JP2853838B2 - Manufacturing method of rare earth permanent magnet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing rare earth permanent magnets having excellent magnetic properties and used for various electric and electronic devices.

[0002]

2. Description of the Related Art Among rare earth magnets, Nd-Fe-B magnets are:
In recent years, Nd, which is a main component, is abundant in resources, low in cost, and excellent in magnetic properties, and its use has been increasing in recent years. Research and development for improving magnetic properties has been energetically conducted since the invention of the Nd-based magnet, and many studies and inventions have been proposed. There are many methods for producing high-performance Nd magnets by mixing and sintering two types of alloy powders having different compositions, which is one of the methods for producing Nd-based sintered magnets (hereinafter referred to as the two-alloy method). Inventions have been proposed.

The two alloy methods proposed so far can be roughly classified into three types. In the first method, one of the raw material alloy powders to be mixed is made into an amorphous or microcrystalline alloy by a liquid quenching method, and a normal rare earth alloy powder is mixed therewith, or both raw material alloy powders are mixed together. A method of producing and mixing by a liquid quenching method [JP-A-63-9
3841, JP 63-115307, JP 63-252403, JP Akira 63 -278
208, JP-A-1-108707, JP-A-1-46310, JP-A-1-146309,
Japanese Patent Application Laid-Open No. 1-155603]. Recently, a 50MG alloy using this liquid quenching alloy has been
Reported that magnetic properties exceeding Oe were obtained [E. Otuki, T. Otuka
and T.Imai; 11th.Int.Workshop on Rare Earth Magnet
s, Pittsburgh, Pennsylvania, USA, October (1990), p. 328
See].

A second method is to prepare an alloy in which the two kinds of raw material alloy powders to be mixed are changed mainly as R ₂ Fe ₁₄ B compounds and the kinds and contents of the rare earth elements contained therein are mixed and sintered. Is the way. That is, a method of mixing two kinds of alloys in which the amount ratio of the contained Nd-rich phase or the kind of the rare earth element is changed [Japanese Patent Application Laid-Open Nos. 61-81603, 61-81604 and 61-816]
05, JP-A-61-81606, JP-A-61-81607, JP-A-61-11900
7, JP 61-207546, JP 63-245 90 3, Hei 1-177335 is the JP reference.

The third method is to use one of the alloys mainly as R ₂
A method of producing an Nd-based rare earth magnet by mixing and sintering powders of various low-melting elements, low-melting alloys, rare-earth alloys, carbides, borides, hydrides and the like into an alloy powder composed of an Fe ₁₄ B compound [ JP-A-60-230959, JP-A-61-263201, JP-A-62-1
81402, JP-A-62-182249, JP-A-62-206802, JP-A-62-270
746, JP-A-63-6808, JP-A-63-104406, JP-A-63-114939,
JP-A-63-272006, JP-A-1-111843, and JP-A-1-146308.

[0006]

There are many points that the two-alloy method according to the prior art is not suitable or insufficient for realizing the truly excellent magnetic properties of the Nd-based magnet alloy. That is, the first energy product is high coercivity of the magnet alloy in the method about 9 _k 0 _e described above, the Nd magnet specific drawbacks that the coercive force is lowered by the temperature rise
Therefore, the magnet properties are insufficient in practical use. The biggest problem is the magnetic field orientation. In the first method, an alloy exhibiting magnetism at room temperature can be obtained by appropriately selecting the composition. However, since the alloy obtained by the liquid quenching method becomes an amorphous amorphous phase or a fine crystal, the alloy is formed into a fine powder and a magnetic field. A specific crystal orientation cannot be oriented in the direction of the magnetic field even if it is oriented in a magnetic field. Therefore, even if the mixed raw material alloy powder is compacted in a magnetic field, the orientation of the compact obtained is poor, and sufficient magnet properties cannot be obtained after sintering.

In the second method, R ₂ in the magnet alloy is
The phase coexisting with the Fe ₁₄ B compound is the Nd-rich phase or the Nd ₁₊ XFe ₄ B ₄ phase, and both phases do not show magnetism at room temperature. Therefore, compounds with no magnetism are mixed
Even disturbs the orientation of the non-magnetic particles child by not obtained excellent magnet magnetic properties. Also, in the third method using various elements and various compounds as powders to be mixed, since these compounds do not have magnetism, the demagnetizing field increases during orientation in a magnetic field, and the effective magnetic field strength decreases. Therefore, the rotation of the magnetic particles in the direction of the magnetic field becomes insufficient, and the orientation is disturbed.

In the third method, there is a proposal to improve the magnetic properties by using a low melting point element or alloy in the powder to be mixed. This is based on the idea that nucleation sites such as lattice defects and oxide phases existing at the grain boundaries of the R ₂ Fe ₁₄ B compound are removed and the grain boundaries are cleaned to improve the coercive force. However, the presence of the low melting point phase is actually a disadvantageous condition for improving the magnetic properties for the following reasons. If the low-melting phase is melted from, for example, around 660 ° C., the viscosity of the low-melting phase becomes considerably small at an actual sintering temperature of 1,100 ° C. As a result, the compact shrinks due to liquid phase sintering, and at the same time, the viscosity of the melt surrounding the grains is low, so that the rotation of the magnetic particles easily occurs, the orientation is disturbed, and the magnetic properties deteriorate. In other words, a desirable liquid phase component in the liquid phase sintering of the Nd magnet needs to maintain an appropriate viscosity without disturbing the orientation of the particles, and also to densify the compact and sufficiently clean up the grain boundaries. In the conventional two-alloy method, the roles of the magnetic field orientation and the coercive force improvement involving the liquid phase component are both sufficiently taken into consideration, and the magnetism and melting point of the liquid phase alloy component are appropriately adjusted so that these become the optimum conditions. I didn't adjust it. An object of the present invention is to improve the above-mentioned drawbacks of the two-alloy method and to provide a method for producing a rare-earth permanent magnet having excellent balanced magnetic properties.

[0009]

Means for Solving the Problems In order to solve the above problems, the present inventors have basically reviewed the two-alloy method, and it is sufficient to properly select and combine the types and characteristics of the constituent phases of the magnetic material. The present inventors have found that satisfactory and well-balanced magnetic properties can be obtained, and have studied the manufacturing conditions in detail to complete the present invention. The gist of the present invention is that A alloy is mainly composed of R ₂ Fe ₁₄
B phase (where R is at least 1 mainly composed of Nd, Pr, Dy)
And alloys composed of representative species more rare earth elements), the B alloy R, Co, Fe, B, contains Ga, and as a phase in the alloy R ₂ T ¹ ₁₄ B phase and / or the R-rich phase ( Where R
Same as above, T ¹ represents a transition metal element mainly Fe, a Co) and RT ² ₄ L-phase, RT ² _3-phase, RT ² ₂ phase, R ₂
T ² ₇ phase and RT ² ₅ phase (wherein R is as defined above, T ² is
Transition metal elements mainly composed of Fe and Co, the same transition metals and Ga
And B, one or two of which L represents B or B and Ga)
An alloy consisting of a mixed phase with one or two or more of the five phases described above is mixed. B alloy powder is mixed in an amount of 99 to 70% by weight with A alloy powder in an amount of 1 to 30% by weight. A method for producing a rare earth permanent magnet, which is performed by press-forming in a magnetic field, sintering the formed body in a vacuum or an inert gas atmosphere, and further performing aging heat treatment at a low temperature equal to or lower than the sintering temperature. is, RT ² ₄ L phase contained in the B alloy, RT ² _3-phase, RT ² ₂
Phase, an R ₂ T ² ₇ phase and RT ² ₅ Phase five least one of a melting point of 1,155 ° C. or less of the intermetallic compound 700 ° C. or more phases of the constituent phases of at least one or more phases at room temperature A method for producing a rare earth magnet, wherein the magnetic material has a Curie temperature as described above, and at least one phase is a magnetic material having a Curie temperature and a crystal magnetic anisotropy of room temperature or higher.

Hereinafter, the present invention will be described in detail. The present invention relates to a rare-earth permanent magnet (hereinafter referred to as a magnet alloy C) called a so-called two-alloy method.
A) as a raw material, the A alloy serving as a raw material is mainly composed of a R ₂ Fe ₁₄ B-former phase, and R is L containing Y.
a, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
At least one or more rare earth elements mainly composed of Nd, Pr, and Dy selected from b, Dy, Ho, Er, Tm, Yb, and Lu. The alloy A is cast by melting the raw material metal in a vacuum or an inert gas, preferably an Ar atmosphere. The raw materials are pure rare earth elements and rare earth alloys , pure iron,
Ferroboron, and further use these alloys ,
Trace impurities inevitable in general industrial production shall be included. The obtained ingot is made of R ₂ Fe ₁₄ B
Since the phase is formed by the peritectic reaction between аFe and the rare earth-rich phase, the аFe phase, the R-rich phase, the B-rich phase and the like may remain even after casting due to solidification segregation.
In the present invention, since it is desirable that the R ₂ Fe ₁₄ B phase in the A alloy is large, a solution treatment is performed if necessary. The conditions are 700 to 1,200 under vacuum or Ar atmosphere.
Heat treatment may be performed in a temperature range of ° C. for 1 hour or more.

[0011] B alloy mainly R, Co, Fe, an alloy consisting of B and Ga, the composition formula _{R a Fe b Co c B d} Ga e ( here R
Is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, T
at least one or more rare earth elements mainly composed of Nd, Pr and Dy selected from m, Yb and Lu, 15 ≦ a ≦ 40, 0 ≦ b ≦ 8
0, 5 ≦ c ≦ 85, 0 ≦ d ≦ 20, 0.1 ≦ e ≦ 20, a + b + c + d + e = 10
0 (each atomic%)), and the raw material metal is melted and cast in a vacuum or an inert gas, preferably an Ar atmosphere, like the A alloy. As a raw material metal, a pure rare earth element, pure iron, pure cobalt, pure gallium, ferroboron, or the like is used, and it is assumed that trace impurities that are inevitable in general industrial production are included. If the amount a of the rare earth element R is less than 15 atomic%, R
Is too small to obtain a sufficient amount of liquid phase in the sintering process, the density of the sintered body does not increase, and if it exceeds 40 atomic%, the melting point of the alloy becomes too low and the effect of improving the magnetic properties is lost . RT ² The amount c of Co is less than 5 atomic% ₄ L
Phase, RT ² _3-phase, RT ² ₂ phase, no longer phase of R ₂ T ² ₇ phase and RT ² ₅ equality appeared not effect of improving magnetic characteristics. When the amount e of Ga exceeds 20 atomic%, the saturation magnetic flux density of the alloy becomes small and high magnetic properties cannot be obtained. Further, a B alloy can be produced by heat-treating a ribbon obtained by the liquid quenching method. That is, in the liquid quenching method, the quenched B alloy is in an amorphous phase or a fine crystalline phase, and is heated at a temperature higher than the crystallization temperature for a certain time to cause crystallization or recrystallization growth. Thus, the predetermined constituent phase of the present invention can be precipitated.

[0012] Phase mainly appears in B alloy in this composition range, R ₂ T ¹ ₁₄ B phase (mainly R ₂ Fe ₁₄ B phase)
R-rich phase (wherein R is as defined above, T ¹ represents a transition metal element Fe, a Co mainly) and RT ² ₄ L-phase, RT
² _3-phase, RT ² _2-phase, R ₂ T ² ₇ phase and RT ² ₅ phase (here R
Is the same as above, T ² is a transition metal element mainly composed of Fe and Co, one or two of the same transition metal and Ga and B, and L represents B or B and Ga. Is characterized by using a B alloy containing at least one or two or more phases out of two phases before and five phases after. Note that the phase described as the R-rich phase represents all the various R-rich phases in which the R component is 35 atomic% or more. Of these seven types of phases, the R ₂ Fe ₁₄ B phase and the R-rich phase are phases that have also appeared by a conventionally known two-alloy method or a normal rare-earth iron-boron-based magnet alloy manufacturing method. is there. The rest of the RT ² ₄ L-phase,
RT ² _3-phase, RT ² _2-phase, R ₂ T ² ₇ phase, five phase RT ² ₅ phase emerges by adding 5 atomic% or more Co in B alloy, 2 alloy of the present invention It is unique in the law.
These five phases first appeared as an equilibrium phase in the B alloy by adding 5 atomic% or more of Co. FIG.
RT ² ₄ in one example the cast structure photograph taken by a scanning electron microscope of B alloy, as determined by the composition EPMA (electron probe X-ray microanalyzer) and X-ray analysis of the present invention
The presence of the L phase, RT ² ₃ phase, RT ² ₂ phase and R rich phase is clearly shown. The two-alloy method according to the present invention is characterized in that at least one of these five phases is contained in the B alloy, and the presence of these phases realizes high magnetic properties in a magnet alloy produced by the two-alloy method. I was able to.

In the present invention, the above alloys A and B are mixed at a specific ratio, and a magnet alloy C is produced by a so-called two-alloy method, whereby high magnetic properties can be exhibited. Less than,
The reason why the presence of these mixed phases in the B alloy resulted in the high magnetic properties of the magnet alloy will be described. The first reason is that these mixed phases have a Curie temperature above room temperature, which was achieved by the additive element Co. Further, these phases have magnetocrystalline anisotropy in a specific crystal direction. Therefore, when a B alloy powder containing one or more of these phases as a main constituent phase is mixed with an A alloy powder mainly composed of R ₂ Fe ₁₄ B phase and oriented in a magnetic field, the B alloy also becomes a ferromagnetic material. , Almost all the grains are oriented with the crystal direction aligned in the direction of the applied magnetic field, and high magnetic properties can be obtained.

The second reason is that the melting points of these phases are in a temperature range suitable for liquid phase sintering of Nd-based rare earth magnets, ie, 700 ° C.
It should be in the range of not less than 1,155 ° C. This temperature range is higher than the melting point of the Nd-rich phase (500-650 ° C),
In addition, the temperature is lower than the melting point of the R ₂ Fe ₁₄ B phase (1,155 ° C.). Therefore, at the normal sintering temperature, only the Nd-rich phase is present and the viscosity of the melt does not decrease too much, so that the orientation of the particles is not disturbed, and the liquid phase is formed. The density is increased while cleaning the grain boundaries, and high magnet properties are realized after sintering. Another effect of the addition of Co is an improvement in corrosion resistance. The B alloy contains more rare earth elements than the A alloy and thus is easily oxidized and deteriorated. However, by adding Co, the oxidized deterioration can be prevented and stable magnetic properties can be obtained. Dy and Ga added to the B alloy are present in large amounts near the grain boundaries even after co-sintering, and have the effect of improving the coercive force of the magnet alloy C.

Next, a method for producing the magnet alloy C by the two-alloy method will be described. The A alloy and the B alloy obtained as described above are separately mixed and then mixed at a predetermined ratio. The pulverization is performed by wet or dry pulverization. Rare earth alloys are very active, and are used in an atmosphere such as Ar or nitrogen in the case of dry grinding and in a non-reactive organic solvent such as Freon in the case of wet grinding in order to prevent oxidation during grinding. Done. The mixing step is also performed in an inert atmosphere or a solvent as necessary. The pulverization is generally performed stepwise as coarse pulverization and fine pulverization, but mixing may be performed at any stage.
That is, a predetermined amount may be mixed after coarse pulverization and then finely pulverized, or may be mixed at a predetermined ratio after all pulverization is completed. It is necessary that both the A and B alloys are uniformly mixed with substantially the same average particle size. The average particle size is preferably in the range of 0.5 to 20 μm, and if it is less than 0.5 μm, it is easily oxidized and deteriorated.
If it exceeds sinterability, the sinterability deteriorates.

The mixing ratio of the A alloy powder and the B alloy powder is
It is preferable to mix the B alloy powder in the range of 1 to 30% by weight with respect to 99 to 70% by weight of the alloy powder. If the B alloy powder is less than 1% by weight, the sintering density does not increase and no coercive force is obtained, If it exceeds 30% by weight, the proportion of the nonmagnetic phase after sintering becomes too large, and the residual magnetic flux density becomes small. The obtained mixed powder of the alloy A and the alloy B is molded into a desired size by a molding press in a magnetic field, and further subjected to a sintering heat treatment. Sintering is performed in a vacuum or argon atmosphere at a temperature in the range of 900 to 1200 ° C. for 30 minutes or more, followed by aging heat treatment at a temperature lower than the sintering temperature for 30 minutes or more. After sintering, magnet alloy C
The compact has a density of 95% or more in terms of true density, and a high residual magnetic flux density can be obtained.

[0017]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to examples, but the present invention is not limited thereto. (Example 1, Comparative Example 1) Nd having a purity of 99.9% by weight,
Composition formula 12.5Nd-6B-81.5 using Fe metal and ferroboron
After an alloy of Fe (atomic%) was melt-cast in an Ar atmosphere of a high-frequency melting furnace, the ingot was solution-solutioned at 1,070 ° C. in an Ar atmosphere for 20 hours. This is an A1 alloy. Next, an alloy of the composition formula 20Nd-10Dy-20Fe-6B-4Ga-40Co is melt-cast in an Ar atmosphere using a high-frequency melting furnace using Nd, Dy, Fe, Ga, Co metal and ferroboron having a purity of 99.9% by weight. This was used as a B1 alloy. A1 alloy ingot and B1 alloy ingot are each roughly crushed in a nitrogen atmosphere.
30 mesh or less, then B1 90% by weight of A1 alloy coarse powder
The alloy coarse powder was weighed at 10% by weight and mixed in a nitrogen-purged V blender for 30 minutes. This mixed coarse powder was finely pulverized with a jet mill using high-pressure nitrogen gas to an average particle size of about 5 μm. The obtained mixed fine powder was press-molded at a pressure of about 1 Ton / cm ² while being oriented in a magnetic field of 15 kOe. Then
This compact was sintered at 1,070 ° C for 1 hour in a sintering furnace in an Ar atmosphere, and further quenched by aging heat treatment at 530 ° C for 1 hour.
Magnet alloy C1 was produced.

For comparison, an alloy having the same composition as in Example 1 was produced by a conventional one-alloy method, and Comparative Example 1 was obtained. That is,
The same composition (magnet alloy C1) as after mixing both alloys A1 and B1 was weighed from the beginning, melted, pulverized, sintered, and subjected to aging heat treatment.
The magnet characteristics were compared with the magnet by the alloy method (magnet composition C1 of Example 1). The composition of this magnet alloy C1 was 13.1 Nd- in both Example 1 by the two-alloy method and Comparative Example 1 by the one-alloy method.
0.8Dy-3.5Co-6.0B--0.3Ga-76.6Fe. Table 1 shows the values of the magnetic properties and the sintered body densities obtained for both sintered body magnets of Example 1 and Comparative Example 1. The magnetic properties of Example 1 are almost the same as those of Comparative Example 1, but the density of the sintered body is almost the same. However, Example 1 is far superior in all values such as residual magnetic flux density, coercive force, and maximum energy product. I have. As described above, even if the composition of the magnet alloy C is exactly the same, there is a considerable difference in the magnetic properties, indicating that the two-alloy method is a very effective method for improving the magnetic properties of the Nd magnet. The metal structure of the B1 alloy in the cast state is shown in FIG. 1 by a backscattered electron image photograph of a scanning electron microscope. As can be seen from the light and dark of the photograph, there are four main constituent phases in the B1 alloy. Each phase, EPMA by (electron probe X-ray microanalyzer) and X-ray analysis, RT ² ₄ L-phase as shown in FIG, RT ² _3-phase, RT ² ₂
Phase, an R-rich phase.

(Examples 2 to 11 and Comparative Examples 2 to 11) As shown in Table 1, corresponding to the alloy compositions of Examples 2 to 11, a composition alloy of A1 and A2 was prepared as an A alloy. B as alloy
A composition alloy of Nos. 2 to B9 was prepared, pulverized in the same manner as in Example 1, mixed at a predetermined ratio, molded in a magnetic field, and sintered (1,05).
0 to 1,120 ° C x 1 hour), Aging treatment (500 to 600 ° C x 1)
To 10 hours) to produce 2-alloy magnet alloys C2 to C11, and their magnetic properties were measured and are shown in Tables 1 and 2. For comparison, magnet alloys C2 to C11 were manufactured under the same conditions as in Examples 2 to 11 except that an alloy having the same composition as in Examples 2 to 11 was prepared by the one alloy method, and the magnetic properties were measured. ~ 11
The results are shown in Tables 1 and 2.

[0020]

[Table 1]

[Table 2]

[0021]

The rare-earth permanent magnet produced according to the present invention has several steps more excellent magnetic properties than conventional rare-earth magnets having the same composition by effectively utilizing expensive additional elements, and has a high coercive force and high coercive force. It has become possible to provide a high-performance magnet with a good balance of residual magnetic flux density and high energy product. Therefore, it is expected that it will be widely used as a high-performance magnet for various electric and electronic devices in the future.

[Brief description of the drawings]

FIG. 1 is a scanning electron micrograph showing a metal structure of a B1 alloy of Example 1 in a cast state.

[EXPLANATION OF SYMBOLS] RT ² ₄ L-phase RT ² _3-phase RT ² ₂ phase R-rich phase

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C22C 33/02 B22F 3/00-3/26 H01F 1 / 057,1 / 08 H01F 41/02

Claims (5)

(57) [Claims] An alloy A is mainly composed of R ₂ Fe ₁₄ B phase (here, R
Represents at least one or more rare earth elements mainly composed of Nd, Pr and Dy), and the B alloy is composed of R, Co, Fe,
R ₂ T ¹ ₁₄ containing B, Ga and as a constituent phase in the alloy
B-phase and / or R-rich phase (wherein R is as defined above, T ¹ represents a transition metal element mainly Fe, a Co) and RT ² ₄ L-phase, RT ² _3-phase, RT ² ₂ phase, R ₂ T ² ₇ phase and RT ² ₅ phase (wherein R is as defined above, T ² is a transition metal element mainly Fe, and Co, among the transition metals and Ga and B 1
Or two or more, and L represents B or B and Ga), and an alloy comprising a mixed phase of one or more of the five phases;
B alloy powder is mixed in an amount of 1 to 30% by weight with respect to 99 to 70% by weight of the A alloy powder, and the mixed alloy powder is compacted under pressure in a magnetic field, and the compact is sintered in a vacuum or an inert gas atmosphere. And a aging heat treatment at a low temperature not higher than the sintering temperature. Wherein RT ² ₄ contained in B alloy according to claim 1
L-phase, RT ² _3-phase, RT ² ₂ phase, a melting point of at least one or more phases of the five constituent phases of R ₂ T ² ₇ phase and RT ² ₅ phase 70
A method for producing a rare earth permanent magnet, which is an intermetallic compound having a temperature of 0 ° C. or more and 1,155 ° C. or less. 3. A rare-earth magnet wherein at least one of the five constituent phases contained in the B alloy according to claim 1 or 2 is a magnetic material having a Curie temperature of room temperature or higher. Manufacturing method. 4. A magnetic material in which at least one of the five constituent phases contained in the B alloy according to claim 1 or 2 or 3 has a Curie temperature of room temperature or higher and a magnetocrystalline anisotropy. A method for producing a rare earth magnet, comprising: 5. The alloy A, B alloy and A according to claim 1.
A method for producing a rare earth magnet, characterized in that the average particle size of the B mixed alloy powder is in the range of 0.5 to 20 μm.