CN1706010A - Hard magnetic composition, permanent magnet powder, method for permanent magnet powder, and bonded magnet - Google Patents

Hard magnetic composition, permanent magnet powder, method for permanent magnet powder, and bonded magnet Download PDF

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CN1706010A
CN1706010A CN 200480001376 CN200480001376A CN1706010A CN 1706010 A CN1706010 A CN 1706010A CN 200480001376 CN200480001376 CN 200480001376 CN 200480001376 A CN200480001376 A CN 200480001376A CN 1706010 A CN1706010 A CN 1706010A
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hard magnetic
phase
permanent magnet
magnetic composition
general formula
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CN100334656C (en
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坂本笃司
中根诚
中村英树
福野亮
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TDK Corp
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TDK Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
    • H01F1/0593—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2 of tetragonal ThMn12-structure
    • 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
    • H01F1/058—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IVa elements, e.g. Gd2Fe14C

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

A hard magnetic composition which is represented by a general formula: R(Fe100-y-wCowTiy)xSizAv, wherein R is at least one element selected from rare earth metals including Y, and Nd accounts for 50 mole % or more of R, and A is N and/or C, and wherein with respect to the mole ratios in the general formula, x is 10 to 12.5, y is (8.3 - 1.7 X z) to 12.3, z is 0.1 to 2.3, v is 0.1 to 3, and w is 0 to 30, and wherein (Fe + Co + Ti + Si)/R > 12 is satisfied. The hard magnetic composition comprises a single phase structure of a phase having a ThMn12 type crystal structure.

Description

The manufacture method of hard magnetic composition, permanent magnet powder, permanent magnet powder and bonded permanent magnet
Technical field
The present invention relates to be suitable for use as the hard magnetic composition that loud speaker and motor etc. need the employed permanent magnet material of machinery equipment in magnetic field.The invention still further relates to the permanent magnet material, particularly be suitable for use as magnet powder and the manufacture method thereof of bonded permanent magnet with material.
Background technology
In rare earth magnet, R-T-B based rare earth permanent magnet because its excellent in magnetic characteristics, as the Nd aboundresources of principal component and less expensive, thereby used in the various uses aspect electric equipments such as loud speaker and motor.
But, in recent years, the requirement of electric equipment miniaturization is further improved, carrying out the exploitation of novel permanent magnet material.
Wherein, for example opening clear 63-273303 communique, spy the spy opens flat 4-241402 communique, spy and opens flat 5-65603 communique and spy and open to disclose in the 2000-114017 communique and have body-centered cubic lattic or ThMn 12The terres rares of type crystal structure-iron series magnet material.
The spy opens clear 63-273303 communique and discloses with formula R xTi yA zFe aCo b(in the formula: R is the rare earth element that contains Y, A be B, C, Al, Si, P, Ga, Ge, Sn, S and N separately a kind or more than, by weight percentage, x is 12～30%, y is 4～10%, z is 0.1～8%, a is 55～85%, b is 34% or following) the terres rares permanent magnet of expression.Open in the clear 63-273303 communique the spy, narrated the A element and entered the direction variation that the Fe interatomic distance is become better.
Te Kaiping 4-241402 communique discloses with formula R xM yA zFe 100-x-y-zThe permanent magnet of (in the formula: at least a kind element of R for from the rare earth element that contains Y, selecting, at least a kind element of M among Si, Cr, V, Mo, W, Ti, Zr, Hf and Al, selecting, at least a kind of element that A selects from N and C) expression.This permanent magnet represents that with atom % then x is 4～20%, y be 20% or below, z is 0.001～16%, and to have ThMn 12Type crystal structure as principal phase.In addition, the spy opens flat 4-241402 communique and also discloses following content, promptly can form by interpolation M element (Si and Ti etc.) to have stable ThMn 12The rare earth, iron based cube crystallization compound of type crystal structure.It is effective for the raising of Curie temperature that Te Kaiping 4-241402 communique also discloses A element (C and N).
Te Kaiping 5-65603 communique discloses a kind of iron-rare earth permanent magnet material, this permanent magnet material is when the combination that R is set at a kind of selecting, two or more elements among Y, Th and all lanthanide series, when X is set at the combination of N (nitrogen) or B (boron) or C (carbon) or these elements, contain R:3～30%, X:0.3～50% in atomic percent, and surplus is made of Fe in fact.This magnet material with have the body-centered cubic lattic structure as principal phase.In addition, Te Kaiping 5-65603 communique also further proposes: by the part of Fe is replaced with the M element combination of two or more elements (select among Ti, Cr, V, Zr, Nb, Al, Mo, Mn, Hf, Ta, W, Mg, Si, Sn, Ge, the Ga a kind), make it contain M:0.5～30% with atomic percent.Open in the flat 5-65603 communique the spy, it is the element with very big effect that the M element is established as for generating the body-centered cubic lattic structure.
In addition, the spy opens the 2000-114017 communique and discloses a kind of general formula (R that uses 1-uM u) (Fe 1-v-wCo vT w) xA y(R in the formula, M, T, A are respectively, R: at least a kind of element selecting from the rare earth element that contains Y; M: at least a kind of element from Ti and Nb, selecting; T: at least a kind of element selecting among Ni, Cu, Sn, V, Ta, Cr, Mo, W, the Mn; A: at least a kind of element from Si, Ge, Al, Ga, selecting; U, v, w, x and y are respectively 0.1≤u≤0.7,0≤v≤0.8,0≤w≤0.1,5≤x≤12,0.1≤y≤1.5) expression permanent magnet material.The main hard magnetic of this permanent magnet material has ThMn mutually 12Type crystal structure.Open in the 2000-114017 communique the spy, narrated by by M element substitution R element, can reduce to make and have ThMn 12The phase of type crystal structure (below be sometimes referred to as " ThMn 12Phase ") element of stabilisation is the amount of Si, Ge etc.
For the terres rares permanent magnet, beyond the demanding magnetic characteristic, require low-cost on the other hand on the one hand.In the rare earth element that constitutes the terres rares permanent magnet, Nd is than Sm low price, and therefore the Sm with high price compares, and cheap Nd preferably becomes the main body of rare earth element.But, when using Nd, ThMn 12The generation difficulty of phase needs high temperature and heat treatment for a long time in it is made.For example open in the flat 5-65603 communique, impose annealing in 7 days in 900 ℃ above-mentioned spy; In addition, open flat 4-241402 communique and the spy opens in the 2000-114017 communique, except part exception, only use Sm as rare earth element the spy.
Summary of the invention
So problem of the present invention is: using under the situation of Nd as rare earth element, also can generate ThMn easily even provide 12The hard magnetic composition of phase and permanent magnet powder etc.
The present inventor has obtained following opinion: by Ti and the Si that adds scheduled volume simultaneously, even using under the situation of Nd as rare earth element, also can generate easily and have ThMn 12The phase of type crystal structure.And obtained following opinion: further add N and/or C in the compound that Ti by adding scheduled volume at the same time and Si obtain,, can obtain sufficient magnetic characteristic as the permanent magnet hard magnetic composition.
The hard magnetic composition of finishing based on above-mentioned opinion provided by the present invention, it is characterized in that: the general formula of this hard magnetic composition is R (Fe 100-y-wCo wTi y) xSi zA v(in the general formula, R is at least a kind of element (wherein rare earth element is the notion that contains Y) of selecting, 50 moles of % or the above Nd of being of while R among rare earth element, A is N and/or C), the mol ratio of above-mentioned general formula satisfies: x=10～12.5, y=(8.3-1.7 * z)～12.3, z=0.1～2.3, v=0.1～3, w=0～30, (Fe+Co+Ti+Si)/R＞12 simultaneously.
In addition, the present inventor has obtained following opinion: by the part with Zr and/or Hf displacement R, just can access the hard magnetic composition of the higher saturation magnetization of demonstration.In this case, can set the composition of hard magnetic composition as following the narration: its general formula is set at R 11-uR2 u(Fe 100-y-wCo wTi y) xSi zA v(in the general formula, R1 is at least a kind of element (wherein rare earth element is the notion that contains Y) of selecting, 50 moles of % or the above Nd of being of while R1 among rare earth element, R2 is Zr and/or Hf, A is N and/or C), and the mol ratio of general formula satisfies: u=0.18 or following, y=4.5～12.3, x=11～12.8, z=0.1～2.3, v=0.1～3, w=0～30, (Fe+Co+Ti+Si)/(R1+R2)＞12 simultaneously.
In order to obtain to improve the effect of saturation magnetization, the amount (u) of R2 element (Zr and/or Hf) is preferably set to 0.04～0.06.
Under the part of the R situation with Zr and/or Hf displacement, the homogeneous structure that also hard magnetic composition can be set in fact by the hard magnetic phase is constituted, and this hard magnetic can also be set at ThMn mutually 12Type crystal structure.In addition, sometimes the part of R is called " Zr (Hf) displacement " with Zr and/or Hf displacement in this manual.
Whether no matter Zr (Hf) displacement arranged, though hard magnetic composition of the present invention the 70 mol ratio % of R or above be under the situation of Nd, also can access the homogeneous structure of hard magnetic phase, and this homogeneous structure can be set at and have ThMn 12The phase of type crystal structure.
In hard composition of the present invention, A is preferably N.
In addition, whether no matter Zr (Hf) displacement arranged, institute preferably: x is 11～12.5, z is 0.2～2.0, v is 0.5～2.5, w is 10～25.
According to above the present invention, can access a kind of hard magnetic composition, this hard magnetic composition is by R-Ti-Fe-Si-A compound or R-Ti-Fe-Co-Si-A compound (in the general formula, R is at least a kind of element (wherein rare earth element is the notion that contains Y) of selecting, 80 moles of % or the above Nd of being of while R among rare earth element, A is N and/or C) form, and the homogeneous structure by the hard magnetic phase constitutes, its saturation magnetization (σ s) be 120emu/g or more than, anisotropy field (H A) be 30kOe or more than.This hard magnetic composition because by Nd account for above-mentioned R 80 moles of % or more than, therefore obtaining to have the advantage on the cost aspect the permanent magnet.
At this, this homogeneous structure can be set at and have ThMn 12The phase of type crystal structure.
Hard magnetic composition of the present invention also can demonstrate good magnetic characteristic, its anisotropy field (H A) be 40kOe or more than, saturation magnetization (σ s) be 130emu/g or more than.
And say from the angle consideration of the manufacturing cost that reduces permanent magnet, under the situation of using Nd, also wish not need to carry out high temperature and heat treatment for a long time.For this reason, the present inventor just by R (at least a kind element (wherein rare earth element be the notion that contain Y) of R) and T for selecting among the rare earth element (with Feo and Ti serve as must composition transition metal) formation and mol ratio that have R and T is that the intermetallic compound of forming about 1:12 is studied.Consequently: under the situation that Si exists as clearance type element (or being called intrusion type element), do not impose high temperature and for a long time heat treatment just can access high saturation magnetization and anisotropy field.Moreover, under the situation that N exists as the clearance type element, find that saturation magnetization and anisotropy field have all obtained further raising.
In addition, the present inventor confirms in above-mentioned research process: Si and N are common on clearance type element this point, but their intrusion there are differences the influence of crystal lattice.Details hereinafter will be narrated, and Si has the effect that lattice is shunk, and a axle of crystal lattice is shunk.In contrast, N has the effect that the lattice isotropism is expanded.Consequently: with the ThMn that knows in the past based on U.S.'s test and materialogy meeting (ASTM:AmericanSociety for Testing and Material) 12The c axle of the crystal lattice of type compound and the axial ratio of a axle (below be designated as c/a) are compared, and have bigger value according to the c/a of present inventor's new intermetallic compound.In addition, based on the ThMn of ASTM 12The c/a of type compound is 0.558.
Based on a kind of hard magnetic composition of the invention provides of above opinion, it is characterized in that: this hard magnetic composition by R and T (R be contain a kind of rare earth element of Y, two or more, T be with Fe and Ti serve as must composition transition metal) mol ratio be that the homogeneous structure of about 1: 12 intermetallic compound constitutes, Si and A (A is a kind or 2 kinds among N and the C) are present between the crystal lattice of above-mentioned intermetallic compound as the clearance type element.
In hard magnetic composition of the present invention, the mol ratio of R and T is preferably 1: 10～and 1: 12.5.
The said ThMn of the present invention 12Type crystal structure is meant in X-ray diffraction to be accredited as ThMn 12Type crystal structure.But, with the ThMn of ASTM regulation 12The c/a value of type compound is different.That is to say, in hard magnetic composition of the present invention, if the ratio of the lattice constant of the lattice constant of the c axle of the crystal lattice of above-mentioned intermetallic compound and a axle is made as c1/a1, will be based on the ThMn of U.S.'s test with materialogy meeting (ASTM:AmericanSociety for Testing and Material) 12The lattice constant of the c axle of the crystal lattice of type compound is made as c2/a2 (c2/a2=0.558), then c1/a1＞c2/a2 with the ratio of the lattice constant of a axle.At this moment, make lattice produce anisotropic contraction, and A makes lattice produce isotropic expansion, can access c1/a1＞c2/a2 by Si.
But as the in the past permanent magnet powder of use in bonded permanent magnet etc., that knows has SmCo magnet powder and a NdFeB magnet powder.Consider that from the angle that reduces cost compare with the Sm of high price, cheap Nd preferably becomes the main body of rare earth element.Therefore, has Nd 2Fe 14B 1The magnet powder of phase has obtained using widely, but still wishes more cheap magnet powder.
In order to obtain such magnet powder, the present inventor has carried out various researchs.Consequently obtained following opinion:, can show sufficient coercive force as permanent magnet powder by making the texture miniaturization of above-mentioned hard magnetic composition of the present invention.That is to say that permanent magnet powder of the present invention is characterised in that: this magnet powder is by general formula R (Fe 100-y-wCo wTi y) xSi zA v(in general formula, R is at least a kind of element (wherein rare earth element is the notion that contains Y) of selecting, 50 moles of % or the above Nd of being of while R among rare earth element, and A is N and/or C) constitutes; And the composition that has is, the mol ratio of above-mentioned general formula satisfies: x=10～12.8, y=(8.3-1.7 * z)～12.3, z=0.1～2.3, v=0.1～3, w=0～30, (Fe+Co+Ti+Si)/R＞12 simultaneously; And be that the aggregation of 200nm or following particle is formed by average crystal grain diameter.
In permanent magnet powder of the present invention, each particle that constitutes powder is preferably to have ThMn 12Type crystal structure be principal phase mutually, particularly preferably be in fact by having ThMn 12The homogeneous structure of the phase of type crystal structure constitutes.
In addition, in permanent magnet powder of the present invention,, also can access and have ThMn in fact even account at Nd under the 70 moles of % or above situation of R 12The homogeneous structure of the phase of type crystal structure, thereby help reducing cost.
As described above, magnet powder of the present invention is characterised in that and has fine texture.And fine like this texture can realize that promptly the amorphous that processing obtains to quench solidification or the powder of crystallite impose predetermined heat treatment by such method.In the manufacture method of permanent magnet powder of the present invention, at first make powder, wherein this powder is by general formula F (Fe 100-y-wCo wTi y) xSi z(in general formula, at least a kind element (wherein rare earth element be the notion that contain Y) of R for selecting among the rare earth element, simultaneously 50 moles of % of R or above be Nd) formation; And the composition that has is, the mol ratio of above-mentioned general formula satisfies: x=10～12.8, y=(8.3-1.7 * z)～12.3, z=0.1～2.3, w=0～30, (Fe+Co+Ti+Si)/R＞12 simultaneously; And be implemented the quench solidification processing.Secondly, this powder temperature range in 600～850 ℃ in inert atmosphere is imposed the heat treatment that kept 0.5～120 hour.Then, impose nitrogen treatment or carbonization treatment to being implemented heat treated powder.
In the manufacture method of permanent magnet powder of the present invention, the powder that has carried out the quench solidification processing presents the mixed phase of amorphous phase, amorphous phase and crystalline phase or any tissue among the crystalline phase.Wherein, the complexity of the crystal grain diameter after the heat treatment then carried out of control is preferably set to the mixed phase of amorphous phase and crystalline phase, and preferred settings is the mixed phase of rich crystalline phase especially.
In the manufacture method of permanent magnet powder of the present invention, do not limit the concrete grammar that quench solidification is handled, still, the reason based on stably obtaining desired tissue etc. after productivity, the cooled and solidified preferably is suitable for single-roller method.The peripheral speed of the roller when being suitable for single-roller method is preferably set to 10～100m/s.The composition of the alloy of wishing to get has some difference according to the difference of other conditions such as the aperture of nozzle of ejection motlten metal and roller material, can present the mixed phase of amorphous phase, amorphous phase and crystalline phase or any tissue among the crystalline phase but carry out the powder that quench solidification handles in this scope.
In the manufacture method of permanent magnet powder of the present invention, the heat treatment that the powder of having implemented the quench solidification processing is carried out is to make the amorphous phase crystallization, perhaps adjusts the particle diameter of the crystal grain that constitutes crystalline phase.
By using the permanent magnet powder that obtains based on the present invention, can make bonded permanent magnet.This bonded permanent magnet possess permanent magnet powder with the bonding permanent magnet powder resin mutually.The hard magnetic particle that constitutes the crystalline of this permanent magnet powder is characterised in that: this hard magnetic particle is by general formula R (Fe 100-y-wCo wTi y) xSi zA v(in general formula, R is at least a kind of element (wherein rare earth element is the notion that contains Y) of selecting, 50 moles of % or the above Nd of being of while R among rare earth element, A is N and/or C) constitute, the mol ratio of above-mentioned general formula satisfies on forming: x=10～12.8, y=(8.3-1.7 * z)～12.3, z=0.1～2.3, v=0.1～3, w=0～30, (Fe+Co+Ti+Si)/R＞12 simultaneously.
Consider from the angle of magnetic characteristic, the hard magnetic particle of bonded permanent magnet of the present invention, its average crystal grain diameter is preferably 200nm or following.
Description of drawings
Fig. 1 is that expression has Nd (Ti 8.2Fe 91.8) 11.9Si zAnd Nd (Ti 8.2Fe 91.8) 11.9Si zN 1.5The lattice constant (a axle, c axle and c axle/a axle) of hard magnetic composition of composition and the curve of the relation between the Si amount (z).
Fig. 2 is composition, the magnetic characteristic of the test portion that obtains of expression the 1st embodiment (experimental example 1) and the chart that constitutes mutually.
Fig. 3 (a) is the curve of the relation between expression Si amount and the saturation magnetization (σ s); Fig. 3 (b) is expression Si amount and anisotropy field (H A) between the curve of relation.
Fig. 4 is expression test portion No.4,7 and the X-ray diffraction result's of test portion No.45 curve chart.
Fig. 5 is test portion No.4,7,33 and the thermomagnetization curve of No.45.
Fig. 6 is composition, the magnetic characteristic of the test portion that obtains of expression the 1st embodiment (experimental example 2) and the chart that constitutes mutually.
Fig. 7 (a) is the curve of the relation between expression (Fe+Ti) amount and the saturation magnetization (σ s); Fig. 7 (b) is expression (Fe+Ti) amount and anisotropy field (H A) between the curve of relation.
Fig. 8 (a) is the curve of the relation between expression (Fe+Ti) amount and the saturation magnetization (σ s); Fig. 8 (b) is expression (Fe+Ti) amount and anisotropy field (H A) between the curve of relation.
Fig. 9 is composition, the magnetic characteristic of the test portion that obtains of expression the 1st embodiment (experimental example 3) and the chart that constitutes mutually.
Figure 10 (a) is the curve of the relation between expression Ti amount and the saturation magnetization (σ s); Figure 10 (b) is expression Ti amount and anisotropy field (H A) between the curve of relation.
Figure 11 (a) is the curve of the relation between expression Ti amount and the saturation magnetization (σ s); Figure 11 (b) is expression Ti amount and anisotropy field (H A) between the curve of relation.
Figure 12 (a) is the curve of the relation between expression Ti amount and the saturation magnetization (σ S); Figure 12 (b) is expression Ti amount and anisotropy field (H A) between the curve of relation.
Figure 13 is composition, the magnetic characteristic of the test portion that obtains of expression the 1st embodiment (experimental example 4) and the chart that constitutes mutually.
Figure 14 (a) is the curve of the relation between expression N amount and the saturation magnetization (σ S); Figure 14 (b) is expression N amount and anisotropy field (H A) between the curve of relation.
Figure 15 is composition, the magnetic characteristic of the test portion that obtains of expression the 1st embodiment (experimental example 5) and the chart that constitutes mutually.
Figure 16 is composition, the magnetic characteristic of the test portion that obtains of expression the 1st embodiment (experimental example 6) and the chart that constitutes mutually.
Figure 17 is composition, the magnetic characteristic of the test portion that obtains of expression the 2nd embodiment (experimental example 7) and the chart that constitutes mutually.
Figure 18 is the result's of expression test portion No.63,91 and 105 X-ray diffraction a curve chart.
Figure 19 is near the enlarged drawing of the angle of diffraction that produces α-Fe peak.
Figure 20 is composition, the magnetic characteristic of the test portion that obtains of expression the 2nd embodiment (experimental example 8) and the chart that constitutes mutually.
Figure 21 is composition, the magnetic characteristic of the test portion that obtains of expression the 2nd embodiment (experimental example 9) and the chart that constitutes mutually.
Figure 22 is composition, the magnetic characteristic of the test portion that obtains of expression the 2nd embodiment (experimental example 10) and the chart that constitutes mutually.
Figure 23 is composition, the magnetic characteristic of the test portion that obtains of expression the 2nd embodiment (experimental example 11) and the chart that constitutes mutually.
Figure 24 is composition, the magnetic characteristic of the test portion that obtains of expression the 2nd embodiment (experimental example 12) and the chart that constitutes mutually.
Figure 25 is composition, the magnetic characteristic of the test portion that obtains of expression the 2nd embodiment (experimental example 13) and the chart that constitutes mutually.
Figure 26 is composition, the magnetic characteristic of the test portion that obtains of expression the 2nd embodiment (experimental example 14) and the chart that constitutes mutually.
Figure 27 is composition, the magnetic characteristic of the test portion that obtains of expression the 3rd embodiment (experimental example 15) and the chart that constitutes mutually.
Figure 28 is the thermomagnetization curve of the test portion that obtains of the 3rd embodiment.
Figure 29 is composition, the magnetic characteristic of the test portion that obtains of expression the 3rd embodiment (experimental example 16) and the chart that constitutes mutually.
Figure 30 is the X-ray diffraction result's that carries out for the thin slice behind the quench solidification of expression a curve chart.
Figure 31 is the X-ray diffraction result's that carries out for the test portion after the heat treatment of expression a curve chart.
Figure 32 is expressed as follows the photo of tissue by the result of transmission electron microscope (TEM) observation, and wherein said tissue is the tissue after heat-treating with the resulting thin slice of the peripheral speed of the roller of 25m/s (Vs).
Figure 33 is expressed as follows the photo of tissue by the result of transmission electron microscope (TEM) observation, and wherein said tissue is the tissue after heat-treating with the resulting thin slice of the peripheral speed of the roller of 75m/s (Vs).
Figure 34 is the result of magnetic characteristic is measured in expression for the 4th embodiment (experimental example 17), behind nitrogen treatment a chart.
Figure 35 is the result of magnetic characteristic is measured in expression for the 4th embodiment (experimental example 18), behind nitrogen treatment a chart.
Embodiment
The embodiment that comprises its preferred plan below with regard to the manufacture method of hard magnetic composition of the present invention, permanent magnet powder, permanent magnet powder and bonded permanent magnet explanation.
The qualification reason of each element of the present invention at first, is described.
[R (rare earth element)]
R obtains the necessary element of high magnetic anisotropy.In order to generate ThMn as the hard magnetic phase 12Phase is favourable though use Sm, and the present invention is for the advantage of acquisition cost aspect, set by Nd account for R 50 moles of % or more than.Though the present invention by Nd account for R 50 moles of % or more than, may make ThMn 12Generate easily mutually.
But except Nd, the present invention allows the rare earth element that contains other.At this moment, when containing Nd, preferably contain at least a kind of element selecting among Y, La, Ce, Pr, the Sm again.Wherein Pr and Nd show roughly equal character, so aspect magnetic characteristic, because also can obtain the value that is equal to Nd, be particularly preferred therefore.
According to the present invention, the ratio that accounts for R at Nd is up to 70 moles of % or above or up under 90 moles of % or the above situation, still can access with hard magnetic is ThMn mutually 12Be the tissue of principal phase mutually, and then obtain by ThMn 12The homogeneous structure of Gou Chenging mutually.As shown in the embodiment described later, according to the present invention, even all be that Nd is that also can access by hard magnetic is ThMn mutually under the situation of Nd 100 moles of % accounting for R at R 12The homogeneous structure of Gou Chenging mutually.
[Si]
When Si adds with respect to R (Nd) and Fe with Ti, then help ThMn as the hard magnetic phase 12The stabilisation of phase.At this moment, Si has intrusion ThMn 12Between the lattice dot matrix of phase and the effect that lattice is dwindled.When making Si quantity not sufficient 0.1 (mol ratio, down together), has Mn 2Th 17The phase of type crystal structure is (to call Mn in the following text 2Th 17Phase) separates out, when surpassing 2.3, then exist and separate out the tendency of α-Fe.Therefore, the present invention recommends and will be set at 0.1～2.3 scope as the z of Si amount.Preferred Si amount (z) is 0.2～2.0, and further preferred Si amount (z) is 0.2～1.0.
In addition, about Si, fastening with the pass of Fe, Co, Ti and R, preferably its content satisfies: (mol ratio of mol ratio+Si of mol ratio+Ti of mol ratio+Co of Fe/(mol ratio of R)＞12 is described below about this point.
[Ti]
Ti helps ThMn 12The generation of phase.Specifically, the Ti replacement of fe by by scheduled volume just makes ThMn 12It is easy that the generation of phase becomes.In order fully to obtain this effect, to fasten with the pass of Si amount, the lower limit of setting Ti amount (y) is necessary.That is to say that as shown in the embodiment described later, Ti amount (y) is then separated out α-Fe and Mn when not enough (8.3-1.7 * z (Si amount)) 2Th 17Phase.In addition, surpass at 12.3 o'clock in Ti amount (y), the reducing of saturation magnetization becomes remarkable.Therefore, the present invention is set at (8.3-1.7 * z (Si amount))～12.3 with Ti amount (y), preferred Ti amount (y) is (8.3-1.7 * z (Si amount))～12, preferred Ti amount (y) is (8.3-1.7 * z (Si amount))～10, and further preferred Ti amount (y) is (8.3-1.7 * z (Si amount))～9.
In addition, when the Fe amount was measured sum (x) less than 10 with Ti, saturation magnetization and anisotropy field were all lower; And surpass at 12.5 o'clock, separating out of α-Fe then arranged.Therefore, Fe amount and Ti amount sum (x) are set at 10～12.5.Preferred Fe amount is 11～12.5 with Ti amount sum (x).
[A (N (nitrogen) and/or C (carbon))]
A is by invading ThMn 12The crystal lattice chien shih ThMn of phase 12The lattice of phase enlarges and to improving the magnetic characteristic effective elements.But, (v) surpass at 3.0 o'clock, can see separating out of α-Fe in the A amount; And (v) during less than 0.1, can not fully obtain the effect of improving of magnetic characteristic in A amount.Therefore, the A amount (v) is set at 0.1～3.0.
(v) be 0.3～2.5, further preferred A amount (v) is 1.0～2.5 to preferred A amount.
[Fe，Fe-Co]
Though hard magnetic composition of the present invention is essentially Fe except above-mentioned element, be effective with the part of Co replacement of fe.Illustrated as embodiment described later, by adding Co, its saturation magnetization (σ s) and anisotropy field (H A) increase.The amount of Co preferably with 30 or following mol ratio add, more preferably be set at 5～20 scope.In addition, the interpolation of Co is not necessary.
[(mol ratio of mol ratio+Si of mol ratio+Ti of mol ratio+Co of Fe)/(mol ratio of R)＞12]
Fe, Co, Ti and Si content separately but is being set at ThMn with hard magnetic composition of the present invention as previously mentioned 12The homogeneous structure aspect of phase, the condition that satisfies (Fe+Co+Ti+Si)/R＞12 is important.As shown in the embodiment described later, in the occasion that can not satisfy above-mentioned condition, saturation magnetization reduces.
[Zr，Hf]
More than be illustrated with regard to the composition of hard magnetic composition of the present invention.
Hard magnetic composition of the present invention can further contain Zr and/or Hf.Zr and/or Hf for magnetic characteristic particularly the raising of saturation magnetization be effective.
Zr and/or Hf replace the part of R in above-mentioned general formula.At this, when the replacement amount u of expression Zr and/or Hf surpassed 0.18, saturation magnetization was that 0 situation is lower than u, and therefore, in the occasion by the part of Zr and/or Hf displacement R, u is set at 0.18 or following (not containing 0).Preferred u is 0.01～0.15, and further preferred u is 0.04～0.06.
Here, the Ti that has expressed when carrying out Zr (Hf) displacement measures (y).
In the occasion of carrying out Zr (Hf) displacement, Ti amount (y) is set at 4.5～12.3.Preferred Ti amount (y) is 5～12 under this occasion, more preferably 6～10, further be preferably set to 7～9.In addition, Fe amount, Co amount and Ti amount sum (x) are 11～12.8, are preferably 11.5～12.5.
The manufacture method of hard magnetic composition of the present invention can enough known manufacture methods obtain.
About as clearance type element N, can use the raw material that contained N originally.But, preferably behind the composition of the element beyond manufacturing contains N, N is invaded by means of in gas that contains N or liquid, handling (nitrogenize).Gas as N is invaded can use N 2Gas, N 2+ H 2Mist, NH 3Gas and their mist.The temperature of nitrogen treatment can be set at 200～1000 ℃, is preferably set to 350～700 ℃.In addition, the nitrogen treatment time can be carried out suitable selection in 0.2～200 hour scope.
About the processing (carbonization treatment) that C is invaded, also the situation with N is identical.That is to say, can use the raw material that contained C originally, also can behind the composition of the element beyond manufacturing contains C, in gas that contains C or liquid, carry out heat treated.Perhaps also can C be invaded by carry out heat treated with the solid that contains C.Gas as C is invaded can list CH 4And C 2H 6Deng.In addition, as the solid that contains C, can use carbon black.In the carbonization of using them to carry out, can with the same temperature of nitrogen treatment and the scope in processing time in set suitable condition.
＜crystal structure 〉
The crystal structure of hard magnetic composition of the present invention describes with that.
Hard magnetic composition of the present invention by R (at least a kind element (wherein rare earth element be the notion that contain Y) of R) and T for selecting among the rare earth element (with Fe and Ti serve as must composition transition metal) form, and have the intermetallic compound of forming formation about 1: 12 by the mol ratio of R and T.Exist Si as the clearance type element between the crystal lattice of this intermetallic compound.In addition, also exist N as the clearance type element at this lattice dot matrix.
As mentioned above, Si and N all are present between the crystal lattice to improve magnetic characteristic.But Si shrinks lattice, and N makes lattice dilatation.Like this, Si and N use different.Describe with regard to this point below.
Fig. 1 is that expression has Nd (Ti 8.2Fe 91.8) 11.9Si zAnd Nd (Ti 8.2Fe 91.8) 11.9Si zN 1.5The lattice constant (c axle, a axle and c axle/a axle) of hard magnetic composition of composition and the curve of the relation between the Si amount (z).In addition, hard magnetic composition shown in Figure 1 is disclosed among the embodiment described later.
In Fig. 1, big variation is arranged even interpolation Si also can't see the lattice constant of c axle.But know: for a axle, by adding Si, lattice constant reduces significantly.That is to say that Si is present between the crystal lattice and has the feature that the crystal lattice of making is anisotropically shunk.
Secondly know: in Fig. 1, by adding N, the lattice constant of c axle and a axle all increases.That is to say that N is present between the lattice and crystal lattice is isotropically expanded.As above,, can improve saturation magnetization, Curie temperature and anisotropy field by making the lattice contraction or expansion.And know from Fig. 1: the effect that lattice anisotropy ground is shunk by Si produces can not change even add N yet yet.And Si shrinks owing to self existence makes lattice, but by with the N coexistence, the effect that anisotropy improves becomes significantly, simultaneously generation homogeneous structure easily.
And in Fig. 1, indicate the ThMn of the curve representation ASTM record of " ASTM " symbol 12The lattice constant of the lattice constant/a axle of the lattice constant of the c axle of type compound, the lattice constant of a axle and c axle.Known Nd (Ti already 8.2Fe 91.8) 11.9Si zAt z is 0 o'clock, the ThMn of the lattice constant of its composition and ASTM record 12The lattice constant of type compound is consistent.
Si is present between the crystal lattice and can confirms by the following fact.For above-mentioned Nd (Ti 8.2Fe 91.8) 119Si zMiddle z is 0 composition that does not promptly contain the composition of Si and contain Si, confirms based on X-ray diffraction method, and the two does not see all what the grown form of the diffraction maximum that obtains has change as a result.And can not confirm to have the peak of compound of the formation element of Si or above-mentioned composition and Si and the peak of α-Fe.Moreover, follow the increase of Si amount, the lattice constant of a axle reduces continuously.Can think that thus Si is present between the crystal lattice.
In addition, in the present invention, the N atom is present between the crystal lattice, and c axle and a axle are all expanded with roughly the same ratio.But,,, thereby can infer Si and be present in privileged site in the crystal lattice because a axle is shunk although Si is present between the crystal lattice.Although can not determine the position of its existence, because show ThMn 12The X ray diffracting spectrum of type compound, thereby can think between crystal lattice in occupation of certain location.
Hard magnetic composition of the present invention shows the ThMn with the ASTM record 12The lattice constant that the type compound is different, but X-ray diffraction demonstrates and can recognize ThMn 12The diffracting spectrum of type compound.Therefore, hard magnetic composition of the present invention is ThMn 12The type compound.In hard magnetic composition of the present invention, preferably hard magnetic is set at ThMn mutually 12Type crystal structure.Consider from the angle of magnetic characteristic, make hard magnetic mutually in fact by ThMn 12It is particularly preferred that the homogeneous structure of type crystal structure constitutes.
More than be illustrated with regard to hard magnetic composition of the present invention.This hard magnetic composition is suitable as magnet material, and the present inventor recognizes: by making the crystalline structure miniaturization of this hard magnetic composition, can show sufficient coercive force as permanent magnet powder.Describe in detail with regard to permanent magnet powder of the present invention and manufacture method thereof below.
[tissue of permanent magnet powder]
At first, the tissue with regard to permanent magnet powder of the present invention describes.
Permanent magnet powder of the present invention is an attritive powder, and its crystal grain diameter average out to 200nm or following is preferably 100nm or following, more preferably 80nm or following.Owing to have such micro organization, thereby the present invention can show and is the necessary coercive force of permanent magnet powder.In the present invention, hereinafter will narrate the means that obtain this micro organization.In addition, crystal grain diameter is a such numerical value, promptly carried out heat treated quick cooling alloy, behind separately crystal grain of identification, obtained the area of crystal grain separately, and crystal grain has been used as a diameter of a circle that has circle of the same area with described area and calculate by image processing by tem observation.Average crystal grain diameter is set to respect to each test portion, the mean value of the crystal grain diameter of the whole mensuration particles that are measured with regard to the crystal grain about 100.
Have the permanent magnet powder of the present invention of fine crystal tissue, be set at ThMn 12As principal phase, more preferably be set at ThMn 12The homogeneous structure of phase.In addition, about whether being ThMn 12The homogeneous structure of phase can be judged according to the standard shown in the embodiment described later.
[manufacture method of permanent magnet powder]
The following describes the manufacture method of permanent magnet powder of the present invention.
Permanent magnet powder of the present invention is characterised in that to have fine texture as described above, has several method can obtain this fine texture.For example, use the method for method, use mechanical lapping or the mechanical alloying of motlten metal quench, the method for use hydrogenation-disproportionation--dehydrogenation-compound (HDDR:Hydrogenation-Decomposition-Desorption-Recombinatio n) method etc.Describe with regard to the manufacture method of using the motlten metal quench below.
Use the manufacture method of motlten metal quench to have motlten metal chilling operation, heat treatment step and 3 main operations of nitrogen treatment operation.Describe successively with regard to each operation below.
＜motlten metal chilling operation 〉
Motlten metal chilling operation is that the feed metal that will be deployed into above-mentioned composition melts, and after obtaining motlten metal, makes this motlten metal chilling and solidifies.As concrete freezing method, there are single-roller method, double roller therapy, centrifugal quench and gas atomization method etc.Wherein preferably use single-roller method.Single-roller method be with molten alloy from nozzle ejection and make the periphery of its collision chill roll, molten alloy is cooled off fast, thereby obtains thin ribbon shaped or laminar quick cooling alloy.Single-roller method is compared with other motlten metal quench, the mass production capabilities height, and the reappearance under the chilling condition is good.
The alloy of quench solidification is because of it is formed, the difference of the peripheral speed of chill roll is different, presents that amorphous is single-phase, the mixed phase of amorphous phase and crystalline phase and crystalline phase any tissue morphology among single-phase.Controlled micro crystallization can take place by the heat treatment of carrying out subsequently in amorphous phase.As a yardstick, when the peripheral speed of chill roll increased, the ratio that amorphous occupies improved.
When the peripheral speed of chill roll is accelerated, the quick cooling alloy attenuation that obtains, thereby can access the more quick cooling alloy of homogeneous.For the purpose of the present invention, most preferably under the state that remains unchanged after the cooled and solidified, have final conceivable microcrystalline structure, but realize this point not a duck soup.On the other hand, after obtaining the single-phase tissue of amorphous phase, carrying out controlled micro crystallization by means of heat treatment also is possible certainly, but has nucleus based on previous formation, crystal grain is grown up unusually and generates the danger of coarse grain.Therefore, for the purpose of the present invention, preferred form is that rich crystallite phase of acquisition and remainder are the solidified structure of amorphous phase.
For this reason, the peripheral speed of chill roll is set at the scope of 10～100m/s usually, is preferably set to the scope of 15～75m/s, further is preferably set to the scope of 25～75m/s.When the not enough 10m/s of the peripheral speed of chill roll, thickization of crystal grain is difficult to obtain desired fine structure; When the peripheral speed of chill roll surpasses 100m/s, the adaptation variation of molten alloy and chill roll periphery, hot transmission can not be carried out effectively, and equipment cost also improves.In addition, motlten metal chilling operation is preferably at Ar gas, N 2Carry out in the non-oxidizing atmospheres such as gas.
＜heat treatment step 〉
Then supply with heat treatment through the quick cooling alloy that motlten metal chilling operation obtains.This heat treated effect is: at quick cooling alloy is under the single-phase situation of amorphous phase, generates the crystallite that particle diameter meets requirement of the present invention; In addition, be under the situation of mixed phase of amorphous phase and crystalline phase at quick cooling alloy, make the amorphous phase controlled micro crystallization, and crystal grain is controlled to be particle diameter of the presently claimed invention; Moreover, be under the situation of homogeneous structure of crystalline phase at quick cooling alloy, its crystal grain is controlled to be particle diameter of the presently claimed invention.Therefore, as long as under the state of quick cooling alloy, can not obtain the desired micro organization of permanent magnet powder of the present invention, just be necessary to impose heat treatment.
This heat treated treatment temperature is 600～850 ℃, is preferably 650～800 ℃, more preferably 670～750 ℃.Processing time is different according to the difference of treatment temperature, but is set at usually about 0.5～120 hour.This heat treatment is preferably carried out in non-oxidizing atmospheres such as Ar, He and vacuum.
＜nitrogen treatment operation 〉
After the heat treatment quick cooling alloy is imposed nitrogen treatment.For N, can use the raw material that contained N originally, but preferably, behind the composition of the element beyond manufacturing contains N, N be invaded by means of in gas that contains N or liquid, handling (nitrogenize) as the clearance type element.Gas as N is invaded can use N 2Gas, N 2+ H 2Mist, NH 3Gas and their mist.In addition, it is preferred making these gases become gases at high pressure and handle accelerating aspect the nitrogen treatment speed.
The temperature of nitrogen treatment is set at 200～450 ℃, is preferably set to 350～420 ℃, and the nitrogen treatment time can be carried out suitable selection in 0.2～200 hour scope.In addition, for the processing (carbonization treatment) that C is invaded too, both can use the raw material that contained C originally, also can behind the composition of the element beyond manufacturing contains C, in gas that contains C or liquid, carry out heat treated.Perhaps also can C be invaded by carry out heat treated with the solid that contains C.As the gas that C is invaded, can enumerate CH4 and C 2H 6Deng.In addition, as the solid that contains C, can use carbon black.In the carbonization of using them to carry out, can with the same temperature of nitrogenize and the scope in processing time in set suitable condition.
More than be the basic working procedure that is used to obtain permanent magnet powder of the present invention, and adopt alloy that the motlten metal quench obtains can be before heat treatment step, before the nitrogen treatment operation or the arbitrary stage after the nitrogen treatment operation pulverize.This is because the alloy that adopts the motlten metal quench to obtain is different with the desired size of permanent magnet powder with bonded permanent magnet usually.Pulverizing is at Ar and N 2Deng carrying out in the inert gas.
The average grain diameter of permanent magnet powder has no particular limits, but preferred particle diameter is not have the excessive zone of crystallinity difference in same particle as far as possible, in addition, preferably can be used as the particle diameter that permanent magnet powder uses.Specifically, be suitable under the situation of bonded permanent magnet, average grain diameter be preferably set to usually 10 μ m or more than, but in order to obtain sufficient non-oxidizability, average grain diameter be preferably set to 30 μ m or more than, more preferably be set at 50 μ m or more than, further be preferably set to 70 μ m or more than.In addition, by being set average grain diameter, just can make highdensity bonded permanent magnet for this degree.On the other hand, the upper limit of average grain diameter is preferably 500 μ m, more preferably 250 μ m.In addition, said here average grain diameter can be stipulated especially by mid diameter D50.D50 be from the little particle of particle diameter begin the cumulative calculation quality, when its accumulative total quality accumulative total quality that is all particles 50% the time particle diameter, the accumulation frequency of grading curve just.
The permanent magnet powder that more than obtains can be supplied with bonded permanent magnet.Bonded permanent magnet can be made by the particle that uses the bonding formation permanent magnet powder of adhesive.Bonded permanent magnet is divided into some kinds according to its manufacture method.For example, compression bonded magnet that working pressure is shaped and with the injection binding magnet of injection moulding is arranged.As adhesive, preferably use various resins, but also can use metal-to-metal adhesive to make the metal bonding magnet.There is no particular limitation for the kind of resin binder, the selection can be from various thermosetting resins such as epoxy resin and nylon and various thermoplastic resin suitable in addition according to the difference of purpose.Also there is no particular limitation for the kind of metal-to-metal adhesive.In addition, also there is no particular limitation for adhesive and conditions such as pressure when being shaped proportional with respect to containing of permanent magnet powder, can be in common scope in addition suitable selection.But,, preferably avoid the method for instructions for use high-temperature heat treatment in order to prevent thickization of crystal grain.
Below be illustrated, but the present invention is not limited to this method with regard to the example that uses the motlten metal quench to obtain the micro crystal tissue.As other method, use the method for mechanical lapping in addition.This method has mechanical lapping operation, heat treatment step and 3 main operations of nitrogen treatment operation.Heat treatment step and nitrogen treatment operation are identical with the method that above-mentioned motlten metal quench adopts, thereby omit its explanation at this.
Mechanical lapping makes the particle amorphous phase conversion in opposite directions of crystalline structure by the alloy particle of making predetermined particle diameter being applied continuously the impact of machinery.The mode that applies of mechanical shock can be undertaken by using as the well known ball mill of pulverizer, vibration grinder (shaker mill) and oscillating mill.By handling alloy particle, can make the tissue of particle become amorphous with these pulverizers.
Alloy particle can be made with conventional method.For example, just can obtain by pulverizing its ingot casting behind the ingot casting that making regulation is formed.Perhaps, also can be with the strip that obtains with the motlten metal quench or thin slice object as mechanical lapping.Undoubtedly needn't be suitable for the strip or the thin slice that just are in noncrystalline state at first this moment.
The decrystallized alloy powder by means of mechanical lapping by heat-treating operation and nitrogen treatment operation successively, just can access permanent magnet powder of the present invention.In addition, use this permanent magnet powder can access bonded permanent magnet of the present invention.
As the method that obtains the micro crystal tissue, the heat treatment (HDDR:Hydrogenation-Decomposition-Desorption-Recombinatio n) of carrying out dehydrogenation in nitrogen atmosphere after keeping under the high temperature is arranged.The present invention uses this HDDR also can access fine texture.For the powder of having implemented HDDR,, can obtain permanent magnet powder of the present invention by implementing heat treatment step and nitrogen treatment operation successively.In addition, use this permanent magnet powder can access bonded permanent magnet of the present invention.
(embodiment)
Secondly, enumerate specific embodiment and further describe the present invention.
[the 1st embodiment]
The experimental result (experimental example 1～6) of basis that will become the qualification reason of above-mentioned compositing range is represented as the 1st embodiment.As top narrate, hard magnetic composition of the present invention show with ASTM in the ThMn that puts down in writing 12The lattice constant that the type compound is different can be accredited as ThMn but show in X-ray diffraction 12The diffracting spectrum of type compound.
＜experimental example 1 〉
At first, with regard to phase state and magnetic characteristic experimental result to the interdependence of z value (Si amount)
(experimental example 1) describes.
Use highly purified Nd, Fe, Ti and Si metal to be raw material, in Ar atmosphere, consist of Nd-(Ti as alloy with the arc-melting legal system 8.3Fe 91.7) 12-Si zTest portion.After then this alloy being pulverized with bruisher and being the screen cloth screening of 38 μ m, in blanket of nitrogen, keep 100 hours heat treatment (nitrogenize) in 430～520 ℃ temperature through mesh.For each test portion after the heat treatment, saturation magnetization (σ s) and anisotropy field (H have been carried out in the discriminating of having carried out chemical composition analysis and having constituted phase simultaneously A) mensuration.Its result such as Fig. 2 and shown in Figure 3.
In addition, the discriminating that constitutes phase is carried out with the basis that is determined as of X-ray diffraction method and thermomagnetization curve.X-ray diffraction uses Cu pipe ball and measures with the output of 15kW, confirms to have or not ThMn 12The peak of phase and other phase in addition exists.But, Th 2Mn 17The peak of phase and ThMn 12The peak of phase is overlapping substantially, thus only with X-ray diffraction method be confirmed to be the difficulty.Therefore, also use thermomagnetization curve for the discriminating that constitutes phase.In addition, thermomagnetization curve applies the magnetic field of 2kOe and measures, to confirm whether to occur corresponding ThMn 12The Tc (Curie temperature) of the phase mutually.In addition, in the present invention, so-called " ThMn 12The homogeneous structure of phase " refer to: can not observe ThMn with above-mentioned X-ray diffraction method 12The peak of the phase mutually; And can not confirm corresponding ThMn by above-mentioned thermomagnetization curve mensuration 12The Tc of the phase mutually; Simultaneously be higher than the high temperature side of this Tc, remanent magnetization be 0.05 or below; And can contain unavoidable impurities that detection do not come out and unreacted reactant etc.For example, it is insufficient owing to thermal uniformity in arc furnace melts, sometimes remaining a small amount of unreacted phase (for example Nd, α-Fe etc.), and contain the unavoidable impurities such as Cu that come from the test portion support sometimes, but, just do not consider unavoidable impurities as long as the mensuration of X-ray diffraction and thermomagnetization curve can not detect.Be base description and the relevant instantiation of discriminating that constitutes phase with Fig. 4 and Fig. 5 below.
Fig. 4 is expression test portion No.4,7 and the result's of the X-ray diffraction of aftermentioned test portion No.45 curve chart.As shown in Figure 4, for test portion No.4 and No.45, only observe demonstration ThMn 12The peak of phase.But test portion No.7 can confirm that α is arranged-existence at Fe peak.In addition, as described above, Mn 2Th 17The peak of phase and ThMn 12Therefore the peak overlaid of phase can not be distinguished the two on this curve.
Fig. 5 represents test portion No.4,7 and the thermomagnetization curve of aftermentioned test portion No.33 and No.45.Near 400 ℃, there is ThMn 12The Tc of phase.And Mn 2Th 17The Tc of phase (2-17 phase) is identified and is present in ThMn as shown in Figure 5 12The low temperature side of the Tc of phase (test portion No.33).At this, can not confirm to have ThMn 12Tc beyond the Tc of phase exists, and is being higher than this Tc high temperature side, remanent magnetization be 0.05 or below, it is single-phase at this moment just can regarding as.That is to say that test portion No.4 and test portion No.45 can not confirm to have ThMn 12Tc beyond the Tc of phase exists, and is being higher than the high temperature side of this Tc, remanent magnetization be 0.05 or below, thereby differentiate to being ThMn 12The homogeneous structure of phase.In addition, although test portion No.7 can not confirm to have ThMn 12Tc beyond the Tc of phase exists, but is being higher than the high temperature side of this Tc, and remanent magnetization surpasses 0.05, and according to Fig. 4, except ThMn 12Mutually, also differentiating has separating out of α-Fe.Moreover test portion No.33 is because confirm to have Mn 2Th 17The Tc of phase exists, and is being higher than ThMn 12The high temperature side of the Tc of phase, remanent magnetization surpasses 0.05, thereby can identify except ThMn 12Mutually, also has Mn 2Th 17Phase and α-Fe separate out.
As mentioned above,, constitute and to confirm to have ThMn mutually among both at Fig. 4 (X-ray diffraction) and Fig. 5 (thermomagnetization curve) 12Existence mutually mutually, the present invention's this moment is defined as ThMn with it 12The homogeneous structure of phase.
In addition, saturation magnetization (σ s) and anisotropy field (H A) try to achieve based on the magnetization curve of easy axis and the magnetization curve of hard axis direction, wherein the mensuration of magnetization curve is used VSM (vibration test portion type magnetometer: Vibrating SampleMagnetometer) apply magnetic field in maximum and carry out under as the condition of 20kOe.But for the ease of measuring, saturation magnetization (σ s) is set at the magnetization value of the maximum on the magnetization curve of easy axis; And anisotropy field (H A) then be defined as: the value in the magnetic field that the value of the tangent line of 10kOe and saturation magnetization on the magnetization curve of hard axis direction (σ s) intersects.
As Fig. 2 and shown in Figure 3, the test portion No.6 that does not add Si is except ThMn 12In addition, also there is Mn in phase (to call the 1-12 phase in the following text) 2Th 17Phase (to call the 2-17 phase in the following text) and α-Fe, particularly anisotropy field (H A) lower.In contrast, test portion No.1～5 of having added Si as can be known are the single-phase of 1-12 phase, and 1-12 becomes stable mutually.And the single-phase composite of these 1-12 phases can access 130emu/g or above saturation magnetization (σ s) and 50kOe or above anisotropy field (H A).But Si amount is that 2.5 test portion No.7 has separating out of α-Fe, and characteristic is lower.In addition, Fe+Ti quantity not sufficient 10 and Si amount are 2.5 test portion No.8, its saturation magnetization (σ s) and anisotropy field (H A) all obviously reduce.In addition, if there is α-Fe as soft magnetic characteristic, then this part is because of being that downfield (demagnetizing field) produces anti-magnetic domain.Therefore, carry out the magnetic domain counter-rotating of hard magnetic phase constituent easily, consequently coercive force reduces, so for requiring the permanent magnet of coercive force, do not wish to have the existence of α-Fe.
In the scope of test portion No.1～5, the tendency that is had is: the Si amount is many more, anisotropy field (H A) high more; Otherwise the Si amount is few more, and (σ s) is high more for saturation magnetization.
＜experimental example 2 〉
Similarly make with experimental example 1 and to consist of Nd-(Ti 8.3Fe 91.7) x-Si z-N 1.5Test portion, and carry out chemical composition analysis, constitute discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration.The composition of the test portion that experimental example 2 obtains, magnetic characteristic and constitute as shown in Figure 6 mutually.In addition, test portion No.9～11,17～20 saturation magnetization (σ s) and anisotropy field (H A) measurement result respectively shown in Fig. 7 (a) and 7 (b).Equally, test portion No.12～16,21,22 saturation magnetization (σ s) and anisotropy field (H A) measurement result respectively shown in Fig. 8 (a) and 8 (b).In addition, experimental example 2 be for confirm x (Fe amount+Ti amount) and x+z (Fe amount+Ti amount+Si amount) to constitute mutually, saturation magnetization (σ s) and anisotropy field (H A) influence and the experiment carried out.
As Fig. 6～shown in Figure 8, when x less than 10 (test portion No.17,21), the not enough 120emu/g of saturation magnetization (σ s); Z (Si amount) is low to moderate 1.1 test portion No.17, its anisotropy field (H A) be low to moderate about 30 simultaneously.Otherwise, when x surpasses 12.5 (test portion No.20,22), separating out of α-Fe arranged then.In addition, even x is 10～12.5 scope, if x+z is 12 or following (test portion No.18,19), the not enough 120emu/g of saturation magnetization (σ s) then, anisotropy field (H A) be low to moderate about 30kOe simultaneously.
With above-mentioned situation comparatively speaking, when in the scope of x 10～12.5 and x+z when surpassing 12 (test portion No.9～16), the characteristic that is had is: saturation magnetization (σ s) for 120emu/g or more than, anisotropy field (H A) be 50kOe or more than, and can obtain the homogeneous structure of 1-12 phase.
＜experimental example 3 〉
Similarly make with experimental example 1 and to consist of Nd-(Ti yFe 100-y)-Si 1.0-N 1.5, Nd-(Ti yFe 100-y)-Si 1.5-N 1.5And Nd-(Ti yFe 100-y)-Si 2.0-N 1.5Test portion, and carry out chemical composition analysis, constitute discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration.The composition of the test portion that experimental example 3 obtains, magnetic characteristic and constitute as shown in Figure 9 mutually.In addition, test portion No.23～25,33～35 saturation magnetization (σ s) and anisotropy field (H A) measurement result respectively shown in Figure 10 (a) and 10 (b).Equally, test portion No.26～28,36,37 saturation magnetization (σ s) and anisotropy field (H A) measurement result respectively shown in Figure 11 (a) and 11 (b), and test portion No.29～32,38 saturation magnetization (σ s) and anisotropy field (H A) measurement result respectively shown in Figure 12 (a) and 12 (b).
In addition, experimental example 3 be for confirm y (Ti amount) to constitute mutually, saturation magnetization (σ s) and anisotropy field (H A) influence and the experiment carried out.
As Fig. 9～shown in Figure 12, be under the situation of the arbitrary numerical value among 1.0,1.5 and 2.0 at z (Si amount), (during 8.3-1.7 * z), α-Fe is then arranged and then separate out (the test portion No.33,34 and 36～38) of 2-17 phase arranged when y (Ti amount) is not enough.On the other hand, be 12.5 to surpass at 12.3 o'clock at y (Ti amount), saturation magnetization (σ s) is reduced to not enough 120emu/g (test portion No.35).
With above-mentioned situation comparatively speaking, when y (Ti amount) (in the scope of 8.3-1.7 * z)～12.3 time, test portion just becomes the homogeneous structure of 1-12 phase, in other words become the homogeneous structure of hard magnetic phase, and can obtain 130emu/g or above and then be 140emu/g or above saturation magnetization (σ s) and 50kOe or above and then be 55kOe or above anisotropy field (H A) (test portion No.23～32).
＜experimental example 4 〉
Similarly make with experimental example 1 and to consist of Nd-(Ti 8.3Fe 91.7) 12-Si 2.0-N vTest portion, and carry out chemical composition analysis, constitute discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration.The composition of the test portion that experimental example 4 obtains, magnetic characteristic and constitute as shown in figure 13 mutually.In addition, saturation magnetization of test portion No.39～44 (σ s) and anisotropy field (H A) measurement result respectively shown in Figure 14 (a) and 14 (b).
In addition, experimental example 4 be for confirm v (N amount) to constitute mutually, saturation magnetization (σ s) and anisotropy field (H A) influence and the experiment carried out.
As Figure 13 and shown in Figure 14, be 0 o'clock at v (N amount), saturation magnetization (σ s) and anisotropy field (H A) all lower (test portion No.43); On the other hand, be 3.5 to surpass at 3 o'clock at v (N amount), separate out (the test portion No.44) of α-Fe then arranged.
With above-mentioned situation comparatively speaking, when in the scope of v (N amount) 0.1～3, test portion just becomes the homogeneous structure of 1-12 phase, in other words become the homogeneous structure of hard magnetic phase, and can access 120emu/g or above saturation magnetization (σ s) and 30kOe or above anisotropy field (H A) (test portion No.39～42).From saturation magnetization (σ s) and anisotropy field (H A) angle consider that v (N amount) is preferably set to 0.5～2.7, further is preferably set to 1.0～2.5 scope.
＜experimental example 5 〉
Similarly make as shown in Figure 15 each test portion with experimental example 1, and constitute discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration, its result is as shown in figure 15.
In addition, experimental example 5 is in order to confirm Nd-(Ti 8.3Fe 91.7-wCo w) 12-Si z-N 1.5In the interdependence of w (Co amount) and the experiment carried out.
As shown in figure 15, be under the situation of the arbitrary numerical value among 0.25 and 1.0 at z (Si amount) as can be known, if increase w (Co amount), then saturation magnetization (σ s) and anisotropy field (H A) raise, when being 20 left and right sides, peak value appears in its effect at w (Co amount).Therefore, take into account if also Co is cost an arm and a leg, then preferably w (Co amount) is set at 30 or below, more preferably be set at 10～25 scope.In addition, when w (Co amount) was in this scope, it was organized as the single-phase of 1-12 phase.
＜experimental example 6 〉
Use highly purified Nd, Fe, Ti and Si metal to be raw material, in Ar atmosphere, adopt the arc-melting legal system to consist of Nd-(Ti as alloy 8.3Fe 91.7-wCo w) 12-Si zTest portion.After then this alloy being pulverized with bruisher and being the screen cloth screening of 38 μ m through mesh, with average grain diameter be 1 μ m or following C powder, in Ar atmosphere, keep 24 hours heat treatment in 400～600 ℃ temperature.For each test portion after the heat treatment, carried out the analysis of chemical composition, the discriminating of formation phase, carried out saturation magnetization (σ s) and anisotropy field (H simultaneously A) mensuration, its result is as shown in figure 16.
As shown in figure 16,, also can access the homogeneous structure of 1-12 phase, can access 120emu/g or above saturation magnetization (σ s) and 30kOe or above anisotropy field (H simultaneously by adding C to replace N A).At this moment, the same effect of C and N performance.
In addition, even under 1～25% situation, also can obtain and the equal result of other test portion with Pr displacement Nd.
[the 2nd embodiment]
For the variation of the magnetic characteristic confirming to cause with Zr or Hf displacement owing to the part of Nd, the result of experiment of being carried out (experimental example 7～14) is expressed as the 2nd embodiment.In addition, the part of experimental example 7～13 usefulness Zr displacement Nd; The part of experimental example 14 usefulness Hf displacement Nd.
＜experimental example 7 〉
Use highly purified Nd, Zr, Fe, Ti and Si metal to be raw material, in Ar atmosphere, adopt the arc-melting legal system to consist of Nd as alloy 1-xZr x(Ti 8.3Fe 91.7) 12Si 1.0Test portion.Then by pulverizing and heat treatment (nitrogenize) with the same technological process of the 1st embodiment.For each test portion after the heat treatment, the discriminating of having carried out the analysis of chemical composition and having constituted phase is simultaneously to have carried out saturation magnetization (σ s) and anisotropy field (H with the same condition of the 1st embodiment A) mensuration, its result is as shown in figure 17.
As shown in figure 17, the part by with Zr displacement Nd can access 140emu/g or above saturation magnetization (σ s).The raising effect of the saturation magnetization (σ s) that is caused by Zr is 0.05 o'clock peak value display in Zr amount (u), and after this along with the increase of Zr amount (u), saturation magnetization (σ s) has the tendency of decline; Reach at 0.20 o'clock in Zr amount (u), compare with the test portion that does not contain Zr, (σ s) is lower for its saturation magnetization.In addition, Zr amount (u) becomes ThMn when 0.02～0.15 scope 12The homogeneous structure of phase (to call the 1-12 phase in the following text).
As from the foregoing, at general formula: R1 1-uR2 u(Ti yFe 100-y-wCo w) xSi zA vIn, Zr amount (u) is preferably set to 0.01～0.18 scope, more preferably is set at 0.04～0.06 scope.
For each test portion after the heat treatment, the discriminating that constitutes phase is carried out according to X-ray diffraction method.The condition of X-ray diffraction and the 1st embodiment are same, have confirmed whether there is ThMn 12The peak of phase and other phase.As other phase, can enumerate α-Fe, Mn 2Th 17The nitride of phase and Nd.In order to obtain higher magnetic characteristic, ThMn 12Main diffraction pattern mutually is with respect to ThMn 12The main diffraction pattern of phase, its peak intensity ratio be preferably 50% or below.The instantiation of the discriminating of relevant formation phase is that the basis describes with Figure 18 and Figure 19.
Figure 18 is the curve chart of expression aftermentioned test portion No.63,91 and 105 X-ray diffraction measurement result, and test portion No.63,91 observe and show ThMn 12The peak of phase.In contrast, test portion 105 can confirm that α is arranged-existence at Fe peak.This can be interpreted as: test portion 105 is measured owing to containing superfluous N, so ThMn 12Decompose mutually, separating out of α-Fe arranged thereupon.This is from the ThMn of test portion 105 12The strong minimizing in the peak of phase and on the other hand the strong increase in the peak of α-Fe can obtain understanding.
Figure 19 is near the enlarged drawing of the angle of diffraction that produces α-Fe peak.Near this angle, ThMn 12The peak of phase and α-Fe peak is adjacent.Test portion No.63 only observes ThMn 12The peak of phase.In addition, test portion No.91 observes ThMn 12With two peaks of α-Fe, still, under the few situation of α-Fe, very little like this to the influence of characteristic.On the other hand, test portion No.105 almost only observes the peak of α-Fe.And as can be seen from Figure 18, the main diffraction pattern of α-Fe is with respect near the ThMn that sees 42 ° 12The peak intensity ratio of the main diffraction pattern of phase be 50% or more than, α-when the Fe volume was separated out, the degeneration of characteristic was more remarkable like this.
＜experimental example 8 〉
Consist of Nd to make with the same technological process of experimental example 7 0.95Zr 0.05(Ti 8.3Fe 91.7) 12Si uN 1.5Test portion, carried out chemical composition analysis, constitute discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration, its result is as shown in figure 20.
In addition, experimental example 8 be for confirm Si amount (z) to constitute mutually, saturation magnetization (σ s) and anisotropy field (H A) influence and the experiment carried out.
For the test portion No.69 that does not add Si, except the 1-12 phase, also there is Mn 2Th 17Phase (to call the 2-17 phase in the following text) and α-Fe phase, particularly anisotropy field (H A) lower.In contrast, test portion No.70～73 of having added Si as can be known are the single-phase of 1-12 phase, and 1-12 becomes stable mutually.And the single-phase composite of these 1-12 phases can access 140 or 145emu/g or above saturation magnetization (σ s) and 50 or 55kOe or above anisotropy field (H A).But Si amount is that 2.5 test portion No.74 separates out a large amount of α-Fe, thereby characteristic is reduced.In addition, if there is α-Fe as soft magnetic characteristic, then this part is because of being that downfield (demagnetizing field) produces anti-magnetic domain.Therefore, carry out the magnetic domain counter-rotating of hard magnetic phase constituent easily, consequently coercive force reduces, so for requiring the permanent magnet of coercive force, do not wish to have the existence of α-Fe.
In the scope of test portion No.70～73, the tendency that is had is: the Si amount is many more, anisotropy field (H A) high more; Otherwise the Si amount is few more, and (σ s) is high more for saturation magnetization.
＜experimental example 9 〉
Consist of Nd to make with the same technological process of experimental example 7 0.95Zr 0.05(Ti 8.3Fe 91.7) xSi 0.5N 1.5, Nd 0.95Zr 0.05(Ti 8.3Fe 91.7) xSi 1.0N 1.5And Nd 0.95Zr 0.05(Ti 8.3Fe 91.7) xSi 1.5N 1.5Test portion, and carried out chemical composition analysis, constitute discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration, its result is as shown in figure 21.
In addition, experimental example 9 is in order to confirm that Fe amount+Co amount+Ti amount (x) and Fe amount+Co amount+Ti amount+Si measure (x+z) to formation, saturation magnetization (σ s) and anisotropy field (H mutually A) influence and the experiment carried out.
As shown in figure 21, when Fe amount+Co amount+Ti amount (x) less than 11 (test portion No.81,83,84,86), the not enough 140emu/g of saturation magnetization (σ s).Otherwise when x reached 13 (test portion No.85), α-Fe separated out in a large number, caused characteristic to reduce.In addition, even x is in 11～12.5 scope, x+z i.e. (mol ratio of mol ratio+Si of mol ratio+Ti of mol ratio+Co of Fe)/(mol ratio of mol ratio+R2 of R1) is 11.6 to be in 12 or when following (test portion No.82), although saturation magnetization (σ s) demonstrates 140emu/g or above value, anisotropy field (H A) but rest on 40kOe or following value.
With above-mentioned situation comparatively speaking, x surpasses 12 test portion No.75～80 at 11～12.8 scope and x+z and has 140emu/g or above saturation magnetization (σ s) and 50kOe or above anisotropy field (H A).
＜experimental example 10 〉
Consist of Nd to make with the same technological process of experimental example 7 0.95Zr 0.05(Ti yFe 100-y) 12Si 1.0N 1.5, Nd 0.95Zr 0.05(Ti yFe 100-y) 12Si 1.5N 1.5And Nd 0.95Zr 0.05(Ti yFe 100-y) 12Si 2.0N 1.5Test portion, and carried out chemical composition analysis, constitute discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration, its result is as shown in figure 22.
In addition, experimental example 10 be for confirm Ti amount (y) to constitute mutually, saturation magnetization (σ s) and anisotropy field (H A) influence and the experiment carried out.
In Si amount (z) is under the situation of the arbitrary numerical value among 1.5 and 2.0, if Ti amount (y) less than 5.0 is then separated out α-Fe and then separated out the 2-17 phase, simultaneously saturation magnetization (σ s) and anisotropy field (H A) rest on lower value (test portion No.94,99).On the other hand, be 12.5 to surpass at 12.3 o'clock in Ti amount (y), saturation magnetization (σ s) is reduced to not enough 130emu/g (test portion No.90).
With above-mentioned situation comparatively speaking, Ti amount (y) test portion No.87～89,91～93,95～98 in 5～12.3 scope become the homogeneous structure of 1-12 phase, in other words become the homogeneous structure of hard magnetic phase, and can access 140 or 150emu/g or above saturation magnetization (σ s) and 50 or 55kOe or above anisotropy field (H A).
＜experimental example 11 〉
Consist of Nd to make with the same technological process of experimental example 7 0.95Zr 0.05(Ti yFe 100-y) 12Si 1.0N vTest portion, and carried out chemical composition analysis, constitute discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration, its result is as shown in figure 23.
In addition, experimental example 11 be for confirm N amount (v) to constitute mutually, saturation magnetization (σ s) and anisotropy field (H A) influence and the experiment carried out.
As shown in figure 23, measure at N (v) be 0 o'clock, saturation magnetization (σ s) and anisotropy field (H A) all reductions (test portion No.100).
With above-mentioned situation comparatively speaking, N amount (v) test portion No.101～104 in 1～3 scope, become the homogeneous structure of 1-12 phase, in other words become the homogeneous structure of hard magnetic phase, and can access 140emu/g or above saturation magnetization (σ s) and 45 or 50kOe or above anisotropy field (H A).From saturation magnetization (σ s) and anisotropy field (H A) angle consider that the N amount (v) is preferably set to 0.5～2.7, further is preferably set to 1.0～2.5 scope.
＜experimental example 12 〉
Consist of Nd to make with the same technological process of experimental example 7 0.95Zr 0.05(Ti 8.3Fe 91.7-wCo w) 12Si 0.25N 1.5, Nd 0.95Zr 0.05(Ti 8.3Fe 91.7-wCo w) 12Si 1.0N 1.5Test portion, and carried out constituting discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration, its result is as shown in figure 24.
In addition, experimental example 12 be for confirm Co amount (w) to constitute mutually, saturation magnetization (σ s) and anisotropy field (H A) influence and the experiment carried out.
As shown in figure 24, be under the situation of the arbitrary numerical value among 0.25 and 1.0 in Si amount (z) as can be known, if Co amount (w) increases, then saturation magnetization (σ s) and anisotropy field (H A) raise, when being 20 left and right sides, peak value appears in its effect at w (Co amount).Therefore, take into account if also Co is cost an arm and a leg, then w (Co amount) be preferably set to 30 or below, more preferably be set at 10～25 scope.In addition, when w (Co amount) was in this scope, it was organized as the single-phase of 1-12 phase.
＜experimental example 13 〉
Use highly purified Nd, Zr, Fe, Ti and Si metal to be raw material, in Ar atmosphere, consist of Nd as alloy with the arc-melting legal system 0.95Zr 0.05(Ti 8.3Fe 91.7-wCo w) 12Si zTest portion.After then this alloy being pulverized with bruisher and being the screen cloth screening of 38 μ m, be that 1 μ m or following C powder mix mutually, in Ar atmosphere, keep 24 hours heat treatment 400～600 ℃ temperature with average grain diameter through mesh.For each test portion after the heat treatment, carry out chemical composition analysis, constituted the discriminating of phase, carried out saturation magnetization (σ s) and anisotropy field (H simultaneously A) mensuration.Its result as shown in figure 25.
As shown in figure 25,, also can access the homogeneous structure of 1-12 phase, can access 140 or 150emu/g or above saturation magnetization (σ s) and 40kOe or above anisotropy field (H simultaneously by adding C to replace N A).At this moment, the same effect of C and N performance.
＜experimental example 14 〉
For the variation of the magnetic characteristic confirming to cause with the Hf displacement owing to the part of Nd, the result of experiment of being carried out is expressed as experimental example 14.
Consist of Nd to make with the same technological process of experimental example 7 1-uHf u(Ti 8.3Fe 91.7) 12Si 1.0N 1.5Test portion, and carried out chemical composition analysis, constituted discriminating and the saturation magnetization (σ s) and the anisotropy field (H of phase A) mensuration.Its result as shown in figure 26.
As shown in figure 26, Hf and Zr have same effect as can be known.
[the 3rd embodiment]
In order to confirm the variation of c/a with Si content, the experimental result of being carried out (experimental example 15 and 16) is represented with the 3rd embodiment.
＜experimental example 15 〉
Use highly purified Nd, Fe, Ti and Si metal to be raw material, in Ar atmosphere, consist of Nd-(Ti as alloy with the arc-melting legal system 8.2Fe 91.8) 119-Si zAnd Nd-(Ti 8.3Fe 91.7) 12-Si zTest portion.After then this alloy being pulverized with bruisher and being the screen cloth screening of 38 μ m, in blanket of nitrogen, keep 100 hours heat treatment (nitrogenize) in 430～520 ℃ temperature through mesh.For each test portion after the heat treatment, carried out chemical composition analysis, constituted the discriminating of phase, simultaneously to have carried out saturation magnetization (σ s) and anisotropy field (H with the same condition of the 1st embodiment A) mensuration, its result is as shown in figure 27.
In addition, same with the 1st embodiment, carried out the discriminating that constitutes mutually according to the mensuration of X-ray diffraction and thermomagnetization curve.
As shown in figure 27, compare with 0.552 of the test portion No.129 that does not add Si as can be known, the magnetic characteristic of test portion No.121～126 that c/a is bigger is anisotropy field (H particularly A) be improved.But also have following tendency as can be known with reference to Figure 28: the lattice constant along with a axle is reduced to predetermined scope, anisotropy field (H on the one hand A) increase, and on the other hand, saturation magnetization (σ s) but decreases.In addition, Si measures more test portion No.131 when separating out α-Fe, its saturation magnetization (σ s) and anisotropy field (H A) all reduce.Moreover the saturation magnetization (σ s) that does not add the test portion No.130 of N is lower.In addition, but do not contain the test portion No.129 of Si and contain Si and do not contain saturation magnetization (σ s) and the anisotropy field (H of the test portion No.130 of N from containing N A) level as can be seen: saturation magnetization of test portion No.121 of the present invention～126 (σ s) and anisotropy field (H A) demonstrate value above intended scope, by contain simultaneously Si and N these two, its magnetic characteristic is significantly improved.
Figure 28 represents the test portion No.127 of Figure 27, the thermomagnetization curve of 128 and 132 composition, and there is Tc in test portion No.127,128 near 430 ℃ as can be known, can not confirm to have Tc in addition to exist.Therefore, test portion No.127,128 can be confirmed to be ThMn 12The homogeneous structure of phase.Test portion No.132 can confirm near 400 ℃ to exist and the 1st corresponding Tc, in addition, has 20% the magnetization that is equivalent to room temperature at 450 ℃.This shows that it is 450 ℃ or above magnetic phase that there is Tc in test portion No.132.When raising the mensuration temperature, near 770 ℃, lose magnetization, thereby can confirm the existence of the 2nd phase.Can confirm that from the result of this result and X-ray diffraction the 2nd is α-Fe mutually.
＜experimental example 16 〉
Obtain composition shown in Figure 29 equally with experimental example 15,, carried out saturation magnetization (σ s) and anisotropy field (H equally with experimental example 15 for said composition A) mensuration, carried out constituting the mensuration of phase simultaneously, its result is shown in Figure 29 in the lump.
As shown in figure 29, Fe+Ti amount (x) is Fe+Ti and test portion No.133～137 of ratio in 10～12.5 scope of R have obtained higher magnetic characteristic, saturation magnetization (σ s) be 120 130emu/g or more than, anisotropy field (H A) be 55kOe or more than.And are ThMn based on the composition of test portion No.133～137 12The homogeneous structure of phase.In contrast, the ratio of Fe+Ti and R is 12.7 test portion No.138, except ThMn 12Outside the phase compound, also confirm to have separating out of α-Fe.In addition, in test portion No.133～137, when the ratio of Fe+Ti and R reduces, although be organized as single-phase, saturation magnetization (σ s) and anisotropy field (H A) all reduce.According to this tendency, the ratio of Fe+Ti and R be preferably set to 10 or more than.
[the 4th embodiment]
More than shown in embodiment (the 1st embodiment～the 3rd embodiment) relate to hard magnetic composition, the 4th embodiment represents then to relate to the specific embodiment of permanent magnet powder.
＜experimental example 17 〉
To melt in Ar atmosphere by the raw material of following composition weighing and carry out chilling, the chilling condition is as follows.
Resulting alloy is laminar, and thickness is 20 μ m, with its in Ar atmosphere in 800 ℃ of heat treatments that keep 2 hours.
Then be crushed to the size that to pass through the screen cloth of 75 μ m with bruisher, to imposing nitrogen treatment through the powder of pulverizing.Nitridation conditions is: 400 ℃ * 64 hours, and N 2Air-flow (atmospheric pressure).
Form: Nd 1Fe 9.15Co 2.0Ti 0.85Si 0.2
Single-roller method (the material of roller: Cu)
Nozzle bore diameter: φ 1mm
Ejection gas pressure: 0.5kg/cm 2
Molten metal temperature: 1400 ℃
The peripheral speed of roller (Vs): 15,25,50 and 75m/s
For the test portion after thin slice behind the quench solidification (test portion) and the heat treatment, by means of the formation of XRD (X-Ray Diffractometer:X ray diffraction device) observation phase, its result such as Figure 30 and shown in Figure 31.In addition, Figure 30 represents the observed result of the test portion behind the quench solidification, and Figure 31 represents the observed result of the test portion after the heat treatment.
As shown in figure 30, the test portion that obtains with the peripheral speed (Vs) of the roller of 15m/s and 25m/s has been observed ThMn 12The peak of phase exists.In contrast, but do not observed ThMn with the resulting test portion of peripheral speed (Vs) of the roller of 50m/s and 75m/s 12The peak of phase exists, but the peculiar diffraction pattern of amorphous.
As shown in figure 31, after heat treatment, no matter any peripheral speed is all confirmed ThMn 12Be principal phase mutually.
Figure 32 is expressed as follows tissue (Transmission ElectronMicroscope: the result's of Guan Chaing photo transmission electron microscope), wherein said tissue is the tissue after heat-treating with the resultant test portion of the peripheral speed of the roller of 25m/s (Vs) by TEM.
Figure 33 is expressed as follows the photo of tissue by the result of tem observation, and wherein said tissue is the tissue after heat-treating with the resulting test portion of the peripheral speed of the roller of 75m/s (Vs).
As Figure 32 and shown in Figure 33, can confirm to present atomic thin crystal structure after the test portion heat treatment.But according to the difference of the peripheral speed (Vs) of roller, there is following difference in heat treatment on microstructure.With the resulting test portion of peripheral speed (Vs) of the roller of 25m/s, observe a lot of particle diameters and be the crystal about 25nm, maximum particle diameter is about 50nm.In comparison, with the resulting test portion of peripheral speed (Vs) of the roller of 75m/s, observe a lot of particle diameters and be the crystal about 10nm, maximum particle diameter is about 100nm.
Secondly, adopt VSM to measure behind the quench solidification, after the heat treatment and the magnetic characteristic of the test portion behind the nitrogen treatment (applies magnetic field: 20kOe).Its result as shown in figure 34.In addition, the N content of the test portion behind the nitrogen treatment is as follows.
During the peripheral speed of roller (Vs)=25m/s: 2.93wt%
During the peripheral speed of roller (Vs)=75m/s: 2.79wt%
As shown in figure 34, by after heat treatment, carrying out nitrogen treatment, can confirm that coercive force (Hcj) and remanent magnetization (σ s) all improve, and can access sufficient characteristic as permanent magnet powder.In addition, Figure 34 shows the measurement result for the magnetic characteristic of the powder of following comparative example in the lump, but coercive force (Hcj) and remanent magnetization (σ s) all rest on the value lower than embodiment.
Comparative example: raw materials weighing makes it to have the composition (Nd same with present embodiment 1Fe 9.15Co 2.0Ti 0.85Si 0.2), after high frequency fusion method fusing, be poured in the water-cooled Cu mold and make alloy (alloy thickness 10mm).After this alloy and embodiment pulverized with bruisher equally, still impose heat treatment and nitrogen treatment equally and obtain powder with present embodiment.
Secondly, for the powder (peripheral speed of roller (Vs) is 50m/s) that nitrogen treatment is crossed, the epoxy resin that mixes 3wt% also stirs, in the metal pattern of cylinder die cavity with φ 10mm with 6 tons/cm 2Forming pressure form, its formed body is imposed 4 hours cured and makes bonded permanent magnet at 150 ℃.Bonded permanent magnet with B-H plotter (tracer) measure magnetic characteristic (apply magnetic field: 25kOe), its result is as follows:
Br＝6700G、Hcj＝7980Oe、(BH) max＝8.5MGOe
＜experimental example 18 〉
Making imposes heat treatment and nitrogen treatment after having the quench solidification alloy of composition shown in Figure 35.In addition, the condition of its quench solidification, heat treatment and nitrogen treatment is as follows.The result of mensuration magnetic characteristic as shown in figure 35 behind the nitrogen treatment.
-quench solidification-
Single-roller method (the material of roller: Cu)
Nozzle bore diameter: φ 1mm
Ejection gas pressure: 0.5kg/cm 2
Fusion temperature: 1400 ℃
The peripheral speed of roller (Vs): 50m/s
-heat treatment-
In Ar atmosphere, kept 2 hours in 800 ℃.
-nitrogen treatment-
At N 2Kept 64 hours in 400 ℃ in the air-flow (atmospheric pressure).
As shown in figure 35, can confirm: imposing nitrogen treatment after the heat treatment is effective for the permanent magnet powder that obtains possessing high magnetic characteristic.
According to the present invention, using under the situation of Nd as rare earth element, also can generate ThMn easily even provide 12The hard magnetic composition of phase.Especially, according to the present invention,, also can access by ThMn even Nd is 100 moles of % 12The homogeneous structure of phase, the hard magnetic composition that in other words constitutes by the homogeneous structure of hard magnetic phase.
In addition, according to the present invention, in intermetallic compound, there are Si that makes the contraction of lattice anisotropy ground and the N that lattice is isotropically expanded as interstitial atom, and R is about 12 with the ratio of T, rely on such intermetallic compound, can access the hard magnetic composition of all higher homogeneous structure of saturation magnetization and anisotropy field.
Moreover, according to the present invention, using under the situation of Nd as rare earth element, also can generate ThMn easily even can provide 12The permanent magnet powder of phase and manufacture method thereof.And, can access the bonded permanent magnet that uses such permanent magnet powder according to the present invention.

Claims (30)

1. hard magnetic composition, it is characterized in that: described hard magnetic composition is by general formula R (Fe 100-y-wCo wTi y) xSi zA vConstitute, and the mol ratio of described general formula satisfies: x=10～12.5, y=(8.3-1.7 * z)～12.3, z=0.1～2.3, v=0.1～3, w=0～30, (Fe+Co+Ti+Si)/R＞12 simultaneously,
In above-mentioned general formula, at least a kind element of R for selecting among the rare earth element, wherein rare earth element is the notion that contains Y, simultaneously 50 moles of % of R or above be Nd, A is N and/or C.
2. hard magnetic composition according to claim 1 is characterized in that: described hard magnetic composition is by having ThMn 12The homogeneous structure of the phase of type crystal structure constitutes.
3. hard magnetic composition according to claim 1 is characterized in that: 70 moles of % of described R or abovely be Nd.
4. hard magnetic composition according to claim 1 is characterized in that: the part of described R is replaced with Zr and/or Hf.
5. hard magnetic composition, it is characterized in that: described hard magnetic composition is by general formula R 1 1-uR2 u(Fe 100-y-wCo wTi y) xSi zA vConstitute, and the mol ratio of described general formula satisfies: u=0.18 or following, y=4.5～12.3, x=11～12.8, z=0.1～2.3, v=0.1～3, w=0～30, (Fe+Co+Ti+Si)/(R1+R2)＞12 simultaneously,
In above-mentioned general formula, at least a kind element of R1 for selecting among the rare earth element, wherein rare earth element is the notion that contains Y, simultaneously 50 moles of % of R1 or above be Nd, R2 is Zr and/or Hf, A is N and/or C.
6. hard magnetic composition according to claim 5 is characterized in that: described hard magnetic composition contains ThMn 12Type crystal structure.
7. hard magnetic composition according to claim 5 is characterized in that: described u is 0.04～0.06.
8. hard magnetic composition according to claim 1 or 5, it is characterized in that: described A is N.
9. hard magnetic composition according to claim 1 or 5, it is characterized in that: described x is 11～12.5.
10. hard magnetic composition according to claim 1 or 5, it is characterized in that: described z is 0.2～2.0.
11. hard magnetic composition according to claim 1 or 5, it is characterized in that: described v is 0.5～2.5.
12. hard magnetic composition according to claim 1 or 5, it is characterized in that: described w is 10～25.
13. hard magnetic composition, it is characterized in that: described hard magnetic composition is made up of R-Ti-Fe-Si-A compound or R-Ti-Fe-Co-Si-A compound, and the homogeneous structure by the hard magnetic phase constitutes, its saturation magnetization σ s be 120emu/g or more than, anisotropy field H AFor 30kOe or more than,
In above-mentioned general formula, at least a kind element of R for selecting among the rare earth element, wherein rare earth element is the notion that contains Y, simultaneously 80 moles of % of R or above be Nd, A is N and/or C.
14. hard magnetic composition according to claim 13 is characterized in that: described hard magnetic is to have ThMn mutually 12The phase of type crystal structure.
15. hard magnetic composition according to claim 13 is characterized in that: described anisotropy field H AFor 40kOe or more than.
16. hard magnetic composition according to claim 13 is characterized in that: described saturation magnetization σ s be 130emu/g or more than.
17. hard magnetic composition, it is characterized in that: described hard magnetic composition is the homogeneous structure formation of about 1: 12 intermetallic compound by the mol ratio of R and T, and Si and A are present between the crystal lattice of described intermetallic compound as the clearance type element, wherein, the at least a kind element of R among rare earth element, selecting, described rare earth element is the notion that contains Y, T be with Fe and Ti serve as must composition transition metal, A is N and/or C.
18. hard magnetic composition according to claim 17 is characterized in that: when the ratio with the lattice constant of the lattice constant of the c axle of the crystal lattice of described intermetallic compound and a axle be made as c1/a1, will based on U.S.'s test and materialogy can ASTM ThMn 12When the ratio of the lattice constant of the c axle of the crystal lattice of type compound and the lattice constant of a axle is made as c2/a2, then c1/a1＞c2/a2, wherein c2/a2=0.558.
19. hard magnetic composition according to claim 17 is characterized in that: make lattice produce anisotropic contraction by Si, and A makes lattice produce isotropic expansion, obtain c1/a1＞c2/a2.
20. hard magnetic composition according to claim 17 is characterized in that: the mol ratio of R and T is 1: 10～1: 12.5.
21. a permanent magnet powder is characterized in that: described magnet powder is by general formula R (Fe 100-y-wCo wTi y) xSi zA vConstitute; And be that the aggregation of 200nm or following particle is formed by average crystal grain diameter; And the composition that described magnet powder has is, the mol ratio of described general formula satisfies: x=10～12.8, y=(8.3-1.7 * z)～12.3, z=0.1～2.3, v=0.1～3, w=0～30, (Fe+Co+Ti+Si)/R＞12 simultaneously;
In above-mentioned general formula, at least a kind element of R for selecting among the rare earth element, wherein rare earth element is the notion that contains Y, simultaneously 50 moles of % of R or above be Nd, A is N and/or C.
22. permanent magnet powder according to claim 21 is characterized in that: described particle is to have ThMn 12Type crystal structure as principal phase.
23. permanent magnet powder according to claim 21 is characterized in that: described particle is in fact by having ThMn 12The homogeneous structure of the phase of type crystal structure constitutes.
24. permanent magnet powder according to claim 21 is characterized in that: Nd account for R 70 moles of % or more than.
25. the manufacture method of a permanent magnet powder is characterized in that: at first make by general formula R (Fe 100-y-wCo wTi y) xSi zConstitute and be implemented the powder of quench solidification processing, the composition that wherein said powder has is, the mol ratio of described general formula satisfies: x=10～12.8, y=(8.3-1.7 * z)～12.3, z=0.1～2.3, w=0～30, (Fe+Co+Ti+Si)/R＞12 simultaneously; Secondly, described powder temperature range in 600～850 ℃ in inert atmosphere is imposed the heat treatment that kept 0.5～120 hour; Then, impose nitrogen treatment or carbonization treatment to being implemented described heat treated described powder,
In above-mentioned general formula, at least a kind element of R for selecting among the rare earth element, wherein rare earth element is the notion that contains Y, simultaneously 50 moles of % of R or above be Nd.
26. the manufacture method of permanent magnet powder according to claim 25 is characterized in that: be implemented the described powder that described quench solidification is handled, it is organized as any among the mixed phase of amorphous phase, amorphous phase and crystalline phase or the crystalline phase.
27. the manufacture method of permanent magnet powder according to claim 25 is characterized in that: described quench solidification is handled and is adopted single-roller method to carry out, and the peripheral speed of employed roller is 10～100m/s.
28. the manufacture method of permanent magnet powder according to claim 25 is characterized in that: described heat treatment is to make the amorphous phase crystallization, perhaps adjusts the particle diameter of the crystal grain that constitutes crystalline phase.
29. a bonded permanent magnet, it possesses permanent magnet powder and the resin that makes described permanent magnet powder bonding mutually, and described bonded permanent magnet is characterised in that: the hard magnetic particle of crystalline that constitutes described permanent magnet powder is by general formula R (Fe 100-y-wCo wTi y) xSi zA vConstitute, and the composition that has is that the mol ratio of described general formula satisfies: x=10～12.8, y=(8.3-1.7 * z)～12.3, z=0.1～2.3, v=0.1～3, w=0～30, (Fe+Co+Ti+Si)/R＞12 simultaneously,
In above-mentioned general formula, at least a kind element of R for selecting among the rare earth element, wherein rare earth element is the notion that contains Y, simultaneously 50 moles of % of R or above be Nd, A is N and/or C.
30. bonded permanent magnet according to claim 29 is characterized in that: the average crystal grain diameter of described hard magnetic particle is 200nm or following.
CNB2004800013769A 2003-01-28 2004-01-28 Hard magnetic composition, permanent magnet powder, method for permanent magnet powder, and bonded magnet Expired - Fee Related CN100334656C (en)

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