JPWO2015182705A1 - Method for producing RTB-based sintered magnet - Google Patents

Abstract

RLAl alloy powder (RL is Nd and / or Pr) and RH compound (RH is Dy and / or Tb, RH compound is RH fluoride, RH oxide, RH And a step of performing a heat treatment at a temperature equal to or lower than the sintering temperature of the R-T-B system sintered magnet in a state where one or more powders selected from oxyfluoride are present. The RLAl alloy contains 65 atomic% or more of RL, and the melting point of the RLAl alloy is equal to or lower than the temperature of the heat treatment. The heat treatment is performed in a state where the powder of the RLAl alloy and the powder of the RH compound are present on the surface of the R-T-B system sintered magnet at a mass ratio of RLAl alloy: RH compound = 96: 4 to 5: 5. .

Description

The present invention relates to a method for producing an R-T-B system sintered magnet (R is a rare earth element, T is Fe or Fe and Co) having an R ₂ T ₁₄ B type compound as a main phase.

R-T-B system sintered magnets mainly composed of R ₂ T ₁₄ B-type compounds are known as the most powerful magnets among permanent magnets, and include hard disk drive voice coil motors (VCM), It is used for various motors such as motors for hybrid vehicles and home appliances.

The _RTB -based sintered magnet has an irreversible thermal demagnetization because its intrinsic coercive force H _cJ (hereinafter simply referred to as “H _cJ ”) decreases at a high temperature. In order to avoid irreversible thermal demagnetization, it is required to maintain high H _cJ even at high temperatures when used for motors and the like.

The R-T-B based sintered magnet is known to improve H _cJ when a part of R in the R ₂ T ₁₄ B-type compound phase is substituted with a heavy rare earth element RH (Dy, Tb). . In order to obtain high H _cJ at a high temperature, it is effective to add a large amount of heavy rare earth element RH in the RTB-based sintered magnet. However, when the light rare earth element RL (Nd, Pr) is replaced as R by the heavy rare earth element RH in the RTB-based sintered magnet, H _cJ is improved, while the residual magnetic flux density B _r (hereinafter simply “ There is a problem that “ _Br ” is greatly reduced. Moreover, since the heavy rare earth element RH is a rare resource, it is required to reduce the amount of use thereof.

In recent years, to reduce the decrease in B _r, to improve the H _cJ of the R-T-B based sintered magnets have been studied with less heavy rare-earth element RH. For example, as a method for effectively supplying and diffusing a heavy rare earth element RH to an RTB-based sintered magnet, Patent Documents 1 to 5 disclose that RH oxide or RH fluoride and various metals M or M alloys are used. By heat-treating the mixed powder on the surface of the RTB-based sintered magnet, RH and M are efficiently absorbed by the RTB-based sintered magnet. A method for increasing the H _cJ of a sintered system magnet is disclosed.

  Patent Document 1 discloses using a mixed powder of a powder containing M (where M is one or more selected from Al, Cu, and Zn) and an RH fluoride powder. Patent Document 2 discloses RTMAH that becomes a liquid phase at a heat treatment temperature (where M is one or more selected from Al, Cu, Zn, In, Si, P, etc., A is boron or carbon, H Is used, and it is disclosed that a mixed powder of the alloy powder and a powder such as RH fluoride may be used.

  In Patent Document 3 and Patent Document 4, powder of an RM alloy (where R is a rare earth element, M is one or more selected from Al, Si, C, P, Ti, etc.) or an M1M2 alloy (M1 and M2) Is a mixed powder of RH oxide with one or more powders selected from Al, Si, C, P, Ti, etc., and partially heats RH oxide by RM alloy or M1M2 alloy during heat treatment It is disclosed that it is possible to introduce a larger amount of R into the magnet.

  Patent Document 5 discloses that the effect of improving the coercive force by Al can be obtained by using powder containing Al in the metal state and RH fluoride or RH oxide. According to the invention described in Patent Document 5, it is disclosed that the oxygen content in the RTB-based sintered magnet needs to be 4000 ppm or less in order to obtain a coercive force improving effect.

JP 2007-287874 A JP 2007-287875 A JP 2012-248827 A JP 2012-248828 A International Publication No. 2008/139690

The methods described in Patent Documents 1 to 4 are notable in that a larger amount of RH can be diffused into the magnet. However, according to these methods, RH present on the magnet surface cannot be effectively linked to improvement of H _cJ , and there is room for improvement. In particular, Patent Document 3 uses a mixed powder of RM alloy and RH oxide, but as far as the examples are concerned, the improvement of H _cJ due to diffusion of the RM alloy itself is large, and the effect of using RH oxide is slight. Therefore, it seems that the reduction effect of the RH oxide by the RM alloy is not so much exhibited. Also in the method described in Patent Document 5, 50% or more of the RH compound is required, and there is room for improvement in terms of reducing the amount of the RH compound.

The present invention has been made in view of the above circumstances, and by reducing the amount of RH present on the magnet surface and effectively diffusing it inside the magnet, _RTB -based sintering having high H _cJ is _achieved. It is to provide a method for manufacturing a magnetized magnet.

  In an exemplary embodiment, the method for producing an RTB-based sintered magnet of the present invention includes an RLAl alloy (RL is Nd and / or Pr) on the surface of the prepared RTB-based sintered magnet. In the state in which the powder and the powder of the RH compound (RH is Dy and / or Tb, and the RH compound is one or more selected from RH fluoride, RH oxide, and RH acid fluoride) are present, A step of performing a heat treatment at a temperature equal to or lower than the sintering temperature of the RTB-based sintered magnet. The RLAl alloy contains 65 atomic% or more of RL, and the melting point of the RLAl alloy is equal to or lower than the temperature of the heat treatment. In the heat treatment, the powder of the RLAl alloy and the powder of the RH compound are present on the surface of the RTB-based sintered magnet at a mass ratio of RLAl alloy: RH compound = 96: 4 to 5: 5. To be done.

In a preferred embodiment, the amount of RH element in the powder present on the surface of the RTB-based sintered magnet is 0.03 to 0.35 mg per 1 mm ^{2 of the} magnet surface.

  In one embodiment, the RLAl alloy powder and the RH compound powder are mixed on the surface of the RTB-based sintered magnet.

According to the embodiment of the present invention, since the RLAl alloy can reduce the RH compound with higher efficiency than the prior art and diffuse the RH into the R-T-B based sintered magnet, relatively less RH. The amount of H _cJ can be improved.

  In the embodiment of the present invention, an R-T-B system sintered magnet (R is a rare earth element, T is Fe or Fe and Co, and B is boron) is produced on the surface of the R-T-B system sintered magnet. RLAl alloy (RL is Nd and / or Pr, Al is aluminum) powder and RH compound (RH is Dy and / or Tb, RH compound is RH fluoride, RH oxide, RH acid fluoride) Or a step of performing a heat treatment at a temperature equal to or lower than the sintering temperature of the RTB-based sintered magnet in the presence of two or more kinds of powders. The RLAl alloy contains RL at 65 atomic% or more, and its melting point is lower than the temperature of the heat treatment. The heat treatment is performed by causing the powder of the RLAl alloy and the powder of the RH compound to exist on the surface of the RTB-based sintered magnet at a mass ratio of RLAl alloy: RH compound = 96: 4 to 5: 5.

As a method for effectively improving H _cJ by effectively using less RH, the present inventor, together with a diffusion aid for reducing the RH compound on the surface of the _RTB -based sintered magnet and reducing the RH compound during the heat treatment, It was thought that the method of heat treatment in the presence was effective. As a result of the study by the present inventor, it was found that an RLAl alloy having RL of 65 atomic% or more and having a melting point of not more than the heat treatment temperature is excellent in reducing ability of the RH compound present on the magnet surface, thereby completing the present invention did. In the present specification, a substance containing RH is referred to as a “diffusion agent”, and a substance capable of reducing and diffusing RH of a diffusion agent such as RLAl is referred to as a “diffusion aid”.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

[RTB-based sintered magnet base material]
First, in the present invention, an RTB-based sintered magnet base material to be diffused of heavy rare earth element RH is prepared. In the present specification, for the sake of easy understanding, an RTB-based sintered magnet that is a target of diffusion of the heavy rare earth element RH may be strictly referred to as an RTB-based sintered magnet base material. The term “R-T-B system sintered magnet” includes such “R-T-B system sintered magnet base material”. As this RTB-based sintered magnet base material, a known material can be used, for example, having the following composition.
Rare earth element R: 12-17 atom%
B (a part of B (boron) may be substituted with C (carbon)): 5 to 8 atomic%
Additive element M ′ (selected from the group consisting of Al, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, In, Sn, Hf, Ta, W, Pb, and Bi At least one): 0 to 2 atomic%
T (a transition metal element mainly composed of Fe and may contain Co) and inevitable impurities: balance

  Here, the rare earth element R is mainly a light rare earth element RL (at least one element selected from Nd and Pr), but may contain a heavy rare earth element. In addition, when a heavy rare earth element is contained, it is preferable that at least one of Dy and Tb is included.

  The RTB-based sintered magnet base material having the above composition is manufactured by an arbitrary manufacturing method.

[Diffusion aid]
As the diffusion aid, RLAl alloy powder, which is an alloy of RL and Al (aluminum), is used. As the RL, a light rare earth element having a high effect of reducing the RH compound is suitable, and RL is Nd and / or Pr. Further, the RLAl alloy uses an alloy containing RL at 65 atomic% or more and having a melting point equal to or lower than the heat treatment temperature. The RLAl alloy preferably contains 70 atomic% or more of RL. Such an RLAl alloy efficiently reduces the RH compound during the heat treatment, and the RH reduced at a higher rate diffuses into the R-T-B system sintered magnet. The H _cJ of the sintered magnet can be improved. According to the inventor's research, an alloy (RLM alloy) of RL and M element such as Cu, Fe, Co, Ni, and Ga has a high effect of reducing the RH compound when mixed with the RH compound and heat-treated. know. As a result of further research, it was found that RLAl, which is an alloy of RL and Al, has a higher reducing effect on the RH compound than an RLM alloy which is an alloy of other metal elements and RL. Also, when the same amount of RH compound is mixed, more RH can be diffused into the R-T-B system sintered magnet by using the RLAl alloy, and therefore other RLM alloys can be used as diffusion aids. It has been found that the H _cJ of the _RTB -based sintered magnet can be improved more than when it is used. The particle size of the RLAl alloy powder is preferably 500 μm or less.

[Diffusion agent]
As the diffusing agent, powder of an RH compound (RH is Dy and / or Tb, and the RH compound is one or more selected from RH fluoride, RH oxide, and RH oxyfluoride) is used. Among them, RH fluoride is preferable because it is easily reduced by _RLAl and has a large effect of improving H _cJ . The particle size of the RH compound powder is preferably 100 μm or less. The RH oxyfluoride in the present invention may be contained in the RH fluoride as an intermediate substance in the production process.

[Diffusion heat treatment]
Any method may be employed in which the powder of the RLAl alloy and the powder of the RH compound are present on the surface of the RTB-based sintered magnet. For example, RLAl alloy powder and RH compound powder are dispersed on the surface of an R-T-B sintered magnet, or RLAl alloy powder and RH compound powder are dispersed in a solvent such as pure water or an organic solvent. And a method in which an RTB-based sintered magnet is dipped and pulled up, and an RLAl alloy powder and an RH fluoride powder are mixed with a binder or a solvent to produce a slurry. -The method of apply | coating to the surface of a B type sintered magnet, etc. are mentioned. The binder or the solvent may be any material that can be removed from the surface of the RTB-based sintered magnet by thermal decomposition or evaporation at a temperature lower than the melting point of the diffusion aid in the subsequent heating process. It is not particularly limited. Examples of the binder include polyvinyl alcohol and ethyl cellulose. Further, the powder of the RLAl alloy and the powder of the RH compound may be present on the surface of the RTB-based sintered magnet in a state where they are mixed, or may be present separately. When these powders are present separately, it is preferable that the RLAl alloy powder is first present on the surface of the RTB-based sintered magnet and then the RH compound powder is present on the upper surface thereof. In the method of the present invention, since the melting point of the RLAl alloy is equal to or lower than the heat treatment temperature, the RLAl alloy is melted during the heat treatment, and the reduced RH on the surface of the R-T-B system sintered magnet is R-T-B. It becomes easy to diffuse inside the sintered magnet. Therefore, before the RLAl alloy powder and the RH compound powder are present on the surface of the RTB-based sintered magnet, the surface of the RTB-based sintered magnet is specially cleaned such as pickling. There is no need to perform the conversion process. Of course, it does not exclude performing such a cleaning process. Even if the surface of the RLAl alloy powder particles is somewhat oxidized, the effect of reducing the RH fluoride is hardly affected.

  The abundance ratio (before heat treatment) of the RLAl alloy and the RH compound in the powder state on the surface of the RTB-based sintered magnet is RLAl alloy: RH compound = 96: 4 to 5: 5 in mass ratio. The abundance ratio is more preferably RLAl alloy: RH compound = 95: 5 to 6: 4. The present invention does not necessarily exclude the presence of a powder (third powder) other than the powder of the RLAl alloy and the RH compound on the surface of the RTB-based sintered magnet, but the RH in the RH compound is changed to R- Care must be taken so that the third powder does not impede diffusion into the interior of the TB sintered magnet. The mass ratio of the “RLAl alloy and RH compound” powder in the entire powder existing on the surface of the RTB-based sintered magnet is desirably 70% or more.

According to the present invention, it is possible to efficiently improve H _cJ of an _RTB -based sintered magnet with a small amount of RH. The amount of RH element in the powder present on the surface of the RTB-based sintered magnet is preferably 0.03 to 0.35 mg per 1 mm ² of the magnet surface, and 0.05 to 0.25 mg. More preferably.

  Heat treatment is performed in a state where the powder of the RLAl alloy and the powder of the RH compound are present on the surface of the RTB-based sintered magnet. Since the RLAl alloy powder melts after the start of the heat treatment, the RLAl alloy need not always maintain the “powder” state during the heat treatment. The atmosphere for the heat treatment is preferably a vacuum or an inert gas atmosphere. The heat treatment temperature is not higher than the sintering temperature of the RTB-based sintered magnet (specifically, for example, 1000 ° C. or lower) and higher than the melting point of the RLAl alloy. The heat treatment time is, for example, 10 minutes to 72 hours. Moreover, you may perform the heat processing for 10 minutes-72 hours at 400-700 degreeC further as needed after the said heat processing.

[Experiment 1]
First, by a known method, the composition ratio Nd = 13.4, B = 5.8, Al = 0.5, Cu = 0.1, Co = 1.1, and the balance = Fe (atomic%) RT -B system sintered magnet was produced. By machining this, an R-T-B system sintered magnet base material of 6.9 mm × 7.4 mm × 7.4 mm was obtained. Magnetic properties of the obtained R-T-B based sintered magnet base material where a measured by B-H tracer, H _cJ is 1035kA / m, B _r was 1.45 T. As will be described later, the magnetic properties of the RTB-based sintered magnet after the heat treatment are measured after removing the surface of the RTB-based sintered magnet by machining. In accordance with the -B-based sintered magnet base material, the surface was further removed by 0.2 mm each by machining, and the size was measured after measuring 6.5 mm × 7.0 mm × 7.0 mm. In addition, when the impurity amount of the R-T-B system sintered magnet base material was separately measured by a gas analyzer, oxygen was 760 ppm, nitrogen was 490 ppm, and carbon was 905 ppm (all in mass ratio).

Next, a diffusion aid having a composition of Nd ₈₀ Al ₂₀ (atomic%) was prepared. The diffusion aid was pulverized with a coffee mill to obtain a particle size of 150 μm or less. The obtained diffusion aid powder and TbF ₃ powder or DyF ₃ powder having a particle size of 20 μm or less were mixed at a mixing ratio shown in Table 1 to obtain a mixed powder. 64 mg of mixed powder was spread over an 8 mm square area on the Mo plate, and an RTB-based sintered magnet base material was placed on the Mo plate with the surface of 7.4 mm × 7.4 mm facing down. At this time, the amount of Tb or Dy per 1 mm ^{2 of the} surface of the RTB-based sintered magnet (diffusion surface) in contact with the dispersed powder mixture is as shown in Table 1. In addition, the melting | fusing point of the diffusion aid shown in a present Example below has described the value shown by the binary system phase diagram of RLAl. The Mo plate on which this RTB-based sintered magnet base material was placed was accommodated in a processing container and covered. (This lid does not hinder the entry and exit of the gas inside and outside the container.) This was accommodated in a heat treatment furnace and subjected to heat treatment at 900 ° C. for 4 hours in an Ar atmosphere of 100 Pa. The heat treatment was carried out under the above conditions after the temperature was raised while evacuating from room temperature and the atmospheric pressure and temperature reached the above conditions. Then, after the temperature was lowered to room temperature, the Mo plate was taken out and the RTB-based sintered magnet was collected. The recovered RTB-based sintered magnet was returned to the processing vessel and accommodated again in a heat treatment furnace, and heat treatment was performed at 500 ° C. for 2 hours in a vacuum of 10 Pa or less. This heat treatment was also performed under the above conditions after the temperature was raised while evacuating from room temperature and the atmospheric pressure and temperature reached the above conditions. Thereafter, the temperature was lowered to room temperature, and then the R-T-B sintered magnet was collected. As described above, the present experimental example is an experiment in which the mixed powder is dispersed only on one diffusion surface of the _RTB -based sintered magnet base material and the improvement effect of H _cJ is compared.

Each surface of the obtained RTB-based sintered magnet was removed by machining by 0.2 mm to obtain Samples 1 to 9 of 6.5 mm × 7.0 mm × 7.0 mm. Magnetic properties of the obtained samples 1 to 9 were measured by a B-H tracer was determined the amount of change in H _cJ and B _r [Delta] H _cJ and .DELTA.B _r. In addition, the introduction amounts ΔAl and ΔRH of Al and RH in the entire RTB-based sintered magnet (AlORRH amount in the RTB-based sintered magnet after heat treatment−AlorRH amount of the base material: mass%) Asked. The results are shown in Table 2 (in Table 2, ΔAl is expressed as ΔM).

Tables 1 and 2 show, as reference examples, examples in which RTd-based sintered magnets were obtained in the same manner using Nd ₇₀ Cu ₃₀ and Nd ₈₀ Fe ₂₀ as diffusion aids. (Samples 10 and 11). Note that the introduction amount ΔM of Fe in the sample 11 is not described. This is because Fe is an element contained in a large amount in the RTB-based sintered magnet base material, and the analysis value of Fe is obtained as a balance (remainder) and does not have the accuracy to measure ΔM.

As can be seen from Table 2, R-T-B based sintered magnet according to the manufacturing method of the present invention is reduced less H _cJ of B _r is improved greatly but, RH than mass mixing ratio defined in the present invention Sample 1 with a large amount of compound shows that although the amount of RH per 1 mm ² of the diffusion surface of the _RTB -based sintered magnet is much higher than that of the present invention, the improvement of H _cJ does not _reach the present invention. It was. Further, the sample 7 containing less RH fluoride (without mixing the RH fluoride) than the mixing mass ratio defined in the present invention does not reach the present invention in the improvement of H _cJ , and the sample 8 _containing only the RH fluoride. 9 shows that although the amount of RH per 1 mm ² of the diffusion surface of the _RTB -based sintered magnet is much larger than that of the examples of the present invention, the improvement of H _cJ does not _reach the present invention. It was. That is, only when the RLAl alloy and the RH fluoride specified in the present invention are mixed and used in the mixing mass ratio specified in the present invention, the RLAl alloy efficiently reduces the RH fluoride, and the RHAl is sufficiently reduced. It was found that _HcJ could be greatly improved with a small amount of RH by diffusing in the R-T-B system sintered magnet base material.

Furthermore, it was found that the _RTB -based sintered magnet produced by the production method of the present invention has a greater improvement in H _cJ than when RLCu or RLFe is used as a diffusion aid. This is because when comparing sample 3 with samples 10 and 11, the amount of RH introduced was larger in sample 3 than in samples 10 and 11 even though the amount of RH per 1 mm ^{2 of} the diffusion surface was the same. I understand. That is, when RLAl is used as a diffusion aid, the reduction ability of the RH compound is higher than when RLM, which is an alloy of other M elements, is used as the diffusion aid, and more RH is sintered in the R-T-B system. Since it can be diffused inside the magnet, it is considered that the improvement of H _cJ is increased. On the other hand, the amount of Al introduced into the _RTB -based sintered magnet is relatively small, and in the _RTB -based sintered magnet according to the manufacturing method of the present invention, the _HcJ of Al is improved. The contribution of is considered to be small.

  In addition, a magnet that was subjected to heat treatment under the same conditions as in Sample 3 and that had not been subjected to surface machining was produced. With respect to this magnet, an EPMA (electron beam microanalyzer) uses a cross-sectional element mapping analysis of the contact interface between the mixture of the diffusing agent and the diffusion aid and the magnet surface, and a cross-sectional element mapping at a depth of 200 μm inside the magnet from the interface. Analysis was performed. At the contact interface between the mixture of the diffusing agent and the diffusion aid and the magnet surface, fluorine was detected together with Nd and oxygen, and the amount of Tb detected in the portion where fluorine was detected was extremely small. On the other hand, fluorine was not detected at a position 200 μm deep from the interface, and Tb was detected in a network form at the crystal grain boundary.

From this, the H _{cJ of the RTB} -based sintered magnet by the production method of the present invention is greatly improved because the RLAl alloy as a diffusion aid reduces RH fluoride and RL becomes fluorine. This is considered to be due to the fact that the reduced and reduced RH diffuses through the grain boundary inside the magnet and contributes to the improvement of H _cJ efficiently. Further, fluorine is not substantially detected in the internal magnet, i.e. the fluorine within the magnet does not penetrate also considered factors that significantly reduce the B _r.

[Experiment 2]
Samples 12, 13 and 38, 39 were obtained in the same manner as in Experimental Example 1 except that a diffusion aid having the composition shown in Table 3 was used and a mixed powder mixed with TbF ₃ powder at the mixing ratio shown in Table 3 was used. . Magnetic properties of the obtained samples 12, 13 and 38 were measured by a B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 4.

As can be seen from Table 4, when a diffusion aid having a composition different from that of the diffusion aid used in Experimental Example 1 is used (sample 12), the RTB-based sintered magnet according to the production method of the present invention has B. It was found that there was little decrease in _r and H _cJ was greatly improved. However, it has been found that the improvement in H _cJ of Sample 13 using a diffusion aid having an RL of less than 65 atomic% does not _reach the present invention.

[Experiment 3]
The same procedure as in Experimental Example 1 was conducted, except that a diffusion aid having the composition shown in Table 5 was used and a mixed powder mixed with TbF ₃ powder at the mixing ratio shown in Table 5 was used and heat treatment was performed under the conditions shown in Table 6. Samples 14 to 16 were obtained. Magnetic properties of the obtained samples 14 to 16 were measured by a B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 7.

As it can be seen from Table 7, even when subjected to heat treatment at various heat treatment conditions shown in Table 6, a large decrease less H _cJ of B _r in R-T-B based sintered magnet according to the manufacturing method of the present invention It turns out that it improves.

[Experimental Example 4]
Samples 17 to 20 were obtained in the same manner as Sample 4 except that the RTB-based sintered magnet base material had the composition, impurity amount, and magnetic properties shown in Samples 17 to 20 of Table 8. Magnetic properties of the obtained samples 17 to 20 were measured by a B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 9.

As can be seen from Table 9, even when the RTB-based sintered magnet base material having various compositions and impurities shown in Table 8 is used, the RTB-based sintered magnet according to the manufacturing method of the present invention is used. in a decrease in B _r is small, it was found that H _cJ is greatly improved. In particular, as can be seen from the results of Sample 20, H _cJ is greatly improved in the present invention even when a magnet having an oxygen content in the magnet exceeding 4000 ppm is used.

[Experimental Example 5]
Samples 21 and 22 were obtained in the same manner as in Experimental Example 1 except that a diffusion aid having the composition shown in Table 10 was used and mixed powder mixed with Tb ₄ O ₇ powder at the mixing ratio shown in Table 10 was used. Magnetic properties of the obtained samples 21 and 22 was measured by a B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 11. Each table shows the conditions and measurement results of Sample 4 as examples for comparison.

R-T-B based sintered magnet according to the manufacturing method of the even present invention when using a RH oxide as a diffusion agent can be seen from Table 11 were found to decrease in B _r is low H _cJ is greatly improved.

[Experimental Example 6]
Experimental Example 1 except that the diffusion aid shown in Table 12 was used and a mixed powder mixed with TbF ₃ powder or Tb ₄ O ₇ powder in the mixing ratio shown in Table 12 was used and heat treatment was performed under the conditions shown in Table 13 In the same manner, samples 23 to 26 were obtained. Magnetic properties of the obtained samples 23 to 26 were measured by a B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 14. In addition, each table | surface has shown the conditions and measurement result of the sample 4 as an Example for a comparison object.

As can be seen from Table 14, in any of Samples 23 to 26, it was found that the improvement in H _cJ did not _reach the present invention. Even when RH oxide was used as the diffusing agent, the results were equivalent or lower. When Al is used alone as a diffusion aid, the improvement in H _cJ decreases as the mixing ratio of Al decreases, as can be seen from the results of Samples 23-25. The large decrease in the B _r is high mixing ratio of Al in the opposite. Therefore, Al alone has almost no effect of reducing RH fluoride, and the improvement in H _cJ of Samples 23 to 26 is considered to be due to Al itself diffusing into the _RTB -based sintered magnet. It is done. That is, it is thought that _Br is lowered by Al that is easy to react with the main phase crystal grains diffused into the main phase crystal grains. In contrast, the small decrease in the R-T-B based sintered magnet is greatly improved in H _cJ B _r examples. As shown in Experimental Example 1, the amount of Al introduced is relatively small, and the improvement of H _{cJ in} the _RTB -based sintered magnet of the example is considered to be _largely due to the introduction of RH.

[Experimental Example 7]
Sample 27 was obtained in the same manner as in Experimental Example 1, except that a diffusion aid having the composition shown in Table 15 was used and mixed powder mixed with TbF ₃ powder at the mixing ratio shown in Table 15 was used. Magnetic properties of the obtained samples 27 measured by the B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 16. In addition, each table | surface has shown the conditions and measurement result of the sample 3, respectively as an Example for a comparison object.

As can be seen from Tables 15 and 16, when an RHAl alloy is used as a diffusion aid, the _HcJ is improved to the same extent as in the examples of the present invention, but the surface of the _RTB -based sintered magnet (diffusion surface) ) The amount of RH per 1 mm ² is much larger than that of the present invention, and the effect of improving H _cJ with a small amount of RH is not obtained.

[Experimental Example 8]
A slurry was obtained by mixing the diffusion aid, diffusion agent, polyvinyl alcohol and pure water shown in Table 17. This slurry is applied to two surfaces of the same RTB-based sintered magnet base material as in Experimental Example 1 (7.4 mm × 7.4 mm) per 1 mm ² of RTB-based sintered magnet surface (diffusion surface). The coating was carried out so that the amount of RH of the sample was the value shown in Table 17. These were heat-treated in the same manner as in Experimental Example 1, and the RTB-based sintered magnet was recovered.

Each surface of the obtained RTB-based sintered magnet was removed by 0.2 mm by machining to obtain samples 28 to 37 of 6.5 mm × 7.0 mm × 7.0 mm. Magnetic properties of the obtained samples 28 to 37 were measured by a B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 18.

As can be seen from Table 18, as a method for causing the powder of the RLAl alloy and the powder of the RH compound to be present on the surface of the R-T-B system sintered magnet, a method of applying a slurry containing these can also be adopted. R-T-B based sintered magnet according to the manufacturing method of the invention H _cJ was significantly improved without B _r drops. However, the sample 28 having more RH fluoride than the mixed mass ratio defined in the present invention and the sample 37 having less RH fluoride (no RH fluoride mixed) than the mixed mass ratio defined in the present invention are: It has been found that the improvement in H _cJ does not _reach the present invention.

[Experimental Example 9]
Sample 40 was obtained in the same manner as in Experimental Example 8, except that a diffusing agent containing an acid fluoride was used and a mixed powder mixed with a diffusion aid shown in Table 19 and a mixing ratio shown in Table 19 was used. Magnetic properties of the obtained samples 40 measured by the B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 20. Table 20 also shows the results of Sample 31 produced under the same conditions using TbF ₃ as a diffusing agent for comparison.

Hereinafter, the diffusing agent containing the acid fluoride used in Sample 40 will be described. For reference, TbF ₃ used in Sample 31 and others is also referred to.

About the diffusing agent powder of sample 40 and the diffusing agent powder of sample 31, the amount of oxygen and the amount of carbon were measured by gas analysis. The diffusing agent powder of Sample 31 is the same as the diffusing agent powder used in other samples using TbF ₃ .

  The oxygen content of the diffusing agent powder of Sample 31 was 400 ppm, but the oxygen content of the diffusing agent powder of Sample 40 was 4000 ppm. Both carbon contents were less than 100 ppm.

  Cross-sectional observation and component analysis of each diffusing agent powder were performed by SEM-EDX. Sample 40 was divided into a region with a large amount of oxygen and a region with a small amount of oxygen. In Sample 31, such a region having a different oxygen content was not observed.

  Table 21 shows the component analysis results of each of Samples 31 and 40.

It is considered that Tb oxyfluoride generated in the process of producing TbF ₃ remained in the region of sample 40 where the amount of oxygen was large. The calculated ratio of oxyfluoride was about 10% by mass.

From the results of Table 20, it can be seen that even in the sample using RH fluoride in which part of the oxyfluoride remains, H _cJ is improved in the same manner as the sample using RH fluoride.

[Experimental Example 10]
A diffusion aid whose surface was oxidized was prepared by allowing the diffusion aid to stand in a normal temperature atmosphere for 50 days. Except for this point, Sample 41 was prepared in the same manner as Sample 3. Note that the diffusion aid after standing for 50 days had an oxygen content of 1800 ppm before standing increased to 6600 ppm.

The RTB-based sintered magnet base material was allowed to stand for 100 hours in an atmosphere having a relative humidity of 90% and a temperature of 60 ° C., and many red rusts were generated on the surface. Sample 42 was produced in the same manner as Sample 3 except that such an R-T-B system sintered magnet base material was used. Magnetic properties of the obtained samples 41 and 42 was measured by a B-H tracer was determined the amount of change in H _cJ and B _r. The results are shown in Table 22. Table 22 also shows the results of Sample 3 for comparison.

From Table 22, it was found that even when the surfaces of the diffusion aid and the _RTB -based sintered magnet base material were oxidized, the _HcJ was hardly affected.

The method for producing an RTB-based sintered magnet according to the present invention can provide an _RTB -based sintered magnet in which _HcJ is greatly improved by a smaller amount of heavy rare earth element RH.

Claims (3)

A step of preparing an R-T-B sintered magnet (R is a rare earth element, T is Fe or Fe and Co);
In the state where the powder of the RLAl alloy (RL is Nd and / or Pr) and the powder of the RH compound (RH is Dy and / or Tb) are present on the surface of the RTB-based sintered magnet, A step of performing a heat treatment at a temperature equal to or lower than a sintering temperature of the RTB-based sintered magnet;
Including
The RLAl alloy contains RL of 65 atomic% or more, and the melting point of the RLAl alloy is equal to or lower than the temperature of the heat treatment;
The RH compound is one or more selected from RH fluoride, RH oxide, and RH oxyfluoride,
In the heat treatment, the powder of the RLAl alloy and the powder of the RH compound are present on the surface of the RTB-based sintered magnet at a mass ratio of RLAl alloy: RH compound = 96: 4 to 5: 5. The manufacturing method of the RTB system sintered magnet performed in the state to do. The mass of the RH element contained in the powder of the RH compound on the surface of the RTB-based sintered magnet is 0.03 to 0.35 mg per 1 mm ^{2 of the} surface. Manufacturing method of RTB-based sintered magnet.   The RTB-based sintering according to claim 1 or 2, wherein the RLAl alloy powder and the RH compound powder are mixed on the surface of the RTB-based sintered magnet. Magnet manufacturing method.