JP2002057017A - Isotropic powdery magnet material, its manufacturing method, and bonded magnet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an SmFeN-based magnet material which is manufactured by quenching a molten magnet material by means of a quenching roller and successively nitriding the material, can be formed in fine crystals even when the molten material is not cooled at an excessively fast cooling speed, does not become excessively thin flakes, and has high magnetic characteristics so that a high-performance bonded magnet can be manufactured. SOLUTION: The powdery magnet material having a TbCu7 structure and a characteristic coercive force of 7-15 kOe is obtained by mixing two kinds of alloy components respectively expressed by SmxFe100-x-vNv and SmxFe100-x-y-zM1yNv or SmxFe100-x-z-vM2zNv (wherein, M1 and M2 respectively denote Hf or Zr, and one or two or more kinds selected from among Si, Nb, Ti, Ga, Al, Ta, and C, and 7<=x<=12, 0.5<=v<=20, 0.1<=y<=1.5, and 0.1<=z<=1.0) together and melting the mixture. Then the molten mixture is quenched by injecting the molten mixture upon the quenching roller while the roller is rotated at a peripheral speed of 30-45 m/sec and heating obtained flaky powder to 500-900 deg.C in an inert atmosphere. After heating, the powder is nitrided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a permanent magnet powder which is excellent in that it has good magnetic properties, particularly exhibits a large maximum energy product and a high coercive force, and can be produced at low cost, and a method for producing the same. The present invention also relates to a bonded magnet using the magnet powder.

[0002]

2. Description of the Related Art Rare earth based isotropic bonded magnets are characterized by high energy product and good moldability.
It is widely used mainly for motor parts used for various electronic devices and OA devices. This kind of equipment has been increasingly improved in performance and downsizing, and accordingly, the bonded magnet used has been required to have higher performance.

At present, the mainstream of the rare earth bonded magnets is NdFe manufactured by a manufacturing method called a roll quenching method.
This is an isotropic bonded magnet in which B-based magnet powder is bound with a binder resin. The maximum energy product of these bonded magnets is about 8 to 12 MOe as a compression molded bonded magnet,
It is about 5 to 8 MOe as an injection-molded bonded magnet. Although isotropic magnets have a smaller maximum energy product than anisotropic magnets, there is no need to apply a magnetic field at the time of molding, so there is an advantage that productivity is high and the degree of freedom of a magnetization pattern is high. These advantages have been accepted by the market, and the majority of rare earth bonded magnets use isotropic magnet materials.

Recently, Sm has been used as a magnet material which can be expected to have high performance equal to or higher than that of NdFeB magnet alloys.
Attention has been paid to FeN-based magnet alloys. For example, Th ₂ Zn ₁₇ is disclosed in Japanese Patent No. 2703218 and the corresponding US Pat. No. 5,186,766.
An SmFeN-based anisotropic magnet material having a type crystal structure is disclosed. Since this material is anisotropic, it is necessary to apply a magnetic field during molding, and the manufacturing process is more complicated than when using an isotropic magnet material.

[0005] An isotropic SmFeN magnet material is described in J. Am. Appl. Phys. (Journal of Applied Physics) 70 6 (1991) 31
There is a research report on pages 88-3196. In this document,
The crystal structure of Sm—Fe powder produced by the roll quenching method and the crystal structure of SmFeN obtained by nitriding the powder differ depending on the composition and cooling conditions, and are of Th ₂ Zn ₁₇ type or
It is reported to have a bCu ₇ type crystal structure.

In this paper, the cooling roll is set at 10 m / sec.
The magnetic properties of the magnet powder obtained by nitriding the powder obtained by rotating at a peripheral speed of 50 m / sec and 60 m / sec and quenching are shown. The best magnetic properties have been obtained at a peripheral speed of 60 m / s, which are as follows: Crystal structure Coercive force iHc Maximum energy product (BH) max Th ₂ Zn ₁₇ type 16.7 kA / cm 65.6 kJ / m ³ (21.0 kOe) (8.24 MGOe) TbCu ₇ type 4.9 kA / cm 69.6 kJ / m ³ (6.2 kOe) (8.75 MGOe)

The latter TbCu ₇ type has insufficient coercive force as a magnet. This document also states that "to obtain high hard magnetic properties, it is necessary to reduce the TbCu _7- type structure as much as possible", that is, to select a Th ₂ Zn _17- type structure. . However, although a high coercive force can be obtained with a Th ₂ Zn ₁₇ type structure, the maximum energy product is good, in the order of 8 MGOe, and that of the currently widely used NdFeB-based quenched magnet powder has reached about 15 MGOe. Given that, the magnet materials presented in this paper are not practical.

Thereafter, efforts were continuously made to improve the performance of the SmFeN-based quenched powder magnet, and practical magnetic characteristics were obtained. Specific examples include “Powder and Powder Metallurgy”, Vol. 46, No. 6, (1999), pp. 581-588, and US Pat. No. 5,750,044. The SmZrFeCoN-based isotropic bonded magnet disclosed therein has improved magnetic properties as compared with the magnet using the SmFeN-based quenched powder described in the above-mentioned 1991 paper, and has a performance close to that of the NdFeB-based isotropic bonded magnet. Show.

However, as can be seen from the graph described in the above-mentioned US Patent Publication, high-speed cooling with a roll peripheral speed of 50 to 100 m / sec is required in order to produce the developed magnetic material. This is several times faster than the roll quenching that has conventionally been performed in the production of NdFeB-based magnet powder. In order to perform cooling at such a high peripheral speed, there is first a mechanical problem. Although it can be overcome, even if it can be overcome, the production yield of the quenched ribbon obtained in the quenching process will be poor, or the product quality will be reduced due to mixing of insufficiently cooled powder, and the production of magnet powder As such, difficulties arise. Relatively expensive Zr as raw material
Is a disadvantage of the SmZrFeCoN-based magnet.

The present inventors have studied with the aim of solving the above-mentioned problems in the SmFeN-based magnet material and providing an SmFeN-based isotropic magnet material having high magnetic performance at low cost.
By adopting conditions different from those of the known production method, it is not necessary to use expensive raw materials, and high magnetic properties can be obtained without cooling at an extremely high cooling rate. It has been found that a powder magnet material that is advantageous for can be produced.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to make use of the above-mentioned new knowledge obtained by the present inventors and to provide an SmFeN-based powder magnet material obtained by powder production by roll quenching of molten metal and subsequent nitriding. To provide a bonded magnet having high magnetic properties despite being cooled at an extremely fast cooling rate, and a suitable method for producing such a powdered magnetic material. is there.

[0012]

A basic aspect of the SmFeN-based powder magnet material of the present invention is a flake-like isotropic SmFeN-based magnet material produced by nitriding a magnet alloy powder obtained by a roll quenching method. In the powder magnet material, in atomic%, Sm _x Fe _100-xv N _v [where, 7 ≦ x ≦ 12 and 0.5 ≦ v ≦ 20. And a TbCu ₇ type crystal structure, and a flake thickness of 10 to 40 μm.

One preferred modification of the SmFeN powder magnetic material of the present invention is a flake-like isotropic SmFeN powder magnet material produced by nitriding a magnet alloy powder obtained by a roll quenching method. atom%
In the formula, Sm _x Fe _100-xy-v M ¹ _{y Nv} [where M ¹ is one or two selected from the group consisting of Hf and Zr, and 7 ≦ x ≦ 12; 1 ≦
y ≦ 1.5 and 0.5 ≦ v ≦ 20. And a TbCu ₇ type crystal structure, and a flake thickness of 10 to 40 μm. According to this aspect, both the saturation magnetization and the coercive force are increased, and the maximum energy product is improved.

Another modification of the SmFeN-based powder magnet material of the present invention is a flake-like isotropic SmFeN-based powder magnet material produced by nitriding a magnet alloy powder obtained by a roll quenching method. % _{in, Sm x Fe 100-xzv M} 2 z N v [ wherein, ^{M 2} is, Si, Nb, Ti, Ga , Al, Ta
And C are one or more selected from the group consisting of: 7 ≦ x ≦ 12, 0.1 ≦ z ≦ 1.0, and
0.5 ≦ v ≦ 20. And a TbCu ₇ type crystal structure, and a flake thickness of 10 to 40 μm. In this embodiment, the coercive force is increased, since the saturation magnetization is slightly lower, maximum energy product is a flat than that without addition of M ^2, is advantageous raw material costs as low.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention for producing an SmFeN-based powder magnet material according to the basic aspect described above is a method for producing the flake-like isotropic SmFeN-based powder magnet material described above, wherein _{in, Sm x Fe 100-xv N} v [ wherein, 7 ≦ x ≦ 12, and a 0.5 ≦ v ≦ 20. ] And a TbCu ₇ structure.
m and Fe are blended and melted, and the molten alloy is sprayed onto a cooling roll rotating at a peripheral speed of 30 to 45 m / sec to be rapidly cooled, and the obtained flake-like powder is cooled in an inert atmosphere. After a heat treatment at 500 to 900 ° C., followed by nitriding.

The method of the present invention for producing the SmFeN-based powder magnet material according to the above-mentioned preferred embodiment is a method for producing the above-mentioned flake-shaped isotropic SmFeN-based powder magnet material, wherein Sm _x Fe _{100-x is used.} during ^{_{-y-v M 1 y N v}} [ equation, ^{M 1} is a one or two chosen from the group consisting of Hf and Zr, 7 ≦ x ≦ 12,0.1 ≦
y ≦ 1.5 and 0.5 ≦ v ≦ 20. And an alloy component comprising Sm, Fe and M are blended and melted so as to have a TbCu ₇ structure, and the molten alloy is sprayed onto a cooling roll rotating at a peripheral speed of 20 to 45 m / sec. After quenching, the obtained flake-like powder is subjected to a heat treatment at 500 to 900 ° C. in an inert atmosphere, followed by nitriding.

The SmFe of another modified embodiment described above
The method of the present invention for producing a N-based powder magnet material, a method of making the flaked isotropic SmFeN-based powder magnet material, in _{atomic%, Sm x Fe 100-xzv} M 2 z N v [Wherein, M ² is Si, Nb, Ti, Ga, Al, Ta
And C are one or more selected from the group consisting of: 7 ≦ x ≦ 12, 0.1 ≦ z ≦ 1.0, and
0.5 ≦ v ≦ 20. And an alloy component comprising Sm, Fe and M are blended and melted so as to have a TbCu ₇ structure, and the molten alloy is melted at a peripheral speed of 20 to 45 m / m.
Sprayed on a cooling roll rotating in seconds, quenched, and the obtained flaky powder was heated to 500 to 900 ° C in an inert atmosphere
And then nitriding.

The roll quenching of the molten metal is suitably performed in an Ar gas atmosphere at a pressure of 0.0001 Torr to 2 atm. At normal pressure for easy operation, usually no problem.

Conventionally, pure Cu having a high thermal conductivity has been used as the material of the cooling roll in order to perform cooling as quickly as possible. However, according to the experience of the inventors,
It may be more appropriate to use a cooling roll made of a Cr-Cu alloy or a Be-Cu alloy. These alloys have a thermal conductivity of only 50-60% of pure Cu. This indicates that rapid cooling is not always better as the cooling rate is higher, but that a certain suitable range exists.

The reasons for limiting the alloy composition in the magnetic powder of the present invention as described above are as follows.

Sm: 7 to 12 atomic% If Sm is less than 7%, α-Fe
Is mixed in a large amount, and the coercive force of the magnet is low. If the amount exceeds 12%, the residual magnetic flux density decreases, and a large maximum energy product (BH) max cannot be obtained.

M ^1, ie, one or two selected from the group consisting of Hf and Zr: 0.1 to 1.5 atomic% By adding these elements in appropriate amounts, the squareness and coercive force are increased, and The energy product increases. This effect becomes apparent with addition of 0.1% or more, but when added excessively, the squareness and the coercive force are lowered, and the maximum energy product also decreases. Therefore, the upper limit is set to 1.5%.

[0023] C other than one of the ^{M 2,} ie Si, Nb,
One or more selected from the group consisting of Ti, Ga, Al and Ta: 0.1 to 1.0 atomic% These elements serve to refine crystal grains when this magnet alloy is rapidly cooled. There is no need for extreme quenching. This effect becomes evident at additions of 0.1% or more. From the viewpoint of magnetic properties, both are unfavorable, so the addition of 1.0% is limited to secure a high residual magnetic flux density.

C: 0.1 to 1.0 at% When M is present in the presence of M, the residual magnetic flux density increases as compared with the case where C is not present. The effect is that C is 0.1
% Is recognized. If it exceeds 1.0%, the coercive force decreases and the maximum energy product also decreases.

In the above basic alloy composition and in the alloy compositions of any of the modified embodiments, the Sm of 3
0 atomic% or less can be replaced by Ce. By this substitution, the magnetic properties of the product magnet powder and, consequently, the magnetic properties of the bonded magnet can be enhanced. Sm also
Rare earth elements other than Ce, for example, Y, Nd, Pr,
It can be replaced with Ce, La or Gd. In this case, no improvement in magnetic properties can be expected, but it is possible to lower the requirement for the purity of the raw material and reduce the cost. However, the replacement amount is still limited to 30 atomic%, and if it exceeds this, the coercive force is significantly reduced.

Similarly, in the basic alloy composition described above and in the alloy composition of any of the modified embodiments, F
35 atomic% or less of e can be replaced by Co. By this substitution, the magnetic properties of the product magnet powder and, consequently, the magnetic properties of the bonded magnet can be enhanced. Fe
Replacing part of Co with Co also has the advantage of increasing the Curie point and giving the magnet high temperature resistance. However, the addition of a large amount of Co is disadvantageous because it reduces the residual magnetic flux density and increases the cost, and the replacement amount is 35%, which is the practical limit.

The powder magnet material of the present invention has a TbCu ₇ structure and has an average crystal grain size of 10 nm to 0.5 μm.
To explain this, first, in order to generally exhibit high magnetic performance in an isotropic magnet material, it is necessary that the material has a high saturation magnetization and a large coercive force.

To increase the saturation magnetization, the proportion of Fe contained in the crystal lattice of SmFeN should be increased as much as possible. SmFe which is an alloy material of SmFeN
Is known to have several crystal structures, and Sm obtained by a melting / casting method which is a normal alloy manufacturing process.
The Fe alloy has a rhombohedral crystal structure of the Th ₂ Zn ₁₇ type, which is an equilibrium phase, and the ratio of the number of atoms of Sm: Fe in the crystal lattice is fixed at 2:17. The content is constant at 89.5 atomic%.

On the other hand, the above-mentioned reference J. et al. Appl. Phys
s. As revealed in Vol. 70, No. 6, pp. 3188-3196, the alloy produced by the roll quenching method is:
Depending on the ratio of Sm: Fe and the cooling rate, not only the Th ₂ Zn _17- type crystal structure which is an equilibrium phase but also a TbCu _7- type hexagonal crystal structure may be formed. The TbCu ₇ type structure is a structure in which the Sm atom in the Th ₂ Zn ₁₇ type structure is randomly substituted with two Fe atoms, so-called dumbbell Fe. The substitution amount is not constant, but changes according to the ratio between Sm and Fe. Thus, for the purpose of realizing high saturation magnetization, TbCu type ₇ is more preferable. Depending alloy composition and by the manufacturing conditions, the phase and the other _Th 2 _{Zn 17} -type structure of the TbCu ₇ structure, sometimes alpha-Fe phase comes mixed slightly, its amount is more than 10% If so, the magnetic properties are not so affected.

In order to realize a large coercive force, it is desirable that the crystal grain size of the material is appropriately reduced. In general, in isotropic rare-earth magnet materials, fine crystal grains are an essential condition for realizing high coercive force, and specifically, a crystal grain size of 10 to 50 nm is preferable. ing. The magnet material of the present invention has a preferable range of crystal grain size,
One of the features is that a high coercive force can be obtained up to a particle size as large as 0.5 μm at a maximum, which is larger than the conventionally preferable range. This is the reason for selecting the range of the crystal grain size from 10 nm to 0.5 μm.

Further, in the powder magnet material of the present invention, the thickness of the flake powder is 10 to 40 μm. This thickness is a method that does not perform extremely rapid roll quenching, specifically,
The roll peripheral speed of 30 to 45 m / sec in the basic mode and 20 to 45 m / sec in the modified mode.

The magnet powder of the present invention can be mixed with an appropriate binder and molded into a desired shape to obtain a bonded magnet. The means is optional, for example, compression molding by mixing with a thermosetting resin such as an epoxy resin,
Any of the known bonded magnet manufacturing techniques can be used, such as injection molding or extrusion molding by mixing with a thermoplastic resin such as nylon.

[0033]

The powder magnetic material of the present invention can be used for the SmFeN magnet powder produced by quenching the roll of the molten metal and then nitriding, compared with the extremely high cooling rate required by the known technology. Despite cooling at a low cooling rate that is easy to implement, the crystals are obtained as flakes that are reasonably fine and of some thickness. Therefore, according to the present invention, not only mechanical problems in the production of magnet powder are reduced, but also problems of flake yield and product quality can be avoided in principle, and a powder magnet having always high magnetic properties The material is obtained.

What is noteworthy is the intrinsic coercive force. As shown in the following examples, it is easy to obtain a magnet powder having a coercive force of 7 kOe or more. In addition, a product having an excellent coercive force with a high maximum energy product can be manufactured.

It is also worth noting that the use of the powder of the present invention, in which the thickness of the flake-like powder is relatively thick, makes it easier to form a bonded magnet than using a thin powder according to the prior art. When filling the mixture of the magnet powder and the resin binder into the mold of the press, thick flakes naturally have better filling properties than thin flakes, and an improvement in magnet density, that is, an improvement in magnetic force can be obtained. The high filling property also contributes to the improvement of the dimensional accuracy of the bonded magnet.

As described above, according to the present invention, a high-performance bonded magnet can be provided at a low cost, and the performance of various devices using the bonded magnet can be further improved.
It is possible to respond to requests for miniaturization and cost reduction.

[0037]

EXAMPLES The method of manufacturing a magnet powder, the conditions of heat treatment and subsequent nitriding treatment, the method of manufacturing a bonded magnet, and the method of measuring the magnetic properties of a magnet powder and a bonded magnet, which are common to the following examples, are as follows. Each is as follows.

[Manufacture of Magnet Powder] A raw material of a magnet alloy is put into a quartz nozzle having a bottom with a pore having a diameter of 0.5 mm, melted by high frequency in an Ar atmosphere, and then rotated at high speed by a copper roll. It is quenched by injecting molten metal on top,
I got a ribbon. The roll peripheral speed was variously changed, and the values are shown in the tables of the examples. The collected ribbons were pulverized with a pin mill, and the resulting flake-like powder was selected to have a thickness of about 300 μm.
Those passing through the sieve were collected. Flake thickness was measured with a micrometer.

[Heat treatment and nitriding treatment] The collected powder was heated in an Ar atmosphere. Except for Examples 16 and 17, the conditions are 750 ° C. × 10 minutes. Nitriding was performed by placing the heat-treated powder in a tubular furnace and heating to 450 ° C. for 30 minutes while passing a mixed gas of ammonia: hydrogen = 1: 3 (volume ratio). The composition after nitriding is shown in the table of each example together with the flake thickness.

[Method of Manufacturing Bonded Magnet] 2% by weight of an epoxy resin is mixed with a magnet powder, and the mixture is placed in a press mold and mixed.
By compression molding at a pressure of 0 t / cm ² , a diameter of 10 m
Thus, a cylindrical molded product having a height of 7 mm and a height of 7 mm was obtained. The molded body was heated at 150 ° C. × 1 hour in a nitrogen atmosphere to cure the epoxy resin.

[Measurement of Magnetic Properties of Magnet Powder] The magnetic properties of the magnet powder were measured with a vibrating sample magnetometer (VSM).
Here, the calculation was performed assuming that the true density of the magnet alloy was 7.6 g / cm ³ . [Measurement of Magnetic Properties of Bonded Magnet] The magnetic properties of the bonded magnet were measured with a BH loop tracer.

Example 1 SmFeN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 1 was produced. Table 1 summarizes the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
FIGS. 13A to 13D show micrographs of the flaky powder obtained by quenching the No. 18 melt. FIG. 1 shows an X-ray diffraction chart of the No. 18 magnet powder.

[0043]

[Table 1] SmFeN (Part 1) Table 1 SmFeN (Part 2)

Example 2 SmFeHfN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 2 was produced. Table 2 shows the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
14A to 13D show micrographs of the flake powder obtained by rapidly cooling the melt of No. 35. FIG. 2 shows an X-ray diffraction chart of the magnet powder of No. 35.

[0045]

[Table 2] SmFeHfN (Part 1) Table 2 SmFeHfN (Part 2) Table 2 SmFeHfN (Part 3)

Example 3 SmFeZrN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 3 was produced. Table 3 summarizes the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
FIG. 3 shows an X-ray diffraction chart of the magnet powder of No. 35.

[0047]

[Table 3] SmFeZrN (Part 1) Table 3 SmFeZrN (Part 2) Table 3 SmFeZrN (Part 3)

Example 4 SmFeSiN magnet powder and bonded magnet A magnet alloy having the composition shown in Table 4 was produced. Table 4 summarizes the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
FIG. 4 shows an X-ray diffraction chart of the magnet powder of No. 11.

[0049]

[Table 4] SmFeSiN

Example 5 SmFeNbN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 5 was produced. Table 5 summarizes the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
FIG. 5 shows an X-ray diffraction chart of the magnet powder No. 11.

[0051]

[Table 5] SmFeNbN

Example 6 SmFeTiN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 6 was produced. Table 6 summarizes the peripheral speed of the quenching roll, the thickness of the flake-like magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
FIG. 6 shows an X-ray diffraction chart of the magnet powder of No. 11.

[0053]

[Table 6] SmFeTiN

Example 7 SmFeGaN magnet powder and bonded magnet A magnet alloy having the composition shown in Table 7 was produced. Table 7 summarizes the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
FIG. 7 shows an X-ray diffraction chart of the magnet powder of No. 11.

[0055]

[Table 7] SmFeGaN

Example 8 SmFeAlN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 8 was produced. Table 8 summarizes the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
FIG. 8 shows an X-ray diffraction chart of the magnet powder of No. 11.

[0057]

[Table 8] SmFeAlN

Example 9 SmFeTaN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 9 was produced. Table 9 summarizes the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet.
FIG. 9 shows an X-ray diffraction chart of the magnet powder of No. 11.

[0059]

[Table 9] SmFeTaN

Example 10 SmFeCN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 10 was produced. Table 10 shows the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet. The X-ray diffraction chart of the magnet powder of No. 11 is shown in FIG.
Shown in

[0061]

[Table 10] SmFeCN

Example 11 SmCeFeN Magnet Powder and Bonded Magnet A magnet alloy having the composition shown in Table 11 was produced by replacing Sm with Ce in the SmFeN magnet. The peripheral speed of the quenching roll is 40 m / sec. Table 11 summarizes the magnetic properties of the magnet powder and the magnetic properties of the bonded magnet. The X-ray diffraction chart of No. 1 magnet powder is shown in FIG.
1 is shown.

[0063]

[Table 11] SmCeFeN

Example 12 SmFeCoN Magnet Powder and Bond Magnet A part of Fe of the SmFeN magnet alloy was replaced with Co.
A magnet alloy having the composition shown in Table 12 was produced. Table 12 summarizes the peripheral speed of the quenching roll, the thickness of the flake-shaped magnet powder, the magnetic properties of the magnet powder, and the magnetic properties of the bonded magnet. The X-ray diffraction chart of the magnet powder of No. 49 is shown in FIG.
Shown in

[0065]

[Table 12] SmFeCoN (Part 1) Table 12 SmFeCoN (Part 2) Table 12 SmFeCoN (Part 3)

Example 13 SmCeFeCoN Magnet Powder and Bonded Magnet In an SmFeN magnet, by replacing part of Sm with Ce and part of Fe with Co,
A magnet alloy having the composition shown in Table 13 was produced. The peripheral speed of the quenching roll is 40 m / sec. Table 13 summarizes the magnetic properties of the magnet powder and the magnetic properties of the bonded magnet.

[0067]

[Table 13] SmCeFeCoN

[Example 14] SmFeCoMN magnet powder and bonded magnet In some examples of Examples 4 to 10, a part of Fe was replaced with C.
By replacing with o, a magnet alloy having the composition shown in Table 14 was produced. The peripheral speed of the quenching roll is 40 m /
Seconds. Table 14 summarizes the magnetic properties of the magnet powder and the magnetic properties of the bonded magnet.

[0069]

Table 14 SmFeCoM ² N

Example 15 SmCeFeCoMN Magnet Powder and Bonded Magnet In the SmFeMN magnet, a part of Sm was replaced by Ce and a part of Fe was replaced by Co to produce a magnet alloy having the composition shown in Table 15. . Table 15 shows the magnetic properties of the magnet powder and the bonded magnet.

[0071]

Table 15 SmCeFeCoM ² N

Example 16 Heat Treatment Temperature (Part 1)
(Sm8.3-Fe79.2-N12.5) Prior to nitriding, No. 18 flake-like powder of Example 1 was heated to various temperatures of 500 to 900 ° C. for various times to obtain appropriate heat treatment conditions. Looked for. Table 16 shows the heat treatment conditions and the magnetic properties of the obtained magnet powder and bonded magnet.
Shown in

[0073]

[Table 16] Heat treatment temperature (No. 1 Sm8.3-Fe79.
2-N12.5)

Example 17 Temperature of Heat Treatment (Part 2)
Sm8.5-Fe78.7-N12.8) The flaky powder of No. 22 of Example 1 was heated to various temperatures of 500 to 900 ° C. for various times prior to nitriding similarly to Example 16. Then, suitable heat treatment conditions were searched. Table 17 shows the heat treatment conditions and the magnetic properties of the obtained magnet powder and bonded magnet.

[0075]

[Table 17] Heat treatment temperature (Part 2 Sm8.5-Fe78.
7-N12.8)

Example 18 A quenching atmosphere (Sm8.3
-Fe79.2-N12.5) In producing the flake powder of No. 18 in Example 1, the influence of the atmosphere pressure was varied between 0.0001 atm and 2 atm to examine the effect. The peripheral speed of the quenching roll is
Both are 40 m / sec. Table 18 shows the magnetic properties of the magnet powder and the bonded magnet obtained at each pressure.

[0077]

[Table 18] Quenching atmosphere (Sm8.3-Fe79.2-N12.
Five)

Example 19 The material of the quenching roll (Sm
8.3-Fe79.2-N12.5) In producing the flake powder of No. 18 of Example 1, the material of the quenching roll was changed to pure copper, Cr-Cu alloy or Be-Cu alloy, and the effect was obtained. Was examined. The peripheral speed of the quenching roll is 40 m / sec. Table 19 shows the magnetic properties of the magnet powder and the bonded magnet obtained for each material.

[0079]

[Table 19] Material of quenching roll (Sm8.3-Fe79.2-
N12.5)

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction chart of a magnet powder manufactured in No. 18 of Example 1 of the present invention. (Co-Kα)

FIG. 2 is an X-ray diffraction chart of the magnet powder manufactured in No. 35 of Example 2 of the present invention. (Co-Kα)

FIG. 3 is an X-ray diffraction chart of the magnet powder manufactured in No. 35 of Example 3 of the present invention. (Co-Kα)

FIG. 4 is an X-ray diffraction chart of the magnet powder produced in No. 11 of Example 4 of the present invention. (Co-Kα)

FIG. 5 is an X-ray diffraction chart of the magnet powder produced in No. 11 of Example 5 of the present invention. (Co-Kα)

FIG. 6 is an X-ray diffraction chart of the magnet powder manufactured in No. 11 of Example 6 of the present invention. (Co-Kα)

FIG. 7 is an X-ray diffraction chart of the magnet powder produced in No. 11 of Example 7 of the present invention. (Co-Kα)

FIG. 8 is an X-ray diffraction chart of the magnet powder produced in No. 11 of Example 8 of the present invention. (Co-Kα)

FIG. 9 is an X-ray diffraction chart of the magnet powder produced in No. 11 of Example 9 of the present invention. (Co-Kα)

FIG. 10 is an X-ray diffraction chart of the magnet powder manufactured in No. 11 of Example 10 of the present invention. (Co-Kα)

FIG. 11 is an X-ray diffraction chart of the magnet powder manufactured in No. 1 of Example 11 of the present invention. (Co-Kα)

FIG. 12 is an X-ray diffraction chart of the magnet powder manufactured in No. 49 of Example 12 of the present invention. (Co-Kα)

FIGS. 13A to 13D show N of Example 1 of the present invention.
Micrograph of flake powder obtained by rapidly cooling the melt of o.18. In each figure, the magnification between the two ends of the short straight line group indicating the scale corresponds to the length described there.

FIGS. 14A to 14D show N in Example 2 of the present invention.
Micrograph of flaky powder obtained by quenching the melt of o.35. The scale display is the same as in FIGS. 13A to 13D.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01F 1/053 H01F 1/04 A (72) Inventor Takayuki Nishio Nachi-me cho 30 Address Daido Steel Co., Ltd. Technology Development Laboratory F-term (reference) 4K017 AA04 BA06 BB12 CA03 DA04 EC02 FA08 4K018 BA18 BB01 BB04 BC01 BC19 BD01 KA46 5E040 AA11 AA19 BB03 HB11 HB17 NN01 NN06 NN12

Claims (14)

[Claims] 1. A manufactured by nitriding a powder of magnet alloy obtained by the roll quenching method, in flake isotropic SmFeN-based powder magnet material, in _{atomic%, Sm x Fe 100-xv} N v [ In the formula, 7 ≦ x ≦ 12 and 0.5 ≦ v ≦ 20. And a flake thickness of 10 to 40 μm, having a TbCu ₇ type crystal structure. 2. In a flake-like isotropic SmFeN-based powder magnet material produced by nitriding a magnet alloy powder obtained by a roll quenching method, Sm _x Fe _{100-x-y- v} M ¹ _y N _v [wherein M ¹ is one or two selected from the group consisting of Hf and Zr, and 7 ≦ x ≦ 12, 0.1 ≦
y ≦ 1.5 and 0.5 ≦ v ≦ 20. And a flake thickness of 10 to 40 μm, having a TbCu ₇ type crystal structure. 3. A produced by nitriding a powder of magnet alloy obtained by the roll quenching method, in flake isotropic SmFeN-based powder magnet material, in _{atomic%, Sm x Fe 100-xzv} M 2 z N _v [where M ² is Si, Nb, Ti, Ga, Al, Ta
And C are one or more selected from the group consisting of: 7 ≦ x ≦ 12, 0.1 ≦ z ≦ 1.0, and
0.5 ≦ v ≦ 20. And a flake thickness of 10 to 40 μm, having a TbCu ₇ type crystal structure. 4. The powder magnetic material according to claim 1, wherein 30 atom% or less of Sm is replaced by Ce. 5. The powder magnetic material according to claim 1, wherein 30 atom% or less of Sm is replaced by a rare earth element other than Ce. 6. The powder magnetic material according to claim 1, wherein 35 atomic% or less of Fe is replaced by Co. 7. The powder magnetic material according to claim 1, wherein the average crystal grain size is 10 nm to 0.5 μm. 8. The powder magnet material according to claim 1, which has a specific coercive force of 7 kOe or more. 9. A method of manufacturing a flaky isotropic SmFeN-based powder magnet material according to claim 1, in _{atomic%, Sm x Fe 100-xv} N v [ wherein, 7 ≦ x ≦ 12, and 0.5 ≦ v ≦ 20. ] And a TbCu ₇ structure.
m and Fe are blended and melted, and the molten alloy is sprayed onto a cooling roll rotating at a peripheral speed of 30 to 45 m / sec to be rapidly cooled, and the obtained flake-like powder is cooled in an inert atmosphere. A heat treatment at 500 to 900 ° C., followed by nitriding. 10. A method for producing a flake-like isotropic SmFeN-based powder magnetic material according to claim 2, wherein
In _{atomic%, Sm x Fe 100-x} -y-v M 1 y N v [ wherein, ^{M 1} is a one or two chosen from the group consisting of Hf and Zr, 7 ≦ x ≦ 12, 0.1 ≦
y ≦ 1.5 and 0.5 ≦ v ≦ 20. ] Becomes the composition, so as to have a TbCu ₇ structure, and dissolved by mixing alloy components consisting of Sm, Fe and M ', and injected onto a cooling roll rotating the molten alloys at a peripheral speed 20～45M / sec And subjecting the obtained flake-shaped powder to a heat treatment at 500 to 900 ° C. in an inert atmosphere, followed by nitriding. 11. A method for producing a flake-like isotropic SmFeN-based powder magnetic material according to claim 3, wherein
In _{atomic%, Sm x Fe 100-xzv} M 2 z N v [ wherein, ^{M 2} is, Si, Nb, Ti, Ga , Al, Ta
And C are one or more selected from the group consisting of: 7 ≦ x ≦ 12, 0.1 ≦ z ≦ 1.0, and
0.5 ≦ v ≦ 20. And an alloy component comprising Sm, Fe and M are blended and melted so as to have a TbCu ₇ structure, and the molten alloy is melted at a peripheral speed of 20 to 45 m / m.
Sprayed on a cooling roll rotating in seconds, quenched, and the obtained flaky powder was heated to 500 to 900 ° C under an inert atmosphere.
A method for producing a powdered magnet material, which comprises heat-treating and then nitriding. 12. The method according to claim 9, wherein the quenching of the roll is performed in an atmosphere of Ar gas at a pressure of 0.0001 Torr to 2 atm. 13. The method according to claim 9, wherein the quenching of the roll is performed using a cooling roll made of a Cr—Cu alloy or a Be—Cu alloy. 14. A bonded magnet obtained by molding the magnet powder according to claim 1 together with a binder into a magnet shape.