JP7247670B2 - RTB permanent magnet and manufacturing method thereof - Google Patents

Description

The present invention relates to an RTB system permanent magnet and a manufacturing method thereof.

RTB system permanent magnets are known to have excellent magnetic properties. Further, RTB system permanent magnets with improved magnetic properties are being developed.

As a method for improving the magnetic properties, particularly the coercive force, of an RTB system permanent magnet, as described in Patent Document 1, after manufacturing an RTB system permanent magnet, a heavy rare earth element is added to the surface of the RTB system permanent magnet. There is a method (grain boundary diffusion method) of diffusing the heavy rare earth element through the grain boundary by attaching the element and heating it.

Patent Document 2 describes an NdFeB permanent magnet produced by a non-pressing magnet production method and having improved magnetic properties due to a low carbon content.

Patent Document 3 describes a rare earth permanent magnet in which abnormal grain growth is suppressed by reducing the amount of oxygen while containing Ga.

Patent Document 4 describes a rare earth permanent magnet with excellent corrosion resistance, and rare earth whose carbon content is reduced by reducing the amount of lubricant kneaded with magnet fine powder in order to improve the magnetic field orientation during molding. A permanent magnet is described.

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

WO2006/043348 Japanese Patent No. 6271425 Japanese Patent Application Laid-Open No. 2006-228992 JP-A-4-330702 JP-A-7-240330 Japanese Patent No. 3193912

At present, however, there is a demand for even smaller, lighter, and more efficient magnetic components in many applications. Therefore, there is a demand for further improvement in the magnetic properties of RTB system permanent magnets such as RTB system sintered magnets.

An object of the present invention is to obtain an RTB system permanent magnet with improved magnetic properties, particularly remanent magnetic flux density (residual magnetization) Br and coercive force Hcj.

In order to achieve the above object, the RTB system permanent magnet according to the first aspect of the present invention comprises:
An RTB system permanent magnet containing 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 consisting essentially of Fe or Fe and Co, B is boron,
The RTB system permanent magnet further contains C,
C concentration in the entire RTB 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 system permanent magnet according to the second aspect of the present invention is
An RTB system permanent magnet containing 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 consisting essentially of Fe or Fe and Co, B is boron,
The RTB system permanent magnet further contains C,
C concentration in the entire RTB permanent magnet is 0.070% by mass or less,
It is characterized by having a crystal orientation degree of 62% or more as measured by the Rodgering method.

The RTB system permanent magnet according to the present invention is an RTB system permanent magnet with improved magnetic properties, particularly Br and Hcj, due to the above characteristics.

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

The RTB system permanent magnet according to the third aspect of the present invention is
An RTB system permanent magnet containing main phase particles made of R ₂ T ₁₄ B crystals,
R is one or more rare earth elements consisting essentially of a heavy rare earth element, T is one or more iron group elements consisting essentially of Fe or Fe and Co, B is boron,
At least part of the main phase particles are core-shell main phase particles having a core portion and a shell portion covering the core portion,
Assuming that the average content ratio of the heavy rare earth element in the shell portion is Cs (atomic %),
It is characterized by satisfying Cs≧1.10.

The RTB system permanent magnet according to the present invention is an RTB system permanent magnet with improved magnetic properties, particularly Br and Hcj, due to the above characteristics.

An average thickness of the shell portion may be 5 nm or more and 30 nm or less.

The average content ratio of the heavy rare earth element in the core portion is Cc (atomic %),
Cs-Cc≧1.10 may be satisfied.

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

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

A method for manufacturing an RTB system permanent magnet containing main phase particles made of R ₂ T ₁₄ B crystals, particularly according to the third aspect of the present invention, comprises:
R is one or more rare earth elements consisting essentially of a heavy rare earth element, T is one or more iron group elements consisting essentially of Fe or Fe and Co, 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 Gibbs energy of formation for forming the metal carbide from the metal is lower than the standard Gibbs energy of formation for forming the carbide of the rare earth element from the rare earth element mainly contained as R.

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

(First embodiment)
<RTB Permanent Magnet>
The RTB system permanent magnet according to this embodiment contains 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 consisting essentially of Fe or Fe and Co, and B is boron. The rare earth elements included as R are Sc, Y, and lanthanoid elements belonging to Group 3 of the long period periodic table. 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. Iron group elements refer to Fe, Co, and Ni.

The content of R is not particularly limited, but may be 25% by mass or more and 35% by mass or less. When the R content is 25% by mass or more, R ₂ T ₁₄ B crystals, which are the main phase particles of the RTB system permanent magnet, are sufficiently easily generated, and α-Fe having soft magnetism, etc. When the content of R is 35% by mass or less, the Br of the RTB system permanent magnet tends to be improved.

The content of B in the RTB system permanent magnet according to this embodiment may be 0.5% by mass or more and 1.5% by mass or less. When the content of B is 0.5% by mass or more, Hcj tends to be improved. Also, when the B content is 1.5% by mass or less, Br tends to be improved.

T may be Fe alone, or part of Fe may be substituted with Co. The content of Fe in the RTB permanent magnet according to the present embodiment may be the substantial remainder when inevitable impurities and N are removed from the RTB permanent magnet. The Co content is preferably 0% by mass or more and 4% by mass or less.

The RTB permanent magnet according to this embodiment may contain Ga, Cu, Al and/or Zr as metallic elements other than R, T and B. The content of each element is arbitrary.

In addition, the RTB system permanent magnet may contain unavoidable impurities such as Mn, Ca, Cl, S, and F as other elements in an amount of 0.001% by mass or more and 1.0% by mass or less. .

The particle size of the main phase particles composed of R ₂ T ₁₄ B crystals 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. Although the type of RL is not particularly limited, it preferably contains at least Nd or Pr. More preferably, it contains Nd. When RH is included, the type of RH is not particularly limited. Preferably, RH contains at least Dy or Tb. More preferably, it contains Tb.

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

The RTB-based permanent magnet according to this embodiment has a low C concentration and a high degree of orientation, and therefore has high Br and high Hcj at the same time. Also, the temperature characteristics can be easily improved.

Temperature characteristics are likely to be improved when an RTB compound is compared with a compound in which a part of B in the RTB compound is replaced with C, the RTB compound This is because the Curie temperature of is higher.

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

A method for measuring the degree of crystal orientation by the Rodgering method in this embodiment will be described below.

To measure the degree of crystal orientation of a permanent magnet, first, the magnetic pole faces of the permanent magnet are mirror-polished. After that, X-ray diffraction measurement is performed on the mirror-polished surface. Then, the degree of orientation is calculated based on diffraction peaks obtained by 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 degree of crystal orientation 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 numerator side of the following equation. In addition, among the diffraction peaks, all of the reflection components in the direction deviating from the orientation direction are all regarded as the (hk0) reflection components, and are integrated on the denominator side of the equation shown below. Only the orientation direction component of the diffraction peak is regarded as the orientation direction component. Then, only the component in the orientation direction is regarded as the component of (00l) reflection, and is integrated on the numerator side of the equation shown below. Therefore, the calculated degree of crystal orientation is considerably smaller than the actual degree of crystal orientation. In order to calculate the practical crystal orientation, it is preferable to perform vector correction on the diffraction peak. However, vector correction is not performed in this embodiment.

<Method for Producing RTB Permanent Magnet>
Next, a method for manufacturing an RTB system permanent magnet according to this embodiment will be described. As an example of a method for producing an RTB permanent magnet, a method for producing an RTB permanent magnet produced by a powder metallurgy method will be described below.

The method for producing an RTB permanent magnet according to the present embodiment includes a forming step of forming a raw material powder to obtain a green body, a sintering step of sintering the green body to obtain a sintered body, It includes an aging treatment step of holding the sintered body at a temperature lower than the sintering temperature for a certain period of time, and a decarburization step of reducing the carbon content of the sintered body.

The method of manufacturing the RTB system permanent magnet will be described in detail below, but for matters not specifically mentioned, known methods may be used.

[Preparation process of raw material powder]
The raw material powder can be produced by a known method. In this embodiment, the RTB system permanent magnet is manufactured by the single alloy method using one raw material alloy mainly composed of the R ₂ T ₁₄ B phase. 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 particular limitation on the method for producing the raw material alloy. For example, the raw material alloy can be produced by a strip casting method.

After producing the raw material alloy, the produced raw material alloy is pulverized (pulverization step). The pulverization process may be carried out in two steps or in one step. The pulverization method is not particularly limited. For example, it is carried out by a method using various pulverizers. For example, the pulverization process can be carried out in two steps, 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 absorbed in the material alloy at room temperature, dehydrogenation can be performed at 400° C. or more and 650° C. or less in an Ar gas atmosphere for 0.5 hours or more and 2 hours or less. In addition, the fine pulverization step is performed by adding a lubricant such as oleic acid amide or zinc stearate as a pulverizing aid to the coarsely pulverized powder, and then using a jet mill, a wet attritor, or the like. be able to. The particle size of the finely pulverized powder (raw material powder) to be obtained is not particularly limited. For example, fine pulverization can be performed so as to obtain a finely pulverized powder (raw material powder) having a particle size (D50) of 1 μm or more and 10 μm or less. In addition, the low-oxygen atmosphere with an oxygen concentration of less than 200 ppm was always maintained from the hydrogen absorption pulverization to the sintering process described later.

In order to reduce the carbon content 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 ratio in the raw material powder does not have to 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. The molding method is not particularly limited, but in the present embodiment, finely pulverized powder (raw material powder) is filled in a mold and pressurized in a magnetic field.

Pressurization during 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 applied magnetic field is not limited to a static magnetic field, and may be a pulsed magnetic field. Also, a static magnetic field and a pulsed magnetic field can be used together. The shape of the molded body obtained by molding the finely pulverized powder (raw material powder) is not particularly limited. can be any shape.

[Sintering process]
The sintering step is a step of sintering the compact in a vacuum or inert gas atmosphere to obtain a sintered compact. The sintering temperature needs to be adjusted according to various conditions such as composition, pulverization method, difference in particle size and particle size distribution. ° C. or less for 1 hour or more and 10 hours or less for sintering. Thereby, a high-density sintered body (permanent magnet) is obtained.

[Aging treatment process]
The aging treatment step is performed by heating the sintered body (permanent magnet) after the sintering step in a vacuum or inert gas atmosphere at a temperature lower than the sintering temperature. Although the temperature and time of the aging treatment are not particularly limited, the aging treatment can be performed, for example, at 450° C. or more and 900° C. or less for 0.2 hours or more and 3 hours or less. Note that this aging treatment step may be omitted.

Moreover, the aging treatment process may be performed in one stage or in two stages. When it is carried out in two stages, for example, the first stage is 700° C. or higher and 900° C. or lower for 0.2 hours or longer and 3 hours or shorter, and the second stage is 450° C. or higher and 700° C. or lower for 0.2 hours or longer and 3 hours or shorter. good too. Moreover, the first step and the second step may be performed continuously, or after the first step, the material may be once cooled to near room temperature and then reheated to perform the second step.

[Decarbonization process]
In this embodiment, after the above steps, a decarbonization step is performed to reduce the carbon content of the obtained sintered body. Br and Hcj can be improved by performing a decarburization step to reduce the carbon content ratio of the sintered body without reducing Br/Js and the degree of crystal orientation. Further, when the sintered body is decarbonized, part of C is removed by decarbonization in the compound in which part of B in the RTB compound is replaced with C. As a result, B may reenter the defect that has occurred, or it may remain as a defect as it is. When B is added again, naturally the temperature characteristics are improved. Further, even if the defects remain as they are, the temperature characteristics are improved as compared with a compound in which a part of B in the RTB compound is replaced with C.

Any decarbonization method may be used, and examples thereof include the following methods. First, a metal is attached to the sintered body obtained in the above steps. Hereinafter, the metal attached to the sintered body may be referred to as the attached metal. The type of deposited metal is the standard Gibbs energy of formation for producing metal carbide from the metal, and the standard Gibbs energy of formation for producing carbide of the rare earth element (e.g., Nd) mainly contained in the sintered body. choose to be lower than Also, the metal to be deposited 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. Although there is no particular limitation on the surface on which the metal is deposited, it is preferable to deposit the metal only on the magnetic pole surface. The rare earth element mainly contained in the sintered body refers to the rare earth element contained in the sintered body in the largest amount. Furthermore, in order to sufficiently obtain the effect of decarbonization, it is preferable to set the amount of the deposited metal to 0.06% by mass or more.

The method of attaching the metal is arbitrary. For example, it can be attached by applying a slurry containing metal. There are also methods of contacting a metal foil or plate, vapor deposition, sputtering, electrodeposition, spray coating, brush coating, jet dispenser, nozzle, screen printing, squeegee printing, sheet construction, and the like.

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

As the solvent used for the slurry, it is preferable to use a solvent that can uniformly disperse the metal without dissolving it. Examples thereof include alcohols, aldehydes, ketones, etc. Among them, ethanol is preferred.

There are no particular restrictions on the metal content in the 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, if necessary. For example, a dispersant for preventing agglomeration of metal particles and the like can be used.

Then, heat treatment is performed. A metal having a low standard Gibbs energy of formation for producing metal carbide from a metal is attached to the surface of an RTB permanent magnet, and heat treatment is performed to remove the carbon inside the RTB permanent magnet. It moves to the surface of the magnet and reacts with the attached metal to form carbide. On the other hand, metal hardly penetrates inside the magnet and stays on the surface of the magnet. As a result, the content of carbon in the RTB system permanent magnet can be reduced.

The heat treatment conditions in the decarburization step are not particularly limited, but the heat treatment is preferably performed at 600° C. or higher and 1000° C. or lower for 1 hour or longer and 50 hours or shorter in a vacuum or an inert gas atmosphere. Decarbonization progresses as the amount of metal adhered 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 residues. Analysis of the residue reveals a high content of the deposited metal and carbon. That is, it can be seen that the deposited metal hardly penetrates into the magnet, and the carbon moves to the surface of the magnet and reacts with the deposited metal to form carbide.

(Second embodiment)
A second embodiment will be described below. Matters not specifically described below are the same as in the first embodiment.

<RTB Permanent Magnet>
In the RTB system permanent magnet according to the present embodiment, R is one or more rare earth elements essentially including the heavy rare earth element RH. It preferably contains a light rare earth element RL and a heavy rare earth element RH. Although there are no particular restrictions on the type of light rare earth element RL, it preferably contains at least Nd or Pr. More preferably, it contains Nd. The type of heavy rare earth element RH is also not particularly limited, but preferably contains at least Dy or Tb. More preferably, it contains Tb.

Also, the C concentration, O concentration, and degree of orientation (Br/Js and degree of crystal orientation) in the entire RTB system permanent magnet are the same as in the first embodiment.

In the RTB permanent magnet according to the present embodiment, at least part of the main phase particles are core-shell main phase particles having a core portion and a shell portion covering the core portion. Preferably, the ratio of core-shell main phase particles to all main phase particles is 60% or more. Any method can be used to confirm that the main phase particles are core-shell main phase particles. For example, an arbitrary cross section of the RTB system permanent magnet is evaluated using a scanning electron microscope (SEM), a transmission electron microscope (TEM), a scanning transmission electron microscope (STEM), and a three-dimensional atom probe (3DAP). Is possible. When using a scanning electron microscope (SEM), transmission electron microscope (TEM), or scanning transmission electron microscope (STEM), observe at a magnification of 2500 times or more and 1000000 times or less, and distinguish between the core part and the shell part by the difference in contrast. be able to. Moreover, when using a three-dimensional atom probe (3DAP), the core portion and the shell portion can be distinguished from the three-dimensional distribution image of atoms. In the core-shell main phase particles, the shell does not need to cover the entire surface of the core, as long as 60% or more of the surface of the core is covered with the shell.

Each parameter of the core-shell main phase particles described below is measured when the distance between the two opposing surfaces of the RTB system permanent magnet is 3 mm or more, and the distance from either surface is 1 0.5 mm for core-shell main phase particles. When the distance between the two facing surfaces of the RTB system permanent magnet is less than 3 mm, the measurement is performed on the core-shell main phase particles including the portions where the distances from the two facing surfaces are equal.

The content of the heavy rare earth element RH in each core-shell main phase particle can be measured by three-dimensional atom probe measurement with a three-dimensional atom probe (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 the highest in line analysis of the shell portion. 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 in line analysis of the core portion.

The average content ratio Cs (atomic %) of the heavy rare earth element RH in the shell portion is the average of the content ratios of the heavy rare earth element RH in the shell portion measured for at least 10 core-shell main phase particles. The average content Cc (atomic %) of the heavy rare earth element RH in the core portion is the average of the content ratios 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 permanent magnet according to the present embodiment have a higher content ratio of the heavy rare earth element RH in the shell portion than the conventional core-shell main phase particles. Specifically, Cs≧1.10 is satisfied. Moreover, it is preferable to satisfy Cs≧1.80.

The RTB system permanent magnet according to this embodiment has a high Cs, so that the magnetic properties can be improved.

In addition, Cs-Cc≧1.10 may be satisfied, and Cs-Cc≧1.80 may be satisfied.

In the RTB system permanent magnet according to the present embodiment, it is preferable that the thickness of the shell portion is thinner than that of the conventional core-shell main phase particles, particularly in order to increase Br. Specifically, the average thickness of the shell portion is preferably 5 nm or more and 30 nm or less. Moreover, it is more preferable to be 5 nm or more and 15 nm or less.

The thickness of the shell portion can be measured by three-dimensional atom probe measurement of the core-shell main phase particles with a three-dimensional atom probe microscope (3DAP). The average thickness of the shell portion can be calculated by measuring the thickness of each shell portion of at least 10 core-shell main phase particles and averaging them.

As described above, the core-shell main phase particles included in the RTB permanent magnet according to the present embodiment have a higher weight in the shell portion than the core-shell main phase particles included in the conventional RTB permanent magnet. The concentration of the rare earth element RH is high, and the thickness of the shell portion is small. As a result, it is possible to achieve a higher Hcj while maintaining a good Br compared to conventional RTB permanent magnets.

Furthermore, in the RTB permanent magnet according to the present embodiment, the average content of carbon in the main phase particles [C] (atomic %) preferably satisfies [C] ≤ 0.25. C]≦0.15 is more preferably satisfied.

Furthermore, in the RTB permanent magnet according to the present embodiment, [C]/[B] ≤ 0.040, where [B] (atomic %) is the average content of boron in the main phase particles, must be satisfied. is preferable, and it is more preferable to satisfy [C]/[B]≦0.030.

In the RTB system permanent magnet according to the present embodiment, Br is well maintained even when the average content of carbon in the main phase particles is reduced. Further, by reducing [C] and/or [C]/[B], it becomes easier to obtain the preferable Cs and average thickness of the shell portion. In general, carbon contained in the main phase grains is mainly contained by substituting part of B in the R ₂ T ₁₄ B crystal. Here, there is a tendency that the smaller the amount of substitution, the higher the Curie temperature. Therefore, the temperature characteristics tend to improve as the amount of carbon contained in the main phase grains decreases.

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

<Method for Producing RTB Permanent Magnet>
Next, a method for manufacturing an RTB system permanent magnet according to this embodiment will be described.

A method of manufacturing an RTB system permanent magnet produced by powder metallurgy and grain boundary diffusion of a heavy rare earth element will be described below. The raw material powder preparation process, molding process, sintering process, and aging treatment process are the same as in the first embodiment.

[Decarbonization process]
In this embodiment, after the above steps, a decarbonization step is performed to reduce the carbon content of the obtained sintered body. By performing the decarburization step and reducing the carbon content ratio of the sintered body without lowering the degree of orientation of the main phase particles, when the core-shell main phase particles are generated in the diffusion treatment step described later, the heavy weight in the shell part is reduced. It becomes easier to increase the content of the rare earth element and to reduce the thickness of the shell portion. The decarbonization method is the same as in the first embodiment. However, if the adhesion amount of the adhered metal becomes too large, the effect of the diffusion treatment process, which will be described later, may decrease, and Hcj may decrease. Specifically, when the diffusion treatment process is performed, it is preferable to set the adhesion amount of the adhesion metal to about 1.0% by mass or less.

After the decarbonization step, the surface to which the metal is attached is polished to remove residues. This is because it is difficult to perform the diffusion treatment step described later without removing the residue. Analysis of the residue reveals a high content of the deposited metal and carbon. That is, it can be seen that the adhered metal hardly penetrates into the magnet, and the carbon moves to the surface of the rare earth permanent magnet and reacts with the adhered metal to form carbide.

[Diffusion treatment process]
This embodiment further includes a diffusion treatment step for diffusing the heavy rare earth element. Diffusion treatment can be carried out by applying a compound or the like containing a heavy rare earth element to the surface of the sintered body and then performing heat treatment. Any type of compound containing a heavy rare earth element can be used. Examples include hydrides of heavy rare earth elements. Any method may be used to deposit the compound containing the heavy rare earth element. For example, it can be attached by applying a slurry containing a heavy rare earth element. By controlling the application amount of the slurry and the concentration of the heavy rare earth element contained in the slurry, it is possible to control the thickness of the shell and the content of the heavy rare earth element in the shell. Note that the content of the heavy rare earth element in the core portion does not substantially change before and after the grain boundary diffusion step.

There is no particular limitation on the method of depositing the 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 slurry, the heavy rare earth compound is preferably in the form of particles. Also, the average particle diameter is preferably 100 nm or more and 50 μm or less, more preferably 1 μm or more and 30 μm or less.

The solvent used for the slurry is preferably a solvent that can uniformly disperse the heavy rare earth compound without dissolving it. Examples thereof include alcohols, aldehydes, ketones, etc. Among them, ethanol is preferred.

There are no particular restrictions on the content of the heavy rare earth compound in the 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, if necessary. For example, a dispersant for preventing agglomeration of heavy rare earth compound particles and the like are included.

By subjecting the sintered body to the above diffusion treatment step, the heavy rare earth element RH is diffused into the grain boundaries of the entire sintered body. Then, a shell portion having a high content of the heavy rare earth element is formed in the main phase particles to form core-shell main phase particles.

The heat treatment conditions in the diffusion treatment step are not particularly limited, but the heat treatment is preferably performed in a vacuum or an inert gas atmosphere at 650° C. or higher and 1000° C. or lower for 1 hour or longer and 24 hours or shorter. Furthermore, an aging treatment step can be performed after the heat treatment in the diffusion treatment step.

The reason why the decarburization process makes it easier to reduce the thickness of the shell portion of the core-shell main phase particles after the grain boundary diffusion process is that decarburization reduces the solubility of the main phase particles. In addition, by reducing the thickness of the shell portion, the content ratio of the heavy rare earth element in the shell portion can be easily increased.

Moreover, when the decarbonization step is performed, the volume ratio of the main phase particles is likely to be improved as compared with the conventional case in which the decarbonization step is not performed. This is because the decarburization process reduces the phase containing the carbide of the rare earth element contained in the grain boundaries. The volume ratio of the grain boundaries decreases and the volume ratio of the main phase grains increases as the carbide of the rare earth element decreases. Br increases as a result of the increase in the volume ratio of the main phase grains.

Furthermore, as a result of the decarburization process reducing the phase containing the carbide of the rare earth element contained in the grain boundaries, the accumulation of the heavy rare earth element in the carbide of the rare earth element is suppressed. As a result, the heavy rare earth element efficiently reacts with the main phase particles to form shell portions. Further, the effect of improving magnetic properties (especially Hcj) due to grain boundary diffusion becomes greater.

Furthermore, when performing the above decarburization step, it is easier to preferably maintain Br than when the amount of carbon in the raw material alloy is reduced. This is because when the carbon content is reduced at the raw material alloy stage, the degree of orientation tends to decrease in the forming process, and the Br of the finally obtained magnet tends to decrease.

In addition, in the method for producing an RTB permanent magnet according to this embodiment, the decarburization step and the grain boundary diffusion step may be performed simultaneously.

When the decarburization process and the grain boundary diffusion process are performed simultaneously, the metal deposited in the decarburization process and the compound containing the heavy rare earth element deposited in the grain boundary diffusion process are deposited at the same time. Heat treatment. After the heat treatment, the attached surface is polished to remove the residue.

Although preferred embodiments of the RTB system permanent magnet of the present invention have been described above, the RTB system permanent magnet of the present invention is not limited to the above embodiments. Various modifications and combinations are possible for the RTB system permanent magnet of the present invention without departing from the gist thereof.

Furthermore, magnets obtained by cutting and dividing the RTB system permanent magnet according to the present embodiment can be used.

Specifically, the RTB permanent magnet according to the present embodiment is suitably used for applications such as motors, compressors, magnetic sensors, and speakers.

Further, the RTB system permanent magnet according to the present embodiment may be used alone, or two or more RTB system permanent magnets may be combined and used as necessary. There is no particular limitation on the binding method. For example, there is a mechanical bonding method and a resin molding method.

A large RTB permanent magnet can be easily manufactured by combining two or more RTB permanent magnets. Magnets in which two or more RTB permanent magnets are combined are preferably used in applications that require particularly large RTB permanent magnets, such as IPM motors, wind power generators, large motors, and 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)
Nd, Pr, electrolytic iron, and a low-carbon ferroboron alloy were prepared as raw material metals. Additionally, Ga, Al, Cu, Co, and Zr were provided in the form of pure metals or alloys with Fe.

The composition of the permanent magnet finally obtained by strip casting the raw metal is
Nd: 23.2% by mass,
Pr: 7.3% by 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 unavoidable impurities, etc.), and
Inevitable impurities, etc.: 1% by mass or less,
An alloy for a sintered body (raw material alloy) was prepared so that Further, the alloy thickness of the raw material alloy was set to 0.2 mm to 0.6 mm.

Next, hydrogen gas was allowed to flow through the raw material alloy at room temperature for 1 hour to cause hydrogen to be occluded. Then, the atmosphere was switched to Ar gas, dehydrogenation was performed at 450° C. for 1 hour, and the raw material alloy was pulverized by hydrogen. Further, after cooling, a sieve was used to obtain a powder having a particle size of 400 μm or less.

Next, a lubricating agent was added as a pulverizing aid in an amount shown in Table 1 in mass ratio to the raw material alloy powder after hydrogen pulverization, and mixed. Oleic acid amide was used as a lubricant.

Then, they were finely pulverized in a nitrogen stream using a collision plate type jet mill to obtain fine powders (raw material powders) each having an average particle size of about 4 μm. The average particle size is the average particle size D50 measured with a laser diffraction particle size distribution meter.

Incidentally, H, Si, Ca, La, Ce, Cr, etc. may be detected as unavoidable 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 raw materials. Moreover, Cr may be mixed from the electrolytic iron.

The obtained fine powder was compacted in a magnetic field to produce a compact. The applied magnetic field at this time is a static magnetic field of 1200 kA/m. Moreover, the pressurizing force at the time of molding was set to 120 MPa. Note that the magnetic field application direction and the pressurizing direction were made orthogonal to each other. When the density of the molded bodies at this time was measured, the densities of all the molded bodies were within 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 condition was 1060° C. and held for 4 hours. The sintering atmosphere was 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. After that, in an Ar atmosphere and atmospheric pressure, a first temporary aging treatment was performed at a first temporary aging temperature T1 of 900°C for 1 hour, and a second aging treatment was further performed at a second aging temperature T2 of 500°C for 1 hour. . Then, the 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. In Examples 106 and 107, the oxygen partial pressure in the atmosphere during sintering and aging treatment was increased to increase the O concentration of the finally obtained permanent magnet. Then, the obtained permanent magnet was subjected to the decarbonization treatment described below. In Comparative Examples 101 to 103, decarbonization treatment was not performed.

In the decarbonization treatment, first, a slurry in which metal particles (D50=20 μm) composed of the attached metal were dispersed in ethanol was applied to the permanent magnet. Table 1 shows the types of deposited metals. The deposition metal used in each example has a lower standard Gibbs energy of formation for forming metal carbide from metal than the standard Gibbs energy of formation for forming Nd carbide from Nd. Two 15 mm×15 mm surfaces of the permanent magnet were coated. The amount of metal adhered to the mass of the permanent magnet was applied in such a manner as shown in Table 1, and the adhered metal was adhered. After applying the slurry, heat treatment was performed at 900° C. for 12 hours while flowing Ar at atmospheric pressure to perform decarbonization. Further, aging treatment was performed at 500° C. for 1 hour in an Ar atmosphere and atmospheric pressure. Then, all six surfaces were polished by 100 μm.

The compositions of the permanent magnets of 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 had the above composition.

The C concentration and O concentration were measured for the permanent magnets of each example and comparative example. The O concentration was measured by an inert gas fusion-nondispersive infrared absorption method. The C concentration was measured by combustion in an oxygen stream-infrared absorption method. As for the C concentration, the entire permanent magnet was pulverized with a stamp mill to a size of about 1 mm in average particle size, five measurement samples were randomly extracted, and the C concentration of each measurement sample was averaged.

For each example and comparative example, the degree of crystal orientation was measured by the Rodgering method.

The magnetic pole faces of the permanent magnets of each example and comparative example were mirror-polished. Thereafter, the mirror-polished surface was subjected to X-ray diffraction measurement, and the degree of crystal orientation was calculated by the Lotgering method based on the obtained diffraction peaks. No vector correction was performed. Table 1 shows the results. A degree of crystal orientation of 62% or more was considered good, and a degree of 66% or more was considered 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 at room temperature (23° C.) for the permanent magnets of each example and comparative example. Furthermore, Hcj was also measured for the permanent magnets of each example and comparative example. Hcj, Br and Js were measured with a BH tracer. Table 1 shows the results. A Br/Js value of 92% or more was considered good, and a value of 93% or more was considered even better. Hcj of 1220 kA/m or more was considered good, and 1250 kA/m or more was considered even better. A Br of 1420 mT or more was considered good, and a Br of 1450 mT or more was considered even better.

All of Examples 101 to 107, in which 0.10% by mass of a lubricant was added as a grinding aid and subjected to decarbonization, had a sufficiently low C concentration of 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. Examples 101 to 106, in which the O concentration was 0.080% by mass or less, had particularly high Br and Hcj.

On the other hand, 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 Examples 101 to 107 in which the decarbonization treatment was performed but the amount of adhered metal was reduced. In Comparative Example 104, which was smaller than, the C concentration exceeded 0.070% by mass. As a result, in Comparative Examples 101 and 104, Br was good, but Hcj was low. Note that Comparative Example 104, in which decarbonization treatment was performed, had an improved Hcj compared to Comparative Example 101, which was performed under the same conditions except that no decarbonization treatment was performed.

In Comparative Examples 102 and 103, in which the amount of lubricant added was reduced, the C concentration was 0.070% by mass or less, but the degree of crystal orientation and Br/Js were lowered. As a result, Comparative Examples 102 and 103 had low Br and Hcj.

(Experimental example 2)
(Permanent magnet manufacturing process)
Nd, Pr, electrolytic iron, and a low-carbon ferroboron alloy were prepared as raw material metals. Additionally, Ga, Al, Cu, Co, and Zr were provided in the form of pure metals or alloys with Fe.

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

Next, hydrogen gas was allowed to flow through the raw material alloy at room temperature for 1 hour to cause hydrogen to be occluded. Then, the atmosphere was switched to Ar gas, dehydrogenation was performed at 450° C. for 1 hour, and the raw material alloy was pulverized by hydrogen. Further, after cooling, a sieve was used to obtain a powder having a particle size of 400 μm or less.

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

Then, they were finely pulverized in a nitrogen stream using a collision plate type jet mill to obtain fine powders (raw material powders) each having an average particle size of about 4 μm. The average particle size is the average particle size D50 measured with a laser diffraction particle size distribution meter.

Incidentally, H, Si, Ca, La, Ce, Cr, etc. may be detected as unavoidable 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 raw materials. Moreover, Cr may be mixed from the electrolytic iron.

The obtained fine powder was compacted in a magnetic field to produce a compact. The applied magnetic field at this time is a static magnetic field of 1200 kA/m. Moreover, the pressurizing force at the time of molding was set to 120 MPa. Note that the magnetic field application direction and the pressurizing direction were made orthogonal to each other. When the density of the molded bodies at this time was measured, the densities of all the molded bodies were within 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 condition was 1060° C. and held for 4 hours. The sintering atmosphere was 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. After that, in an Ar atmosphere and atmospheric pressure, a first temporary aging treatment was performed at a first temporary aging temperature T1 of 900°C for 1 hour, and a second aging treatment was further performed at a second aging temperature T2 of 500°C for 1 hour. .

The composition of the obtained pre-diffusion permanent magnet was evaluated by fluorescent X-ray analysis. The content of B was evaluated by ICP. As a result, it was confirmed that the composition was substantially the same as that of the raw material alloy. Then, the obtained pre-diffusion permanent magnets were subjected to the treatments of Examples 1 to 5 and Comparative Examples 1 to 4 shown below.

(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. After that, a slurry of _TbH2 particles (D50=5 μm) dispersed in ethanol was applied to two 15 mm×15 mm faces of the permanent magnet before diffusion so that the total weight of Tb relative to the weight of the permanent magnet was 0.5% by weight. Tb was adhered by applying so as to be After application of the slurry, heat treatment was performed at 950° C. for 12 hours while flowing Ar at atmospheric pressure to diffuse Tb at grain boundaries. Further, aging treatment was performed at 500° C. for 1 hour in an Ar atmosphere and atmospheric pressure.

For the obtained permanent magnet, a three-dimensional distribution image of atoms was acquired using 3DAP for at least 10 main phase particles 1.5 mm inside from the magnet surface. 3DAP was used to confirm that each main phase particle had a core-shell structure. Next, the thickness of the shell portion of each main phase grain was measured using 3DAP and averaged to calculate the average thickness of the shell portion.

In addition, Cs was calculated by measuring the heavy rare earth element (Tb) content in the shell portion of each main phase particle and averaging them. Furthermore, Cc was calculated by measuring the heavy rare earth element (Tb) content ratio of the core portion of each main phase particle and averaging them. However, in the examples and comparative examples of Experimental Examples 2 to 4, Cc was less than 0.01 atomic %, which was negligibly small. That is, in Examples 2 to 4 and Comparative Examples, 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.) using a BH tracer. In this experimental example, Hcj of 1800 kA/m or more was considered good. A Br of 1450 mT or more was considered good. Also, 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). When the absolute value of the temperature coefficient was 0.500%/°C or less, the temperature characteristic was judged to be good.

(Comparative Examples 2-3, Examples 1-5)
In Comparative Examples 2 to 3 and Examples 1 to 5, as in Comparative Example 1, the pre-diffusion permanent magnet obtained by the above steps was shaped 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. processed into Then, unlike Comparative Example 1, a decarbonization treatment was performed before applying a slurry of TbH ₂ particles (D50=5 μm) dispersed in ethanol.

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

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

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

(Experimental example 3)
Experimental Example 3 describes an example and a comparative example in which the deposited metal in Example 3 was changed from Zr to another metal. The deposited metal used in each example has a lower standard Gibbs energy of formation for forming metal carbide from metal than the standard Gibbs energy for forming Nd carbide from Nd. On the other hand, for Fe used in Comparative Example 11, the standard Gibbs energy of formation for forming Fe carbides from Fe is higher than the standard Gibbs energy for forming Nd carbides from Nd.

From Table 3, the standard Gibbs energy of formation for forming metal carbides from metals is lower than the standard Gibbs energy for forming Nd carbides from Nd, even if the type of deposited metal used for decarbonization treatment is changed. In the case, Cs≧1.10 (atomic %) was satisfied, and Hcj and Br were excellent. Furthermore, Examples 11 to 15 had good temperature characteristics. On the other hand, in Comparative Example 11 in which Fe was used for the decarbonization treatment, decarbonization was not performed, the Tb content ratio Cs in the shell portion decreased, and the thickness of the shell portion increased compared to the Examples.

(Experimental example 4)
In Experimental Example 4, a rare earth permanent magnet was produced in the same manner as in Comparative Example 1, except that the composition of the slurry in Comparative Example 1 was changed. Specifically, the composition of the metal (metallic compound) contained in the slurry was a mixed composition of _TbH2 powder and Zr powder and/or Ti powder. Table 4 shows the results.

From Table 4, in each example in which the metal contained in the slurry was a mixed composition of _TbH2 powder and Zr powder and/or Ti powder, the Tb content ratio Cs in the shell part was 1.10 atomic % or more. , showed good magnetic properties and temperature properties. This is because the grain boundary diffusion and the decarbonization process proceeded at the same time by making the composition of the metal (metal compound) contained in the slurry a mixed composition of _TbH2 powder and Zr powder and/or Ti powder. Conceivable.

The degree of crystal orientation and Br/Js were measured for each of Experimental Examples 2 to 4 and Comparative Example. The degree of crystal orientation was all 66% and the Br/Js was all 93%.

Claims (8)

An RTB system permanent magnet containing main phase particles composed of R ₂ T ₁₄ B crystals,
R is one or more rare earth elements, T is one or more iron group elements consisting essentially of Fe or Fe and Co, B is boron,
The RTB system permanent magnet further contains C,
C concentration in the entire RTB system permanent magnet is 0.049 % by mass or less,
A rare earth permanent magnet having a degree of orientation of 92% or more obtained by dividing residual magnetization in the orientation direction by saturation magnetization. An RTB system permanent magnet containing main phase particles composed of R ₂ T ₁₄ B crystals,
R is one or more rare earth elements, T is one or more iron group elements consisting essentially of Fe or Fe and Co, B is boron,
The RTB system permanent magnet further contains C,
C concentration in the entire RTB system permanent magnet is 0.049 % by mass or less,
A rare earth permanent magnet having a degree of crystal orientation of 62% or more as measured by the Rodgering method. The RTB system permanent magnet further contains O,
3. The RTB system permanent magnet according to claim 1, wherein the O concentration in the entire RTB system permanent magnet is 0.080% by mass or less. An RTB system permanent magnet containing main phase particles composed of R ₂ T ₁₄ B crystals,
R is one or more rare earth elements consisting essentially of a heavy rare earth element, T is one or more iron group elements consisting essentially of Fe or Fe and Co, B is boron,
At least part of the main phase particles are core-shell main phase particles having a core portion and a shell portion covering the core portion,
Let Cs (atomic %) be the average content of heavy rare earth elements in the shell , and Cc (atomic %) be the average content of heavy rare earth elements in the core ,
A rare earth permanent magnet that satisfies 1.80≦Cs−Cc≦2.20 . 5. The rare earth permanent magnet according to claim 4, wherein the shell portion has an average thickness of 5 nm or more and 30 nm or less. 6. The rare earth permanent magnet according to claim 4, wherein the average content of carbon in said main phase particles is 0.25 atomic % or less. Assuming that the average content of carbon in the main phase particles is [C] (atomic %) and the average content of boron in the main phase particles is [B] (atomic %),
7. The rare earth permanent magnet according to any one of claims 4 to 6 , wherein [C]/[B]≤0.040. A method for producing an RTB system permanent magnet containing main phase particles made of R ₂ T ₁₄ B crystals, comprising:
R is one or more rare earth elements consisting essentially of a heavy rare earth element, T is one or more iron group elements consisting essentially of Fe or Fe and Co, 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 Gibbs energy of formation for producing a metal carbide from the metal is lower than the standard Gibbs energy of formation for producing a carbide of the rare earth element from the rare earth element mainly contained as R;
A method for producing an RTB permanent magnet , wherein in the step of attaching a metal to the sintered compact, the metal is attached by applying a slurry containing the metal.