonded permanent magnet of formation is with mixture and includes the bonded permanent magnet of above-mentioned MnBi based magnetic powders and resinoid bond.This
The mixture and bonded permanent magnet of sample contain MnBi based magnetic powders as characterized above, therefore, even if in hot and humid ring
Keeping for a long time is carried out under border can also maintain high saturation and magnetic intensity.
The present invention is in other sides, there is provided contains the hexagonal crystal MnBi magnetic phases comprising Zn, above-mentioned hexagonal crystal MnBi magnetic
Property phase in, relative to the total of Mn, Bi and Zn, Zn contents be 0.5~8 mass % metallic magnet.The metallic magnet
The formed body that can be carried out press molding to above-mentioned MnBi based magnetic powders and make is implemented heat treatment or sintering and obtained.It is right
In such metallic magnet, the Zn containing 0.5~8 mass % in the low hexagonal crystal MnBi magnetic phases of oxidative resistance.Thus, push away
The oxidative resistance for the hexagonal crystal MnBi magnetic phases being scheduled under hot and humid environment improves.As a result, even if metallic magnet is in high temperature
Keeping for a long time is carried out under high humidity environment can also maintain high saturation and magnetic intensity.
The effect of invention
Even if high saturation can also be maintained according to the present invention it is possible to provide and keeping for a long time is carried out under hot and humid environment
The method of MnBi based magnetic powders as the MnBi based magnetic powders of the intensity of magnetization and manufacture.In addition, the present invention can carry
Even if the bonded permanent magnet of high saturation and magnetic intensity, Yi Jike can also be maintained for carrying out keeping for a long time under hot and humid environment
With the bonded permanent magnet mixture of bonded permanent magnet as manufacture.And then even if the present invention provides to enter under hot and humid environment
Row keeping for a long time, the metallic magnet of high saturation and magnetic intensity can also be maintained.
Brief description of the drawings
Fig. 1 (A) is one of the electron micrograph shown in the part in the section of amplification MnBi based magnetic powders
Individual example.Fig. 1 (B) is the figure of the cross section structure shown in the electron micrograph for schematically show Fig. 1 (A).
Fig. 2 (A) for amplify MnBi based magnetic powders section a part shown in electron micrograph its
Its example.Fig. 2 (B) is the result for showing to carry out linear analysis (EDX analyses) in the electron micrograph of Fig. 2 (A)
Figure.
Fig. 3 is a specific example for showing to manufacture the method for MnBi based magnetic powders, bonded permanent magnet and metallic magnet
Flow chart.
Fig. 4 is another specific example for showing to manufacture the method for MnBi based magnetic powders, bonded permanent magnet and metallic magnet
Flow chart.
Fig. 5 is another specific example for showing to manufacture the method for MnBi based magnetic powders, bonded permanent magnet and metallic magnet
Flow chart.
Fig. 6 is the stereogram for an embodiment for showing MnBi systems metallic magnet.
Embodiment
According to circumstances while referring to the drawings while explain an embodiment of the invention.It is it should be noted that following
Embodiment be for illustrate the present invention illustration, the present invention be not limited to following content.
The MnBi based magnetic powders of present embodiment contain hexagonal crystal MnBi magnetic phases as main component.Except hexagonal crystal
, can be containing at least one of Bi phases and Mn phases as accessory ingredient beyond MnBi magnetic phases.Mn phases are by Mn and Mn oxides
Formed.Bi phases are formed by Bi.MnBi based magnetic powders are by containing Bi phases, hexagonal crystal MnBi magnetic phases when being heat-treated in magnetic field
Orientation it is good, the high magnet powder of anisotropy can be readily derived.Mn's and Bi in MnBi based magnetic powders
Content is amounted to, such as can be more than 90 mass %, can also be more than 94 mass %.
Mn relative to the containing ratio of Mn and Bi total be preferably 35~65mol%, more preferably 37.5~
50mol%.When Mn containing ratio becomes too low, Mn deficiencies be present, the ratio of hexagonal crystal MnBi magnetic phases reduces, the intensity of magnetization
Value reduce tendency.On the other hand, when Mn containing ratio becomes too high, Bi deficiencies be present, hexagonal crystal MnBi magnetic phases
Ratio reduces, the tendency of the value reduction of the intensity of magnetization.It is each when tailing off additionally, there are the ratio of Bi phases and being heat-treated in magnetic field
Anisotropy becomes insufficient tendency.In addition, in the presence of excessive Mn, exist and easily form MnZn, in MnBi magnetic phases
The tendency of Zn content reductions.
Zn contents in MnBi based magnetic powders from the viewpoint of maintaining high magnetic characteristic and improving corrosion resistance, such as
It can be 0.3~5 mass %, can also be 0.4~4 mass %.The average grain diameter of MnBi based magnetic powders, for example, 3~150
μm。
Fig. 1 (A) is by the MnBi based magnetic powder resin embeddings of present embodiment, will utilize Cross section polishing machine
The electron microscope that the part in section obtained from (Cross section polisher) is ground is amplified and shown shines
One example of piece.Fig. 1 (B) is the cross section structure shown in the electron micrograph for schematically show Fig. 1 (A)
Figure.
As shown in Fig. 1 (A) and Fig. 1 (B), MnBi based magnetic powders contain hexagonal crystal MnBi magnetic phase 10 and and its
Adjacent Bi phases 20.The resin used to embed MnBi based magnetic powders is also showed that in Fig. 1 (A) and Fig. 1 (B)
30。
Hexagonal crystal MnBi magnetic phase 10 contains Zn on the basis of Mn and Bi.Zn in hexagonal crystal MnBi magnetic phase 10 contains
Measure as 0.5~8 mass %, preferably 0.9~6 mass %.When the content of the Zn becomes too small, it is excellent corrosion-resistant to there is infringement
The tendency of property.On the other hand, when the content of the Zn becomes too much, non-magnetic constituents increase be present, the value reduction of the intensity of magnetization
Tendency.
Fig. 2 (A) is by the MnBi based magnetic powder resin embeddings of present embodiment, will be carried out using Cross section polishing machine
The other examples for the electron micrograph that the part in section obtained from grinding is amplified and shown.Fig. 2 (B) is to show
In the electron micrograph of Fig. 2 (A), the result of linear analysis (EDX analyses) is carried out along line segment using point a as starting point
Figure.
As shown in Fig. 2 (A), MnBi based magnetic powders include hexagonal crystal MnBi magnetic phase 10 and to be clamped to it
Mode include Bi phases 20,20.According to the linear analysis shown in (B) such as Fig. 2, in hexagonal crystal MnBi magnetic phase 10 comprising Mn,
Bi and Zn.On the other hand, Mn and Zn is contained substantially no in Bi phases 20.
As shown in Fig. 2 (A) and Fig. 2 (B), by making Zn be the hexagonal crystal MnBi magnetic of MnBi based magnetic powders partially
In property phase 10, so as to maintain the ratio of relatively low non-magnetic constituents, and hexagonal crystal MnBi magnetic can be efficiently improved
The corrosion resistance of phase 10.From such a viewpoint, in Bi phases 20 Zn content, for example, below 0.01 mass %.From same
From the viewpoint of, Zn content in Mn phases, for example, below 10 mass %.
For the ratio of the hexagonal crystal MnBi magnetic phase 10 in MnBi based magnetic powders, (A) and Fig. 2 as Fig. 1
(A) area ratio in the electron micrograph in the section shown in, such as can be 60~98%, or 70~
95%.When the area ratio becomes too low, the ratio that non-magnetic phase be present uprises, the tendency of the value step-down of saturation magnetization.
On the other hand, when the area ratio becomes too high, for example, when particle is bigger than the size of single magnetic domain, it is heat-treated in magnetic field is carried out
And the Bi phases 20 for obtaining melting during magnet powder tail off.Thus, hexagonal crystal MnBi magnetic phase 10 be present when being heat-treated in magnetic field
It is difficult to the tendency being orientated.But particle it is roughly the same with single magnetic domain size when, it is not necessary to make hexagonal crystal MnBi magnetic phase 10
Intragranular is orientated, therefore the ratio of hexagonal crystal MnBi magnetic phase 10 can also be high.
The MnBi based magnetic powders of present embodiment can be to implement the magnet powder being heat-treated in magnetic field.For this reality
The MnBi based magnetic powders of mode are applied, hexagonal crystal MnBi magnetic mutually has high oxidation resistance.Therefore, for MnBi systems magnetic powder
End, even if keeping for a long time is carried out under hot and humid environment can also reduce the reduction of saturation magnetization.For using this
The MnBi based magnetic powders of sample and the bonded permanent magnet and metallic magnet formed, even if being carried out for a long time under hot and humid environment
Keeping, can also reduce the reduction of saturation magnetization.Then, the several of the manufacture method of MnBi based magnetic powders are illustrated below
Embodiment.
For the manufacture method of the MnBi based magnetic powders described in an embodiment, there is following process：Obtain MnBi
The process of alloy powder；And the mixed-powder comprising MnBi alloy powders and Zn powder is heated to 280~380 under reduced pressure
DEG C and generate hexagonal crystal MnBi magnetic phases, and Zn is diffused to the inside of hexagonal crystal MnBi magnetic phases, obtain hexagonal crystal MnBi
The content of Zn in magnetic phase is the process of 0.5~8 mass % MnBi based magnetic powders.In this way, it will make in this manual
The Magnaglo for include MnBi for main component, including Zn etc. as accessory ingredient is referred to as MnBi based magnetic powders.
MnBi alloy powders can manufacture with the following method：(i) powder is carried out after Mn and Bi crushing is sintered
It is broken, so as to obtain the powder metallurgic method of MnBi alloy powders；(ii) by MnBi alloy moltens, its atomization is made, so as to obtain MnBi
The atomization of alloy powder；(iii) MnBi alloy blocks obtained from being melted in electric arc furnaces crush, so as to obtain MnBi
The fusion method of alloy powder；(iv) the MnBi alloys melted are quenched with roller, resulting quenching strip is crushed, so as to
Liquid to MnBi alloy powders is quenched method.In each method, as Mn raw materials and Bi raw materials, can suitably select piece bits,
Pellet (シ ョ ッ ト) or powder etc. use.In addition, Zn raw materials can also suitably select piece bits, pellet or powder etc. to use.
Among above-mentioned (i)~(iv) method, preferably the liquid of (iv) is quenched method.In the liquid quenching method of (iv),
It will be quenched strip obtained from molten alloy will be quenched with roller to crush, so as to obtain the sufficiently small MnBi alloyed powders of particle diameter
End.Thus, in heat treatment step, Zn is allow fully to diffuse to the inside of hexagonal crystal MnBi magnetic phases.
Fig. 3 is the manufacture for showing MnBi based magnetic powders, bonded permanent magnet mixture, bonded permanent magnet and metallic magnet
The flow chart of the specific example of method.In this example embodiment, it is quenched method using above-mentioned (iv) liquid and prepares MnBi alloy powders.
I.e., first, Mn raw materials and Bi raw materials are prepared, such as by electric arc melting etc., (melting is cast so as to carry out melting to MnBi alloys
Make) melting process S1.Afterwards, carry out being quenched method by liquid, obtain being quenched the liquid quenching process S2 of strip.Then, enter
Row carries out the coarse crushing process S3 of coarse crushing to resulting quenching strip, obtains MnBi alloy powders.
In mixed processes S4, MnBi alloy powders and Zn powder obtained from mixing as described above.Mixing ratio now
It is the Zn powder that 1~10 mass % is mixed relative to MnBi alloy powders.Due in heat treatment step in the bar of Zn powders
Implement under part, therefore the more Zn powder of mixing preferably compared with as the Zn contents of the MnBi based magnetic powders of target.
In heat treatment step S5, by the mixed-powder of MnBi alloy powders and Zn powder in a vacuum or in subtracting
Depress (preferably below 10Pa) non-active gas atmosphere in, under 280~380 DEG C (preferably 300~370 DEG C) heat 30~
200 minutes.As non-active gas, argon gas, nitrogen etc. can be included.By implementing under such heating condition at heat
Reason, so as to which the Zn that has gasified is from the diffusion into the surface of MnBi particles to the inside of hexagonal crystal MnBi phases.So operation, obtain have contain
There are the MnBi based magnetic powders of ormal weight Zn hexagonal crystal MnBi magnetic phases.
When heating-up temperature in above-mentioned heating condition is less than 280 DEG C, Zn is fully vaporization, therefore heat treatment work be present
Tendency elongated sequence S5.Additionally, there are the tendency that hexagonal crystal MnBi magnetic does not generate fully mutually.On the other hand, the heating temperature
When degree is more than 380 DEG C, the structure phase produced from the opposite paramagnetism high-temperature-phase of ferromagnetism low temperature of hexagonal crystal MnBi magnetic phases be present
Transfer, the tendency that ferromagnetism disappears.In addition, Bi is melted, Bi phases separate out, therefore the ratio drop of hexagonal crystal MnBi magnetic phases be present
It is low, the tendency of the value reduction of saturation magnetization.When the processing time of above-mentioned heating condition is too short, Zn diffusion is not abundant sometimes
Ground is carried out, and is not obtained enough corrosion resistances and is improved effect.Additionally, there are what hexagonal crystal MnBi magnetic did not generated fully mutually to incline
To.On the other hand, when the processing time becomes long, hexagonal crystal MnBi magnetic be present and mutually grow, the tendency that coercivity reduces.
Hexagonal crystal MnBi magnetic in the MnBi based magnetic powders as obtained from above-mentioned manufacture method mutually has high resistance to
Oxidisability.Therefore, for MnBi systems magnetic powder, even if keeping for a long time is carried out under hot and humid environment can also reduce saturation
The reduction of the intensity of magnetization.
Heat treatment step S6 in magnetic field is carried out after heat treatment step S5., can be with for heat treatment step S6 in magnetic field
Apply 0.4~0.8T (4000~8000G) magnetic field for MnBi based magnetic powders, such as side, while in 260~380 DEG C of temperature
Degree is lower heat so as to implement within 30~600 minutes.By heat treatment step S6 in magnetic field as progress, so as to obtain
Anisotropic magnet powder.
When heating-up temperature in magnetic field in heat treatment step S6 is too low, the tendency for being difficult to fully anisotropisation be present.
On the other hand, when the heating-up temperature is too high, exists and produce hexagonal crystal MnBi magnetic mutually from the opposite paramagnetism high temperature of ferromagnetism low temperature
The structure phase transfer of phase, the tendency that ferromagnetism disappears.When heat time in magnetic field in heat treatment step S6 is too short, exists and be difficult to
The fully tendency of anisotropisation.On the other hand, the heat time is sufficient when if carrying out 600 minutes or so, even if than
Above-mentioned time length, does not almost have effect yet.
In magnetic field after heat treatment step S6, pulverizing process S7 is carried out, can also be made with each of desired particle diameter
The magnet powder of anisotropy.Wherein, such order is not limited to, for example, fully generating six in heat treatment step S5
After prismatic crystal MnBi magnetic phases, in pulverizing process S7 particle is crushed to single magnetic domain size and without magnetic field in be heat-treated work
Sequence S6, anisotropic magnet powder can also be obtained.
Then, shaped in the magnetic field for implementing to carry out anisotropic magnet powder and make in the magnetic field of formed body and shape work
Sequence S8.The magnetic field of application is, for example, 0.4~0.8T (4000~8000G), and forming pressure is, for example, 1~10t/cm2.Then, it is real
Apply the heat that resulting formed body is carried out to heating in 1~10 hour in non-active gas atmosphere, at a temperature of 200~380 DEG C
Treatment process S9.Or it can also implement to replace heat treatment step S9 in the hot compression process band pressurize during heating.By
This, can manufacture anisotropic MnBi systems metallic magnet.In this way, use MnBi systems metal obtained from MnBi based magnetic powders
Even if magnet uses under hot and humid environment, high saturation and magnetic intensity can also be maintained.
MnBi systems metallic magnet can also be come using the MnBi based magnetic powders carried out in magnetic field before heat treatment step S6
Manufacture.Now, enter to be about to the shaping of MnBi based magnetic powders and make the forming process S20 of formed body.It is formed in 1~10t/cm2
Forming pressure under carried out in method known to compression molding and injection moulding etc..Carried out using resulting formed body
Sintering circuit S21 in magnetic field.Thus, it is possible to obtain anisotropic MnBi systems metallic magnet.Sintering can be non-live in magnetic field
Property gas atmosphere in side apply 0.4~0.6T (4000~6000G) magnetic field, while at a temperature of 280~380 DEG C carry out 1~
Heat to implement within 10 hours.By MnBi systems metallic magnet obtained from the manufacture method be also using MnBi based magnetic powders and
Obtain, so even use can also maintain high saturation and magnetic intensity under hot and humid environment.
Magnet powder can be used, makes the mixture and bonded permanent magnet of bonded permanent magnet.At this time it is also possible to implement
In magnet powder addition comprising thermoplastic resin, coupling material and lubriation material resinoid bond and be kneaded mixed
Refine process S10.Can enter the mixture being about to be kneaded resulting bonded permanent magnet such as 0.4~0.8T (4000~
The forming process S11 that is shaped in magnetic field 8000G) manufactures bonded permanent magnet.It is formed in 1~10t/cm2Forming pressure under with
Method known to compression molding and injection moulding etc. is carried out.
Resinoid bond can also be the heat-curing resins such as epoxy resin.At this point it is possible to by by magnet powder and tree
The mixing of fat binding agent, press molding etc. and shape after, be heat-treated, so as to manufacture bonded permanent magnet.So using MnBi systems
Even if the use under hot and humid environment of bonded permanent magnet obtained from Magnaglo can also suppress the reduction of saturation magnetization.
Then, the other embodiment of the manufacture method of MnBi based magnetic powders is illustrated.The MnBi systems magnetic of present embodiment
The manufacture method of property powder has following process：After Mn raw materials, Bi raw materials and Zn raw materials melts, it is quenched and is obtained rapid
After the melting quenching method of cold strip, implement the heat treatment and crushing of quenching strip, so as to obtain containing hexagonal crystal MnBi magnetic
Property phase, the MnBi based magnetic powders that Zn content is 0.5~8 mass % in hexagonal crystal MnBi magnetic phases.
Fig. 4 is to show the manufacture method of MnBi based magnetic powders and using the MnBi systems as obtained from the manufacture method
The stream of other specific examples of the manufacture method of the bonded permanent magnet mixture of Magnaglo, bonded permanent magnet and metallic magnet
Cheng Tu.In this example embodiment, carry out using Mn raw materials and Bi raw materials, according to any in (i) of above-mentioned embodiment~(iv)
Method and the preparation section S31 for preparing MnBi alloys.
Zn with the MnBi alloys prepared from preparation section S31.MnBi alloys and Zn can be pellet, piece bits,
Any kind of the various forms such as powder or ingot casting.Then, enter to be about to MnBi alloys and the melting process S32 of Zn meltings.In this way,
The alloy for including MnBi as main component, including Zn etc. as accessory ingredient is referred to as MnBiZn alloys in this manual.
Melt in process S32, a vaporized Zn part is dispersed, therefore the Zn preferably with the MnBi based magnetic powders as target contains
Amount Zns more compared to cooperation.For example, coordinate 1~10 mass % Zn relative to MnBi alloys.
Then, implement by melt the liquid that quenching method is quenched to the fused mass of MnBiZn alloys be quenched process S33,
And coarse crushing process S34.Coarse crushing is carried out to obtain MnBi to quenching strip by known method in coarse crushing process S34
Series alloy powder.The MnBi series alloy powders are to include MnBi as main component, include the non magnetic of Zn etc. as accessory ingredient
Powder.After pulverizing process S34, heat treatment step S6 in magnetic field, pulverizing process S7 can be carried out, obtains MnBi systems magnetic
Powder (magnet powder).Heat treatment step S6 and pulverizing process S7 can be in the same manner as the flow chart shown in Fig. 3 in magnetic field
Carry out.In this case, however it is not limited to such order, for example, it is also possible to fully generate hexagonal crystal in heat treatment step S5
After MnBi magnetic phases, in pulverizing process S7 particle is crushed to single magnetic domain size and without magnetic field in heat treatment step
S6, so as to obtain anisotropic magnet powder.
Then, can be with carrying out forming process S8 and heat treatment step in magnetic field in the same manner as the flow chart shown in Fig. 3
S9, manufacture MnBi system metallic magnet.Furthermore, it is possible to use MnBi based magnetic powders in the same manner as the flow chart shown in Fig. 3, enter
Sintering circuit S21 in row forming process S20 and magnetic field, manufacture MnBi system metallic magnet.Furthermore, it is possible to showing in Fig. 3
Flow chart similarly uses MnBi based magnetic powders and resinoid bond, carries out compounding procedure S10 and forming process S11, system
Make bonded permanent magnet.
Hexagonal crystal MnBi magnetic in the MnBi based magnetic powders as obtained from the manufacture method mutually has highly oxidation resistant
Property.Therefore, for MnBi based magnetic powders, even if keeping for a long time is carried out under hot and humid environment can also reduce saturation magnetic
Change the reduction of intensity.
Fig. 5 is to show the manufacture method of MnBi based magnetic powders and using the MnBi as obtained from the manufacture method
Other specific examples of the manufacture method of the bonded permanent magnet mixture of based magnetic powder, bonded permanent magnet and metallic magnet
Flow chart.
In the specific example, carried out in the same manner as the flow chart shown in Fig. 4 preparation section S31, melting process S32,
And after liquid quenching process S33, carry out heat treatment step S34.It is rapid after liquid is quenched in heat treatment step S34
Cold strip heats 30~200 minutes in non-active gas atmosphere, under 280~380 DEG C (being preferably 300~370 DEG C).At heat
Science and engineering sequence S34 can also be carried out in the non-active gas atmosphere under the decompression for instance in below 10Pa or in vacuum.At this
MnBiZn alloys are implemented to be heat-treated in the heating condition of sample, so as to which Zn is diffused into the inside of hexagonal crystal MnBi phases.In this way, obtain
The MnBi systems alloy of hexagonal crystal MnBi magnetic phases with the Zn containing ormal weight.Can be by pulverizing process S35 by MnBi systems
Alloy crushes, so as to obtain MnBi based magnetic powders.Wherein, crush and each powder is crushed to as single such as using ball mill
10 μm (monocrystalline sizes) left and right of magnetic field level.If being crushed to the degree, obtain while magnetic field can not be applied anisotropic
MnBi series magnet powder.
Using the MnBi based magnetic powders obtained in pulverizing process S35, by carrying out forming process S8 and heat in magnetic field
Treatment process S9, so as to obtain MnBi systems metallic magnet.It can be carried out with the same manner as the flow chart shown in Fig. 4 in magnetic field
Forming process S8 or compounding procedure S10 and later process, manufacture MnBi system's metallic magnets and bonded permanent magnet.
Fig. 6 is the stereogram of MnBi systems metallic magnet 50.For the shape of MnBi systems metallic magnet, however it is not limited to such as Fig. 6
Such ground cylindrical shape, such as can also be prism shape, can also be spherical shape.Bonded permanent magnet can also be as shown in Figure 6
Cylindrical shape, or prism shape or spherical shape.
The composition of MnBi systems metallic magnet 50 contains the hexagonal crystal MnBi magnetic phases comprising Zn.Relative to hexagonal crystal MnBi magnetic
The total of Mn, Bi and Zn, Zn contents in property phase are 0.5~8 mass %.The content is from the high magnetic characteristic of maintenance and improves
From the viewpoint of corrosion resistance, for example, can be 0.3~5 mass %, can also be 0.4~4 mass %.
The content of Mn, Bi and Zn in the hexagonal crystal MnBi magnetic phases of MnBi systems metallic magnet 50 can be and MnBi systems
The content illustrated in the embodiment of Magnaglo is identical., can be by above-mentioned MnBi systems for MnBi systems metallic magnet 50
The formed body that Magnaglo carries out press molding and made is heat-treated or is sintered and obtained.
Bonded permanent magnet is with mixture in one embodiment by the mixed of above-mentioned MnBi based magnetic powders and resinoid bond
Thing is refined to form.Bonded permanent magnet is obtained from such bonded permanent magnet is shaped with mixture.Bonded permanent magnet includes above-mentioned reality
Apply MnBi based magnetic powders and the resinoid bond described in mode.Contained by bonded permanent magnet mixture and bonded permanent magnet
The composition of MnBi based magnetic powders can be identical with the content illustrated in above-mentioned embodiment.
More than, illustrate several embodiments of the invention, but the present invention is not limited to above-mentioned several embodiments.
Embodiment
Hereinafter, enumerating embodiment and comparative example, present disclosure is described in more detail.But the present invention is not
It is limited to following embodiments.
(embodiment 1)
The making ＞ of ＜ magnet powders
Mn pieces are considered to be worth doing with electric arc melting furnace and Bi pellets melt, so as to prepare MnBi alloys.In MnBi alloys
Mn and Bi mol ratio is set to Mn：Bi=45：55.By MnBi ladle refinings resulting in electric arc melting stove 5g in bottom
The transparent quartz tube of bore open with φ 0.45mm goes out nozzle for liquid.After being vacuumized in the chamber of liquid chilling apparatus,
In 50kPa argon gas atmosphere, by high-frequency melting, the MnBi alloy moltens that will go out in nozzle for liquid.Then, sprayed in molten metal
Under injection pressure 10kPa, MnBi molten metals are ejected on roller made of copper and obtain being quenched strip.The rotary speed of roller is set to
20m/s, roller and go out the distance of nozzle for liquid and be set to 0.4mm.Resulting quenching strip is crushed, obtains particle diameter as less than 150 μm
MnBi alloy powders.
Zn powder (3.0 mass %) is mixed in MnBi alloy powders (100 mass %) and prepares mixed-powder.In 10Pa
In following non-active gas (nitrogen) atmosphere, 320 DEG C of temperature, under conditions of 120 minutes time carry out mixed-powder heat at
Reason, makes Zn be diffused into MnBi.Temperature now is shown in a manner of " heat treatment temperature " in table 1.So operate and obtain
To MnBi based magnetic powders.Afterwards, (the atmosphere under defined heating condition is implemented：Argon gas, temperature：300 DEG C, time：240 points
Clock) to being heat-treated in the magnetic field in MnBi based magnetic powders application 0.6T (6000G) magnetic field, obtain magnet powder.
＜ evaluates 1 ＞
Use ICP emission spectroanalysis device (Thermo Fisher Scientific K.K. systems, device name：
ICAP6000), the Zn contents in magnet powder are determined.The Zn contents are relative to the overall Zn contents of magnet powder.In table 1 with
" Zn contents (1) " shows measurement result.
Use FE-SEM (JEOL systems, device name：JSM-7800F), magnet powder is amplified 500 times and observed.
In the observation image, contained hexagonal crystal MnBi magnetic phase, Bi phases and Mn phases in specific magnet powder.Attached using FE-SEM
EDX, determine hexagonal crystal MnBi magnetic phases in Zn contents.The measure of Zn contents is in the 5 hexagonal crystal MnBi arbitrarily selected
Carried out in magnetic phase.Table 1 is shown in using the average value of the measured value of Zn contents as " Zn contents (2) ".
Use vibration sample type magnetic flux gauge (VSM：Eastern English industry VSM-5 types), determine the saturated magnetization of magnet powder
Intensity (4 π Imax), residual magnetic flux density (Br) and coercivity (Hcj).Measurement result is as shown in the column of " before the keeping " of table 2.
＜ evaluates 2 ＞
By the magnet powder of preparation 40 DEG C of temperature, relative humidity 50% air in take care of 4 days.Magnetic after keeping is special
Property with " evaluation 1 " in the same manner as determine.And then melt-non-dispersive type infrared absorption (HORIBA systems by non-active gas：
Device name：EMGA-930), the oxygen content of the magnet powder after measure keeping.The column of " after the keeping " of these measurement results such as table 2
It is shown.
(embodiment 2)
The mixing Zn powder (5.0 mass %) in the MnBi alloy powders (100 mass %) and prepare mixed-powder, except this with
Operate similarly to Example 1 outside, prepare MnBi based magnetic powders, obtain magnet powder.Also, enter similarly to Example 1
Row evaluation 1,2.Evaluation result is as shown in table 1 and table 2.
(embodiment 3)
The temperature during heat treatment of mixed-powder is set to 360 DEG C, operated similarly to Example 1 in addition, is prepared
MnBi based magnetic powders, obtain magnet powder.Also, evaluation 1,2 is carried out similarly to Example 1.Evaluation result such as table 1 and
Shown in table 2.
(embodiment 4)
The mixing Zn powder (5.0 mass %) in the MnBi alloy powders (100 mass %) and prepare mixed-powder, except this with
Operate similarly to Example 3 outside, prepare MnBi based magnetic powders, obtain magnet powder.Also, grasp similarly to Example 3
Make, carry out the evaluation of magnet powder.Evaluation result is as shown in table 1 and table 2.
(embodiment 5)
Mn in MnBi alloys and Bi mol ratio are set to Mn：Bi=37.5：62.5, it is same with embodiment 1 in addition
Operate sample, prepare MnBi based magnetic powders, obtain magnet powder.Also, evaluation 1,2 is carried out similarly to Example 1.Evaluation
As a result as shown in table 1 and table 2.
(embodiment 6)
Mn pieces are considered to be worth doing with electric arc melting furnace and Bi pellets melt, and prepare MnBi alloys.Mn in MnBi alloys
Mn is set to Bi mol ratio：Bi=37.5：62.5.Relative to resulting MnBi alloys (100 matter in electric arc melting stove
Measure %), 1 mass %Zn is added, is melted again in electric arc melting stove.By the MnBiZn ladle refinings obtained by 5g the bottom of at
What portion had a transparent quartz tube of φ 0.45mm bore open goes out nozzle for liquid.It will be vacuumized in the chamber of liquid chilling apparatus
Afterwards, by high-frequency melting in 50kPa argon gas atmosphere, the MnBiZn alloy moltens that will go out in nozzle for liquid.Also, melted in metal
MnBiZn molten metals are ejected on roller made of copper under liquid injection pressure 10kPa, so as to obtain being quenched strip.The rotation speed of roller
Degree is set to 20m/s, roller and goes out the distance of nozzle for liquid to be set to 0.4mm.Coarse crushing is carried out to resulting quenching strip, obtains particle diameter
For less than 150 μm of MnBi series alloy powders.
Implement (the atmosphere under defined heating condition：Argon gas, temperature：300 DEG C, time：240 minutes) to MnBi systems alloy
Powder applies to be heat-treated in the magnetic field in 0.6T (6000G) magnetic field, obtains MnBi based magnetic powders (magnet powder).Show in table 1
Go out in magnetic field now the temperature being heat-treated.Also, evaluation 1,2 is carried out similarly to Example 1.Evaluation result such as table 1 and
Shown in table 2.
(embodiment 7)
Relative to the MnBi alloys (100 mass %) obtained by electric arc melting stove, add 2 mass %Zn, except this with
Operate similarly to Example 6 outside, prepare MnBi series alloy powders, obtain magnet powder.Also, carry out similarly to Example 1
Evaluation 1,2.Evaluation result is as shown in table 1 and table 2.
(embodiment 8)
Operate similarly to Example 6, MnBiZn molten metals are ejected on roller and obtain being quenched strip.It is rapid to carry out this
Heat treatment (the atmosphere of cold strip：Argon gas, temperature：300 DEG C, time：240 minutes).The heat treatment is in the nonactive of below 10Pa
Carried out in gas atmosphere.The temperature of heat treatment now is shown in table 1.Use ball mill (condition：50rpm, 2 hours), will be rapid
Cold strip is crushed to particle diameter as less than 63 μm, obtains MnBi based magnetic powders (magnet powder).The average grain diameter of magnet powder is
15μm.Also, evaluation 1,2 is carried out similarly to Example 1.Evaluation result is as shown in table 1 and table 2.
(comparative example 1)
Zn powder is not mixed, is operated similarly to Example 1 in addition, is prepared MnBi Magnaglos and is obtained magnet powder
End.Also, evaluation 1,2 is carried out similarly to Example 1.Evaluation result is as shown in table 1 and table 2.
(comparative example 2)
The mixing Zn powder (8.0 mass %) in the MnBi alloy powders (100 mass %) and prepare mixed-powder, except this with
Operate similarly to Example 1 outside, prepare MnBi based magnetic powders, obtain magnet powder.Also, enter similarly to Example 1
Row evaluation 1,2.Evaluation result is as shown in table 1 and table 2.
[table 1]
[table 2]
Shown in table 2 according to 40 DEG C of temperature, relative humidity 50% air in take care of 4 days before and keeping after saturation magnetic
Change the value of intensity, by following formula and the saturation magnetization deterioration rate that calculates.
Saturation magnetization deterioration rate (%)=100- [saturation magnetization after the keeping]/[saturated magnetization before keeping
Intensity] × 100
As shown in table 1, the Zn contents (2) of the magnet powder of each embodiment are in the range of 0.5~8 mass %.Such as the institute of table 2
Show, even if the magnet powder of each embodiment 40 DEG C of temperature, relative humidity 50% air in keeping 4 days after, saturated magnetization is strong
The deterioration rate of degree is also less than 5%.In addition, oxygen content is below 3000ppm.Accordingly, for the magnet powder of each embodiment, really
Recognize the Zn containing ormal weight in hexagonal crystal MnBi magnetic phases, so as to suppress oxidative degradation, saturation magnetization can be reduced
Deterioration rate.On the other hand, confirming in comparative example 1, hexagonal crystal MnBi magnetic does not contain Zn mutually, therefore oxidative degradation is carried out,
The deterioration rate of saturation magnetization becomes big.The oxygen content of the magnet powder of comparative example 1 is high compared with embodiment.
In comparative example 2, Zn content (2) is more, therefore suppresses oxidative degradation.However, non-magnetic constituents is big containing quantitative change, because
The value of this saturation magnetization is low.
＜ evaluates 3 ＞
By the magnet powder prepared in embodiment 1,6,7,8 and comparative example 1 in atmosphere, the keeping 1 hour of 100 DEG C of temperature
(condition (1)).In addition, by the magnet powder prepared in embodiment 1,6,7,8 and comparative example 1 in atmosphere, 250 DEG C of temperature guarantor
Pipe 1 hour (condition (2)).The magnetic characteristic of magnet powder after being taken care of under condition (1) or condition (2) is respectively with " evaluating
1 " similarly determines.And then saturation magnetization deterioration rate is calculated in the same manner as table 2.Result when will be taken care of under condition (1)
Table 3 is shown in, result when being taken care of under condition (2) is shown in table 4.
[table 3]
[table 4]
As shown in table 3, the deterioration rate of the saturation magnetization of the embodiment 1,6,7,8 when being taken care of under condition (1) is 15%
Hereinafter, the deterioration rate of saturation magnetization significantly diminishes compared with comparative example 1.When as shown in table 4, being taken care of under condition (2)
The deterioration rate of the saturation magnetization of embodiment 1,6,7,8 is less than 20%, the deterioration of saturation magnetization compared with comparative example 1
Rate significantly diminishes.
(embodiment 9, comparative example 3~12)
The comparison of the resistance to oxidation characteristic of MnBi based magnetic powders when being added Zn with adding the element in addition to Zn.
The element added in MnBi alloys is as shown in table 5, operates similarly to Example 6 in addition, obtains magnet powder.In order to than
Compared with the MnBi alloy powders without addition element are heat-treated with condition same as Example 6, prepare magnet powder
(comparative example 3).
The magnet powder of preparation is taken care of in an atmosphere, under normal temperature (about 20 DEG C).Will keeping before and keeping after (after 4 days
And after 15 days) saturation magnetization (4 π Imax), residual magnetic flux density (Br) and coercivity (Hcj) use vibration sample
Type magnetic flux gauge (VSM：Eastern English industry VSM-5 types) determine.Measurement result is shown in table 5.
[table 5]
As shown in table 5, even if the magnet powder for adding Zn embodiment 9 also has high saturation strong after keeping in 15 days
Degree.That is, confirm by using Zn, so as to be adequately suppressed oxidation, high saturation and magnetic intensity can be maintained.Need what is illustrated
It is that comparative example 9~12 is because the saturation magnetization of initial (before keeping) is too low, therefore the evaluation after not taken care of.
Industrial applicability
Even if high saturation can also be maintained according to the present invention it is possible to provide and keeping for a long time is carried out under hot and humid environment
The method of MnBi based magnetic powders as the MnBi based magnetic powders of the intensity of magnetization and manufacture.In addition, the present invention can carry
Even if it can also maintain the bonded permanent magnet of high saturation and magnetic intensity for carrying out keeping for a long time under hot and humid environment, can make
Make bonded permanent magnet mixture and the metallic magnet of such bonded permanent magnet.
Description of reference numerals
10 ... hexagonal crystal MnBi magnetic phases, 20 ... Bi phases, 30 ... resins, 50 ... MnBi systems metallic magnets.
Claims (7)
1. a kind of MnBi based magnetic powders, wherein, containing hexagonal crystal MnBi magnetic phases, the Zn in the hexagonal crystal MnBi magnetic phases
Content is 0.5~8 mass %.
2. a kind of manufacture method of MnBi based magnetic powders, it has following process：
MnBi alloy powders and Zn powder are mixed, in a vacuum or in the non-active gas atmosphere under decompression, 280
It is heat-treated at~380 DEG C, obtains the MnBi based magnetic powders containing the hexagonal crystal MnBi magnetic phases comprising Zn,
Zn contents in the hexagonal crystal MnBi magnetic phases are 0.5~8 mass %.
3. a kind of manufacture method of MnBi based magnetic powders, it has following process：
Implement to carry out MnBiZn alloys to be quenched obtained from melting quenching the heat treatment and crushing of strip, obtain containing comprising
The MnBi based magnetic powders of Zn hexagonal crystal MnBi magnetic phases,
Zn contents in the hexagonal crystal MnBi magnetic phases are 0.5~8 mass %.
4. the manufacture method of MnBi based magnetic powders according to claim 3, wherein, the heat treatment is in non-active gas
Implement in atmosphere at 280~380 DEG C.
5. a kind of bonded permanent magnet mixture, it is as including the MnBi based magnetic powders and resinoid bond described in claim 1
Mixture formed.
6. a kind of bonded permanent magnet, it includes the MnBi based magnetic powders and resinoid bond described in claim 1.
7. a kind of metallic magnet, wherein, containing the hexagonal crystal MnBi magnetic phases comprising Zn,
It is in the hexagonal crystal MnBi magnetic phases, be 0.5~8 mass % relative to the total of Mn, Bi and Zn, Zn contents.
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| JP2015-044962 | 2015-03-06 | ||
| JP2015044962 | 2015-03-06 | ||
| PCT/JP2016/056609 WO2016143664A1 (en) | 2015-03-06 | 2016-03-03 | Mnbi-based magnetic powder, method for producing same, compound for bonded magnets, bonded magnet and metal magnet |
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|---|---|---|---|---|
| JPH08138921A (en) * | 1994-04-14 | 1996-05-31 | Hitachi Maxell Ltd | Magnetic powder and manufacture thereof, magnetic recording medium by use thereof, and recording/ reproducing method and device thereof |
| CN1149174A (en) * | 1995-06-19 | 1997-05-07 | 日立马库塞鲁株式会社 | Magnetic recording media and recording and rewriting method |
| JPH09139304A (en) * | 1995-11-14 | 1997-05-27 | Hitachi Maxell Ltd | Mnnibi alloy magnetic powder |
| JPH1167511A (en) * | 1997-08-11 | 1999-03-09 | Hitachi Maxell Ltd | Magnetic material |
| JP2000040611A (en) * | 1998-07-23 | 2000-02-08 | Hitachi Maxell Ltd | Resin coupled permanent magnet material and magnetization thereof as well as encoder using the same |
| JP2001257110A (en) * | 2000-03-09 | 2001-09-21 | Hitachi Maxell Ltd | Magnetic material and magnetic recording medium formed by use thereof |
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2016
- 2016-03-03 JP JP2017505280A patent/JPWO2016143664A1/en active Pending
- 2016-03-03 WO PCT/JP2016/056609 patent/WO2016143664A1/en active Application Filing
- 2016-03-03 CN CN201680013880.3A patent/CN107408438A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08138921A (en) * | 1994-04-14 | 1996-05-31 | Hitachi Maxell Ltd | Magnetic powder and manufacture thereof, magnetic recording medium by use thereof, and recording/ reproducing method and device thereof |
| CN1149174A (en) * | 1995-06-19 | 1997-05-07 | 日立马库塞鲁株式会社 | Magnetic recording media and recording and rewriting method |
| JPH09139304A (en) * | 1995-11-14 | 1997-05-27 | Hitachi Maxell Ltd | Mnnibi alloy magnetic powder |
| JPH1167511A (en) * | 1997-08-11 | 1999-03-09 | Hitachi Maxell Ltd | Magnetic material |
| JP2000040611A (en) * | 1998-07-23 | 2000-02-08 | Hitachi Maxell Ltd | Resin coupled permanent magnet material and magnetization thereof as well as encoder using the same |
| JP2001257110A (en) * | 2000-03-09 | 2001-09-21 | Hitachi Maxell Ltd | Magnetic material and magnetic recording medium formed by use thereof |
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| JPWO2016143664A1 (en) | 2017-12-21 |
| WO2016143664A1 (en) | 2016-09-15 |
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