JP2019062155A - Method of manufacturing RTB based sintered magnet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the magnet characteristics of an RTB-based sintered magnet. SOLUTION: In the method for manufacturing an R-TB-based sintered magnet of the present disclosure, a step of preparing an R-TB-based sintered magnet material and a powder of Pr-Ga alloy produced by an atomizing method are used. In the step of preparation, the Pr-Ga alloy powder is heat-treated at a temperature 250 ° C. lower than the melting point of the Pr-Ga alloy powder and below the melting point, and a diffusion source is obtained from the Pr-Ga alloy powder. The step of obtaining and the R-TB-based sintered magnet material and the diffusion source are arranged in a processing container, and the R-TB-based sintered magnet material and the diffusion source are placed in a vacuum or an inert gas atmosphere. , A step of diffusing Pr and Ga from the diffusion source into the inside of the RTB-based sintered magnet material by heating at a temperature of more than 600 ° C. and 950 ° C. or lower. [Selection diagram] Fig. 1

Description

  The present invention relates to a method of producing an RTB-based sintered magnet.

  RTB sintered magnet (R is at least one of rare earth elements and must contain Nd. T is Fe or Fe and Co, B is boron) is the highest among permanent magnets. It is known as a high performance magnet, and is used in voice coil motors (VCMs) for hard disk drives, motors for electric vehicles (EV, HV, PHV etc.) motors, various motors such as motors for industrial equipment, and home appliances.

The RTB-based sintered magnet is composed of a main phase mainly composed of an R ₂ T ₁₄ B compound and a grain boundary phase located in a grain boundary portion of the main phase. The main phase R ₂ T ₁₄ B compound is a ferromagnetic material having high saturation magnetization and anisotropic magnetic field, and forms the basis of the characteristics of the RTB-based sintered magnet.

At high temperatures, the coercive force H _cJ (hereinafter sometimes simply referred to as “H _cJ ”) of the _RTB -based sintered magnet decreases, so that irreversible thermal demagnetization occurs. Therefore, in the _RTB -based sintered magnet used particularly for a motor for an electric vehicle, it is required to have a high _HcJ .

In the RTB-based sintered magnet, part of the light rare earth element RL (eg, Nd or Pr) contained in R in the R ₂ T ₁₄ B compound is a heavy rare earth element RH (eg, Dy or Tb) It is known that substitution improves H _cJ . H _cJ improves as the amount of substitution of RH increases.

However, replacing RL in the R ₂ T ₁₄ B compound with RH improves H _{cJ of the RTB} -based sintered magnet, while the residual magnetic flux density B _r (hereinafter simply referred to as “B _r ” There is a decline). In addition, RH such as Dy has problems such as unstable supply and large price fluctuation due to the small amount of resources and limited production area. Therefore, in recent years, it is required to improve H _cJ without using RH as much as possible.

Patent Document 1 discloses an RTB-based rare earth sintered magnet having a high coercive force while suppressing the content of Dy. The composition of this sintered magnet is limited to a specific range in which the amount of B is relatively small compared to the R-T-B based alloy generally used, and is selected from Al, Ga, and Cu 1 It contains metal element M of a species or more. As a result, _R 2 _{T 17} phase is produced in the grain boundary, by the volume ratio of the _R 2 _{T 17} transition metal-rich phase formed in the grain boundary from phase _{(R 6 T 13} M) _{increases, H cJ} Improve.

International Publication No. 2013/008756

The R-T-B rare earth sintered magnets disclosed in Patent Document 1, although a high H _cJ is obtained while reducing the content of Dy, there is a problem that B _r is greatly reduced. Also, in recent years, _RTB -based sintered magnets having higher H _cJ have been required in applications such as motors for electric vehicles.

Various embodiments of the present invention, while reducing the content of RH, to provide a method of manufacturing a R-T-B based sintered magnet having a high B _r and high H _cJ.

A method of producing the RTB-based sintered magnet of the present disclosure is
R: 27.5 to 35.0% by mass (R is at least one of rare earth elements and necessarily includes Nd),
B: 0.80 to 0.99 mass%,
Ga: 0 to 0.8% by mass,
M: 0 to 2% by mass (M is at least one of Cu, Al, Nb and Zr),
Remainder T (T is Fe or Fe and Co) and unavoidable impurities,
Preparing an R-T-B-based sintered magnet material containing
Preparing a powder of Pr-Ga alloy produced by atomization method;
Heat treating the powder of the Pr-Ga alloy at a temperature lower than the melting point of the powder of the Pr-Ga alloy by 250 ° C. or more and at a temperature not more than the melting point to obtain a diffusion source from the powder of the Pr-Ga alloy;
The RTB-based sintered magnet material and the diffusion source are disposed in a processing vessel, and the RTB-based sintered magnet material and the diffusion source are heated to over 600 ° C. in a vacuum or inert gas atmosphere. And D. a diffusion step of diffusing Pr and Ga contained in the diffusion source from the surface of the RTB based sintered magnet material to the inside by heating at a temperature of 950 ° C. or lower.

In one embodiment, the RTB-based sintered magnet material satisfies the following inequality (1).
[T] /55.85> 14 [B] /10.8 (1)
([T] is the content of T in mass%, [B] is the content of B in mass%)

  In one embodiment, the amount of Ga in the RTB-based sintered magnet material is 0 to 0.5% by mass.

  In one embodiment, the Nd content of the Pr—Ga alloy is equal to or less than the unavoidable impurity content.

According to an embodiment of the present disclosure, a diffusion source and a RTB-based sintered magnet material obtained by heat-treating a powder of a Pr—Ga alloy manufactured by an atomizing method are disposed in a processing container and a diffusion step is performed. And Pr and Ga are diffused from particles having a homogenized structure of Pr—Ga alloy powder. Thus, it is possible to obtain a high _{B r} and _{H cJ.} Further, to suppress variations in the magnetic properties due to diffusion, it is possible to suppress the deterioration of the B _r and H _cJ due to variations in the magnetic properties.

It is a flowchart which shows the example of the process in the manufacturing method of the RTB type | system | group sintered magnet by embodiment of this indication. FIG. 2 is a cross-sectional view schematically showing a part of the RTB-based sintered magnet in an enlarged manner. It is sectional drawing which expands the inside of the broken-line rectangular area | region of FIG. 2A further, and is shown typically. In an embodiment of the present disclosure, it is a cross-sectional view schematically showing a part of a prepared RTB-based sintered magnet material. In embodiment of this indication, it is sectional drawing which shows typically a part of RTB type | system | group sintered magnet raw material in the state in contact with a diffusion source.

  The manufacturing method of the RTB-based sintered magnet according to the present disclosure is, as exemplified in FIG. 1, a step S10 of preparing a RTB-based sintered magnet material, and Pr produced by the atomizing method. And-S20 of preparing a powder of a Ga alloy. The order of the step S10 of preparing the RTB-based sintered magnet material and the step S20 of preparing the powder of the Pr-Ga alloy is arbitrary, and the RTB-based sintered products manufactured at different places are respectively used. It is also possible to use a powder of a magnet material and a Pr-Ga alloy. Furthermore, the manufacturing method of the RTB-based sintered magnet according to the present disclosure performs heat treatment on a powder of a Pr-Ga alloy at a temperature not lower than 250 ° C. and not higher than the melting point of the powder of the Pr-Ga alloy. And S21 of obtaining a diffusion source from the powder of the Pr-Ga alloy.

The RTB-based sintered magnet material is
R: 27.5 to 35.0% by mass (R is at least one of rare earth elements and necessarily includes Nd),
B: 0.80 to 0.99 mass%,
Ga: 0 to 0.8% by mass,
M: 0 to 2% by mass (M is at least one of Cu, Al, Nb and Zr),
Remainder T (T is Fe or Fe and Co) and unavoidable impurities,
Contains

In an exemplary embodiment, the RTB based sintered magnet material satisfies the following inequality (1).
[T] /55.85> 14 [B] /10.8 (1)
Here, [T] is the content of T shown by mass%, and [B] is the content of B shown by mass%.
The fact that satisfies this inequality, the content of B is less than the stoichiometric ratio of the R _{2 T} 14 _B compound, i.e., the main phase (R 2 _T 14 _B compound) T amount used for formation to This means that the amount of B is relatively small.

  In the present disclosure, a powder of a Pr—Ga alloy produced by an atomization method is prepared. And a diffusion source is obtained by heat-processing with respect to the powder of a Pr-Ga alloy by temperature 250 degreeC or more lower than melting | fusing point of the powder of said Pr-Ga alloy, and below melting | fusing point.

  According to the present disclosure, the RTB-based sintered magnet material and the diffusion source are disposed in the processing vessel, and the RTB-based sintered magnet material and the diffusion source are in a vacuum or an inert gas atmosphere. By heating at a temperature of more than 600 ° C. and not more than 950 ° C., Pr and Ga can be diffused from the diffusion source into the interior of the RTB-based sintered magnet material.

  In the present disclosure, a powder of a Pr—Ga alloy is produced by an atomizing method. The powder produced by the atomization method may be called "atomized powder".

  The atomization method is one of powder production methods also referred to as a melt spray method, and includes known atomization methods such as gas atomization and plasma atomization. For example, according to the gas atomization method, a metal or alloy is melted in a melting furnace to form a molten metal, and the molten metal is sprayed and solidified in an inert gas atmosphere such as nitrogen or argon. Since the molten metal sprayed is scattered as fine droplets, it is cooled and solidified at high speed. Since the powder particles to be produced each have a spherical shape, it is not necessary to grind them. The size of powder particles produced by the atomization method is distributed, for example, in the range of 10 μm to 200 μm.

  According to the atomizing method, since the droplets of the molten alloy to be sprayed are small and the surface area relative to the weight of each droplet is relatively large, the cooling rate becomes high. Thus, the powder particles formed are amorphous or microcrystalline. However, in the present disclosure, by performing a heat treatment on these powder particles, the amorphous crystallizes and the microcrystals coarsen, and finally, it has a texture suitable as a diffusion source. .

When the melt of a Pr—Ga alloy is rapidly solidified by atomization, it is difficult to precisely control the cooling rate. For this reason, the structure of the tissue is likely to vary among the powder particles. For example, the size of the fine grains formed within the powder particles can vary widely from particle to particle. Specifically, particles having an average crystal grain size of 1 μm are formed, or particles having an average crystal grain size of 3 μm are formed. Such variations in the structure of the structure and the average grain size cause variations in the melting temperature of the phase constituting the particles and in the rate at which Pr and Ga are supplied as diffusion sources in the diffusion step described later. Such variations eventually lead to variations in magnet characteristics. As a result, there is a case where the R-T-B based sintered magnet having no high _{B r} and high _{H cJ} obtained.

  In order to solve such a subject, in the embodiment of the present disclosure, heat treatment described below is performed.

  Thereby, the crystallinity of the powder particle which comprises the powder of Pr-Ga alloy can be modify | reformed, and the diffusion source excellent in the uniformity can be obtained from the powder of Pr-Ga alloy. And the dispersion | variation in the magnetic characteristic in a spreading | diffusion process can be suppressed by using the said spreading | diffusion source. For example, the heat treatment time may be 30 minutes or more and 10 hours or less. In such a diffusion source, the average crystal grain size of the intermetallic compound phase is more than 3 μm. Preferably, the average crystal grain size of the intermetallic compound phase in the diffusion source is 3.5 μm or more and 20 μm or less. Here, the intermetallic compound phase refers to the entire crystal grains of the intermetallic compound in the powder particle constituting the diffusion source. When there are a plurality of types of intermetallic compounds in the powder particle constituting the diffusion source, the whole grains of the intermetallic compound having the highest content are said.

  If the heat treatment temperature for the Pr-Ga alloy powder is less than 250 ° C. lower than the melting point of the Pr-Ga alloy powder, the temperature may be too low and the crystallinity of the powder particles constituting the alloy powder may not be improved. If the temperature exceeds the melting point, the powders may be welded together and the diffusion process may not be performed efficiently.

  In the heat treatment, it is preferable to adjust the oxygen content in the diffusion source after the heat treatment to 0.5 mass% or more and 4.0 mass% or less by adjusting the atmosphere in the furnace. By intentionally oxidizing the entire surface of the alloy particles that make up the atomized powder, it is possible to reduce the characteristic variation among particles that may occur due to the contact time between the powder particles and the atmosphere, the difference in humidity, etc. It is possible to further reduce the variation of the magnetic characteristics in In addition, the possibility of ignition on contact with oxygen in the atmosphere is reduced. This facilitates quality control of the diffusion source.

  The diffusion source, in embodiments, is in the form of a powder. The particle size of the diffusion source in powder form can be adjusted by sieving. Moreover, since the influence is small if the powder excluded by sieving is 10 mass% or less, it may be used without sieving.

  In one embodiment, as shown in FIG. 1, the method of manufacturing an RTB-based sintered magnet includes disposing the RTB-based sintered magnet material and the diffusion source in a processing container, and -Pr and Ga contained in the diffusion source are heated by heating the T-B-based sintered magnet material and the diffusion source in a vacuum or inert gas atmosphere at a temperature of more than 600.degree. C. and 950.degree. C. or less. And-a diffusion step (diffusion step S30) of diffusing from the surface of the B-based sintered magnet material to the inside. In addition, after the diffusion step S30, the second heat treatment may be performed in a vacuum or an inert gas atmosphere at a temperature lower than the temperature performed in the diffusion step and at a temperature of 450 ° C. to 750 ° C. . Between the diffusion step S30 and the step of performing the second heat treatment, another step, for example, a cooling step, from the state in which the diffusion source and the R-T-B-based sintered magnet material are mixed, R-T-B A step of taking out the system sintered magnet material can be performed.

  As described above, in the present invention, the heat treatment performed on the powder of the Pr—Ga alloy is simply referred to as “heat treatment”, and the RTB-based sintered magnet material and the diffusion source are disposed in the processing container. A heat treatment of heating the RTB-based sintered magnet material and the diffusion source at a temperature of 600 ° C. or more and 950 ° C. or less in a vacuum or inert gas atmosphere is referred to as “diffusion step”, and the diffusion step is performed. Heat treatment is performed on the R-T-B-based sintered magnet material in a vacuum or inert gas atmosphere at a temperature lower than the temperature performed in the diffusion step and at a temperature of 450 ° C. to 750 ° C. It is called "second heat treatment".

The R-T-B sintered magnet has a structure in which powder particles of a raw material alloy are bonded by sintering, and a main phase mainly composed of an R ₂ T ₁₄ B compound and a grain boundary portion of this main phase It is composed of the located grain boundary phase.

FIG. 2A is a cross-sectional view schematically showing a part of the R-T-B-based sintered magnet in an enlarged manner, and FIG. 2B is a cross-sectional view schematically showing in enlarged a dashed rectangular area in FIG. 2A. It is. In FIG. 2A, an arrow of 5 μm in length as an example is described for reference as a reference length indicating the size. As shown in FIGS. 2A and 2B, the RTB-based sintered magnet includes a main phase 12 mainly composed of an R ₂ T ₁₄ B compound, and a grain boundary phase 14 located in the grain boundary portion of the main phase 12. And consists of In addition, as shown in FIG. 2B, the grain boundary phase 14 is a two-grain grain boundary phase 14a in which two R ₂ T ₁₄ B compound particles (grains) are adjacent and three R ₂ T ₁₄ B compound particles are adjacent. And the grain boundary triple point 14b.

The R ₂ T ₁₄ B compound which is the main phase 12 is a ferromagnetic material having high saturation magnetization and anisotropic magnetic field. Therefore, in the R-T-B based sintered magnet, it is possible to improve the _{B r} by increasing the existence ratio of _R 2 _{T 14} B compound is the main phase 12. In order to increase the abundance ratio of the R ₂ T ₁₄ B compound, the R amount, T amount, B amount in the raw material alloy and the stoichiometric ratio of the R ₂ T ₁₄ B compound (R amount: T amount: B amount = It should be close to 2: 14: 1).

According to the present invention, Pr and Ga can be diffused through grain boundaries by using a powder of a Pr-Ga alloy as a diffusion source. Also, as the presence of Pr promotes grain boundary diffusion, Ga can be diffused deep inside the magnet. Accordingly, it is considered possible to obtain a high _{B r} and high _{H cJ.}

2. Definition of terms (R-T-B-based sintered magnet material and R-T-B-based sintered magnet)
In the present invention, the RTB-based sintered magnet in the diffusion step and the diffusion step is referred to as "RTB-based sintered magnet material", and the RTB-based sintered magnet after the diffusion step is referred to as "R-T-B-based sintered magnet material". It is simply referred to as "R-T-B based sintered magnet".

(R)
The content of R is 27.5 to 35.0% by mass. R is at least one of rare earth elements and necessarily contains Nd. If R is less than 27.5% by mass, the liquid phase is not sufficiently formed in the sintering process, and it becomes difficult to fully densify the sintered body. On the other hand, although the effect of the present invention can be obtained even if R exceeds 35.0% by mass, the alloy powder becomes very active during the manufacturing process of the sintered body, and significant oxidation or ignition of the alloy powder occurs. 35 mass% or less is preferable since it may occur. R is more preferably 28% by mass to 33% by mass or less, and further preferably 29% by mass to 33% by mass or less. As for content of RH, 5 mass% or less of the whole RTB type sintered magnet raw material is preferable. Because the present invention can obtain a high B _r and high H _cJ without using RH, it can reduce the amount of RH even be asked a higher H _cJ.

(B)
Content of B is 0.80-0.99 mass%. The content of B with respect to 0.80 to 0.99 wt% content are R-T-B based sintered magnet material was, by diffusing the Pr-Ga alloy to be described later, a high _{B r} and high _{H cJ} You can get There is a possibility that the content of B is lowered and _{B r} is less than 0.80 wt%, there is a possibility _{that H cJ} is reduced when it exceeds 0.99 wt%. Also, part of B can be replaced by C.

(Ga)
The content of Ga in the RTB-based sintered magnet material before diffusing Ga from the powder of the Pr—Ga alloy is 0 to 0.8 mass%. The present invention introduces Ga by diffusing a powder of a Pr-Ga alloy into an RTB-based sintered magnet material, so the amount of Ga in the RTB-based sintered magnet material is relatively small. (Or contains no Ga). If the content of Ga exceeds 0.8% by mass, the magnetization of the main phase may be reduced by the inclusion of Ga in the main phase, and a high B _r may not be obtained. Preferably, the content of Ga is 0.5% by mass or less. Higher _Br can be obtained.

(M)
The content of M is 0 to 2% by mass. M is at least one of Cu, Al, Nb, and Zr, and even if it is 0% by mass, the effect of the present invention can be exhibited, but containing 2% by mass or less in total of Cu, Al, Nb, and Zr Can. H _cJ can be improved by containing Cu and Al. Cu and Al may be positively added, or may be those which are inevitably introduced in the process of producing the used raw materials and the alloy powder. Further, by containing Nb and Zr, abnormal grain growth of crystal grains can be suppressed at the time of sintering. Preferably, M always contains Cu and contains 0.05 to 0.30% by mass of Cu. By containing 0.05 to _0.30 mass% of Cu, it is because _HcJ can be improved more.

(Remaining part T)
The balance is T (T is Fe or Fe and Co) and impurities. In one embodiment, T satisfies inequality (1). It is preferable that 90% or more of T in mass ratio is Fe. A part of Fe can be replaced by Co. However, the substitution amount of Co is greater than 10% of the total T by mass ratio is not preferable because the B _r drops. Furthermore, the RTB-based sintered magnet material of the present invention is an unavoidable impurity usually contained in alloys such as didymium alloy (Nd-Pr), electrolytic iron, ferroboron, etc. and in the manufacturing process, and a small amount of other than the above. Elements (elements other than R, B, Ga, M, and T described above) may be contained. For example, Ti, V, Cr, Mn, Ni, Si, La, Ce, Sm, Ca, Mg, O (oxygen), N (carbon), C (nitrogen), Mo, Hf, Ta, W, etc. You may

Preferably, the RTB based sintered magnet material of the present disclosure satisfies inequality (1).
[T] /55.85> 14 [B] /10.8 (Inequality (1))

By satisfying this inequality (1), the content of B is smaller than that of a general R-T-B-based sintered magnet. A general R-T-B-based sintered magnet does not form an Fe phase or R ₂ T ₁₇ phase other than the R ₂ T ₁₄ B phase which is the main phase [T] /55.85 (atomic weight of Fe) Is less than 14 [B] /10.8 (atomic weight of B) ([T] is the content of T in mass%, and [B] is the content of B in mass% Is). In a preferred embodiment of the present disclosure, the RTB-based sintered magnet material is different from a general RTB-based sintered magnet in that [T] /55.85 (atomic weight of Fe) is 14 [14]. B) is defined by inequality (1) so as to be greater than 10.8 (atomic weight of B). In addition, since T is Fe as a main component in the RTB-based sintered magnet material of the present invention, the atomic weight of Fe is used.

  In one embodiment, the Pr of the Pr—Ga alloy is 65 to 97 wt% of the total of the Pr—Ga alloy. Up to 30% by mass of this Pr can be replaced by Nd, and up to 20% by mass of Pr can be replaced by Dy and / or Tb. Ga is 3% by mass to 35% by mass of the whole of the Pr—Ga alloy, and 50% by mass or less of Ga can be replaced with Cu. The Pr-Ga alloy may contain unavoidable impurities. In the present invention, “30% or less of Pr can be substituted with Nd” means that the content (mass%) of Pr in the Pr—Ga alloy is 100%, and 30% of them can be substituted with Nd. Means For example, if Pr in a Pr—Ga alloy is 70% by mass (Ga is 30% by mass), Nd can be substituted up to 21% by mass. That is, 49% by mass of Pr and 21% by mass of Nd are obtained. The same applies to Dy, Tb, and Cu.

By performing a diffusion process to be described later with respect to the R-T-B-based sintered magnet material of the composition range of the present invention, a powder of a Pr-Ga alloy containing Pr and Ga in the above range allows Ga to pass through grain boundaries. It can be diffused deep inside the magnet. Pr is, Nd, may be replaced with Dy and / or Tb, for each of the substitution amount is too small, Pr exceeds the above range, it is impossible to obtain a high B _r and high H _cJ. Preferably, the Nd content of the Pr-Ga alloy is equal to or less than the unavoidable impurity content (approximately 1 mass% or less). Although 50% or less of Ga can be substituted by Cu, if the substitution amount of Cu exceeds 50%, there is a possibility that _HcJ may decrease.

  The RTB-based sintered magnet material can be prepared using a general RT-B-based sintered magnet manufacturing method represented by an Nd-Fe-B-based sintered magnet. As an example, a raw material alloy produced by a strip casting method or the like is crushed to 1 μm or more and 10 μm or less using a jet mill or the like, then formed in a magnetic field and sintered at a temperature of 900 ° C. or more and 1100 ° C. or less Can be prepared by

If the ground particle size of the raw material alloy (volume center value obtained by measurement by the air flow dispersion type laser diffraction method = D50) is less than 1 μm, it is very difficult to produce a ground powder and the production efficiency is significantly reduced. Absent. On the other hand, if the crushed particle size exceeds 10 μm, the crystal particle size of the _finally obtained _RTB -based sintered magnet material becomes too large, and it becomes difficult to obtain high _HcJ, which is not preferable. The RTB-based sintered magnet material may be produced from one kind of raw material alloy (single raw material alloy) as long as the above-mentioned respective conditions are satisfied, or using two or more kinds of raw material alloys You may produce by the method (blend method) which mixes them.

  The powder of the Pr—Ga alloy in the present disclosure is produced by the atomization method. For this reason, even without mechanical grinding, it has a spherical shape as described above.

  In addition, since the heat treatment is performed on the powder of the Pr—Ga alloy, as described above, the crystal grains can be largely grown to promote the uniformity of the characteristics.

The RTB-based sintered magnet material and the diffusion source are disposed in a processing vessel, and the RTB-based sintered magnet material and the diffusion source are heated to over 600 ° C. in a vacuum or inert gas atmosphere. By heating at a temperature of 950 ° C. or lower, Pr and Ga contained in the diffusion source are diffused from the surface of the RTB-based sintered magnet material to the inside. As a result, a liquid phase containing Pr and Ga is generated from the diffusion source, and the liquid phase is diffused and introduced from the surface of the sintered material through grain boundaries in the RTB-based sintered magnet material. . As a result, Ga together with Pr can be diffused deep through the grain boundaries of the RTB-based sintered magnet material. If the temperature of the heat treatment is 600 ° C. or less, the amount of liquid phase containing Pr and Ga may be too small to obtain high H _cJ, and if it exceeds 950 ° C., the H _cJ may decrease. is there. In addition, preferably, the RTB-based sintered magnet in which the diffusion step (more than 600 ° C. and not more than 950 ° C.) is performed is cooled to 300 ° C. at a cooling rate of 5 ° C./min or more from the temperature performed in the diffusion step. It is preferable to Higher H _cJ can be obtained. More preferably, the cooling rate to 300 ° C. is 15 ° C./min or more.

  In the diffusion step, first, the RTB-based sintered magnet material and the diffusion source are disposed in the processing container. At this time, it is preferable that the RTB-based sintered magnet material and the diffusion source be in contact in the processing container. For example, the surface of the RTB-based sintered magnet material can be covered with a diffusion source (powder layer) to perform the diffusion process. For example, after a slurry in which a diffusion source is dispersed in a dispersion medium is applied to the surface of an RTB-based sintered magnet material, the dispersion medium is evaporated to diffuse the diffusion source and the RTB-based sintered magnet material You may make contact. In addition, alcohol (ethanol etc.), an aldehyde, and a ketone can be illustrated as a dispersion medium. Furthermore, for example, a method of adhering a powdery diffusion source to an RTB-based sintered magnet material to which an adhesive has been applied by using a fluid immersion method, to an RTB-based sintered magnet material There is a method of sprinkling a powdery diffusion source, and the like. Alternatively, the processing container containing the diffusion source may be vibrated, shaken, rotated, or the powder of the diffusion source may be flowed in the processing container.

  FIG. 3A is a cross-sectional view schematically showing a part of an RTB-based sintered magnet material 100 that can be used in the method of producing an RTB-based sintered magnet according to the present disclosure. The upper surface 100a and the side surfaces 100b and 100c of the RTB-based sintered magnet material 100 are shown in the drawing. The shape and size of the RTB-based sintered magnet material used in the manufacturing method of the present disclosure are not limited to the shape and size of the illustrated RTB-based sintered magnet material 100. The upper surface 100a and the side surfaces 100b and 100c of the R-T-B-based sintered magnet material 100 illustrated are flat, but the surface of the R-T-B-based sintered magnet material 100 has irregularities or steps. It may be curved or may be curved.

  FIG. 3B is a cross-sectional view schematically showing a part of the RTB-based sintered magnet material 100 in a state where the powder particles 30 constituting the diffusion source are located on the surface. The powder particles 30 constituting the diffusion source positioned on the surface of the R-T-B-based sintered magnet material 100 are the surface of the R-T-B-based sintered magnet material 100 via an adhesive layer (not shown). It may adhere to Such an adhesive layer may be applied to the surface of the RTB-based sintered magnet material 100, for example. If the adhesive layer is used, the powder of the diffusion source can be applied to a plurality of regions (for example, the upper surface 100a and the side surface 100b) having different normal directions without changing the orientation of the RTB-based sintered magnet material 100 It can be easily attached in one application step.

  Examples of usable pressure-sensitive adhesives include PVA (polyvinyl alcohol), PVB (polyvinyl butyral), PVP (polyvinyl pyrrolidone) and the like. When the pressure-sensitive adhesive is a water-based pressure-sensitive adhesive, the R1-T-B-based sintered magnet may be preliminarily heated before coating. The purpose of the preheating is to remove excess solvent and control the adhesion, and to adhere the adhesive uniformly. The heating temperature is preferably 60 to 100 ° C. In the case of a highly volatile organic solvent-based adhesive, this step may be omitted.

  Any method may be used to apply the adhesive to the surface of the RTB-based sintered magnet material. Specific examples of the application include a spray method, an immersion method, application by a dispenser, and the like.

In a preferred embodiment, the adhesive is applied to the entire surface (entire surface) of the RTB-based sintered magnet material. You may make it adhere to not the whole surface of RTB system sintered magnet raw material but one part. In particular, when the thickness of the R-T-B-based sintered magnet material is thin (for example, about 2 mm), one of the surfaces of the R-T-B-based sintered magnet material with the largest area is the diffusion source In some cases, Pr and Ga can be diffused throughout the magnet simply by depositing the powder of H. It is possible to improve H _cJ .

  As described above, the powder particles constituting the diffusion source in contact with the surface of the RTB-based sintered magnet material 100 have a structure with excellent uniformity. For this reason, when heating for diffusion to be described later is performed, Pr and Ga contained in the diffusion source can be efficiently diffused from the surface of the RTB-based sintered magnet material to the inside without waste.

  The coating amount of the diffusion source on the magnet surface is, for example, 0.1 to 1.0% by mass (preferably 0%) of the amount of Ga of the diffusion source with respect to 100% by mass of the RTB based sintered magnet. .1 to 0.5 mass%) can be set.

  The amounts of Pr and Ga contained in the diffusion source depend not only on the concentrations of Pr and Ga in the powder particles, but also on the particle size of the powder particles constituting the diffusion source. Therefore, it is possible to adjust the amount of Pr and Ga diffused also by adjusting the particle size of the powder particles constituting the diffusion source while keeping the concentrations of Pr and Ga constant.

Experimental Example 1
[Preparation of RTB based sintered magnet material]
The R-T-B based sintered magnet material is approximately No. 1 in Table 1. Raw materials of the respective elements were weighed so as to obtain the compositions shown in A-1 and A-2, and an alloy was produced by a strip casting method. The obtained alloys were roughly pulverized by a hydrogen pulverizing method to obtain roughly pulverized powder. Next, 0.04 mass% of zinc stearate as a lubricant is added to the obtained coarsely pulverized powder with respect to 100% by mass of roughly pulverized powder and mixed, and then using an air flow crusher (jet mill apparatus) was dry milled in a nitrogen stream, the crushed particle diameter D ₅₀ was obtained finely pulverized powder of 4μm (the material alloy powder). Zinc stearate as a lubricant was added to the finely pulverized powder in an amount of 0.05% by mass with respect to 100% by mass of the finely pulverized powder, and the mixture was mixed in a magnetic field to obtain a compact. As a forming apparatus, a so-called perpendicular magnetic field forming apparatus (transverse magnetic field forming apparatus) in which the magnetic field application direction and the pressing direction are orthogonal to each other was used. The resulting molded body is sintered in vacuum at 1060 ° C. or more and 1090 ° C. or less (select the temperature at which densification by sintering sufficiently occurs for each sample) for 4 hours, and an RTB-based sintered magnet material is obtained Obtained. The density of the obtained RTB-based sintered magnet material was 7.5 Mg / m ³ or more. Table 1 shows the results of the components of the obtained RTB-based sintered magnet material. Each component in Table 1 was measured using high frequency inductively coupled plasma emission spectrometry (ICP-OES). The same applies to Tables 2 and 4 below. Further, when the inequality (1) of the present invention is satisfied, “o” is described, and when not satisfied, “x” is described. In addition, even if each composition of Table 1 is totaled, it does not become 100 mass%. This is because components other than the components listed in Table 1 (for example, O (oxygen), N (nitrogen), etc.) are present.

[Step of obtaining diffusion source]
No. shown in Table 2. A powder of the Pr-Ga alloy of a-1 was prepared by atomization and prepared. The particle size of the obtained Pr—Ga alloy powder was 106 μm or less. Next, the powder of the Pr-Ga alloy is heat-treated at 500 ° C. (temperature lower by 80 ° C. than 580 ° C. which is the melting point of Pr-Ga alloy of No. a-1) for 2 hours. The diffusion source was obtained from the powder of Pr-Ga alloy.

[Diffusion process]
Table 1 No. The RTB based sintered magnet materials of A-1 and A-2 were cut and ground to form cubes of 7.4 mm × 7.4 mm × 7.4 mm. Next, No. In the RTB-based sintered magnet material of A-1, 3 parts by mass of the diffusion source per 100 parts by mass of the RTB-based sintered magnet material in a plane (two planes) perpendicular to the orientation direction (1.5 parts by mass per side) was dispersed. Thereafter, a diffusion step of heating at 900 for 4 hours in a reduced pressure argon controlled at 50 Pa was performed. Furthermore, the RTB-based sintered magnet after the diffusion step and the No. 1 sintered magnet. A-2 (R-T-B sintered magnet material not subjected to the diffusion step) was subjected to a second heat treatment at 500 ° C. for 3 hours in reduced pressure argon controlled at 50 Pa. B-based sintered magnets (No. 1 and 2) were produced. The No. of the obtained RTB-based sintered magnet. The entire surface of each sample is cut by 0.2 mm using a surface grinder to remove the concentrated part of the Pr—Ga alloy relative to No. 1, and a cube of 7.0 mm × 7.0 mm × 7.0 mm I got a sample of No. 3 of RTB-based sintered magnets. The same cutting process was applied to 2 to obtain a cube-shaped sample of 7.0 mm × 7.0 mm × 7.0 mm. The obtained No. The composition of the R-T-B-based sintered magnet (a sample in which Pr or Ga is diffused using a diffusion source) is measured using high-frequency inductively coupled plasma emission spectrometry (ICP-OES). , No. The composition was the same as that of No. 2 (No. 2 has the same composition as No. A-2 because no diffusion source was used).

[sample test]
The obtained sample was measured for B _r and H _cJ by B-H tracer. The measurement results are shown in Table 3.

As described above, No. 1 and 2 despite the almost same composition, high B _r and high H _cJ towards as shown in Table 3 embodiment of the present invention (No.1) is obtained.

Experimental Example 2
Similarly to Experimental Example 1, Nd: 24.0%, Pr: 7.0%, B: 0.86%, Cu: 0.1%, Al: 0.1%, Ga: 0: 2 in mass ratio. An RTB-based sintered magnet material having a composition of 2%, Co: 0.8%, Fe: 67.0% was produced (the inequality (1) is satisfied). The dimensions of the RTB-based sintered magnet material were: thickness 5.0 mm × width 7.5 mm × length 35 mm.

  Next, a powder of a Pr—Ga alloy having a composition shown in Table 4 was prepared by atomization and prepared. The particle size of the obtained Pr—Ga alloy powder was 106 μm or less. Next, the powder of the Pr-Ga alloy is heat-treated under the conditions (temperature and time) shown in Table 4 (with the exception that No. 3 is not heat-treated), the powder of the alloy is diffused (No. 3 to 17). Further, the average grain size of the intermetallic compound phase in the obtained diffusion source was measured by the following method. First, the cross section of the powder particle constituting the diffusion source is observed with a scanning electron microscope (SEM), the phase is separated from the contrast, the composition of each phase is analyzed using energy dispersive X-ray spectroscopy (EDX), and the intermetallic compound phase is Identified. Next, using an image analysis software (Scandium), the intermetallic compound phase with the highest area ratio was regarded as the intermetallic compound phase with the highest content, and the crystal grain size of the intermetallic compound phase was determined. Specifically, the number of crystal grains and the total area of crystal grains in the intermetallic compound phase are determined using image analysis software (Scandium), and the total area of crystal grains thus determined is divided by the number of crystal grains to obtain an average area. I asked. The crystal grain size D was determined from the average area obtained by Equation 1.

Here, D is a crystal grain size, and S is an average area.

  These operations were performed five times (five powder particles were examined), and the average value was determined to determine the average grain size of the intermetallic compound phase in the diffusion source. The results are shown in Table 4 average grain size. No. Since No. 3 did not heat-process to a diffusion source, the crystal grain size of the intermetallic compound phase was too small, and it was not able to measure (micro crystal grain of 1 micrometer or less).

  Next, an adhesive was applied to the RTB-based sintered magnet material. The coating method was such that the RTB-based sintered magnet material was heated to 60 ° C. on a hot plate, and then the adhesive was applied to the entire surface of the RTB-based sintered magnet material by a spray method. As an adhesive, PVP (polyvinyl pyrrolidone) was used.

  Next, with respect to the R-T-B-based sintered magnet material coated with the pressure-sensitive adhesive, the No. 1 in Table 4 was used. Three to seventeen diffusion sources were deposited. Fifty R-T-B-based sintered magnet materials having diffusion sources attached thereto were prepared for each type of diffusion sources (for each of Nos. 3 to 17). In the adhesion method, the diffusion source (alloy powder) is spread in a container, and the RTB-based sintered magnet material coated with the adhesive is cooled to room temperature, and then the diffusion source is RTB-based in the container. It was made to adhere to the entire surface of the sintered magnet material.

Next, the R-T-B-based sintered magnet material and the diffusion source are placed in a processing vessel and heated at 900 ° C. for 8 hours to remove Pr and Ga contained in the diffusion source as the R-T- A diffusion step of diffusing from the surface of the B-based sintered magnet material to the inside was performed. From the central part of the R-T-B sintered magnet after diffusion, a cube of 4.5 mm in thickness × 7.0 mm in width × 7.0 mm in length is cut out, and for each type of diffusion source (for each of Nos. 3 to 17) The coercivity was measured by B-H tracer every 10 pieces, and the value obtained by subtracting the minimum value of the coercivity from the maximum value of the obtained coercivity was determined as the magnetic characteristic variation ( _{ΔH cJ} ). The values of _{ΔH cJ} are shown in Table 4.

As shown in Table 4, the powder of the Pr—Ga alloy powder not subjected to heat treatment No. 3 (comparative example) and the heat processing temperature are out of the range of this indication. As compared with No. 9 (comparative example), in each of the inventive examples (No. 4 to 8, No. 10 to 17), ΔH _cJ is about half, and the variation of the magnetic characteristics in the diffusion process is suppressed.

  According to the present invention, an RTB-based sintered magnet having a high residual magnetic flux density and a high coercive force can be manufactured. The sintered magnet of the present invention is suitable for various motors such as a motor for hybrid vehicle mounting exposed to high temperature, home appliances, and the like.

12 R ₂ T ₁₄ B compound main phase 14 grain boundary phase 14 a two particle grain boundary phase 14 b grain boundary triple point 30 powder particle 100 R-T-B based sintered magnet material 100 a R-T- Top surface 100b of the B-based sintered magnet material Side surface 100c of the R-T-B-based sintered magnet material 100c Side surface of the R-T-B-based sintered magnet material

Claims (4)

R: 27.5 to 35.0% by mass (R is at least one of rare earth elements and necessarily includes Nd),
B: 0.80 to 0.99 mass%,
Ga: 0 to 0.8% by mass,
M: 0 to 2% by mass (M is at least one of Cu, Al, Nb and Zr),
Remainder T (T is Fe or Fe and Co) and unavoidable impurities,
Preparing an R-T-B-based sintered magnet material containing
Preparing a powder of Pr-Ga alloy produced by atomization method;
Heat treating the powder of the Pr-Ga alloy at a temperature lower than the melting point of the powder of the Pr-Ga alloy by 250 ° C. or more and at a temperature not more than the melting point to obtain a diffusion source from the powder of the Pr-Ga alloy;
The RTB-based sintered magnet material and the diffusion source are disposed in a processing vessel, and the RTB-based sintered magnet material and the diffusion source are heated to over 600 ° C. in a vacuum or inert gas atmosphere. A diffusion step of diffusing Pr and Ga contained in the diffusion source from the surface to the inside of the RTB-based sintered magnet material by heating at a temperature of 950 ° C. or lower;
A method for producing an RTB-based sintered magnet, comprising: The method for producing an R-T-B-based sintered magnet according to claim 1, wherein the RTB-based sintered magnet material satisfies the following inequality (1).
[T] /55.85> 14 [B] /10.8 (1)
([T] is the content of T in mass%, [B] is the content of B in mass%)   The method according to claim 1 or 2, wherein the Ga content of the RTB-based sintered magnet material is 0 to 0.5% by mass.   The method for manufacturing an RTB-based sintered magnet according to any one of claims 1 to 3, wherein the Nd content of the Pr-Ga alloy is equal to or less than the unavoidable impurity content.

Images