JP2019208013A - R-t-b based permanent magnet and method of producing the same - Google Patents

Abstract

To obtain an R-T-B based permanent magnet improved in magnetic characteristics, specifically residual magnetic flux density (residual magnetization) Br and coercive force Hcj.SOLUTION: An R-T-B based permanent magnet includes main phase particles comprising RTB crystals. R represents one or more rare earth elements, T represents one or more iron group elements containing Fe, or Fe and Co, as essential elements, and B represents boron. The R-T-B based permanent magnet further includes C. C concentration in the entire R-T-B based permanent magnet is 0.070 mass% or less. The R-T-B based permanent magnet has a degree of orientation of a predetermined value or more.SELECTED DRAWING: None

Description

  The present invention relates to an R-T-B permanent magnet and a method for manufacturing the same.

  R-T-B permanent magnets are known to have excellent magnetic properties. And the development of the RTB system permanent magnet which further improved the magnetic characteristic is performed.

  As a method for improving the magnetic properties, particularly the coercive force, of an R-T-B system permanent magnet, as described in Patent Document 1, after producing an R-T-B system permanent magnet, a heavy rare earth is formed on the surface. There is a method of diffusing heavy rare earth elements through grain boundaries by attaching elements and heating them (grain boundary diffusion method).

  Patent Document 2 describes an NdFeB permanent magnet manufactured by a pressless magnet manufacturing method and having improved magnetic properties due to a low carbon content.

  Patent Document 3 describes a rare earth permanent magnet that suppresses abnormal grain growth by reducing the amount of oxygen while containing Ga.

  Patent Document 4 describes a rare earth permanent magnet having excellent corrosion resistance, and a rare earth whose carbon content has been reduced by reducing a lubricant kneaded with magnet fine powder in order to improve magnetic field orientation during molding. Permanent magnets are described.

  In addition, as a method for adding the lubricant, as described in Patent Document 5, a method of adding before pulverization, or as described in Patent Document 6, the lubricant is applied to the wall surface of the mold. The method is known.

International Publication No. 2006/043348 Japanese Patent No. 6271425 JP 2006-228992 A JP-A-4-330702 JP-A-7-240330 Japanese Patent No. 3193912

  However, at present, there are demands for further miniaturization, weight reduction, and high efficiency of magnetic components in many applications. For this reason, further improvement in magnetic properties is demanded for RTB-based permanent magnets such as RTB-based sintered magnets.

  An object of the present invention is to obtain an RTB-based permanent magnet having improved magnetic characteristics, particularly residual magnetic flux density (residual magnetization) Br and coercive force Hcj.

In order to achieve the above object, an R-T-B system permanent magnet according to the first aspect of the present invention provides:
An RTB-based permanent magnet including main phase particles composed of an R ₂ T ₁₄ B crystal,
R is one or more rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, B is boron,
The RTB-based permanent magnet further includes C,
C concentration in the entire RTB-based permanent magnet is 0.070% by mass or less,
The degree of orientation obtained by dividing the residual magnetization in the orientation direction by the saturation magnetization Js is 92% or more.

The RTB-based permanent magnet according to the second aspect of the present invention is:
An RTB-based permanent magnet including main phase particles composed of an R ₂ T ₁₄ B crystal,
R is one or more rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, B is boron,
The RTB-based permanent magnet further includes C,
The C concentration in the entire RTB-based permanent magnet is 0.070% by mass or less,
The crystal orientation degree measured by the rod-gering method is 62% or more.

  The RTB-based permanent magnet according to the present invention is an RTB-based permanent magnet having improved magnetic characteristics, particularly Br and Hcj, by having the above-described characteristics.

The RTB-based permanent magnet according to the first aspect and the second aspect may further contain O,
The O concentration in the entire RTB-based permanent magnet may be 0.080% by mass or less.

The RTB-based permanent magnet according to the third aspect of the present invention is:
An RTB-based permanent magnet including main phase particles composed of an R ₂ T ₁₄ B crystal,
R is one or more rare earth elements essential for heavy rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, and B is boron,
At least a part of the main phase particles are core shell main phase particles having a core part and a shell part covering the core part,
The average content ratio of heavy rare earth elements in the shell portion is Cs (atomic%),
It is characterized by satisfying Cs ≧ 1.10.

  The RTB-based permanent magnet according to the present invention is an RTB-based permanent magnet having improved magnetic characteristics, particularly Br and Hcj, by having the above-described characteristics.

  The average thickness of the shell part may be 5 nm or more and 30 nm or less.

The average content ratio of heavy rare earth elements in the core portion is Cc (atomic%),
Cs−Cc ≧ 1.10.

  The average content ratio of carbon in the main phase particles may be 0.25 atomic% or less.

The average content ratio of carbon in the main phase particles is [C] (atomic%), and the average content ratio of boron in the main phase particles is [B] (atomic%),
[C] / [B] ≦ 0.040 may be satisfied.

In particular method for producing the R-T-B-based permanent magnets containing main-phase particles consisting of R _{2 T} 14 _B crystal according to a third aspect of the present invention,
R is one or more rare earth elements essential for heavy rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, and B is boron,
A step of sintering a raw material alloy to form a sintered body, a step of attaching a metal to the sintered body, and a step of heat-treating the sintered body to which the metal is attached in an inert atmosphere. ,
The standard production Gibbs energy for producing metal carbide from the metal is lower than the standard production Gibbs energy for producing carbide of the rare earth element from rare earth elements mainly contained as R.

  Hereinafter, the present invention will be described based on specific embodiments.

(First embodiment)
<R-T-B permanent magnet>
The RTB-based permanent magnet according to this embodiment includes main phase particles made of R ₂ T ₁₄ B crystals. R is one or more rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, and B is boron. Note that the rare earth element contained as R means Sc, Y, and a lanthanoid element belonging to Group 3 of the long-period periodic table. The rare earth elements R are classified into heavy rare earth elements RH and light rare earth elements RL. RH means Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. RL means a rare earth element other than RH. An iron group element means Fe, Co, and Ni.

Although there is no restriction | limiting in particular in content of R, 25 mass% or more and 35 mass% or less may be sufficient. When the R content is 25% by mass or more, R ₂ T ₁₄ B crystals that are the main phase particles of the R—T—B system permanent magnet are sufficiently generated, and α-Fe having soft magnetism, etc. When the R content is 35% by mass or less, Br of the RTB-based permanent magnet tends to be improved.

  0.5 mass% or more and 1.5 mass% or less may be sufficient as content of B in the RTB type | system | group permanent magnet which concerns on this embodiment. When the content of B is 0.5% by mass or more, Hcj tends to be improved. Moreover, it exists in the tendency for Br to improve because content of B is 1.5 mass% or less.

  T may be Fe alone or a part of Fe may be substituted with Co. The content of Fe in the R-T-B system permanent magnet according to the present embodiment may be a substantial balance when unavoidable impurities and N are removed from the R-T-B system permanent magnet. The Co content is preferably 0% by mass or more and 4% by mass or less.

  The RTB-based permanent magnet according to the present embodiment may include Ga, Cu, Al, and / or Zr as a metal element other than R, T, and B. The content of each element is arbitrary.

  The R-T-B permanent magnet may contain inevitable impurities such as Mn, Ca, Cl, S, and F as other elements in an amount of 0.001% by mass to 1.0% by mass. .

The particle size of the main phase particles made of R ₂ T ₁₄ B crystal is arbitrary. Usually, it is 1 μm or more and 10 μm or less.

  The type of R is not particularly limited, but preferably includes at least RL. The type of RL is not particularly limited, but preferably includes at least Nd or Pr. More preferably, Nd is contained. In the case of including RH, there is no particular limitation on the type of RH. Preferably, at least Dy or Tb is included as RH. More preferably, Tb is included.

  In the R-T-B system permanent magnet according to the present embodiment, the C concentration in the entire R-T-B system permanent magnet is 0.070 mass% or less, preferably 0.050 mass% or less. Furthermore, the degree of orientation (Br / Js) obtained by dividing the residual magnetization in the orientation direction by the saturation magnetization is 92% or more, or the degree of crystal orientation measured by the rod-gering method is 62% or more. That is, the RTB system permanent magnet according to the present embodiment has a low C concentration and a high degree of orientation. Note that Br / Js is preferably 93% or more. The degree of crystal orientation is preferably 66% or more.

  Since the RTB-based permanent magnet according to the present embodiment has a low C concentration and a high degree of orientation, it has a high Br and a high Hcj at the same time. In addition, temperature characteristics are easily improved.

  The temperature characteristics are easily improved when the R-T-B compound is compared with the compound in which part of B of the R-T-B compound is substituted with C. This is because the Curie temperature is higher.

  Furthermore, it is preferable that O concentration is 0.080 mass% or less.

  Hereinafter, a method for measuring the degree of crystal orientation by the rod-gering method in the present embodiment will be described.

  In order to measure the degree of crystal orientation of the permanent magnet, first, the magnetic pole face of the permanent magnet is mirror-polished. Thereafter, X-ray diffraction measurement is performed on the mirror-polished surface. Then, the degree of orientation is calculated based on the diffraction peak obtained by the X-ray diffraction measurement. In the Lotgering method, based on the X-ray diffraction intensity I (00l) of the (00l) reflection component and the X-ray diffraction intensity I (hk0) of the (hk0) reflection component, the crystal orientation degree fc is calculated by the following formula. Can be calculated

  When the degree of crystal orientation is calculated by the Lotgering method, only the reflection component in the orientation direction of the diffraction peak, that is, the (00l) reflection component is integrated on the molecular side of the following equation. In addition, reflection components in the diffraction peak in a direction slightly deviating from the orientation direction are all regarded as (hk0) reflection components, and are integrated on the denominator side of the following equation. Of the diffraction peaks, only the component in the alignment direction is regarded as the component in the alignment direction. Only the component in the orientation direction is regarded as a component of (00l) reflection, and is integrated on the molecular side of the following formula. Therefore, the degree of crystal orientation calculated compared to the actual degree of crystal orientation is a considerably small value. In order to calculate the degree of crystal orientation according to the actual condition, it is preferable to perform vector correction on the diffraction peak. However, in this embodiment, vector correction is not performed.

<Method for producing R-T-B permanent magnet>
Next, the manufacturing method of the RTB system permanent magnet which concerns on this embodiment is demonstrated. Hereinafter, as an example of a method for manufacturing an R-T-B system permanent magnet, a method for manufacturing an R-T-B system permanent magnet manufactured by a powder metallurgy method will be described.

  The manufacturing method of the R-T-B system permanent magnet according to the present embodiment includes a forming step of forming a raw material powder to obtain a formed body, a sintering step of sintering the formed body to obtain a sintered body, An aging treatment step of holding the sintered body at a temperature lower than the sintering temperature for a predetermined time; and a decarbonization step of reducing the carbon content of the sintered body.

  Hereinafter, although the manufacturing method of a R-T-B system permanent magnet is demonstrated in detail, what is necessary is just to use a well-known method about the matter which is not specified.

[Preparation process of raw material powder]
The raw material powder can be produced by a known method. In this embodiment, an R-T-B system permanent magnet is manufactured by one alloy method using one kind of raw material alloy mainly composed of an R ₂ T ₁₄ B phase, but by two alloy methods using two kinds of raw material alloys. It may be manufactured.

  First, a raw material metal corresponding to the composition of the raw material alloy according to the present embodiment is prepared, and a raw material alloy corresponding to the present embodiment is produced from the raw material metal. There is no restriction | limiting in particular in the preparation methods of raw material alloy. For example, a raw material alloy can be produced by a strip casting method.

  After producing the raw material alloy, the produced raw material alloy is pulverized (grinding step). The pulverization process may be performed in two stages or in one stage. There is no particular limitation on the grinding method. For example, it is carried out by a method using various pulverizers. For example, the pulverization process can be performed in two stages, a coarse pulverization process and a fine pulverization process, and the coarse pulverization process can be performed, for example, by hydrogen pulverization. Specifically, after hydrogen is stored in the raw material alloy at room temperature, dehydrogenation can be performed in an Ar gas atmosphere at 400 ° C. or higher and 650 ° C. or lower, 0.5 hour or longer and 2 hours or shorter. Further, the fine pulverization step is performed using, for example, a jet mill, a wet attritor or the like after adding a lubricant such as oleic acid amide or zinc stearate as a pulverization aid to the powder after coarse pulverization. be able to. There is no restriction | limiting in particular in the particle size of the finely pulverized powder (raw material powder) obtained. For example, fine pulverization can be performed so that the particle diameter (D50) is a fine pulverized powder (raw material powder) having a particle size of 1 μm to 10 μm. From the hydrogen occlusion and pulverization to the sintering step described later, a low oxygen atmosphere having an oxygen concentration of less than 200 ppm was always used.

  In addition, in order to reduce the carbon content ratio in the raw material powder, the amount of carbon contained in the raw material alloy and the amount of lubricant used as a grinding aid may be reduced. However, the carbon content in the raw material powder need not be reduced. The reason will be described later.

[Molding process]
In the forming step, the finely pulverized powder (raw material powder) obtained in the pulverizing step is formed into a predetermined shape. Although there is no limitation in particular in a shaping | molding method, in this embodiment, finely pulverized powder (raw material powder) is filled in a metal mold | die, and it pressurizes in a magnetic field.

  The pressing at the time of molding is preferably performed at 30 MPa or more and 300 MPa or less. The applied magnetic field is preferably 950 kA / m or more and 1600 kA / m or less. The magnetic field to be applied is not limited to a static magnetic field, and may be a pulsed magnetic field. A static magnetic field and a pulsed magnetic field can also be used in combination. The shape of the molded body obtained by molding the finely pulverized powder (raw material powder) is not particularly limited. For example, depending on the desired shape of the R-T-B system permanent magnet such as a rectangular parallelepiped, a flat plate, or a column. And can have any shape.

[Sintering process]
A sintering process is a process of sintering a molded object in a vacuum or inert gas atmosphere, and obtaining a sintered compact. The sintering temperature needs to be adjusted depending on various conditions such as composition, pulverization method, difference in particle size and particle size distribution, etc., but for a molded body, for example, 1000 ° C. or higher and 1200 ° C. in a vacuum or in the presence of an inert gas. It sinters by performing the process heated at 1 degreeC or less for 1 to 10 hours. Thereby, a high-density sintered body (permanent magnet) is obtained.

[Aging process]
The aging treatment step is performed by heating the sintered body (permanent magnet) after the sintering step in a vacuum or an inert gas atmosphere at a temperature lower than the sintering temperature. There is no particular limitation on the temperature and time of the aging treatment, but for example, it can be performed at 450 ° C. or higher and 900 ° C. or lower for 0.2 hours or longer and 3 hours or shorter. This aging treatment step may be omitted.

  Further, the aging treatment process may be performed in one stage or in two stages. When performing in two stages, for example, the first stage is 700 ° C. to 900 ° C. for 0.2 hours to 3 hours, and the second stage is 450 ° C. to 700 ° C. for 0.2 hours to 3 hours. Also good. Alternatively, the first stage and the second stage may be performed continuously, or after the first stage, the second stage may be performed by cooling to near room temperature and then reheating.

[Decarbonization process]
In the present embodiment, a decarbonization step for reducing the carbon content of the obtained sintered body is performed after the above step. Br and Hcj can be improved by performing a decarbonization step and reducing the carbon content of the sintered body without reducing Br / Js or the degree of crystal orientation. Moreover, when performing the decarbonization process of a sintered compact, in the compound by which a part of B of the RTB compound was substituted by C, a part of C is removed by decarbonization. As a result, B may reenter the generated defect, or it may remain as a defect as it is. When B enters again, the temperature characteristic is naturally improved. Even if the defect remains as it is, the temperature characteristics are improved as compared with a compound in which a part of B of the RTB compound is substituted with C.

  Although the method of decarbonization is arbitrary, the following method is mentioned, for example. First, a metal is adhered to the sintered body obtained in the above process. Hereinafter, the metal attached to the sintered body may be referred to as an attached metal. The type of deposited metal is a standard generation Gibbs energy for generating a carbide of the rare earth element from a rare earth element (for example, Nd) mainly contained in the sintered body. Choose to be lower. The attached metal is preferably a pure metal, and one kind of pure metal may be used, or two or more kinds of pure metals may be used. There is no particular limitation on the surface on which the deposited metal is deposited, but it is preferable to deposit the metal only on the magnetic pole surface. In addition, the rare earth element mainly contained in a sintered compact refers to the rare earth element contained most in a sintered compact. Furthermore, in order to sufficiently obtain the effect of decarbonization, it is preferable that the amount of attached metal is 0.06% by mass or more.

  The method for attaching the metal is arbitrary. For example, it can be made to adhere by applying a slurry containing metal. In addition, there are a method in which a metal foil or plate is brought into contact, a method using vapor deposition, sputtering, electrodeposition, spray coating, brush coating, jet dispenser, nozzle, screen printing, squeegee printing, sheet method, or the like.

  When applying the slurry, the metal is preferably particulate. The average particle size is preferably 100 nm or more and 50 μm or less, and more preferably 1 μm or more and 30 μm or less.

  As the solvent used in the slurry, a solvent that can be uniformly dispersed without dissolving the metal is preferable. For example, alcohol, aldehyde, ketone and the like can be mentioned, and ethanol is particularly preferable.

  There is no restriction | limiting in particular in content of the metal in a slurry. For example, it may be 50% by weight or more and 90% by weight or less. The slurry may further contain components other than metals as necessary. For example, a dispersant for preventing aggregation of metal particles can be used.

  Then, heat treatment is performed. By performing heat treatment in a state where a metal having a low standard Gibbs energy for generating metal carbide from metal is attached to the surface of the RTB system permanent magnet, the carbon inside the RTB system permanent magnet is reduced. It reacts with the metal that has moved and adhered to the magnet surface to form carbide. On the other hand, the metal hardly penetrates into the magnet and remains on the magnet surface. As a result, the carbon content in the R-T-B permanent magnet can be reduced.

  There are no particular restrictions on the conditions for the heat treatment in the decarbonization step, but it is preferable to perform the heat treatment in a vacuum or an inert gas atmosphere at 600 ° C. to 1000 ° C. for 1 hour to 50 hours. Decarbonization proceeds as the amount of deposited metal increases, the heat treatment temperature increases, and the heat treatment time increases. Furthermore, an aging treatment step can be performed after the heat treatment in the decarbonization step.

  After the decarbonization step, at least the surface to which the metal is attached is polished to remove the residue. In addition, when the residue is analyzed, the content ratio of the deposited metal and carbon is high. That is, it can be seen that the deposited metal hardly penetrates into the magnet, and the carbon moves to the magnet surface and reacts with the deposited metal to become a carbide.

(Second Embodiment)
Hereinafter, a second embodiment will be described. Hereinafter, items not particularly described are the same as those in the first embodiment.

<R-T-B permanent magnet>
In the RTB-based permanent magnet according to the present embodiment, R is one or more rare earth elements that essentially require the heavy rare earth element RH. Preferably, light rare earth element RL and heavy rare earth element RH are included. The type of the light rare earth element RL is not particularly limited, but preferably includes at least Nd or Pr. More preferably, Nd is contained. The type of heavy rare earth element RH is not particularly limited, but preferably includes at least Dy or Tb. More preferably, Tb is included.

  Further, the C concentration, O concentration, and orientation degree (Br / Js and crystal orientation degree) in the entire RTB-based permanent magnet are the same as those in the first embodiment.

  The RTB-based permanent magnet according to the present embodiment is a core-shell main phase particle in which at least a part of the main phase particle has a core portion and a shell portion that covers the core portion. Preferably, the ratio of the core-shell main phase particles to the total main phase particles is 60% or more. The method for confirming that the main phase particles are core-shell main phase particles is arbitrary. For example, an arbitrary cross section of an R-T-B permanent magnet is evaluated by a scanning electron microscope (SEM), a transmission electron microscope (TEM), a scanning transmission electron microscope (STEM), and a three-dimensional atom probe (3DAP). It is possible. When using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a scanning transmission electron microscope (STEM), the observation is made at a magnification of 2500 to 1000000 times, and the core portion and the shell portion are distinguished by the difference in contrast. be able to. When a three-dimensional atom probe (3DAP) is used, the core portion and the shell portion can be distinguished from the three-dimensional distribution image of atoms. The core-shell main phase particles do not need to cover the entire surface of the core portion, and the shell portion only needs to cover 60% or more of the surface of the core portion.

  The measurement of each parameter of the core-shell main phase particles described below is such that when the distance between two facing surfaces of the R-T-B system permanent magnet is 3 mm or more, the distance from any one surface is 1 Conducted on core-shell main phase particles including a portion of 5 mm. When the distance between the two facing surfaces of the RTB-based permanent magnet is less than 3 mm, the measurement is performed on the core-shell main phase particles including the portion where the distance from the facing two surfaces is equal.

  The content ratio of the heavy rare earth element RH in each core-shell main phase particle can be measured by performing a three-dimensional atom probe measurement with a three-dimensional atom probe microscope (3DAP). The content ratio of the heavy rare earth element RH in the shell portion is the content ratio of the heavy rare earth element RH at the point where the content ratio of the heavy rare earth element RH is highest when the shell portion is subjected to line analysis. The content ratio of the heavy rare earth element RH in the core portion is calculated by averaging the content ratio of the heavy rare earth element RH when the core portion is subjected to line analysis.

  The average content ratio Cs (atomic%) of the heavy rare earth element RH in the shell portion is an average of the content ratio of the heavy rare earth element RH in the shell portion measured in at least 10 core-shell main phase particles. The average content ratio Cc (atomic%) of the heavy rare earth element RH in the core portion is an average of the content ratio of the heavy rare earth element RH in the core portion measured in at least 10 core-shell main phase particles.

  The core-shell main phase particles contained in the RTB-based permanent magnet according to the present embodiment have a high content ratio of the heavy rare earth element RH in the shell portion as compared with the conventional core-shell main phase particles. Specifically, Cs ≧ 1.10. Moreover, it is preferable to satisfy Cs ≧ 1.80.

  The RTB-based permanent magnet according to the present embodiment can improve the magnetic characteristics due to the high Cs.

  Further, Cs−Cc ≧ 1.10 may be satisfied, or Cs−Cc ≧ 1.80 may be satisfied.

  In the R-T-B system permanent magnet according to the present embodiment, it is preferable that the thickness of the shell portion is smaller than that of the conventional core-shell main phase particles, particularly for increasing Br. Specifically, the average thickness of the shell part is preferably 5 nm or more and 30 nm or less. Further, it is more preferably 5 nm or more and 15 nm or less.

  The thickness of the shell portion can be measured by performing three-dimensional atom probe measurement on the core-shell main phase particles with a three-dimensional atom probe microscope (3DAP). And the average thickness of a shell part can be computed by measuring the thickness of each shell part with respect to at least 10 core-shell main phase particles, and averaging.

  From the above, the core-shell main phase particles included in the RTB-based permanent magnet according to the present embodiment are more heavy than the core-shell main phase particles included in the conventional RTB-based permanent magnet. The concentration of the rare earth element RH is high and the thickness of the shell portion is small. As a result, a higher Hcj can be realized while maintaining Br better than the conventional RTB permanent magnet.

  Furthermore, in the RTB-based permanent magnet according to the present embodiment, it is preferable that [C] ≦ 0.25 is satisfied, where the average content ratio of carbon in the main phase particles is [C] (atomic%). More preferably, C] ≦ 0.15 is satisfied.

  Furthermore, in the RTB-based permanent magnet according to this embodiment, the average content ratio of boron in the main phase particles is [B] (atomic%) and satisfies [C] / [B] ≦ 0.040. Is preferable, and it is more preferable to satisfy [C] / [B] ≦ 0.030.

In the R-T-B system permanent magnet according to the present embodiment, Br is well maintained even if the average content ratio of carbon in the main phase particles is reduced. Further, by reducing [C] and / or [C] / [B], it is easy to obtain the preferable Cs and the average thickness of the shell part. Generally, the carbon contained in the main phase particles is contained mainly by substituting a part of B in the R ₂ T ₁₄ B crystal. Here, the Curie temperature tends to increase as the substitution amount decreases. Therefore, the temperature characteristics tend to improve as the amount of carbon contained in the main phase particles decreases.

  [C] and [B] in the main phase particles can be measured by performing a three-dimensional atom probe measurement with a three-dimensional atom probe (3DAP) on at least 10 main phase particles.

<Method for producing R-T-B permanent magnet>
Next, the manufacturing method of the RTB system permanent magnet which concerns on this embodiment is demonstrated.

  Hereinafter, a method for producing an RTB-based permanent magnet produced by powder metallurgy and having heavy rare earth elements diffused at grain boundaries will be described. The raw material powder preparation step, the forming step, the sintering step, and the aging treatment step are the same as in the first embodiment.

[Decarbonization process]
In the present embodiment, a decarbonization step for reducing the carbon content of the obtained sintered body is performed after the above step. When the core shell main phase particles are generated in the diffusion treatment step described later by reducing the carbon content of the sintered body without reducing the orientation degree of the main phase particles by performing a decarbonization step, It becomes easy to increase the content of the rare earth element and to easily reduce the thickness of the shell portion. The method of decarbonization is the same as in the first embodiment. However, if the amount of attached metal is too large, the effect of the diffusion treatment step described later may be reduced, and Hcj may be reduced. Specifically, when the diffusion treatment step is performed, it is preferable that the amount of attached metal be about 1.0% by mass or less.

  After the decarbonization step, the surface to which the metal is attached is polished to remove the residue. This is because it is difficult to carry out the diffusion treatment step described later without removing the residue. In addition, when the residue is analyzed, the content ratio of the deposited metal and carbon is high. That is, it is understood that the deposited metal hardly penetrates into the magnet, and the carbon moves to the surface of the rare earth permanent magnet and reacts with the deposited metal to become a carbide.

[Diffusion treatment process]
In this embodiment, it further has a diffusion treatment step of diffusing heavy rare earth elements. The diffusion treatment can be performed by applying a heat treatment after attaching a compound containing a heavy rare earth element to the surface of the sintered body. The kind of the compound containing heavy rare earth elements is arbitrary. For example, hydrides of heavy rare earth elements can be mentioned. The method of attaching the compound containing heavy rare earth elements is arbitrary. For example, it can be made to adhere by applying a slurry containing heavy rare earth elements. By controlling the amount of slurry applied and the concentration of heavy rare earth elements contained in the slurry, the thickness of the shell portion and the content of heavy rare earth elements in the shell portion can be controlled. Note that the content ratio of the heavy rare earth element in the core portion does not substantially change before and after the grain boundary diffusion step.

  In addition, there is no restriction | limiting in particular in the method to attach the said heavy rare earth element. For example, there are methods using vapor deposition, sputtering, electrodeposition, spray coating, brush coating, jet dispenser, nozzle, screen printing, squeegee printing, sheet construction method and the like.

  When applying the slurry, the heavy rare earth compound is preferably particulate. The average particle size is preferably 100 nm or more and 50 μm or less, and more preferably 1 μm or more and 30 μm or less.

  As the solvent used for the slurry, a solvent capable of uniformly dispersing the heavy rare earth compound without dissolving it is preferable. For example, alcohol, aldehyde, ketone and the like can be mentioned, and ethanol is particularly preferable.

  There is no restriction | limiting in particular in content of the heavy rare earth compound in a slurry. For example, it may be 50% by weight or more and 90% by weight or less. The slurry may further contain components other than the heavy rare earth compound as necessary. For example, a dispersant for preventing aggregation of heavy rare earth compound particles can be used.

  By performing the above diffusion treatment process on the sintered body, the heavy rare earth element RH diffuses to the grain boundaries of the entire sintered body. Then, a shell portion having a high content of heavy rare earth elements is formed in the main phase particles, and becomes core-shell main phase particles.

  There are no particular restrictions on the conditions for the heat treatment in the diffusion treatment step, but it is preferably performed at 650 ° C. to 1000 ° C. for 1 hour to 24 hours in a vacuum or an inert gas atmosphere. Furthermore, an aging treatment step can be performed after the heat treatment in the diffusion treatment step.

  The reason why it is easy to reduce the thickness of the shell part of the core-shell main phase particles after the grain boundary diffusion step by performing the decarbonization step is that the solubility of the main phase particles is reduced by decarbonization. Moreover, the content rate of the heavy rare earth element in a shell part becomes easy to improve because the thickness of a shell part reduces.

  Moreover, when performing a decarbonization process, the volume ratio of a main phase particle becomes easy to improve compared with the conventional case which does not perform a decarbonization process. This is because the phase containing rare earth element carbides contained in the grain boundaries is reduced by the decarbonization step. As the rare earth element carbides decrease, the volume ratio of the grain boundaries decreases, and the volume ratio of the main phase particles improves. As a result of improvement in the volume ratio of the main phase particles, Br increases.

  Further, as a result of the reduction in the phase containing rare earth element carbides contained in the grain boundaries by the decarbonization step, accumulation of heavy rare earth elements in the rare earth element carbides is suppressed. As a result, the heavy rare earth element efficiently reacts with the main phase particles to form a shell portion. And the improvement effect of the magnetic characteristic (especially Hcj) by grain boundary diffusion becomes larger.

  Furthermore, when performing said decarbonization process, it is easy to maintain Br suitably, compared with the case where the amount of carbon in a raw material alloy is reduced. This is because when the amount of carbon is reduced at the stage of the raw material alloy, the degree of orientation tends to decrease in the forming process, and the Br of the finally obtained magnet tends to decrease.

  Moreover, in the manufacturing method of the RTB system permanent magnet which concerns on this embodiment, you may perform a decarbonizing process and a grain boundary diffusion process simultaneously.

  When the decarbonization step and the grain boundary diffusion step are performed simultaneously, the metal deposited in the decarbonization step and the compound containing the heavy rare earth element deposited in the grain boundary diffusion step are adhered simultaneously. Heat treatment is performed. Then, the surface adhered after the heat treatment is polished to remove the residue.

  The preferred embodiment of the RTB-based permanent magnet of the present invention has been described above, but the RTB-based permanent magnet of the present invention is not limited to the above-described embodiment. The RTB-based permanent magnet of the present invention can be variously modified and variously combined without departing from the gist thereof.

  Furthermore, a magnet obtained by cutting and dividing the R-T-B permanent magnet according to the present embodiment can be used.

  Specifically, the RTB-based permanent magnet according to the present embodiment is suitably used for applications such as a motor, a compressor, a magnetic sensor, and a speaker.

  In addition, the R-T-B system permanent magnet according to the present embodiment may be used alone, or two or more R-T-B system permanent magnets may be combined and used as necessary. There is no particular limitation on the bonding method. For example, there are a mechanical bonding method and a resin mold bonding method.

  By combining two or more RTB-based permanent magnets, a large RTB-based permanent magnet can be easily manufactured. A magnet in which two or more R-T-B permanent magnets are combined is preferably used in applications where a particularly large R-T-B permanent magnet is required, for example, an IPM motor, a wind power generator, a large motor, or the like. .

  Next, the present invention will be described in more detail based on specific examples, but the present invention is not limited to the following examples.

(Experimental example 1)
As raw materials, Nd, Pr, electrolytic iron, and a low carbon ferroboron alloy were prepared. Furthermore, Ga, Al, Cu, Co, and Zr were prepared in the form of a pure metal or an alloy with Fe.

The composition of the permanent magnet finally obtained by strip casting for the raw metal is
Nd: 23.2% by mass,
Pr: 7.3 mass%,
B: 1.00% by mass,
Co: 0.50% by mass,
Cu: 0.10% by mass,
Al: 0.20% by mass,
Zr: 0.10% by mass,
Fe: balance (excluding inevitable impurities), and
Inevitable impurities, etc .: 1% by mass or less,
An alloy for sintered body (raw material alloy) was prepared so that The alloy thickness of the raw material alloy was 0.2 mm to 0.6 mm.

  Next, hydrogen was occluded by flowing hydrogen gas to the raw material alloy at room temperature for 1 hour. Next, the atmosphere was switched to Ar gas, dehydrogenation treatment was performed at 450 ° C. for 1 hour, and the raw material alloy was hydrogen crushed. Further, after cooling, a sieve having a particle size of 400 μm or less was obtained using a sieve.

  Next, the amount of lubricant shown in Table 1 in terms of mass ratio as a grinding aid was added to and mixed with the raw material alloy powder after hydrogen grinding. Oleic acid amide was used as the lubricant.

  Subsequently, it was finely pulverized in a nitrogen stream using a collision plate type jet mill device to obtain fine powder (raw material powder) having an average particle diameter of about 4 μm. The average particle diameter is an average particle diameter D50 measured with a laser diffraction particle size distribution meter.

  In addition, H, Si, Ca, La, Ce, Cr, etc. may be detected as inevitable impurities. Si is mainly mixed from the ferroboron raw material and the crucible during melting of the alloy. Ca, La, and Ce are mixed from rare earth materials. Moreover, Cr may be mixed from electrolytic iron.

The obtained fine powder was molded in a magnetic field to produce a molded body. The applied magnetic field at this time is a static magnetic field of 1200 kA / m. The pressing force during molding was 120 MPa. The magnetic field application direction and the pressurizing direction were orthogonal to each other. When the density of the molded body at this time was measured, the density of all the molded bodies was in the range of 4.10 Mg / m ³ or more and 4.25 Mg / m ³ or less.

Next, the compact was sintered to obtain a permanent magnet. The sintering conditions were held at 1060 ° C. for 4 hours. The sintering atmosphere was in a vacuum. At this time, the sintered density was in the range of 7.50 Mg / m ³ or more and 7.55 Mg / m ³ or less. Thereafter, a first aging treatment was performed for 1 hour at a first tempering temperature T1 = 900 ° C. in an Ar atmosphere and atmospheric pressure, and further a second aging treatment was performed for 1 hour at a second aging temperature T2 = 500 ° C. . And the permanent magnet obtained by said process was processed so that it might become a rectangular parallelepiped of width 15mm, length 15mm, and thickness 4mm of an orientation direction. In Examples 106 and 107, the O concentration of the permanent magnet finally obtained was increased by increasing the oxygen partial pressure in the atmosphere during sintering and aging treatment. And the decarbonization process shown below was performed with respect to the obtained permanent magnet. In Comparative Examples 101 to 103, no decarbonization treatment was performed.

  In the decarbonization treatment, first, a slurry in which metal particles (D50 = 20 μm) made of attached metal were dispersed in ethanol was applied to a permanent magnet. Table 1 shows the types of deposited metal. In the deposited metal used in each example, the standard production Gibbs energy for producing metal carbide from metal is lower than the standard production Gibbs energy for producing Nd carbide from Nd. The coated surfaces were two surfaces of 15 mm × 15 mm among the permanent magnets. The metal was applied so that the amount of metal attached to the mass of the permanent magnet was in the ratio shown in Table 1, and the attached metal was attached. Then, after the slurry was applied, decarbonization treatment was performed by performing a heat treatment at 900 ° C. for 12 hours while flowing Ar at atmospheric pressure. Furthermore, an aging treatment was performed at 500 ° C. for 1 hour in an Ar atmosphere and atmospheric pressure. Then, all 6 surfaces were polished by 100 μm.

  The compositions of the permanent magnets of the examples and comparative examples obtained by the above steps were measured by fluorescent X-ray analysis. B concentration was measured by ICP. As a result, it was confirmed that the composition was substantially the same as that of the raw material alloy and the above composition was obtained.

  The C concentration and the O concentration were measured for the permanent magnets of the examples and comparative examples. The O concentration was measured by an inert gas melting-non-dispersive infrared absorption method. The C concentration was measured by combustion in an oxygen stream-infrared absorption method. Regarding the C concentration, the whole permanent magnet was pulverized to a size of an average particle diameter of about 1 mm by a stamp mill, the measurement samples were randomly extracted five times, and the C concentration of each measurement sample was averaged.

  About each Example and the comparative example, the degree of crystal orientation was measured by the rod-gering method.

  About the permanent magnet of each Example and the comparative example, the magnetic pole surface was mirror-polished. Thereafter, X-ray diffraction measurement of the mirror-polished surface was performed, and the degree of crystal orientation was calculated by the Lotgering method based on the obtained diffraction peak. Vector correction was not performed. The results are shown in Table 1. The degree of crystal orientation was 62% or more, and 66% or more was even better.

  Further, the degree of orientation (Br / Js) obtained by dividing the residual magnetization in the orientation direction by the saturation magnetization was measured for the permanent magnets of the examples and comparative examples at room temperature (23 ° C.). Furthermore, Hcj was also measured for the permanent magnets of the examples and comparative examples. Hcj, Br and Js were measured with a BH tracer. The results are shown in Table 1. Br / Js was determined to be 92% or higher and 93% or higher. Hcj was 1220 kA / m or higher, and 1250 kA / m or higher was further improved. Br made 1420 mT or more favorable, and 1450 mT or more made further favorable.

  In Examples 101 to 107 in which 0.10% by mass of a lubricant was added as a grinding aid and subjected to decarbonization treatment, the C concentration was sufficiently low at 0.070% by mass or less. In Examples 101 to 107, the degree of crystal orientation and Br / Js were sufficiently high, and Br and Hcj were good. In Examples 101 to 106 in which the O concentration was 0.080% by mass or less, Br and Hcj were particularly high.

  In contrast, Comparative Example 101 in which 0.10% by mass of a lubricant was added as a grinding aid but no decarbonization treatment was performed, and the amount of adhered metal deposited in Examples 101 to 107 was subjected to decarbonization treatment. In Comparative Example 104, which was smaller than that, the C concentration exceeded 0.070 mass%. As a result, in Comparative Examples 101 and 104, Br was good but Hcj was low. In addition, the comparative example 104 which performed the decarbonization process improved Hcj compared with the comparative example 101 implemented on the same conditions except the point which did not perform a decarbonization process.

  Further, in Comparative Examples 102 and 103 in which the addition amount of the lubricant was decreased, the C concentration was 0.070% by mass or less, but the crystal orientation and Br / Js were decreased. As a result, in Comparative Examples 102 and 103, Br and Hcj were low.

(Experimental example 2)
(Permanent magnet manufacturing process)
As raw materials, Nd, Pr, electrolytic iron, and a low carbon ferroboron alloy were prepared. Furthermore, Ga, Al, Cu, Co, and Zr were prepared in the form of a pure metal or an alloy with Fe.

For the raw metal, the composition of the permanent magnet before grain boundary diffusion, which will be described later, by strip casting,
Nd: 23.4% by mass,
Pr: 6.5% by mass,
B: 0.96 mass%,
Ga: 0.15% by mass,
Cu: 0.20 mass%,
Al: 0.15% by mass,
Zr: 0.15% by mass,
Fe: balance (excluding inevitable impurities), and
Inevitable impurities, etc .: 1% by mass or less,
An alloy for sintered body (raw material alloy) was prepared so that The alloy thickness of the raw material alloy was 0.2 mm to 0.6 mm.

  Next, hydrogen was occluded by flowing hydrogen gas to the raw material alloy at room temperature for 1 hour. Next, the atmosphere was switched to Ar gas, dehydrogenation treatment was performed at 450 ° C. for 1 hour, and the raw material alloy was hydrogen crushed. Further, after cooling, a sieve having a particle size of 400 μm or less was obtained using a sieve.

  Next, a lubricant (oleic amide) having a mass ratio of 0.1% was added as a grinding aid to the raw material alloy powder after hydrogen grinding and mixed.

  Subsequently, it was finely pulverized in a nitrogen stream using a collision plate type jet mill device to obtain fine powder (raw material powder) having an average particle diameter of about 4 μm. The average particle diameter is an average particle diameter D50 measured with a laser diffraction particle size distribution meter.

  In addition, H, Si, Ca, La, Ce, Cr, etc. may be detected as inevitable impurities. Si is mainly mixed from the ferroboron raw material and the crucible during melting of the alloy. Ca, La, and Ce are mixed from rare earth materials. Moreover, Cr may be mixed from electrolytic iron.

The obtained fine powder was molded in a magnetic field to produce a molded body. The applied magnetic field at this time is a static magnetic field of 1200 kA / m. The pressing force during molding was 120 MPa. The magnetic field application direction and the pressurizing direction were orthogonal to each other. When the density of the molded body at this time was measured, the density of all the molded bodies was in the range of 4.10 Mg / m ³ or more and 4.25 Mg / m ³ or less.

Next, the compact was sintered to obtain a permanent magnet. The sintering conditions were held at 1060 ° C. for 4 hours. The sintering atmosphere was in a vacuum. At this time, the sintered density was in the range of 7.50 Mg / m ³ or more and 7.55 Mg / m ³ or less. Thereafter, a first aging treatment was performed for 1 hour at a first tempering temperature T1 = 900 ° C. in an Ar atmosphere and atmospheric pressure, and further a second aging treatment was performed for 1 hour at a second aging temperature T2 = 500 ° C. .

  The composition of the obtained permanent magnet before diffusion was evaluated by fluorescent X-ray analysis. The content of B was evaluated by ICP. As a result, it was confirmed that the composition of the raw material alloy was substantially the same. And the process of each Examples 1-5 and Comparative Examples 1-4 shown below was performed with respect to the obtained permanent magnet before spreading | diffusion.

(Comparative Example 1)
The pre-diffusion permanent magnet obtained by the above process was processed into a rectangular parallelepiped having a width of 15 mm, a length of 15 mm, and a thickness of 4 mm in the orientation direction. Thereafter, a slurry in which TbH ₂ particles (D50 = 5 μm) are dispersed in ethanol on two surfaces of 15 mm × 15 mm of the permanent magnet before diffusion, and the total weight of Tb with respect to the weight of the permanent magnet is 0.5% by weight. Tb was made to adhere by applying as follows. After applying the slurry, heat treatment was performed at 950 ° C. for 12 hours while flowing Ar at atmospheric pressure to diffuse Tb at the grain boundaries. Furthermore, an aging treatment was performed at 500 ° C. for 1 hour in an Ar atmosphere and atmospheric pressure.

  About the obtained permanent magnet, the three-dimensional distribution image of the atom was acquired using 3DAP about the at least 10 main phase particle | grains inside 1.5 mm from the magnet surface. And it confirmed using 3DAP that each main phase particle | grain has a core-shell structure. Next, the average thickness of the shell part was calculated by measuring and averaging the thickness of the shell part of each main phase particle using 3DAP.

  Moreover, Cs was computed by measuring the heavy rare earth element (Tb) content rate of the shell part in each main phase particle, and averaging. Furthermore, Cc was calculated by measuring the heavy rare earth element (Tb) content ratio of the core part in each main phase particle and averaging it. However, in the Examples and Comparative Examples of Experimental Examples 2 to 4, Cc was less than 0.01 atomic% and was negligibly small. That is, in the Examples and Comparative Examples of Experimental Examples 2 to 4, Cs and Cs-Cc are substantially equal.

  Furthermore, the carbon content [C] and the boron content [B] contained in the main phase particles having a core-shell structure were measured using a three-dimensional atom probe (3DAP).

  The obtained permanent magnet was evaluated for magnetic properties (Br and Hcj) at room temperature (23 ° C.) with a BH tracer. In this experimental example, Hcj was set to 1800 kA / m or higher. Br made 1450 mT or more favorable. Further, Hcj at 150 ° C. was measured, and the temperature coefficient of Hcj was measured. Specifically, Hcj at 150 ° C. is Hcj (150), Hcj at room temperature is Hcj (23), and 100 × ((Hcj (150) −Hcj (23)) / (150-23)) / Hcj The temperature coefficient was calculated in (23). The temperature characteristics were good when the absolute value of the temperature coefficient was 0.500% / ° C. or less.

(Comparative Examples 2-3, Examples 1-5)
In Comparative Examples 2-3 and Examples 1-5, as in Comparative Example 1, the pre-diffusion permanent magnet obtained by the above process is a rectangular parallelepiped having a width of 15 mm, a length of 15 mm, and a thickness of 4 mm in the orientation direction. It was processed into. And, unlike Comparative Example 1, before applying the slurry prepared by dispersing TbH ₂ particles (D50 = 5 [mu] m) in ethanol and subjected to decarbonization process.

  In the present experimental example, the decarbonization treatment was performed by the following method. First, a slurry in which metal Zr particles (D50 = 20 μm) were dispersed in ethanol was applied to a permanent magnet before diffusion. The coated surfaces were two 15 mm × 15 mm surfaces of the pre-diffusion permanent magnet. The Zr was applied so that the amount of Zr attached to the weight of the permanent magnet before diffusion would be the ratio shown in the table below. Then, after the slurry was applied, decarbonization treatment was performed by performing a heat treatment at 900 ° C. for 12 hours while flowing Ar at atmospheric pressure.

  The surface to which the slurry was applied after decarbonization was polished by 50 μm. Thereafter, in the same manner as in Comparative Example 1, grain boundary diffusion was performed to produce a permanent magnet. The results are shown in Table 2 below.

  From Table 2, Examples 1-5 whose Tb content rate Cs of a shell part is 1.10 atomic% or more are compared with Comparative Examples 1-3 whose Tb content rate Cs of a shell part is less than 1.10 atomic%. Hcj and Br were excellent. Further, Examples 1 to 5 had good temperature characteristics. In Examples 1 to 5, the average thickness of the shell portion was in the range of 5 to 30 nm, and [C] ≦ 0.25 (atomic%) and [C] / [B] ≦ 0.040 were satisfied. .

(Experimental example 3)
In Experimental Example 3, an example and a comparative example were described in which the deposited metal of Example 3 was changed from Zr to another metal. In addition, as for the adhesion metal used in each Example, the standard production | generation Gibbs energy for producing | generating a metal carbide from a metal is lower than the standard production | generation Gibbs energy for producing | generating Nd carbide | carbonized_material from Nd. On the other hand, regarding the Fe used in Comparative Example 11, the standard production Gibbs energy for producing Fe carbide from Fe is higher than the standard production Gibbs energy for producing Nd carbide from Nd.

  From Table 3, the standard production Gibbs energy for producing metal carbide from metal is lower than the standard production Gibbs energy for producing Nd carbide from Nd even if the kind of deposited metal used for decarbonization treatment is changed. In some cases, Cs ≧ 1.10 (atomic%) was satisfied, and Hcj and Br were excellent. Further, Examples 11 to 15 had good temperature characteristics. In contrast, in Comparative Example 11 in which Fe was used for the decarbonization treatment, decarbonization was not performed, and the Tb content ratio Cs in the shell portion was decreased and the thickness of the shell portion was increased as compared with the Example.

(Experimental example 4)
In Experimental Example 4, a rare earth permanent magnet was produced in the same manner as Comparative Example 1 except that the composition of the slurry of Comparative Example 1 was changed. Specifically, the composition of the metal (metal compound) contained in the slurry was a mixed composition of TbH ₂ powder and Zr powder and / or Ti powder. The results are shown in Table 4.

From Table 4, in each Example in which the metal contained in the slurry was a mixed composition of TbH ₂ powder, Zr powder and / or Ti powder, the Tb content Cs of the shell part was 1.10 atomic% or more. Good magnetic characteristics and temperature characteristics were exhibited. Because the composition of the metal (metal compound) contained in the slurry is a mixed composition of TbH ₂ powder and Zr powder and / or Ti powder, grain boundary diffusion and decarbonization proceeded simultaneously. Conceivable.

  In addition, about each Example and Comparative example of Experimental Examples 2-4, the crystal orientation degree and Br / Js were measured. All the crystal orientations were 66%, and all Br / Js was 93%.

Claims (9)

An RTB-based permanent magnet including main phase particles composed of an R ₂ T ₁₄ B crystal,
R is one or more rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, B is boron,
The RTB-based permanent magnet further includes C,
C concentration in the entire RTB-based permanent magnet is 0.070% by mass or less,
An RTB-based permanent magnet having a degree of orientation of 92% or more obtained by dividing the residual magnetization in the orientation direction by the saturation magnetization. An RTB-based permanent magnet including main phase particles composed of an R ₂ T ₁₄ B crystal,
R is one or more rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, B is boron,
The RTB-based permanent magnet further includes C,
C concentration in the entire RTB-based permanent magnet is 0.070% by mass or less,
An RTB-based permanent magnet having a crystal orientation degree of 62% or more measured by a rod-gering method. The RTB-based permanent magnet further contains O,
The RTB-based permanent magnet according to claim 1 or 2, wherein an O concentration in the entire RTB-based permanent magnet is 0.080 mass% or less. An RTB-based permanent magnet including main phase particles composed of an R ₂ T ₁₄ B crystal,
R is one or more rare earth elements essential for heavy rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, and B is boron,
At least a part of the main phase particles are core shell main phase particles having a core part and a shell part covering the core part,
The average content ratio of heavy rare earth elements in the shell portion is Cs (atomic%),
An RTB-based permanent magnet satisfying Cs ≧ 1.10.   The R-T-B system permanent magnet according to claim 4, wherein an average thickness of the shell portion is 5 nm or more and 30 nm or less. The average content ratio of heavy rare earth elements in the core portion is Cc (atomic%),
The RTB system permanent magnet according to claim 4 or 5 satisfying Cs-Cc> = 1.10.   The R-T-B permanent magnet according to any one of claims 4 to 6, wherein an average content ratio of carbon in the main phase particles is 0.25 atomic% or less. The average content ratio of carbon in the main phase particles is [C] (atomic%), and the average content ratio of boron in the main phase particles is [B] (atomic%),
The RTB-based permanent magnet according to any one of claims 4 to 7, wherein [C] / [B] ≦ 0.040 is satisfied. A manufacturing method of the R-T-B-based permanent magnets containing main-phase particles consisting of R ₂ T ₁₄ B crystal,
R is one or more rare earth elements essential for heavy rare earth elements, T is one or more iron group elements essential for Fe or Fe and Co, and B is boron,
A step of sintering a raw material alloy to form a sintered body, a step of attaching a metal to the sintered body, and a step of heat-treating the sintered body to which the metal is attached in an inert atmosphere. ,
R-T characterized in that the standard production Gibbs energy for producing metal carbide from the metal is lower than the standard production Gibbs energy for producing the rare earth element carbide from the rare earth element mainly contained as R -Manufacturing method of B type permanent magnet.