JP6972886B2 - RT-B-based sintered magnet and its manufacturing method - Google Patents

Description

The present invention relates to an R-TB based sintered magnet and a method for manufacturing the same.

The RT-B-based sintered magnet (R is at least one of the rare earth elements, T is at least one of the transition metal elements and always contains Fe, and B is boron) is the most permanent magnet. Known as a high-performance magnet, it is used in various motors such as voice coil motors (VCM) for hard disk drives, motors for electric vehicles (EV, HV, PHV, etc.), motors for industrial equipment, and home appliances. .. As used herein, the rare earth element refers to at least one element selected from the group consisting of scandium (Sc), yttrium (Y), and lanthanoids. Here, lanthanoid is a general term for 15 elements from lanthanum to lutetium.

R-T-B based sintered magnet is mainly grain boundary phase located in the grain boundary of the main phase and the main phase consisting of R _{2 T} 14 _B compound (hereinafter, simply referred to as "grain boundary") from the It is configured. The R ₂ T ₁₄ B compound is a ferromagnetic phase with high magnetization and forms the basis of the characteristics of the R-TB based sintered magnet.

_{The RTB} -based sintered magnet has a problem that irreversible thermal demagnetization occurs because the coercive force H cJ (hereinafter, may be simply referred to as “coercive force” or “H _{cJ”) decreases at a high temperature.} Therefore, in a particularly R-T-B based sintered magnet used in an electric vehicle motor, having a high H _cJ even at high temperatures, that is, required to have a higher H _cJ at room temperature.

In the R-TB based sintered magnet, a part of the light rare earth element (mainly Nd and / or Pr) contained in R _{in the R 2} T _{14 B compound is a heavy rare earth element (mainly Dy and / or Tb).} Substitution is known to improve _{H cJ. HcJ} improves as the amount of replacement of heavy rare earth elements increases.

_However, while improving the _{H cJ} of R _{2 T 14} B when the light rare earth element in the compound is replaced with the heavy rare-earth element R-T-B based sintered magnet, the remanence _{B r} (hereinafter, simply _{"B r"} In some cases) decreases. In addition, heavy rare earth elements, especially Dy, have problems such as unstable supply due to a small amount of resources present and limited production areas, and prices fluctuate significantly. Therefore, in recent years, users _{have requested to improve HcJ} without using heavy rare earth elements as much as possible.

Patent Document 1 discloses an RTB-based rare earth sintered magnet having an increased coercive force while reducing the Dy content. The composition of this sintered magnet is limited to a specific range in which the amount of B is relatively small as compared with the generally used R-TB alloy, and is selected from Al, Ga, and Cu1. It contains more than a kind of metal element M. As a result, an R ₂ T ₁₇ phase is generated at the grain boundary, and the volume ratio of the transition metal rich phase (R ₆ T _{13 M) formed at the grain boundary from this R 2} T _{17 phase increases, so that H cJ} Is improved.

International Publication No. 2013/008756

It is noteworthy that the method described in Patent Document 1 can increase the coercive magnetic force of the RTB-based sintered magnet while suppressing the content of heavy rare earth elements. However, there is a problem that _{Br is significantly reduced.} Further, in recent years, R-TB-based sintered magnets having a _{higher HcJ} have been demanded in applications such as motors for electric vehicles.

Embodiments of the present disclosure, while reducing the content of heavy rare earth elements, providing a R-T-B based sintered magnet and a manufacturing method thereof with high B _r and a high H _cJ.

The method for producing an R-TB-based sintered magnet of the present disclosure is a step of preparing an R1-T1-B-based sintered body and a step of preparing an R2-Si-based alloy in a non-limiting exemplary embodiment. At least a part of the R2-Si alloy is brought into contact with at least a part of the surface of the R1-T1-B-based sintered body, and the temperature is 450 ° C. or higher and 1100 ° C. or lower in a vacuum or an inert gas atmosphere. In the R1-T1-B-based sintered body, R1 is at least one of rare earth elements, and always contains at least one of Nd and Pr, and the content of R1 is The total content of the R1-T1-B-based sintered body is 27 mass% or more and 35 mass% or less, T1 is Fe or at least one of Co, Al, Mn, and Si and Fe, and the content of Fe with respect to the entire T1 is 80 mass% or more. The mol ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less, and in the R2-Si alloy, R2 is at least one of the rare earth elements, and Pr. The content of R2 is 74.4 mass% or more and 96.6 mass% or less of the whole R2-Si alloy, and the ratio of Pr to the whole rare earth element is R1-T1-B-based sintered body. It is higher than the ratio of Pr to the whole rare earth element, and the content of Si is 0.7 mass% or more and 14.0 mass% or less of the whole R2-Si alloy.

In a certain embodiment, Pr in the R2-Si alloy is 50% by mass or more of the total amount of R2.

In certain embodiments, R2 in the R2-Si alloy is Pr (including impurities).

In a certain embodiment, the R2-Si alloy contains Cu, and the Cu content is 0.1 mass% or more and 24.1 mass% or less of the whole R2-Si alloy.

In a certain embodiment, when [Pr] / [R1] in the R1-T1-B-based sintered body is α and [Pr] / [R2] in the R2-Si-based alloy is β, β / α. ≧ 1.2.

In one embodiment, the total content of R2 and Si in the R2-Si alloy is 80 mass% or more.

In a certain embodiment, in the step of preparing the R1-T1-B-based sintered body, the raw material alloy is _{pulverized to a particle size D 50} of 3 μm or more and 10 μm or less, and then oriented in a magnetic field for sintering. include.

The R-TB based sintered magnets of the present disclosure are R3: 27 mass% or more and 38 mass% or less (R3 is at least one of rare earth elements, and R3 as a whole, in an exemplary embodiment without limitation. 50 mass% or more is Nd and always contains Pr), X: 0.85 mass% or more and 0.93 mass% or less (X is at least one of B and C and always contains B), Si: 0.1 mass % Or more and 2.0 mass% or less, T2: 61.0 mass% or more (T2 is at least one kind of transition metal element, and 90 mass% or more of the whole T2 is Fe), and the mol ratio of T2 to X ( [T2] / [X]) is 13.0 or more, the concentration of Pr is higher in the magnet surface than in the center of the magnet, and the concentration of Si is higher in the surface of the magnet than in the center of the magnet. R4-T3-A compound (R4 is at least one of rare earth elements, and 50 mass% or more of R4 is Pr. T3 is at least one of Fe, Co, Ni, Mn, Ti, and Cr. , 50 mass% or more of the whole T3 is Fe. A is at least one of Zn, Cu, Ga, Al, Ge, and Si, and always contains Si).

In a certain embodiment, the R-TB-based sintered magnet contains Cu, and the concentration of Cu is higher in the magnet surface portion than in the magnet central portion.

In one embodiment, the concentration of Pr is 2.0 mass% or more higher in the surface portion of the magnet than in the central portion of the magnet.

In one embodiment, the concentration of Si is 0.1 mass% or more higher in the magnet surface portion than in the magnet central portion.

In a certain embodiment, the R-TB-based sintered magnet contains Cu, and the concentration of Cu is 0.1 mass% or more higher in the magnet surface portion than in the magnet central portion.

In certain embodiments, the R4-T3-A compound has a La ₆ Co ₁₁ Ga _{type 3} crystal structure.

According to embodiments of the present disclosure, while reducing the content of heavy rare-earth element, R-T-B based sintered magnet and a manufacturing method thereof with high B _r and a high H _cJ can be provided.

It is a flowchart which shows the example of the process in the manufacturing method of the R-TB system sintered magnet by this disclosure. It is a schematic diagram which shows the main phase and the grain boundary phase of the RTB system sintered magnet. It is a schematic diagram which further enlarged in the broken line rectangular area of FIG. 2A. It is explanatory drawing which shows the magnet surface part and the magnet center part when the magnet has a tile shape. It is explanatory drawing which shows typically the arrangement form of the R1-T1-B-based sintered body and the R2-Si-based alloy in a heat treatment step. No. It is a photograph which observed the cross section of the magnet surface part of 2-4 with a scanning electron microscope. No. It is a photograph which observed the cross section of the magnet surface part of 2-4 further enlarged. No. It is a photograph which observed the cross section of the central part of the magnet of 2-4 with a scanning electron microscope. No. It is a photograph which observed the cross section of the central part of the magnet of 2-4 further magnified. No. It is a photograph which observed the cross section of the magnet surface part of 1-1 with a scanning electron microscope. No. It is a photograph which observed the cross section of the magnet surface part of 1-1 further enlarged. No. It is a photograph which observed the cross section of the central part of the magnet of 1-1 with a scanning electron microscope. No. It is a photograph which observed the cross section of the central part of the magnet of 1-1 further enlarged. No. It is a photograph which observed the cross section of the magnet surface part of 1-3 with a scanning electron microscope. No. It is a photograph which observed the cross section of the magnet surface part of 1-3 further enlarged. No. It is a photograph which observed the cross section of the central part of the magnet of 1-3 with a scanning electron microscope. No. It is a photograph which observed the cross section of the central part of the magnet of 1-3 further diffused.

In the present disclosure, rare earth elements may be collectively referred to as "R". When referring to a specific element or group of rare earth elements R, for example, the reference numerals "R1", "R2", "R3" and "R4" are used to distinguish them from other rare earth elements. Further, in the present disclosure, the entire transition metal element including Fe is referred to as "T". When both a specific element or element group of the transition metal element T and a specific element or element group other than the transition metal element easily replaced with the Fe site of the main phase are included, "T1", "T2" and The code "T3" is used to distinguish it from other transition metal elements.

As shown in FIG. 1, the method for manufacturing an R-TB-based sintered magnet according to the present disclosure includes a step S10 for preparing an R1-T1-B-based sintered body and a step S20 for preparing an R2-Si-based alloy. And include. The order of the step S10 for preparing the R1-T1-B-based sintered body and the step S20 for preparing the R2-Si-based alloy is arbitrary, and the R1-T1-B-based sintered body manufactured at different locations, respectively. Body and R2-Si based alloys may be used.

In the present disclosure, the R-TB-based sintered magnets before and during the heat treatment are referred to as R1-T1-B-based sintered bodies, and the R1-T1-B-based sintered magnets after the heat treatment are simply RT-. It is called a B-based sintered magnet.

In the R1-T1-B system sintered body, the following (1) to (3) are established.
(1) R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is 27 mass% or more and 35 mass% or less of the entire R1-T1-B-based sintered body.
(2) T1 is Fe or at least one of Co, Al, Mn, and Si and Fe, and the content of Fe with respect to the whole T1 is 80 mass% or more.
(3) The mol ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.

The mol ratio of T1 to B ([T1] / [B]) in the present disclosure is an analytical value (mass%) of each element (at least one of Fe or Co, Al, Mn, Si and Fe) constituting T1. Was divided by the atomic weight of each element, and the ratio (a /) of the sum of these values (a) and the analytical value of B (mass%) divided by the atomic weight of B (b). b).

Mol ratio of T1 for B ([T1] / [B ]) that is greater than 14.0, the content ratio of B is meant that less than the stoichiometric composition ratio of _R 2 _{T 14} B compound There is. In other words, the R1-T1-B based sintered body, relative B amount relative to the amount of T1 to be used in the formation of the main phase _{(R 2 T 14} B compound) is small.

In the R2-Si alloy, the following (4) and (5) are established.
(4) R2 is at least one of rare earth elements and always contains Pr, and the content of R2 is 74.4 mass% or more and 96.6 mass% or less of the whole R2-Si alloy, and the whole rare earth element. The ratio of Pr to the total of the rare earth elements of the R1-T1-B based sintered body is higher than the ratio of Pr to the whole.
(5) The Si content is 0.7 mass% or more and 14.0 mass% or less of the entire R2-Si alloy.

The R-T-B based sintered magnet production method of the present disclosure, the main phase (R 2 _T 14 _B compound) relatively B amount in stoichiometric ratio to the amount of T used for forming a small R1 An R2-Si alloy is brought into contact with at least a part of the surface of the −T1-B-based sintered body, and heat treatment is performed at a temperature of 450 ° C. or higher and 1100 ° C. or lower in a vacuum or an inert gas atmosphere as shown in FIG. The step S30 to be carried out is carried out. Thus, it is possible to obtain the R-T-B based sintered magnet having a high _{B r} and a high _{H cJ.}

First, the basic structure of the RTB-based sintered magnet will be described.

R-T-B based sintered magnet, the powder particles of the raw material alloy has a structure bonded by sintering, mainly a main phase consisting of R _{2 T} 14 _B compound, the grain boundary portion of the main phase It is composed of the grain boundary phase in which it is located.

FIG. 2A is a schematic diagram showing the main phase and the grain boundary phase of the R-TB-based sintered magnet, and FIG. 2B is a schematic diagram further enlarging the inside of the broken line rectangular region of FIG. 2A. In FIG. 2A, as an example, an arrow having a length of 5 μm is shown for reference as a reference length indicating the size. As shown in FIGS. 2A and 2B, R-T-B based sintered magnet includes a main phase 12 mainly composed of _R 2 _{T 14} B compound, the grain boundary phase located grain boundary of the main phase 12 14 It is composed of and. Further, as shown in FIG. 2B, the grain boundary phase 14 is _{a two-particle grain boundary phase 14a in which two R 2} T ₁₄ B compound particles (grains) are adjacent to each other, and three or more R ₂ T ₁₄ B compound particles. Includes adjacent grain boundary triple points 14b.

_{The R 2} T ₁₄ B compound, which is the main phase 12, is a ferromagnetic phase having a high saturation magnetization and an 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, and B amount in the raw material alloy _{are mixed with the stoichiometric ratio of the R 2} T ₁₄ B compound (R amount: T amount: B amount =). It should be close to 2:14: 1). When the _{amount of B or R for forming the R 2} T ₁₄ B compound is lower than the stoichiometric ratio, generally, _{a ferromagnet such as Fe phase or R 2} T ₁₇ phase is generated in the grain boundary phase 14. , H _cJ drops sharply. However, as in the method described in Patent Document 1, the B amount is less than the stoichiometric ratio of R _{2 T} 14 _B compound, and, Al, Ga, of one or more selected among Cu When the metal element M is contained, a transitional rich phase (for example, R-T-Ga phase) is generated from the _{R 2} T _{17 phase to the grain boundary, and a high H cJ} can be obtained. However, in the method described in Patent Document 1, _Br is significantly reduced.

As a result of the study, the present inventors carried out a specific heat treatment by contacting at least a part of the surface of the R1-T1-B-based sintered body having a specific composition having a low B composition with an R2-Si-based alloy. Then, finally sintered magnet obtained has been found to be achieved a high B _r and high H _cJ. At this time, in the content of R2 in the R2-Si alloy, the ratio of Pr to the whole rare earth element is higher than the ratio of Pr to the whole rare earth element of the R1-T1-B-based sintered magnet body. It has been found that the presence of Pr in R2 at such a ratio promotes grain boundary diffusion and makes it possible to diffuse Si inside the magnet. Then, it was found that by diffusing Si into the sintered body having the specific composition, a thick two-particle grain boundary containing Si can be easily formed even inside the sintered body.

Method for producing R-T-B based sintered magnet according to the present disclosure, the Pr and Si by R2-Si based alloy of the particular composition of the present disclosure by introducing inside from the magnet surface, high B _r and high H _cJ Can be realized.

(Step of preparing R1-T1-B system sintered body)
First, the composition of the sintered body in the step of preparing the R1-T1-B-based sintered body (hereinafter, may be simply referred to as “sintered body”) will be described.

R1 is at least one of rare earth elements and always contains at least one of Nd and Pr. _{In order to improve the HcJ} of the R1-T1-B-based sintered body, a small amount of heavy rare earth elements such as Dy, Tb, Gd, and Ho, which are generally used, may be contained. However, according to the production method according to the present disclosure, a sufficiently high _HcJ can be obtained without using a large amount of heavy rare earth elements. Therefore, the content of the heavy rare earth element is preferably 1 mass% or less, more preferably 0.5 mass% or less, and not contained (substantially 0 mass%) of the R1-T1-B-based sintered body. ) Is more preferable.

The content of R1 is 27 mass% or more and 35 mass% or less of the entire R1-T1-B-based sintered body. If the content of R1 is less than 27 mass%, a liquid phase is not sufficiently formed in the sintering process, and it becomes difficult to sufficiently densify the R1-T1-B-based sintered body. On the other hand, although the effect of the present disclosure can be obtained even if the content of R1 exceeds 35 mass%, the alloy powder in the manufacturing process of the R1-T1-B-based sintered body becomes very active. As a result, significant oxidation or ignition of the alloy powder may occur, so 35 mass% or less is preferable. The content of R1 is more preferably 27.5 mass% or more and 33 mass% or less, and further preferably 28 mass% or more and 32 mass% or less.

T1 is Fe or at least one of Co, Al, Mn, and Si and Fe, and the content of Fe with respect to the whole T1 is 80 mass% or more. That is, T1 may be Fe alone, or may be composed of at least one of Co, Al, Mn, and Si and Fe. However, the content of Fe with respect to the whole T1 is 80 mass% or more. When the content of Fe is less than 80 mass%, _{B r} and _{H cJ} may be reduced. Here, "the content of Fe with respect to the whole T1 is 80 mass% or more" means, for example, when the content of T1 in the R1-T1-B-based sintered body is 70 mass%, R1-T1-B-based sintered body. It means that 56 mass% or more of the body is Fe. Preferably, the Fe content with respect to the whole T1 is 90 mass% or more. This is because it is possible to obtain a higher _{B r} and a high _{H cJ.} When Co, Al, Mn, and Si are contained, the preferable contents of the entire R1-T1-B-based sintered body are 5.0 mass% or less for Co, 1.5 mass% or less for Al, and 0 for Mn and Si, respectively. It is .2 mass% or less.

The mol ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.

When the mol ratio of T1 to B ([T1] / [B]) is 14.0 or less, high H _cJ cannot be obtained. On the other hand, if the mol ratio of T1 to B ([T1] / [B]) exceeds 15.0, _Br may decrease. The mol ratio of T1 to B ([T1] / [B]) is preferably 14.3 or more and 15.0 or less. It is possible to obtain a higher _{B r} and a high _{H cJ.} The B content is preferably 0.85 mass% or more and less than 1.0 mass% of the entire R1-T1-B-based sintered body.

In addition to the above elements, the R1-T1-B based sintered body includes Ga, Cu, Ag, Zn, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, and It may contain La, Ce, Sm, Ca, Mg, Cr, H, F, P, S, Cl, O, N, C and the like. The contents of Ga, Cu, Ag, Zn, In, Sn, Zr, Nb, and Ti are 0.5 mass% or less, respectively, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg and Cr are preferably 0.2 mass% or less, H, F, P, S and Cl are preferably 500 ppm or less, O is 6000 ppm or less, N is 1000 ppm or less, and C is 1500 ppm or less. The total content of these elements is preferably 5 mass% or less of the entire R1-T1-B-based sintered body. The total content of these elements may not be able to obtain the high _{B r} and high _{H cJ} exceeds 5 mass% of the total R1-T1-B based sintered body.

Next, a step of preparing the R1-T1-B system sintered body will be described. The step of preparing the R1-T1-B-based sintered body can be prepared by using a general manufacturing method typified by the R-TB-based sintered magnet. In the R1-T1-B-based sintered body, the raw material alloy is _{pulverized to a particle size D 50} (volume center value obtained by measurement by an air flow dispersion laser diffraction method = D ₅₀ ) of 3 μm or more and 10 μm or less, and then in a magnetic field. It is preferable to orient and perform sintering. As an example, a material alloy that has been prepared in such a strip casting method, after the particle size D ₅₀ by using a jet mill is ground to 3μm over 10μm or less, and molded in a magnetic field, 900 ° C. or higher 1100 ° C. or less It can be prepared by sintering at the temperature of. If the particle size D _{50 of the} raw material alloy is less than 3 μm, it is very difficult to produce pulverized powder, and the production efficiency is significantly reduced, which is not preferable. On the other hand, if the particle size D ₅₀ exceeds 10 μm, the crystal particle size of the finally obtained R1-T1-B-based sintered body becomes too large, and it becomes difficult to obtain _{a high HcJ, which is not preferable.} The particle size D ₅₀ is preferably 3 μm or more and 5 μm or less.

The R1-T1-B-based sintered body may be produced from one kind of raw material alloy (single raw material alloy) as long as each of the above conditions is satisfied, or may be made from two or more kinds of raw material alloys. May be produced by a method of mixing (blending method). Further, the obtained R1-T1-B-based sintered body may be subjected to known machining such as cutting or cutting as necessary, and then heat treatment described later may be carried out.

(Step of preparing R2-Si alloy)
First, the composition of the R2-Si alloy in the step of preparing the R2-Si alloy will be described. By containing R2 and Si in a specific range described below, R2 and Si in the R2-Si alloy are introduced into the inside of the R1-T1-B sintered body in the step of performing the heat treatment described later. Can be done.

R2 is at least one of rare earth elements and always contains Pr, and the content of R2 is 74.4 mass% or more and 96.6 mass% or less of the whole R2-Si alloy. If the content of R2 is less than 74.4 mass%, diffusion may not proceed sufficiently by the heat treatment described later. On the other hand, although the effect of the present disclosure can be obtained even if the content of R2 exceeds 96.6 mass%, the alloy powder in the manufacturing process of the R2-Si alloy becomes very active. As a result, the alloy powder may be significantly oxidized or ignited. Therefore, the content of R2 is preferably 95 mass% or less of the entire R2-Si alloy. The content of R2 is more preferably 85 mass% or more and 94 mass% or less. This is because a higher H _cJ can be obtained.

Further, in R2, the ratio of Pr to the whole rare earth element is higher than the ratio of Pr to the whole rare earth element of the R1-T1-B based sintered body. As a result, grain boundary diffusion is promoted, and Si can be diffused inside the magnet. If the ratio of Pr is lower than the ratio of Pr to the entire rare earth element of the R1-T1-B-based sintered body, the intergranular diffusion is not promoted and the diffusion of Si may stay near the surface of the sintered body. Therefore, the introduction amount to the inside from the magnet surface of Si is insufficient, there is a possibility that it is impossible to obtain a R-T-B based sintered magnet having a high B _r and high H _cJ. Preferably, β / α ≧ 1 when [Pr] / [R1] in the R1-T1-B-based sintered body is α and [Pr] / [R2] in the R2-Si-based alloy is β. .2.

It is preferable that 50 mass% or more of R2 is Pr. This is because a higher H _cJ can be obtained. Here, "50 mass% or more of R2 is Pr" means that, for example, when the content of R2 in the R2-Si alloy is 50 mass%, 25 mass% or more of the R2-Si alloy is Pr. More preferably, 70 mass% or more of R2 is Pr, and most preferably R2 is Pr only (including impurities). Thereby, even higher H _cJ can be obtained.

R2 may contain a small amount of heavy rare earth elements such as Dy, Tb, Gd, and Ho. However, according to the production method of the present disclosure, a sufficiently high _HcJ can be obtained without using a large amount of heavy rare earth elements. Therefore, the content of the heavy rare earth element is preferably 10 mass% or less of the entire R2-Si alloy (the heavy rare earth element in the R2-Si alloy is 10 mass% or less), and more preferably 5 mass% or less. It is preferable that it is not contained (substantially 0 mass%). Further, even when R2 of the R2-Si alloy contains a heavy rare earth element, it is preferable that 50 mass% or more of R2 is Pr, and R2 excluding the heavy rare earth element is Pr only (including unavoidable impurities). It is more preferable to have.

Si is 0.7 mass% or more and 14.0 mass% or less of the entire R2-Si alloy. If Si is less than 0.7 mass%, it becomes difficult for Si in the R2-Si alloy to be introduced into the R1-T1-B-based sintered body in the step of performing the heat treatment described later, and high _HcJ cannot be obtained. .. On the other hand, when the Si is at least 14.0mass%, _{B r} may be lowered significantly. Si is more preferably 0.7 mass% or more and 10 mass% or less, and further preferably 1.0 mass% or more and 6 mass% or less. This is because it is possible to obtain a higher _{B r} and a high _{H cJ.}

Preferably, the R2-Si-based alloy contains Cu, and contains 0.1 mass% or more and 24.1 mass% or less of the entire R2-Si based alloy. If Cu exceeds 24.1 mass%, the abundance ratio of Si at the grain boundaries may decrease, so 24.1 mass% or less is preferable.

In addition to the above elements, R2-Si alloys include Co, Al, Ag, Zn, Ga, In, Sn, Zr, Nb, Ti, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, etc. It may contain Ce, Sm, Ca, Mg, Mn, Cr, H, F, P, S, Cl, O, N, C and the like.

Co is preferably contained in an amount of 0.5 mass% or more and 10 mass% or less in order to improve corrosion resistance. The content of Al is 1.0 mass% or less, Ag, Zn, Ga, In, Sn, Zr, Nb, and Ti are 0.5 mass% or less, respectively, Ni, Hf, Ta, W, Ge, Mo, V, Y, La, Ce, Sm, Ca, Mg, Mn, Si, Cr are 0.2 mass% or less, H, F, P, S, Cl are 500 ppm or less, O is 6000 ppm or less, N is 1000 ppm or less, and C is. It is preferably 1500 ppm or less. However, the total content of these elements exceeds 20 mass%, then the amount of R2 and Si in R2-Si-based alloy, there is a possibility that it is impossible to obtain a high _{B r} and high _{H cJ.} Therefore, the total content of R2 and Si in the R2-Si alloy is preferably 80 mass% or more, and more preferably 90 mass% or more.

Next, the process of preparing the R2-Si alloy will be described. The R2-Si alloy is a method for producing a raw material alloy adopted in a general manufacturing method represented by an Nd-Fe-B sintered magnet, for example, a mold casting method, a strip casting method, or a single roll super. It can be prepared by using a quenching method (melt spinning method) or an atomizing method. Further, the R2-Si alloy may be an alloy obtained by pulverizing the alloy obtained by the above by a known pulverizing means such as a pin mill. Further, in order to improve the pulverizability of the alloy obtained as described above, pulverization may be performed after performing a heat treatment at 700 ° C. or lower in a hydrogen atmosphere to contain hydrogen.

(Step of performing heat treatment)
At least a part of the R2-Si alloy is brought into contact with at least a part of the surface of the R1-T1-B-based sintered body prepared as described above, and the temperature is 450 ° C. or higher and 1100 ° C. or lower in a vacuum or an inert gas atmosphere. Heat treat at temperature. As a result, a liquid phase containing R2 and Si is generated from the R2-Si alloy, and the liquid phase is diffused and introduced from the surface of the sintered body to the inside via the grain boundaries of the R1-T1-B sintered body. , R-T-Si phase is generated at the grain boundaries. If the heat treatment temperature is lower than 450 ° C., and too small amount of liquid phase containing R2 and Si, there is a possibility that it is impossible to obtain a high B _r and high H _cJ. On the other hand, if the temperature exceeds 1100 ° C., abnormal grain growth of the main phase may occur and _HcJ may decrease. The heat treatment temperature is preferably 450 ° C. or higher and 900 ° C. or lower. This is because it is possible to obtain a higher _{B r} and a high _{H cJ.} The heat treatment time is set to an appropriate value depending on the composition and dimensions of the R1-T1-B-based sintered body and the R2-Si-based alloy, the heat treatment temperature, etc., but is preferably 5 minutes or more and 20 hours or less, preferably 10 minutes or more and 15 hours. The following is more preferable, and 30 minutes or more and 10 hours or less are further preferable. Further, the heat treatment may be performed only once or may be performed a plurality of times. For example, heat treatment (one-step heat treatment) may be performed only at a relatively low temperature (400 ° C. or higher and 600 ° C. or lower), or heat treatment may be performed at a relatively high temperature (700 ° C. or higher and sintering temperature or lower (for example, 1050 ° C. or lower)). After that, heat treatment (two-stage heat treatment) may be performed at a relatively low temperature (400 ° C. or higher and 600 ° C. or lower). Further, it is preferable to prepare the R2-Si alloy in an amount of 2 mass% or more and 30 mass% or less with respect to the weight of the R1-T1-B-based sintered body. If the R2-Si alloy is less than 2 mass% with respect to the weight of the R1-T1-B sintered body, H _cJ may decrease. On the other hand, there is a possibility _{that the B r} decreases exceeds 30 mass%.

The heat treatment can be performed by arranging an R2-Si alloy having an arbitrary shape on the surface of the R1-T1-B sintered body and using a known heat treatment apparatus. For example, the surface of the R1-T1-B-based sintered body can be covered with a powder layer of the R2-Si-based alloy and heat-treated. For example, after applying a slurry in which an R2-Si alloy is dispersed in a dispersion medium to the surface of an R1-T1-B sintered body, the dispersion medium is evaporated to form an R2-Si alloy and an R1-T1-B based. It may be brought into contact with the sintered body. Further, as shown in the experimental examples described later, it is preferable that the R2-Si alloy is arranged so as to be in contact with the surface perpendicular to the orientation direction of at least the R1-T1-B sintered body. Examples of the dispersion medium include alcohol (ethanol and the like), NMP (N-methylpyrrolidone), aldehydes and ketones. Further, known machining such as cutting or cutting may be performed on the heat-treated R1-T1-B-based sintered body.

[RTB-based sintered magnet]
The RTB-based sintered magnet according to the present disclosure may be referred to as an R3-T2-X-based (or R3-T2-X-Si-based) sintered magnet, but is manufactured by the above-mentioned method for manufacturing an RTB-based sintered magnet. To clarify that, it is called "RTB-based sintered magnet".

The RTB-based sintered magnet produced according to the present embodiment has the following features.
R3: 27 mass% or more and 38 mass% or less (R3 is at least one of rare earth elements, and 50 mass% or more of R3 as a whole is Nd and always contains Pr).
X: 0.85 mass% or more and 0.93 mass% or less (X is at least one of B and C, and always includes B),
Si: 0.1 mass% or more and 2.0 mass% or less,
T2: 61.0 mass% or more (T1 is at least one kind of transition metal element, and 90 mass% or more of the whole T1 is Fe),
Contains,
The mol ratio of T2 to X ([T2] / [X]) is 13.0 or more.
The concentration of Pr is higher on the surface of the magnet than in the center of the magnet.
The concentration of Si is higher on the surface of the magnet than in the center of the magnet.
R4-T3-A compound (R4 is at least one of rare earth elements, and 50 mass% or more of R4 is Pr. T3 is at least one of Fe, Co, Ni, Mn, Ti, and Cr. , 50 mass% or more of the whole T3 is Fe. A is at least one of Zn, Cu, Ga, Al, Ge, and Si, and always contains Si).

The R4-T3-A compound typically has a La ₆ Co ₁₁ Ga ₃ type crystal structure and _{is typically an R 6} Fe ₁₃ Si compound. The composition of the R4-T3-A compound is such that R4 is 5 mol% or more and 50 mol% or less (preferably 20 mol% or more and 40 mol% or less), and T3 is 30 mol% or more and 94 mol% or less (preferably 50 mol% or more and 70 mol% or less). Yes, A is 1 mol% or more and 20 mol% or less (preferably 2 mol% or more and 20 mol% or less).

In order to make Pr of 50 mass% or more of the whole R4 of the R4-T3-A compound, the ratio of Pr to the whole rare earth element is higher than the ratio of Pr to the whole rare earth element of the R1-T1-B-based sintered magnet body R2. This can be achieved by diffusing the R1-T1-B-based sintered magnet body using a −Si-based alloy.

In certain embodiments, the R4-T3-A compound is present at least at the grain boundaries in the central portion of the magnet, and the thickness of the grain boundaries in the central portion of the magnet is 100 nm or more. Grain boundary thickness can be determined by measurement from micrographs of cross sections. According to the examples described later, grain boundaries having a thickness of 100 nm or more are present throughout the magnet.

The fact that the concentrations of Pr and Si are higher in the magnet surface than in the center of the magnet indicates that Pr and Si are diffused from the magnet surface to the inside. When Cu is contained in the R2-Si alloy, the concentration of Cu is higher in the magnet surface than in the magnet center.

"The concentration of Pr and Si is higher on the surface of the magnet than in the center of the magnet" is confirmed as follows.

Within the range of 100 μm × 100 μm in the region of the magnet surface from the plane orthogonal to the orientation direction (magnetization direction) to a thickness of up to 200 μm along the orientation direction (hereinafter, may be simply referred to as “magnet surface portion”). It is confirmed by checking whether the Pr concentration is higher than the Pr concentration in the central part of the magnet (also in the range of 100 μm × 100 μm in the central part of the magnet). Si (and Cu) are also confirmed by the same method. For "Pr concentration" and "Si (Cu) concentration", for example, in a cross section that passes through the center of the magnet and is parallel to the orientation direction, the center of the magnet and the surface of the magnet are observed with a scanning electron microscope and further observed. Average of the entire range measured by performing energy dispersion X-ray spectroscopy (EDX) while scanning a range of ± 50 μm, that is, 100 μm × 100 μm from the center point of the central part of the magnet and the area of the surface part of the magnet. Just find the value.

Further, when the magnet has a tile shape as shown in FIG. 3 and the orientation direction is the thickness direction of the magnet (direction of arrow 101), the surface of the magnet surface orthogonal to the orientation direction is the first curved surface. At least one of the (upper surface) 104 and the second curved surface (back surface) 105. Therefore, a region having a thickness of 200 μm measured along the orientation direction from the first curved surface 104 and the second curved surface 105 becomes the magnet surface portion.

When the magnet has a tile shape and the orientation direction is the direction in which the magnet extends (direction of arrow 102), the first end face 106 and the second end face 107 are the faces of the magnet surface orthogonal to the orientation direction. Become.

When the magnet has a cylindrical shape, if the direction of the arrow 102 in FIG. 3 is aligned with the direction of the central axis and the direction of the arrow 101 is the radial direction, the description of the tile-shaped magnet is applied.

Further, in the present disclosure, when the magnet has a tile shape and the orientation direction is the width direction of the magnet (direction of arrow 103), the surface of the magnet surface orthogonal to the orientation direction is substantially orthogonal to the orientation direction. It is referred to as a first side surface 108 and a second side surface 109 inside. Therefore, in this case, the region having a thickness of 200 μm measured from the first side surface 108 and the second side surface 109 along the orientation direction becomes the magnet surface portion.

The central portion of the magnet is a portion located in the center of the magnet, and is typically the center of gravity when the magnet has a polyhedral shape or a cylindrical shape. When the magnet has a tile shape as shown in FIG. 3, the central portion of the magnet is in the thickness direction (direction of arrow 101), the length direction (direction of arrow 102), and the width direction (direction of arrow 103) of the magnet. Let it be a portion 100 located at the center of all of the above. When the magnet has a cylindrical shape, the central portion of the magnet is a portion located at the center of both the thickness direction and the length direction of the magnet. The above-mentioned "magnet surface portion" is a portion that comes into contact with the R2-Si alloy during the manufacturing process and receives Pr and Si from the R2-Si alloy. Due to such diffusion, a concentration gradient of Pr and Si is generated inside the magnet, and this concentration gradient remains inside the finally obtained magnet. The "magnet surface portion" having a higher concentration of Pr and Si than the central portion of the magnet does not need to be located on the entire surface of the magnet.

The concentration of Pr is preferably 2.0 mass% or more higher in the surface portion of the magnet than in the central portion of the magnet, and the concentration of Si and Cu is 0.1 mass% or more higher in the surface portion of the magnet than in the central portion of the magnet. Is preferable. Here, "the concentration of Pr in the magnet surface portion is 2.0 mass% or more higher than that in the magnet central portion" in the present disclosure means that the orientation direction is from the plane of the magnet surface orthogonal to the orientation direction (magnetization direction). It means that the Pr concentration in the region (“magnet surface portion”) having a thickness of 200 μm measured along the above line is 2.0 or more higher at the percentage point (mass%) than the Pr concentration in the central portion of the magnet. For example, when the Pr concentration in the central portion of the magnet is 5.0 mass%, it means that the Pr concentration in the surface portion of the magnet is 7.0 mass% or more. The same applies to the concentrations of Si and Cu. For the concentrations of Pr, SI and Cu, for example, in a cross section that passes through the center of the magnet and is parallel to the orientation direction, the center of the magnet and the surface of the magnet are observed with a scanning electron microscope, and the center of the magnet and the observed portion are further observed. This can be done by measuring the magnet surface with an EDX. By having the above configuration, the R-TB based sintered magnet according to the present disclosure improves the coercive force inside the magnet as well as near the magnet surface. This is because the two-particle grain boundaries are thick. Further, the effect of improving the coercive force is not significantly impaired by surface grinding for adjusting the magnet size. Then, without using a heavy rare-earth element, it can achieve high _{B r} and high _{H cJ.}

The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Experimental Example 1
[Preparation of R1-T1-B system sintered body]
Using Nd metal, Pr metal, ferroboron alloy, ferrocarbon alloy, and electrolytic iron (all metals have a purity of 99% or more), the sintered body has a composition of reference numerals 1-A to 1-C shown in Table 1. The raw materials were melted and cast by a strip casting method to obtain a flake-shaped raw material alloy having a thickness of 0.2 to 0.4 mm. The obtained flake-shaped raw material alloy was pulverized with hydrogen, and then subjected to a dehydrogenation treatment of heating to 550 ° C. in a vacuum and then cooling to obtain a coarsely pulverized powder. Next, to the obtained coarse pulverized powder, zinc stearate as a lubricant was added in an amount of 0.04 mass% to 100 mass% of the coarsely pulverized powder, mixed, and then nitrogen was used using an air flow type pulverizer (jet mill device). Dry pulverization was performed in an air stream to obtain a finely pulverized powder (alloy powder) having _{a pulverized particle size D 50 of 4 μm.} The crushed particle size D ₅₀ is a volume center value (volume-based median diameter) obtained by a laser diffraction method using an air flow dispersion method.

Zinc stearate as a lubricant was added to the finely pulverized powder in an amount of 0.05 mass% with respect to 100 mass% of the finely pulverized powder, mixed, and then molded in a magnetic field to obtain a molded product. As the molding apparatus, a so-called right-angled magnetic field forming apparatus (transverse magnetic field forming apparatus) in which the magnetic field application direction and the pressurizing direction are orthogonal to each other was used.

The obtained molded product was sintered in vacuum at 1000 ° C. or higher and 1040 ° C. or lower (select a temperature at which sufficient densification occurs by sintering for each sample) for 4 hours, and then quenched, and then R1-T1-B-based sintering. I got a body. The density of the obtained sintered body was 7.5 Mg / m ³ or more. The composition of the obtained sintered body is shown in Table 1. Each component in Table 1 was measured using high frequency inductively coupled plasma emission spectroscopy (ICP-OES). As a result of measuring the amount of oxygen in the sintered body by the gas melting-infrared absorption method, it was confirmed that all of them were around 0.4 mass%. “[T1] / [B]” in Table 1 is an analytical value (mass%) for each element constituting T1 (including unavoidable impurities, Fe, Al, Si, Mn in this experimental example). Divided by the atomic weight of the element, the sum of those values (a) and the analytical value of B (mass%) divided by the analytical value of B (mass%) by the atomic weight of B (b) The ratio with (a / b). The same applies to all the tables below. It should be noted that the total of the compositions in Table 1 does not reach 100 mass%. This is because, as described above, the analysis method differs depending on each component, and further, there are components other than the components listed in Table 1 (for example, C (carbon), N (nitrogen), etc.). The same applies to other tables.

[Preparation of R2-Si alloy]
Using Pr metal, Cu metal, and Si metal (all of the metals have a purity of 99% or more), the alloys are blended so as to have the composition of reference numeral 1-a shown in Table 2, and the raw materials thereof are dissolved. A ribbon or flake-shaped alloy was obtained by a single-roll ultra-quenching method (melt spinning method). The obtained alloy was pulverized in an argon atmosphere using a mortar and then passed through a sieve having an opening of 425 μm to prepare an R2-Si alloy. The composition of the obtained R2-Si alloy is shown in Table 2.

[Heat treatment]
The R1-T1-B-based sintered bodies of reference numerals 1-A to 1-C in Table 1 were cut and machined to obtain 11.0 mm × 5.0 mm × 4.4 mm (orientation direction) rectangular parallelepipeds. Next, as shown in FIG. 4, in the processing container 3 made of niobium foil, the plane perpendicular to the orientation direction (arrow direction in the figure) of the R1-T1-B-based sintered body 1 is mainly R2-. The R2-Si alloys of reference numerals 1-a shown in Table 2 are placed above and below each of the R1-T1-B-based sintered bodies of reference numerals 1-A to 1-C so as to be in contact with the Si-based alloy 2. bottom.

Then, using a tubular air oven, heat treatment was performed at the heat treatment temperature and time shown in Table 3 in reduced pressure argon controlled at 200 Pa, and then the mixture was cooled. In order to remove the concentrated portion of the R2-Si alloy existing near the surface of each sample after heat treatment, the entire surface of each sample was machined by 0.2 mm using a surface grinding machine, 4.0 mm × 4. A cubic sample (RTB-based sintered magnet) having a size of 0 mm × 4.0 mm was obtained. The composition of the R-TB based sintered magnet was measured using high frequency inductively coupled plasma emission spectroscopy (ICP-OES). However, C (carbon content) was measured using a gas analyzer by the combustion-infrared absorption method. The results are shown in Table 3. “[T2] / [X]” in Table 3 indicates the analytical value (mass%) for each element constituting T2 (including unavoidable impurities, Fe, Al, Mn, Si in this experimental example). Divided by the atomic weight of the element, the sum of those values (a') and the analytical value (mass%) of X (B and C) divided by the atomic weight of each element were obtained, and they were obtained. It is a ratio (a'/ b') to the sum of the values of (b').

[Sample evaluation]
The coercive force (H _cJ ) of the obtained sample was measured by a BH tracer. The measurement results are shown in Table 3. As shown in Table 3, the mol ratio ([T1] / [B]) of T1 to B in the R1-T1-B-based sintered body is 14.0 or more, and T2 to X in the R-TB-based sintered magnet. _{A high HcJ} was obtained when the mol ratio ([T2] / [X]) was 13.0 or more.

Among the samples shown in Table 3, No. 1-1 (example of the present invention) and No. The cross section of 1-3 (Comparative Example) was observed with a scanning electron microscope (SEM: JCM-7001F manufactured by JEOL Ltd.). As a result, No. In 1-1 (example of the present invention), a thick two-particle boundary of 100 nm or more was formed from the vicinity of the magnet surface to the central portion of the magnet. On the other hand, No. In 1-3 (comparative example), the formation of thick two-particle grain boundaries was limited to the vicinity of the magnet surface. Furthermore, No. 1 which is an example of the present invention. As a result of performing energy dispersive X-ray spectroscopic analysis (EDX) with an SEM (JEOL JSM-7001F) accessory device (JED-2300 SD10 manufactured by JEOL Ltd.) on the cross section 1-1, the grain boundary at the center of the magnet was also obtained. The amount of Si that was originally possessed by the R1-T1-B-based sintered body before the diffusion treatment was detected, and a part of it was _{interpreted as the R 6} T ₁₃ (Si, Cu) phase based on the content. Was done.

Experimental Example 2
A plurality of R1-T1-B-based sintered bodies were prepared in the same manner as in Experimental Example 1 except that the sintered bodies were blended so as to have the composition of reference numeral 2-A shown in Table 4. Table 4 shows the results of component analysis of the obtained sintered body.

An R2-Si alloy was produced in the same manner as in Experimental Example 1 except that the R2-Si alloy was blended so as to have a composition of reference numerals 2-a to 2-p shown in Table 5. The composition of the obtained R2-Si alloy is shown in Table 5.

After processing a plurality of R1-T1-X-based sintered bodies in the same manner as in Experimental Example 1, R2-Si-based alloys of reference numerals 2-a to 2-p and R1 of reference numeral 2-A are similarly processed in the same manner as in Experimental Example 1. -Arranged so as to be in contact with the T1-B-based sintered body, and heat-treated and processed in the same manner as in Experimental Example 1 to obtain a sample (RT-B-based sintered magnet). The obtained sample was measured by the same method as in Experimental Example 1 to determine the coercive force (H _cJ ). The results are shown in Table 6. _{As shown in Table 6, high HcJ} was obtained in each of the examples of the present invention. Further, as R2, in all the examples of the present invention in which Pr was 50 mass% or more with respect to the whole R2, high H _cJ was obtained, whereas in Sample No., where Pr was less than 50 mass% of the whole R2. _{2-10 had a relatively low HcJ} in the examples of the present invention. On the other hand, No. 1 in which the amount of Si in the R2-Si alloy is off. 2-1. No. where the amount of R and the amount of Si are out of alignment. 2-11 and 2-14, No. where the amount of R is off. In both 2-16, high H _cJ was not obtained.

FIGS. 5A to 5D show No. 1 shown in Table 6. The cross section of 2-4 (example of the present invention) was observed with a scanning electron microscope (SEM: JCM-7001F manufactured by JEOL Ltd.). FIG. 5A is a photograph of observing the region of the magnet surface, FIG. 5B is a photograph of further magnifying the magnet surface, FIG. 5C is a photograph of observing the region of the magnet center, and FIG. 5D is a photograph. It is a photograph which observed the central part of a magnet further magnified. Similarly, FIGS. 6A to 6D show No. 1 shown in Table 3. 1-1 (example of the present invention), FIGS. 7A to 7D are No. 1 shown in Table 3. It is a photograph observed about 1-3 (comparative example). As shown in FIGS. 5A to 7D, in the examples of the present invention of FIGS. 5A to 6D and FIGS. 6A to 6D, a thick two-particle boundary of 100 nm or more is formed up to the center of the magnet, whereas in FIGS. In the comparative example, a thick two-particle boundary of 100 nm or more is not obtained at the central portion of the magnet.

In FIGS. 5A to D, FIGS. 6A to D, and FIGS. 7A to D, the analysis was performed in the 100 μm × 100 μm region shown by □ 1 to □ 6 and the point region indicated by ○ (white circle) 1 to ○ (white circle) 6. The results of composition analysis by EDX are shown in Table 7. As shown in □ 1 to □ 4 (example of the present invention), it can be seen that the concentrations of Pr and Si are higher in the magnet surface portion than in the magnet central portion. On the other hand, in □ 5 and □ 6 (comparative example), the concentration of Si is the same in the magnet surface portion and the magnet center portion.

In Table 7, Symbols 〇 (open circles) 1-6-existing contrast in the magnet surface part and the magnet central part in the observation of a scanning electron microscope _{R 6 Fe 13 (Si, Cu} ) is considered to phase R4-T3 The composition of the −A compound was evaluated, and in each case, 50 mass% or more of the entire R4 was Pr. As a representative, the measurement points of 〇 (white circles) 2 in Table 7 were evaluated using a field emission transmission electron microscope (FE-TEM: HF-2100 manufactured by Hitachi High Technology). From the diffraction pattern, La ₆ Co ₁₁ Ga was evaluated. _{It was shown to have a type 3} crystal structure, and it was confirmed from the composition ratio that it was a (Nd, Pr) ₆ Fe ₁₃ (Cu, Si) phase.

The RTB-based sintered magnets obtained by the embodiment of the present invention include voice coil motors (VCMs) for hard disk drives, motors for electric vehicles (EV, HV, PHV, etc.), motors for industrial equipment, and the like. It can be suitably used for various motors and home appliances.

1 R1-T1-X-based sintered body 2 R2-Si-based alloy 3 Processing container

Claims (13)

The process of preparing the R1-T1-B system sintered body and
The process of preparing R2-Si alloy and
At least a part of the R2-Si alloy is brought into contact with at least a part of the surface of the R1-T1-B-based sintered body, and heat-treated at a temperature of 450 ° C. or higher and 1100 ° C. or lower in a vacuum or an inert gas atmosphere. Including the process of carrying out
In the R1-T1-B system sintered body,
R1 is at least one of rare earth elements and always contains at least one of Nd and Pr, and the content of R1 is 27 mass% or more and 35 mass% or less of the entire R1-T1-B-based sintered body.
T1 is Fe or at least one of Co, Al, Mn, and Si and Fe, and the content of Fe with respect to the whole T1 is 80 mass% or more.
The mol ratio of T1 to B ([T1] / [B]) is more than 14.0 and 15.0 or less.
In the R2-Si alloy,
R2 is at least one of rare earth elements and always contains Pr, and the content of R2 is 74.4 mass% or more and 96.6 mass% or less of the whole R2-Si alloy, and Pr is contained in the whole rare earth element. The ratio is higher than the ratio of Pr to the total rare earth elements of the R1-T1-B based sintered body.
A method for producing an R-TB-based sintered magnet, wherein the Si content is 0.7 mass% or more and 14.0 mass% or less of the entire R2-Si alloy. The method for producing an R-TB-based sintered magnet according to claim 1, wherein Pr in the R2-Si-based alloy is 50% by mass or more of the total amount of R2. The method for producing an R-TB-based sintered magnet according to claim 1, wherein R2 in the R2-Si-based alloy is Pr (including impurities). The R- according to any one of claims 1 to 3, wherein the R2-Si alloy contains Cu, and the Cu content is 0.1 mass% or more and 24.1 mass% or less of the entire R2-Si alloy. A method for manufacturing a TB-based sintered magnet. When [Pr] / [R1] in the R1-T1-B-based sintered body is α and [Pr] / [R2] in the R2-Si-based alloy is β, β / α ≧ 1.2. The method for manufacturing an R-TB-based sintered magnet according to any one of claims 1 to 4. The method for producing an R-TB-based sintered magnet according to any one of claims 1 to 5, wherein the total content of R2 and Si in the R2-Si-based alloy is 80 mass% or more. The step of preparing the R1-T1-B-based sintered body _{includes claim 1, wherein the raw material alloy is pulverized to a particle size D 50} of 3 μm or more and 10 μm or less, and then oriented in a magnetic field and sintered. A method for manufacturing an R-TB-based sintered magnet according to any one of 6 to 6. R3: 27 mass% or more and 38 mass% or less (R3 is at least one of rare earth elements, and 50 mass% or more of R3 as a whole is Nd and always contains Pr).
X: 0.85 mass% or more and 0.93 mass% or less (X is at least one of B and C, and always includes B),
Si: 0.1 mass% or more and 2.0 mass% or less,
T2: 61.0 mass% or more (T2 is at least one kind of transition metal element, and 90 mass% or more of the whole T2 is Fe),
Contains,
The mol ratio of T2 to X ([T2] / [X]) is 13.0 or more.
The concentration of Pr is higher on the surface of the magnet than in the center of the magnet.
The concentration of Si is higher on the surface of the magnet than in the center of the magnet.
R4-T3-A compound (R4 is at least one of rare earth elements, and 50 mass% or more of R4 is Pr. T3 is at least one of Fe, Co, Ni, Mn, Ti, and Cr. , 50 mass% or more of T3 is Fe. A is at least one of Zn, Cu, Ga, Al, Ge, and Si, and Si is always contained). .. The R-TB-based sintered magnet according to claim 8, wherein the R-TB-based sintered magnet contains Cu, and the concentration of Cu is higher in the magnet surface portion than in the central portion of the magnet. The RTB-based sintered magnet according to claim 8 or 9, wherein the concentration of Pr is 2.0 mass% or more higher in the magnet surface portion than in the magnet central portion. The RTB-based sintered magnet according to any one of claims 8 to 10, wherein the concentration of Si is 0.1 mass% or more higher in the magnet surface portion than in the magnet central portion. The method according to any one of claims 8 to 11, wherein the RTB-based sintered magnet contains Cu, and the concentration of Cu is 0.1 mass% or more higher in the magnet surface portion than in the magnet central portion. R-TB system sintered magnet. The R-TB-based sintered magnet according to any one of claims 8 to 12, wherein the R4-T3-A compound has a La ₆ Co ₁₁ Ga _{3 type crystal structure.}

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