WO1992013353A1 - Aimant a base de terres rares, de fer et de bore et a base de terres rares de fer, de cobalt et de bore ayant des proprietes anisotropes - Google Patents

Aimant a base de terres rares, de fer et de bore et a base de terres rares de fer, de cobalt et de bore ayant des proprietes anisotropes Download PDF

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WO1992013353A1
WO1992013353A1 PCT/JP1992/000073 JP9200073W WO9213353A1 WO 1992013353 A1 WO1992013353 A1 WO 1992013353A1 JP 9200073 W JP9200073 W JP 9200073W WO 9213353 A1 WO9213353 A1 WO 9213353A1
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atomic
anisotropic magnet
hot
anisotropic
rare earth
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PCT/JP1992/000073
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English (en)
Japanese (ja)
Inventor
Takuo Takeshita
Ryoji Nakayama
Yoshinari Ishii
Tamotsu Ogawa
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Mitsubishi Materials Corporation
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Priority claimed from JP3060828A external-priority patent/JP2773444B2/ja
Priority claimed from JP03060833A external-priority patent/JP3092672B2/ja
Priority claimed from JP03060837A external-priority patent/JP3092673B2/ja
Priority claimed from JP06086091A external-priority patent/JP3196224B2/ja
Application filed by Mitsubishi Materials Corporation filed Critical Mitsubishi Materials Corporation
Priority to EP92903728A priority Critical patent/EP0522177B2/fr
Priority to DE69203405T priority patent/DE69203405T3/de
Publication of WO1992013353A1 publication Critical patent/WO1992013353A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0573—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes obtained by reduction or by hydrogen decrepitation or embrittlement

Definitions

  • the present invention provides an R having excellent magnetic anisotropy and a small temperature coefficient of coercive force (where R represents at least one rare earth element containing Y).
  • R represents at least one rare earth element containing Y.
  • Anisotropic magnets more specifically, from hot-press moldings or hot isostatic press moldings. Background technology for anisotropic magnets
  • Japanese Unexamined Patent Publication No. Hei. 1-132106 discloses that an R-Fe-B-based permanent magnet powder obtained by hydrotreating an R-Fe-B-based master alloy is provided. It describes R-Fe-Co-B permanent magnet powder obtained by hydrogenating R-Fe-Co-B-based master alloy.
  • the R - F e - B based permanent magnet powder is a ferromagnetic phase der Ru R s F e 14 B type intermetallic compound phase (? Hereinafter, will have an R 2 F e 4 B-type phase) and a main phase R — Fe — B-based master alloy is used as a raw material, and this mother alloy raw material is heat-treated in an H 2 atmosphere within a predetermined temperature range, and each phase of RH X , Fe 2 B, and the remaining Fe is after prompting the phase transformation, collected material or et of H 2 with deionized H 2 steps As a result, an R 2 Fe 14 B-type phase, which is a ferromagnetic phase, was again formed, and the resulting R — Fe — B-based permanent magnet powder was obtained.
  • the microstructure is a texture mainly composed of a recrystallized microstructure of an extremely small R 2 Fe B type phase having an average particle size of 0.05 to 3 / m.
  • the R - F e - C o - B based permanent magnet powder likewise strongly magnetic phase der Ru R 2 (F e, C o ) 14 B type intermetallic compound phase (hereinafter, R a (F e, C o)
  • the main phase is an R-F e —C o —B-based master alloy with a main phase of 14 B), which is the same as the R-F e —B-based alloy described above.
  • the average grain size is from 0.05 to 301, and the texture becomes a texture mainly composed of the recrystallized microstructure of the fine R 2 (Fe, Co) t 4 B phase. ing.
  • R — F 6 — 8 series 11-? e-Co-B-based permanent magnet powder is not hot-pressed into a hot-blow molded body, but sufficient magnetic anisotropy cannot be obtained.
  • the hot-press molded body is subjected to a hot rolling process such as a hot rolling process to form a rolled structure.
  • R 2 F e i4 B Kashiwaa Ru have causes the E direction the C axis R 2 (F e, C o ) i 4 B -type phase crystal grains, the magnetic anisotropy Was improved.
  • the R-Fe-B and R-Fe-Co-B rolled magnets obtained by further hot rolling the hot pressed compacts are:
  • the temperature coefficient of the coercive force is increased compared to a magnet that has been hot-brushed with magnet powder, and these rolled magnets are incorporated into motors, etc. In such a case, the performance of the motor and the like was changed by the change in temperature, and there were problems such as lack of stability.
  • the present inventors have considered from the viewpoint that the increase in the temperature coefficient of the coercive force is caused by hot rolling of a hot-press molded body. If a magnet with excellent magnetic anisotropy can be obtained without hot rolling, a study was conducted based on the recognition that an increase in the temperature coefficient of coercive force would not occur.
  • the R—Fe—B and R—Fe—Co—B anisotropic magnets of the present invention have been obtained. Disclosure of the invention
  • the first anisotropic magnet according to the present invention includes R: 10 to 20 at%, B: 3 to 20 at%, and one of Ga, Zr, and Hi. Or a total of two or more of them: a hot-press compact or a composition containing from 0.001 to 5.0 atomic%, with the balance being Fe and unavoidable impurities.
  • An R-Fe—B-based anisotropic magnet which is a hot isostatic press molded body (hereinafter, referred to as a HIP molded body), and is a hot press molded body or a hot press molded body.
  • the HIP compact has an average grain size of Rs Fei 4 B type intermetallic compound having a tetragonal structure as a main phase: a texture of crystal grains having a size of 0.05 to 20 zm.
  • Each of the individual grains having 50% by volume or more of the total grains constituting It is characterized in that the value of the ratio b / a of the short particle size a to the longest particle size b is less than 2.
  • the first anisotropic magnet has a small temperature coefficient of coercive force, has little variation in magnetic anisotropy depending on the location, and has excellent corrosion resistance compared to conventional rolled magnets. ing.
  • R - F e - B system anisotropic magnet in order to have a grain texture, near R 2 F e 14 B type compound composition, i.e. R 1 1. 8 F e ba i B 5.9 (atomic%) Excellent magnetic anisotropy and high coercive force near the composition.
  • composition of the first R—Fe′—B system anisotropic magnet described above includes one, two or more of Al, V, and Si: 0.01 to 2.0. Atomic% may be further added. In this case, the maximum energy product is further improved, and a more remarkable magnetic anisotropy is exhibited, and the temperature coefficient of the coercive force is reduced.
  • a R-Fe-B master alloy is produced having a predetermined composition and containing.
  • the R—Fe—B-based master alloy is heated in a hydrogen gas atmosphere, and the temperature is from 500 to 100: 000, and inert with hydrogen gas or hydrogen gas. After heat treatment in a mixed gas atmosphere, temperature: 500 to 100 ° C, hydrogen gas pressure: ltorr or less, or hydrogen gas partial pressure: 1 torr In the following inert gas atmosphere Dehydrogenation treatment is carried out to obtain R-Fe-B-based permanent magnet powder having excellent magnetic anisotropy and corrosion resistance by cooling.
  • a heat treatment step at 300-1000 R-Fe-B-based permanent magnet powder with even better magnetic anisotropy and corrosion resistance can be obtained. Can be manufactured.
  • the structure of the R-Fe-B permanent magnet powder produced as described above has no impurities or strains in the grains and at the grain boundaries.
  • the average crystal grain size of the recrystallized grains constituting this recrystallized texture should suffice to be in the range of 0.05 to 20 m. More preferably, it is in the range of 0.05 to 3 mm, which is close to 3 m).
  • the individual recrystallized grains having the above dimensions preferably have a shape in which the ratio of the shortest particle size a to the longest particle size b is b / a ⁇ 2, and thus have this shape.
  • the recrystallized grains need to be present in an amount of 50% by volume or more of the total recrystallized grains in the structure of each powder. Since the ratio b / a of the shortest particle size a to the longest particle size b has a recrystallized grain shape smaller than 2, the coercive force of the R-Fe-B system permanent magnet powder Is improved, and the temperature coefficient ai Hc of the coercive force in the range of 25 eC to 100 ° C becomes smaller than -0.6% / ° C.
  • the R-Fe-B-based permanent magnet powder is compacted in a magnetic field to form a green compact, and the green compact is heated at a temperature of 600 to 900 ° C.
  • R-Fe-B system anisotropy that maintains the excellent characteristics of the R-Fe-B system permanent magnet powders as described above by performing torpess or HIP. Magnets can be manufactured.
  • the coercive force can be improved by performing heat treatment at 300 to 100 as necessary. I can do it.
  • the sintering temperature is generally high, so that fine recrystallized grains of R-Fe-B permanent magnet powder grow and become large. This is not preferable because the magnetic properties, especially the coercive force, are reduced. Therefore, it is not preferable to adopt a normal sintering method as a method for producing the R—Fe—B system anisotropic magnet of the present invention, and the sintering is performed at a relatively low temperature. It is necessary to adopt the hot-bless method or the HIP method, which can be combined, to suppress the growth of crystal grains. Also, since the application of magnetic anisotropy is performed by molding in a magnetic field, it is not necessary to perform hot plastic working after hot pressing or HIP.
  • R is Nd, Pr, Tb, Dy, La, Ce, Ho, Er, Eu, Sm, Gd, Tm, Yb, Lu, and Y
  • One or two or more elements, generally consisting mainly of Nd, and used by adding other rare earth elements to them, especially Tb, Dy and P r has the effect of improving the coercive force iHc.
  • Anisotropic magnets with an R content lower than 10 atomic% or higher than 20 atomic% Coercive force is reduced, and excellent magnetic properties cannot be obtained. Therefore, the content of R is set at 10 to 20 atomic%.
  • the B content is lower than 3 atomic% or higher than 20 atomic%, the coercive force of the anisotropic magnet is reduced, and excellent magnetic properties cannot be obtained.
  • the amount was determined to be 3 to 20 atomic%. It is also possible to replace part of B with one or more of C, N, 0, P, and F, as described in the second to fourth sections below. The same applies to anisotropic magnets.
  • G a, Z r and H i have the effect of improving the coercive force and stably imparting excellent magnetic anisotropy and corrosion resistance. If the total content of one or more of Zr and Hf is less than 0.01 atomic%, the desired effect cannot be obtained, while 5.0 atomic% is not obtained. If contained in excess, the magnetic properties will be degraded. Therefore, the total content of one, two or more of Ga, Zr and Hf is set to 0.001 to 5.0 atomic%.
  • a 1, V and Si are added as necessary as components of the R—Fe—B anisotropic magnet. These have the effect of improving the coercive force, but if the total content of one or more of AI, V and Si is less than 0.01 atomic%, The desired effect cannot be obtained. On the other hand, if the content exceeds 2.0 atomic%, the magnetic properties are lowered. Therefore, it is desirable that the total content of one, two or more of Al, V and Si is 0.01 to 2.0 atomic%.
  • the average crystal grain size of the crystal grains constituting the structure of the anisotropic magnet is smaller than 0.05 ⁇ m, magnetization becomes difficult, which is not preferable. Larger values are not preferred because the coercive force and the squareness of the hysteresis loop decrease, and the temperature coefficient of the coercive force increases. Therefore, the average grain size was set to 0.05 to 20 m. More preferably, the average crystal grain size is 0.05 to 3 #m, which is close to the size of a single magnetic domain grain size (0.3 m).
  • the individual crystal grains preferably have a shape in which the ratio of the shortest particle size a to the longest particle size b is a 2 and the crystal grains having this shape are 50% by volume of all the crystal grains. It must exist.
  • the second anisotropic magnet according to the present invention includes R: 10 to 20 atomic%, B: 3 to 20 atomic%, and Ti, V, Nb, Ta, A 1, and the like. Total of one or more of Si and Si: 0.0001 to 5.0 atomic%, with the balance being Fe and unavoidable impurities.
  • An R-Fe-B based anisotropic magnet which is a hot-press molded article or a HIP molded article.
  • the P compact has an average particle diameter of R 2 Fe, 4B type intermetallic compound having a tetragonal structure as a main phase: a crystal grain having a size of 0.05 to 20 / m.
  • Each of the individual crystal grains having the texture 5 and having a volume fraction of 50% by volume or more of all the crystal grains constituting the texture has a value b Z a of the ratio of the shortest particle diameter a to the longest particle diameter b. It is less than two.
  • the same excellent effects as those of the first anisotropic magnet can be obtained in the second R-Fe-B anisotropic magnet.
  • the second anisotropic magnet In order to manufacture the second anisotropic magnet, first, a specified material containing one or more of Ti, V, Nb, Ta, A1 and Si is required.
  • the R-Fe-B system master alloy having the following component composition is melted and formed, and then the same process as the first anisotropic magnet described above may be performed using this raw material. .
  • T i, V, Nb, T a, A 1 and S i one or more of these elements are used for R-Fe-B anisotropic magnets.
  • the effect of improving the coercive force and stably imparting excellent magnetic anisotropy and corrosion resistance can be obtained. If the total content is less than 0.001 at%, the desired effect cannot be obtained. On the other hand, if the total content exceeds 5.0 at%, the magnetic properties deteriorate. Therefore, the total content of one or more of Ti, V, Nb, Ta, AI and Si is 0.001 to 5.0 atomic%. I decided.
  • the third anisotropic magnet according to the present invention comprises: R: 10 to 20 atomic%, Co: 0 .:!
  • R-Fe-Co-B type anisotropic magnet which is a hot press molded article or a HIP molded article having Or, the HIP compact has an average particle size of 0.05 to 20 m with a main phase of R 2 (F e, C o) 14 B type intermetallic compound having a tetragonal structure.
  • Each crystal grain having a texture of 50% by volume or more of all the grains constituting the above texture has a ratio b between the shortest grain size a and the longest grain size b.
  • the value of Z a is less than 2 o
  • This third anisotropic magnet also has a small temperature coefficient of coercive force, similar to the first and second anisotropic magnets, and has a smaller magnetic anisotropy depending on the location than a conventional rolled magnet. It has almost no variation and excellent corrosion resistance.
  • the composition is close to the composition of the R 2 ( Fe, Co ) type compound, that is, the composition of R tl . 8 ( Fe, Co ) bel B 5.9 (atomic%). However, it has excellent magnetic anisotropy and high coercive force.
  • the composition of the third anisotropic magnet further includes a total of one or more of Al, V and Si: 0.01 to 2.0 atomic%. It may be added. In that case, the maximum energy product is further improved.
  • the R—Fe—Co—B system master alloy is heated in a hydrogen gas atmosphere, and the temperature is set to 500 to 100000. After heat treatment in a mixed atmosphere of inert gas and inert gas, the temperature is from 500 to 10000.
  • Hydrogen gas pressure Vacuum atmosphere of less than l Torr or hydrogen gas partial pressure: Inert gas of less than 1 Torr. Dehydrogenate until the atmosphere becomes lower, then cool.
  • R-Fe-C0-B permanent magnet powder is manufactured.
  • the structure of the R-Fe-Co-B-based permanent magnet powder produced as described above is free from impurities and strains in the grains and at the grain boundaries.
  • C o Consists of a recrystallized texture in which recrystallized grains of the 14 B-type intermetallic compound phase are aggregated. It is sufficient if the average recrystallized grain size of the recrystallized grains constituting this recrystallized texture is in the range of 0.05 to 20 #m. 3 m) and more preferably in the range of 0.05 to 3 m.
  • the individual recrystallized grains having the above-mentioned dimensions preferably have a shape in which the ratio of the shortest particle size a to the longest particle size b is t> / a ⁇ 2, and the recrystallized grains having this shape
  • the grains must be present in at least 50% by volume of the total recrystallized grains of the individual powder braid. Since the ratio t »Z a of the shortest particle size a to the longest particle size b has a shape of recrystallized grains smaller than 2, R-Fe-Co-B-based permanent magnet powder
  • the coercive force of the steel is improved and 25.
  • the temperature coefficient ai He of the coercive force at C ⁇ 100 becomes smaller than -0.6% noC.
  • the recrystallized microstructure of the R—Fe—Co—B permanent magnet powder produced in this manner is substantially identical to that of R 2 Fe—Co—B, which has almost no grain boundary phase.
  • (F e, C o) 14 Re-crystallized aggregate composed only of B-type intermetallic compound phase the magnetization value can be increased by the absence of grain boundary phase.
  • corrosion that progresses through grain boundaries is prevented, and since there is no stress strain due to hot plastic working, the possibility of stress corrosion is also reduced. And the corrosion resistance is improved.
  • the R-Fe-Co-B permanent magnet powder is compacted in a magnetic field to form a green compact, and the green compact is heated to a temperature of 600.
  • the excellent characteristics of the above R-Fe-Co-B permanent magnet powder are maintained as they are.
  • T R — F e — Co — B Anisotropic magnets can be manufactured.
  • the coercive force can be improved by performing a heat treatment at a temperature of 300 to 100 as necessary.
  • the sintering temperature is generally low, and fine recrystallized grains of the R-Fe-Co-B-based permanent magnet powder grow and become large. This is not preferred because of the poor crystal grain size and reduced magnetic properties, especially the coercive force. Also, since the application of magnetic anisotropy is performed by molding in a magnetic field, it is not necessary to perform hot plastic working after hot pressing and HIP.
  • the content of Co by adding Co to the composition of the anisotropic magnet, the coercive force and magnetic temperature characteristics of the anisotropic magnet (e.g., This has the effect of improving corrosion resistance, but if the content is less than 0.1 atomic%, this effect cannot be obtained. On the other hand, 50 atomic% Exceeding this value is not preferred because the magnetic properties are degraded. Therefore, the content of Co was set to 0.1 to 50 atomic%. If the content of Co is 0 :: to 20 atomic%, the coercive force becomes the highest, so that Co: 0 ::! More preferably, it is set to 20 at%.
  • the fourth anisotropic magnet according to the present invention comprises: R: 10 to 20 atom, Co: 0.1 to 50 atom%, B: 3 to 20 atom%, and Ti, V , Nb, Ta, Al, and Si in total of one or more: 0.001 to 5.0 atomic%, with the remainder Fe and R-Fe-Co-B anisotropic magnet, which is a hot-blow molded body or a HIP molded body having a composition consisting of
  • the compacts or HIP compacts have an average particle size of 0.05 to 20 #m, mainly composed of R 2 (Fe, Co) type intermetallic compound having a tetragonal structure.
  • Each of the individual grains having a texture of crystal grains having a size and at least 50% by volume of all the crystal grains constituting the texture has a ratio bZ of the shortest grain size a to the longest grain size b.
  • the fourth anisotropic magnet also has a small temperature coefficient of coercive force, similar to the above-described first to third anisotropic magnets, and has a different magnetic field depending on the location as compared with a conventional rolled magnet. Almost no anisotropy and excellent corrosion resistance, and due to the crystal texture, the composition around the R 2 (Fe, Co) type compound R lt . 8 (F e, Co) repeal ⁇ 1 B 5
  • the fourth anisotropic magnet In order to manufacture the fourth anisotropic magnet, first, a predetermined material containing one or more of Ti, V, Nb, Ta, A1 and Si is used. A R-Fe-Co-B system master alloy having a component composition is melt-processed, and the raw material is used. Thereafter, the same treatment as that for the third anisotropic magnet is performed. Just do it.
  • R, B, Co, the average crystal grain size and the crystal grain shape among the component compositions of the anisotropic magnet of the present invention are limited as described above is that the third anisotropic magnet is used. This is exactly the same as in the case of.
  • the reason for limiting the total amount of T i, V, Nb, T a, A 1, and S i is completely the same as that of the second anisotropic magnet.
  • the fourth anisotropic magnet has at least one kind of Ni, Cu, Zn, Ga, Ge, Zr, Mo, Hf, W. It has excellent magnetic anisotropy and corrosion resistance even if it contains 1 to 5.0 atomic%.
  • the first to fourth anisotropic magnets according to the present invention were manufactured as described below, and the performance was examined.
  • the above raw material alloy was heated from room temperature to 830 in a hydrogen atmosphere of 1 atm, heat-treated in a hydrogen atmosphere maintained at 830 and held for 4 hours, and then vacuumed at 830 ° C. Degree: 1 X 10-1 Torr or less Immediately after dehydrogenation, argon gas was introduced and quenched. After the completion of this hydrogen treatment, it was 650 in argon gas. C heat treatment was performed. The obtained raw material alloy was lightly pulverized in a mortar to obtain R-Fe-B permanent magnet powder having an average particle size of 50 / zm.
  • R-Fe-B permanent magnet powders are pressed in a magnetic field of 25 KOe to produce green compacts, and these green compacts are heated to a temperature of: Hot pressing was performed under the conditions of 720 and a pressure of 1.5 Ton / cm 2 . Further, by heat-treating these compacts in vacuum at 62 ° C. for 2 hours, the R—Fe-B based anisotropic magnets 1 to 26 of the present invention and the comparative R were obtained. — F e — B type anisotropic magnets 1 to 12 were obtained. The green compact formed in the magnetic field was hot-placed by placing the se so that the direction of E coincided with the direction of the hot-brace.
  • R-Fe-B permanent magnet powder manufactured from an alloy ingot that does not contain any of Ga, Zr, and Hf is filled and sealed in a copper can in vacuum.
  • a conventional R-Fe-B based anisotropic magnet 1 was obtained.
  • the present invention R-Fe-B based anisotropic magnets 1 to 26 obtained as described above, comparative R-Fe-B based anisotropic magnets 1 to 12 and conventional R-F Tables 1 to 3 show the component compositions of the e-B anisotropic magnet 1.
  • the present invention R-Fe-B anisotropic magnets 1 to 26 having the component compositions shown in Tables 1 to 3 and Comparative R-Fe-B-based anisotropic magnet 1 1 and the conventional R-Fe-B anisotropic magnet 1, the average grain size and the longest grain size of each crystal grain are 2
  • the abundance (volume%) of small-sized crystal grains, temperature coefficient of coercive force ⁇ i H c, and magnetic properties were measured. Tables 4 to 6 show these measured values.
  • the coercivity temperature coefficient ai H c is, 2 5 ° that put the C coercivity i H c 25 Contact good beauty 1 0 0 ° C in contact only that coercivity i H c, the beta ⁇ measured, the coercive force the percentage difference (i H c tee- i H c 25) / i H c 25 Ru value der was Tsu divided by the temperature difference 7 5 ° C a.
  • R_Fe-B-based permanent magnet powder containing one or more of Ga, Zr, and Hi of the present invention was magnetized.
  • R-Fe-B anisotropic magnets obtained by hot pressing the green compact obtained by press forming have magnetic properties, especially maximum energy product (BH), It is clear that ⁇ and the residual magnetic flux density B r are excellent, and the magnetic anisotropy is excellent.
  • comparative anisotropic magnets that do not include Ga, Zr, and Hf at all, and comparative anisotropic magnets that do not satisfy the requirements of the present invention have magnetic properties and Low magnetic anisotropy.
  • the anisotropic magnet of the present invention has almost the same magnetic properties as the conventional anisotropic magnet obtained by drawing, but has a temperature coefficient of coercive force ai He of 10%. . Five % . You can see that it is much smaller than C.
  • R-Fe-B-based alloys containing one or more of Ga, Zr and Hf obtained by high-frequency melting and forging contain A Various alloy ingots with a component composition including one or more of 1, V, and Si were prepared, and these ingots were each used as an ingot. In a gas atmosphere, temperature: 1130. C. After homogenization under the condition of holding for 30 hours, the homogenized ingot was crushed to about 20 mm square to obtain a raw material alloy.
  • This raw material alloy is heated from room temperature to 850 ° C in a hydrogen atmosphere at 1 atm, heat-treated in a hydrogen atmosphere maintained at 850 for 30 minutes, and then heated at 850 ° C.
  • R-Fe-B-based permanent magnet powders were molded in a magnetic field to produce a compact, and the compact was vacuum-filled and sealed in a stainless steel container. Temperature: 700. C, pressure: HIP was applied under the condition of 1.8 Ton / cm 2 , and the R-Fe-B anisotropic magnets 27-36 of the present invention and the comparative R-Fe-B anisotropic magnet were obtained. Magnets 13 to 15 were fabricated.
  • Table 7 shows the component compositions of the R-Fe-B anisotropic magnets 27 to 36 of the present invention and comparative R-Fe-B anisotropic magnets 13 to 15 described above.
  • the average crystal grain size of these anisotropic magnets, the abundance (volume%) of crystal grains having a value of the maximum grain size Z and the shortest grain size of each crystal grain smaller than 2 were determined by the above-described measurement.
  • Coercivity temperature coefficient ai Hc, magnetic properties Table 8 shows the measurement results.
  • R-F e-B 1 4 0.50 -0.51 11.0 10.3 21.3
  • the second anisotropic magnet according to the present invention was manufactured as follows, and the performance was examined.
  • This raw material alloy was heated from room temperature to 840 ° C in a hydrogen atmosphere at 1 atm, heat-treated in a hydrogen atmosphere maintained at 840 for 1 hour, and then heated at 830 Vacuum degree: Dehydrogenation was performed until the pressure became less than lxl O ⁇ Torr, and then argon gas was introduced immediately to cool rapidly. After the completion of this hydrogen treatment, a heat treatment was performed in vacuum for 6 hours for 2 hours. The obtained raw material alloy is lightly pulverized in a mortar and the average particle size
  • the obtained magnet powder was press-formed in a magnetic field of 25 KOe to produce green compacts, and these green compacts were subjected to a temperature of 730 * C and pressure. : 1. 5 T on / cm 2 of Ho Tsu door Breakfast Les vinegar, Oh Ru stomach temperature
  • R — Fe produced from an alloy ingot that does not contain any of Ti, V, Nb, Ta, Al, and Si -Fill the B-based permanent magnet powder in a copper can in a vacuum, heat it at 700, and roll it several times until the rolling rate reaches 80%, to obtain the conventional anisotropic magnet 2.
  • the average crystal grain size of each anisotropic magnet and the abundance (capacity%) of crystal grains in which the value of the longest grain size of each crystal grain is less than 2 The temperature coefficient ai He of the coercive force was measured, and these measured values are shown in Tables 15 to 19.
  • the method of calculating the coercive force temperature coefficient i He is the same as described above.
  • the magnetic field containing one or more of Ti, V, Nb, Ta, A1, and Si was used.
  • the anisotropic magnets 37 to 78 of the present invention obtained by subjecting the formed green compact to hot pressing or HIP have magnetic properties, especially the maximum energy product ( BH) Be x and residual magnetic flux density Br are excellent, and have magnetic anisotropy characteristics equal to or better than those of the conventional anisotropic magnet 2 obtained by rolling.
  • the temperature coefficient ai He of the coercive force is much smaller than that of the anisotropic magnet 2.
  • the specific anisotropic magnets 16 to 29 one or two of Ti, V, Nb, Ta, A1 and Si are used. If the content is out of the range of the present invention, the magnetic anisotropy decreases, which is not preferable.
  • composition composition (atomic%)
  • a third anisotropic magnet according to the present invention was manufactured as follows, and its performance was examined.
  • This raw material alloy was heated to 830 from room temperature in a hydrogen atmosphere at 1 atm, heat-treated in a hydrogen atmosphere maintained at 830 for 4 hours, and then vacuumed at 830. Degree: Dehydrogenation was performed until the temperature fell below lxl O -i Torr, and then argon gas immediately flowed in for rapid cooling.
  • the ingot after the above-mentioned hydrogen treatment was lightly powdered with a mortar to obtain various R-Fe-Co-B permanent magnet powders having an average particle size of 50 5 ⁇ .
  • R-Fe-Co-B permanent magnet powder manufactured from an alloy ingot that does not contain any of G a, Z r, and ⁇ ⁇ is placed in a copper can in a vacuum. It was filled and sealed, heated to 700, and rolled several times until the rolling reduction reached 80%, whereby a conventional anisotropic magnet 3 shown in Table 23 was obtained.
  • Each structure of the isotropic magnet 3 was observed with a scanning electron microscope, and the average crystal grain size and the maximum / minimum diameter of individual crystal grains were determined to be smaller than 2.
  • the abundance (capacity) was measured, and the coercivity temperature coefficient, iHe :, and the magnetic properties were measured.
  • the measured values obtained are shown in Tables 24 to 27.
  • the method of calculating the coercive force temperature coefficient a i H c is as described above.
  • the anisotropic magnets 79 to 109 of the present invention containing one or more of Ga, Zr, and Hi are , magnetic properties, especially in Ri your excellent maximum error, channel ghee product (BH) « ⁇ ⁇ your good beauty residual magnetic flux density B r, that if this and the side that has excellent magnetic anisotropy.
  • the anisotropic magnets 79 to 109 of the present invention have almost the same magnetic properties as the conventional anisotropic magnet 3 obtained by rolling, but have a temperature coefficient ⁇ of coercive force. i H c is much smaller — about 0.5% Z.
  • the comparative anisotropic magnets 30 to 3 whose compositions are outside the IS range of the present invention. In, the magnetic properties and magnetic anisotropy decreased.
  • various alloy ingots having a component composition including one or more of Al, V, and Si were prepared, and these ingots were used in the book described above.
  • R—F e -Co- with an average particle size of 40 / m B-type permanent magnet powder was produced.
  • This permanent magnet powder is pressed in a magnetic field and in a non-magnetic field to produce a green compact, and the green compact is heated at a temperature of 710 ° C and a pressure of 1.7 ton. / cm 2 under the condition of hot isostatic pressure, the anisotropic magnet of the present invention having the composition shown in Table 28, 110 to 119 and comparative anisotropy Magnets 40 to 42 were obtained.
  • a fourth anisotropic magnet according to the present invention was manufactured as follows, and the performance was examined.
  • R — Fe — C containing one or more of Ti, V, Nb, Ta, A1 and Si obtained by plasma melting and fabrication o-B-based alloy ingots and R-Fe-Co-B-based base metals that do not include any of Ti, V, Nb, Ta, A1 and Si
  • Each of the ingots was homogenized in an argon atmosphere at a temperature of 113 ° C for 20 hours and then homogenized.
  • the raw material alloy was formed by framing the got to a size of about 15 mm square.
  • This raw material alloy was heated from room temperature to 830 ° C in a hydrogen atmosphere at 1 atm, heat-treated in a hydrogen atmosphere maintained at 830 for 1 hour, and then 830 ° C. vacuum degree C: 1 X 1 0 - 1 T orr after Do that until in dehydrogenation below, and quenched by introducing the a Le Gore emission gas immediately. After the completion of such hydrogen treatment, heat treatment was performed in vacuum for 60 hours for 2 hours. The obtained material alloy was lightly pulverized in a mortar to obtain a magnet powder having an average particle size of 40 m.
  • the anisotropic magnets of the present invention produced in this way, 120-164 and the specific anisotropic magnets 43-56, of which the anisotropic magnets of the present invention, 120- 14 4 and Comparative Anisotropic Magnets 43 to 49 are manufactured by hot pressing, and the anisotropic magnets of the present invention 144 to 164 and Comparative The anisotropic magnets 50 to 56 were manufactured by the above 11 IP.
  • the densities were 7.5 to 7.6 g / cm 3, which was sufficiently dense.
  • R — F manufactured from alloy ingots that do not include any of Ti, V, Nb, Ta, Al, and Si e-Co-B-based permanent magnet powder is filled in a copper can in a vacuum, heated to 720 and rolled several times until the rolling reduction reaches 80%. Magnet 4 was obtained.
  • the component compositions of the anisotropic magnets 120 to 164 of the present invention, the comparative anisotropic magnets 43 to 56, and the conventional anisotropic magnet 4 obtained as described above were set to the 30th. The results are shown in Tables to Table 35. In addition, the average crystal grain size of these anisotropic magnets, and the abundance (volume%) of crystal grains in which the value of the longest ghost / the maximum valley grain size of each crystal grain is smaller than 2 The magnetic properties and the temperature coefficient ai He of the coercive force were measured in the same manner as described above, and the measured values are shown in Tables 36 to 40.
  • the present invention R containing one or two or more of Ti, V, Nb, Ta, A1, and Si—
  • the Fe-Co-B-based anisotropic magnets 120-164 have a magnetic force that is almost equivalent to that of the conventional anisotropic magnet 4 not containing these elements. ⁇ Temperature coefficient of coercive force is extremely small.
  • the comparative anisotropic magnet 43 When the contents of Ti, V, Nb, Ta, Al and Si are out of the range of the present invention as in 56, the magnetic anisotropy decreases, and the crystal grain size and It can be seen that the crystal grain shape also has a large effect on the magnetic properties.
  • composition Composition (atomic%)
  • Table 37 Average crystal shortest grain size a and longest grain size b Coercive force temperature Magnetic property Ratio of grain size b / a ⁇ 2 Coefficient a i H c
  • an anisotropic magnet having a large magnetic anisotropy and a small coercive force temperature coefficient, and a magnetic anisotropic means such as hot plastic working as in the past. This eliminates the necessity of performing the process, and the manufacturing cost can be greatly reduced. Therefore, it greatly contributes to improving the performance and stability of electric devices such as motors.

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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

L'invention se rapporte à un produit de moulage par compression à chaud ou à un produit de moulage par compression isostatique à chaud, qui est constitué soit par une composition contenant un pourcentage atomique de R compris entre 10 et 20, un pourcentage atomique de B compris entre 3 et 20, et un pourcentage atomique d'un ou de plusieurs atomes choisis parmi Ga, Zr et Hf compris entre 0,001 et 5,0, le reste étant formé de Fe et des impuretés inévitables, soit par une composition contenant un pourcentage atomique de R compris entre 10 et 20, un pourcentage atomique de B compris entre 3 et 20 et un pourcentage atomique d'un ou de plusieurs atomes choisis parmi Ti, V, Nb, Ta, Al et Si compris entre 0,001 et 5,0, le reste étant formé de Fe et des impuretés inévitables, soit encore par une composition contenant un pourcentage atomique de Co compris entre 0,1 et 50, en plus de l'une des deux compositions mentionnées ci-dessus. Ce produit possède une structure d'agrégat de grains cristallins d'un diamètre moyen compris entre 0,05 et 20 mum, dans laquelle un composé intermétallique R2Fe14B ou R2(Fe, Co)14B tétragonal forment une phase principale et dans laquelle les grains cristallins présentant un rapport grand axe (b)/petit axe (a) inférieur à 2 constituent au moins 50 % en volume de la totalité des grains cristallins.
PCT/JP1992/000073 1991-01-28 1992-01-28 Aimant a base de terres rares, de fer et de bore et a base de terres rares de fer, de cobalt et de bore ayant des proprietes anisotropes WO1992013353A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP92903728A EP0522177B2 (fr) 1991-01-28 1992-01-28 Aimant ayant des propriétés anisotropiques à base de terres rares
DE69203405T DE69203405T3 (de) 1991-01-28 1992-01-28 Anisotroper Seltenerd-Magnet.

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP3/60828 1991-01-28
JP3060828A JP2773444B2 (ja) 1991-01-28 1991-01-28 希土類−Ｆｅ−Ｂ系異方性磁石
JP3/60833 1991-01-30
JP03060833A JP3092672B2 (ja) 1991-01-30 1991-01-30 希土類−Ｆｅ−Ｃｏ−Ｂ系異方性磁石
JP03060837A JP3092673B2 (ja) 1991-01-31 1991-01-31 希土類−Ｆｅ−Ｂ系異方性磁石
JP3/60837 1991-01-31
JP3/60860 1991-02-01
JP06086091A JP3196224B2 (ja) 1991-02-01 1991-02-01 希土類−Ｆｅ−Ｃｏ−Ｂ系異方性磁石

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EP0599365A1 (fr) * 1992-11-20 1994-06-01 General Motors Corporation Aimants, pressés à chaud, formés de poudres anisotropes

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JPS6217149A (ja) * 1985-07-16 1987-01-26 Sumitomo Special Metals Co Ltd 高性能焼結永久磁石材料の製造方法
JPS62202506A (ja) * 1985-11-21 1987-09-07 Tdk Corp 永久磁石およびその製法

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JPS63211706A (ja) * 1987-02-27 1988-09-02 Hitachi Metals Ltd ボンド磁石用磁粉の製造方法
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JPS61295342A (ja) * 1985-06-24 1986-12-26 Hitachi Metals Ltd 永久磁石合金の製造方法
JPS6217149A (ja) * 1985-07-16 1987-01-26 Sumitomo Special Metals Co Ltd 高性能焼結永久磁石材料の製造方法
JPS62202506A (ja) * 1985-11-21 1987-09-07 Tdk Corp 永久磁石およびその製法

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Publication number Priority date Publication date Assignee Title
EP0599365A1 (fr) * 1992-11-20 1994-06-01 General Motors Corporation Aimants, pressés à chaud, formés de poudres anisotropes
US5352301A (en) * 1992-11-20 1994-10-04 General Motors Corporation Hot pressed magnets formed from anisotropic powders

Also Published As

Publication number Publication date
CA2079223A1 (fr) 1992-07-29
EP0522177A4 (en) 1993-09-15
EP0522177B2 (fr) 2003-07-30
DE69203405T2 (de) 1996-02-15
EP0522177A1 (fr) 1993-01-13
DE69203405D1 (de) 1995-08-17
DE69203405T3 (de) 2004-05-06
EP0522177B1 (fr) 1995-07-12

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