CN105189805B - R T B series magnet raw alloys - Google Patents
R T B series magnet raw alloys Download PDFInfo
- Publication number
- CN105189805B CN105189805B CN201480023759.XA CN201480023759A CN105189805B CN 105189805 B CN105189805 B CN 105189805B CN 201480023759 A CN201480023759 A CN 201480023759A CN 105189805 B CN105189805 B CN 105189805B
- Authority
- CN
- China
- Prior art keywords
- phases
- magnet
- rich
- alloy
- principal phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
In R T B series magnets with raw alloy (at least a kind among wherein, R is the rare earth element comprising Y, T be using Fe as necessary more than a kind transition elements), by comprising the R as principal phase2T14Rich R phases that B phases and R have been concentrated, richness R phases at intervals of more than 10 μm and the oval length ratio of richness R phases is more than 0.6, the mobility of pulverized micro mist is excellent, can obtain the sintered magnet of complicated shape.When R T B series magnet raw alloys contain any one of Dy and Tb or both and are used as R, the total concentration A of the Dy and Tb in principal phase divided by the Dy in rich R phases and Tb total concentration B obtained by percentage (A/B) be desired for more than 180%.In addition, the impurity concentration D of richness R phases divided by principal phase impurity concentration C obtained by percentage (D/C) be desired for more than 230%.
Description
Technical field
The present invention relates to the R-T-B series magnet raw alloys used in the raw material of rare-earth magnet.More specifically, it is related to
Be made using crushing the excellent micro mist of mobility, can obtain complicated shape sintered magnet R-T-B series magnet raw materials
Alloy.In addition, so as to obtain the R-T-B of bonded permanent magnet the time required to being related to omit melt treatment or reduce melt treatment
Series magnet raw alloy.
Background technology
In recent years, as the alloy used in the raw material of rare-earth magnet, there is the R-T-B systems alloy that magnet characteristics are excellent.This
Place, " R " in " R-T-B systems alloy " represents that rare earth element, " T " are represented and represents boron as necessary transition metal, " B " using Fe.
R-T-B series magnets include above-mentioned R-T-B systems alloy, the raw material as rare-earth magnet with raw alloy.The R-T-B series magnets are former
Material alloy can be manufactured by the alloy strip cast using thin strap continuous casting method.
Fig. 1 is the ideograph for representing the casting device used during using thin strap continuous casting method casting alloy band.Shown in the figure
Casting device possesses chamber 5, crucible 1, tundish 2 and chill roll 3.Decompression state or non-is maintained by by the inside of chamber 5
Reactive gas atmosphere, so as to the alloy strip for preventing alloy molten solution and being cast is oxidized.
When using this casting device and casting the alloy strip formed by R-T-B systems alloy using thin strap continuous casting method, for example
Can be carried out using following steps.
(A) raw material is loaded in crucible 1, is heated the raw material using induction heating apparatus (not shown).Thus, by raw material
Melt and form alloy molten solution.
(B) alloy molten solution is supplied by tundish 2 to the outer peripheral face of chill roll 3.The inside of chill roll 3 has makes system
Cryogen circulation structure, therefore alloy molten solution chill roll 3 outer peripheral face quenching and solidify.
(C) so operation carrys out the alloy thin band 4 that cast thickness is 0.2~1.0mm.Chill roll 3 is applied with along the figure
Direction shown in the arrow of hachure is rotated, therefore alloy strip 4 is peeled off with the rotation from chill roll 3.
After the alloy strip cast using thin strap continuous casting method is made alloy sheet by crushing, carried out according to the condition of regulation cold
But.In order to prevent the oxidation of alloy sheet, the broken and alloy of alloy strip is generally carried out under reduced pressure or under non-active gas atmosphere
The cooling of piece.It should be noted that in thin strap continuous casting method, alloy sheet is obtained sometimes through the thin slice of casting alloy.In addition,
Also alloy sheet is obtained sometimes through further being crushed after the thin slice of casting alloy.
R-T-B series magnets have with raw alloy (hereinafter also referred to as " raw material for magnet ") obtained from so operating
Have by R2T14The texture that the rich R phases that crystalline phase (principal phase) and the concentration that B phases are formed have rare earth element (mainly Nd) coexist.
Principal phase contributes to the ferromagnetism phase of magnetization, and rich R phases are the non-magnetic phases for being helpless to magnetization.Comprising principal phase and richness R
The texture of phase can be evaluated using the interval of richness R phases.The interval of rich R phases is from a richness in the section of thickness direction
R phases play the average value at the interval to the rich R phases of adjacent position.
The raw material for magnet is mainly used as R-T-B based sintered magnets (hereinafter also referred to as " sintered magnet "), R-
The raw material of T-B systems bonded permanent magnet (hereinafter also referred to as " bonded permanent magnet ").
R-T-B based sintered magnets can for example be obtained by following manufacturing process.
(1) in pulverizing process, after R-T-B series magnets are carried out into hydrogenolysis broken (coarse crushing) with raw alloy, using injection
Formula pulverizer etc. carries out Crushing of Ultrafine and is made micro mist.(such as air current classifying, sieve classification) is classified, so as to from the micro mist
Except the particle and particle diameter of particle diameter deficiency lower limit exceed the particle of higher limit.
(2) in molding procedure, classified micro mist is press-formed in magnetic field with mould, so as to obtain press-powder
Body.
(3) in sintering circuit, after the powder compact being press-formed is sintered in a vacuum, heat is implemented to sintered body
Treatment (tempering).Thus R-T-B based sintered magnets are obtained.
Assumed a variety of shapes according to its purposes by the shape of the sintered magnet that this manufacturing process is obtained.As will burn
Knot magnet is processed into variously-shaped method, for example, setting cutting process after sintering circuit sometimes, processed using perforate,
Machining is refined to arbitrary shape.In addition, being finish-machined to when being also press-formed in molding procedure sometimes any
Shape (near-net-shape, near net shape).
In the method for setting cutting process, the yield rate of product can be reduced because of machining.On the other hand, using plus
It is molded to be finish-machined in the method for arbitrary shape, if the mobility of micro mist is low, in the case of complicated shape, with thin-walled
In the case of, it is impossible to micro mist is filled uniformly with to mould, density can significantly change because of the difference at position.Like this, exist
Filled in the state of Density inhomogeneity during to mould, sintering becomes insufficient, as a result, the magnetic characteristic of sintered magnet deteriorates.
On R-T-B based sintered magnets, such as shown in patent document 1~3, various motions were proposed in the past.Specially
The manufacture method of the sintered magnet proposed in sharp document 1 is to have carried out the alloy powder of hot demagnetization treatment as object.To the conjunction
The binding agent of the organic solvent comprising methylcellulose, polyacrylamide, polyvinyl alcohol etc is added in bronze end and is mixed
Refining, so as to be made pulp-like.The slurry is made the spherical pelletizing that average grain diameter is 20~400 μm of spray-drying installation.
If being molded using the pelletizing, being sintered and obtained sintered magnet, even thin wall profile, complicated shape can also realize compared with
Magnetic characteristic high.Because, pelletizing is by that binding agent itself that mobility spherical and pelletizing high is included has is excellent
Different mobility.
In addition, the manufacture method of the sintered magnet proposed in patent document 2 is having carried out the fine alloy powder of wet type
As object.In the same manner as patent document 1 in the slurry of the alloy powder addition comprising organic solvent binding agent and carry out
Mixing, so as to be made pulp-like.The slurry for being kneaded is made average grain diameter of spray-drying installation for 20~400 μm
Spherical pelletizing.If being molded using the pelletizing, being sintered and obtained sintered magnet, even thin wall profile, complexity
Shape can also realize magnetic characteristic higher.Because, pelletizing is by gluing that mobility spherical and pelletizing high is included
Knot agent itself has excellent mobility.
But, the manufacture method of the sintered magnet proposed in patent document 1 and 2 bonds micro mist using binding agent
Grain, therefore, it is difficult to carry out magnetic field orientating.In addition, organic solvent is included in binding agent, therefore the organic solvent is difficult in sintering
It is completely removed, so as to remain a part in gained sintered magnet.Therefore, the carbon that is mixed into from organic solvent, oxygen can be formed
Rare earth compound, as a result, deteriorating magnetic characteristic.
For the sintered magnet raw alloy proposed in patent document 3, the alloy is being observed using 100 times of multiplying power
In the micro- sem observation image on the surface contacted with roller cooling surface, there is point with the nucleus for crossing the line segment equivalent to 880 μm and make
Centered on, the draw ratio that dendrite grows into round shape is 0.5~1.0 and the crystallization quantity of more than 30 μm of particle diameter is more than 5.Separately
Outward, for the sintered magnet raw alloy, being approximately perpendicular to and roller cooling surface for the alloy is being observed using 200 times of multiplying power
In the micro- sem observation image of the section on the surface of contact, the equispaced of rich R phases is 10~30 μm.
The sintered magnet proposed in this patent document 3 utilizes the grinders of the manufacturing process of sintered magnet with raw alloy
Sequence and the powder size is become uniform.However, the mobility of even-grained micro mist (micro mist of narrow particle size distribution) is simultaneously
It is not necessarily good.During the epigranular of the micro mist obtained by raw material for magnet, atmosphere is easily propagated through between its particle, therefore
In the presence of the tendency for being difficult to liquidation.Therefore, the mobility reduction of micro mist, as a result, the magnetic characteristic reduction of sintered magnet.
On the other hand, R-T-B systems bonded permanent magnet is for example by will crush the powder of raw material for magnet and combine
The mixture (compound) of agent (resin, low-melting-point metal) is compressed shaping, injection moulding and solidifies, so as to manufacture.As
Bonded permanent magnet powder, commonly uses the so-called MQ powder of マ グ ネ Network エ Application チ company systems.In addition, as bonded permanent magnet powder,
Also commonly use and implement HDDR (suction hydrogen-disproportionation-dehydrogenations-be combined again, Hydrogenation to raw material for magnet
Disproportionation Desorption Recombination) treatment after implement pulverization process obtained from powder.
It is thick to raw material for magnet requirement principal phase (crystal grain) when being processed using HDDR.The magnetic is made by HDDR treatment
The thick principal phase of body raw alloy occur chemical breakdown and in conjunction with.Thus, it is possible to fine Ground Split principal phase and unified easy magnetization
The direction of axle, as a result, the coercivity and remanence of bonded permanent magnet can be improved.
In pulverization process after HDDR treatment, even if after principal phase is made by fine Ground Split by HDDR treatment,
It is crushed readily along the rich R phases of alloy and turns into powder.When compound comprising the powder and bonding agent is molded, if
The particle diameter of powder is small, then briquetting pressure rises and is difficult to be molded.In order to prevent the powder diameter obtained by pulverization process from diminishing,
Need to carry out coarsening to principal phase.Therefore, in the manufacture of conventional bonded permanent magnet, as the pre-treatment that HDDR is processed, to magnetic
Body raw alloy is implemented to be referred to as the heat treatment of melt treatment and make principal phase that coarsening to occur.
But, in melt treatment, due to the dissolution from raw material for magnet (alloy sheet) of rich R phases, therefore sometimes
Alloy sheet is fused to other alloy sheets.In addition, the composition of alloy sheet is sometimes also unstable.Therefore, it is difficult in melt treatment
Treatment raw material for magnet (alloy sheet).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 8-107034 publications
Patent document 2：Japanese Unexamined Patent Publication 8-88111 publications
Patent document 3：International Publication WO2012/002531 publications
The content of the invention
Problems to be solved by the invention
As described above, in the molding procedure of the manufacturing process of R-T-B based sintered magnets, it is important that former by magnet
The mobility of the micro mist that material alloy is crushed.It is 20~400 μm to be proposed in patent document 1 and 2 and for micro mist to be made average grain diameter
Spherical pelletizing is so as to improve mobility.But, the binding agent comprising organic solvent, therefore organic solvent are used during due to granulation
A part residue in sintered magnet and form rare earth compound, as a result cause magnetic characteristic to deteriorate.In addition, being carried in patent document 3
The sintered magnet raw alloy for going out becomes uniformly (to make size distribution become narrow) due to the granularity for making micro mist, therefore micro mist
Mobility reduction, the magnetic characteristic of sintered magnet deteriorate.
On the other hand, for R-T-B systems bonded permanent magnet, when being processed using HDDR, magnetic is made by melt treatment
There is coarsening in the principal phase of body raw alloy.But, in melt treatment, it is difficult to process raw material for magnet (alloy
Piece).
The present invention is carried out in light of this situation, its object is to, there is provided mobility can be made by crushing excellent
The R-T-B series magnet raw alloys of different micro mist and the sintered magnet that complicated shape can be obtained.In addition, it is intended that carrying
The R-T-B series magnet raw materials of bonded permanent magnet are obtained the time required to energy supply is enough omitted melt treatment or reduces melt treatment
Alloy.
The scheme for solving problem
The present inventor is studied for the mobility for improving the micro mist crushed by raw material for magnet, is as a result sent out
It is existing：In raw material for magnet, make principal phase that coarsening to occur, make rich R phases at intervals of more than 10 μm and make the ellipse of rich R phases
Length ratio is more than 0.6.It is thus found that：The size distribution of pulverized micro mist is broadened, mobility is improved.
In addition, raw material for magnet is sometimes with Dy and Tb (they are also referred to as " heavy rare earth " below) as R.This
When, the inventors discovered that：The heavy rare earth distribution of principal phase and richness R phases is set to change with the coarsening of principal phase, in making rich R phases
Comprising heavy rare earth be expelled to principal phase and spread.Coercivity thus, it is possible to improve rare-earth magnet.
And then, the inventors discovered that：Impurity (such as Mn, Si etc.) is discharged from principal phase by the coarsening with principal phase
To richness R phases, it is possible to increase the coercivity of rare-earth magnet.
The present invention is completed based on above-mentioned opinion, and its purport is that the R-T-B series magnets of following (1)~(3) are former
Material alloy.
(1) a kind of R-T-B series magnets raw alloy, it is characterised in that it is R-T-B series magnet raw alloy (its
In, R is at least a kind among the rare earth element comprising Y, T is using Fe as necessary more than a kind transition elements), comprising conduct
The R of principal phase2T14The rich R phases that B phases and R have been concentrated, rich R phases at intervals of more than 10 μm and richness R phases oval length ratio be 0.6
More than.
(2) the R-T-B series magnet raw alloys according to above-mentioned (1), it is characterised in that foregoing R-T-B series magnets
Contain any one of Dy and Tb or both with raw alloy and be used as R, the total concentration A (matter of the Dy in foregoing principal phase and Tb
Amount %) divided by the Dy in foregoing rich R phases and Tb total concentration B (quality %) obtained by percentage be more than 180%.
(3) the R-T-B series magnet raw alloys according to above-mentioned (1) or (2), it is characterised in that foregoing rich R phases
Impurity concentration D (quality %) divided by foregoing principal phase impurity concentration C (quality %) obtained by percentage be more than 230%.
In the present invention, " the oval length ratio of rich R phases is more than 0.6 " refers to, as described later like that, rich R phases are thicker (to be become
It is wide) and it is deformed into the shape close to positive round.The oval length of rich R phases than using with the center of gravity of rich R phases as former as described later
The ratio between section second moment (Ix, Iy) (with reference to aftermentioned formula (1)) in the coordinate system of point is calculated.
The effect of invention
The alternate oval length ratios for being divided into more than 10 μm and richness R phases of the rich R of R-T-B series magnets raw alloy of the invention
It is more than 0.6.Therefore, the size distribution of the micro mist for obtaining is crushed by raw material for magnet in the manufacturing process of sintered magnet
Broaden and mobility raising, as a result, the sintered magnet of complicated shape can be obtained.In addition, in the manufacturing process of bonded permanent magnet
In can omit melt treatment or reduce melt treatment needed for time.
Brief description of the drawings
The ideograph of the casting device that Fig. 1 is used when being and representing and make alloy strip using thin strap continuous casting legal system.
Fig. 2 be illustrate the oval length of richness R phases than determination step figure, (a) of the figure represented the anti-of alloy section
Radio subgraph carries out the image of 2 values, and (b) of the figure represents the image of the position of centre of gravity for obtaining each rich R phases.
Fig. 3 is the image of the plot analysis result of the EPMA in the conventional example 2 for represent embodiment, and (a) of the figure is represented and used
The photo that electron microscope shoots, (b) of the figure represents the analysis result of Dy, and (c) of the figure represents the analysis result of Si, the figure
(d) represent Mn analysis result.
Fig. 4 is the image of the plot analysis result of the EPMA in the example of the present invention 7 for represent embodiment, and (a) of the figure is represented
With the photo of electronics microscope photographing, (b) of the figure represents the analysis result of Dy, and (c) of the figure represents the analysis result of Si, should
(d) of figure represents the analysis result of Mn.
Specific embodiment
Hereinafter, illustrated with raw alloy for R-T-B series magnets of the invention.
1. R-T-B series magnets raw alloy of the invention
Raw material for magnet of the invention is characterised by that it is included as the R of principal phase2T14What B phases and R be concentrated
Rich R phases, rich R phases at intervals of more than 10 μm and richness R phases oval length ratio be more than 0.6.
Rich R phases refer at intervals of more than 10 μm：A part for rich R phases is diffused in principal phase and disappears so as to principal phase occurs
The state of coarsening.In addition, the oval length ratio of the rich R phases of raw material for magnet of the invention is more than 0.6.
Herein, the oval length of rich R phases than be rich R phases shape, the index of correlation of especially rugosity (width), its measure
Method refers to aftermentioned.The oval length of rich R phases is defined according to it than R and is 0 ＜ R≤1, and its value is closer to 1 shape of richness R phases
Closer to positive round, the value becomes thinner (narrowing) closer to 0, the then shape of richness R phases.
The oval length ratio of rich R phases refers to for more than 0.6：With the coarsening of principal phase, a part of thicker of rich R phases (becomes
It is wide), it is to be deformed into the shape close to positive round is stablized from from the viewpoint of thermodynamics.
On this raw material for magnet of the invention, as be described hereinafter as shown in embodiment, in the manufacture of sintered magnet
When being crushed to raw material for magnet in the pulverizing process of technique, the excellent micro mist of mobility can be obtained.Its reason is still
It is indefinite, but speculate it is based on following effect.Micro mist obtained from being classified after by the way that raw material for magnet is crushed
Size distribution broaden, due to the thick particle of the comparing included in micro mist, atmosphere is easily remaining between particle.Like this,
Reservation atmosphere between particles function as lubriation material, there is liquidation in micro mist, as a result, making the flowing of micro mist
Property improve.
Therefore, even if raw material for magnet of the invention has again in the molding procedure of the manufacturing process of sintered magnet
In the case of during miscellaneous shape, with thin-walled portion, it is also possible to micro mist is filled uniformly with to mould, can suppress sintered magnet
Magnetic characteristic deteriorate.
In addition, the principal phase of raw material for magnet of the invention there occurs coarsening, therefore in the original as bonded permanent magnet
During material, the time needed for melt treatment can be omitted or melt treatment is reduced.Therefore, raw material for magnet of the invention
Manufacture efficiency can be improved in the manufacture of bonded permanent magnet.In addition, the alloy sheet composition that can suppress in melt treatment becomes
It is unstable, can stably obtain the bonded permanent magnet of high-quality.
When the interval of the rich R phases of raw material for magnet of the invention is more than 40 μm, the time needed for the coarsening of principal phase
Increase and manufacture efficiency deteriorate, it is therefore desirable for richness R phases at intervals of less than 40 μm.The oval length ratio of rich R phases is defined by it
Hair turns into the upper limit with 1.0.
On heavy rare earth it is known that：In raw material for magnet, the weight for adding Dy and Tb etc sometimes as R is dilute
Soil.It is known that magnetic reversal is prevented from rare-earth magnet by adding heavy rare earth, as a result, coercivity is improved.In addition also
Know：There is denseization in rich R phases by making added heavy rare earth, be prevented from the life of the nucleating point as magnetic reversal basic point
Into, prevent magnetic reversal.But, raw material for magnet of the invention make rich R phases at intervals of more than 10 μm, that principal phase occurs is thick
Bigization, therefore diminish using the effect that the dense chemoprevention of heavy rare earth in rich R phases stops magnetic reversal is relative.
Therefore, during principal phase occurs the raw material for magnet of the invention of coarsening, principal phase is diffused in by making heavy rare earth
In and improve that coercitive effect is relative to become big.Therefore, any in Dy and Tb is contained in raw material for magnet of the invention
When person or both is as R, the total concentration B of total concentration A (quality %) of the Dy and Tb in principal phase divided by the Dy in rich R phases and Tb
Percentage obtained by (quality %) (A/B, hereinafter also referred to as " distribution ratio of heavy rare earth ") is desired for more than 180%.
When the distribution ratio of heavy rare earth is more than 180%, it is presented what is included in a part of richness R phases with the coarsening of principal phase
The state that heavy rare earth is discharged to principal phase and spreads.Like this, it is diffused in principal phase by making heavy rare earth, it is possible to increase Rare-Earth Magnetic
The coercivity of body.
On impurity, when in the principal phase of raw material for magnet comprising impurity such as Mn, Si, Rare-Earth Magnetic is produced because of the impurity
The low position of the coercivity of body.The easy magnetic reversal in the low position of coercivity and cause the coercivity of rare-earth magnet to reduce, it is therefore right
Expect for impurity to be expelled to rich R phases from principal phase for raw material for magnet.
Therefore, impurity concentration D (quality %) of the rich R phases of raw material for magnet of the invention is dense divided by the impurity of principal phase
Percentage (D/C, hereinafter also referred to as " distribution ratio of impurity ") obtained by degree C (quality %) is desired for more than 230%.Impurity
When distribution ratio is more than 230%, the state that impurity is discharged to rich R phases from principal phase is presented, can suppress by dilute caused by impurity
The coercivity reduction of native magnet.
In the present invention, impurity refers to when industrially manufacturing alloy, headed by raw material, due to the various factors of manufacturing process
And the material being inevitably mixed into, headed by example Mn, Si as described above, O (oxygen), C, N, H, Ca, Mg, S, P, Na, K, Ar etc.
Meet.
2. chemical composition
R-T-B series magnets of the invention raw alloy has following composition：Containing among the rare earth element comprising Y extremely
Few a kind of R, using Fe as the T and B (boron) of necessary more than a kind transition elements.Desirably：On R-T- of the invention
B series magnet raw alloys, in terms of atom %, as R in terms of the total content of Nd and Pr containing more than 11.6% and 16.4% with
Under Nd and Pr and containing more than 5.0% and less than 10% B, surplus is as necessary more than a kind transition elements by using Fe
T and impurity are constituted.Hereinafter illustrate its restriction reason and more desirable scope.
Expect to be used as R containing Nd and Pr among the rare earth element comprising Y, because they are in various R2Fe14Bization
Saturated magnetization highest among compound.Now, when the total content of Nd and Pr is less than 11.6 atom %, raw material for magnet is used
When making the raw material of sintered magnet, rare earth element amount, coercivity needed for sound sintering cannot be ensured in sintering circuit are reduced.Separately
On the one hand, when the total content of Nd and Pr is more than 16.4 atom %, principal phase is tailed off relatively, remanence Br is reduced.Therefore, it is desirable to
The total content for making Nd and Pr is more than 11.6 atom % and below 16.4 atom %, the total content of Nd and Pr it is more desirable be 12.2 former
Sub- more than % and below 15.2 atom %.
When B content is less than 5.0 atom %, cannot get sufficient coercivity, remanence sometimes in rare earth series magnet.
When B content is more than 10 atom %, cannot get sufficient remanence sometimes in rare earth series magnet.It is 5.6 that B content is more desirable
More than atom % and 7.5 below atom %.
If in addition, substituting a part of T and containing as the Dy and Tb of R, the coercivity of rare-earth magnet can be improved.Contain
When having Dy and Tb, coercitive effect is improved in order to obtain, their total content is desired for more than 1 atom %.On the other hand, it
Total content more than 4.1 atom % when, remanence is significantly reduced, it is therefore desirable for make the upper limit be 4.1 atom %.
If substitute a part of T and contain Al, the effect of coercivity and weatherability can be improved, so expect.
When containing Al to obtain the effect, expect to make Al content be more than 0.1 atom %.On the other hand, Al content is former more than 2.0
During sub- %, magnetic flux density is together reduced with coercivity, it is therefore desirable for making the upper limit be 0.7 former for 2.0 atom %, the upper limit are more desirable
Sub- %.
3. assay method
The interval of foregoing rich R phases and the oval length of richness R phases are used than in the present invention and clapped by scanning electron microscope
The image taken the photograph is measured.
Made by following steps in the present invention using the sample used in the image that scanning electron microscope shoots
Make.
(1) 10 raw material for magnet (alloy sheet) are taken, the alloy is imbedded into heat-curing resin to be fixed.
(2) expose by grinding the section of the thickness direction of the alloy sheet fixed by resin, make the section that mirror is presented
Surface state.
(3) etching of 5 seconds is implemented to the alloy section of mirror status using nital.
[interval of rich R phases]
The interval of rich R phases is measured using following step in the present invention.
(1) using the sample made by above-mentioned steps, for the section of each alloy sheet, using scanning electron microscope with
1000 times of shooting reflected electron images.Now, by the section of alloy sheet along thickness direction to be divided into 3 part at equal intervals when, with
Centrally located region is integrally incorporated in interior mode and shoots reflected electron image.
(2) for 10 captured images, read to image analysis apparatus, 2 values are carried out on the basis of brightness, carry out
Treatment for recognizing rich R phases and principal phase.
(3) for 10 images for having carried out 2 values, drawn in the middle position of thickness parallel with the face of contact chill roll
Straight line, determine mutual interval of adjacent on straight line rich R phase and simultaneously obtain between average value, the rich R phases as the alloy sheet
Every.
(4) average value is obtained by the interval of 10 rich R phases of alloy sheet, using the average value as the raw material for magnet
Rich R phases interval.
The reason for shooting reflected electron image for middle section when being divided into 3 part in above-mentioned (1) is as follows.
In the region of the surface side contacted with chill roll during casting, it is possible to partially there are the fine position of excessive tissue.It is another
Aspect, in the region of opposing face side, it is possible to partially there are the thick position of excessive tissue.It is this excessively fine
Position, excessively thick position belong to so-called exceptional value statistically.Therefore, by for when being divided into 3 part
Middle section shoots reflected electron image, for the interval of rich R phases, can remove exceptional value to determine typical value.Herein, " phase
The face that reverse side " is contacted when referring to relative to casting with chill roll, positioned at the face (face for being let cool) of its opposition side.
[the oval length ratio of rich R phases]
Fig. 2 be illustrate the oval length of richness R phases than determination step figure, (a) of the figure represented the anti-of alloy section
Radio subgraph has carried out the image of 2 values, and (b) of the figure represents the image of the position of centre of gravity for obtaining each rich R phases.In the figure,
The Dark grey of principal phase 8 is represented, richness R phases 9 are represented with light gray.
The oval length of rich R phases using following steps than being determined in the present invention.
(1) using the sample made by above-mentioned steps, for the section of each alloy sheet, using scanning electron microscope with
1000 times of shooting reflected electron images.Now, by the section of alloy sheet in a thickness direction to be divided into 3 part at equal intervals when,
By centrally located region be integrally incorporated in in the way of shoot reflected electron image.
(2) for captured image, read to image analysis apparatus, 2 values are carried out as benchmark using brightness, known
The not treatment of richness R phases and principal phase, obtains 10 images shown in (a) of the figure.
(3) for 10 each images for having carried out 2 values, as shown in (b) of the figure, image analysis software pin is used
Center of gravity 9a is obtained to each rich R phases in image.
(4) for each the rich R phase in each image, section second moment is calculated respectively using above-mentioned image analysis software
(Ix、Iy).Now, for each rich R phases, rectangular coordinate system is set as：Origin is the center of gravity 9a of rich R phases, X-axis parallel in casting
Face, the Y-axis of chill roll are contacted when making parallel to thickness direction.
(5) for each the rich R phase in each image, using value the greater among section second moment (Ix, Iy) as length
Axle, using value smaller as short axle, calculates the ratio between short axle and major axis r.Specifically, ratio r is calculated using following formula (1).
R=Min { Ix, Iy }/Max { Ix, Iy } (1)
Herein, Max { a, b } be a values that will be input into and b values contrasted and exported larger one value function.Separately
Outward, Min { a, b } be a values that will be input into and b values contrasted and exported smaller one value function.
(6) for the ratio between each the rich R phase calculated using above-mentioned formula (1) in each image r, average value is calculated, as the conjunction
The oval length ratio of the rich R phases of gold plaque.
(7) average value is obtained by the oval length ratio of 10 rich R phases of alloy sheet, is averaged value former as the magnet
Expect the oval length ratio of the rich R phases of alloy.
The reason for shooting reflected electron image for middle section when being divided into 3 part in above-mentioned (1) and measure richness R
The situation at the interval of phase is identical.By to being divided into middle section during 3 part to shoot reflected electron image, for rich R
The oval length ratio of phase, can remove exceptional value to determine typical value.
Total concentration B, the impurity concentration D of richness R phases of Dy and Tb in total concentration A, the richness R phases of the Dy and Tb in foregoing principal phase
Impurity concentration C with principal phase is determined using the plot analysis based on EPMA and linear analysis in the present invention.
The sample used in plot analysis and linear analysis based on EPMA is made using following step in the present invention
Make.
(1) 9 raw material for magnet (alloy sheet) are taken, the alloy is imbedded into heat-curing resin to be fixed.
(2) expose by grinding the section of the thickness direction of the alloy sheet fixed by resin, make the section that mirror is presented
Surface state.
(3) the alloy section in a vacuum to mirror status carries out carbon evaporation.
[concentration of element]
In the present invention, the concentration of each element is determined using following steps.
(1) using the sample made by above-mentioned steps, using EPMA, carry out plot analysis to the concentration of element of each alloy and
Obtain image.Now, among the section of alloy sheet, the middle body for thickness direction is analyzed, and obtains image.
(2) in the way of comprising the region for carrying out plot analysis by EPMA, shoot anti-with 1000 times using electron microscope
Radio subgraph.
(3) image and the image of electron microscope according to plot analysis, using EPMA, for comprising principal phase and richness R phases
Both and parallel to casting when contact chill roll face line on carry out linear analysis.
(4) according to the image of electron microscope, the result of linear analysis is divided into principal phase and richness R phases, will be respective average
It is worth as the principal phase concentration and richness R phase concentrations of the alloy sheet.
(5) average value is obtained by the principal phase concentration of 9 alloy sheets, is denoted as the principal phase concentration of the raw material for magnet.Separately
Outward, average value is obtained by the rich R phase concentrations of 9 alloy sheets, is denoted as the rich R phase concentrations of the raw material for magnet.
4. the manufacture method of R-T-B series magnets raw alloy of the invention
As the commercial run of the alloy of manufacture coarse grain, there is the side cast using the slow mold of cooling velocity
Method.In addition, also, there are as below methods：The comparatively faster atomization of cooling velocity, using thin strap continuous casting method or melt spin- ning method (melt
Spin method) method of implement heat treatment after casting alloy.It is general in R-T-B series magnet raw alloys, can
Obtain the thin strap continuous casting method of the alloy strip of advantageous crystalline orientation.Raw material for magnet of the invention can also be connected by using strip
The alloy strip of casting casting makes.The alloy strip of the R-T-B systems alloy cast using thin strap continuous casting method is under reduced pressure or non-live
Crushed and be made alloy sheet under property gas atmosphere.
R-T-B series magnets raw alloy of the invention can by high operating temperatures directly with more than 950 DEG C and
Cooled down to make after less than 1140 DEG C holding stipulated times, without cooling down the alloy sheet.By by the alloy of the condition of high temperature
Piece is kept for the stipulated time with more than 950 DEG C and less than 1140 DEG C, and a part of rich R phases of alloy sheet diffuse to principal phase and disappear.Its
As a result, there is coarsening and the interval of rich R phases is reached more than 10 μm in principal phase.In addition, with the coarsening of principal phase, a part compared with
Carefully the rich R phases of (narrow width) are thicker (width is wide), and its shape is close to positive round.As a result, the oval length ratio of richness R phases reaches 0.6
More than.
When alloy sheet contains heavy rare earth, kept with more than 950 DEG C and less than 1140 DEG C by by the alloy sheet of the condition of high temperature
Stipulated time, the heavy rare earth included in rich R phases is discharged to principal phase and spreads.As a result, the distribution ratio that can make heavy rare earth is
More than 180%.
In addition, being kept for the stipulated time with more than 950 DEG C and less than 1140 DEG C by by the alloy sheet of the condition of high temperature, Mn, Si
Deng impurity rich R phases are discharged to from principal phase.As a result, the distribution ratio that can make impurity is more than 230%.
When keeping the temperature of alloy sheet less than 950 DEG C, the oval length ratio of rich R phases becomes less than 0.6, chippy micro mist
Mobility become insufficient.On the other hand, when keeping the temperature of alloy sheet more than 1140 DEG C, alloy sheet is fused to other alloys
Piece and assemble.
The time that alloy sheet is remained into more than 950 DEG C and less than 1140 DEG C can be according to required by raw material for magnet
The interval of rich R phases, the chemical composition of alloy, cooling velocity on chill roll etc. suitably set.
Cooling after on alloy sheet is kept with more than 950 DEG C and less than 1140 DEG C, will be from keeping temperature to 500
The cooling velocity of the temperature range untill DEG C is set to less than 65 DEG C/min to carry out.Because：The cooling of said temperature scope
When speed is more than 65 DEG C/min, as be described hereinafter as shown in embodiment, gained raw material for magnet will not inhale hydrogen, it is impossible to crush.
The cooling of the alloy sheet of the temperature range less than 500 DEG C is not particularly limited.
Embodiment
In order to verify the effect brought by raw material for magnet of the invention, tested.In the experiment, by making
Raw material for magnet is simultaneously crushed and obtains micro mist, confirms the mobility of the micro mist.
[test method]
In this experiment (conventional example, example of the present invention and comparative example), using the casting device shown in earlier figures 1, using foregoing
(A)~(C) the step of, the strip of casting alloy is carried out by the R-T-B systems alloy molten solution for being heated to regulation melt temperature.Cast
Alloy strip is crushed in the back segment of chill roll and is made alloy sheet.During casting alloy band, reservoir quantity and the cooling of liquation are adjusted
The rotating speed of roller, makes the thickness about 0.3mm or about 0.5mm of cast alloy strip.Atmospheric condition is set as nonactive gas
The argon gas atmosphere of body, its pressure is set to 300torr.
In this experiment, by changing surface temperature, atmospheric condition, the cooling velocity on chill roll is adjusted to 850 DEG C/sec
~1500 DEG C/sec.Herein, cooling velocity is removed by the difference of alloy strip temperature (DEG C) at melt temperature (DEG C) and stripping position
The time (second) position is peeled off with a little being reached from fluid injection position on the outer peripheral face of chill roll to calculate.In addition, cooling
Roller is used so that Cu is as principal component and surface forms irregular chill roll.Herein, positional representation is peeled off to be peeled off from chill roll
The position of alloy strip.
In the prior embodiment, the alloy sheet that will have been crushed is put into water-cooled container, and alloy sheet is cooled in the container
Untill reaching 150 DEG C.Atmospheric condition now is set to non-active gas i.e. argon gas atmosphere in the same manner as casting, and its pressure is set to
300torr.When the temperature of alloy sheet reaches 150 DEG C, alloy sheet is discharged from container, let cool in an atmosphere to normal temperature,
So as to obtain raw material for magnet.
In example of the present invention and comparative example, to after the alloy sheet implement heat treatment that has crushed, then implement cooling treatment.Heat treatment
In, the alloy sheet that will have been crushed is direct plungeed into barrel shape heater at high operating temperatures, and rule are kept with the heating-up temperature for specifying
The fixed retention time.Now, input alloy sheet is stirred using the rotation of bucket, and is heated using heater.
The atmospheric condition of heat treatment is set to non-active gas i.e. argon gas atmosphere, its pressure is set into 300torr in the same manner as casting.
In cooling treatment, alloy sheet is put into barrel shape cooler, input alloy is stirred using the rotation of bucket
Piece, and cooled down by circulating cooling water in the wall to bucket.Cooling velocity in barrel shape cooler is cooled down by changing
The quantity delivered of water is adjusted to 45~70 DEG C/min.The atmospheric condition of barrel shape cooler is set to nonactive gas in the same manner as casting
Body is argon gas atmosphere, its pressure is set into 300torr.When the temperature of alloy sheet reaches 500 DEG C, by alloy sheet from barrel shape
Discharged in cooler, let cool to normal temperature in non-active gas, so as to obtain raw material for magnet.
In this experiment, by changing the compounding of raw material, the chemical composition of gained raw material for magnet is denoted as in A~C
Any one.Chemical composition A~the C of its alloy is shown in table 1.
[table 1]
Table 1
In this experiment, the sample of regulation piece number is taken by gained raw material for magnet, using foregoing " 3. assay method "
Described in the step of, determine interval and the oval length ratio of richness R phases of richness R phases.In addition, being taken by gained raw material for magnet
Specify the sample of piece number, the step of using described in foregoing " 3. assay method ", for principal phase and richness R phases, impurity is determined respectively
The concentration of Si and Mn, calculates the distribution ratio of Si and Mn.In addition, in the raw material for magnet of chemical composition B and C, it is dilute as weight
Soil and only contain Dy, therefore the step of using described in foregoing " 3. assay method ", Dy concentration A's and richness R phases for principal phase
Dy concentration B is measured respectively.Using its measurement result, the distribution ratio (A/B) of heavy rare earth is calculated.
In addition, the pulverizing process in the manufacturing process of simulation sintered magnet, hydrogenolysis is carried out to gained raw material for magnet
After broken (coarse crushing), carry out Crushing of Ultrafine using jet pulverizer and be made micro mist, the micro mist is classified.During hydrogenolysis is broken,
Hydrogen is set to attract deposit in after raw material for magnet under the hydrogen atmosphere of normal temperature and 90kPa~100kPa (660~760torr),
The Dehydroepiandrosterone derivative of 600 DEG C × 1 hour is carried out in an ar atmosphere.By using the broken corase meal for obtaining of hydrogenolysis amount of oxygen be 150ppm
Following non-active gas (N2Gas) in atmosphere with gas pressure 6kgf/cm2, quantity delivered 200g/min condition injecting type
Pulverizer is crushed and is made micro mist.The classification of micro mist is carried out using whizzer using air current classifying, is used to remove
Particle diameter is more than 40 μm of the particle of particle and particle diameter less than 1 μm.
Use gained micro mist, determines angle of repose and avalanche angle using following step in an ar atmosphere.
(1) circular slab of a diameter of 80mm is placed in pedestal, funnel is configured in the center of its circular slab.Now,
The distance between upper surface by the front end of funnel and circular slab is set to 130mm, the use of the internal diameter of pipe portion is the funnel of 6mm.
Micro mist is fallen by funnel under the state, falling for micro mist will be stopped before avalanche on the mountain formed by the micro mist for falling
Under.
(2) for the mountain of the micro mist formed on circular slab, base angle (inclined-plane on mountain and circular slab upper surface are determined at three
Institute angle degree), value is averaged as angle of repose.
(3) counterweight for making weight be 109g falls from the height of 160mm to pedestal 3 times and assigns impact, so that circular
Landslide on plate is collapsed.
(4) for the mountain of avalanche, base angle is determined at 3, is averaged value as avalanche angle.
The angle of repose of micro mist represents the scope filled micro mist and extended in mould to micro mist during mould, and angle of repose is smaller,
The interior on a large scale, mobility that then can be more filled in micro mist in mould is more excellent.In addition, avalanche angle represent by micro mist fill to
Mould and the scope that micro mist extends in mould when assigning impact, avalanche angle are smaller, then more micro mist can be filled in mould
Interior on a large scale, mobility it is more excellent.
[result of the test]
Table 2 is for each chemical composition, casting condition for showing raw material for magnet tested (on melt temperature, chill roll
Cooling velocity, the thickness of alloy strip), heat treatment condition (heating-up temperature, retention time) and cooling treatment condition (cooling treatment
In cooling velocity).In addition, table 2 shows angle of repose and the avalanche angle of gained micro mist.And then, table 2 is directed to gained magnet raw material
Alloy shows the oval length of the interval of rich R phases, richness R phases than, the distribution ratio of heavy rare earth and the distribution ratio of impurity (Si and Mn).
[table 2]
According to table 2, in conventional example 1~3, the alloy strip that will be cast is crushed and is made alloy sheet, by the alloy sheet
Cool down and heat treatment is not carried out.As a result, the interval of the rich R phases of gained raw material for magnet reaches 3.0~6.7 μm, ellipse
Length ratio reaches 0.30~0.41.The angle of repose of the micro mist that the raw material for magnet is crushed is 55~58 °, avalanche angle
It is 34 or 35 °.
On the other hand, in example of the present invention 1~10, the alloy strip that will be cast is crushed and is made alloy sheet, in high temperature
Under state directly to alloy sheet implement heat treatment after, implement cooling treatment, the interval of the rich R phases of gained raw material for magnet reaches
To more than 10 μm and oval length ratio reaches more than 0.6.The angle of repose of the micro mist that the raw material for magnet is crushed reaches
20~25 ° are reached to 40~46 °, avalanche angle.
Like this, compared with conventional example 1~3, the angle of repose of example of the present invention 1~10 and avalanche angle diminish, the flowing of micro mist
Property improve.Therefore, can explicitly by make the rich R phases of raw material for magnet at intervals of more than 10 μm and oval length ratio is
More than 0.6, for the micro mist for crushing the raw material for magnet, it is possible to increase mobility.
Then distribution ratio and the distribution ratio of impurity, for heavy rare earth, are verified with reference to the analysis result of EPMA.
Fig. 3 is the image of the plot analysis result of the EPMA for representing conventional example 2, (a) expression electron microscope of the figure
The photo of shooting, (b) of the figure represents the analysis result of Dy, and (c) of the figure represents the analysis result of Si, and (d) of the figure is represented
The analysis result of Mn.
Fig. 4 is the image of the plot analysis result of the EPMA for representing example of the present invention 7, (a) expression electron microscopic of the figure
The photo that mirror shoots, (b) of the figure represents the analysis result of Dy, and (c) of the figure represents the analysis result of Si, (d) table of the figure
Show the analysis result of Mn.
In the electron micrograph of (a) of Fig. 3 and (a) of Fig. 4, grey portion is principal phase, white portion is richness R phases.In addition,
In (b)~(d) of (b) of Fig. 3~(d) and Fig. 4, the concentration of Dy, Si or Mn is represented by the depth, the concentration in white portion is most
Height, with darkening, concentration step-down, the concentration of black part is minimum.(b) of Fig. 3~(d) represents area shown in (a) of Fig. 3 respectively
The concentration distribution of each element in domain, (b)~(d) of Fig. 4 represents the concentration distribution of each element in region shown in (a) of Fig. 4 respectively.
Distribution ratio on heavy rare earth, as R the experiment containing heavy rare earth be conventional example 2 and 3 and example of the present invention 6~
10.In conventional example therein 2, according to (a) and (b) of Fig. 3, compared with rich R phases, Dy is in principal phase with the state of high concentration
It is distributed in entirety.On the other hand, in example of the present invention 7, according to (a) and (b) of Fig. 4, concentration differences of the Dy in principal phase and richness R phases expands
Greatly, the state with high concentration in principal phase is distributed in entirety, is distributed with the extremely low state of concentration in rich R phases.
On the other hand, according to table 2, in conventional example 2 and 3, the distribution ratio of heavy rare earth is 160% and 140%, but example of the present invention
In 6~10, the distribution ratio of heavy rare earth is more than 180%.Thus can be clear and definite：In the raw material for magnet of example of the present invention 6~10,
With the coarsening of principal phase, the heavy rare earth included in rich R phases is discharged to principal phase, and heavy rare earth is presented is diffused in principal phase
State.
Distribution ratio on impurity, in conventional example 2, according to (a) and (c) of Fig. 3, compared with principal phase, Si is in rich R phases
In entirety is distributed in the state of high concentration.On the other hand, in example of the present invention 7, according to (a) and (c) of Fig. 4, Si in rich R phases and
Concentration difference in principal phase expands, and is distributed with the state of very high concentrations in rich R phases, and the state with low concentration in principal phase is entered
Row distribution.On Mn, (a) and (d) of (a) and (d) and Fig. 4 according to Fig. 3 is distributed with Si identical states.
According to table 2, in conventional example 1~3, the distribution ratio that the distribution ratio of Si reaches 130% and 160%, Mn reaches 200% and
210%.On the other hand, in example of the present invention 1~10, the distribution ratio of Si and Mn reaches more than 230%.Thus can be clear and definite：This hair
The raw material for magnet of bright example 1~10 is presented the state that impurity is discharged to rich R phases from principal phase.
On the other hand, in comparative example 1, the keeping temperature of heat treatment is set to 930 DEG C, the oval length of richness R phases is than not enough
0.6.Therefore, in comparative example 1, compared with example of the present invention 1~10, the angle of repose of micro mist and avalanche angle become the big, mobility of micro mist
Reduce.In addition, in comparative example 2, the cooling velocity of cooling treatment is set to 70 DEG C/min, as a result, to raw material for magnet
Carry out hydrogenolysis it is broken when, alloy will not inhale hydrogen, it is impossible to obtain micro mist.In comparative example 3, the keeping temperature of heat treatment is set to 1150
DEG C, alloy sheet in barrel shape heater welding and condense.Therefore raw material for magnet cannot be obtained.
Thus can confirm：Implement to be protected with more than 950 DEG C and less than 1140 DEG C for the alloy sheet for crushing alloy strip
After holding the heat treatment of stipulated time, implementation is cooled to the temperature range 500 DEG C from keeping temperature with less than 65 DEG C/min
Cooling treatment such that it is able to obtain raw material for magnet of the invention.
Industrial applicability
If R-T-B series magnets of the invention are used for into sintered magnet with raw alloy, flowing can be made using crushing
The excellent micro mist of property, therefore, it is possible to obtain the sintered magnet of complicated shape.On the other hand, if being used for bonded permanent magnet, can save
Slightly melt treatment or reduce melt treatment needed for time and obtain bonded permanent magnet.Therefore, R-T-B series magnets of the invention
Can be effectively utilized in the manufacture field of sintered magnet and bonded permanent magnet with raw alloy.
Description of reference numerals
1：Crucible, 2：Tundish, 3：Chill roll, 4：Alloy strip,
5：Chamber, 6：Liquation, 8：Principal phase, 9：Rich R phases,
9a：The center of gravity of rich R phases.
Claims (3)
1. a kind of R-T-B series magnets raw alloy, it is characterised in that it is R-T-B series magnet raw alloys, and the R is
At least a kind among rare earth element comprising Y, the T be using Fe as necessary more than a kind transition elements,
The R-T-B series magnets include the R as principal phase with raw alloy2T14The rich R phases that B phases and R have been concentrated,
The rich R phases at intervals of more than 10 μm and the rich R phases oval length ratio be more than 0.6.
2. R-T-B series magnets raw alloy according to claim 1, it is characterised in that the R-T-B series magnets are former
Material alloy contains any one of Dy and Tb or both and is used as the R,
The total concentration in terms of quality % of the Dy and Tb in the principal phase is divided by the Dy and Tb in the rich R phases in terms of quality %
Total concentration obtained by percentage be more than 180%.
3. R-T-B series magnets raw alloy according to claim 1 and 2, it is characterised in that the rich R phases with matter
Amount % meter impurity concentration D divided by the principal phase with percentage obtained by the impurity concentration C that quality % is counted be more than 230%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013090819 | 2013-04-24 | ||
| JP2013-090819 | 2013-04-24 | ||
| PCT/JP2014/002123 WO2014174795A1 (en) | 2013-04-24 | 2014-04-15 | Raw material alloy for r-t-b-based magnet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105189805A CN105189805A (en) | 2015-12-23 |
| CN105189805B true CN105189805B (en) | 2017-06-30 |
Family
ID=51791384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480023759.XA Active CN105189805B (en) | 2013-04-24 | 2014-04-15 | R T B series magnet raw alloys |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6005263B2 (en) |
| CN (1) | CN105189805B (en) |
| WO (1) | WO2014174795A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108133796B (en) * | 2017-12-11 | 2019-10-22 | 北京科技大学 | A kind of preparation method of sintered magnet NdFeB magnetic powder |
| CN108831648A (en) * | 2018-06-21 | 2018-11-16 | 宁波招宝磁业有限公司 | The method of spray drying preparation performance Nd Fe B sintered magnet |
| JP7251157B2 (en) * | 2019-01-16 | 2023-04-04 | Tdk株式会社 | Evaluation method of raw material alloy for rare earth magnet, apparatus for evaluating raw material alloy for rare earth magnet, and manufacturing method of rare earth magnet |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013008756A1 (en) * | 2011-07-08 | 2013-01-17 | 昭和電工株式会社 | Alloy for r-t-b-based rare earth sintered magnet, process for producing alloy for r-t-b-based rare earth sintered magnet, alloy material for r-t-b-based rare earth sintered magnet, r-t-b-based rare earth sintered magnet, process for producing r-t-b-based rare earth sintered magnet, and motor |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2817624B2 (en) * | 1994-06-29 | 1998-10-30 | 昭和電工株式会社 | Rare earth magnet alloy manufacturing method |
| JP3536943B2 (en) * | 1994-12-21 | 2004-06-14 | 昭和電工株式会社 | Alloy for rare earth magnet and method for producing the same |
| JPH08264363A (en) * | 1995-03-24 | 1996-10-11 | Hitachi Metals Ltd | Manufacture of rare earth permanent magnet |
| JP4106099B2 (en) * | 1995-03-29 | 2008-06-25 | 日立金属株式会社 | Method for producing slab for R-Fe-B magnet alloy |
| DE10291720T5 (en) * | 2001-05-30 | 2004-08-05 | Sumitomo Special Metals Co., Ltd. | Process for producing a sintered compact for a rare earth magnet |
| JP4442597B2 (en) * | 2001-06-22 | 2010-03-31 | 日立金属株式会社 | Rare earth magnet and manufacturing method thereof |
| JP4689652B2 (en) * | 2002-11-22 | 2011-05-25 | 昭和電工株式会社 | Method for evaluating metal structure of RTB-based magnet alloy |
| WO2005105343A1 (en) * | 2004-04-30 | 2005-11-10 | Neomax Co., Ltd. | Methods for producing raw material alloy for rare earth magnet, powder and sintered magnet |
| EP2226137A4 (en) * | 2007-12-13 | 2012-01-25 | Showa Denko Kk | R-t-b alloy, process for production of r-t-b alloy, fine powder for r-t-b rare earth permanent magnets, and r-t-b rare earth permanent magnets |
| JP2011199069A (en) * | 2010-03-19 | 2011-10-06 | Tdk Corp | Method for manufacturing rare earth sintered magnet, and material for the rare earth sintered magnet |
| JP5753481B2 (en) * | 2011-11-28 | 2015-07-22 | 中央電気工業株式会社 | Rare earth alloy and method for producing the same |
-
2014
- 2014-04-15 JP JP2015513523A patent/JP6005263B2/en active Active
- 2014-04-15 CN CN201480023759.XA patent/CN105189805B/en active Active
- 2014-04-15 WO PCT/JP2014/002123 patent/WO2014174795A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013008756A1 (en) * | 2011-07-08 | 2013-01-17 | 昭和電工株式会社 | Alloy for r-t-b-based rare earth sintered magnet, process for producing alloy for r-t-b-based rare earth sintered magnet, alloy material for r-t-b-based rare earth sintered magnet, r-t-b-based rare earth sintered magnet, process for producing r-t-b-based rare earth sintered magnet, and motor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014174795A1 (en) | 2014-10-30 |
| CN105189805A (en) | 2015-12-23 |
| JP6005263B2 (en) | 2016-10-12 |
| JPWO2014174795A1 (en) | 2017-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103858185B (en) | R-T-B based sintered magnet and production method for same, and rotary machine | |
| JP6005257B2 (en) | Raw material alloy for RTB-based magnet and method for producing the same | |
| CN1212626C (en) | Iron-based rare earth alloy nanocomposite magnet and method for producing the same | |
| CN101541999A (en) | R-T-B base alloy, process for production thereof, fine powder for R-T-B base rare earth permanent magnet, and R-T-B base rare earth permanent magnet | |
| US20170221616A1 (en) | Alloy for r-t-b based sintered magnet and r-t-b based sintered magnet | |
| CN102282279A (en) | Method for producing R-T-B sintered magnet | |
| US6797081B2 (en) | Centrifugal casting method, centrifugal casting apparatus, and cast alloy produced by same | |
| CN105448444B (en) | A kind of method and rare earth permanent-magnetic material of the rare earth permanent-magnetic material that processability improves | |
| CN106910615A (en) | The preparation method of corrosion-resistant Ne-Fe-B magnet | |
| CN106298138B (en) | The manufacture method of rare-earth permanent magnet | |
| CN106319323B (en) | A kind of Sintered NdFeB magnet assistant alloy slab and preparation method thereof | |
| CN105189805B (en) | R T B series magnet raw alloys | |
| WO2003066922A1 (en) | Sinter magnet made from rare earth-iron-boron alloy powder for magnet | |
| CN105655077A (en) | Manufacturing method of high-coercive-force neodymium iron boron | |
| CN106504838A (en) | A kind of preparation method of neodymium iron boron magnetic body | |
| CN104114305B (en) | R-T-B-Ga series magnet raw alloy and manufacture method thereof | |
| JP6849806B2 (en) | Fine-grained rare earth alloy slabs, their manufacturing methods, and rotary cooling roll equipment | |
| JP4449900B2 (en) | Method for producing rare earth alloy powder and method for producing rare earth sintered magnet | |
| CN104112558B (en) | R-T-B based sintered magnet | |
| CN203170931U (en) | Novel vacuum melting rapid-hardening melt-spinning furnace | |
| JP2004181531A (en) | Method for producing rare-earth containing alloy flake, alloy flake for rare-earth magnet, alloy powder for rare-earth sintered magnet, rare-earth sintered magnet, alloy powder for bonded magnet and bonded magnet, and evaluation method for metallic structure | |
| EP1652606B1 (en) | Centrifugal casting method, centrifugal casting apparatus, and cast alloy produced by same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160530 Address after: Wakayama County Applicant after: Wakayama Rare Earth Co., Ltd. Address before: Tokyo, Japan, Japan Applicant before: Chuo Denki Kogyo Co., Ltd. |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20170524 Address after: Hyogo Applicant after: Santoku Corp. Address before: Wakayama County Applicant before: Wakayama Rare Earth Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |