WO2019065481A1 - Method for manufacturing r-t-b-based sintered magnet - Google Patents

Method for manufacturing r-t-b-based sintered magnet Download PDF

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Publication number
WO2019065481A1
WO2019065481A1 PCT/JP2018/034973 JP2018034973W WO2019065481A1 WO 2019065481 A1 WO2019065481 A1 WO 2019065481A1 JP 2018034973 W JP2018034973 W JP 2018034973W WO 2019065481 A1 WO2019065481 A1 WO 2019065481A1
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mass
alloy
content
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sintered body
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PCT/JP2018/034973
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French (fr)
Japanese (ja)
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宣介 野澤
恭孝 重本
西内　武司
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日立金属株式会社
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Priority to JP2019500604A priority Critical patent/JP6508447B1/en
Priority to CN201880053770.9A priority patent/CN111052276B/en
Publication of WO2019065481A1 publication Critical patent/WO2019065481A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets

Definitions

  • the present invention relates to a method for producing an RTB-based sintered magnet.
  • RTB-based sintered magnet (R is at least one of rare earth elements. T is at least one of transition metal elements and necessarily contains Fe. B is boron.) Is a permanent magnet. It is known as the most powerful magnet, and is used for voice coil motor (VCM) of hard disk drive, electric motor (EV, HV, PHV etc.) motor for electric car, various motors such as motor for industrial equipment, home electric appliance etc. There is.
  • VCM voice coil motor
  • EV, HV, PHV etc. electric motor for electric car
  • various motors such as motor for industrial equipment, home electric appliance etc. There is.
  • the RTB-based sintered magnet is mainly composed of a main phase consisting of an R 2 T 14 B compound and a grain boundary phase located at grain boundaries of the main phase (hereinafter sometimes referred to simply as “grain boundaries”). It is configured.
  • the R 2 T 14 B compound is a ferromagnetic phase with high magnetization, and forms the basis of the characteristics of the RTB-based sintered magnet.
  • the RTB -based sintered magnet has a problem that irreversible thermal demagnetization occurs because the coercivity H cJ (hereinafter, sometimes simply referred to as "coercivity" or "H cJ ”) decreases at high temperature. Therefore, in the RTB -based sintered magnet used particularly for a motor for an electric vehicle, it is required to have high H cJ even under high temperature, that is, to have higher H cJ at room temperature.
  • part of the light rare earth elements (mainly Nd and / or Pr) contained in R in the R 2 T 14 B compound is a heavy rare earth element (mainly Dy and / or Tb) It is known that substitution improves H cJ . H cJ improves as the substitution amount of heavy rare earth elements increases.
  • Patent Document 1 discloses an RTB-based rare earth sintered magnet in which the coercive force is increased while reducing the content of Dy.
  • the composition of this sintered magnet is limited to a specific range in which the amount of B is relatively small compared to a commonly used RTB-based alloy, and is selected from Al, Ga, and Cu 1 It contains metal element M of a species or more.
  • R 2 T 17 phase is produced in the grain boundary, by the volume ratio of the R 2 T 17 transition metal-rich phase formed in the grain boundary from phase (R 6 T 13 M) increases, H cJ Improve.
  • Patent Document 1 The method described in Patent Document 1 is noteworthy in that the coercive force of the RTB-based sintered magnet can be increased while suppressing the content of heavy rare earth elements. However, there is a problem that B r is greatly reduced. Further, in recent years, RTB -based sintered magnets having higher H cJ have been required in applications such as motors for electric vehicles.
  • Embodiments of the present disclosure while reducing the content of heavy rare earth elements, to provide a method of manufacturing a R-T-B based sintered magnet having a high B r and a high H cJ.
  • the method of producing the RTB-based sintered magnet of the present disclosure is, in a non-limiting exemplary embodiment, preparing an R1-T1-B-based sintered body, R2-Ga-Cu-Co, and And preparing at least a part of the R2-Ga-Cu-Co alloy on at least a part of the surface of the R1-T1-B sintered body, in a vacuum or inert gas atmosphere. And a step of performing the first heat treatment at a temperature of 700 ° C. or more and 1100 ° C. or less, and a vacuum or inert gas atmosphere for the R1-T1-B-based sintered body subjected to the first heat treatment. And performing a second heat treatment at a temperature of 450 ° C.
  • R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is the entire R1-T1-B-based sintered body.
  • T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si, T1 always contains Fe, and the Fe content relative to the entire T1 is It is 80 mass% or more, and the molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.
  • R2 is at least one of rare earth elements and necessarily contains at least one of Nd and Pr, and the content of R2 is that of the entire R2-Ga-Cu-Co-based alloy
  • the content of Ga is 35 mass% to less than 85 mass%
  • the content of Ga is 2.5 mass% to 30 mass% of the entire R2-Ga-Cu-Co alloy
  • the content of Cu is R2-Ga-Cu-Co.
  • the content of Co is more than 10 mass% and less than 45 mass% of the whole R2-Ga-Cu-Co alloy, and the content of R> the content of Co. > Ga content> Cu content inequality is satisfied.
  • the molar ratio of T to B ([T1] / [B]) is 14.5 or more and 15.0 or less.
  • 50 mass% or more of R2 in the R2-Ga-Cu-Co based alloy is Pr.
  • 70 mass% or more of R2 in the R2-Ga-Cu-Co based alloy is Pr.
  • the total content of R 2 -Ga-Cu-Co in the R 2 -Ga-Cu-Co-based alloy is 80 mass% or more.
  • the temperature in the first heat treatment is 800 ° C. or more and 1000 ° C. or less.
  • the temperature in the second heat treatment is 480 ° C. or more and 560 ° C. or less.
  • Preparing the R1-T1-B based sintered body comprises performing after the material alloy particle size D 50 was pulverized to 3 ⁇ m or 10 ⁇ m or less, the sintering being oriented in a magnetic field.
  • the manufacturing method of the RTB-based sintered magnet of the present disclosure is, in another exemplary embodiment not limiting, preparing an R1-T1-Cu-B-based sintered body; And preparing at least a part of the R2-Ga-Co alloy on at least a part of the surface of the R1-T1-Cu-B sintered body, in a vacuum or inactive state.
  • the step of performing the first heat treatment at a temperature of 700 ° C. or more and 1100 ° C. or less in a gas atmosphere, and vacuum or failure for the R1-T1-Cu-B-based sintered body for which the first heat treatment is performed.
  • Carrying out the second heat treatment at a temperature of 450 ° C. to 600 ° C.
  • R1 in an active gas atmosphere, and in the R1-T1-Cu-B-based sintered body, R1 is at least one of rare earth elements Yes, including at least one of Nd and Pr
  • the content of R1 is 27 mass% or more and 35 mass% or less of the entire R1-T1-Cu-B-based sintered body, and T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si.
  • T1 always contains Fe, the content of Fe with respect to the whole T1 is 80 mass% or more, and the molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less
  • the content of Cu is 0.1 mass% or more and 1.5 mass% or less of the entire R1-T1-Cu-B-based sintered body, and in the R2-Ga-Co-based alloy, R2 is a rare earth element.
  • the content of R2 is at least 35 mass% and less than 87 mass% of the whole R2-Ga-Co alloy, and the content of Ga is R2-G.
  • the content of Co is more than 10 mass% and 45 mass% or less of the whole R2-Ga-Co alloy, the content of R2> the content of Co
  • the inequality of the content of Ga is established.
  • the molar ratio of T1 to B ([T1] / [B]) is 14.3 or more and 15.0 or less.
  • 50 mass% or more of R2 in the R2-Ga-Co-based alloy is Pr.
  • 70 mass% or more of R2 in the R2-Ga-Co-based alloy is Pr.
  • the total content of R2, Ga, and Co in the R2-Ga-Co-based alloy is 80 mass% or more.
  • the temperature in the first heat treatment is 800 ° C. or more and 1000 ° C. or less.
  • the temperature in the second heat treatment is 480 ° C. or more and 560 ° C. or less.
  • the step of preparing the R1-T1-Cu-B based sintered body, after the material alloy particle size D 50 was pulverized to 3 ⁇ m or 10 ⁇ m or less, sintering is performed by orienting in a magnetic field Including.
  • FIG. 2 is a schematic view showing a main phase and a grain boundary phase of an RTB-based sintered magnet. It is the schematic diagram which further expanded the inside of the broken-line rectangular area
  • rare earth elements may be collectively referred to as “R”.
  • R When referring to a specific element or group of elements among the rare earth elements R, for example, the sign of “R1” or “R2” is used to distinguish from other rare earth elements.
  • the entire transition metal element including Fe is denoted as “T”.
  • T When the transition metal element T includes both a specific element or element group and a specific element or element group other than the transition metal element which is easily substituted with the Fe site of the main phase, using the symbol of “T1” Distinguish from other transition metal elements.
  • a method of manufacturing an RTB-based sintered magnet according to the first embodiment of the present disclosure includes, as shown in FIG. 1, a step S10 of preparing an R1-T1-B-based sintered body, and R2-Ga- And S20 of preparing a Cu--Co alloy.
  • the order of the step S10 of preparing the R1-T1-B-based sintered body and the step S20 of preparing the R2-Ga-Cu-Co-based alloy is arbitrary, and each of the R1-T1-B manufactured in different places.
  • a B-based sintered body and an R2-Ga-Cu-Co-based alloy may be used.
  • the RTB-based sintered magnet before the second heat treatment and during the second heat treatment is referred to as an R1-T1-B-based sintered body, and the R1-T1-B system after the second heat treatment
  • the sintered body is simply referred to as an RTB-based sintered magnet.
  • (A1) to (A3) hold.
  • (A1) R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is 27 mass% or more and 35 mass% or less of the entire R1-T1-B-based sintered body.
  • (A2) T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si. T1 necessarily contains Fe, and the content of Fe with respect to the entire T1 is 80 mass% or more.
  • the molar ratio of T1 to (A3) B ([T1] / [B]) is more than 14.0 and 15.0 or less.
  • the molar ratio of T1 to B ([T1] / [B]) in the present disclosure is the analysis value (mass%) of each element (Fe or at least one of Fe, Co, Al, Mn, Si and Fe) constituting T1. Calculate the ratio of the atomic weight of each element divided by the atomic weight of each element (a) and the ratio (a /) of the analytical value (mass%) of B divided by the atomic weight of B (b) b).
  • R2 is at least one of rare earth elements and necessarily contains at least one of Nd and Pr, and the content of R2 is 35 mass% or more and less than 85 mass% of the entire R2-Ga-Cu-Co alloy.
  • the content of (A5) Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Cu-Co alloy.
  • the content of (A6) Cu is 2.5 mass% or more and 20 mass% or less of the entire R2-Ga-Cu-Co alloy.
  • the content of (A7) Co is more than 10% by weight and 45% by weight or less of the entire R2-Ga-Cu-Co based alloy.
  • R1 having a relatively small amount of B in a stoichiometric ratio relative to the amount of T used to form the main phase (R 2 T 14 B compound)
  • An R2-Ga-Cu-Co alloy is brought into contact with at least a part of the surface of the -T1-B sintered body, and as shown in FIG. 1, in a vacuum or inert gas atmosphere, at 700.degree. C. or more and 1100.degree. Temperature of 450 ° C. or more and 600 ° C.
  • step S40 the second heat treatment is performed.
  • the R-T-B based sintered magnet having a high B r and a high H cJ.
  • Another step such as a cooling step, may be performed between the step S30 of performing the first heat treatment and the step S40 of performing the second heat treatment.
  • the RTB-based sintered magnet has a structure in which powder particles of a raw material alloy are bonded by sintering, and a main phase mainly composed of an R 2 T 14 B compound and a grain boundary portion of this main phase It is composed of the located grain boundary phase.
  • FIG. 2A is a schematic view showing the main phase and the grain boundary phase of the RTB-based sintered magnet
  • FIG. 2B is a schematic view further enlarging the inside of the dashed rectangular area of FIG. 2A.
  • an arrow of 5 ⁇ m in length as an example is described for reference as a reference length indicating the size.
  • the RTB-based sintered magnet includes a main phase 12 mainly composed of an R 2 T 14 B compound, and a grain boundary phase 14 located in the grain boundary portion of the main phase 12.
  • the grain boundary phase 14 is a two-grain grain boundary phase 14a in which two R 2 T 14 B compound particles (grains) are adjacent, and three or more R 2 T 14 B compound particles. And the adjacent grain boundary triple point 14b.
  • the R 2 T 14 B compound which is the main phase 12 is a ferromagnetic phase having high saturation magnetization and anisotropic magnetic field. Therefore, in the R-T-B based sintered magnet, it is possible to improve the B r by increasing the existence ratio of R 2 T 14 B compound is the main phase 12.
  • the amount of B or R for forming the R 2 T 14 B compound is less than the stoichiometric ratio, generally, a ferromagnetic substance such as an Fe phase or an R 2 T 17 phase is formed in the grain boundary phase 14 , H cJ falls sharply.
  • the amount of B is less than the stoichiometric ratio of the R 2 T 14 B compound, and at least one selected from Al, Ga, and Cu.
  • a transition metal rich phase for example, RT-Ga phase
  • Br is significantly reduced.
  • the manufacturing method of the RTB-based sintered magnet according to the present disclosure is to introduce R2, Ga, Cu and Co into the interior from the magnet surface by the R2-Ga-Cu-Co-based alloy of the specific composition of the present disclosure. , it is possible to achieve high B r and high H cJ.
  • Step of preparing R1-T1-B sintered body First, the composition of the sintered body in the step of preparing an R1-T1-B-based sintered body (hereinafter sometimes simply referred to as “sintered body”) will be described.
  • R1 is at least one of rare earth elements and always contains at least one of Nd and Pr.
  • a small amount of heavy rare earth elements such as Dy, Tb, Gd, and Ho generally used may be contained.
  • the content of the heavy rare earth element is preferably 1 mass% or less of the R1-T1-B-based sintered body, more preferably 0.5 mass% or less, and it is not contained (substantially 0 mass%) Is more preferred.
  • the content of R1 is 27 mass% or more and 35 mass% or less of the whole of the R1-T1-B-based sintered body. If the content of R1 is less than 27 mass%, a liquid phase is not sufficiently generated in the sintering process, and it becomes difficult to fully densify the R1-T1-B-based sintered body. On the other hand, although the effect of the present disclosure can be obtained even if the content of R1 exceeds 35 mass%, the alloy powder in the manufacturing process of the R1-T1-B-based sintered body becomes very active. As a result, significant oxidation or ignition of the alloy powder may occur, so 35 mass% or less is preferable.
  • the content of R1 is more preferably 27.5 mass% or more and 33 mass% or less, and still more preferably 28 mass% or more and 32 mass% or less.
  • T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si, and T1 always contains Fe. That is, T1 may be Fe alone, or may be Fe and at least one of Co, Al, Mn, and Si. However, the content of Fe with respect to the whole T1 is 80 mass% or more. When the content of Fe is less than 80 mass%, B r and H cJ may be reduced. Here, "the content of Fe with respect to the whole T1 is 80 mass% or more" means, for example, when the content of T1 in the R1-T1-B-based sintered body is 70 mass%, the R1-T1-B-based sintering It says that 56 mass% or more of the body is Fe.
  • the content of Fe with respect to the whole of T1 is 90 mass% or more. This is because it is possible to obtain a higher B r and a high H cJ.
  • the preferable content in the case of containing Co, Al, Mn, and Si is 5.0 mass% or less of Co in the entire R1-T1-Cu-B sintered body, 1.5 mass% or less of Al, and Mn and Si Each is 0.2 mass% or less.
  • the molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.
  • the molar ratio of T1 to B ([T1] / [B]) in the present disclosure is the analysis value (mass%) of each element (Fe or at least one of Fe, Co, Al, Mn, Si and Fe) constituting T1. Calculate the ratio of the atomic weight of each element divided by the atomic weight of each element (a) and the ratio (a /) of the analytical value (mass%) of B divided by the atomic weight of B (b) b).
  • the condition that the molar ratio of T1 to B ([T1] / [B]) exceeds 14.0 means that the amount of B is relatively to the amount of T1 used to form the main phase (R 2 T 14 B compound) It shows that there are few. If the molar ratio of T1 to B ([T1] / [B]) is 14.0 or less, high H cJ can not be obtained. On the other hand, mol ratio of T1 for B ([T1] / [B ]) is likely to decrease B r exceeds 15.0.
  • the molar ratio of T1 to B ([T1] / [B]) is preferably 14.5 or more and 15.0 or less. It is possible to obtain a higher B r and a high H cJ. Further, the content of B is preferably 0.9 mass% or more and less than 1.0 mass% of the entire R1-T1-B-based sintered body.
  • the R1-T1-B-based sintered body may contain Ga, Cu, Ag, Zn, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
  • each of Ga, Cu, Ag, Zn, In, Sn, Zr, Nb and Ti is 0.5 mass% or less, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, It is preferable that Sm, Ca, Mg and Cr each be 0.2 mass% or less, H, F, P, S and Cl be 500 ppm or less, O be 6000 ppm or less, N be 1000 ppm or less and C be 1500 ppm or less.
  • the total content of these elements is preferably 5% by mass or less of the entire R1-T1-B-based sintered body. The total content of these elements may not be able to obtain the high B r and high H cJ exceeds 5 mass% of the total R1-T1-B based sintered body.
  • the step of preparing the R1-T1-B based sintered body can be prepared using a general manufacturing method typified by the RTB based sintered magnet.
  • a material alloy that has been prepared in such a strip casting method after the particle size D 50 by using a jet mill is ground to 3 ⁇ m over 10 ⁇ m or less, and molded in a magnetic field, 900 ° C. or higher 1100 ° C. or less It can be prepared by sintering at a temperature of
  • the size less than D 50 of the material alloy is 3 ⁇ m is very difficult to prepare a pulverized powder is not preferable because production efficiency is greatly reduced.
  • particle diameter D 50 is eventually only the crystal grain size of the resulting R1-T1-B based sintered body increases exceeds 10 [mu] m, it becomes difficult to obtain a high H cJ.
  • the particle size D 50 is preferably 3 ⁇ m or more and 5 ⁇ m or less.
  • the R1-T1-B based sintered body may be produced from one kind of raw material alloy (single raw material alloy) as long as the above-mentioned respective conditions are satisfied, or two or more kinds of raw material alloys may be used to produce them. It may be produced by the method of mixing (blending method).
  • the obtained R1-T1-B-based sintered body may be subjected to known machining such as cutting or cutting if necessary, and then may be subjected to the first heat treatment and the second heat treatment described later. .
  • Step of preparing R2-Ga-Cu-Co alloy First, the composition of the R2-Ga-Cu-Co alloy in the step of preparing the R2-Ga-Cu-Co alloy will be described. By including all of R, Ga, Cu, and Co within the specific range described below, R2, Ga, Cu, and R2 in the R2-Ga-Cu-Co alloy in the step of performing the first heat treatment described later Co can be introduced into the interior of the R1-T1-B sintered body.
  • R2 is at least one of rare earth elements and always contains at least one of Nd and Pr. It is preferable that 50 mass% or more of R2 is Pr. It is because higher H cJ can be obtained.
  • “50 mass% or more of R2 is Pr” means, for example, 25 mass of R2-Ga-Cu-Co alloy when the content of R2 in R2-Ga-Cu-Co alloy is 50 mass%. It says that% or more is Pr. More preferably, 70 mass% or more of R2 is Pr, and most preferably, R2 is only Pr (including unavoidable impurities). Thereby, a further higher HcJ can be obtained.
  • a small amount of heavy rare earth elements such as Dy, Tb, Gd and Ho may be contained as R2.
  • the content of the heavy rare earth element is preferably 10 mass% or less of the entire R2-Ga-Cu-Co alloy (the heavy rare earth element in the R2-Ga-Cu-Co alloy is 10 mass% or less), It is more preferable that it is 5 mass% or less, and it is still more preferable that it does not contain (substantially 0 mass%).
  • R2 of the R2-Ga-Cu-Co alloy contains a heavy rare earth element, it is preferable that 50% or more of R2 is Pr, and R2 excluding the heavy rare earth element is only Pr (including unavoidable impurities) It is more preferred that
  • the content of R2 is 35 mass% or more and less than 85 mass% of the entire R2-Ga-Cu-Co alloy. If the content of R2 is less than 35 mass%, diffusion may not sufficiently proceed in the first heat treatment described later. On the other hand, although the effect of the present disclosure can be obtained even if the content of R2 is 85 mass% or more, the alloy powder in the manufacturing process of the R2-Ga-Cu-Co based alloy becomes very active. As a result, significant oxidation, ignition and the like of the alloy powder may occur, so the content of R2 is preferably less than 85 mass% of the entire R2-Ga-Cu-Co alloy.
  • the content of R2 is more preferably 50 mass% or more and less than 85 mass%, and still more preferably 60 mass% or more and less than 85 mass%. It is because higher H cJ can be obtained.
  • Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Cu-Co alloy. If Ga is less than 2.5 mass%, it is difficult to introduce Co in the R2-Ga-Cu-Co alloy into the interior of the R1-T1-B sintered body in the step of performing the first heat treatment described later, which is high. I can not get B r . Furthermore, the amount of RT-Ga phase formed is too small to obtain high HcJ . On the other hand, if Ga is more than 30 mass%, B r may be lowered significantly. Ga is more preferably 4 mass% or more and 20 mass% or less, and still more preferably 4 mass% or more and 10 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
  • Cu is 2.5 mass% or more and 20 mass% or less of the entire R2-Ga-Cu-Co alloy. If Cu is less than 2.5 mass%, Ga, Cu and Co in the R2-Ga-Cu-Co alloy are introduced into the interior of the R1-T1-B sintered body in the step of performing the first heat treatment described later hardly be, it is impossible to obtain a high B r. On the other hand, if Cu exceeds 20 mass%, the abundance ratio of Ga at the grain boundaries decreases, so the amount of RT-Ga phase generated may be too small to obtain high HcJ . Cu is more preferably 4 mass% or more and 15 mass% or less, and still more preferably 4 mass% or more and 10 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
  • Co is more than 10% by mass and 45% by mass or less of the entire R2-Ga-Cu-Co alloy. Co is in the following 10 mass%, it is impossible to sufficiently enhance the finally obtained R-T-B based sintered magnet of B r. On the other hand, when Co exceeds 45Mass%, it may not be able to spread with a first heat treatment to be described later does not proceed sufficiently to obtain a high B r and high H cJ. As for Co, it is more preferable that they are 15 mass% or more and 30 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
  • the inequality of R2 content> Co content> Ga content> Cu content is satisfied. Therefore, it is possible to obtain a high B r and a high H cJ. It is considered that this is because a phase containing appropriate amounts of R, Co, Ga and Cu is generated at two grain boundaries by satisfying the inequality of the present disclosure.
  • the R2-Ga-Cu-Co alloy may contain Al, Ag, Zn, Si, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
  • the content of Al is 1.0 mass% or less
  • Ag, Zn, Si, In, Sn, Zr, Nb, and Ti are 0.5 mass% or less, respectively, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Si, Cr each 0.2 mass% or less, H, F, P, S, Cl 500 ppm or less, O 6000 ppm or less, N 1000 ppm or less, C 1500 ppm or less is preferable.
  • the total content of these elements is more than 20mass%, R2-Ga-Cu -Co -based then the amount of R2-Ga-Cu-Co in the alloy, to obtain a high B r and high H cJ It may not be possible. Therefore, the total content of R2-Ga-Cu-Co in the R2-Ga-Cu-Co alloy is preferably 80 mass% or more, and more preferably 90 mass% or more.
  • the R2-Ga-Cu-Co alloy is a method of preparing a raw material alloy employed in a general manufacturing method represented by a Nd-Fe-B sintered magnet, for example, a die casting method and a strip casting method And single roll ultra-quenching method (melt spinning method) or atomization method.
  • the R2-Ga-Cu-Co based alloy may be one obtained by pulverizing the alloy obtained as described above by a known pulverizing means such as a pin mill.
  • heat treatment at 700 ° C. or less in a hydrogen atmosphere may be performed to contain hydrogen and then grinding.
  • Step of carrying out the first heat treatment At least a portion of the R2-Ga-Cu-Co alloy is brought into contact with at least a portion of the surface of the R1-T1-B sintered body prepared as described above, and the temperature is 700 ° C. or higher in a vacuum or inert gas atmosphere. Heat treatment is performed at a temperature of 1100 ° C. or less. In the present disclosure, this heat treatment is referred to as a first heat treatment. As a result, a liquid phase containing Cu, Ga and Co is generated from the R2-Ga-Cu-Co alloy, and the liquid phase passes through the grain boundaries of the R1-T1-B sintered body, and the surface of the sintered body is produced. It is diffused from inside to inside.
  • the first heat treatment temperature is lower than 700 ° C., Cu, and amount of liquid phase containing Ga and Co is too small, it may not be able to obtain a high B r and high H cJ.
  • the first heat treatment temperature is preferably 800 ° C. or more and 1000 ° C. or less. This is because it is possible to obtain a higher B r and a high H cJ.
  • the heat treatment time is set to an appropriate value depending on the composition and dimensions of the R1-T1-B sintered body and R2-Ga-Cu-Co alloy, the heat treatment temperature, etc., but 5 minutes or more and 20 hours or less is preferable, 10 More preferably, minutes to 15 hours and still more preferably 30 minutes to 10 hours. Further, it is preferable to prepare the R2-Ga-Cu-Co-based alloy in an amount of 2 mass% or more and 30 mass% or less with respect to the weight of the R1-T1-B-based sintered body. If the R2-Ga-Cu-Co alloy is less than 2 mass% with respect to the weight of the R1-T1-B sintered body, there is a possibility that HcJ may be reduced. On the other hand, there is a possibility that the B r decreases exceeds 30 mass%.
  • the first heat treatment can be performed by disposing an R2-Ga-Cu-Co alloy having an arbitrary shape on the surface of the R1-T1-B-based sintered body and using a known heat treatment apparatus.
  • the first heat treatment can be performed by covering the surface of the R1-T1-B-based sintered body with a powder layer of an R2-Ga-Cu-Co-based alloy.
  • the dispersion medium is evaporated to form an R2-Ga-Cu-Co system.
  • the alloy and the R1-T1-B sintered body may be in contact with each other.
  • the R2-Ga-Cu-Co alloy may be arranged to be in contact with the surface perpendicular to the orientation direction of at least the R1-T1-B sintered body.
  • the dispersion medium include alcohols (ethanol etc.), NMP (N-methylpyrrolidone), aldehydes and ketones.
  • known machining such as cutting or cutting may be performed on the R1-T1-B-based sintered body subjected to the first heat treatment.
  • Step of carrying out the second heat treatment The R1-T1-B-based sintered body subjected to the first heat treatment is heat-treated at a temperature of 450 ° C. to 600 ° C. in a vacuum or an inert gas atmosphere.
  • this heat treatment is referred to as a second heat treatment.
  • the second heat treatment it is possible to obtain a high B r and high H cJ.
  • the temperature of the second heat treatment is less than 450 ° C. and more than 600 ° C.
  • the amount of RT-Ga phase typically, R 6 T 13 Z phase (Z is at least one of Cu and Ga)
  • high B r and high H cJ can not be obtained due to too little.
  • the second heat treatment temperature is preferably 480 ° C. or more and 560 ° C. or less. Higher H cJ can be obtained.
  • the heat treatment time is appropriately set depending on the composition and dimensions of the R1-T1-B sintered body, the heat treatment temperature, etc., but it is preferably 5 minutes to 20 hours, more preferably 10 minutes to 15 hours, and 30 More preferably, minutes to 10 hours.
  • R is at least one rare earth element and necessarily includes at least one of Pr and Nd
  • T is at least one transition metal element. Yes Fe must be included.
  • the R 6 T 13 Z compound is typically an Nd 6 Fe 13 Ga compound. Further, the R 6 T 13 Z compound has a La 6 Co 11 Ga 3 type crystal structure.
  • the R 6 T 13 Z compound may be an R 6 T 13 ⁇ ⁇ Z 1+ ⁇ compound depending on the state. When relatively large amounts of Cu, Al, and Si are contained in the RTB-based sintered magnet, the R 6 T 13- ⁇ (Ga 1 -abc Cu a Al b Si c ) 1+ ⁇ It may have been.
  • the RTB-based sintered magnet obtained by the step of carrying out the second heat treatment described above is subjected to known surface treatment such as plating for imparting corrosion resistance or performing known machining such as cutting or cutting. It can be performed.
  • the RTB-based sintered magnet obtained by the production method of the present disclosure is characterized in that at least one of Fe or Co, Al, Mn, Si and Fe in the RTB-based sintered magnet is T2 ( The molar ratio of T2 to B ([T2] / [B]) is more than 14.0, and R, Fe, B, Cu, and Ga are equivalent to T1 in the R1-T1-B-based sintered body.
  • the method of manufacturing the RTB-based sintered magnet according to the second embodiment of the present disclosure includes a step S110 of preparing an R1-T1-Cu-B-based sintered body; And S120 of preparing a Ga—Co alloy.
  • the order of the step S110 of preparing the R1-T1-Cu-B-based sintered body and the step S120 of preparing the R2-Ga-Co-based alloy is arbitrary, and each of the R1-T1-made in different places is manufactured.
  • a Cu-B based sintered body and an R2-Ga-Co based alloy may be used.
  • R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is 27 mass% or more and 35 mass% or less of the whole R1-T1-Cu-B sintered body .
  • T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si. T1 necessarily contains Fe, and the content of Fe with respect to the entire T1 is 80 mass% or more.
  • the molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.
  • the content of (B4) Cu is 0.1 mass% or more and 1.5 mass% or less of the entire R1-T1-Cu-B-based sintered body.
  • the molar ratio of T1 to B ([T1] / [B]) in the present disclosure is the analysis value (mass%) of each element (Fe or at least one of Fe, Co, Al, Mn, Si and Fe) constituting T1. Calculate the ratio of the atomic weight of each element divided by the atomic weight of each element (a) and the ratio (a /) of the analytical value (mass%) of B divided by the atomic weight of B (b) b).
  • R2 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R2 is 35 mass% or more and less than 87 mass% of the entire R2-Ga-Co alloy.
  • the content of (B6) Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Co alloy.
  • the content of (B7) Co is more than 10% by mass and 45% by mass or less of the entire R2-Ga-Co-based alloy.
  • the relative stoichiometric ratio to the amount of T used to form the main phase (R 2 T 14 B compound)
  • the R2-Ga-Co alloy is brought into contact with at least a part of the surface of the R1-T1-Cu-B sintered body having a small amount of B, as shown in FIG. 4, in a vacuum or inert gas atmosphere, Step S130 of performing the first heat treatment at a temperature of 700 ° C. or more and 1100 ° C.
  • Step S140 of performing the second heat treatment at a temperature of 450 ° C. or more and 600 ° C. or less is performed.
  • the R-T-B based sintered magnet having a high B r and a high H cJ.
  • Another step such as a cooling step, may be performed between step S130 of performing the first heat treatment and step S140 of performing the second heat treatment.
  • the method for producing an RTB-based sintered magnet according to the present disclosure introduces R2, Ga, and Co into the interior from the magnet surface with the R2-Ga-Co-based alloy of the specific composition of the present disclosure. by, it is possible to realize a high B r and high H cJ.
  • Step of preparing R1-T1-Cu-B sintered body First, the composition of the sintered body in the step of preparing the R1-T1-Cu-B-based sintered body will be described.
  • R1 is at least one of rare earth elements and always contains at least one of Nd and Pr.
  • a small amount of heavy rare earth elements such as Dy, Tb, Gd, and Ho generally used may be contained.
  • the content of the heavy rare earth element is preferably 1 mass% or less of the R1-T1-Cu-B-based sintered body, more preferably 0.5 mass% or less, and it is not contained (substantially) More preferably, 0 mass%).
  • the content of R1 is 27 mass% or more and 35 mass% or less of the whole of the R1-T1-Cu-B-based sintered body. If the content of R1 is less than 27 mass%, a liquid phase is not sufficiently generated in the sintering process, and it becomes difficult to fully densify the R1-T1-Cu-B-based sintered body. On the other hand, although the effect of the present disclosure can be obtained even if the content of R1 exceeds 35 mass%, the alloy powder in the manufacturing process of the R1-T1-Cu-B-based sintered body becomes very active. As a result, significant oxidation or ignition of the alloy powder may occur, so 35 mass% or less is preferable.
  • the content of R1 is more preferably 27.5 mass% or more and 33 mass% or less, and still more preferably 28 mass% or more and 32 mass% or less.
  • T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si, and T1 always contains Fe. That is, T1 may be Fe alone, or may be Fe and at least one of Co, Al, Mn, and Si. However, the content of Fe with respect to the whole T1 is 80 mass% or more. When the content of Fe is less than 80 mass%, B r and H cJ may be reduced. Here, "the content of Fe with respect to the whole T1 is 80 mass% or more" means, for example, when the content of T1 in the R1-T1-Cu-B-based sintered body is 70 mass%, R1-T1-Cu- It says that 56 mass% or more of B-type sintered compact is Fe.
  • the content of Fe with respect to the whole of T1 is 90 mass% or more. This is because it is possible to obtain a higher B r and a high H cJ.
  • the preferable content in the case of containing Co, Al, Mn, and Si is 5.0 mass% or less of Co in the entire R1-T1-Cu-B sintered body, 1.5 mass% or less of Al, and Mn and Si Each is 0.2 mass% or less.
  • the molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.
  • the molar ratio of T1 to B ([T1] / [B]) in the present disclosure is an analysis of each element (Fe or at least one of Co, Al, Mn, Si, and Fe) constituting T1.
  • the value (mass%) divided by the atomic weight of each element is determined, and the sum of the values (a) and the analytical value of B (mass%) divided by the atomic weight of B (b) Ratio (a / b).
  • the condition that the molar ratio of T1 to B ([T1] / [B]) exceeds 14.0 means that the amount of B is relatively to the amount of T1 used to form the main phase (R 2 T 14 B compound) It shows that there are few. If [T1] / [B] is 14.0 or less, high H cJ can not be obtained. On the other hand, there is a possibility to lower the B r exceeds the 15.0 [T1] / [B] . [T1] / [B] is preferably 14.3 or more and 15.0 or less. It is possible to obtain a higher B r and a high H cJ.
  • the content of B is preferably 0.9 mass% or more and less than 1.0 mass% of the entire R1-T1-Cu-B-based sintered body.
  • the content of Cu is 0.1 mass% or more and 1.5 mass% or less of the whole of the R1-T1-Cu-B-based sintered body. If Cu is less than 0.1 mass%, diffusion may not sufficiently proceed in the first heat treatment described later, and high H cJ may not be obtained. On the other hand, Cu is the exceeding 1.5 mass% B r may be reduced.
  • the R1-T1-Cu-B-based sintered body contains Ga, Ag, Zn, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, in addition to the above elements.
  • Mo, V, Y, La, Ce, Sm, Ca, Mg, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
  • each of Ga, Ag, Zn, In, Sn, Zr, Nb and Ti is 0.5 mass% or less, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, It is preferable that Ca, Mg and Cr each be 0.2 mass% or less, H, F, P, S and Cl be 500 ppm or less, O be 6000 ppm or less, N be 1000 ppm or less and C be 1500 ppm or less.
  • the total content of these elements is preferably 5% by mass or less of the entire R1-T1-Cu-B-based sintered body. The total content of these elements may not be able to obtain more than the high B r and high H cJ of 5 mass% of the total R1-T1-Cu-B-based sintered body.
  • the step of preparing the R1-T1-Cu-B based sintered body can be prepared using a general manufacturing method typified by an RTB based sintered magnet.
  • a material alloy that has been prepared in such a strip casting method after the particle size D 50 by using a jet mill is ground to 3 ⁇ m over 10 ⁇ m or less, and molded in a magnetic field, 900 ° C. or higher 1100 ° C. or less It can be prepared by sintering at a temperature of
  • the size less than D 50 of the material alloy is 3 ⁇ m is very difficult to prepare a pulverized powder is not preferable because production efficiency is greatly reduced.
  • particle diameter D 50 is eventually only the crystal grain size of the R1-T1-Cu-B based sintered body obtained becomes large exceeding 10 [mu] m, it becomes difficult to obtain a high H cJ.
  • the particle size D 50 is preferably 3 ⁇ m or more and 5 ⁇ m or less.
  • the R1-T1-Cu-B sintered body may be produced from one kind of raw material alloy (single raw material alloy) as long as the above-mentioned respective conditions are satisfied, or two or more kinds of raw material alloys are used. It may be produced by a method of mixing them (blending method). In addition, the obtained R1-T1-Cu-B-based sintered body is subjected to known machining such as cutting and cutting, if necessary, and is then subjected to the first heat treatment and the second heat treatment described later. It is also good.
  • Step of preparing R2-Ga-Co alloy First, the composition of the R2-Ga-Co based alloy in the step of preparing the R2-Ga-Co based alloy will be described. By including all of R, Ga, and Co within the specific range described below, in the step of performing the first heat treatment described later, R1, Ga, and Co in the R2-Ga-Co alloy are R1-T1- It can be introduced into the inside of a Cu-B-based sintered body.
  • R2 is at least one of rare earth elements and always contains at least one of Nd and Pr. It is preferable that 50 mass% or more of R2 is Pr. It is because higher H cJ can be obtained.
  • “50 mass% or more of R2 is Pr” means that, for example, when the content of R2 in the R2-Ga-Co alloy is 50 mass%, 25 mass% or more of the R2-Ga-Co alloy is Pr Say that. More preferably, 70 mass% or more of R2 is Pr, and most preferably, R2 is only Pr (including unavoidable impurities). Thereby, a further higher HcJ can be obtained.
  • a small amount of heavy rare earth elements such as Dy, Tb, Gd and Ho may be contained as R2.
  • the content of the heavy rare earth element is preferably 10 mass% or less of the entire R2-Ga-Co alloy (heavy rare earth element in the R2-Ga-Co alloy is 10 mass% or less), and is 5 mass% or less Some are more preferable, and it is more preferable not to contain (substantially 0 mass%). Even when R2 of the R2-Ga-Co alloy contains a heavy rare earth element, it is preferable that 50% or more of R2 is Pr, and R2 excluding the heavy rare earth element is only Pr (including unavoidable impurities). It is more preferable that
  • the content of R2 is 35 mass% or more and less than 87 mass% of the entire R2-Ga-Co alloy. If the content of R2 is less than 35 mass%, diffusion may not sufficiently proceed in the first heat treatment described later. On the other hand, although the effect of the present disclosure can be obtained even if the content of R2 is 87 mass% or more, the alloy powder in the manufacturing process of the R2-Ga-Co based alloy becomes very active. As a result, significant oxidation or ignition of the alloy powder may occur, so the content of R2 is preferably less than 85 mass% of the entire R2-Ga-Co based alloy. The content of R2 is more preferably 50 mass% or more and less than 85 mass%, and still more preferably 60 mass% or more and less than 85 mass%. It is because higher H cJ can be obtained.
  • Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Co alloy. If Ga is less than 2.5 mass%, it is difficult to introduce Co in the R2-Ga-Co-based alloy into the inside of the R1-T1-Cu-B-based sintered body in the step of performing the first heat treatment described later, which is high. I can not get B r . Furthermore, the amount of RT-Ga phase formed is too small to obtain high HcJ . On the other hand, if Ga is more than 30 mass%, B r may be lowered significantly. Ga is more preferably 4 mass% or more and 20 mass% or less, and still more preferably 4 mass% or more and 10 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
  • Co is more than 10 mass% and 45 mass% or less of the entire R2-Ga-Co alloy. Co is in the following 10 mass%, it is impossible to sufficiently enhance the finally obtained R-T-B based sintered magnet of B r. On the other hand, when Co exceeds 45Mass%, it may not be able to spread with a first heat treatment to be described later does not proceed sufficiently to obtain a high B r and high H cJ. As for Co, it is more preferable that they are 15 mass% or more and 30 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
  • the inequality of R2 content> Co content> Ga content is satisfied. Therefore, it is possible to obtain a high B r and a high H cJ. It is considered that this is because a phase containing appropriate amounts of R, Co and Ga is generated at two grain boundaries by satisfying the inequality of the present disclosure.
  • the R2-Ga-Co alloy includes Cu, Al, Ag, Zn, Si, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
  • the content of Cu, Al is 1.0 mass% or less, Ag, Zn, Si, In, Sn, Zr, Nb, and Ti is 0.5 mass% or less, respectively, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Si, Cr each 0.2 mass% or less, H, F, P, S, Cl 500 ppm or less, O 6000 ppm or less, N 1000 ppm or less, As for C, 1500 ppm or less is preferable.
  • the total content of these elements exceeds 20mass%, R2-Ga-Co-based R2 in the alloy, Ga, then the amount of Co, can not be obtained a high B r and high H cJ There is sex. Therefore, the total content of R2, Ga and Co in the R2-Ga-Co alloy is preferably 80 mass% or more, and more preferably 90 mass% or more.
  • the R2-Ga-Co alloy is a method of preparing a raw material alloy employed in a general manufacturing method represented by a Nd-Fe-B sintered magnet, for example, a die casting method, a strip casting method or a single It can be prepared using a roll ultra-quenching method (melt spinning method) or an atomizing method.
  • the R2-Ga-Co based alloy may be one obtained by pulverizing the alloy obtained as described above by a known pulverizing means such as a pin mill. Further, in order to improve the grindability of the alloy obtained as described above, heat treatment at 700 ° C. or less in a hydrogen atmosphere may be performed to contain hydrogen and then grinding.
  • Step of carrying out the first heat treatment At least a portion of the R2-Ga-Co alloy is brought into contact with at least a portion of the surface of the R1-T1-Cu-B-based sintered body prepared as described above, and the temperature is 700 ° C. or higher in a vacuum or inert gas atmosphere. Heat treatment is performed at a temperature of 1100 ° C. or less. In the present disclosure, this heat treatment is referred to as a first heat treatment. As a result, a liquid phase containing Ga and Co is generated from the R2-Ga-Co alloy, and the liquid phase passes from the surface of the sintered body via the grain boundary of the R1-T1-Cu-B sintered body. Diffusion is introduced.
  • the first heat treatment temperature is lower than 700 ° C., and too small amount of liquid phase containing Ga and Co, there is a possibility that it is impossible to obtain a high B r and high H cJ.
  • the first heat treatment temperature is preferably 800 ° C. or more and 1000 ° C. or less. This is because it is possible to obtain a higher B r and a high H cJ.
  • the heat treatment time is set to an appropriate value depending on the composition and dimensions of the R1-T1-Cu-B sintered body and R2-Ga-Co alloy, the heat treatment temperature, etc., but 5 minutes or more and 20 hours or less is preferable, 10 More preferably, minutes to 15 hours and still more preferably 30 minutes to 10 hours.
  • the R2-Ga-Co alloy is preferably prepared in an amount of 2 mass% or more and 30 mass% or less based on the weight of the R1-T1-Cu-B sintered body. If the R2-Ga-Co based alloy is less than 2 mass% with respect to the weight of the R1-T1-Cu-B based sintered body, there is a possibility that HcJ may be reduced. On the other hand, there is a possibility that the B r decreases exceeds 30 mass%.
  • the first heat treatment can be performed by disposing an R2-Ga-Co-based alloy having an arbitrary shape on the surface of the R1-T1-Cu-B-based sintered body and using a known heat treatment apparatus.
  • the first heat treatment can be performed by covering the surface of the R1-T1-Cu-B-based sintered body with a powder layer of an R2-Ga-Co-based alloy.
  • a slurry in which an R2-Ga-Co alloy is dispersed in a dispersion medium is applied to the surface of an R1-T1-Cu-B sintered body, and then the dispersion medium is evaporated to form an R2-Ga-Co alloy.
  • the sintered body of R1-T1-Cu-B may be brought into contact.
  • the R2-Ga-Co based alloy may be arranged to be in contact with the surface perpendicular to the orientation direction of at least the R1-T1-Cu-B based sintered body.
  • the dispersion medium include alcohols (ethanol etc.), NMP (N-methylpyrrolidone), aldehydes and ketones.
  • known machining such as cutting or cutting may be performed on the R1-T1-Cu-B-based sintered body subjected to the first heat treatment.
  • Step of carrying out the second heat treatment The R1-T1-Cu-B-based sintered body subjected to the first heat treatment is heat-treated at a temperature of 450 ° C. to 600 ° C. in a vacuum or an inert gas atmosphere.
  • this heat treatment is referred to as a second heat treatment.
  • the second heat treatment it is possible to obtain a high B r and high H cJ.
  • the temperature of the second heat treatment is less than 450 ° C.
  • the second heat treatment temperature is preferably 480 ° C. or more and 560 ° C. or less. Higher H cJ can be obtained.
  • the heat treatment time is set appropriately depending on the composition and dimensions of the R1-T1-Cu-B sintered body, the heat treatment temperature, etc., but it is preferably 5 minutes to 20 hours and more preferably 10 minutes to 15 hours. More preferably, 30 minutes or more and 10 hours or less.
  • R is at least one rare earth element and necessarily includes at least one of Pr and Nd
  • T is at least one transition metal element. Yes Fe must be included.
  • the R 6 T 13 Z compound is typically an Nd 6 Fe 13 Ga compound. Further, the R 6 T 13 Z compound has a La 6 Co 11 Ga 3 type crystal structure.
  • the R 6 T 13 Z compound may be an R 6 T 13 ⁇ ⁇ Z 1+ ⁇ compound depending on the state. When relatively large amounts of Cu, Al, and Si are contained in the RTB-based sintered magnet, the R 6 T 13- ⁇ (Ga 1 -abc Cu a Al b Si c ) 1+ ⁇ It may have been.
  • the RTB-based sintered magnet obtained by the step of carrying out the second heat treatment described above is subjected to known surface treatment such as plating for imparting corrosion resistance or performing known machining such as cutting or cutting. It can be performed.
  • the RTB-based sintered magnet obtained by the production method of the present disclosure is characterized in that at least one of Fe or Co, Al, Mn, Si and Fe in the RTB-based sintered magnet is T2 ( The molar ratio of T2 to B ([T2] / [B]) is more than 14.0, and R, Fe, B, and Cu are equivalent to T1 in the R1-T1-Cu-B sintered body. And Ga are contained.
  • R Fe, B, Cu, Ga, Co, Al, Ag, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Si, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
  • the particle diameter D 50 is the volume center value obtained by the laser diffraction method by air flow dispersion method (volume-based median diameter).
  • the mixture After adding and mixing 0.05 mass% of zinc stearate as a lubricant with respect to 100 mass% of the finely pulverized powder to the finely pulverized powder, the mixture is molded in a magnetic field to obtain a compact.
  • a so-called perpendicular magnetic field forming apparatus transverse magnetic field forming apparatus in which the magnetic field application direction and the pressing direction are orthogonal to each other was used.
  • the obtained compact was sintered for 4 hours in vacuum at 1030 ° C. (the temperature at which sufficient densification by sintering occurs is selected) and then quenched to obtain an R1-T1-B-based sintered body.
  • the density of the obtained sintered body was 7.5 Mg / m 3 or more.
  • the results of the components of the obtained sintered body are shown in Table 1. Each component in Table 1 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES). In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%.
  • the C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
  • “[T1] / [B]” in Table 1 is obtained by dividing the analysis value (mass%) by the atomic weight of each element with respect to each element (here, Fe, Al, Si, Mn) constituting T1.
  • the same is true for all the following tables.
  • the amount of oxygen, and the amount of carbon it does not become 100 mass%. This is because, as described above, the analysis method differs depending on each component. The same applies to the other tables.
  • Step of preparing R2-Ga-Cu-Co based alloy Each element is weighed so that R2-Ga-Cu-Co alloy has a composition of code 1-a to 1-g of Table 2 approximately, and those raw materials are melted to perform single roll super-quenching method (melt spinning method) ) Gave a ribbon or flake-like alloy.
  • the obtained alloy was ground in an argon atmosphere using a mortar, and then passed through a sieve having an opening of 425 ⁇ m to prepare an R2-Ga-Cu-Co based alloy.
  • the composition of the obtained R2-Ga-Cu-Co based alloy is shown in Table 2. Each component in Table 2 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES).
  • a total of 20 mass% of 10 mass% of the R1-T1-B based sintered body was arranged above and below the body.
  • R2-Ga-Cu-Co alloys and R1-T1-B alloys were fired at the temperature and time shown in the first heat treatment of Table 3 in vacuum argon controlled at 200 Pa using a tubular flow air furnace. The body was heated to carry out the first heat treatment and then cooled.
  • the heating temperature of the R2-Ga-Cu-Co alloy and the R1-T1-B sintered body in the step of performing the first heat treatment, and R1-T1-B in the step of performing the second heat treatment was measured by attaching a thermocouple.
  • sample test The obtained samples were measured for B r and H cJ of the obtained samples by B-H tracer. The measurement results are shown in Table 3.
  • Table 3 the present invention examples of the Co content is less than 10 mass% ultra 45Mass% of R2-Cu-Ga-Fe-based alloy it can be seen that the high B r and a high H cJ are achieved.
  • the sample No. 1 in which the amount of Co in the R2-Ga-Cu-Co alloy is 10 mass% or less, and the content of Co ⁇ the content of Ga. 1-1 and 1-2 do not have high Br .
  • the amount of Co of the R2-Cu-Ga-Co alloy exceeds 45 mass%, and the sample No. 2 in which the content of Pr ⁇ the content of Co is satisfied. 1-7, high H cJ is not obtained.
  • Experimental Example 2 [Step of preparing R1-T1-B based sintered body] A sintered body was produced in the same manner as in Experimental Example 1 except that each element was weighed so that the R1-T1-B-based sintered body had a composition approximately as indicated by symbol 2-A in Table 4. Sintering was performed in the range of 1000 ° C. or more and 1050 ° C. or less (selecting the temperature at which densification by sintering sufficiently occurs for each sample). The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 4. Each component in Table 4 was measured by the same method as Experimental Example 1.
  • R2-Ga-Cu-Co based alloy [Step of preparing R2-Ga-Cu-Co based alloy]
  • R2-Ga-Cu- was prepared in the same manner as in Experimental Example 1 except that each element was weighed so that the R2-Ga-Cu-Co alloy had a composition as shown by symbols 2-a to 2-m in Table 5.
  • a Co-based alloy was prepared.
  • the composition of the R2-Ga-Cu-Co based alloy is shown in Table 5. Each component in Table 5 was measured by the same method as Experimental Example 1.
  • the first heat treatment was carried out in the same manner as in Experimental Example 1 except that the R2-Ga-Cu-Co based alloy and the R1-T1-B based sintered body were heated at the temperature and time shown in the first heat treatment of Table 6. Carried out.
  • Example test The obtained sample of B r and H cJ was measured by B-H tracer.
  • the measurement results are shown in Table 6.
  • the R2 content of the R2-Ga-Cu-Co alloy is 35 mass% to less than 85 mass%
  • the Ga content is 2.5 mass% to 30 mass%
  • the Cu content is 2.5 mass% to 20 mass%
  • the present invention examples in a composition satisfying the inequality of content> content of Co> content of Ga> content of Cu of R2 it is found that a high B r and a high H cJ are achieved.
  • any one of R, Cu and Ga in the R2-Ga-Cu-Co based alloy is out of the range of the present disclosure (for sample Nos.
  • R2 and Co are out of the range; 2-4, 2-6, and 2-12 are out of the range of Ga, sample Nos. 2-7 and 2-9 are out of the range of Cu, sample No. 2-13 is out of the range of Cu and Ga) Or the content of R2> the content of Co> the content of Ga> the composition not satisfying the inequality of the content of Cu (the sample No.2-8 is the content of Ga ⁇ content of Cu, sample No.2 If -10 is the content of Co ⁇ the content of Ga), high H cJ can not be obtained.
  • the content of R, Cu, Ga (and Co as shown in Experimental Example 1) of the R2-Ga-Cu-Co alloy is within the range of the present disclosure, and the content of R2> the content of Co by having a composition satisfying the formula of the content of an amount> the content of Ga> Cu, it is possible to obtain a high B r and a high H cJ.
  • Experimental Example 3 [Step of preparing R1-T1-B based sintered body] A sintered body was produced in the same manner as in Experimental Example 1 except that each element was weighed so that the R1-T1-B-based sintered body had a composition approximately as shown by symbol 3-A in Table 7. Sintering was performed in the range of 1000 ° C. or more and 1050 ° C. or less (selecting the temperature at which densification by sintering sufficiently occurs for each sample). The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 7. Each component in Table 7 was measured by the same method as Experimental example 1.
  • Step of preparing R2-Ga-Cu-Co based alloy The R2-Ga-Cu-Co alloy was prepared in the same manner as in Experimental Example 1 except that each element was weighed so that the R2-Ga-Cu-Co alloy had a composition as shown by the symbol 3-a in Table 8. Got ready. The composition of the R2-Ga-Cu-Co alloy is shown in Table 8. Each component in Table 8 was measured by the same method as Experimental Example 1.
  • the first heat treatment was conducted in the same manner as in Experimental Example 1 except that the R2-Ga-Cu-Co alloy and the R1-T1-B sintered body were heated at the temperature and time shown in the first heat treatment of Table 9. Carried out.
  • Example test The obtained sample of B r and H cJ was measured by B-H tracer.
  • the measurement results are shown in Table 9.
  • the first heat treatment temperature (700 ° C. or higher 1100 ° C. or less) and the present invention embodiment is a second heat treatment temperature (450 ° C. or higher 600 ° C. or less) of the present disclosure is higher B r and a high H cJ is obtained It is understood that it is being done.
  • Table 9 a further higher HcJ is obtained when the temperature in the first heat treatment is 800 ° C. or more and 1000 ° C. or less and the temperature in the second heat treatment is 480 ° C. or more and 560 ° C. or less.
  • any of the first heat treatment temperature and the second heat treatment temperature is out of the range of the present disclosure (the sample No. 3-1 is out of the range of the first heat treatment, sample Nos. 3-4 and 3-9 are If the second heat treatment is out of the range, high H cJ can not be obtained.
  • the particle size D 50 is the volume center value obtained by the laser diffraction method by air flow dispersion method (volume-based median diameter).
  • the mixture After adding and mixing 0.05 mass% of zinc stearate as a lubricant with respect to 100 mass% of the finely pulverized powder to the finely pulverized powder, the mixture is molded in a magnetic field to obtain a compact.
  • a so-called perpendicular magnetic field forming apparatus transverse magnetic field forming apparatus in which the magnetic field application direction and the pressing direction are orthogonal to each other was used.
  • the resulting compact is sintered for 4 hours in vacuum at 1000 ° C. or more and 1050 ° C. or less (select the temperature at which densification by sintering sufficiently occurs for each sample), and then quench it, R1-T1-B based sintering I got a body.
  • the density of the obtained sintered body was 7.5 Mg / m 3 or more.
  • the results of the components of the obtained sintered body are shown in Table 10. Each component in Table 10 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES). In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%.
  • the C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
  • “[T1] / [B]” in Table 10 is obtained by dividing the analysis value (mass%) by the atomic weight of each element with respect to each element (here, Fe, Al, Si, Mn) constituting T1.
  • the same is true for all the following tables.
  • the amount of oxygen, and the amount of carbon it does not become 100 mass%. This is because, as described above, the analysis method differs depending on each component. The same applies to the other tables.
  • Step of preparing R2-Ga-Co based alloy Each element is weighed so that the R2-Ga-Co alloy has a composition as shown by symbol 4-a in Table 11, and the raw materials are melted to obtain ribbons or flakes by a single roll super-quenching method (melt spinning method). An alloy of the shape of a circle is obtained. The obtained alloy was ground in an argon atmosphere using a mortar, and then passed through a sieve having an opening of 425 ⁇ m to prepare an R 2 -Ga-Co based alloy. The composition of the obtained R2-Ga-Co alloy is shown in Table 11. Each component in Table 11 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES).
  • ICP-OES inductively coupled plasma emission spectrometry
  • a plane perpendicular to the orientation direction (the direction of the arrow in the figure) of the R1-T1-Cu-B sintered body 1 is mainly
  • the R2-Ga-Co alloy of the code 4-a shown in Table 11 can be sintered with the R1-T1-Cu-B alloy of the code 4-A to 4-E.
  • a total of 20 mass% of 10 mass% of the R1-T1-Cu-B based sintered body was disposed above and below the body.
  • R2-Ga-Co alloys and R1-T1-Cu-B alloys are fired at the temperature and time shown in the first heat treatment of Table 12 in vacuum argon controlled at 200 Pa using a tubular flow air furnace. The body was heated to carry out the first heat treatment and then cooled.
  • Step of carrying out second heat treatment R1-T1-B system in which the first heat treatment was carried out at the temperature and time shown in the second heat treatment of Table 12 in a reduced pressure argon atmosphere where the second heat treatment was controlled to 200 Pa using a tubular flow air furnace It cooled after implementing with respect to the sintered compact.
  • the entire surface of each sample is cut using a surface grinder, and 4.0 mm ⁇ 4.0 mm ⁇ A 4.0 mm cube-shaped sample (R-T-B sintered magnet) was obtained.
  • the heating temperature of the B-based sintered body was measured by attaching a thermocouple.
  • sample test Each sample of B r and H cJ obtained was measured by B-H tracer. The measurement results are shown in Table 12. As shown in Table 12, sample No. 1 in which the Cu content of the R1-T1-Cu-B-based sintered body is less than 0.1 mass%. In 4-1, high H cJ is not obtained. In addition, sample No. 1 in which the content of Cu exceeds 1.5 mass%. 4-5 does not obtain a high B r and H cJ.
  • Experimental Example 5 [Step of preparing R1-T1-Cu-B based sintered body] A sintered body was produced in the same manner as in Experimental Example 4 except that each element was weighed so that the R1-T1-Cu-B-based sintered body had a composition as indicated by the symbol 5-A in Table 13. The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 13. Each component in Table 13 was measured by the same method as Experimental Example 4. In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
  • Step of preparing R2-Ga-Co based alloy The R2-Ga-Co alloy is prepared in the same manner as in Experimental Example 4 except that each element is weighed so that the R2-Ga-Co alloy has a composition as indicated by symbols 5-a to 5-g in Table 14. Got ready. The composition of the R2-Ga-Co based alloy is shown in Table 14. Each component in Table 14 was measured by the same method as Experimental Example 4.
  • the first heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the first heat treatment of Table 15. did.
  • Example test Each sample of B r and H cJ obtained was measured by B-H tracer. The measurement results are shown in Table 15.
  • Table 15 the present invention example Co amount of R-Ga-Co-based alloy is at most 10 mass% ultra 45Mass% It can be seen that the high B r and a high H cJ are achieved.
  • the sample No. 1 in which the amount of Co in the R-Ga-Co alloy exceeds 45 mass% the content of Pr ⁇ the content of Co. In 5-7, high H cJ is not obtained.
  • Experimental Example 6 [Step of preparing R1-T1-Cu-B based sintered body] A sintered body was produced in the same manner as in Experimental Example 4 except that each element was weighed so that the R1-T1-Cu-B-based sintered body had a composition shown in the code 6-A in Table 16. The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 16. Each component in Table 16 was measured by the same method as Experimental Example 4. In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
  • Step of preparing R2-Ga-Co based alloy The R2-Ga-Co alloy is prepared in the same manner as in Experimental Example 4 except that each element is weighed so that the R2-Ga-Co alloy has a composition as shown by symbols 6-a to 6-i in Table 17. Got ready. The composition of the R2-Ga-Co based alloy is shown in Table 17. Each component in Table 17 was measured by the same method as Experimental Example 4.
  • the first heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the first heat treatment of Table 18 did.
  • Example test Each sample of B r and H cJ obtained was measured by B-H tracer. The measurement results are shown in Table 18. As shown in Table 18, R2 content of R2-Ga-Co alloy is 35 mass% or more and 87 mass% or less, Ga content is 2.5 mass% or more and 30 mass% or less, and R2 content> Co content> Ga content the present invention examples in a composition satisfying the inequality is seen that a high B r and a high H cJ are achieved. On the other hand, any one of R and Ga in the R2-Ga-Co alloy is out of the range of the present disclosure (sample No. 6-1 has R2 out of the range, sample No. 6-3 has R2 and Co out of the range Sample Nos.
  • Experimental Example 7 [Step of preparing R1-T1-B based sintered body] A sintered body was produced in the same manner as in Experimental Example 4 except that each element was weighed so that the R1-T1-B-based sintered body had a composition approximately as shown by symbol 7-A in Table 19. The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 19. Each component in Table 19 was measured by the same method as Experimental Example 4. In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
  • the first heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the first heat treatment of Table 21. did.
  • sample test The obtained samples were subjected to B-H tracer to measure B r and H c J of each sample.
  • the measurement results are shown in Table 21.
  • the first heat treatment temperature (700 ° C. or higher 1100 ° C. or less) and the present invention embodiment is a second heat treatment temperature (450 ° C. or higher 600 ° C. or less) of the present disclosure is higher B r and a high H cJ is obtained It is understood that it is being done.
  • a further higher HcJ is obtained when the temperature in the first heat treatment is 800 ° C. or more and 1000 ° C. or less and the temperature in the second heat treatment is 480 ° C. or more and 560 ° C. or less.
  • the first heat treatment temperature or the second heat treatment temperature is out of the range of the present disclosure (the sample No. 7-1 is out of the range of the first heat treatment, the sample Nos. 7-4 and 7-9 are If the second heat treatment is out of the range, high H cJ can not be obtained.
  • the RTB-based sintered magnet obtained by the present disclosure includes various motors such as a voice coil motor (VCM) of a hard disk drive, a motor for electric vehicles (EV, HV, PHV, etc.), a motor for industrial equipment, It can be suitably used for home appliances and the like.
  • VCM voice coil motor
  • EV electric vehicles
  • HV PHV
  • industrial equipment a motor for industrial equipment
  • R1-T1-B based sintered body (R1-T1-Cu-B based sintered body) 2 R2-Ga-Cu-Co alloy (R2-Ga-Co alloy) 3 treatment vessel 12 main phase 14 grain boundary phase 14a double grain grain boundary phase 14b grain boundary triple point

Abstract

The present invention discloses a method for manufacturing an R-T-B-based sintered magnet, including: a step for preparing an R1-T1-B-based sintered body; a step for preparing an R2-Ga-Cu-Co-based alloy; a step for executing, by bringing at least a section of the alloy into contact with at least a section of a surface of the sintered body, a first heat treatment in a vacuum or inert-gas atmosphere at a temperature of 700ºC to 1100ºC; and a step for executing, on the R1-T1-B-based sintered body that has been subjected to the first heat treatment, a second heat treatment in the vacuum or inert-gas atmosphere at a temperature of 450ºC to 600ºC. R1 and R2 are at least one type of rare-earth element, and at least one of Nd and Pr is always included. The molar ratio of T1 with respect to B ([T1]/[B]) is greater than 14.0 and equal to or less than 15.0.

Description

Ｒ－Ｔ－Ｂ系焼結磁石の製造方法Method of manufacturing RTB-based sintered magnet
　本発明は、Ｒ－Ｔ－Ｂ系焼結磁石の製造方法に関する。 The present invention relates to a method for producing an RTB-based sintered magnet.
　Ｒ－Ｔ－Ｂ系焼結磁石（Ｒは希土類元素のうちの少なくとも一種である。Ｔは遷移金属元素のうち少なくとも一種でありＦｅを必ず含む。Ｂは硼素である）は永久磁石の中で最も高性能な磁石として知られており、ハードディスクドライブのボイスコイルモータ（ＶＣＭ）、電気自動車用（ＥＶ、ＨＶ、ＰＨＶなど）モータ、産業機器用モータなどの各種モータや家電製品などに使用されている。 RTB-based sintered magnet (R is at least one of rare earth elements. T is at least one of transition metal elements and necessarily contains Fe. B is boron.) Is a permanent magnet. It is known as the most powerful magnet, and is used for voice coil motor (VCM) of hard disk drive, electric motor (EV, HV, PHV etc.) motor for electric car, various motors such as motor for industrial equipment, home electric appliance etc. There is.
　Ｒ－Ｔ－Ｂ系焼結磁石は主としてＲ2Ｔ14Ｂ化合物からなる主相とこの主相の粒界部分に位置する粒界相（以下、単に「粒界」という場合がある）とから構成されている。Ｒ2Ｔ14Ｂ化合物は高い磁化を持つ強磁性相でありＲ－Ｔ－Ｂ系焼結磁石の特性の根幹をなしている。 The RTB-based sintered magnet is mainly composed of a main phase consisting of an R 2 T 14 B compound and a grain boundary phase located at grain boundaries of the main phase (hereinafter sometimes referred to simply as “grain boundaries”). It is configured. The R 2 T 14 B compound is a ferromagnetic phase with high magnetization, and forms the basis of the characteristics of the RTB-based sintered magnet.
　Ｒ－Ｔ－Ｂ系焼結磁石は、高温で保磁力ＨcJ（以下、単に「保磁力」又は「ＨcJ」という場合がある）が低下するため不可逆熱減磁が起こるという問題がある。そのため、特に電気自動車用モータに使用されるＲ－Ｔ－Ｂ系焼結磁石では、高温下でも高いＨcJを有する、すなわち室温においてより高いＨcJを有することが要求されている。 The RTB -based sintered magnet has a problem that irreversible thermal demagnetization occurs because the coercivity H cJ (hereinafter, sometimes simply referred to as "coercivity" or "H cJ ") decreases at high temperature. Therefore, in the RTB -based sintered magnet used particularly for a motor for an electric vehicle, it is required to have high H cJ even under high temperature, that is, to have higher H cJ at room temperature.
　Ｒ－Ｔ－Ｂ系焼結磁石において、Ｒ2Ｔ14Ｂ化合物中のＲに含まれる軽希土類元素（主としてＮｄ及び／又はＰｒ）の一部を重希土類元素（主としてＤｙ及び／又はＴｂ）で置換すると、ＨcJが向上することが知られている。重希土類元素の置換量の増加に伴いＨcJは向上する。 In the RTB-based sintered magnet, part of the light rare earth elements (mainly Nd and / or Pr) contained in R in the R 2 T 14 B compound is a heavy rare earth element (mainly Dy and / or Tb) It is known that substitution improves H cJ . H cJ improves as the substitution amount of heavy rare earth elements increases.
　しかし、Ｒ2Ｔ14Ｂ化合物中の軽希土類元素を重希土類元素で置換するとＲ－Ｔ－Ｂ系焼結磁石のＨcJが向上する一方、残留磁束密度Ｂr（以下、単に「Ｂr」という場合がある）が低下する。また、重希土類元素、特にＤｙなどは資源存在量が少ないうえ産出地が限定されているなどの理由から供給が安定しておらず、価格が大きく変動するなどの問題を有している。そのため、近年、ユーザーから重希土類元素をできるだけ使用することなくＨcJを向上させることが求められている。 However, replacing the light rare earth element in the R 2 T 14 B compound with a heavy rare earth element improves H cJ of the RTB -based sintered magnet, while the residual magnetic flux density B r (hereinafter simply referred to as “B r ” May fall down). In addition, heavy rare earth elements, in particular Dy, etc., have a problem that supply is not stable due to a small amount of resources and limited production areas, and the price fluctuates significantly. Therefore, in recent years, the user is required to improve H cJ without using heavy rare earth elements as much as possible.
　特許文献１には、Ｄｙの含有量を低減しつつ保磁力を高めたＲ－Ｔ－Ｂ系希土類焼結磁石が開示されている。この焼結磁石の組成は、一般に用いられてきたＲ－Ｔ－Ｂ系合金に比べてＢ量が相対的に少ない特定の範囲に限定され、かつ、Ａｌ、Ｇａ、Ｃｕのうちから選ばれる１種以上の金属元素Ｍを含有している。その結果、粒界にＲ2Ｔ17相が生成され、このＲ2Ｔ17相から粒界に形成される遷移金属リッチ相（Ｒ6Ｔ13Ｍ）の体積比率が増加することにより、ＨcJが向上する。 Patent Document 1 discloses an RTB-based rare earth sintered magnet in which the coercive force is increased while reducing the content of Dy. The composition of this sintered magnet is limited to a specific range in which the amount of B is relatively small compared to a commonly used RTB-based alloy, and is selected from Al, Ga, and Cu 1 It contains metal element M of a species or more. As a result, R 2 T 17 phase is produced in the grain boundary, by the volume ratio of the R 2 T 17 transition metal-rich phase formed in the grain boundary from phase (R 6 T 13 M) increases, H cJ Improve.
国際公開第２０１３／００８７５６号International Publication No. 2013/008756
　特許文献１に記載されている方法は、重希土類元素の含有量を抑制しつつＲ－Ｔ－Ｂ系焼結磁石を高保磁力化できる点で注目に値する。しかし、Ｂrが大幅に低下するという問題があった。また、近年、電気自動車用モータ等の用途において更に高いＨcJを有するＲ－Ｔ－Ｂ系焼結磁石が求められている。 The method described in Patent Document 1 is noteworthy in that the coercive force of the RTB-based sintered magnet can be increased while suppressing the content of heavy rare earth elements. However, there is a problem that B r is greatly reduced. Further, in recent years, RTB -based sintered magnets having higher H cJ have been required in applications such as motors for electric vehicles.
　本開示の実施形態は、重希土類元素の含有量を低減しつつ、高いＢr及び高いＨcJを有するＲ－Ｔ－Ｂ系焼結磁石の製造方法を提供する。 Embodiments of the present disclosure, while reducing the content of heavy rare earth elements, to provide a method of manufacturing a R-T-B based sintered magnet having a high B r and a high H cJ.
　本開示のＲ－Ｔ－Ｂ系焼結磁石の製造方法は、限定的ではない例示的な実施形態において、Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程と、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程と、前記Ｒ１－Ｔ１－Ｂ系焼結体の表面の少なくとも一部に、前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金の少なくとも一部を接触させ、真空又は不活性ガス雰囲気中、７００℃以上１１００℃以下の温度で第一の熱処理を実施する工程と、前記第一の熱処理が実施されたＲ１－Ｔ１－Ｂ系焼結体に対して、真空又は不活性ガス雰囲気中、４５０℃以上６００℃以下の温度で第二の熱処理を実施する工程とを含む。前記Ｒ１－Ｔ１－Ｂ系焼結体において、Ｒ１は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含み、Ｒ１の含有量は、Ｒ１－Ｔ１－Ｂ系焼結体全体の２７ｍａｓｓ％以上３５ｍａｓｓ％以下であり、Ｔ１はＦｅ、Ｃｏ、Ａｌ、Ｍｎ、及びＳｉからなる群から選択された少なくとも１つであり、Ｔ１は必ずＦｅを含有し、Ｔ１全体に対するＦｅの含有量が８０ｍａｓｓ％以上であり、Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０超１５．０以下である。前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金において、Ｒ２は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含み、Ｒ２の含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の３５ｍａｓｓ％以上８５ｍａｓｓ％未満であり、Ｇａの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上３０ｍａｓｓ％以下であり、Ｃｕの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上２０ｍａｓｓ％以下であり、Ｃｏの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の１０ｍａｓｓ％超４５ｍａｓｓ％以下であり、Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量＞Ｃｕの含有量の不等式が成立する。 The method of producing the RTB-based sintered magnet of the present disclosure is, in a non-limiting exemplary embodiment, preparing an R1-T1-B-based sintered body, R2-Ga-Cu-Co, and And preparing at least a part of the R2-Ga-Cu-Co alloy on at least a part of the surface of the R1-T1-B sintered body, in a vacuum or inert gas atmosphere. And a step of performing the first heat treatment at a temperature of 700 ° C. or more and 1100 ° C. or less, and a vacuum or inert gas atmosphere for the R1-T1-B-based sintered body subjected to the first heat treatment. And performing a second heat treatment at a temperature of 450 ° C. or more and 600 ° C. or less. In the R1-T1-B-based sintered body, R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is the entire R1-T1-B-based sintered body. 27 mass% or more and 35 mass% or less, T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si, T1 always contains Fe, and the Fe content relative to the entire T1 is It is 80 mass% or more, and the molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less. In the R2-Ga-Cu-Co-based alloy, R2 is at least one of rare earth elements and necessarily contains at least one of Nd and Pr, and the content of R2 is that of the entire R2-Ga-Cu-Co-based alloy The content of Ga is 35 mass% to less than 85 mass%, the content of Ga is 2.5 mass% to 30 mass% of the entire R2-Ga-Cu-Co alloy, and the content of Cu is R2-Ga-Cu-Co. The content of Co is more than 10 mass% and less than 45 mass% of the whole R2-Ga-Cu-Co alloy, and the content of R> the content of Co. > Ga content> Cu content inequality is satisfied.
　ある実施形態において、前記Ｂに対するＴのｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．５以上１５．０以下である。 In one embodiment, the molar ratio of T to B ([T1] / [B]) is 14.5 or more and 15.0 or less.
　ある実施形態において、前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金中のＲ２の５０ｍａｓｓ％以上がＰｒである。 In one embodiment, 50 mass% or more of R2 in the R2-Ga-Cu-Co based alloy is Pr.
　ある実施形態において、前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金中のＲ２の７０ｍａｓｓ％以上がＰｒである。 In one embodiment, 70 mass% or more of R2 in the R2-Ga-Cu-Co based alloy is Pr.
　ある実施形態では、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金におけるＲ２－Ｇａ－Ｃｕ－Ｃｏの合計の含有量が８０ｍａｓｓ％以上である。 In one embodiment, the total content of R 2 -Ga-Cu-Co in the R 2 -Ga-Cu-Co-based alloy is 80 mass% or more.
　ある実施形態では、前記第一の熱処理における温度が８００℃以上１０００℃以下である。 In one embodiment, the temperature in the first heat treatment is 800 ° C. or more and 1000 ° C. or less.
　ある実施形態では、前記第二の熱処理における温度が４８０℃以上５６０℃以下である。 In one embodiment, the temperature in the second heat treatment is 480 ° C. or more and 560 ° C. or less.
　前記Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程は、原料合金を粒径Ｄ50が３μｍ以上１０μｍ以下に粉砕した後、磁界中で配向させて焼結を行うことを含む。 Preparing the R1-T1-B based sintered body comprises performing after the material alloy particle size D 50 was pulverized to 3μm or 10μm or less, the sintering being oriented in a magnetic field.
　本開示のＲ－Ｔ－Ｂ系焼結磁石の製造方法は、限定的ではない例示的な他の実施形態において、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程と、Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程と、前記Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体の表面の少なくとも一部に、前記Ｒ２－Ｇａ－Ｃｏ系合金の少なくとも一部を接触させ、真空又は不活性ガス雰囲気中、７００℃以上１１００℃以下の温度で第一の熱処理を実施する工程と、前記第一の熱処理が実施されたＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体に対して、真空又は不活性ガス雰囲気中、４５０℃以上６００℃以下の温度で第二の熱処理を実施する工程と、を含み、前記Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体において、Ｒ１は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含み、Ｒ１の含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の２７ｍａｓｓ％以上３５ｍａｓｓ％以下であり、Ｔ１はＦｅ、Ｃｏ、Ａｌ、Ｍｎ、及びＳｉからなる群から選択された少なくとも１つであり、Ｔ１は必ずＦｅを含有し、Ｔ１全体に対するＦｅの含有量が８０ｍａｓｓ％以上であり、Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０超１５．０以下であり、Ｃｕの含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の０．１ｍａｓｓ％以上１．５ｍａｓｓ％以下であり、前記Ｒ２－Ｇａ－Ｃｏ系合金において、Ｒ２は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含み、Ｒ２の含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の３５ｍａｓｓ％以上８７ｍａｓｓ％未満であり、Ｇａの含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上３０ｍａｓｓ％以下であり、Ｃｏの含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の１０ｍａｓｓ％超４５ｍａｓｓ％以下であり、Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量の不等式が成立する。 The manufacturing method of the RTB-based sintered magnet of the present disclosure is, in another exemplary embodiment not limiting, preparing an R1-T1-Cu-B-based sintered body; And preparing at least a part of the R2-Ga-Co alloy on at least a part of the surface of the R1-T1-Cu-B sintered body, in a vacuum or inactive state. The step of performing the first heat treatment at a temperature of 700 ° C. or more and 1100 ° C. or less in a gas atmosphere, and vacuum or failure for the R1-T1-Cu-B-based sintered body for which the first heat treatment is performed. Carrying out the second heat treatment at a temperature of 450 ° C. to 600 ° C. in an active gas atmosphere, and in the R1-T1-Cu-B-based sintered body, R1 is at least one of rare earth elements Yes, including at least one of Nd and Pr The content of R1 is 27 mass% or more and 35 mass% or less of the entire R1-T1-Cu-B-based sintered body, and T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si. T1 always contains Fe, the content of Fe with respect to the whole T1 is 80 mass% or more, and the molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less The content of Cu is 0.1 mass% or more and 1.5 mass% or less of the entire R1-T1-Cu-B-based sintered body, and in the R2-Ga-Co-based alloy, R2 is a rare earth element. The content of R2 is at least 35 mass% and less than 87 mass% of the whole R2-Ga-Co alloy, and the content of Ga is R2-G. 2.5 mass% or more and 30 mass% or less of the whole -Co alloy, the content of Co is more than 10 mass% and 45 mass% or less of the whole R2-Ga-Co alloy, the content of R2> the content of Co The inequality of the content of Ga is established.
　ある実施形態において、前記Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．３以上１５．０以下である。 In one embodiment, the molar ratio of T1 to B ([T1] / [B]) is 14.3 or more and 15.0 or less.
　ある実施形態において、前記Ｒ２－Ｇａ－Ｃｏ系合金中のＲ２の５０ｍａｓｓ％以上がＰｒである。 In one embodiment, 50 mass% or more of R2 in the R2-Ga-Co-based alloy is Pr.
　ある実施形態において、前記Ｒ２－Ｇａ－Ｃｏ系合金中のＲ２の７０ｍａｓｓ％以上がＰｒである。 In one embodiment, 70 mass% or more of R2 in the R2-Ga-Co-based alloy is Pr.
　ある実施形態において、Ｒ２－Ｇａ－Ｃｏ系合金におけるＲ２、Ｇａ、Ｃｏの合計の含有量が８０ｍａｓｓ％以上である。 In one embodiment, the total content of R2, Ga, and Co in the R2-Ga-Co-based alloy is 80 mass% or more.
　ある実施形態において、前記第一の熱処理における温度が８００℃以上１０００℃以下である。 In one embodiment, the temperature in the first heat treatment is 800 ° C. or more and 1000 ° C. or less.
　ある実施形態において、前記第二の熱処理における温度が４８０℃以上５６０℃以下である。 In one embodiment, the temperature in the second heat treatment is 480 ° C. or more and 560 ° C. or less.
　ある実施形態において、前記Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程は、原料合金を粒径Ｄ50が３μｍ以上１０μｍ以下に粉砕した後、磁界中で配向させて焼結を行うことを含む。 In certain embodiments, the step of preparing the R1-T1-Cu-B based sintered body, after the material alloy particle size D 50 was pulverized to 3μm or 10μm or less, sintering is performed by orienting in a magnetic field Including.
　本開示の実施形態によると、重希土類元素の含有量を低減しつつ、高いＢr及び高いＨcJを有するＲ－Ｔ－Ｂ系焼結磁石の製造方法を提供することができる。 According to embodiments of the present disclosure, while reducing the content of heavy rare earth elements, it is possible to provide a manufacturing method of the R-T-B based sintered magnet having a high B r and a high H cJ.
本開示によるＲ－Ｔ－Ｂ系焼結磁石の製造方法（第１の実施形態）における工程の例を示すフローチャートである。It is a flowchart which shows the example of the process in the manufacturing method (1st Embodiment) of the RTB type | system | group sintered magnet by this indication. Ｒ－Ｔ－Ｂ系焼結磁石の主相と粒界相を示す模式図である。FIG. 2 is a schematic view showing a main phase and a grain boundary phase of an RTB-based sintered magnet. 図２Ａの破線矩形領域内を更に拡大した模式図である。It is the schematic diagram which further expanded the inside of the broken-line rectangular area | region of FIG. 2A. 熱処理工程におけるＲ１－Ｔ１－Ｂ系合金焼結体（またはＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体）とＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金（またはＲ２－Ｇａ－Ｃｏ系合金）との配置形態を模式的に示す説明図である。Arrangement of R1-T1-B based alloy sintered body (or R1-T1-Cu-B based sintered body) and R2-Ga-Cu-Co based alloy (or R2-Ga-Co based alloy) in heat treatment process It is explanatory drawing which shows a form typically. 本開示によるＲ－Ｔ－Ｂ系焼結磁石の製造方法（第２の実施形態）における工程の例を示すフローチャートである。It is a flowchart which shows the example of the process in the manufacturing method (2nd Embodiment) of the RTB type | system | group sintered magnet by this indication.
　本開示において、希土類元素を総称して「Ｒ」と表記する場合がある。希土類元素Ｒのうちの特定の元素又は元素群を指すとき、例えば「Ｒ１」又は「Ｒ２」の符号を用いて他の希土類元素から区別する。また、本開示において、Ｆｅを含む遷移金属元素の全体を「Ｔ」と表記する。遷移金属元素Ｔのうちの特定の元素または元素群及び主相のＦｅサイトと容易に置換される遷移金属元素以外の特定の元素又は元素群の両方を含むとき、「Ｔ１」の符号を用いて他の遷移金属元素から区別する。 In the present disclosure, rare earth elements may be collectively referred to as “R”. When referring to a specific element or group of elements among the rare earth elements R, for example, the sign of “R1” or “R2” is used to distinguish from other rare earth elements. Further, in the present disclosure, the entire transition metal element including Fe is denoted as “T”. When the transition metal element T includes both a specific element or element group and a specific element or element group other than the transition metal element which is easily substituted with the Fe site of the main phase, using the symbol of “T1” Distinguish from other transition metal elements.
＜第１の実施形態＞
　本開示による第１の実施形態におけるＲ－Ｔ－Ｂ系焼結磁石の製造方法は、図１に示すように、Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程Ｓ１０と、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程Ｓ２０とを含む。Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程Ｓ１０と、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程Ｓ２０との順序は任意であり、それぞれ、異なる場所で製造されたＲ１－Ｔ１－Ｂ系焼結体及びＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金を用いてもよい。 First Embodiment
A method of manufacturing an RTB-based sintered magnet according to the first embodiment of the present disclosure includes, as shown in FIG. 1, a step S10 of preparing an R1-T1-B-based sintered body, and R2-Ga- And S20 of preparing a Cu--Co alloy. The order of the step S10 of preparing the R1-T1-B-based sintered body and the step S20 of preparing the R2-Ga-Cu-Co-based alloy is arbitrary, and each of the R1-T1-B manufactured in different places. A B-based sintered body and an R2-Ga-Cu-Co-based alloy may be used.
　本開示において、第二の熱処理前及び第二の熱処理中のＲ－Ｔ－Ｂ系焼結磁石をＲ１－Ｔ１－Ｂ系焼結体と称し、第二の熱処理後のＲ１－Ｔ１－Ｂ系焼結体を単にＲ－Ｔ－Ｂ系焼結磁石と称する。 In the present disclosure, the RTB-based sintered magnet before the second heat treatment and during the second heat treatment is referred to as an R1-T1-B-based sintered body, and the R1-T1-B system after the second heat treatment The sintered body is simply referred to as an RTB-based sintered magnet.
　Ｒ１－Ｔ１－Ｂ系焼結体においては、下記（A１）～（A３）が成立している。
（A１）Ｒ１は希土類元素のうち少なくとも一種でありＮｄ及びＰｒの少なくとも一方を必ず含み、Ｒ１の含有量は、Ｒ１－Ｔ１－Ｂ系焼結体全体の２７ｍａｓｓ％以上３５ｍａｓｓ％以下である。
（A２）Ｔ１はＦｅ、Ｃｏ、Ａｌ、Ｍｎ、及びＳｉからなる群から選択された少なくとも１つであり、Ｔ１は必ずＦｅを含有し、Ｔ１全体に対するＦｅの含有量が８０ｍａｓｓ％以上である。
（A３）Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０超１５．０以下である。 In the R1-T1-B based sintered body, the following (A1) to (A3) hold.
(A1) R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is 27 mass% or more and 35 mass% or less of the entire R1-T1-B-based sintered body.
(A2) T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si. T1 necessarily contains Fe, and the content of Fe with respect to the entire T1 is 80 mass% or more.
The molar ratio of T1 to (A3) B ([T1] / [B]) is more than 14.0 and 15.0 or less.
　本開示におけるＢに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）とは、Ｔ１を構成する各元素（Ｆｅ又はＣｏ、Ａｌ、Ｍｎ、Ｓｉの少なくとも１つとＦｅ）の分析値（ｍａｓｓ％）をそれぞれの元素の原子量で除したものを求め、それらの値を合計したもの（ａ）と、Ｂの分析値（ｍａｓｓ％）をＢの原子量で除したもの（ｂ）との比（ａ／ｂ）である。 The molar ratio of T1 to B ([T1] / [B]) in the present disclosure is the analysis value (mass%) of each element (Fe or at least one of Fe, Co, Al, Mn, Si and Fe) constituting T1. Calculate the ratio of the atomic weight of each element divided by the atomic weight of each element (a) and the ratio (a /) of the analytical value (mass%) of B divided by the atomic weight of B (b) b).
　Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０を超えるということは、Ｂの含有比率がＲ2Ｔ14Ｂ化合物の化学量論組成比よりも低いことを意味している。言い換えると、Ｒ１－Ｔ１－Ｂ系焼結体において、主相（Ｒ2Ｔ14Ｂ化合物）の形成に使われるＴ１の量に対して相対的にＢ量が少ない。 The fact that the molar ratio of T1 to B ([T1] / [B]) exceeds 14.0 means that the content ratio of B is lower than the stoichiometric composition ratio of the R 2 T 14 B compound. There is. In other words, in the R1-T1-B based sintered body, the amount of B is relatively smaller than the amount of T1 used for forming the main phase (R 2 T 14 B compound).
　Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金においては、以下の（A４）～（A８）が成立している。
（A４）Ｒ２は希土類元素のうち少なくとも一種でありＮｄ及びＰｒの少なくとも一方を必ず含み、Ｒ２の含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の３５ｍａｓｓ％以上８５ｍａｓｓ％未満である。
（A５）Ｇａの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上３０ｍａｓｓ％以下である。
（A６）Ｃｕの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上２０ｍａｓｓ％以下である。
（A７）Ｃｏの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の１０ｍａｓｓ％超４５ｍａｓｓ％以下である。
（A８）Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量＞Ｃｕの含有量の不等式が成立する。 In the R2-Ga-Cu-Co based alloy, the following (A4) to (A8) hold true.
(A4) R2 is at least one of rare earth elements and necessarily contains at least one of Nd and Pr, and the content of R2 is 35 mass% or more and less than 85 mass% of the entire R2-Ga-Cu-Co alloy.
The content of (A5) Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Cu-Co alloy.
The content of (A6) Cu is 2.5 mass% or more and 20 mass% or less of the entire R2-Ga-Cu-Co alloy.
The content of (A7) Co is more than 10% by weight and 45% by weight or less of the entire R2-Ga-Cu-Co based alloy.
(A8) Content of R2> Content of Co> Content of Ga> Inequalities of Content of Cu are satisfied.
　本開示によるＲ－Ｔ－Ｂ系焼結磁石の製造方法では、主相（Ｒ2Ｔ14Ｂ化合物）形成に使われるＴの量に対して化学量論比で相対的にＢ量が少ないＲ１－Ｔ１－Ｂ系焼結体の表面の少なくとも一部にＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金を接触させ、図１に示すように、真空又は不活性ガス雰囲気中、７００℃以上１１００℃以下の温度で第一の熱処理を実施する工程Ｓ３０と、この第一の熱処理が実施されたＲ１－Ｔ１－Ｂ系焼結体に対して真空又は不活性ガス雰囲気中、４５０℃以上６００℃以下の温度で第二の熱処理を実施する工程Ｓ４０を行う。これにより、高いＢr及び高いＨcJを有するＲ－Ｔ－Ｂ系焼結磁石を得ることができる。 In the method of producing an RTB-based sintered magnet according to the present disclosure, R1 having a relatively small amount of B in a stoichiometric ratio relative to the amount of T used to form the main phase (R 2 T 14 B compound) An R2-Ga-Cu-Co alloy is brought into contact with at least a part of the surface of the -T1-B sintered body, and as shown in FIG. 1, in a vacuum or inert gas atmosphere, at 700.degree. C. or more and 1100.degree. Temperature of 450 ° C. or more and 600 ° C. or less in a vacuum or inert gas atmosphere with respect to the step S30 of performing the first heat treatment at a temperature and the R1-T1-B-based sintered body subjected to the first heat treatment In step S40, the second heat treatment is performed. Thus, it is possible to obtain the R-T-B based sintered magnet having a high B r and a high H cJ.
　第一の熱処理を実施する工程Ｓ３０と、第二の熱処理を実施する工程Ｓ４０との間に他の工程、例えば冷却工程などが実行され得る。 Another step, such as a cooling step, may be performed between the step S30 of performing the first heat treatment and the step S40 of performing the second heat treatment.
　まず、Ｒ－Ｔ－Ｂ系焼結磁石の基本構造を説明する。 First, the basic structure of the RTB-based sintered magnet will be described.
　Ｒ－Ｔ－Ｂ系焼結磁石は、原料合金の粉末粒子が焼結によって結合した構造を有しており、主としてＲ2Ｔ14Ｂ化合物からなる主相と、この主相の粒界部分に位置する粒界相とから構成されている。 The RTB-based sintered magnet has a structure in which powder particles of a raw material alloy are bonded by sintering, and a main phase mainly composed of an R 2 T 14 B compound and a grain boundary portion of this main phase It is composed of the located grain boundary phase.
　図２Ａは、Ｒ－Ｔ－Ｂ系焼結磁石の主相と粒界相を示す模式図であり、図２Ｂは図２Ａの破線矩形領域内を更に拡大した模式図である。図２Ａには、一例として長さ５μｍの矢印が大きさを示す基準の長さとして参考のために記載されている。図２Ａ及び図２Ｂに示されるように、Ｒ－Ｔ－Ｂ系焼結磁石は、主としてＲ2Ｔ14Ｂ化合物からなる主相１２と、主相１２の粒界部分に位置する粒界相１４とから構成されている。また、粒界相１４は、図２Ｂに示されるように、２つのＲ2Ｔ14Ｂ化合物粒子（グレイン）が隣接する二粒子粒界相１４ａと、３つ以上のＲ2Ｔ14Ｂ化合物粒子が隣接する粒界三重点１４ｂとを含む。 FIG. 2A is a schematic view showing the main phase and the grain boundary phase of the RTB-based sintered magnet, and FIG. 2B is a schematic view further enlarging the inside of the dashed rectangular area of FIG. 2A. In FIG. 2A, an arrow of 5 μm in length as an example is described for reference as a reference length indicating the size. As shown in FIGS. 2A and 2B, the RTB-based sintered magnet includes a main phase 12 mainly composed of an R 2 T 14 B compound, and a grain boundary phase 14 located in the grain boundary portion of the main phase 12. And consists of In addition, as shown in FIG. 2B, the grain boundary phase 14 is a two-grain grain boundary phase 14a in which two R 2 T 14 B compound particles (grains) are adjacent, and three or more R 2 T 14 B compound particles. And the adjacent grain boundary triple point 14b.
　主相１２であるＲ2Ｔ14Ｂ化合物は高い飽和磁化と異方性磁界を持つ強磁性相である。したがって、Ｒ－Ｔ－Ｂ系焼結磁石では、主相１２であるＲ2Ｔ14Ｂ化合物の存在比率を高めることによってＢrを向上させることができる。Ｒ2Ｔ14Ｂ化合物の存在比率を高めるためには、原料合金中のＲ量、Ｔ量、Ｂ量を、Ｒ2Ｔ14Ｂ化合物の化学量論比（Ｒ量：Ｔ量：Ｂ量＝２：１４：１）に近づければよい。Ｒ2Ｔ14Ｂ化合物を形成するためのＢ量又はＲ量が化学量論比を下回ると、一般的には、粒界相１４にＦｅ相又はＲ2Ｔ17相等の強磁性体が生成し、ＨcJが急激に低下する。しかし、特許文献１に記載されている方法のように、Ｂ量をＲ2Ｔ14Ｂ化合物の化学量論比よりも少なくし、且つ、Ａｌ、Ｇａ、Ｃｕのうちから選ばれる１種以上の金属元素Ｍを含有させると、Ｒ2Ｔ17相から粒界に遷移金属リッチ相（例えばＲ－Ｔ－Ｇａ相）が生成されて高いＨcJを得ることができる。しかし、特許文献１に記載されている方法では、Ｂrが大幅に低下してしまう。 The R 2 T 14 B compound which is the main phase 12 is a ferromagnetic phase having high saturation magnetization and anisotropic magnetic field. Therefore, in the R-T-B based sintered magnet, it is possible to improve the B r by increasing the existence ratio of R 2 T 14 B compound is the main phase 12. In order to increase the abundance ratio of the R 2 T 14 B compound, the R amount, T amount, B amount in the raw material alloy and the stoichiometric ratio of the R 2 T 14 B compound (R amount: T amount: B amount = It should be close to 2: 14: 1). When the amount of B or R for forming the R 2 T 14 B compound is less than the stoichiometric ratio, generally, a ferromagnetic substance such as an Fe phase or an R 2 T 17 phase is formed in the grain boundary phase 14 , H cJ falls sharply. However, as in the method described in Patent Document 1, the amount of B is less than the stoichiometric ratio of the R 2 T 14 B compound, and at least one selected from Al, Ga, and Cu. When the metal element M is contained, a transition metal rich phase (for example, RT-Ga phase) is generated at grain boundaries from the R 2 T 17 phase, and high H cJ can be obtained. However, in the method described in Patent Document 1, Br is significantly reduced.
　本発明者らは検討の結果、低Ｂ組成である特定の組成を有するＲ１－Ｔ１－Ｂ系焼結体の表面の少なくとも一部に、Ｃｏの含有量が比較的多いＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金を接触させて特定の熱処理を実施すると、意外にも、最終的に得られる焼結磁石は、高いＢrと高いＨcJを実現できることがわかった。 As a result of investigations, the present inventors have found that R2-Ga-Cu- containing a relatively large amount of Co on at least a part of the surface of the R1-T1-B-based sintered body having a specific composition having a low B composition. When contacting the Co-based alloy that perform particular heat treatment, surprisingly, finally sintered magnet obtained has been found to be achieved a high B r and high H cJ.
　本開示によるＲ－Ｔ－Ｂ系焼結磁石の製造方法は、本開示の特定組成のＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金によりＲ２、Ｇａ、Ｃｕ及びＣｏを磁石表面から内部に導入することで、高いＢrと高いＨcJを実現することができる。 The manufacturing method of the RTB-based sintered magnet according to the present disclosure is to introduce R2, Ga, Cu and Co into the interior from the magnet surface by the R2-Ga-Cu-Co-based alloy of the specific composition of the present disclosure. , it is possible to achieve high B r and high H cJ.
　（Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程）
　まず、Ｒ１－Ｔ１－Ｂ系焼結体（以下、単に「焼結体」という場合がある）を準備する工程における焼結体の組成を説明する。 (Step of preparing R1-T1-B sintered body)
First, the composition of the sintered body in the step of preparing an R1-T1-B-based sintered body (hereinafter sometimes simply referred to as “sintered body”) will be described.
　Ｒ１は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含む。Ｒ１－Ｔ１－Ｂ系焼結体のＨcJを向上させるために、一般的に用いられるＤｙ、Ｔｂ、Ｇｄ、Ｈｏなどの重希土類元素を少量含有してもよい。ただし、本開示による製造方法によれば、重希土類元素を多量に用いずとも十分に高いＨcJを得ることができる。そのため、前記重希土類元素の含有量は、Ｒ１－Ｔ１－Ｂ系焼結体の１ｍａｓｓ％以下であることが好ましく、０．５ｍａｓｓ％以下であることがより好ましく、含有しない（実質的に０ｍａｓｓ％）ことが更に好ましい。 R1 is at least one of rare earth elements and always contains at least one of Nd and Pr. In order to improve HcJ of the R1-T1-B-based sintered body, a small amount of heavy rare earth elements such as Dy, Tb, Gd, and Ho generally used may be contained. However, according to the manufacturing method according to the present disclosure, sufficiently high HcJ can be obtained without using a large amount of heavy rare earth elements. Therefore, the content of the heavy rare earth element is preferably 1 mass% or less of the R1-T1-B-based sintered body, more preferably 0.5 mass% or less, and it is not contained (substantially 0 mass%) Is more preferred.
　Ｒ１の含有量は、Ｒ１－Ｔ１－Ｂ系焼結体全体の２７ｍａｓｓ％以上３５ｍａｓｓ％以下である。Ｒ１の含有量が２７ｍａｓｓ％未満では焼結過程で液相が十分に生成せず、Ｒ１－Ｔ１－Ｂ系焼結体を十分に緻密化することが困難になる。一方、Ｒ１の含有量が３５ｍａｓｓ％を超えても本開示の効果を得ることはできるが、Ｒ１－Ｔ１－Ｂ系焼結体の製造工程中における合金粉末が非常に活性になる。その結果、合金粉末の著しい酸化や発火などを生じることがあるため、３５ｍａｓｓ％以下が好ましい。Ｒ１の含有量は、２７．５ｍａｓｓ％以上３３ｍａｓｓ％以下であることがより好ましく、２８ｍａｓｓ％以上３２ｍａｓｓ％以下であることが更に好ましい。 The content of R1 is 27 mass% or more and 35 mass% or less of the whole of the R1-T1-B-based sintered body. If the content of R1 is less than 27 mass%, a liquid phase is not sufficiently generated in the sintering process, and it becomes difficult to fully densify the R1-T1-B-based sintered body. On the other hand, although the effect of the present disclosure can be obtained even if the content of R1 exceeds 35 mass%, the alloy powder in the manufacturing process of the R1-T1-B-based sintered body becomes very active. As a result, significant oxidation or ignition of the alloy powder may occur, so 35 mass% or less is preferable. The content of R1 is more preferably 27.5 mass% or more and 33 mass% or less, and still more preferably 28 mass% or more and 32 mass% or less.
　Ｔ１はＦｅ、Ｃｏ、Ａｌ、Ｍｎ、及びＳｉからなる群から選択された少なくとも１つであり、Ｔ１は必ずＦｅを含有する。すなわち、Ｔ１はＦｅのみであってもよいし、Ｃｏ、Ａｌ、Ｍｎ、Ｓｉの少なくとも１つとＦｅからなってもよい。ただし、Ｔ１全体に対するＦｅの含有量は８０ｍａｓｓ％以上である。Ｆｅの含有量が８０ｍａｓｓ％未満であると、Ｂr及びＨcJが低下する可能性がある。ここで、「Ｔ１全体に対するＦｅの含有量は８０ｍａｓｓ％以上」とは、例えばＲ１－Ｔ１－Ｂ系焼結体中におけるＴ１の含有量が７０ｍａｓｓ％である場合、Ｒ１－Ｔ１－Ｂ系焼結体の５６ｍａｓｓ％以上がＦｅであることを言う。好ましくはＴ１全体に対するＦｅの含有量は９０ｍａｓｓ％以上である。より高いＢrと高いＨcJを得ることができるからである。Ｃｏ、Ａｌ、Ｍｎ、Ｓｉを含有する場合の好ましい含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体のＣｏは５．０ｍａｓｓ％以下、Ａｌは１．５ｍａｓｓ％以下、Ｍｎ及びＳｉはそれぞれ０．２ｍａｓｓ％以下である。 T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si, and T1 always contains Fe. That is, T1 may be Fe alone, or may be Fe and at least one of Co, Al, Mn, and Si. However, the content of Fe with respect to the whole T1 is 80 mass% or more. When the content of Fe is less than 80 mass%, B r and H cJ may be reduced. Here, "the content of Fe with respect to the whole T1 is 80 mass% or more" means, for example, when the content of T1 in the R1-T1-B-based sintered body is 70 mass%, the R1-T1-B-based sintering It says that 56 mass% or more of the body is Fe. Preferably, the content of Fe with respect to the whole of T1 is 90 mass% or more. This is because it is possible to obtain a higher B r and a high H cJ. The preferable content in the case of containing Co, Al, Mn, and Si is 5.0 mass% or less of Co in the entire R1-T1-Cu-B sintered body, 1.5 mass% or less of Al, and Mn and Si Each is 0.2 mass% or less.
　Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）は１４．０超１５．０以下である。 The molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.
　本開示におけるＢに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）とは、Ｔ１を構成する各元素（Ｆｅ又はＣｏ、Ａｌ、Ｍｎ、Ｓｉの少なくとも１つとＦｅ）の分析値（ｍａｓｓ％）をそれぞれの元素の原子量で除したものを求め、それらの値を合計したもの（ａ）と、Ｂの分析値（ｍａｓｓ％）をＢの原子量で除したもの（ｂ）との比（ａ／ｂ）である。 The molar ratio of T1 to B ([T1] / [B]) in the present disclosure is the analysis value (mass%) of each element (Fe or at least one of Fe, Co, Al, Mn, Si and Fe) constituting T1. Calculate the ratio of the atomic weight of each element divided by the atomic weight of each element (a) and the ratio (a /) of the analytical value (mass%) of B divided by the atomic weight of B (b) b).
　Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０を超えるという条件は、主相（Ｒ2Ｔ14Ｂ化合物）形成に使われるＴ１量に対して相対的にＢ量が少ないことを示している。Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０以下であると高いＨcJを得ることができない。一方、Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１５．０を超えるとＢrが低下する可能性がある。Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）は１４．５以上１５．０以下であることが好ましい。更に高いＢrと高いＨcJを得ることができる。また、Ｂの含有量はＲ１－Ｔ１－Ｂ系焼結体全体の０．９ｍａｓｓ％以上１．０ｍａｓｓ％未満が好ましい。 The condition that the molar ratio of T1 to B ([T1] / [B]) exceeds 14.0 means that the amount of B is relatively to the amount of T1 used to form the main phase (R 2 T 14 B compound) It shows that there are few. If the molar ratio of T1 to B ([T1] / [B]) is 14.0 or less, high H cJ can not be obtained. On the other hand, mol ratio of T1 for B ([T1] / [B ]) is likely to decrease B r exceeds 15.0. The molar ratio of T1 to B ([T1] / [B]) is preferably 14.5 or more and 15.0 or less. It is possible to obtain a higher B r and a high H cJ. Further, the content of B is preferably 0.9 mass% or more and less than 1.0 mass% of the entire R1-T1-B-based sintered body.
　Ｒ１－Ｔ１－Ｂ系焼結体は、上記元素の他にＧａ、Ｃｕ、Ａｇ、Ｚｎ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、Ｔｉ、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｃｒ、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌ、Ｏ、Ｎ、Ｃ等を含有してもよい。含有量は、Ｇａ、Ｃｕ、Ａｇ、Ｚｎ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、及びＴｉはそれぞれ０．５ｍａｓｓ％以下、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｃｒはそれぞれ０．２ｍａｓｓ％以下、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌは５００ｐｐｍ以下、Ｏは６０００ｐｐｍ以下、Ｎは１０００ｐｐｍ以下、Ｃは１５００ｐｐｍ以下が好ましい。これらの元素の合計の含有量は、Ｒ１－Ｔ１－Ｂ系焼結体全体の５ｍａｓｓ％以下が好ましい。これらの元素の合計の含有量がＲ１－Ｔ１－Ｂ系焼結体全体の５ｍａｓｓ％を超えると高いＢrと高いＨcJを得ることができない可能性がある。 In addition to the above elements, the R1-T1-B-based sintered body may contain Ga, Cu, Ag, Zn, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Cr, H, F, P, S, Cl, O, N, C and the like may be contained. The content of each of Ga, Cu, Ag, Zn, In, Sn, Zr, Nb and Ti is 0.5 mass% or less, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, It is preferable that Sm, Ca, Mg and Cr each be 0.2 mass% or less, H, F, P, S and Cl be 500 ppm or less, O be 6000 ppm or less, N be 1000 ppm or less and C be 1500 ppm or less. The total content of these elements is preferably 5% by mass or less of the entire R1-T1-B-based sintered body. The total content of these elements may not be able to obtain the high B r and high H cJ exceeds 5 mass% of the total R1-T1-B based sintered body.
　次にＲ１－Ｔ１－Ｂ系焼結体を準備する工程について説明する。Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程は、Ｒ－Ｔ－Ｂ系焼結磁石に代表される一般的な製造方法を用いて準備することができる。Ｒ１－Ｔ１－Ｂ系焼結体は、原料合金を粒径Ｄ50（気流分散式レーザー回折法による測定で得られる体積中心値＝Ｄ50）が３μｍ以上１０μｍ以下に粉砕した後、磁界中で配向させて焼結を行うことが好ましい。一例を挙げると、ストリップキャスト法などで作製された原料合金を、ジェットミル装置などを用いて粒径Ｄ50が３μｍ以上１０μｍ以下に粉砕した後、磁界中で成形し、９００℃以上１１００℃以下の温度で焼結することにより準備することができる。原料合金の粒径Ｄ50が３μｍ未満では粉砕粉を作製するのが非常に困難であり、生産効率が大幅に低下するため好ましくない。一方、粒径Ｄ50が１０μｍを超えると最終的に得られるＲ１－Ｔ１－Ｂ系焼結体の結晶粒径が大きくなり過ぎ、高いＨcJを得ることが困難となるため好ましくない。粒径Ｄ50は好ましくは、３μｍ以上５μｍ以下である。 Next, the process of preparing the R1-T1-B based sintered body will be described. The step of preparing the R1-T1-B based sintered body can be prepared using a general manufacturing method typified by the RTB based sintered magnet. The R1-T1-B-based sintered body is crushed in a magnetic field after the raw material alloy is pulverized to a particle size D 50 (volume center value obtained by measurement by air flow dispersion type laser diffraction = D 50 ) of 3 μm to 10 μm. It is preferable to perform orientation and sintering. As an example, a material alloy that has been prepared in such a strip casting method, after the particle size D 50 by using a jet mill is ground to 3μm over 10μm or less, and molded in a magnetic field, 900 ° C. or higher 1100 ° C. or less It can be prepared by sintering at a temperature of The size less than D 50 of the material alloy is 3μm is very difficult to prepare a pulverized powder is not preferable because production efficiency is greatly reduced. Meanwhile, undesirably particle diameter D 50 is eventually only the crystal grain size of the resulting R1-T1-B based sintered body increases exceeds 10 [mu] m, it becomes difficult to obtain a high H cJ. The particle size D 50 is preferably 3 μm or more and 5 μm or less.
　Ｒ１－Ｔ１－Ｂ系焼結体は、前記の各条件を満たしていれば、一種類の原料合金（単一原料合金）から作製してもよいし、二種類以上の原料合金を用いてそれらを混合する方法（ブレンド法）によって作製してもよい。また、得られたＲ１－Ｔ１－Ｂ系焼結体は、必要に応じて切断や切削など公知の機械加工を行った後、後述する第一の熱処理及び第二の熱処理を実施してもよい。 The R1-T1-B based sintered body may be produced from one kind of raw material alloy (single raw material alloy) as long as the above-mentioned respective conditions are satisfied, or two or more kinds of raw material alloys may be used to produce them. It may be produced by the method of mixing (blending method). The obtained R1-T1-B-based sintered body may be subjected to known machining such as cutting or cutting if necessary, and then may be subjected to the first heat treatment and the second heat treatment described later. .
　（Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程）
　まず、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程におけるＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金の組成を説明する。以下に説明する特定の範囲でＲ、Ｇａ、Ｃｕ、Ｃｏを全て含有することにより、後述する第一の熱処理を実施する工程においてＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金中のＲ２、Ｇａ、Ｃｕ及びＣｏをＲ１－Ｔ１－Ｂ系焼結体内部に導入することができる。 (Step of preparing R2-Ga-Cu-Co alloy)
First, the composition of the R2-Ga-Cu-Co alloy in the step of preparing the R2-Ga-Cu-Co alloy will be described. By including all of R, Ga, Cu, and Co within the specific range described below, R2, Ga, Cu, and R2 in the R2-Ga-Cu-Co alloy in the step of performing the first heat treatment described later Co can be introduced into the interior of the R1-T1-B sintered body.
　Ｒ２は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含む。Ｒ２の５０ｍａｓｓ％以上がＰｒであることが好ましい。より高いＨcJを得ることができるからである。ここで「Ｒ２の５０ｍａｓｓ％以上がＰｒである」とは、例えばＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金中におけるＲ２の含有量が５０ｍａｓｓ％である場合、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金の２５ｍａｓｓ％以上がＰｒであることを言う。更に好ましくは、Ｒ２の７０ｍａｓｓ％以上がＰｒであり、最も好ましくはＲ２がＰｒのみ（不可避的不純物は含む）である。これにより、更に高いＨcJを得ることができる。また、Ｒ２として、Ｄｙ、Ｔｂ、Ｇｄ、Ｈｏなどの重希土類元素を少量含有してもよい。ただし、本開示の製造方法によれば、重希土類元素を多量に用いずとも十分に高いＨcJを得ることができる。そのため、前記重希土類元素の含有量はＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の１０ｍａｓｓ％以下（Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金中の重希土類元素が１０ｍａｓｓ％以下）であることが好ましく、５ｍａｓｓ％以下であることがより好ましく、含有しない（実質的に０ｍａｓｓ％）ことが更に好ましい。Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金のＲ２が重希土類元素を含有する場合も、Ｒ２の５０％以上がＰｒであることが好ましく、重希土類元素を除いたＲ２がＰｒのみ（不可避的不純物は含む）であることがより好ましい。 R2 is at least one of rare earth elements and always contains at least one of Nd and Pr. It is preferable that 50 mass% or more of R2 is Pr. It is because higher H cJ can be obtained. Here, "50 mass% or more of R2 is Pr" means, for example, 25 mass of R2-Ga-Cu-Co alloy when the content of R2 in R2-Ga-Cu-Co alloy is 50 mass%. It says that% or more is Pr. More preferably, 70 mass% or more of R2 is Pr, and most preferably, R2 is only Pr (including unavoidable impurities). Thereby, a further higher HcJ can be obtained. In addition, a small amount of heavy rare earth elements such as Dy, Tb, Gd and Ho may be contained as R2. However, according to the manufacturing method of the present disclosure, sufficiently high HcJ can be obtained without using a large amount of heavy rare earth elements. Therefore, the content of the heavy rare earth element is preferably 10 mass% or less of the entire R2-Ga-Cu-Co alloy (the heavy rare earth element in the R2-Ga-Cu-Co alloy is 10 mass% or less), It is more preferable that it is 5 mass% or less, and it is still more preferable that it does not contain (substantially 0 mass%). Even when R2 of the R2-Ga-Cu-Co alloy contains a heavy rare earth element, it is preferable that 50% or more of R2 is Pr, and R2 excluding the heavy rare earth element is only Pr (including unavoidable impurities) It is more preferred that
　Ｒ２の含有量はＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の３５ｍａｓｓ％以上８５ｍａｓｓ％未満である。Ｒ２の含有量が３５ｍａｓｓ％未満では後述する第一の熱処理で拡散が十分に進行しない可能性がある。一方、Ｒ２の含有量が８５ｍａｓｓ％以上でも本開示の効果を得ることはできるが、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金の製造工程中における合金粉末が非常に活性になる。その結果、合金粉末の著しい酸化や発火などを生じることがあるため、Ｒ２の含有量はＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の８５ｍａｓｓ％未満が好ましい。Ｒ２の含有量は５０ｍａｓｓ％以上８５ｍａｓｓ％未満であることがより好ましく、６０ｍａｓｓ％以上８５ｍａｓｓ％未満であることが更に好ましい。より高いＨcJを得ることができるからである。 The content of R2 is 35 mass% or more and less than 85 mass% of the entire R2-Ga-Cu-Co alloy. If the content of R2 is less than 35 mass%, diffusion may not sufficiently proceed in the first heat treatment described later. On the other hand, although the effect of the present disclosure can be obtained even if the content of R2 is 85 mass% or more, the alloy powder in the manufacturing process of the R2-Ga-Cu-Co based alloy becomes very active. As a result, significant oxidation, ignition and the like of the alloy powder may occur, so the content of R2 is preferably less than 85 mass% of the entire R2-Ga-Cu-Co alloy. The content of R2 is more preferably 50 mass% or more and less than 85 mass%, and still more preferably 60 mass% or more and less than 85 mass%. It is because higher H cJ can be obtained.
　Ｇａは、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上３０ｍａｓｓ％以下である。Ｇａが２．５ｍａｓｓ％未満では、後述する第一の熱処理を実施する工程においてＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金中のＣｏがＲ１－Ｔ１－Ｂ系焼結体の内部に導入され難くなり高いＢrを得ることができない。更に、Ｒ－Ｔ－Ｇａ相の生成量が少なすぎて、高いＨcJを得ることができない。一方、Ｇａが３０ｍａｓｓ％を超えると、Ｂrが大幅に低下する可能性がある。Ｇａは４ｍａｓｓ％以上２０ｍａｓｓ％以下であることがより好ましく、４ｍａｓｓ％以上１０ｍａｓｓ％以下であることが更に好ましい。より高いＢrと高いＨcJを得ることができるからである。 Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Cu-Co alloy. If Ga is less than 2.5 mass%, it is difficult to introduce Co in the R2-Ga-Cu-Co alloy into the interior of the R1-T1-B sintered body in the step of performing the first heat treatment described later, which is high. I can not get B r . Furthermore, the amount of RT-Ga phase formed is too small to obtain high HcJ . On the other hand, if Ga is more than 30 mass%, B r may be lowered significantly. Ga is more preferably 4 mass% or more and 20 mass% or less, and still more preferably 4 mass% or more and 10 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
　Ｃｕは、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上２０ｍａｓｓ％以下である。Ｃｕが２．５ｍａｓｓ％未満では、後述する第一の熱処理を実施する工程においてＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金中のＧａ、Ｃｕ及びＣｏがＲ１－Ｔ１－Ｂ系焼結体の内部に導入され難くなり、高いＢrを得ることができない。一方、Ｃｕが２０ｍａｓｓ％を超えると、粒界におけるＧａの存在比率が低下するため、Ｒ－Ｔ－Ｇａ相の生成量が少なすぎて、高いＨcJを得ることができない可能性がある。Ｃｕは４ｍａｓｓ％以上１５ｍａｓｓ％以下であることがより好ましく、４ｍａｓｓ％以上１０ｍａｓｓ％以下であることが更に好ましい。より高いＢrと高いＨcJを得ることができるからである。 Cu is 2.5 mass% or more and 20 mass% or less of the entire R2-Ga-Cu-Co alloy. If Cu is less than 2.5 mass%, Ga, Cu and Co in the R2-Ga-Cu-Co alloy are introduced into the interior of the R1-T1-B sintered body in the step of performing the first heat treatment described later hardly be, it is impossible to obtain a high B r. On the other hand, if Cu exceeds 20 mass%, the abundance ratio of Ga at the grain boundaries decreases, so the amount of RT-Ga phase generated may be too small to obtain high HcJ . Cu is more preferably 4 mass% or more and 15 mass% or less, and still more preferably 4 mass% or more and 10 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
　Ｃｏは、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の１０ｍａｓｓ％超４５ｍａｓｓ％以下である。Ｃｏが１０ｍａｓｓ％以下では、最終的に得られるＲ－Ｔ－Ｂ系焼結磁石のＢrを充分に高めることができない。一方、Ｃｏが４５ｍａｓｓ％を超えると、後述する第一の熱処理で拡散が十分に進行せず、高いＢrと高いＨcJを得ることができない可能性がある。Ｃｏは１５ｍａｓｓ％以上３０ｍａｓｓ％以下であることがより好ましい。より高いＢrと高いＨcJを得ることができるからである。 Co is more than 10% by mass and 45% by mass or less of the entire R2-Ga-Cu-Co alloy. Co is in the following 10 mass%, it is impossible to sufficiently enhance the finally obtained R-T-B based sintered magnet of B r. On the other hand, when Co exceeds 45Mass%, it may not be able to spread with a first heat treatment to be described later does not proceed sufficiently to obtain a high B r and high H cJ. As for Co, it is more preferable that they are 15 mass% or more and 30 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
　また、本開示におけるＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金では、Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量＞Ｃｕの含有量の不等式が成立している。このため、高いＢr及び高いＨcJを得ることができる。これは本開示の不等式を満足することにより、適切な量のＲ、Ｃｏ、Ｇａ及びＣｕを含む相が二粒子粒界に生成されるからだと考えられる。 Further, in the R2-Ga-Cu-Co-based alloy in the present disclosure, the inequality of R2 content> Co content> Ga content> Cu content is satisfied. Therefore, it is possible to obtain a high B r and a high H cJ. It is considered that this is because a phase containing appropriate amounts of R, Co, Ga and Cu is generated at two grain boundaries by satisfying the inequality of the present disclosure.
　Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金は、上記元素の他にＡｌ、Ａｇ、Ｚｎ、Ｓｉ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、Ｔｉ、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｍｎ、Ｃｒ、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌ、Ｏ、Ｎ、Ｃ等を含有してもよい。 In addition to the above elements, the R2-Ga-Cu-Co alloy may contain Al, Ag, Zn, Si, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
　含有量は、Ａｌは１．０ｍａｓｓ％以下、Ａｇ、Ｚｎ、Ｓｉ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、及びＴｉはそれぞれ０．５ｍａｓｓ％以下、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｍｎ、Ｓｉ、Ｃｒはそれぞれ０．２ｍａｓｓ％以下、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌは５００ｐｐｍ以下、Ｏは６０００ｐｐｍ以下、Ｎは１０００ｐｐｍ以下、Ｃは１５００ｐｐｍ以下が好ましい。ただし、これらの元素の合計の含有量が２０ｍａｓｓ％を超えると、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金におけるＲ２－Ｇａ－Ｃｕ－Ｃｏの含有量が少なくなり、高いＢrと高いＨcJを得ることができない可能性がある。そのため、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金におけるＲ２－Ｇａ－Ｃｕ－Ｃｏの合計の含有量は８０ｍａｓｓ％以上が好ましく、９０ｍａｓｓ％以上が更に好ましい。 The content of Al is 1.0 mass% or less, Ag, Zn, Si, In, Sn, Zr, Nb, and Ti are 0.5 mass% or less, respectively, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Si, Cr each 0.2 mass% or less, H, F, P, S, Cl 500 ppm or less, O 6000 ppm or less, N 1000 ppm or less, C 1500 ppm or less is preferable. However, the total content of these elements is more than 20mass%, R2-Ga-Cu -Co -based then the amount of R2-Ga-Cu-Co in the alloy, to obtain a high B r and high H cJ It may not be possible. Therefore, the total content of R2-Ga-Cu-Co in the R2-Ga-Cu-Co alloy is preferably 80 mass% or more, and more preferably 90 mass% or more.
　次にＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程について説明する。Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金は、Ｎｄ－Ｆｅ－Ｂ系焼結磁石に代表される一般的な製造方法において採用されている原料合金の作製方法、例えば、金型鋳造法やストリップキャスト法や単ロール超急冷法（メルトスピニング法）やアトマイズ法などを用いて準備することができる。また、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金は、前記によって得られた合金をピンミルなどの公知の粉砕手段によって粉砕されたものであってもよい。また、前記によって得られた合金の粉砕性を向上させるために、水素雰囲気中で７００℃以下の熱処理を行って水素を含有させてから粉砕を行っても良い。 Next, a process of preparing an R2-Ga-Cu-Co based alloy will be described. The R2-Ga-Cu-Co alloy is a method of preparing a raw material alloy employed in a general manufacturing method represented by a Nd-Fe-B sintered magnet, for example, a die casting method and a strip casting method And single roll ultra-quenching method (melt spinning method) or atomization method. Further, the R2-Ga-Cu-Co based alloy may be one obtained by pulverizing the alloy obtained as described above by a known pulverizing means such as a pin mill. Further, in order to improve the grindability of the alloy obtained as described above, heat treatment at 700 ° C. or less in a hydrogen atmosphere may be performed to contain hydrogen and then grinding.
　（第一の熱処理を実施する工程）
　前記によって準備したＲ１－Ｔ１－Ｂ系焼結体の表面の少なくとも一部に、前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金の少なくとも一部を接触させ、真空又は不活性ガス雰囲気中、７００℃以上１１００℃以下の温度で熱処理をする。本開示において、この熱処理を第一の熱処理という。これにより、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金からＣｕ、Ｇａ及びＣｏを含む液相が生成し、その液相がＲ１－Ｔ１－Ｂ系焼結体の粒界を経由して焼結体表面から内部に拡散導入される。第一の熱処理温度が７００℃未満であると、Ｃｕ、Ｇａ及びＣｏを含む液相量が少なすぎて、高いＢrと高いＨcJを得ることができない可能性がある。一方、１１００℃を超えると主相の異常粒成長が起こり、ＨcJが低下する可能性がある。第一の熱処理温度は、８００℃以上１０００℃以下が好ましい。より高いＢrと高いＨcJを得ることができるからである。なお、熱処理時間はＲ１－Ｔ１－Ｂ系焼結体やＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金の組成や寸法、熱処理温度などによって適正値を設定するが、５分以上２０時間以下が好ましく、１０分以上１５時間以下がより好ましく、３０分以上１０時間以下が更に好ましい。また、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金は、Ｒ１－Ｔ１－Ｂ系焼結体の重量に対し２ｍａｓｓ％以上３０ｍａｓｓ％以下準備した方が好ましい。Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金がＲ１－Ｔ１－Ｂ系焼結体の重量に対し２ｍａｓｓ％未満であるとＨcJが低下する可能性がある。一方、３０ｍａｓｓ％を超えるとＢrが低下する可能性がある。 (Step of carrying out the first heat treatment)
At least a portion of the R2-Ga-Cu-Co alloy is brought into contact with at least a portion of the surface of the R1-T1-B sintered body prepared as described above, and the temperature is 700 ° C. or higher in a vacuum or inert gas atmosphere. Heat treatment is performed at a temperature of 1100 ° C. or less. In the present disclosure, this heat treatment is referred to as a first heat treatment. As a result, a liquid phase containing Cu, Ga and Co is generated from the R2-Ga-Cu-Co alloy, and the liquid phase passes through the grain boundaries of the R1-T1-B sintered body, and the surface of the sintered body is produced. It is diffused from inside to inside. When the first heat treatment temperature is lower than 700 ° C., Cu, and amount of liquid phase containing Ga and Co is too small, it may not be able to obtain a high B r and high H cJ. On the other hand, when the temperature exceeds 1100 ° C., abnormal grain growth of the main phase occurs and H cJ may decrease. The first heat treatment temperature is preferably 800 ° C. or more and 1000 ° C. or less. This is because it is possible to obtain a higher B r and a high H cJ. The heat treatment time is set to an appropriate value depending on the composition and dimensions of the R1-T1-B sintered body and R2-Ga-Cu-Co alloy, the heat treatment temperature, etc., but 5 minutes or more and 20 hours or less is preferable, 10 More preferably, minutes to 15 hours and still more preferably 30 minutes to 10 hours. Further, it is preferable to prepare the R2-Ga-Cu-Co-based alloy in an amount of 2 mass% or more and 30 mass% or less with respect to the weight of the R1-T1-B-based sintered body. If the R2-Ga-Cu-Co alloy is less than 2 mass% with respect to the weight of the R1-T1-B sintered body, there is a possibility that HcJ may be reduced. On the other hand, there is a possibility that the B r decreases exceeds 30 mass%.
　第一の熱処理は、Ｒ１－Ｔ１－Ｂ系焼結体表面に、任意形状のＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金を配置し、公知の熱処理装置を用いて行うことができる。例えば、Ｒ１－Ｔ１－Ｂ系焼結体表面をＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金の粉末層で覆い、第一の熱処理を行うことができる。例えば、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を分散媒中に分散させたスラリーをＲ１－Ｔ１－Ｂ系焼結体表面に塗布した後、分散媒を蒸発させてＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金とＲ１－Ｔ１－Ｂ系焼結体とを接触させてもよい。また、後述する実験例に示すように、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金は、少なくともＲ１－Ｔ１－Ｂ系焼結体の配向方向に対して垂直な表面に接触させるように配置することが好ましい。なお、分散媒として、アルコール（エタノール等）、ＮＭＰ（Ｎ－メチルピロリドン）、アルデヒド及びケトンを例示できる。また、第一の熱処理が実施されたＲ１－Ｔ１－Ｂ系焼結体に対して切断や切削など公知の機械加工を行ってもよい。 The first heat treatment can be performed by disposing an R2-Ga-Cu-Co alloy having an arbitrary shape on the surface of the R1-T1-B-based sintered body and using a known heat treatment apparatus. For example, the first heat treatment can be performed by covering the surface of the R1-T1-B-based sintered body with a powder layer of an R2-Ga-Cu-Co-based alloy. For example, after a slurry in which an R2-Ga-Cu-Co alloy is dispersed in a dispersion medium is applied to the surface of an R1-T1-B sintered body, the dispersion medium is evaporated to form an R2-Ga-Cu-Co system. The alloy and the R1-T1-B sintered body may be in contact with each other. In addition, as shown in the experimental example described later, the R2-Ga-Cu-Co alloy may be arranged to be in contact with the surface perpendicular to the orientation direction of at least the R1-T1-B sintered body. preferable. Examples of the dispersion medium include alcohols (ethanol etc.), NMP (N-methylpyrrolidone), aldehydes and ketones. Also, known machining such as cutting or cutting may be performed on the R1-T1-B-based sintered body subjected to the first heat treatment.
　（第二の熱処理を実施する工程）
　第一の熱処理が実施されたＲ１－Ｔ１－Ｂ系焼結体に対して、真空又は不活性ガス雰囲気中、４５０℃以上６００℃以下の温度で熱処理を行う。本開示においてこの熱処理を第二の熱処理という。第二の熱処理を行うことにより、高いＢrと高いＨcJを得ることができる。第二の熱処理の温度が４５０℃未満及び６００℃超の場合は、Ｒ－Ｔ－Ｇａ相（典型的にはＲ6Ｔ13Ｚ相（ＺはＣｕ及びＧａの少なくとも１つ））の生成量が少なすぎて、高いＢrと高いＨcJを得ることができない可能性がある。第二の熱処理温度は、４８０℃以上５６０℃以下が好ましい。より高いＨcJを得ることができる。なお、熱処理時間はＲ１－Ｔ１－Ｂ系焼結体の組成や寸法、熱処理温度などによって適正値を設定するが、５分以上２０時間以下が好ましく、１０分以上１５時間以下がより好ましく、３０分以上１０時間以下が更に好ましい。 (Step of carrying out the second heat treatment)
The R1-T1-B-based sintered body subjected to the first heat treatment is heat-treated at a temperature of 450 ° C. to 600 ° C. in a vacuum or an inert gas atmosphere. In the present disclosure, this heat treatment is referred to as a second heat treatment. By performing the second heat treatment, it is possible to obtain a high B r and high H cJ. When the temperature of the second heat treatment is less than 450 ° C. and more than 600 ° C., the amount of RT-Ga phase (typically, R 6 T 13 Z phase (Z is at least one of Cu and Ga)) There is a possibility that high B r and high H cJ can not be obtained due to too little. The second heat treatment temperature is preferably 480 ° C. or more and 560 ° C. or less. Higher H cJ can be obtained. The heat treatment time is appropriately set depending on the composition and dimensions of the R1-T1-B sintered body, the heat treatment temperature, etc., but it is preferably 5 minutes to 20 hours, more preferably 10 minutes to 15 hours, and 30 More preferably, minutes to 10 hours.
　なお、前記のＲ6Ｔ13Ｚ相（Ｒ6Ｔ13Ｚ化合物）において、Ｒは希土類元素のうち少なくとも一種でありＰｒ及びＮｄの少なくとも一方を必ず含み、Ｔは遷移金属元素のうち少なくとも一種でありＦｅを必ず含む。Ｒ6Ｔ13Ｚ化合物は代表的にはＮｄ6Ｆｅ13Ｇａ化合物である。また、Ｒ6Ｔ13Ｚ化合物はＬａ6Ｃｏ11Ｇａ3型結晶構造を有する。Ｒ6Ｔ13Ｚ化合物はその状態によってはＲ6Ｔ13-δＺ1+δ化合物になっている場合がある。なお、Ｒ－Ｔ－Ｂ系焼結磁石中に比較的多くのＣｕ、Ａｌ及びＳｉが含有される場合、Ｒ6Ｔ13-δ（Ｇａ1-a-b-cＣｕaＡｌbＳｉc）1+δになっている場合がある。 In the above R 6 T 13 Z phase (R 6 T 13 Z compound), R is at least one rare earth element and necessarily includes at least one of Pr and Nd, and T is at least one transition metal element. Yes Fe must be included. The R 6 T 13 Z compound is typically an Nd 6 Fe 13 Ga compound. Further, the R 6 T 13 Z compound has a La 6 Co 11 Ga 3 type crystal structure. The R 6 T 13 Z compound may be an R 6 T 13 − δZ 1+ δ compound depending on the state. When relatively large amounts of Cu, Al, and Si are contained in the RTB-based sintered magnet, the R 6 T 13- δ (Ga 1 -abc Cu a Al b Si c ) 1+ δ It may have been.
　前記の第二の熱処理を実施する工程によって得られたＲ－Ｔ－Ｂ系焼結磁石は、切断や切削など公知の機械加工を行ったり、耐食性を付与するためのめっきなど、公知の表面処理を行うことができる。また、本開示の製造方法により得られたＲ－Ｔ－Ｂ系焼結磁石は、前記Ｒ－Ｔ－Ｂ系焼結磁石におけるＦｅ又はＣｏ、Ａｌ、Ｍｎ、Ｓｉの少なくとも１つとＦｅをＴ２（Ｒ１－Ｔ１－Ｂ系焼結体におけるＴ１に相当）としたとき、Ｂに対するＴ２のｍｏｌ比（［Ｔ２］／［Ｂ］）が１４．０超であり、Ｒ、Ｆｅ、Ｂ、Ｃｕ、Ｇａを含有している。更に、Ｒ、Ｆｅ、Ｂ、Ｃｕ、Ｇａ以外にもＣｏ、Ａｌ、Ａｇ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、Ｔｉ、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｍｎ、Ｓｉ、Ｃｒ、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌ、Ｏ、Ｎ、Ｃ等を含有してもよい。 The RTB-based sintered magnet obtained by the step of carrying out the second heat treatment described above is subjected to known surface treatment such as plating for imparting corrosion resistance or performing known machining such as cutting or cutting. It can be performed. In addition, the RTB-based sintered magnet obtained by the production method of the present disclosure is characterized in that at least one of Fe or Co, Al, Mn, Si and Fe in the RTB-based sintered magnet is T2 ( The molar ratio of T2 to B ([T2] / [B]) is more than 14.0, and R, Fe, B, Cu, and Ga are equivalent to T1 in the R1-T1-B-based sintered body. Contains In addition to R, Fe, B, Cu, Ga, Co, Al, Ag, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Si, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
＜第２の実施形態＞
　次に、本開示による第２の実施形態におけるＲ－Ｔ－Ｂ系焼結磁石の製造方法を説明する。 Second Embodiment
Next, a method of manufacturing the RTB-based sintered magnet according to the second embodiment of the present disclosure will be described.
　本開示による第２の実施形態におけるＲ－Ｔ－Ｂ系焼結磁石の製造方法は、図４に示すように、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程Ｓ１１０と、Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程Ｓ１２０とを含む。Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程Ｓ１１０と、Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程Ｓ１２０との順序は任意であり、それぞれ、異なる場所で製造されたＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体及びＲ２－Ｇａ－Ｃｏ系合金を用いてもよい。 As shown in FIG. 4, the method of manufacturing the RTB-based sintered magnet according to the second embodiment of the present disclosure includes a step S110 of preparing an R1-T1-Cu-B-based sintered body; And S120 of preparing a Ga—Co alloy. The order of the step S110 of preparing the R1-T1-Cu-B-based sintered body and the step S120 of preparing the R2-Ga-Co-based alloy is arbitrary, and each of the R1-T1-made in different places is manufactured. A Cu-B based sintered body and an R2-Ga-Co based alloy may be used.
　Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体においては、下記（B１）～（B４）が成立している。
（B１）Ｒ１は希土類元素のうち少なくとも一種でありＮｄ及びＰｒの少なくとも一方を必ず含み、Ｒ１の含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の２７ｍａｓｓ％以上３５ｍａｓｓ％以下である。
（B２）Ｔ１はＦｅ、Ｃｏ、Ａｌ、Ｍｎ、及びＳｉからなる群から選択された少なくとも１つであり、Ｔ１は必ずＦｅを含有し、Ｔ１全体に対するＦｅの含有量が８０ｍａｓｓ％以上である。
（B３）Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０超１５．０以下である。
（B４）Ｃｕの含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の０．１ｍａｓｓ％以上１．５ｍａｓｓ％以下である。 In the R1-T1-Cu-B based sintered body, the following (B1) to (B4) hold.
(B1) R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is 27 mass% or more and 35 mass% or less of the whole R1-T1-Cu-B sintered body .
(B2) T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si. T1 necessarily contains Fe, and the content of Fe with respect to the entire T1 is 80 mass% or more.
(B3) The molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.
The content of (B4) Cu is 0.1 mass% or more and 1.5 mass% or less of the entire R1-T1-Cu-B-based sintered body.
　本開示におけるＢに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）とは、Ｔ１を構成する各元素（Ｆｅ又はＣｏ、Ａｌ、Ｍｎ、Ｓｉの少なくとも１つとＦｅ）の分析値（ｍａｓｓ％）をそれぞれの元素の原子量で除したものを求め、それらの値を合計したもの（ａ）と、Ｂの分析値（ｍａｓｓ％）をＢの原子量で除したもの（ｂ）との比（ａ／ｂ）である。 The molar ratio of T1 to B ([T1] / [B]) in the present disclosure is the analysis value (mass%) of each element (Fe or at least one of Fe, Co, Al, Mn, Si and Fe) constituting T1. Calculate the ratio of the atomic weight of each element divided by the atomic weight of each element (a) and the ratio (a /) of the analytical value (mass%) of B divided by the atomic weight of B (b) b).
　Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０を超えるということは、Ｂの含有比率がＲ2Ｔ14Ｂ化合物の化学量論組成比よりも低いことを意味している。言い換えると、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体において、主相（Ｒ2Ｔ14Ｂ化合物）の形成に使われるＴ１の量に対して相対的にＢ量が少ない。 The fact that the molar ratio of T1 to B ([T1] / [B]) exceeds 14.0 means that the content ratio of B is lower than the stoichiometric composition ratio of the R 2 T 14 B compound. There is. In other words, in the R1-T1-Cu-B-based sintered body, the amount of B is relatively smaller than the amount of T1 used to form the main phase (R 2 T 14 B compound).
　Ｒ２－Ｇａ－Ｃｏ系合金においては、以下の（B５）～（B８）が成立している。
（B５）Ｒ２は希土類元素のうち少なくとも一種でありＮｄ及びＰｒの少なくとも一方を必ず含み、Ｒ２の含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の３５ｍａｓｓ％以上８７ｍａｓｓ％未満である。
（B６）Ｇａの含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上３０ｍａｓｓ％以下である。
（B７）Ｃｏの含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の１０ｍａｓｓ％超４５ｍａｓｓ％以下である。
（B８）Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量の不等式が成立する。 The following (B5) to (B8) hold true for the R2-Ga-Co based alloy.
(B5) R2 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R2 is 35 mass% or more and less than 87 mass% of the entire R2-Ga-Co alloy.
The content of (B6) Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Co alloy.
The content of (B7) Co is more than 10% by mass and 45% by mass or less of the entire R2-Ga-Co-based alloy.
(B8) R2 content> Co content> Ga content inequality holds.
　本開示によるＲ－Ｔ－Ｂ系焼結磁石の製造方法(第２の実施形態)では、主相（Ｒ2Ｔ14Ｂ化合物）形成に使われるＴの量に対して化学量論比で相対的にＢ量が少ないＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の表面の少なくとも一部にＲ２－Ｇａ－Ｃｏ系合金を接触させ、図４に示すように、真空又は不活性ガス雰囲気中、７００℃以上１１００℃以下の温度で第一の熱処理を実施する工程Ｓ１３０と、この第一の熱処理が実施されたＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体に対して真空又は不活性ガス雰囲気中、４５０℃以上６００℃以下の温度で第二の熱処理を実施する工程Ｓ１４０を行う。これにより、高いＢr及び高いＨcJを有するＲ－Ｔ－Ｂ系焼結磁石を得ることができる。 In the method of producing an RTB-based sintered magnet according to the present disclosure (the second embodiment), the relative stoichiometric ratio to the amount of T used to form the main phase (R 2 T 14 B compound) The R2-Ga-Co alloy is brought into contact with at least a part of the surface of the R1-T1-Cu-B sintered body having a small amount of B, as shown in FIG. 4, in a vacuum or inert gas atmosphere, Step S130 of performing the first heat treatment at a temperature of 700 ° C. or more and 1100 ° C. or less, and in a vacuum or inert gas atmosphere for the R1-T1-Cu-B-based sintered body subjected to the first heat treatment Step S140 of performing the second heat treatment at a temperature of 450 ° C. or more and 600 ° C. or less is performed. Thus, it is possible to obtain the R-T-B based sintered magnet having a high B r and a high H cJ.
　第一の熱処理を実施する工程Ｓ１３０と、第二の熱処理を実施する工程Ｓ１４０との間に他の工程、例えば冷却工程などが実行され得る。 Another step, such as a cooling step, may be performed between step S130 of performing the first heat treatment and step S140 of performing the second heat treatment.
　本発明者らは検討の結果、低Ｂ組成である特定の組成を有するＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の表面の少なくとも一部に、Ｃｏ含有量が比較的多いＲ２－Ｇａ－Ｃｏ系合金を接触させて特定の熱処理を実施した場合でも、最終的に得られる焼結磁石は、高いＢrと高いＨcJを実現できることがわかった。 As a result of investigations, the present inventors have found that R2-Ga-Co having a relatively high Co content on at least a part of the surface of the R1-T1-Cu-B-based sintered body having a specific composition having a low B composition. even if after specific heat treatment by contacting the system alloy, finally sintered magnet obtained has been found to be achieved a high B r and high H cJ.
　本開示によるＲ－Ｔ－Ｂ系焼結磁石の製造方法（第２の実施形態）は、本開示の特定組成のＲ２－Ｇａ－Ｃｏ系合金によりＲ２、Ｇａ、Ｃｏを磁石表面から内部に導入することで、高いＢrと高いＨcJを実現することができる。 The method for producing an RTB-based sintered magnet according to the present disclosure (the second embodiment) introduces R2, Ga, and Co into the interior from the magnet surface with the R2-Ga-Co-based alloy of the specific composition of the present disclosure. by, it is possible to realize a high B r and high H cJ.
　（Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程）
　まず、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程における焼結体の組成を説明する。 (Step of preparing R1-T1-Cu-B sintered body)
First, the composition of the sintered body in the step of preparing the R1-T1-Cu-B-based sintered body will be described.
　Ｒ１は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含む。Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体のＨcJを向上させるために、一般的に用いられるＤｙ、Ｔｂ、Ｇｄ、Ｈｏなどの重希土類元素を少量含有してもよい。ただし、本開示による製造方法によれば、重希土類元素を多量に用いずとも十分に高いＨcJを得ることができる。そのため、前記重希土類元素の含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体の１ｍａｓｓ％以下であることが好ましく、０．５ｍａｓｓ％以下であることがより好ましく、含有しない（実質的に０ｍａｓｓ％）ことが更に好ましい。 R1 is at least one of rare earth elements and always contains at least one of Nd and Pr. In order to improve HcJ of the R1-T1-Cu-B-based sintered body, a small amount of heavy rare earth elements such as Dy, Tb, Gd, and Ho generally used may be contained. However, according to the manufacturing method according to the present disclosure, sufficiently high HcJ can be obtained without using a large amount of heavy rare earth elements. Therefore, the content of the heavy rare earth element is preferably 1 mass% or less of the R1-T1-Cu-B-based sintered body, more preferably 0.5 mass% or less, and it is not contained (substantially) More preferably, 0 mass%).
　Ｒ１の含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の２７ｍａｓｓ％以上３５ｍａｓｓ％以下である。Ｒ１の含有量が２７ｍａｓｓ％未満では焼結過程で液相が十分に生成せず、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を十分に緻密化することが困難になる。一方、Ｒ１の含有量が３５ｍａｓｓ％を超えても本開示の効果を得ることはできるが、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体の製造工程中における合金粉末が非常に活性になる。その結果、合金粉末の著しい酸化や発火などを生じることがあるため、３５ｍａｓｓ％以下が好ましい。Ｒ１の含有量は、２７．５ｍａｓｓ％以上３３ｍａｓｓ％以下であることがより好ましく、２８ｍａｓｓ％以上３２ｍａｓｓ％以下であることが更に好ましい。 The content of R1 is 27 mass% or more and 35 mass% or less of the whole of the R1-T1-Cu-B-based sintered body. If the content of R1 is less than 27 mass%, a liquid phase is not sufficiently generated in the sintering process, and it becomes difficult to fully densify the R1-T1-Cu-B-based sintered body. On the other hand, although the effect of the present disclosure can be obtained even if the content of R1 exceeds 35 mass%, the alloy powder in the manufacturing process of the R1-T1-Cu-B-based sintered body becomes very active. As a result, significant oxidation or ignition of the alloy powder may occur, so 35 mass% or less is preferable. The content of R1 is more preferably 27.5 mass% or more and 33 mass% or less, and still more preferably 28 mass% or more and 32 mass% or less.
　Ｔ１はＦｅ、Ｃｏ、Ａｌ、Ｍｎ、及びＳｉからなる群から選択された少なくとも１つであり、Ｔ１は必ずＦｅを含有する。すなわち、Ｔ１はＦｅのみであってもよいし、Ｃｏ、Ａｌ、Ｍｎ、Ｓｉの少なくとも１つとＦｅからなってもよい。ただし、Ｔ１全体に対するＦｅの含有量は８０ｍａｓｓ％以上である。Ｆｅの含有量が８０ｍａｓｓ％未満であると、Ｂr及びＨcJが低下する可能性がある。ここで、「Ｔ１全体に対するＦｅの含有量は８０ｍａｓｓ％以上」とは、例えばＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体中におけるＴ１の含有量が７０ｍａｓｓ％である場合、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体の５６ｍａｓｓ％以上がＦｅであることを言う。好ましくはＴ１全体に対するＦｅの含有量は９０ｍａｓｓ％以上である。より高いＢrと高いＨcJを得ることができるからである。Ｃｏ、Ａｌ、Ｍｎ、Ｓｉを含有する場合の好ましい含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体のＣｏは５．０ｍａｓｓ％以下、Ａｌは１．５ｍａｓｓ％以下、Ｍｎ及びＳｉはそれぞれ０．２ｍａｓｓ％以下である。 T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si, and T1 always contains Fe. That is, T1 may be Fe alone, or may be Fe and at least one of Co, Al, Mn, and Si. However, the content of Fe with respect to the whole T1 is 80 mass% or more. When the content of Fe is less than 80 mass%, B r and H cJ may be reduced. Here, "the content of Fe with respect to the whole T1 is 80 mass% or more" means, for example, when the content of T1 in the R1-T1-Cu-B-based sintered body is 70 mass%, R1-T1-Cu- It says that 56 mass% or more of B-type sintered compact is Fe. Preferably, the content of Fe with respect to the whole of T1 is 90 mass% or more. This is because it is possible to obtain a higher B r and a high H cJ. The preferable content in the case of containing Co, Al, Mn, and Si is 5.0 mass% or less of Co in the entire R1-T1-Cu-B sintered body, 1.5 mass% or less of Al, and Mn and Si Each is 0.2 mass% or less.
　Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）は１４．０超１５．０以下である。 The molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.
　本開示におけるＢに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）とは、前述したように、Ｔ１を構成する各元素（Ｆｅ又はＣｏ、Ａｌ、Ｍｎ、Ｓｉの少なくとも１つとＦｅ）の分析値（ｍａｓｓ％）をそれぞれの元素の原子量で除したものを求め、それらの値を合計したもの（ａ）と、Ｂの分析値（ｍａｓｓ％）をＢの原子量で除したもの（ｂ）との比（ａ／ｂ）である。 As described above, the molar ratio of T1 to B ([T1] / [B]) in the present disclosure is an analysis of each element (Fe or at least one of Co, Al, Mn, Si, and Fe) constituting T1. The value (mass%) divided by the atomic weight of each element is determined, and the sum of the values (a) and the analytical value of B (mass%) divided by the atomic weight of B (b) Ratio (a / b).
　Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０を超えるという条件は、主相（Ｒ2Ｔ14Ｂ化合物）形成に使われるＴ１量に対して相対的にＢ量が少ないことを示している。［Ｔ１］／［Ｂ］が１４．０以下であると高いＨcJを得ることができない。一方、［Ｔ１］／［Ｂ］が１５．０を超えるとＢrが低下する可能性がある。［Ｔ１］／［Ｂ］は１４．３以上１５．０以下であることが好ましい。更に高いＢrと高いＨcJを得ることができる。また、Ｂの含有量はＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の０．９ｍａｓｓ％以上１．０ｍａｓｓ％未満が好ましい。 The condition that the molar ratio of T1 to B ([T1] / [B]) exceeds 14.0 means that the amount of B is relatively to the amount of T1 used to form the main phase (R 2 T 14 B compound) It shows that there are few. If [T1] / [B] is 14.0 or less, high H cJ can not be obtained. On the other hand, there is a possibility to lower the B r exceeds the 15.0 [T1] / [B] . [T1] / [B] is preferably 14.3 or more and 15.0 or less. It is possible to obtain a higher B r and a high H cJ. The content of B is preferably 0.9 mass% or more and less than 1.0 mass% of the entire R1-T1-Cu-B-based sintered body.
　Ｃｕの含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の０．１ｍａｓｓ％以上１．５ｍａｓｓ％以下である。Ｃｕが０．１ｍａｓｓ％未満であると、後述する第一の熱処理で拡散が十分に進行せず、高いＨcJを得ることができない可能性がある。一方、Ｃｕが１．５ｍａｓｓ％を超えるとＢrが低下する可能性がある。 The content of Cu is 0.1 mass% or more and 1.5 mass% or less of the whole of the R1-T1-Cu-B-based sintered body. If Cu is less than 0.1 mass%, diffusion may not sufficiently proceed in the first heat treatment described later, and high H cJ may not be obtained. On the other hand, Cu is the exceeding 1.5 mass% B r may be reduced.
　本実施形態においても、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体は、上記元素の他にＧａ、Ａｇ、Ｚｎ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、Ｔｉ、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｃｒ、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌ、Ｏ、Ｎ、Ｃ等を含有してもよい。含有量は、Ｇａ、Ａｇ、Ｚｎ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、及びＴｉはそれぞれ０．５ｍａｓｓ％以下、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｃｒはそれぞれ０．２ｍａｓｓ％以下、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌは５００ｐｐｍ以下、Ｏは６０００ｐｐｍ以下、Ｎは１０００ｐｐｍ以下、Ｃは１５００ｐｐｍ以下が好ましい。これらの元素の合計の含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の５ｍａｓｓ％以下が好ましい。これらの元素の合計の含有量がＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の５ｍａｓｓ％を超えると高いＢrと高いＨcJを得ることができない可能性がある。 Also in this embodiment, the R1-T1-Cu-B-based sintered body contains Ga, Ag, Zn, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, in addition to the above elements. Mo, V, Y, La, Ce, Sm, Ca, Mg, Cr, H, F, P, S, Cl, O, N, C and the like may be contained. The content of each of Ga, Ag, Zn, In, Sn, Zr, Nb and Ti is 0.5 mass% or less, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, It is preferable that Ca, Mg and Cr each be 0.2 mass% or less, H, F, P, S and Cl be 500 ppm or less, O be 6000 ppm or less, N be 1000 ppm or less and C be 1500 ppm or less. The total content of these elements is preferably 5% by mass or less of the entire R1-T1-Cu-B-based sintered body. The total content of these elements may not be able to obtain more than the high B r and high H cJ of 5 mass% of the total R1-T1-Cu-B-based sintered body.
　次にＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程について説明する。Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程は、Ｒ－Ｔ－Ｂ系焼結磁石に代表される一般的な製造方法を用いて準備することができる。Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体は、原料合金を粒径Ｄ50（気流分散式レーザー回折法による測定で得られる体積中心値＝Ｄ50）が３μｍ以上１０μｍ以下に粉砕した後、磁界中で配向させて焼結を行うことが好ましい。一例を挙げると、ストリップキャスト法などで作製された原料合金を、ジェットミル装置などを用いて粒径Ｄ50が３μｍ以上１０μｍ以下に粉砕した後、磁界中で成形し、９００℃以上１１００℃以下の温度で焼結することにより準備することができる。原料合金の粒径Ｄ50が３μｍ未満では粉砕粉を作製するのが非常に困難であり、生産効率が大幅に低下するため好ましくない。一方、粒径Ｄ50が１０μｍを超えると最終的に得られるＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の結晶粒径が大きくなり過ぎ、高いＨcJを得ることが困難となるため好ましくない。粒径Ｄ50は好ましくは、３μｍ以上５μｍ以下である。 Next, the process of preparing the R1-T1-Cu-B based sintered body will be described. The step of preparing the R1-T1-Cu-B based sintered body can be prepared using a general manufacturing method typified by an RTB based sintered magnet. The R1-T1-Cu-B sintered body is a magnetic field after the raw material alloy is crushed to a particle size D 50 (volume center value obtained by measurement by air flow distribution laser diffraction = D 50 ) of 3 μm to 10 μm. It is preferable to carry out sintering by orientating in the inside. As an example, a material alloy that has been prepared in such a strip casting method, after the particle size D 50 by using a jet mill is ground to 3μm over 10μm or less, and molded in a magnetic field, 900 ° C. or higher 1100 ° C. or less It can be prepared by sintering at a temperature of The size less than D 50 of the material alloy is 3μm is very difficult to prepare a pulverized powder is not preferable because production efficiency is greatly reduced. Meanwhile, undesirably particle diameter D 50 is eventually only the crystal grain size of the R1-T1-Cu-B based sintered body obtained becomes large exceeding 10 [mu] m, it becomes difficult to obtain a high H cJ. The particle size D 50 is preferably 3 μm or more and 5 μm or less.
　Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体は、前記の各条件を満たしていれば、一種類の原料合金（単一原料合金）から作製してもよいし、二種類以上の原料合金を用いてそれらを混合する方法（ブレンド法）によって作製してもよい。また、得られたＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体は、必要に応じて切断や切削など公知の機械加工を行った後、後述する第一の熱処理及び第二の熱処理を実施してもよい。 The R1-T1-Cu-B sintered body may be produced from one kind of raw material alloy (single raw material alloy) as long as the above-mentioned respective conditions are satisfied, or two or more kinds of raw material alloys are used. It may be produced by a method of mixing them (blending method). In addition, the obtained R1-T1-Cu-B-based sintered body is subjected to known machining such as cutting and cutting, if necessary, and is then subjected to the first heat treatment and the second heat treatment described later. It is also good.
　（Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程）
　まず、Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程におけるＲ２－Ｇａ－Ｃｏ系合金の組成を説明する。以下に説明する特定の範囲でＲ、Ｇａ、Ｃｏを全て含有することにより、後述する第一の熱処理を実施する工程においてＲ２－Ｇａ－Ｃｏ系合金中のＲ２、Ｇａ、ＣｏをＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体内部に導入することができる。 (Step of preparing R2-Ga-Co alloy)
First, the composition of the R2-Ga-Co based alloy in the step of preparing the R2-Ga-Co based alloy will be described. By including all of R, Ga, and Co within the specific range described below, in the step of performing the first heat treatment described later, R1, Ga, and Co in the R2-Ga-Co alloy are R1-T1- It can be introduced into the inside of a Cu-B-based sintered body.
　Ｒ２は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含む。Ｒ２の５０ｍａｓｓ％以上がＰｒであることが好ましい。より高いＨcJを得ることができるからである。ここで「Ｒ２の５０ｍａｓｓ％以上がＰｒである」とは、例えばＲ２－Ｇａ－Ｃｏ系合金中におけるＲ２の含有量が５０ｍａｓｓ％である場合、Ｒ２－Ｇａ－Ｃｏ系合金の２５ｍａｓｓ％以上がＰｒであることを言う。更に好ましくは、Ｒ２の７０ｍａｓｓ％以上がＰｒであり、最も好ましくはＲ２がＰｒのみ（不可避的不純物は含む）である。これにより、更に高いＨcJを得ることができる。また、Ｒ２として、Ｄｙ、Ｔｂ、Ｇｄ、Ｈｏなどの重希土類元素を少量含有してもよい。ただし、本開示の製造方法によれば、重希土類元素を多量に用いずとも十分に高いＨcJを得ることができる。そのため、前記重希土類元素の含有量はＲ２－Ｇａ－Ｃｏ系合金全体の１０ｍａｓｓ％以下（Ｒ２－Ｇａ－Ｃｏ系合金中の重希土類元素が１０ｍａｓｓ％以下）であることが好ましく、５ｍａｓｓ％以下であることがより好ましく、含有しない（実質的に０ｍａｓｓ％）ことが更に好ましい。Ｒ２－Ｇａ－Ｃｏ系合金のＲ２が重希土類元素を含有する場合も、Ｒ２の５０％以上がＰｒであることが好ましく、重希土類元素を除いたＲ２がＰｒのみ（不可避的不純物は含む）であることがより好ましい。 R2 is at least one of rare earth elements and always contains at least one of Nd and Pr. It is preferable that 50 mass% or more of R2 is Pr. It is because higher H cJ can be obtained. Here, "50 mass% or more of R2 is Pr" means that, for example, when the content of R2 in the R2-Ga-Co alloy is 50 mass%, 25 mass% or more of the R2-Ga-Co alloy is Pr Say that. More preferably, 70 mass% or more of R2 is Pr, and most preferably, R2 is only Pr (including unavoidable impurities). Thereby, a further higher HcJ can be obtained. In addition, a small amount of heavy rare earth elements such as Dy, Tb, Gd and Ho may be contained as R2. However, according to the manufacturing method of the present disclosure, sufficiently high HcJ can be obtained without using a large amount of heavy rare earth elements. Therefore, the content of the heavy rare earth element is preferably 10 mass% or less of the entire R2-Ga-Co alloy (heavy rare earth element in the R2-Ga-Co alloy is 10 mass% or less), and is 5 mass% or less Some are more preferable, and it is more preferable not to contain (substantially 0 mass%). Even when R2 of the R2-Ga-Co alloy contains a heavy rare earth element, it is preferable that 50% or more of R2 is Pr, and R2 excluding the heavy rare earth element is only Pr (including unavoidable impurities). It is more preferable that
　Ｒ２の含有量はＲ２－Ｇａ－Ｃｏ系合金全体の３５ｍａｓｓ％以上８７ｍａｓｓ％未満である。Ｒ２の含有量が３５ｍａｓｓ％未満では後述する第一の熱処理で拡散が十分に進行しない可能性がある。一方、Ｒ２の含有量が８７ｍａｓｓ％以上でも本開示の効果を得ることはできるが、Ｒ２－Ｇａ－Ｃｏ系合金の製造工程中における合金粉末が非常に活性になる。その結果、合金粉末の著しい酸化や発火などを生じることがあるため、Ｒ２の含有量はＲ２－Ｇａ－Ｃｏ系合金全体の８５ｍａｓｓ％未満が好ましい。Ｒ２の含有量は５０ｍａｓｓ％以上８５ｍａｓｓ％未満であることがより好ましく、６０ｍａｓｓ％以上８５ｍａｓｓ％未満であることが更に好ましい。より高いＨcJを得ることができるからである。 The content of R2 is 35 mass% or more and less than 87 mass% of the entire R2-Ga-Co alloy. If the content of R2 is less than 35 mass%, diffusion may not sufficiently proceed in the first heat treatment described later. On the other hand, although the effect of the present disclosure can be obtained even if the content of R2 is 87 mass% or more, the alloy powder in the manufacturing process of the R2-Ga-Co based alloy becomes very active. As a result, significant oxidation or ignition of the alloy powder may occur, so the content of R2 is preferably less than 85 mass% of the entire R2-Ga-Co based alloy. The content of R2 is more preferably 50 mass% or more and less than 85 mass%, and still more preferably 60 mass% or more and less than 85 mass%. It is because higher H cJ can be obtained.
　Ｇａは、Ｒ２－Ｇａ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上３０ｍａｓｓ％以下である。Ｇａが２．５ｍａｓｓ％未満では、後述する第一の熱処理を実施する工程においてＲ２－Ｇａ－Ｃｏ系合金中のＣｏがＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の内部に導入され難くなり高いＢrを得ることができない。更に、Ｒ－Ｔ－Ｇａ相の生成量が少なすぎて、高いＨcJを得ることができない。一方、Ｇａが３０ｍａｓｓ％を超えると、Ｂrが大幅に低下する可能性がある。Ｇａは４ｍａｓｓ％以上２０ｍａｓｓ％以下であることがより好ましく、４ｍａｓｓ％以上１０ｍａｓｓ％以下であることが更に好ましい。より高いＢrと高いＨcJを得ることができるからである。 Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Co alloy. If Ga is less than 2.5 mass%, it is difficult to introduce Co in the R2-Ga-Co-based alloy into the inside of the R1-T1-Cu-B-based sintered body in the step of performing the first heat treatment described later, which is high. I can not get B r . Furthermore, the amount of RT-Ga phase formed is too small to obtain high HcJ . On the other hand, if Ga is more than 30 mass%, B r may be lowered significantly. Ga is more preferably 4 mass% or more and 20 mass% or less, and still more preferably 4 mass% or more and 10 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
　Ｃｏは、Ｒ２－Ｇａ－Ｃｏ系合金全体の１０ｍａｓｓ％超４５ｍａｓｓ％以下である。Ｃｏが１０ｍａｓｓ％以下では、最終的に得られるＲ－Ｔ－Ｂ系焼結磁石のＢrを充分に高めることができない。一方、Ｃｏが４５ｍａｓｓ％を超えると、後述する第一の熱処理で拡散が十分に進行せず、高いＢrと高いＨcJを得ることができない可能性がある。Ｃｏは１５ｍａｓｓ％以上３０ｍａｓｓ％以下であることがより好ましい。より高いＢrと高いＨcJを得ることができるからである。 Co is more than 10 mass% and 45 mass% or less of the entire R2-Ga-Co alloy. Co is in the following 10 mass%, it is impossible to sufficiently enhance the finally obtained R-T-B based sintered magnet of B r. On the other hand, when Co exceeds 45Mass%, it may not be able to spread with a first heat treatment to be described later does not proceed sufficiently to obtain a high B r and high H cJ. As for Co, it is more preferable that they are 15 mass% or more and 30 mass% or less. This is because it is possible to obtain a higher B r and a high H cJ.
　また、本開示におけるＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金では、Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量の不等式が成立している。このため、高いＢr及び高いＨcJを得ることができる。これは本開示の不等式を満足することにより、適切な量のＲ、Ｃｏ及びＧａを含む相が二粒子粒界に生成されるからだと考えられる。 Further, in the R2-Ga-Cu-Co based alloy in the present disclosure, the inequality of R2 content> Co content> Ga content is satisfied. Therefore, it is possible to obtain a high B r and a high H cJ. It is considered that this is because a phase containing appropriate amounts of R, Co and Ga is generated at two grain boundaries by satisfying the inequality of the present disclosure.
　Ｒ２－Ｇａ－Ｃｏ系合金は、上記元素の他にＣｕ、Ａｌ、Ａｇ、Ｚｎ、Ｓｉ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、Ｔｉ、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｍｎ、Ｃｒ、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌ、Ｏ、Ｎ、Ｃ等を含有してもよい。 In addition to the above-mentioned elements, the R2-Ga-Co alloy includes Cu, Al, Ag, Zn, Si, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
　含有量は、Ｃｕ、Ａｌは１．０ｍａｓｓ％以下、Ａｇ、Ｚｎ、Ｓｉ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、及びＴｉはそれぞれ０．５ｍａｓｓ％以下、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｍｎ、Ｓｉ、Ｃｒはそれぞれ０．２ｍａｓｓ％以下、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌは５００ｐｐｍ以下、Ｏは６０００ｐｐｍ以下、Ｎは１０００ｐｐｍ以下、Ｃは１５００ｐｐｍ以下が好ましい。ただし、これらの元素の合計の含有量が２０ｍａｓｓ％を超えると、Ｒ２－Ｇａ－Ｃｏ系合金におけるＲ２、Ｇａ、Ｃｏの含有量が少なくなり、高いＢrと高いＨcJを得ることができない可能性がある。そのため、Ｒ２－Ｇａ－Ｃｏ系合金におけるＲ２、Ｇａ、Ｃｏの合計の含有量は８０ｍａｓｓ％以上が好ましく、９０ｍａｓｓ％以上が更に好ましい。 The content of Cu, Al is 1.0 mass% or less, Ag, Zn, Si, In, Sn, Zr, Nb, and Ti is 0.5 mass% or less, respectively, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Si, Cr each 0.2 mass% or less, H, F, P, S, Cl 500 ppm or less, O 6000 ppm or less, N 1000 ppm or less, As for C, 1500 ppm or less is preferable. However, when the total content of these elements exceeds 20mass%, R2-Ga-Co-based R2 in the alloy, Ga, then the amount of Co, can not be obtained a high B r and high H cJ There is sex. Therefore, the total content of R2, Ga and Co in the R2-Ga-Co alloy is preferably 80 mass% or more, and more preferably 90 mass% or more.
　次にＲ２－Ｇａ－Ｃｏ系合金を準備する工程について説明する。Ｒ２－Ｇａ－Ｃｏ系合金は、Ｎｄ－Ｆｅ－Ｂ系焼結磁石に代表される一般的な製造方法において採用されている原料合金の作製方法、例えば、金型鋳造法やストリップキャスト法や単ロール超急冷法（メルトスピニング法）やアトマイズ法などを用いて準備することができる。また、Ｒ２－Ｇａ－Ｃｏ系合金は、前記によって得られた合金をピンミルなどの公知の粉砕手段によって粉砕されたものであってもよい。また、前記によって得られた合金の粉砕性を向上させるために、水素雰囲気中で７００℃以下の熱処理を行って水素を含有させてから粉砕を行っても良い。 Next, a process of preparing an R2-Ga-Co based alloy will be described. The R2-Ga-Co alloy is a method of preparing a raw material alloy employed in a general manufacturing method represented by a Nd-Fe-B sintered magnet, for example, a die casting method, a strip casting method or a single It can be prepared using a roll ultra-quenching method (melt spinning method) or an atomizing method. In addition, the R2-Ga-Co based alloy may be one obtained by pulverizing the alloy obtained as described above by a known pulverizing means such as a pin mill. Further, in order to improve the grindability of the alloy obtained as described above, heat treatment at 700 ° C. or less in a hydrogen atmosphere may be performed to contain hydrogen and then grinding.
　（第一の熱処理を実施する工程）
　前記によって準備したＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の表面の少なくとも一部に、前記Ｒ２－Ｇａ－Ｃｏ系合金の少なくとも一部を接触させ、真空又は不活性ガス雰囲気中、７００℃以上１１００℃以下の温度で熱処理をする。本開示において、この熱処理を第一の熱処理という。これにより、Ｒ２－Ｇａ－Ｃｏ系合金からＧａ及びＣｏを含む液相が生成し、その液相がＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の粒界を経由して焼結体表面から内部に拡散導入される。第一の熱処理温度が７００℃未満であると、Ｇａ及びＣｏを含む液相量が少なすぎて、高いＢrと高いＨcJを得ることができない可能性がある。一方、１１００℃を超えると主相の異常粒成長が起こり、ＨcJが低下する可能性がある。第一の熱処理温度は、８００℃以上１０００℃以下が好ましい。より高いＢrと高いＨcJを得ることができるからである。なお、熱処理時間はＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体やＲ２－Ｇａ－Ｃｏ系合金の組成や寸法、熱処理温度などによって適正値を設定するが、５分以上２０時間以下が好ましく、１０分以上１５時間以下がより好ましく、３０分以上１０時間以下が更に好ましい。また、Ｒ２－Ｇａ－Ｃｏ系合金は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体の重量に対し２ｍａｓｓ％以上３０ｍａｓｓ％以下準備した方が好ましい。Ｒ２－Ｇａ－Ｃｏ系合金がＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の重量に対し２ｍａｓｓ％未満であるとＨcJが低下する可能性がある。一方、３０ｍａｓｓ％を超えるとＢrが低下する可能性がある。 (Step of carrying out the first heat treatment)
At least a portion of the R2-Ga-Co alloy is brought into contact with at least a portion of the surface of the R1-T1-Cu-B-based sintered body prepared as described above, and the temperature is 700 ° C. or higher in a vacuum or inert gas atmosphere. Heat treatment is performed at a temperature of 1100 ° C. or less. In the present disclosure, this heat treatment is referred to as a first heat treatment. As a result, a liquid phase containing Ga and Co is generated from the R2-Ga-Co alloy, and the liquid phase passes from the surface of the sintered body via the grain boundary of the R1-T1-Cu-B sintered body. Diffusion is introduced. When the first heat treatment temperature is lower than 700 ° C., and too small amount of liquid phase containing Ga and Co, there is a possibility that it is impossible to obtain a high B r and high H cJ. On the other hand, when the temperature exceeds 1100 ° C., abnormal grain growth of the main phase occurs and H cJ may decrease. The first heat treatment temperature is preferably 800 ° C. or more and 1000 ° C. or less. This is because it is possible to obtain a higher B r and a high H cJ. The heat treatment time is set to an appropriate value depending on the composition and dimensions of the R1-T1-Cu-B sintered body and R2-Ga-Co alloy, the heat treatment temperature, etc., but 5 minutes or more and 20 hours or less is preferable, 10 More preferably, minutes to 15 hours and still more preferably 30 minutes to 10 hours. The R2-Ga-Co alloy is preferably prepared in an amount of 2 mass% or more and 30 mass% or less based on the weight of the R1-T1-Cu-B sintered body. If the R2-Ga-Co based alloy is less than 2 mass% with respect to the weight of the R1-T1-Cu-B based sintered body, there is a possibility that HcJ may be reduced. On the other hand, there is a possibility that the B r decreases exceeds 30 mass%.
　第一の熱処理は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体表面に、任意形状のＲ２－Ｇａ－Ｃｏ系合金を配置し、公知の熱処理装置を用いて行うことができる。例えば、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体表面をＲ２－Ｇａ－Ｃｏ系合金の粉末層で覆い、第一の熱処理を行うことができる。例えば、Ｒ２－Ｇａ－Ｃｏ系合金を分散媒中に分散させたスラリーをＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体表面に塗布した後、分散媒を蒸発させてＲ２－Ｇａ－Ｃｏ系合金とＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体とを接触させてもよい。また、後述する実験例に示すように、Ｒ２－Ｇａ－Ｃｏ系合金は、少なくともＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の配向方向に対して垂直な表面に接触させるように配置することが好ましい。なお、分散媒として、アルコール（エタノール等）、ＮＭＰ（Ｎ－メチルピロリドン）、アルデヒド及びケトンを例示できる。また、第一の熱処理が実施されたＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体に対して切断や切削など公知の機械加工を行ってもよい。 The first heat treatment can be performed by disposing an R2-Ga-Co-based alloy having an arbitrary shape on the surface of the R1-T1-Cu-B-based sintered body and using a known heat treatment apparatus. For example, the first heat treatment can be performed by covering the surface of the R1-T1-Cu-B-based sintered body with a powder layer of an R2-Ga-Co-based alloy. For example, a slurry in which an R2-Ga-Co alloy is dispersed in a dispersion medium is applied to the surface of an R1-T1-Cu-B sintered body, and then the dispersion medium is evaporated to form an R2-Ga-Co alloy. The sintered body of R1-T1-Cu-B may be brought into contact. In addition, as shown in the experimental example described later, the R2-Ga-Co based alloy may be arranged to be in contact with the surface perpendicular to the orientation direction of at least the R1-T1-Cu-B based sintered body. preferable. Examples of the dispersion medium include alcohols (ethanol etc.), NMP (N-methylpyrrolidone), aldehydes and ketones. Also, known machining such as cutting or cutting may be performed on the R1-T1-Cu-B-based sintered body subjected to the first heat treatment.
　（第二の熱処理を実施する工程）
　第一の熱処理が実施されたＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体に対して、真空又は不活性ガス雰囲気中、４５０℃以上６００℃以下の温度で熱処理を行う。本開示においてこの熱処理を第二の熱処理という。第二の熱処理を行うことにより、高いＢrと高いＨcJを得ることができる。第二の熱処理の温度が４５０℃未満及び６００℃超の場合は、Ｒ－Ｔ－Ｇａ相（典型的にはＲ6Ｔ13Ｚ相（ＺはＣｕ及びＧａの少なくとも１つ））の生成量が少なすぎて、高いＢrと高いＨcJを得ることができない可能性がある。第二の熱処理温度は、４８０℃以上５６０℃以下が好ましい。より高いＨcJを得ることができる。なお、熱処理時間はＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の組成や寸法、熱処理温度などによって適正値を設定するが、５分以上２０時間以下が好ましく、１０分以上１５時間以下がより好ましく、３０分以上１０時間以下が更に好ましい。 (Step of carrying out the second heat treatment)
The R1-T1-Cu-B-based sintered body subjected to the first heat treatment is heat-treated at a temperature of 450 ° C. to 600 ° C. in a vacuum or an inert gas atmosphere. In the present disclosure, this heat treatment is referred to as a second heat treatment. By performing the second heat treatment, it is possible to obtain a high B r and high H cJ. When the temperature of the second heat treatment is less than 450 ° C. and more than 600 ° C., the amount of RT-Ga phase (typically, R 6 T 13 Z phase (Z is at least one of Cu and Ga)) There is a possibility that high B r and high H cJ can not be obtained due to too little. The second heat treatment temperature is preferably 480 ° C. or more and 560 ° C. or less. Higher H cJ can be obtained. The heat treatment time is set appropriately depending on the composition and dimensions of the R1-T1-Cu-B sintered body, the heat treatment temperature, etc., but it is preferably 5 minutes to 20 hours and more preferably 10 minutes to 15 hours. More preferably, 30 minutes or more and 10 hours or less.
　なお、前記のＲ6Ｔ13Ｚ相（Ｒ6Ｔ13Ｚ化合物）において、Ｒは希土類元素のうち少なくとも一種でありＰｒ及びＮｄの少なくとも一方を必ず含み、Ｔは遷移金属元素のうち少なくとも一種でありＦｅを必ず含む。Ｒ6Ｔ13Ｚ化合物は代表的にはＮｄ6Ｆｅ13Ｇａ化合物である。また、Ｒ6Ｔ13Ｚ化合物はＬａ6Ｃｏ11Ｇａ3型結晶構造を有する。Ｒ6Ｔ13Ｚ化合物はその状態によってはＲ6Ｔ13-δＺ1+δ化合物になっている場合がある。なお、Ｒ－Ｔ－Ｂ系焼結磁石中に比較的多くのＣｕ、Ａｌ及びＳｉが含有される場合、Ｒ6Ｔ13-δ（Ｇａ1-a-b-cＣｕaＡｌbＳｉc）1+δになっている場合がある。 In the above R 6 T 13 Z phase (R 6 T 13 Z compound), R is at least one rare earth element and necessarily includes at least one of Pr and Nd, and T is at least one transition metal element. Yes Fe must be included. The R 6 T 13 Z compound is typically an Nd 6 Fe 13 Ga compound. Further, the R 6 T 13 Z compound has a La 6 Co 11 Ga 3 type crystal structure. The R 6 T 13 Z compound may be an R 6 T 13 − δZ 1+ δ compound depending on the state. When relatively large amounts of Cu, Al, and Si are contained in the RTB-based sintered magnet, the R 6 T 13- δ (Ga 1 -abc Cu a Al b Si c ) 1+ δ It may have been.
　前記の第二の熱処理を実施する工程によって得られたＲ－Ｔ－Ｂ系焼結磁石は、切断や切削など公知の機械加工を行ったり、耐食性を付与するためのめっきなど、公知の表面処理を行うことができる。また、本開示の製造方法により得られたＲ－Ｔ－Ｂ系焼結磁石は、前記Ｒ－Ｔ－Ｂ系焼結磁石におけるＦｅ又はＣｏ、Ａｌ、Ｍｎ、Ｓｉの少なくとも１つとＦｅをＴ２（Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体におけるＴ１に相当）としたとき、Ｂに対するＴ２のｍｏｌ比（［Ｔ２］／［Ｂ］）が１４．０超であり、Ｒ、Ｆｅ、Ｂ、Ｃｕ、Ｇａを含有している。更に、Ｒ、Ｆｅ、Ｂ、Ｃｕ、Ｇａ以外にもＣｏ、Ａｌ、Ａｇ、Ｉｎ、Ｓｎ、Ｚｒ、Ｎｂ、Ｔｉ、Ｎｉ、Ｈｆ、Ｔａ、Ｗ、Ｇｅ、Ｍｏ、Ｖ、Ｙ、Ｌａ、Ｃｅ、Ｓｍ、Ｃａ、Ｍｇ、Ｍｎ、Ｓｉ、Ｃｒ、Ｈ、Ｆ、Ｐ、Ｓ、Ｃｌ、Ｏ、Ｎ、Ｃ等を含有してもよい。 The RTB-based sintered magnet obtained by the step of carrying out the second heat treatment described above is subjected to known surface treatment such as plating for imparting corrosion resistance or performing known machining such as cutting or cutting. It can be performed. In addition, the RTB-based sintered magnet obtained by the production method of the present disclosure is characterized in that at least one of Fe or Co, Al, Mn, Si and Fe in the RTB-based sintered magnet is T2 ( The molar ratio of T2 to B ([T2] / [B]) is more than 14.0, and R, Fe, B, and Cu are equivalent to T1 in the R1-T1-Cu-B sintered body. And Ga are contained. In addition to R, Fe, B, Cu, Ga, Co, Al, Ag, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Si, Cr, H, F, P, S, Cl, O, N, C and the like may be contained.
＜第１の実施形態の実施例＞
　本発明を実施例により更に詳細に説明するが、本発明はそれらに限定されるものではない。 <Example of First Embodiment>
The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
　実験例１
［Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程］
　Ｒ１－Ｔ１－Ｂ系焼結体がおよそ表１の符号１－Ａとなるよう各元素を秤量しストリップキャスト法により鋳造し、厚さ０．２～０．４ｍｍのフレーク状の原料合金を得た。得られたフレーク状の原料合金を水素粉砕した後、５５０℃まで真空中で加熱後冷却する脱水素処理を施し粗粉砕粉を得た。次に、得られた粗粉砕粉に、潤滑剤としてステアリン酸亜鉛を粗粉砕粉１００ｍａｓｓ％に対して０．０４ｍａｓｓ％添加、混合した後、気流式粉砕機（ジェットミル装置）を用いて、窒素気流中で乾式粉砕し、粒径Ｄ５０が４μｍの微粉砕粉（合金粉末）を得た。なお、粒径Ｄ50は、気流分散法によるレーザー回折法で得られた体積中心値（体積基準メジアン径）である。 Experimental Example 1
[Step of preparing R1-T1-B based sintered body]
Each element is weighed so that R1-T1-B sintered body is approximately 1-A in Table 1 and cast by a strip casting method to obtain a flake-like material alloy having a thickness of 0.2 to 0.4 mm. The After the obtained flake-like raw material alloy was subjected to hydrogen grinding, it was heated in vacuum to 550 ° C. and then dehydrogenated to cool, thereby obtaining roughly crushed powder. Next, 0.04 mass% of zinc stearate as a lubricant is added to the obtained coarsely pulverized powder with respect to 100 mass% of the roughly pulverized powder and mixed, and then nitrogen is added using an air flow crusher (jet mill apparatus) It was dry-pulverized in an air stream to obtain a finely pulverized powder (alloy powder) having a particle diameter D50 of 4 μm. The particle diameter D 50 is the volume center value obtained by the laser diffraction method by air flow dispersion method (volume-based median diameter).
　前記微粉砕粉に、潤滑剤としてステアリン酸亜鉛を微粉砕粉１００ｍａｓｓ％に対して０．０５ｍａｓｓ％添加、混合した後磁界中で成形し成形体を得た。なお、成形装置には、磁界印加方向と加圧方向とが直交するいわゆる直角磁界成形装置（横磁界成形装置）を用いた。 After adding and mixing 0.05 mass% of zinc stearate as a lubricant with respect to 100 mass% of the finely pulverized powder to the finely pulverized powder, the mixture is molded in a magnetic field to obtain a compact. As a forming apparatus, a so-called perpendicular magnetic field forming apparatus (transverse magnetic field forming apparatus) in which the magnetic field application direction and the pressing direction are orthogonal to each other was used.
　得られた成形体を、真空中、１０３０℃（焼結による緻密化が十分起こる温度を選定）で４時間焼結した後急冷し、Ｒ１－Ｔ１－Ｂ系焼結体を得た。得られた焼結体の密度は７．５Ｍｇ／ｍ3以上であった。得られた焼結体の成分の結果を表１に示す。表１における各成分は、高周波誘導結合プラズマ発光分光分析法（ＩＣＰ－ＯＥＳ）を使用して測定した。なお、焼結体の酸素量をガス融解－赤外線吸収法で測定した結果、すべて０．２ｍａｓｓ％前後であることを確認した。また、Ｃ（炭素量）は、燃焼－赤外線吸収法によるガス分析装置を使用して測定した結果、０．１ｍａｓｓ％前後であることを確認した。表１における「［Ｔ１］／［Ｂ］」は、Ｔ１を構成する各元素（ここではＦｅ、Ａｌ、Ｓｉ、Ｍｎ）に対し、分析値（ｍａｓｓ％）をそれぞれの元素の原子量で除したものを求め、それらの値を合計したもの（ａ）と、Ｂの分析値（ｍａｓｓ％）をＢの原子量で除したもの（ｂ）との比（ａ／ｂ）である。以下の全ての表も同様である。なお、表１の各組成及び酸素量、炭素量を合計しても１００ｍａｓｓ％にはならない。これは、前記の通り、各成分によって分析方法が異なるためである。その他の表についても同様である。 The obtained compact was sintered for 4 hours in vacuum at 1030 ° C. (the temperature at which sufficient densification by sintering occurs is selected) and then quenched to obtain an R1-T1-B-based sintered body. The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 1. Each component in Table 1 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES). In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%. “[T1] / [B]” in Table 1 is obtained by dividing the analysis value (mass%) by the atomic weight of each element with respect to each element (here, Fe, Al, Si, Mn) constituting T1. The ratio (a / b) of the sum of those values (a) and the value (mass%) of B analyzed divided by the atomic weight of B (b). The same is true for all the following tables. In addition, even if it adds each composition of Table 1, the amount of oxygen, and the amount of carbon, it does not become 100 mass%. This is because, as described above, the analysis method differs depending on each component. The same applies to the other tables.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程］
　Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金がおよそ表２の符号１－ａから１－gの組成になるよう各元素を秤量し、それらの原料を溶解して、単ロール超急冷法（メルトスピニング法）により、リボン又はフレーク状の合金を得た。得られた合金を、乳鉢を用いてアルゴン雰囲気中で粉砕した後、目開き４２５μｍの篩を通過させ、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備した。得られたＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金の組成を表２に示す。なお、表２における各成分は、高周波誘導結合プラズマ発光分光分析法（ＩＣＰ－ＯＥＳ）を使用して測定した。 [Step of preparing R2-Ga-Cu-Co based alloy]
Each element is weighed so that R2-Ga-Cu-Co alloy has a composition of code 1-a to 1-g of Table 2 approximately, and those raw materials are melted to perform single roll super-quenching method (melt spinning method) ) Gave a ribbon or flake-like alloy. The obtained alloy was ground in an argon atmosphere using a mortar, and then passed through a sieve having an opening of 425 μm to prepare an R2-Ga-Cu-Co based alloy. The composition of the obtained R2-Ga-Cu-Co based alloy is shown in Table 2. Each component in Table 2 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［第一の熱処理を実施する工程］
　表１の符号１－ＡのＲ１－Ｔ１－Ｂ系焼結体を切断、切削加工し、４．４ｍｍ×１０．０ｍｍ×１１．０ｍｍの直方体（１０．０ｍｍ×１１．０ｍｍの面が配向方向と垂直な面）とした。次に、図３に示すように、ニオブ箔により作製した処理容器３中に、主にＲ１－Ｔ１－Ｂ系焼結体１の配向方向（図中の矢印方向）と垂直な面がＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金２と接触するように、表２に示す符号１－ａから１－gのＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金を、符号１－ＡのＲ１－Ｔ１－Ｂ系焼結体の上下にＲ１－Ｔ１－Ｂ系焼結体の重量に対し１０ｍａｓｓ％ずつ計２０ｍａｓｓ％を配置した。次に、管状流気炉を用いて、２００Ｐａに制御した減圧アルゴン中で、表３の第一の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金及びＲ１－Ｔ１－Ｂ系焼結体を加熱して第一の熱処理を実施した後、冷却した。 [Step of carrying out first heat treatment]
The R1-T1-B sintered body of code 1-A in Table 1 is cut and cut to form a 4.4 mm × 10.0 mm × 11.0 mm rectangular solid (10.0 mm × 11.0 mm face is oriented) Perpendicular to the Next, as shown in FIG. 3, in the processing vessel 3 made of niobium foil, the plane perpendicular to the orientation direction (the direction of the arrow in the figure) of the R1-T1-B-based sintered body 1 is mainly R2-. In order to make contact with the Ga-Cu-Co alloy 2, the R2-Ga-Cu-Co alloy of the codes 1-a to 1-g shown in Table 2 is R1-T1-B baked with the code 1-A. A total of 20 mass% of 10 mass% of the R1-T1-B based sintered body was arranged above and below the body. Next, R2-Ga-Cu-Co alloys and R1-T1-B alloys were fired at the temperature and time shown in the first heat treatment of Table 3 in vacuum argon controlled at 200 Pa using a tubular flow air furnace. The body was heated to carry out the first heat treatment and then cooled.
［第二の熱処理を実施する工程］
　第二の熱処理を、管状流気炉を用いて２００Ｐａに制御した減圧アルゴン中で、表３の第二の熱処理に示す温度及び時間で、第一の熱処理が実施されたＲ１－Ｔ１－Ｂ系焼結体に対して実施した後、冷却した。熱処理後の各サンプルの表面近傍に存在するＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金の濃化部を除去するため、表面研削盤を用いて各サンプルの全面を切削加工し、４．０ｍｍ×４．０ｍｍ×４．０ｍｍの立方体状のサンプル（Ｒ－Ｔ－Ｂ系焼結磁石）を得た。なお、第一の熱処理を実施する工程におけるＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金及びＲ１－Ｔ１－Ｂ系焼結体の加熱温度、並びに、第二の熱処理を実施する工程におけるＲ１－Ｔ１―Ｂ系焼結体の加熱温度は、それぞれ熱電対を取り付けることにより測定した。 [Step of carrying out second heat treatment]
R1-T1-B system in which the first heat treatment was carried out at a temperature and for a time indicated in the second heat treatment of Table 3 in a reduced pressure argon atmosphere where the second heat treatment was controlled to 200 Pa using a tubular flow air furnace. It cooled after implementing with respect to the sintered compact. In order to remove the concentrated part of the R2-Ga-Cu-Co based alloy existing near the surface of each sample after heat treatment, the entire surface of each sample is cut using a surface grinder, and 4.0 mm × 4. A cubic sample (R-T-B-based sintered magnet) of 0 mm × 4.0 mm was obtained. The heating temperature of the R2-Ga-Cu-Co alloy and the R1-T1-B sintered body in the step of performing the first heat treatment, and R1-T1-B in the step of performing the second heat treatment The heating temperature of the sintered body was measured by attaching a thermocouple.
［サンプル評価］
　得られたサンプルを、得られたサンプルのＢr及びＨcJをＢ－Ｈトレーサによって測定した。測定結果を表３に示す。表３の通り、Ｒ２－Ｃｕ－Ｇａ－Ｆｅ系合金のＣｏ量が１０ｍａｓｓ％超４５ｍａｓｓ％以下である本発明例は高いＢr及び高いＨcJが得られていることがわかる。これに対し、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金のＣｏ量が１０ｍａｓｓ％以下であり、Ｃｏの含有量＜Ｇａの含有量であるサンプルＮｏ．１－１及び１－２は、高いＢrが得られていない。また、Ｒ２－Ｃｕ－Ｇａ－Ｃｏ系合金のＣｏ量が４５ｍａｓｓ％を超えており、Ｐｒの含有量＜Ｃｏの含有量であるサンプルＮｏ．１－７は、高いＨcJが得られていない。 [sample test]
The obtained samples were measured for B r and H cJ of the obtained samples by B-H tracer. The measurement results are shown in Table 3. As Table 3, the present invention examples of the Co content is less than 10 mass% ultra 45Mass% of R2-Cu-Ga-Fe-based alloy it can be seen that the high B r and a high H cJ are achieved. On the other hand, in the sample No. 1 in which the amount of Co in the R2-Ga-Cu-Co alloy is 10 mass% or less, and the content of Co <the content of Ga. 1-1 and 1-2 do not have high Br . Moreover, the amount of Co of the R2-Cu-Ga-Co alloy exceeds 45 mass%, and the sample No. 2 in which the content of Pr <the content of Co is satisfied. 1-7, high H cJ is not obtained.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実験例２
［Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程］
　Ｒ１－Ｔ１－Ｂ系焼結体がおよそ表４の符号２－Ａに示す組成となるように、各元素を秤量する以外は実験例１と同じ方法で焼結体を作製した。なお、焼結は、１０００℃以上１０５０℃以下（サンプル毎に焼結による緻密化が十分起こる温度を選定）の範囲で行った。得られた焼結体の密度は７．５Ｍｇ／ｍ3以上であった。得られた焼結体の成分の結果を表４に示す。表４における各成分は実験例１と同じ方法で測定した。なお、焼結体の酸素量をガス融解－赤外線吸収法で測定した結果、すべて０．２ｍａｓｓ％前後であることを確認した。また、Ｃ（炭素量）は、燃焼－赤外線吸収法によるガス分析装置を使用して測定した結果、０．１ｍａｓｓ％前後であることを確認した。 Experimental Example 2
[Step of preparing R1-T1-B based sintered body]
A sintered body was produced in the same manner as in Experimental Example 1 except that each element was weighed so that the R1-T1-B-based sintered body had a composition approximately as indicated by symbol 2-A in Table 4. Sintering was performed in the range of 1000 ° C. or more and 1050 ° C. or less (selecting the temperature at which densification by sintering sufficiently occurs for each sample). The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 4. Each component in Table 4 was measured by the same method as Experimental Example 1. In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
［Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程］　
　Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金がおよそ表５の符号２－ａから２－ｍに示す組成となるように、各元素を秤量する以外は実験例１と同じ方法でＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備した。Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金の組成を表５に示す。表５における各成分は実験例１と同じ方法で測定した。 [Step of preparing R2-Ga-Cu-Co based alloy]
R2-Ga-Cu- was prepared in the same manner as in Experimental Example 1 except that each element was weighed so that the R2-Ga-Cu-Co alloy had a composition as shown by symbols 2-a to 2-m in Table 5. A Co-based alloy was prepared. The composition of the R2-Ga-Cu-Co based alloy is shown in Table 5. Each component in Table 5 was measured by the same method as Experimental Example 1.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
［第一の熱処理を実施する工程］
　表６の第一の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金及びＲ１－Ｔ１－Ｂ系焼結体を加熱すること以外は実験例１と同じ方法で第一の熱処理を実施した。 [Step of carrying out first heat treatment]
The first heat treatment was carried out in the same manner as in Experimental Example 1 except that the R2-Ga-Cu-Co based alloy and the R1-T1-B based sintered body were heated at the temperature and time shown in the first heat treatment of Table 6. Carried out.
［第二の熱処理を実施する工程］
　表６の第二の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金及びＲ１－Ｔ１－Ｂ系焼結体を加熱すること以外は実験例１と同じ方法で第二の熱処理を実施した。熱処理後の各サンプルを実験例１と同じ方法で加工しＲ－Ｔ－Ｂ系焼結磁石を得た。 [Step of carrying out second heat treatment]
The second heat treatment was conducted in the same manner as in Experimental Example 1 except that the R2-Ga-Cu-Co alloy and the R1-T1-B sintered body were heated at the temperature and time shown in the second heat treatment of Table 6. Carried out. Each sample after the heat treatment was processed in the same manner as in Experimental Example 1 to obtain a sintered RTB-based magnet.
［サンプル評価］
　得られたサンプルのＢr及びＨcJをＢ－Ｈトレーサによって測定した。測定結果を表６に示す。表６の通り、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金のＲ２量が３５ｍａｓｓ％以上８５ｍａｓｓ％未満、Ｇａ量が２．５ｍａｓｓ％以上３０ｍａｓｓ％以下、Ｃｕ量が２．５ｍａｓｓ％以上２０ｍａｓｓ％以下、及びＲ２の含有量＞Ｃｏの含有量＞Ｇａの含有量＞Ｃｕの含有量の不等式を満たす組成である本発明例は高いＢr及び高いＨcJが得られていることがわかる。これに対し、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金におけるＲ、Ｃｕ、Ｇａのいずれかが本開示の範囲外（サンプルＮｏ．２－１及び２－３はＲ２及びＣｏが範囲外、サンプルＮｏ．２－４、２－６、及び２－１２はＧａが範囲外、サンプルＮｏ．２－７及び２－９はＣｕが範囲外、サンプルＮｏ．２－１３は、Ｃｕ及びＧａが範囲外）であったり、Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量＞Ｃｕの含有量の不等式を満たさない組成（サンプルＮｏ．２－８はＧａの含有量＜Ｃｕの含有量、サンプルＮｏ．２－１０はＣｏの含有量＜Ｇａの含有量）であると高いＨcJを得ることができない。このように、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金のＲ、Ｃｕ、Ｇａ（及び実験例１に示すようにＣｏ）の含有量が本開示の範囲内にあり、Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量＞Ｃｕの含有量の式を満たす組成であることにより、高いＢr及び高いＨcJを得ることができる。 [sample test]
The obtained sample of B r and H cJ was measured by B-H tracer. The measurement results are shown in Table 6. As shown in Table 6, the R2 content of the R2-Ga-Cu-Co alloy is 35 mass% to less than 85 mass%, the Ga content is 2.5 mass% to 30 mass%, the Cu content is 2.5 mass% to 20 mass%, and the present invention examples in a composition satisfying the inequality of content> content of Co> content of Ga> content of Cu of R2 it is found that a high B r and a high H cJ are achieved. On the other hand, any one of R, Cu and Ga in the R2-Ga-Cu-Co based alloy is out of the range of the present disclosure (for sample Nos. 2-1 and 2-3, R2 and Co are out of the range; 2-4, 2-6, and 2-12 are out of the range of Ga, sample Nos. 2-7 and 2-9 are out of the range of Cu, sample No. 2-13 is out of the range of Cu and Ga) Or the content of R2> the content of Co> the content of Ga> the composition not satisfying the inequality of the content of Cu (the sample No.2-8 is the content of Ga <content of Cu, sample No.2 If -10 is the content of Co <the content of Ga), high H cJ can not be obtained. Thus, the content of R, Cu, Ga (and Co as shown in Experimental Example 1) of the R2-Ga-Cu-Co alloy is within the range of the present disclosure, and the content of R2> the content of Co by having a composition satisfying the formula of the content of an amount> the content of Ga> Cu, it is possible to obtain a high B r and a high H cJ.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　実験例３
［Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程］
　Ｒ１－Ｔ１－Ｂ系焼結体がおよそ表７の符号３－Ａに示す組成となるように、各元素を秤量する以外は実験例１と同じ方法で焼結体を作製した。なお、焼結は、１０００℃以上１０５０℃以下（サンプル毎に焼結による緻密化が十分起こる温度を選定）の範囲で行った。得られた焼結体の密度は７．５Ｍｇ／ｍ3以上であった。得られた焼結体の成分の結果を表７に示す。表７における各成分は実験例１と同じ方法で測定した。なお、焼結体の酸素量をガス融解－赤外線吸収法で測定した結果、すべて０．２ｍａｓｓ％前後であることを確認した。また、Ｃ（炭素量）は、燃焼－赤外線吸収法によるガス分析装置を使用して測定した結果、０．１ｍａｓｓ％前後であることを確認した。 Experimental Example 3
[Step of preparing R1-T1-B based sintered body]
A sintered body was produced in the same manner as in Experimental Example 1 except that each element was weighed so that the R1-T1-B-based sintered body had a composition approximately as shown by symbol 3-A in Table 7. Sintering was performed in the range of 1000 ° C. or more and 1050 ° C. or less (selecting the temperature at which densification by sintering sufficiently occurs for each sample). The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 7. Each component in Table 7 was measured by the same method as Experimental example 1. In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
［Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程］
　Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金がおよそ表８の符号３－ａに示す組成となるように、各元素を秤量する以外は実験例１と同じ方法でＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備した。Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金の組成を表８に示す。表８における各成分は実験例１と同じ方法で測定した。 [Step of preparing R2-Ga-Cu-Co based alloy]
The R2-Ga-Cu-Co alloy was prepared in the same manner as in Experimental Example 1 except that each element was weighed so that the R2-Ga-Cu-Co alloy had a composition as shown by the symbol 3-a in Table 8. Got ready. The composition of the R2-Ga-Cu-Co alloy is shown in Table 8. Each component in Table 8 was measured by the same method as Experimental Example 1.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
［第一の熱処理を実施する工程］
　表９の第一の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金及びＲ１－Ｔ１－Ｂ系焼結体を加熱すること以外は実験例１と同じ方法で第一の熱処理を実施した。 [Step of carrying out first heat treatment]
The first heat treatment was conducted in the same manner as in Experimental Example 1 except that the R2-Ga-Cu-Co alloy and the R1-T1-B sintered body were heated at the temperature and time shown in the first heat treatment of Table 9. Carried out.
［第二の熱処理を実施する工程］
　表９の第二の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｕ－Ｃｏ系合金及びＲ１－Ｔ１－Ｂ系焼結体を加熱すること以外は実験例１と同じ方法で第二の熱処理を実施した。熱処理後の各サンプルを実験例１と同じ方法で加工しＲ－Ｔ－Ｂ系焼結磁石を得た。 [Step of carrying out second heat treatment]
The second heat treatment was conducted in the same manner as in Experimental Example 1 except that the R2-Ga-Cu-Co alloy and the R1-T1-B sintered body were heated at the temperature and time shown in the second heat treatment of Table 9. Carried out. Each sample after the heat treatment was processed in the same manner as in Experimental Example 1 to obtain a sintered RTB-based magnet.
［サンプル評価］
　得られたサンプルのＢr及びＨcJをＢ－Ｈトレーサによって測定した。測定結果を表９に示す。表９の通り、本開示の第一の熱処理温度（７００℃以上１１００℃以下）及び第二の熱処理温度（４５０℃以上６００℃以下）である本発明例は高いＢr及び高いＨcJが得られていることがわかる。また、表９の通り、第一の熱処理における温度が８００℃以上１０００℃以下及び第二の熱処理における温度が４８０℃以上５６０℃以下であると、更に高いＨcJが得られている。これに対し、第一の熱処理温度及び第二の熱処理温度のいずれか本開示の範囲外（サンプルＮｏ．３－１は第一の熱処理が範囲外、サンプルＮｏ．３－４及び３－９は第二の熱処理が範囲外）であると高いＨcJを得ることができない。 [sample test]
The obtained sample of B r and H cJ was measured by B-H tracer. The measurement results are shown in Table 9. As shown in Table 9, the first heat treatment temperature (700 ° C. or higher 1100 ° C. or less) and the present invention embodiment is a second heat treatment temperature (450 ° C. or higher 600 ° C. or less) of the present disclosure is higher B r and a high H cJ is obtained It is understood that it is being done. Further, as shown in Table 9, a further higher HcJ is obtained when the temperature in the first heat treatment is 800 ° C. or more and 1000 ° C. or less and the temperature in the second heat treatment is 480 ° C. or more and 560 ° C. or less. On the other hand, any of the first heat treatment temperature and the second heat treatment temperature is out of the range of the present disclosure (the sample No. 3-1 is out of the range of the first heat treatment, sample Nos. 3-4 and 3-9 are If the second heat treatment is out of the range, high H cJ can not be obtained.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
＜第２の実施形態の実施例＞
　実験例４
［Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程］
　Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体がおよそ表１０の符号４－Ａから４－Ｅとなるよう各元素を秤量しストリップキャスト法により鋳造し、厚さ０．２～０．４ｍｍのフレーク状の原料合金を得た。得られたフレーク状の原料合金を水素粉砕した後、５５０℃まで真空中で加熱後冷却する脱水素処理を施し粗粉砕粉を得た。次に、得られた粗粉砕粉に、潤滑剤としてステアリン酸亜鉛を粗粉砕粉１００ｍａｓｓ％に対して０．０４ｍａｓｓ％添加、混合した後、気流式粉砕機（ジェットミル装置）を用いて、窒素気流中で乾式粉砕し、粒径Ｄ50が４μｍの微粉砕粉（合金粉末）を得た。なお、粒径Ｄ50は、気流分散法によるレーザー回折法で得られた体積中心値（体積基準メジアン径）である。 <Example of Second Embodiment>
Experimental Example 4
[Step of preparing R1-T1-Cu-B based sintered body]
Each element is weighed so that the R1-T1-Cu-B sintered body is approximately 4-A to 4-E in Table 10 and cast by a strip casting method, and flakes having a thickness of 0.2 to 0.4 mm The raw material alloy was obtained. After the obtained flake-like raw material alloy was subjected to hydrogen grinding, it was heated in vacuum to 550 ° C. and then dehydrogenated to cool, thereby obtaining roughly crushed powder. Next, 0.04 mass% of zinc stearate as a lubricant is added to the obtained coarsely pulverized powder with respect to 100 mass% of the roughly pulverized powder and mixed, and then nitrogen is added using an air flow crusher (jet mill apparatus) dry milled in an air stream, the particle size D 50 was obtained finely pulverized powder of 4μm (the alloy powder). The particle diameter D 50 is the volume center value obtained by the laser diffraction method by air flow dispersion method (volume-based median diameter).
　前記微粉砕粉に、潤滑剤としてステアリン酸亜鉛を微粉砕粉１００ｍａｓｓ％に対して０．０５ｍａｓｓ％添加、混合した後磁界中で成形し成形体を得た。なお、成形装置には、磁界印加方向と加圧方向とが直交するいわゆる直角磁界成形装置（横磁界成形装置）を用いた。 After adding and mixing 0.05 mass% of zinc stearate as a lubricant with respect to 100 mass% of the finely pulverized powder to the finely pulverized powder, the mixture is molded in a magnetic field to obtain a compact. As a forming apparatus, a so-called perpendicular magnetic field forming apparatus (transverse magnetic field forming apparatus) in which the magnetic field application direction and the pressing direction are orthogonal to each other was used.
　得られた成形体を、真空中、１０００℃以上１０５０℃以下（サンプル毎に焼結による緻密化が十分起こる温度を選定）で４時間焼結した後急冷し、Ｒ１－Ｔ１－Ｂ系焼結体を得た。得られた焼結体の密度は７．５Ｍｇ／ｍ3以上であった。得られた焼結体の成分の結果を表１０に示す。表１０における各成分は、高周波誘導結合プラズマ発光分光分析法（ＩＣＰ－ＯＥＳ）を使用して測定した。なお、焼結体の酸素量をガス融解－赤外線吸収法で測定した結果、すべて０．２ｍａｓｓ％前後であることを確認した。また、Ｃ（炭素量）は、燃焼－赤外線吸収法によるガス分析装置を使用して測定した結果、０．１ｍａｓｓ％前後であることを確認した。表１０における「［Ｔ１］／［Ｂ］」は、Ｔ１を構成する各元素（ここではＦｅ、Ａｌ、Ｓｉ、Ｍｎ）に対し、分析値（ｍａｓｓ％）をそれぞれの元素の原子量で除したものを求め、それらの値を合計したもの（ａ）と、Ｂの分析値（ｍａｓｓ％）をＢの原子量で除したもの（ｂ）との比（ａ／ｂ）である。以下の全ての表も同様である。なお、表１０の各組成及び酸素量、炭素量を合計しても１００ｍａｓｓ％にはならない。これは、前記の通り、各成分によって分析方法が異なるためである。その他の表についても同様である。 The resulting compact is sintered for 4 hours in vacuum at 1000 ° C. or more and 1050 ° C. or less (select the temperature at which densification by sintering sufficiently occurs for each sample), and then quench it, R1-T1-B based sintering I got a body. The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 10. Each component in Table 10 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES). In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%. “[T1] / [B]” in Table 10 is obtained by dividing the analysis value (mass%) by the atomic weight of each element with respect to each element (here, Fe, Al, Si, Mn) constituting T1. The ratio (a / b) of the sum of those values (a) and the value (mass%) of B analyzed divided by the atomic weight of B (b). The same is true for all the following tables. In addition, even if it adds each composition of Table 10, the amount of oxygen, and the amount of carbon, it does not become 100 mass%. This is because, as described above, the analysis method differs depending on each component. The same applies to the other tables.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
［Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程］
　Ｒ２－Ｇａ－Ｃｏ系合金がおよそ表１１の符号４－ａの組成になるよう各元素を秤量し、それらの原料を溶解して、単ロール超急冷法（メルトスピニング法）により、リボン又はフレーク状の合金を得た。得られた合金を、乳鉢を用いてアルゴン雰囲気中で粉砕した後、目開き４２５μｍの篩を通過させ、Ｒ２－Ｇａ－Ｃｏ系合金を準備した。得られたＲ２－Ｇａ－Ｃｏ系合金の組成を表１１に示す。なお、表１１における各成分は、高周波誘導結合プラズマ発光分光分析法（ＩＣＰ－ＯＥＳ）を使用して測定した。 [Step of preparing R2-Ga-Co based alloy]
Each element is weighed so that the R2-Ga-Co alloy has a composition as shown by symbol 4-a in Table 11, and the raw materials are melted to obtain ribbons or flakes by a single roll super-quenching method (melt spinning method). An alloy of the shape of a circle is obtained. The obtained alloy was ground in an argon atmosphere using a mortar, and then passed through a sieve having an opening of 425 μm to prepare an R 2 -Ga-Co based alloy. The composition of the obtained R2-Ga-Co alloy is shown in Table 11. Each component in Table 11 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES).
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
［第一の熱処理を実施する工程］
　表１０の符号４－Ａから４－ＥのＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を切断、切削加工し、４．４ｍｍ×１０．０ｍｍ×１１．０ｍｍの直方体（１０．０ｍｍ×１１．０ｍｍの面が配向方向と垂直な面）とした。次に、図３に示すように、ニオブ箔により作製した処理容器３中に、主にＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体１の配向方向（図中の矢印方向）と垂直な面がＲ２－Ｇａ－Ｃｏ系合金２と接触するように、表１１に示す符号４－ａのＲ２－Ｇａ－Ｃｏ系合金を、符号４－Ａから４－ＥのＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の上下にＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の重量に対し１０ｍａｓｓ％ずつ計２０ｍａｓｓ％を配置した。次に、管状流気炉を用いて、２００Ｐａに制御した減圧アルゴン中で、表１２の第一の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｏ系合金及びＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を加熱して第一の熱処理を実施した後、冷却した。 [Step of carrying out first heat treatment]
The R1-T1-Cu-B-based sintered body having a symbol 4-A to 4-E in Table 10 is cut and cut to form a rectangular solid (10.0 mm × 11.4) having a size of 4.4 mm × 10.0 mm × 11.0 mm. A plane of 0 mm was a plane perpendicular to the orientation direction). Next, as shown in FIG. 3, in the processing vessel 3 made of niobium foil, a plane perpendicular to the orientation direction (the direction of the arrow in the figure) of the R1-T1-Cu-B sintered body 1 is mainly In order to make contact with the R2-Ga-Co alloy 2, the R2-Ga-Co alloy of the code 4-a shown in Table 11 can be sintered with the R1-T1-Cu-B alloy of the code 4-A to 4-E. A total of 20 mass% of 10 mass% of the R1-T1-Cu-B based sintered body was disposed above and below the body. Next, R2-Ga-Co alloys and R1-T1-Cu-B alloys are fired at the temperature and time shown in the first heat treatment of Table 12 in vacuum argon controlled at 200 Pa using a tubular flow air furnace. The body was heated to carry out the first heat treatment and then cooled.
［第二の熱処理を実施する工程］
　第二の熱処理を、管状流気炉を用いて２００Ｐａに制御した減圧アルゴン中で、表１２の第二の熱処理に示す温度及び時間で、第一の熱処理が実施されたＲ１－Ｔ１－Ｂ系焼結体に対して実施した後、冷却した。熱処理後の各サンプルの表面近傍に存在するＲ２－Ｇａ－Ｃｏ系合金の濃化部を除去するため、表面研削盤を用いて各サンプルの全面を切削加工し、４．０ｍｍ×４．０ｍｍ×４．０ｍｍの立方体状のサンプル（Ｒ－Ｔ－Ｂ系焼結磁石）を得た。なお、第一の熱処理を実施する工程におけるＲ２－Ｇａ－Ｃｏ合金及びＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体の加熱温度、並びに、第二の熱処理を実施する工程におけるＲ１－Ｔ１―Ｃｕ－Ｂ系焼結体の加熱温度は、それぞれ熱電対を取り付けることにより測定した。 [Step of carrying out second heat treatment]
R1-T1-B system in which the first heat treatment was carried out at the temperature and time shown in the second heat treatment of Table 12 in a reduced pressure argon atmosphere where the second heat treatment was controlled to 200 Pa using a tubular flow air furnace It cooled after implementing with respect to the sintered compact. In order to remove the concentrated part of R2-Ga-Co based alloy existing near the surface of each sample after heat treatment, the entire surface of each sample is cut using a surface grinder, and 4.0 mm × 4.0 mm × A 4.0 mm cube-shaped sample (R-T-B sintered magnet) was obtained. The heating temperature of the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body in the step of performing the first heat treatment, and R1-T1-Cu- in the step of performing the second heat treatment. The heating temperature of the B-based sintered body was measured by attaching a thermocouple.
［サンプル評価］
　得られた各サンプルのＢr及びＨcJをＢ－Ｈトレーサによって測定した。測定結果を表１２に示す。表１２の通り、Ｒ１－Ｔ１―Ｃｕ－Ｂ系焼結体のＣｕ含有量が０．１ｍａｓｓ％未満であるサンプルＮｏ．４－１は、高いＨcJが得られていない。また、Ｃｕの含有量が１．５ｍａｓｓ％を超えているサンプルＮｏ．４－５は、高いＢr及びＨcJが得られていない。 [sample test]
Each sample of B r and H cJ obtained was measured by B-H tracer. The measurement results are shown in Table 12. As shown in Table 12, sample No. 1 in which the Cu content of the R1-T1-Cu-B-based sintered body is less than 0.1 mass%. In 4-1, high H cJ is not obtained. In addition, sample No. 1 in which the content of Cu exceeds 1.5 mass%. 4-5 does not obtain a high B r and H cJ.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　実験例５
［Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程］
　Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体がおよそ表１３の符号５－Ａに示す組成となるように、各元素を秤量する以外は実験例４と同じ方法で焼結体を作製した。得られた焼結体の密度は７．５Ｍｇ／ｍ3以上であった。得られた焼結体の成分の結果を表１３に示す。表１３における各成分は実験例４と同じ方法で測定した。なお、焼結体の酸素量をガス融解－赤外線吸収法で測定した結果、すべて０．２ｍａｓｓ％前後であることを確認した。また、Ｃ（炭素量）は、燃焼－赤外線吸収法によるガス分析装置を使用して測定した結果、０．１ｍａｓｓ％前後であることを確認した。 Experimental Example 5
[Step of preparing R1-T1-Cu-B based sintered body]
A sintered body was produced in the same manner as in Experimental Example 4 except that each element was weighed so that the R1-T1-Cu-B-based sintered body had a composition as indicated by the symbol 5-A in Table 13. The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 13. Each component in Table 13 was measured by the same method as Experimental Example 4. In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
［Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程］
　Ｒ２－Ｇａ－Ｃｏ系合金がおよそ表１４の符号５－ａから５－ｇに示す組成となるように、各元素を秤量する以外は実験例４と同じ方法でＲ２－Ｇａ－Ｃｏ系合金を準備した。Ｒ２－Ｇａ－Ｃｏ系合金の組成を表１４に示す。表１４における各成分は実験例４と同じ方法で測定した。 [Step of preparing R2-Ga-Co based alloy]
The R2-Ga-Co alloy is prepared in the same manner as in Experimental Example 4 except that each element is weighed so that the R2-Ga-Co alloy has a composition as indicated by symbols 5-a to 5-g in Table 14. Got ready. The composition of the R2-Ga-Co based alloy is shown in Table 14. Each component in Table 14 was measured by the same method as Experimental Example 4.
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
［第一の熱処理を実施する工程］
　表１５の第一の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｏ合金及びＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を加熱すること以外は実験例４と同じ方法で第一の熱処理を実施した。 [Step of carrying out first heat treatment]
The first heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the first heat treatment of Table 15. did.
［第二の熱処理を実施する工程］
　表１５の第二の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｏ合金及びＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を加熱すること以外は実験例４と同じ方法で第二の熱処理を実施した。熱処理後の各サンプルを実験例４と同じ方法で加工しＲ－Ｔ－Ｂ系焼結磁石を得た。 [Step of carrying out second heat treatment]
The second heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the second heat treatment of Table 15. did. Each sample after heat treatment was processed in the same manner as in Experimental Example 4 to obtain an RTB-based sintered magnet.
［サンプル評価］
　得られた各サンプルのＢr及びＨcJをＢ－Ｈトレーサによって測定した。測定結果を表１５に示す。表１５の通り、Ｒ－Ｇａ－Ｃｏ系合金のＣｏ量が１０ｍａｓｓ％超４５ｍａｓｓ％以下である本発明例は高いＢr及び高いＨcJが得られていることがわかる。これに対し、Ｒ－Ｇａ－Ｃｏ系合金のＣｏ量が１０ｍａｓｓ％以下及びＣｏの含有量＜Ｇａ含有量であるサンプルＮｏ．５－１及び５－２は、高いＢrが得られていない。また、Ｒ－Ｇａ－Ｃｏ系合金のＣｏ量が４５ｍａｓｓ％を超えており、Ｐｒの含有量＜Ｃｏ含有量であるサンプルＮｏ．５－７は、高いＨcJが得られていない。 [sample test]
Each sample of B r and H cJ obtained was measured by B-H tracer. The measurement results are shown in Table 15. As Table 15, the present invention example Co amount of R-Ga-Co-based alloy is at most 10 mass% ultra 45Mass% It can be seen that the high B r and a high H cJ are achieved. On the other hand, Sample No. 1 in which the Co content of the R-Ga-Co based alloy is 10 mass% or less and the content of Co <Ga content. 5-1 and 5-2 are not high B r is obtained. Further, in the sample No. 1 in which the amount of Co in the R-Ga-Co alloy exceeds 45 mass%, the content of Pr <the content of Co. In 5-7, high H cJ is not obtained.
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　実験例６
［Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程］
　Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体がおよそ表１６の符号６－Ａに示す組成となるように、各元素を秤量する以外は実験例４と同じ方法で焼結体を作製した。得られた焼結体の密度は７．５Ｍｇ／ｍ3以上であった。得られた焼結体の成分の結果を表１６に示す。表１６における各成分は実験例４と同じ方法で測定した。なお、焼結体の酸素量をガス融解－赤外線吸収法で測定した結果、すべて０．２ｍａｓｓ％前後であることを確認した。また、Ｃ（炭素量）は、燃焼－赤外線吸収法によるガス分析装置を使用して測定した結果、０．１ｍａｓｓ％前後であることを確認した。 Experimental Example 6
[Step of preparing R1-T1-Cu-B based sintered body]
A sintered body was produced in the same manner as in Experimental Example 4 except that each element was weighed so that the R1-T1-Cu-B-based sintered body had a composition shown in the code 6-A in Table 16. The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 16. Each component in Table 16 was measured by the same method as Experimental Example 4. In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
［Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程］
　Ｒ２－Ｇａ－Ｃｏ系合金がおよそ表１７の符号６－ａから６－ｉに示す組成となるように、各元素を秤量する以外は実験例４と同じ方法でＲ２－Ｇａ－Ｃｏ系合金を準備した。Ｒ２－Ｇａ－Ｃｏ系合金の組成を表１７に示す。表１７における各成分は実験例４と同じ方法で測定した。 [Step of preparing R2-Ga-Co based alloy]
The R2-Ga-Co alloy is prepared in the same manner as in Experimental Example 4 except that each element is weighed so that the R2-Ga-Co alloy has a composition as shown by symbols 6-a to 6-i in Table 17. Got ready. The composition of the R2-Ga-Co based alloy is shown in Table 17. Each component in Table 17 was measured by the same method as Experimental Example 4.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
［第一の熱処理を実施する工程］
　表１８の第一の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｏ合金及びＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を加熱すること以外は実験例４と同じ方法で第一の熱処理を実施した。 [Step of carrying out first heat treatment]
The first heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the first heat treatment of Table 18 did.
［第二の熱処理を実施する工程］
　表１８の第二の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｏ合金及びＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を加熱すること以外は実験例４と同じ方法で第二の熱処理を実施した。熱処理後の各サンプルを実験例４と同じ方法で加工しＲ－Ｔ－Ｂ系焼結磁石を得た。 [Step of carrying out second heat treatment]
The second heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the second heat treatment of Table 18 did. Each sample after heat treatment was processed in the same manner as in Experimental Example 4 to obtain an RTB-based sintered magnet.
［サンプル評価］
　得られた各サンプルのＢr及びＨcJをＢ－Ｈトレーサによって測定した。測定結果を表１８に示す。表１８の通り、Ｒ２－Ｇａ－Ｃｏ系合金のＲ２量が３５ｍａｓｓ％以上８７ｍａｓｓ％以下、Ｇａ量が２．５ｍａｓｓ％以上３０ｍａｓｓ％以下、及びＲ２の含有量＞Ｃｏの含有量＞Ｇａの含有量の不等式を満たす組成である本発明例は高いＢr及び高いＨcJが得られていることがわかる。これに対し、Ｒ２－Ｇａ－Ｃｏ系合金におけるＲ、Ｇａのいずれかが本開示の範囲外（サンプルＮｏ．６－１はＲ２が範囲外、サンプルＮｏ．６－３はＲ２及びＣｏが範囲外、サンプルＮｏ．６－４、６－６及び６－９はＧａが範囲外）であったり、Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量の不等式を満たさない組成（サンプルＮｏ．６－７はＣｏの含有量＜Ｇａの含有量）であったりすると、高いＨcJを得ることができない。このように、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金のＲ、Ｇａ（及び実験例５に示すようにＣｏ）の含有量が本開示の範囲内にあり、Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量の不等式を満たす組成であることにより、高いＢr及び高いＨcJを得ることができる。 [sample test]
Each sample of B r and H cJ obtained was measured by B-H tracer. The measurement results are shown in Table 18. As shown in Table 18, R2 content of R2-Ga-Co alloy is 35 mass% or more and 87 mass% or less, Ga content is 2.5 mass% or more and 30 mass% or less, and R2 content> Co content> Ga content the present invention examples in a composition satisfying the inequality is seen that a high B r and a high H cJ are achieved. On the other hand, any one of R and Ga in the R2-Ga-Co alloy is out of the range of the present disclosure (sample No. 6-1 has R2 out of the range, sample No. 6-3 has R2 and Co out of the range Sample Nos. 6-4, 6-6, and 6-9 have a composition that does not satisfy the inequality of “Ga out of range” or R2 content> Co content> Ga content inequality (Sample No. 6) If -7 is the content of Co <the content of Ga), high H cJ can not be obtained. Thus, the content of R and Ga (and Co as shown in Experimental Example 5) of the R2-Ga-Cu-Co alloy is within the range of the present disclosure, and the content of R2> the content of Co> by a composition satisfying the inequality of the content of Ga, it is possible to obtain a high B r and a high H cJ.
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
　実験例７
［Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程］
　Ｒ１－Ｔ１－Ｂ系焼結体がおよそ表１９の符号７－Ａに示す組成となるように、各元素を秤量する以外は実験例４と同じ方法で焼結体を作製した。得られた焼結体の密度は７．５Ｍｇ／ｍ3以上であった。得られた焼結体の成分の結果を表１９に示す。表１９における各成分は実験例４と同じ方法で測定した。なお、焼結体の酸素量をガス融解－赤外線吸収法で測定した結果、すべて０．２ｍａｓｓ％前後であることを確認した。また、Ｃ（炭素量）は、燃焼－赤外線吸収法によるガス分析装置を使用して測定した結果、０．１ｍａｓｓ％前後であることを確認した。 Experimental Example 7
[Step of preparing R1-T1-B based sintered body]
A sintered body was produced in the same manner as in Experimental Example 4 except that each element was weighed so that the R1-T1-B-based sintered body had a composition approximately as shown by symbol 7-A in Table 19. The density of the obtained sintered body was 7.5 Mg / m 3 or more. The results of the components of the obtained sintered body are shown in Table 19. Each component in Table 19 was measured by the same method as Experimental Example 4. In addition, as a result of measuring the oxygen amount of the sintered compact by the gas melting-infrared absorption method, it was confirmed that it was all around 0.2 mass%. The C (carbon content) was measured using a gas analyzer by a combustion-infrared absorption method, and as a result, it was confirmed to be around 0.1 mass%.
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
［Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程］
　Ｒ２－Ｇａ－Ｃｏ系合金がおよそ表２０の符号７－ａに示す組成となるように、各元素を秤量する以外は実験例４と同じ方法でＲ２－Ｇａ－Ｃｏ系合金を準備した。Ｒ２－Ｇａ－Ｃｏ系合金の組成を表２０に示す。表２０における各成分は実験例４と同じ方法で測定した。 [Step of preparing R2-Ga-Co based alloy]
An R2-Ga-Co-based alloy was prepared in the same manner as in Experimental Example 4 except that each element was weighed so that the R2-Ga-Co-based alloy had a composition as shown by symbol 7-a in Table 20. Table 20 shows the composition of the R2-Ga-Co based alloy. Each component in Table 20 was measured by the same method as Experimental Example 4.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
［第一の熱処理を実施する工程］
　表２１の第一の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｏ合金及びＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を加熱すること以外は実験例４と同じ方法で第一の熱処理を実施した。 [Step of carrying out first heat treatment]
The first heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the first heat treatment of Table 21. did.
［第二の熱処理を実施する工程］
　表２１の第二の熱処理に示す温度及び時間でＲ２－Ｇａ－Ｃｏ合金及びＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体を加熱すること以外は実験例４と同じ方法で第二の熱処理を実施した。熱処理後の各サンプルを実験例４と同じ方法で加工しＲ－Ｔ－Ｂ系焼結磁石を得た。 [Step of carrying out second heat treatment]
The second heat treatment is performed in the same manner as in Experimental Example 4 except that the R2-Ga-Co alloy and the R1-T1-Cu-B sintered body are heated at the temperature and time shown in the second heat treatment of Table 21. did. Each sample after heat treatment was processed in the same manner as in Experimental Example 4 to obtain an RTB-based sintered magnet.
［サンプル評価］
　得られたサンプルを、Ｂ－Ｈトレーサによって各試料のＢr及びＨcJを測定した。測定結果を表２１に示す。表２１の通り、本開示の第一の熱処理温度（７００℃以上１１００℃以下）及び第二の熱処理温度（４５０℃以上６００℃以下）である本発明例は高いＢr及び高いＨcJが得られていることがわかる。また、表２１の通り、第一の熱処理における温度が８００℃以上１０００℃以下及び第二の熱処理における温度が４８０℃以上５６０℃以下であると、更に高いＨcJが得られている。これに対し、第一の熱処理温度及び第二の熱処理温度のいずれか本開示の範囲外（サンプルＮｏ．７－１は第一の熱処理が範囲外、サンプルＮｏ．７－４及び７－９は第二の熱処理が範囲外）であると高いＨcJを得ることができない。 [sample test]
The obtained samples were subjected to B-H tracer to measure B r and H c J of each sample. The measurement results are shown in Table 21. As Table 21, the first heat treatment temperature (700 ° C. or higher 1100 ° C. or less) and the present invention embodiment is a second heat treatment temperature (450 ° C. or higher 600 ° C. or less) of the present disclosure is higher B r and a high H cJ is obtained It is understood that it is being done. Further, as shown in Table 21, a further higher HcJ is obtained when the temperature in the first heat treatment is 800 ° C. or more and 1000 ° C. or less and the temperature in the second heat treatment is 480 ° C. or more and 560 ° C. or less. On the other hand, either the first heat treatment temperature or the second heat treatment temperature is out of the range of the present disclosure (the sample No. 7-1 is out of the range of the first heat treatment, the sample Nos. 7-4 and 7-9 are If the second heat treatment is out of the range, high H cJ can not be obtained.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　本開示により得られたＲ－Ｔ－Ｂ系焼結磁石は、ハードディスクドライブのボイスコイルモータ（ＶＣＭ）や、電気自動車用（ＥＶ、ＨＶ、ＰＨＶなど）モータ、産業機器用モータなどの各種モータや家電製品などに好適に利用することができる。 The RTB-based sintered magnet obtained by the present disclosure includes various motors such as a voice coil motor (VCM) of a hard disk drive, a motor for electric vehicles (EV, HV, PHV, etc.), a motor for industrial equipment, It can be suitably used for home appliances and the like.
　１　Ｒ１－Ｔ１－Ｂ系焼結体（Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体）
　２　Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金（Ｒ２－Ｇａ－Ｃｏ系合金）
　３　処理容器
　１２　主相
　１４　粒界相
　１４ａ　二粒子粒界相
　１４ｂ　粒界三重点 1 R1-T1-B based sintered body (R1-T1-Cu-B based sintered body)
2 R2-Ga-Cu-Co alloy (R2-Ga-Co alloy)
3 treatment vessel 12 main phase 14 grain boundary phase 14a double grain grain boundary phase 14b grain boundary triple point

Claims (16)

  1. 　Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程と、
    　Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金を準備する工程と、
    　前記Ｒ１－Ｔ１－Ｂ系焼結体の表面の少なくとも一部に、前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金の少なくとも一部を接触させ、真空又は不活性ガス雰囲気中、７００℃以上１１００℃以下の温度で第一の熱処理を実施する工程と、
    　前記第一の熱処理が実施されたＲ１－Ｔ１－Ｂ系焼結体に対して、真空又は不活性ガス雰囲気中、４５０℃以上６００℃以下の温度で第二の熱処理を実施する工程と、
    を含み、
    　前記Ｒ１－Ｔ１－Ｂ系焼結体において、
    　Ｒ１は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含み、Ｒ１の含有量は、Ｒ１－Ｔ１－Ｂ系焼結体全体の２７ｍａｓｓ％以上３５ｍａｓｓ％以下であり、
    　Ｔ１はＦｅ、Ｃｏ、Ａｌ、Ｍｎ、及びＳｉからなる群から選択された少なくとも１つであり、Ｔ１は必ずＦｅを含有し、Ｔ１全体に対するＦｅの含有量が８０ｍａｓｓ％以上であり、
    　Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０超１５．０以下であり、
    　前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金において、
    　Ｒ２は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含み、Ｒ２の含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の３５ｍａｓｓ％以上８５ｍａｓｓ％未満であり、
    　Ｇａの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上３０ｍａｓｓ％以下であり、
    　Ｃｕの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上２０ｍａｓｓ％以下であり、
    　Ｃｏの含有量は、Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金全体の１０ｍａｓｓ％超４５ｍａｓｓ％以下であり、
    　Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量＞Ｃｕの含有量の不等式が成立する、Ｒ－Ｔ－Ｂ系焼結磁石の製造方法。     Preparing a R1-T1-B sintered body;
    Preparing an R2-Ga-Cu-Co alloy;
    At least a portion of the R2-Ga-Cu-Co alloy is brought into contact with at least a portion of the surface of the R1-T1-B sintered body, and the temperature is 700 ° C. or more and 1100 ° C. or less in a vacuum or inert gas atmosphere. Carrying out a first heat treatment at a temperature of
    Performing a second heat treatment on the R1-T1-B-based sintered body subjected to the first heat treatment in a vacuum or an inert gas atmosphere at a temperature of 450 ° C. to 600 ° C .;
    Including
    In the R1-T1-B based sintered body,
    R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is 27 mass% or more and 35 mass% or less of the entire R1-T1-B-based sintered body,
    T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si, T1 necessarily contains Fe, and the content of Fe with respect to the entire T1 is 80 mass% or more,
    The molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and not more than 15.0,
    In the R2-Ga-Cu-Co alloy,
    R2 is at least one of rare earth elements and necessarily contains at least one of Nd and Pr, and the content of R2 is 35 mass% or more and less than 85 mass% of the entire R2-Ga-Cu-Co alloy,
    The content of Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Cu-Co alloy,
    The content of Cu is 2.5 mass% or more and 20 mass% or less of the entire R2-Ga-Cu-Co alloy,
    The content of Co is more than 10 mass% and 45 mass% or less of the whole R2-Ga-Cu-Co alloy,
    R2 content> Co content> Ga content> Cu content The manufacturing method of an RTB-based sintered magnet in which the inequality of the content is satisfied.
  2. 　前記Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．５以上１５．０以下である、請求項１に記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for producing an RTB-based sintered magnet according to claim 1, wherein a molar ratio of T1 to B ([T1] / [B]) is 14.5 or more and 15.0 or less.
  3. 　前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金中のＲ２の５０ｍａｓｓ％以上がＰｒである、請求項１又は２に記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for producing a sintered RTB-based magnet according to claim 1 or 2, wherein 50 mass% or more of R2 in the R2-Ga-Cu-Co based alloy is Pr.
  4. 　前記Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金中のＲ２の７０ｍａｓｓ％以上がＰｒである、請求項１又は２に記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for producing an RTB-based sintered magnet according to claim 1 or 2, wherein 70 mass% or more of R2 in the R2-Ga-Cu-Co-based alloy is Pr.
  5. 　Ｒ２－Ｇａ－Ｃｕ－Ｃｏ系合金におけるＲ２－Ｇａ－Ｃｕ－Ｃｏの合計の含有量が８０ｍａｓｓ％以上である、請求項１から４のいずれかに記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The RTB-based sintered magnet according to any one of claims 1 to 4, wherein the total content of R2-Ga-Cu-Co in the R2-Ga-Cu-Co alloy is 80 mass% or more. Production method.
  6. 　前記第一の熱処理における温度が８００℃以上１０００℃以下である、請求項１から５のいずれかに記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for producing an RTB-based sintered magnet according to any one of claims 1 to 5, wherein a temperature in the first heat treatment is 800 ° C to 1000 ° C.
  7. 　前記第二の熱処理における温度が４８０℃以上５６０℃以下である、請求項１から６のいずれかに記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for manufacturing an RTB-based sintered magnet according to any one of claims 1 to 6, wherein a temperature in the second heat treatment is 480 ° C or more and 560 ° C or less.
  8. 　前記Ｒ１－Ｔ１－Ｂ系焼結体を準備する工程は、原料合金を粒径Ｄ50が３μｍ以上１０μｍ以下に粉砕した後、磁界中で配向させて焼結を行うことを含む、請求項１から７いずれかに記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The step of preparing the R1-T1-B based sintered body includes pulverizing the raw material alloy to a particle diameter D 50 of 3 μm or more and 10 μm or less, and then performing orientation and sintering in a magnetic field. 7. The method for producing an RTB-based sintered magnet according to any one of 7) to 7).
  9. 　Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程と、
    　Ｒ２－Ｇａ－Ｃｏ系合金を準備する工程と、
    　前記Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体の表面の少なくとも一部に、前記Ｒ２－Ｇａ－Ｃｏ系合金の少なくとも一部を接触させ、真空又は不活性ガス雰囲気中、７００℃以上１１００℃以下の温度で第一の熱処理を実施する工程と、
    　前記第一の熱処理が実施されたＲ１－Ｔ１－Ｃｕ－Ｂ系焼結体に対して、真空又は不活性ガス雰囲気中、４５０℃以上６００℃以下の温度で第二の熱処理を実施する工程と、
    を含み、
    　前記Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体において、
    　Ｒ１は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含み、Ｒ１の含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の２７ｍａｓｓ％以上３５ｍａｓｓ％以下であり、
    　Ｔ１はＦｅ、Ｃｏ、Ａｌ、Ｍｎ、及びＳｉからなる群から選択された少なくとも１つであり、Ｔ１は必ずＦｅを含有し、Ｔ１全体に対するＦｅの含有量が８０ｍａｓｓ％以上であり、
    　Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．０超１５．０以下であり、
    　Ｃｕの含有量は、Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体全体の０．１ｍａｓｓ％以上１．５ｍａｓｓ％以下であり、
    　前記Ｒ２－Ｇａ－Ｃｏ系合金において、
    　Ｒ２は希土類元素のうち少なくとも一種であり、Ｎｄ及びＰｒの少なくとも一方を必ず含み、Ｒ２の含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の３５ｍａｓｓ％以上８７ｍａｓｓ％未満であり、
    　Ｇａの含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の２．５ｍａｓｓ％以上３０ｍａｓｓ％以下であり、
    　Ｃｏの含有量は、Ｒ２－Ｇａ－Ｃｏ系合金全体の１０ｍａｓｓ％超４５ｍａｓｓ％以下であり、
    　Ｒ２の含有量＞Ｃｏの含有量＞Ｇａの含有量の不等式が成立する、
    Ｒ－Ｔ－Ｂ系焼結磁石の製造方法。     Preparing an R1-T1-Cu-B sintered body;
    Preparing an R2-Ga-Co alloy;
    At least a part of the R2-Ga-Co alloy is brought into contact with at least a part of the surface of the R1-T1-Cu-B sintered body, and the temperature is 700 ° C. or more and 1100 ° C. or less in a vacuum or inert gas atmosphere. Carrying out a first heat treatment at a temperature of
    Performing a second heat treatment on the R1-T1-Cu-B-based sintered body subjected to the first heat treatment at a temperature of 450 ° C. to 600 ° C. in a vacuum or an inert gas atmosphere; ,
    Including
    In the R1-T1-Cu-B sintered body,
    R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is 27 mass% or more and 35 mass% or less of the whole R1-T1-Cu-B sintered body,
    T1 is at least one selected from the group consisting of Fe, Co, Al, Mn, and Si, T1 necessarily contains Fe, and the content of Fe with respect to the entire T1 is 80 mass% or more,
    The molar ratio of T1 to B ([T1] / [B]) is more than 14.0 and not more than 15.0,
    The content of Cu is 0.1 mass% or more and 1.5 mass% or less of the entire R1-T1-Cu-B-based sintered body,
    In the R2-Ga-Co based alloy,
    R2 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R2 is 35 mass% or more and less than 87 mass% of the entire R2-Ga-Co alloy,
    The content of Ga is 2.5 mass% or more and 30 mass% or less of the entire R2-Ga-Co alloy,
    The content of Co is more than 10 mass% and 45 mass% or less of the entire R2-Ga-Co alloy,
    R2 content> Co content> Ga content inequality holds,
    The manufacturing method of RTB based sintered magnet.
  10. 　前記Ｂに対するＴ１のｍｏｌ比（［Ｔ１］／［Ｂ］）が１４．３以上１５．０以下である、請求項９に記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 10. The method of producing an RTB-based sintered magnet according to claim 9, wherein a molar ratio of T1 to B ([T1] / [B]) is 14.3 or more and 15.0 or less.
  11. 　前記Ｒ２－Ｇａ－Ｃｏ系合金中のＲ２の５０ｍａｓｓ％以上がＰｒである、請求項９又は１０に記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for producing an RTB-based sintered magnet according to claim 9, wherein 50 mass% or more of R2 in the R2-Ga-Co-based alloy is Pr.
  12. 　前記Ｒ２－Ｇａ－Ｃｏ系合金中のＲ２の７０ｍａｓｓ％以上がＰｒである、請求項９又は１０に記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for producing an RTB-based sintered magnet according to claim 9, wherein 70 mass% or more of R2 in the R2-Ga-Co-based alloy is Pr.
  13. 　Ｒ２－Ｇａ－Ｃｏ系合金におけるＲ２、Ｇａ、Ｃｏの合計の含有量が８０ｍａｓｓ％以上である、請求項９から１２のいずれかに記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method of producing an RTB-based sintered magnet according to any one of claims 9 to 12, wherein a total content of R2, Ga and Co in the R2-Ga-Co-based alloy is 80 mass% or more.
  14. 　前記第一の熱処理における温度が８００℃以上１０００℃以下である、請求項９から１３のいずれかに記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for producing an RTB-based sintered magnet according to any one of claims 9 to 13, wherein the temperature in the first heat treatment is 800 ° C to 1000 ° C.
  15. 　前記第二の熱処理における温度が４８０℃以上５６０℃以下である、請求項９から１４のいずれかに記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 The method for producing an RTB-based sintered magnet according to any one of claims 9 to 14, wherein a temperature in the second heat treatment is 480 ° C or more and 560 ° C or less.
  16. 　前記Ｒ１－Ｔ１－Ｃｕ－Ｂ系焼結体を準備する工程は、原料合金を粒径Ｄ50が３μｍ以上１０μｍ以下に粉砕した後、磁界中で配向させて焼結を行うことを含む、請求項９から１５のいずれかに記載のＲ－Ｔ－Ｂ系焼結磁石の製造方法。 Preparing the R1-T1-Cu-B based sintered body comprises performing after the material alloy particle size D 50 was pulverized to 3μm or 10μm or less, the sintering being oriented in a magnetic field, wherein Item 16. A method for producing an RTB-based sintered magnet according to any one of items 9 to 15.
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