JPH0864408A - Permanent magnet - Google Patents

Abstract

PURPOSE: To realize a permanent magnet of good magnetic characteristic by developing exchange magnetic anisotropy by cooling a material such as iron- sulfur-cobalt in a magnetic field regarding a permanent magnet wherein exchange magnetic anisotropy is developed. CONSTITUTION: The title permanent magnet is comprised of atomic number ratio of (Fe1- YCoY)1- X SX wherein 0.05<=X<=0.4, 0.02<=Y<=0.5 and exchange magnetic anisotropy is developed by cooling it in a magnetic field.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a permanent magnet having exchange magnetic anisotropy.

[0002]

2. Description of the Related Art Conventionally, Fe--Cr--C has been used as a permanent magnet.
o magnets, Al, Ni, Co, Cu, Fe-based alnico magnets, Fe ferrite-based hard ferrite magnets, Sm-containing rare earth cobalt magnets, Nd-containing Nd-Fe-B magnets. Known as the representative.

Ferrite magnets are the most commonly used magnets. Residual magnetic flux density (hereinafter called Br) is 4kG (4k Gauss) at maximum, coercive force (hereinafter called iHc)
Is up to 4kOe (4k Oersted)
8-41645).

B of Fe-Cr-Co magnet and alnico magnet
r is 10 kG or more, and iHc is about 1 kOe at the maximum (Japanese Patent Publication No. 57-23747, Japanese Patent Publication No. 54-4345).
0). The rare earth cobalt magnet has high characteristics for both Br and iHc. Nd-Fe-B magnets have higher magnetic properties than rare earth cobalt magnets (Japanese Patent Publication No. 61-34242).

Here, the situation of the raw material of Co used in the Fe—Cr—Co magnet, the alnico magnet and the rare earth cobalt magnet is unstable. Further, hard ferrite magnets are currently the mainstream of permanent magnets because the rare earth elements used for rare earth magnets are very small in quantity and extremely expensive.

[0006]

The above-mentioned ferrite magnet has a large iHc but a small Br of 4 kG. Fe-
Br of Cr-Co magnets and alnico magnets is as large as 10 kG or more, but iHc is small as about 1 kOe. Rare earth magnets contain very expensive rare earth elements. For these reasons, it does not contain rare earth elements, and is more than Br of ferrite magnet, that is, 4k.
G or more and iHc or more of alnico magnet, that is, 1 kOe
It is desired to provide a practical permanent magnet having the above magnetic properties.

The present invention solves these problems.
The purpose of the present invention is to realize a permanent magnet having excellent magnetic characteristics by cooling a material such as iron-sulfur-cobalt in a magnetic field to exhibit exchange magnetic anisotropy.

[0008]

Means for Solving the Problems The means for solving the problems will be described with reference to FIGS. 1, 6, 11, 16, 21, and 26.

In FIG. 1, S1 weighs. In this, the raw materials are weighed in a ratio of (Fe _1-Y Co _Y ) _1-X S _X 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5 in terms of atomic number ratio.

In step S7, cooling in a magnetic field is performed. In FIG. 6, S11 weighs. In terms of the atomic ratio, (Fe _1-Y M _Y ) _1-X S _X M is one or more of Cr, Mn, and Ni 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0. The raw materials are weighed in the ratio of 3.

The atomic ratio ((Fe _{1 -Z} Co _Z ) _1-Y M _Y ) _1-X S _X M is one or more of Cr, Mn, and Ni 0.05 ≤ X ≤ 0. 4 0.02 ≦ Y ≦ 0.3 0 <
Raw materials are weighed at a ratio of Z ≦ 0.5.

In step S17, cooling is performed in a magnetic field. In FIG. 11, in S21, weighing is performed. This is because the atomic ratio of Fe _1-X (S _1-Y α _Y ) _X α is one or more of Sn, Se, Te, Sb, As 0.05 ≦ X ≦ 0.4 0.02 ≦ The raw materials are weighed at a ratio of Y ≦ 0.5.

The atomic ratio of (Fe _{1 -Z} Co _Z ) _1-X (S _1-Y α _Y ) _X α is one or more of Sn, Se, Te, Sb and As 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5 0 <
Raw materials are weighed at a ratio of Z ≦ 0.5.

In S27, cooling is performed in the magnetic field. In FIG. 16, S31 performs weighing. In terms of atomic ratio, Fe _1-XY S _X β _Y β is one or more of Si, B, C, P and Ge 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.25 The raw materials are weighed in the ratio of.

In terms of atomic ratio, (Fe _1-Z Co _Z ) _1-XY S _X β _Y β is one or more of Si, B, C, P and Ge 0.05 ≦ X ≦ 0.4 0.01 ≤ Y ≤ 0.25
Raw materials are weighed at a ratio of <Z ≦ 0.5.

In step S37, cooling is performed in the magnetic field. In FIG. 21, in S41, weighing is performed. In terms of atomic ratio, Fe _1-XY S _X T _Y T is one or more of Ti, V, Zr, Nb, Mo, Hf, Ta and W 0.05 ≦ X ≦ 0.4 0.01 Raw materials are weighed at a ratio of ≦ Y ≦ 0.2.

In terms of atomic ratio, (Fe _1-Z Co _Z ) _1-XY S _X T _Y T is one or more of Ti, V, Zr, Nb, Mo, Hf, Ta and W 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.2 0 <
Raw materials are weighed at a ratio of Z ≦ 0.5.

In S47, cooling is performed in the magnetic field. In FIG. 26, S51 performs weighing. In terms of atomic ratio, Fe _1-XY S _X γ _Y γ is one or more of Cu, Ag, In, Ga, Al and Be 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0 The raw materials are weighed in a ratio of 0.15.

In terms of atomic ratio, (Fe _{1 -Z} Co _Z ) _1-XY S _X γ _Y γ is one or more of Cu, Ag, In, Ga, Al and Be 0.05 ≦ X ≦ 0 0.4 0.01 ≦ Y ≦ 0.150
Raw materials are weighed at a ratio of <Z ≦ 0.5.

In step S57, cooling is performed in the magnetic field.

[0021]

According to the present invention, as shown in FIG. 1, (Fe _1-Y Co _Y ) _1-X S _X 0.05 ≦ X ≦ 0.4 0.02 ≦ Y in atomic number ratio in weighing S1 The raw materials are weighed in a ratio of ≦ 0.5, and cooled in a magnetic field in S7 to develop exchange magnetic anisotropy, thereby producing a permanent magnet.

In the present invention, as shown in FIG. 6, (Fe _1-Y M _Y ) _1-X S _X M is one or more of Cr, Mn and Ni in the atomic number ratio in the weighing of S11. .05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.3, the raw materials are weighed and cooled in a magnetic field in S17 to develop exchange magnetic anisotropy so that a permanent magnet is produced. There is.

In the weighing of S11, the atomic ratio ((Fe _{1 -Z} Co _Z ) _1-Y M _Y ) _1-X S _X M is one or more of Cr, Mn and Ni. ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.3 0 <
The raw material is weighed at a ratio of Z ≦ 0.5, and cooled in a magnetic field in S17 to develop exchange magnetic anisotropy, thereby producing a permanent magnet.

According to the present invention, as shown in FIG. 11, in the weighing of S21, Fe _1-X (S _1-Y α _Y ) _X α is one of Sn, Se, Te, Sb, As in atomic number ratio or Two or more kinds: 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5 The raw materials are weighed and cooled in a magnetic field in S27 to develop exchange magnetic anisotropy, and a permanent magnet is manufactured. I am trying to do it.

In the weighing of S21, the atomic ratio of (Fe _{1 -Z} Co _Z ) _1-X (S _1-Y α _Y ) _X α is one or two of Sn, Se, Te, Sb and As. Above 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5 0 <
The raw material is weighed in a ratio of Z ≦ 0.5, and cooled in a magnetic field in S27 to develop exchange magnetic anisotropy, and a permanent magnet is manufactured.

According to the present invention, as shown in FIG. 16, in the weighing of S31, Fe _1-XY S _X β _Y β is one or more of Si, B, C, P and Ge in the atomic ratio. The raw material is weighed in a ratio of 05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.25, and cooled in a magnetic field in S37 to develop exchange magnetic anisotropy to produce a permanent magnet. .

In the weighing of S31, the atomic ratio of (Fe _{1 -Z} Co _Z ) _1-XY S _X β _Y β is one or more of Si, B, C, P and Ge 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.25 0
The raw materials are weighed in a ratio of <Z ≦ 0.5, and cooled in a magnetic field in S37 to develop exchange magnetic anisotropy, thereby producing a permanent magnet.

In the present invention, as shown in FIG. 21, in the weighing of S41, Fe _1-XY S _X T _Y T is one of Ti, V, Zr, Nb, Mo, Hf, Ta, and W. Alternatively, two or more kinds of materials are weighed in a ratio of 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.2, and cooled in a magnetic field in S47 to develop exchange magnetic anisotropy, and permanent magnets are formed. I am trying to make it.

In the weighing of S41, the atomic ratio of (Fe _{1 -Z} Co _Z ) _1-XY S _X T _Y T is one or two of Ti, V, Zr, Nb, Mo, Hf, Ta and W. Type or more 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.2 0 <
The raw materials are weighed in a ratio of Z ≦ 0.5, and cooled in a magnetic field in S47 to develop exchange magnetic anisotropy, thereby producing a permanent magnet.

According to the present invention, as shown in FIG. 26, Fe _1-XY S _X γ _Y γ is one or more kinds of Cu, Ag, In, Ga, Al and Be in atomic ratio in weighing S51. The raw material is weighed in a ratio of 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.15, and cooled in a magnetic field in S57 to develop exchange magnetic anisotropy so that a permanent magnet is manufactured. ing.

Further, in the weighing of S51, (Fe _1-Z Co _Z ) _1-XY S _X γ _Y γ in atomic ratio is _one or more of Cu, Ag, In, Ga, Al and Be. 05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.150
The raw materials are weighed in a ratio of <Z ≦ 0.5, and cooled in a magnetic field in S57 to develop the exchange magnetic anisotropy to produce a permanent magnet.

Therefore, (Fe-Co) -S, (Fe-
M) -S, ((Fe-Co) -M) -S, Fe- (S-
α), (Fe-Co)-(S-α), Fe-S-β,
(Fe-Co) -S-β, Fe-S-T, (Fe-C
o) -S-T, Fe-S-γ, (Fe-Co) -S-γ
A permanent magnet having excellent magnetic properties (large Br and iHc and being easily magnetized) can be obtained by cooling the material made of (1) in a magnetic field to exhibit exchange magnetic anisotropy. Here, M, α, β, T and γ are as described above.

-M: Cr, Mn, Ni-α: Sn, Se, Te, Sb, As-β: Si, B, C, P, Ge-T: Ti, V, Zr, Nb, Mo, Hf, Ta, W .γ: Cu, Ag, In, Ga, Al, Be

[0034]

【Example】

(1) The configuration and operation of one embodiment of the present invention will be described in detail with reference to FIGS. 1 to 5. In this example, (Fe-
Co) -S is cooled in a magnetic field to develop exchange magnetic anisotropy and a permanent magnet is produced.

FIG. 1 is a structural explanatory view of one embodiment of the present invention. In FIG. 1, S1 performs weighing. This is Fe
The raw material of —Co—S is weighed in the atomic ratio of (Fe _{1 -Y} Co _Y ) _1-X S _X 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5.

In step S2, high frequency melting is performed. This high frequency melting is performed in an inert gas atmosphere. In S3, liquid quenching (roll speed adjustment) is performed. This is because, in order to reduce the crystal grain size, in the experiment, at a roll speed of 45 m / s,
While the water-cooled roll was rotated, the solution in which the high frequency was dissolved was introduced from the upper portion and rapidly cooled to form a thin plate having a small crystal grain size.

S4 is crushing (300 μm or less). For this, the thin plate produced in S3 was crushed into a flaky shape of 300 μm or less. S5 is heat treatment (temperature x time, atmosphere)
I do. In order to increase the coercive force iHc, heat treatment was performed in an Ar gas atmosphere at 500 ° C. for 1 hr in the experiment.

In step S6, molding (pressure) is performed. Here, 4
The powder, which had been crushed and heat-treated, was filled in a mold at a pressure of t / cm ² and compression-molded. In S7, the molded body after compression molding in S6 was cooled in a magnetic field (temperature, magnetic field strength). In order to develop the exchange magnetic anisotropy, the temperature is higher than the Neel temperature, the natural cooling is performed, and the magnetic field is cooled by a magnetic field that magnetizes the soft magnetic phase in one direction. Specifically, for example, F
After being heated to a Neel temperature of e-Co-S of about 320 ° C. or higher, in the experiment, to 400 ° C., a magnetic field that only magnetizes the soft magnetic phase in one direction (for example, 1 kO in the experimental example shown in FIG. 4).
With e) applied, the material is naturally cooled to a temperature below the Neel temperature, and further close to room temperature.

S8 is magnetic measurement (measurement of BH curve)
To do. Regarding the result of S7, when the BH curve is illustrated, the characteristic (the characteristic in which the values of iHc and + iHc are asymmetrically shifted) as shown in FIG. 5 is obtained. .

Step S9 is the completion of the permanent magnet. By the above, the raw materials weighed in the atomic ratio of (Fe _1-Y Co _Y ) _1-X S _X 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5 are melted, quenched, crushed, and heat-treated. , Molding, cooling in a magnetic field, BH curve measurement
Thus, as shown in FIG. 5, a permanent magnet having exchange magnetic anisotropy could be manufactured. Here, the experiment was conducted on the premise of a process for producing an actual bonded magnet, but by cooling a mixture of the above raw materials uniformly in a magnetic field, exchange magnetic anisotropy is exhibited, and a permanent magnet having good magnetic properties is obtained. Could be manufactured. The experimental results will be described in detail below with reference to FIGS.

FIG. 2 shows an example (1) of the experimental result of the present invention. The results of this experiment are for (Fe _0.8 Co _0.2 ) _1-X S _X when X is changed within the range of 0.03 to 0.45 as shown in the figure. This notation is equivalent to (Fe _{0.8 * (1-X)} , Co _{0.2 * (1-X)} ) S _X. The same applies hereinafter.

Here, Br (kG) is the value (kG) at the intersection with the B axis on the BH loop of FIG. iHc (k
Oe) is the value (kOe) at the intersection with the -H axis on the B-H loop in FIG.

+ IHc (kOe) is the value (kOe) at the intersection with the + H axis on the BH loop of FIG. In the experimental result example of FIG. 2, the amounts of Fe, Co, and S corresponding to the value of X are melted in a high-frequency melting furnace according to S2 to S8 of FIG. 1, and are rapidly cooled in a liquid quencher at a roll speed of 45 m / s. 300μ
Grind to m or less. This fine powder at 500 ° C for 1 hour, A
Heat treatment in r gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. Br, iHc and + iHc of the obtained product were measured, and the obtained results are the results shown in FIG.

When X is less than 0.05, Br, i
Hc becomes smaller. When X exceeds 0.4, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0.05 ≦ X ≦ 0.4. Preferably,
If 0.1 ≦ X ≦ 0.35, a larger value of Br and a larger value of iHc can be obtained.

FIG. 3 shows an example (2) of the experimental result of the present invention. The results of this experiment are for (Fe _{1 -Y} Co _Y ) _0.8 S _0.2 when Y is changed within the range of 0 to 0.55 as shown in the figure.

In the experimental result example of FIG. 3, Fe, Co, and S in amounts corresponding to the value of Y are melted in the high-frequency melting furnace in the same manner as in FIG. 2 according to S2 to S8 of FIG. The liquid is rapidly cooled at a speed of 45 m / s and then pulverized to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. Next, the powder is heated from 400 ° C to room temperature at 10 kO.
It cooled in the magnetic field of e. For this obtained product, B
The results obtained by measuring r, iHc, and + iHc are the results shown in FIG.

When Y is less than 0.02, Br, i
Hc becomes smaller. When Y exceeds 0.5, Br becomes small. Therefore, Br was large and iHc was large in the range of 0.02 ≦ Y ≦ 0.5. Preferably,
If 0.05 ≦ X ≦ 0.4, a larger Br value and a larger iHc value can be obtained.

FIG. 4 shows an example (3) of the experimental result of the present invention. The result of this experiment is that of (Fe _0.8 Co _0.2 ) _0.8 S _0.2 when the magnetic field for cooling in the magnetic field is changed within the range of 1 to 10 kOe as illustrated.

In the example of the experimental result of FIG. 4, the amounts of Fe and C shown in the figure are shown.
According to S2 to S8 in FIG. 1, melted in a high-frequency melting furnace and rolled in a liquid quencher at a roll speed of 45 m /
After the liquid is rapidly cooled with s, it is ground to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. Next, the powder was cooled in each magnetic field from 400 ° C. to room temperature with the magnetic field strength shown. Br, iHc, and + iHc were measured for the obtained product, and the obtained results are the results shown in FIG.

In the range of the magnetic field (kOe) toughness of 1 to 10 kOe for cooling in a magnetic field, sufficient magnetic properties due to sufficient exchange anisotropy were obtained. In particular, a large value of iHc (kOe) of 4.8 to 5.2 kOe was obtained even when the magnetic field applied during cooling in the magnetic field was smaller than iHc (for example, 1 kOe).

FIG. 5 shows an example of BH loop measurement of the present invention. This is when the atomic ratio (Fe _0.8 Co _0.2 ) _0.8 S _0.2 in FIG. 4 and the magnetic field for cooling in the magnetic field is 10 kOe.
In the B-H curve shown, + iHc in the + direction is 1.9.
It is kOe, iHc in the-direction is 5.1 kOe, and both are asymmetric, and it is revealed that exchange magnetic anisotropy is exhibited.

Due to the manifestation of exchange magnetic anisotropy, iHc
Is as large as 5.1 kOe, which means that a strong permanent magnet is obtained. + IHc becomes as small as 1.9 kOe, and it is possible to magnetize with a small magnetizing magnetic field.

As described above, a permanent magnet having a large Br and a large iHc was obtained by cooling the material having a predetermined ratio of Fe—Co—S in the magnetic field to exhibit the exchange magnetic anisotropy. .

(2) The configuration and operation of another embodiment of the present invention will be described in detail with reference to FIGS. 6 to 10. Other embodiments include (Fe-M) -S or ((Fe-C
o) -M) -S is cooled in a magnetic field to exhibit exchange magnetic anisotropy and a permanent magnet is produced.

FIG. 6 is a structural explanatory view of another embodiment of the present invention. In FIG. 6, S11 weighs. this is,
The material of the Fe-Co-M-S, the atomic ratio of _{(Fe 1-Y M Y)} 1-X S X M is Cr, Mn, one or two or more 0.05 ≦ X ≦ 0.4 for Ni 0.02 ≦ Y ≦ 0.3, or ((Fe _1-Z Co _Z ) _1-Y M _Y ) _1-X S _X M is one or more of Cr, Mn, and Ni. 05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.3 0 <
Weigh at a ratio of Z ≦ 0.5.

In step S12, high frequency melting is performed. This high frequency melting is performed in an inert gas atmosphere. In S13, the liquid is rapidly cooled (roll speed is adjusted). In order to reduce the crystal grain size, in the experiment, for example, at a roll speed of 55 m / s, a water-cooled roll was rotated and a high-frequency-dissolved solution was introduced from the upper portion to rapidly cool the thin plate having a small crystal grain size. Was generated.

At S14, the material is crushed (300 μm or less).
For this, the thin plate produced in S13 was crushed into a flaky shape of 300 μm or less. In S15, heat treatment (temperature × time, atmosphere) is performed. In order to increase the coercive force iHc, heat treatment was performed in an Ar gas atmosphere at 550 ° C. for 1 hr in the experiment.

In S16, molding (pressure) is performed. here,
The powder that had been crushed and heat-treated was filled in a mold at a pressure of 4 t / cm ² and compression molded. In S17, the molded body after compression molding in S16 was cooled in a magnetic field (temperature, strength of magnetic field). In order to develop the exchange magnetic anisotropy, the temperature is higher than the Neel temperature, the natural cooling is performed, and the magnetic field is cooled by a magnetic field that magnetizes the soft magnetic phase in one direction. Specifically, for example, F
After being heated to 400 ° C. or higher in the experiment at the Neel temperature of e-M-S, Fe-Co-M-S, etc., it was naturally cooled in a state where a magnetic field was applied to magnetize the soft magnetic phase in one direction. Then, the temperature is cooled to below the nail temperature and close to room temperature.

In S18, magnetic measurement (measurement of BH curve) is performed. With respect to the result of S17, when the BH curve is measured, a characteristic (a characteristic in which the values of iHc and + iHc are asymmetrically shifted) as shown in FIGS. Was obtained.

S19 is the completion of the permanent magnet. From the above, (Fe _1-Y M _Y ) _1-X S _X M is one or more of Cr, Mn, and Ni 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.3 or (( Fe _1-Z Co _Z ) _1-Y M _Y ) _1-X S _X M is one or more of Cr, Mn and Ni 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.3 0 <
By melting, quenching, crushing, heat treatment, molding, cooling in a magnetic field, and measurement of a BH curve, the raw materials weighed in an atomic ratio of Z ≦ 0.5 were used.
Thus, as shown in FIG. 10, a permanent magnet having exchange magnetic anisotropy could be manufactured. Here, the experiment was conducted on the premise of the process of manufacturing an actual bonded magnet, but by cooling a mixture of the above raw materials uniformly in a magnetic field, exchange magnetic anisotropy is exhibited and a permanent magnet having good magnetic properties is obtained. Could be manufactured. Hereinafter, the experimental results will be sequentially described in detail with reference to FIGS.

FIG. 7 shows an example of experimental results of the present invention (part 11).
Indicates. The experimental results are for (Fe _0.8 Mn _0.2 ) _1-X S _X when X is changed within the range of 0.03 to 0.45 as shown in the figure.

In the experimental result example of FIG. 7, the amounts of Fe, Mn and S corresponding to the value of X are melted in the high frequency melting furnace according to S12 to S18 of FIG. 6, and the roll speed is 55 m / m in the liquid quenching device.
After the liquid is rapidly cooled with s, it is ground to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br, iH
The results obtained by measuring c and + iHc are the results shown in FIG. 7.

When X is less than 0.05, Br, i
Hc becomes smaller. When X exceeds 0.4, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0.05 ≦ X ≦ 0.4. Preferably,
If 0.2 ≦ X ≦ 0.35, a larger Br value and a larger iHc value can be obtained.

FIG. 8 shows an example of experimental results of the present invention (12).
Indicates. The results of this experiment are for (Fe _1-Y Mn _Y ) _0.65 S _0.35 when Y is changed within the range of 0 to _0.35 as shown in the figure.

In the experimental result example of FIG. 8, the amounts of Fe, Mn and S corresponding to the value of Y are melted in the high frequency melting furnace according to S12 to S18 of FIG. 6, and the roll speed is 55 m / m in the liquid quenching device.
After the liquid is rapidly cooled with s, it is ground to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br, iH
The results obtained by measuring c and + iHc are the results shown in FIG. 7.

When Y is less than 0.02, Br, i
Hc becomes smaller. When Y exceeds 0.3, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0.02 ≦ Y ≦ 0.3. Preferably,
If 0.1 ≦ Y ≦ 0.25, a larger Br value and a larger iHc value can be obtained.

FIG. 9 shows an example of experimental results of the present invention (13).
Indicates. The results of this experiment are (Fe _0.8 M _0.2 ) _0.8 S _0.2 when M is variously changed as shown in the drawing.

In the example of the experimental result of FIG. 9, the amount of F corresponding to M is
According to S12 to S18 of FIG. 6, e, M, and S are melted in a high-frequency melting furnace, rapidly cooled by a liquid quenching device at a roll speed of 55 m / s, and then pulverized to 300 μm or less. 55 of this fine powder
Heat treatment is performed in Ar gas at 0 ° C. for 1 hour. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. About this obtained product, Br, iHc, + i
The Hc was measured and the obtained results are the results shown in FIG.

If M is one or more of Mn, Cr, and Ni, high magnetic properties were obtained. FIG. 10 shows an example (14) of the experimental result of the present invention. The result of this experiment is that in ((Fe ₁ -Z Co _Z ) _0.8 Mn _0.2 ) _0.8 S _0.2 , Z is changed within the range of 0 to 0.55 as shown in the figure.

In the example of the experimental result of FIG. 10, Fe, Co, Mn and S in the amounts corresponding to the value of Z are melted in the high frequency melting furnace according to S12 to S18 of FIG. 6, and the roll speed is 55 m / s in the liquid quenching device. After the liquid is rapidly cooled with, it is pulverized to 300 μm or less.
This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The iHc and + iHc were measured, and the obtained results are the results shown in FIG.

When a part of Fe is replaced by Co, iHc
Grows larger. However, when Z exceeds 0.5, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0 <Z ≦ 0.5. Preferably 0.05
When ≦ Z ≦ 0.4, a value of Br and a value of iHc are further increased.

(3) The configuration and operation of another embodiment of the present invention will be described in detail with reference to FIGS. 11 to 15. In other examples, Fe- (S-α), (Fe-Co)-
This is a case where (S-α) is cooled in a magnetic field to exhibit exchange magnetic anisotropy to produce a permanent magnet.

FIG. 11 is a structural explanatory view of another embodiment of the present invention. In FIG. 11, in S21, weighing is performed. This is for the raw material of Fe-Co-S-α, in terms of the atomic ratio, Fe _1-X (S _1-Y α _Y ) _X α is one or more of Sn, Se, Te, Sb, As. 05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5, or (Fe _1-Z Co _Z ) _1-X (S _1-Y α _Y ) _X α is Sn, Se, Te, One or more of Sb and As 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5 0 <
Weigh at a ratio of Z ≦ 0.5.

In step S22, high frequency melting is performed. This high frequency melting is performed in an inert gas atmosphere. In S23, liquid quenching (roll speed adjustment) is performed. In order to reduce the crystal grain size, in the experiment, for example, at a roll speed of 50 m / s, a water-cooled roll was rotated and a high-frequency dissolved solution was introduced from the upper portion to quench the solution, and the thin plate having a small crystal grain size was cooled. Was generated.

In S24, the material is crushed (300 μm or less).
For this, the thin plate produced in S23 was crushed into a thin piece of 300 μm or less. In S25, heat treatment (temperature × time, atmosphere) is performed. In order to increase the coercive force iHc, heat treatment was performed in an Ar gas atmosphere at 500 ° C. for 1 hr in the experiment.

In S26, molding (pressure) is performed. here,
The powder that had been crushed and heat-treated was filled in a mold at a pressure of 4 t / cm ² and compression molded. In S27, the molded body after compression molding in S26 was cooled in a magnetic field (temperature, strength of magnetic field). In order to develop the exchange magnetic anisotropy, the temperature is higher than the Neel temperature, the natural cooling is performed, and the magnetic field is cooled by a magnetic field that magnetizes the soft magnetic phase in one direction. Specifically, for example, F
In the experiment, after being heated to 400 ° C or higher than the Neel temperature of e-α-S, Fe-Co-α-S, etc., it was naturally cooled while applying a magnetic field for magnetizing the soft magnetic phase in one direction. Then, the temperature is cooled to below the nail temperature and close to room temperature.

In S28, magnetic measurement (measurement of BH curve) is performed. When the BH curve is measured for the result of S27, a characteristic (a characteristic in which the values of iHc and + iHc are asymmetrically shifted) as shown in FIGS. Was obtained.

S29 is the completion of the permanent magnet. As described above, Fe _1-X (S _1-Y α _Y ) _X α is one or more of Sn, Se, Te, Sb, As 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0. 5 or (Fe _1-Z Co _Z ) _1-X (S _1-Y α _Y ) _X α is one or more of Sn, Se, Te, Sb and As 0.05 ≦ X ≦ 0.4 0. 02 ≦ Y ≦ 0.5 0 <
By melting, quenching, pulverizing, heat treating, molding, cooling in a magnetic field, and measuring the BH curve of the raw material weighed at an atomic ratio of Z ≦ 0.5, FIG.
As shown in FIGS. 2 to 15, permanent magnets having exchange magnetic anisotropy could be manufactured. Here, the experiment was conducted on the premise of the process of manufacturing an actual bonded magnet, but by cooling a mixture of the above raw materials uniformly in a magnetic field, exchange magnetic anisotropy is exhibited and a permanent magnet having good magnetic properties is obtained. Could be manufactured. Hereinafter, the experimental results will be sequentially described in detail with reference to FIGS. 12 to 15.

FIG. 12 shows an example of the experimental result of the present invention (part 2).
1) is shown. The result of this experiment is that of Fe _{1 -X} (S _0.8 Sn _0.2 ) _X when X is changed within the range of 0.03 to 0.45 as shown in the figure.

In the experimental result example of FIG. 12, the amounts of Fe, S and Sn corresponding to the value of X are melted in the high frequency melting furnace according to S22 to S28 of FIG.
After the liquid is rapidly cooled at 0 m / s, it is ground to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The results obtained by measuring iHc and + iHc are the results shown in FIG.

When X is less than 0.05, Br, i
Hc becomes smaller. When X exceeds 0.4, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0.05 ≦ X ≦ 0.4. Preferably,
If 0.1 ≦ X ≦ 0.35, a larger value of Br and a larger value of iHc can be obtained.

FIG. 13 shows an example of the experimental result of the present invention (part 2).
2) is shown. The results of this experiment are for Fe _0.8 (S _{1 -Y} Sn _Y ) _0.2 when Y is changed within the range of 0 to 0.55 as shown in the figure.

In the example of the experimental result of FIG. 13, the amounts of Fe, S and Sn corresponding to the value of Y are melted in the high frequency melting furnace according to S22 to S28 of FIG.
After the liquid is rapidly cooled at 0 m / s, it is ground to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The results obtained by measuring iHc and + iHc are the results shown in FIG.

When Y is less than 0.02, Br, i
Hc becomes smaller. When Y exceeds 0.5, Br becomes small. Therefore, Br was large and iHc was large in the range of 0.02 ≦ Y ≦ 0.5. Preferably,
If 0.1 ≦ X ≦ 0.4, Br is further increased, and i
A large value of Hc can be obtained.

FIG. 14 shows an example of the experimental result of the present invention (part 2).
3) is shown. The result of this experiment is that in the case of Fe _0.8 (S _0.8 α _0.2 ) _0.2 , when α is changed as shown in the figure.

In the example of the experimental result of FIG. 14, Fe, S and α in the amounts corresponding to α are melted in the high frequency melting furnace according to S22 to S28 of FIG. 11, and the roll speed is 50 m / s in the liquid quenching device.
After the liquid is rapidly cooled with, it is pulverized to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. next,
The powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the obtained product, Br, iHc, +
The iHc was measured, and the obtained results are the results shown in FIG.

When α is one or more of Sn, Se, Te, Sb and As, high magnetic properties were obtained.
FIG. 15 shows an example (24) of the experimental result of the present invention. The results of this experiment are for (Fe ₁ -Z Co _Z ) _0.8 (S _0.8 Sn _0.2 ) _0.2 when Z is changed within the range of 0 to 0.55 as shown in the figure.

In the example of the experimental result of FIG. 15, the amounts of Fe, Co, S and Sn corresponding to the value of Z are changed from S22 to S28 of FIG.
According to the same manner as in FIG. 12, after melting in a high-frequency melting furnace, liquid quenching in a liquid quenching device at a roll speed of 50 m / s, 300 μm
Grind to m or less. This fine powder at 500 ° C for 1 hour, A
Heat treatment in r gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. The Br, iHc, and + iHc of the obtained product were measured, and the obtained results are the results shown in FIG.

When a part of Fe is replaced with Co, iHc
Grows larger. However, when Z exceeds 0.5, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0 <Z ≦ 0.5. Preferably 0.05
If ≦ Z ≦ 0.4, a value in which Br is larger and iHc is larger can be obtained.

(4) The configuration and operation of another embodiment of the present invention will be described in detail with reference to FIGS. 16 to 20. Other examples are Fe-S-β, (Fe-Co) -S-β.
In a magnetic field to develop exchange anisotropy and produce a permanent magnet.

FIG. 16 is a structural explanatory view of another embodiment of the present invention. In FIG. 16, S31 performs weighing. This is for the raw material of Fe-Co-S-β, in terms of atomic ratio, Fe _1-XY S _X β _Y β is one or more of Si, B, C, P and Ge 0.05 ≦ X ≦ 0 0.4 Weighed in a ratio of 0.01 ≦ Y ≦ 0.25, or (Fe _1-Z Co _Z ) _1-XY S _X β _Y β is one or more of Si, B, C, P and Ge 0 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.25 0
Weigh at a ratio of <Z≤0.5.

In step S32, high frequency melting is performed. This high frequency melting is performed in an inert gas atmosphere. In S33, the liquid is rapidly cooled (roll speed is adjusted). In order to reduce the crystal grain size, in the experiment, for example, at a roll speed of 60 m / s, a water-cooled roll was rotated and a high-frequency melted solution was introduced from the upper portion and rapidly cooled to obtain a thin plate having a small crystal grain size. Was generated.

At S34, the material is crushed (300 μm or less).
For this, the thin plate produced in S33 was crushed into a thin piece of 300 μm or less. In S35, heat treatment (temperature × time, atmosphere) is performed. In order to increase the coercive force iHc, heat treatment was performed in an Ar gas atmosphere at 550 ° C. for 1 hr in the experiment.

In S36, molding (pressure) is performed. here,
The powder that had been crushed and heat-treated was filled in a mold at a pressure of 4 t / cm ² and compression molded. In S37, the molded body after compression molding in S36 was cooled in a magnetic field (temperature, strength of magnetic field). In order to develop the exchange magnetic anisotropy, the temperature is higher than the Neel temperature, the natural cooling is performed, and the magnetic field is cooled by a magnetic field that magnetizes the soft magnetic phase in one direction. Specifically, for example, F
In the experiment, after heating to 400 ° C or higher than the Neel temperature of e-β-S, Fe-Co-β-S, etc., it was naturally cooled while applying a magnetic field that magnetized the soft magnetic phase in one direction. Then, the temperature is cooled to below the nail temperature and close to room temperature.

In S38, magnetic measurement (BH curve measurement) is performed. When the BH curve is measured for the result of S37, a characteristic (a characteristic in which the values of iHc and + iHc are not symmetrically displaced) as shown in FIG. 17 to FIG. Was obtained.

S39 is the completion of the permanent magnet. From the above, Fe _1-XY S _X β _Y β is _one or more of Si, B, C, P and Ge 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.25 or (Fe _1-Z Co _Z ) _1-XY S _X β _Y β is one or more of Si, B, C, P and Ge 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.25 0
By melting, quenching, crushing, heat treatment, molding, cooling in a magnetic field, and measurement of a BH curve, the raw materials weighed in an atomic ratio of <Z ≦ 0.5 were used.
As shown in FIGS. 7 to 20, permanent magnets having exchange magnetic anisotropy could be manufactured. Here, the experiment was conducted on the premise of the process of manufacturing an actual bonded magnet, but by cooling a mixture of the above raw materials uniformly in a magnetic field, exchange magnetic anisotropy is exhibited and a permanent magnet having good magnetic properties is obtained. Could be manufactured. Hereinafter, the experimental results will be sequentially described in detail with reference to FIGS.

FIG. 17 shows an example of experimental results of the present invention (part 3).
1) is shown. The results of this experiment are for Fe _0.9-X S _X Si _0.1 when X is changed within the range of 0.03 to 0.45 as shown in the figure.

In the experimental result example of FIG. 17, the amounts of Fe, S and Si corresponding to the value of X are melted in the high frequency melting furnace according to S32 to S38 of FIG.
After the liquid is rapidly cooled at 0 m / s, it is ground to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The iHc and + iHc were measured, and the obtained results are the results shown in FIG.

When X is less than 0.05, Br, i
Hc becomes smaller. When X exceeds 0.4, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0.05 ≦ X ≦ 0.4. Preferably,
If 0.1 ≦ X ≦ 0.35, a larger value of Br and a larger value of iHc can be obtained.

FIG. 18 shows an example of experimental results of the present invention (part 3).
2) is shown. The results of this experiment are for Fe _0.8-Y S _0.2 Si _Y when Y is changed within the range of 0 to 0.3 as shown in the figure.

In the example of the experimental results of FIG. 18, the amounts of Fe, S and Si corresponding to the value of Y are melted in the high frequency melting furnace according to S32 to S38 of FIG.
After the liquid is rapidly cooled at 0 m / s, it is ground to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The results obtained by measuring iHc and + iHc are the results shown in FIG.

When Y is less than 0.01, Br, i
Hc becomes smaller. When Y exceeds 0.2, Br becomes small. Therefore, a large Br value and a large iHc value were obtained within the range of 0.01 ≦ Y ≦ 0.25. Preferably,
If 0.05 ≦ X ≦ 0.2, a larger Br value and a larger iHc value can be obtained.

FIG. 19 shows an example of experimental results of the present invention (part 3).
3) is shown. The results of this experiment are those of Fe _0.7 S _0.2 β _0.1 when β is changed as shown.

In the experiment result example of FIG. 19, amounts of Fe, S and β corresponding to β are melted in a high frequency melting furnace according to S32 to S38 of FIG. 16, and a roll speed is 60 m / s in a liquid quenching device.
After the liquid is rapidly cooled with, it is pulverized to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. next,
The powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the obtained product, Br, iHc, +
The iHc was measured, and the obtained results are the results shown in FIG.

When β is one or more of Si, B, C, P and Ge, high magnetic characteristics were obtained. FIG. 20 shows an example (34) of the experimental result of the present invention. The result of this experiment is (Fe _{1 -Z} Co _Z ) _0.7 In S _0.2 Si _0.1 , Z is changed within the range of 0 to 0.55 as illustrated.

In the example of the experimental result of FIG. 20, the amounts of Fe, Co, S and Si corresponding to the value of Z are changed from S32 to S38 of FIG.
According to the above, the sample is melted in a high-frequency melting furnace, quenched in a liquid quencher at a roll speed of 60 m / s, and then pulverized to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder is heated from 400 ° C to room temperature at 10 kO.
It cooled in the magnetic field of e. For this obtained product, B
r, iHc, + iHc were measured, and the obtained results are shown in FIG.
The results are shown in.

When a part of Fe is replaced by Co, iHc
Grows larger. However, when Z exceeds 0.5, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0 <Z ≦ 0.5. Preferably 0.05
If ≦ Z ≦ 0.4, a value in which Br is larger and iHc is larger can be obtained.

(5) The configuration and operation of another embodiment of the present invention will be described in detail with reference to FIGS. 21 to 25. Other examples are Fe-S-T, (Fe-Co) -S-T.
In a magnetic field to develop exchange anisotropy and produce a permanent magnet.

FIG. 21 is a structural explanatory view of another embodiment of the present invention. In FIG. 21, in S41, weighing is performed. This is for the raw material of Fe-Co-S-T, in terms of atomic ratio, Fe _1-XY S _X T _Y T is one or more of Ti, V, Zr, Nb, Mo, Hf, Ta, W 0 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.2, or (Fe _1-Z Co _Z ) _1-XY S _X T _Y T is Ti, V, Zr, Nb, Mo, One or more of Hf, Ta and W 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.2 0 <
Weigh at a ratio of Z ≦ 0.5.

In step S42, high frequency melting is performed. This high frequency melting is performed in an inert gas atmosphere. In S43, the liquid is rapidly cooled (roll speed is adjusted). In order to reduce the crystal grain size, in the experiment, for example, at a roll speed of 40 m / s, a water-cooled roll was rotated and a high-frequency-dissolved solution was introduced from the top to rapidly cool the thin plate. Was generated.

At S44, the material is crushed (300 μm or less).
For this, the thin plate produced in S43 was crushed into a flaky shape of 300 μm or less. In S45, heat treatment (temperature × time, atmosphere) is performed. In order to increase the coercive force iHc, heat treatment was performed in an Ar gas atmosphere at 550 ° C. for 1 hr in the experiment.

In S46, molding (pressure) is performed. here,
The powder that had been crushed and heat-treated was filled in a mold at a pressure of 4 t / cm ² and compression molded. In S47, the molded body after compression molding in S46 was cooled in a magnetic field (temperature, magnetic field strength). In order to develop the exchange magnetic anisotropy, the temperature is higher than the Neel temperature, the natural cooling is performed, and the magnetic field is cooled by a magnetic field that magnetizes the soft magnetic phase in one direction. Specifically, for example, F
After being heated to 400 ° C or higher in Neel temperature of e-T-S, Fe-Co-T-S, etc., it was naturally cooled in a state where a magnetic field was applied to magnetize the soft magnetic phase in one direction. Then, the temperature is cooled to below the nail temperature and close to room temperature.

At S48, magnetic measurement (measurement of BH curve) is performed. With respect to the result of S47, when the BH curve is measured, a characteristic (a characteristic in which the values of iHc and + iHc are asymmetrically shifted) as shown in FIGS. Was obtained.

At S49, the permanent magnet is completed. As described above, Fe _1-XY S _X T _Y T is _one or more of Ti, V, Zr, Nb, Mo, Hf, Ta and W 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0 .2 or (Fe _1-Z Co _Z ) _1-XY S _X T _Y T is one or more of Ti, V, Zr, Nb, Mo, Hf, Ta and W 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.2 0 <
By melting, quenching, crushing, heat treatment, molding, cooling in a magnetic field, and BH curve measurement of the raw material weighed in the atomic ratio of Z ≦ 0.5, FIG.
As shown in FIGS. 2 to 25, permanent magnets having exchange magnetic anisotropy could be manufactured. Here, the experiment was conducted on the premise of the process of manufacturing an actual bonded magnet, but by cooling a mixture of the above raw materials uniformly in a magnetic field, exchange magnetic anisotropy is exhibited and a permanent magnet having good magnetic properties is obtained. Could be manufactured. 22 to 25 showing the experimental results will be sequentially described in detail below.

FIG. 22 shows an example of experimental results of the present invention (part 4).
1) is shown. The result of this experiment is that of Fe _0.9-X S _X Zr _0.1 when X is changed within the range of 0.03 to 0.45 as shown in the figure.

In the experiment result example of FIG. 22, the amounts of Fe, S, and Zr corresponding to the value of X are melted in the high-frequency melting furnace according to S42 to S48 of FIG.
After the liquid is rapidly cooled at 0 m / s, it is ground to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The results obtained by measuring iHc and + iHc are the results shown in FIG.

When X is less than 0.05, Br, i
Hc becomes smaller. When X exceeds 0.4, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0.05 ≦ X ≦ 0.4. Preferably,
If 0.1 ≦ X ≦ 0.35, a larger value of Br and a larger value of iHc can be obtained.

FIG. 23 shows an example of experimental results of the present invention (part 4).
2) is shown. The results of this experiment are for Fe _0.65-Y S _0.35 Zr _Y when Y is changed within the range of 0 to 0.25 as shown in the figure.

In the experimental result example of FIG. 23, the amounts of Fe, S and Zr corresponding to the value of Y are melted in the high frequency melting furnace according to S42 to S48 of FIG.
After the liquid is rapidly cooled at 0 m / s, it is ground to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The results obtained by measuring iHc and + iHc are the results shown in FIG.

When Y is less than 0.01, Br, i
Hc becomes smaller. When Y exceeds 0.2, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0.01 ≦ Y ≦ 0.2. Preferably, 0.
If 05 ≦ X ≦ 0.15, Br is further increased, and i
A large value of Hc can be obtained.

FIG. 24 shows an example of experimental results of the present invention (part 4).
3) is shown. The result of this experiment is that when T is changed as shown in the drawing in Fe _0.55 S _0.35 T _0.1 .

In the example of the experimental result of FIG. 24, the amounts of Fe, S and T corresponding to T are melted in the high frequency melting furnace according to S42 to S48 of FIG. 21, and the roll speed is 40 m / s in the liquid quenching device.
After the liquid is rapidly cooled with, it is pulverized to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. next,
The powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the obtained product, Br, iHc, +
The iHc was measured, and the obtained results are the results shown in FIG.

T is Ti, V, Zr, Nb, Mo, H
If one, two or more of f, Ta and W are used, high magnetic properties were obtained. FIG. 25 shows an example of experimental results of the present invention (part 4
4) is shown. The results of this experiment are for (Fe _1-Z Co _Z ) _0.55 S _0.35 Zr _0.1 when Z is changed within the range of 0 to 0.55 as shown in the figure.

In the experimental result example of FIG. 24, the amounts of Fe, Co, S, and Zr corresponding to the value of Z are S42 to S4 in FIG. 216.
In accordance with No. 8, melt in a high frequency melting furnace, quench liquid with a liquid quenching device at a roll speed of 40 m / s, and then pulverize to 300 μm or less. This fine powder is heat-treated at 550 ° C. for 1 hour in Ar gas. Next, the powder is heated from 400 ° C to room temperature at 10 kO.
It cooled in the magnetic field of e. For this obtained product, B
r, iHc, + iHc were measured, and the obtained results are shown in FIG.
The results are shown in.

When a part of Fe is replaced by Co, iHc
Grows larger. However, when Z exceeds 0.5, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0 <Z ≦ 0.5. Preferably 0.05
If ≦ Z ≦ 0.4, a value in which Br is larger and iHc is larger can be obtained.

(6) The configuration and operation of another embodiment of the present invention will be described in detail with reference to FIGS. 26 to 30. Other examples are Fe-S-γ, (Fe-Co) -S-γ.
In a magnetic field to develop exchange anisotropy and produce a permanent magnet.

FIG. 26 is a structural explanatory view of another embodiment of the present invention. In FIG. 26, S51 performs weighing. This is for the raw material of Fe-Co-S-γ, in terms of atomic ratio, Fe _1-XY S _X γ _Y γ is Cu, Ag, In, Ga, Al, Be one or more kinds 0.05 ≦ X. ≦ 0.4 0.01 ≦ Y ≦ 0.15, or (Fe _1-Z Co _Z ) _1-XY S _X γ _Y γ is one of Cu, Ag, In, Ga, Al, Be or Two or more types 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.150
Weigh at a ratio of <Z≤0.5.

In step S52, high frequency melting is performed. This high frequency melting is performed in an inert gas atmosphere. In S53, liquid quenching (roll speed adjustment) is performed. In order to reduce the crystal grain size, in the experiment, for example, at a roll speed of 55 m / s, a water-cooled roll was rotated and a high-frequency-dissolved solution was introduced from the upper portion to rapidly cool the thin plate having a small crystal grain size. Was generated.

At S54, the material is crushed (300 μm or less).
For this, the thin plate produced in S53 was crushed into a flaky shape of 300 μm or less. In S55, heat treatment (temperature × time, atmosphere) is performed. In order to increase the coercive force iHc, heat treatment was performed in an Ar gas atmosphere at 500 to 550 ° C. for 1 hr in the experiment.

In S56, molding (pressure) is performed. here,
The powder that had been crushed and heat-treated was filled in a mold at a pressure of 4 t / cm ² and compression molded. In S57, the molded body after compression molding in S56 was cooled in a magnetic field (temperature, strength of magnetic field). In order to develop the exchange magnetic anisotropy, the temperature is higher than the Neel temperature, the natural cooling is performed, and the magnetic field is cooled by a magnetic field that magnetizes the soft magnetic phase in one direction. Specifically, for example, F
In the experiment, after being heated to a Neel temperature of e-γ-S, Fe-Co-γ-S, etc., to 400 ° C., it was naturally cooled while applying a magnetic field for magnetizing the soft magnetic phase in one direction. Then, the temperature is cooled to below the nail temperature and close to room temperature.

In S58, magnetic measurement (measurement of BH curve) is performed. With respect to the result of S57, when the BH curve is measured, a characteristic (a characteristic in which the values of iHc and + iHc are asymmetrically shifted) as shown in FIG. 27 to FIG. Was obtained.

S59 is the completion of the permanent magnet. From the above, Fe _1-XY S _X γ _Y γ is _one or more of Cu, Ag, In, Ga, Al and Be 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.15 or (Fe _1-Z Co _Z ) _1-XY S _X γ _Y γ is one or more of Cu, Ag, In, Ga, Al and Be 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0 .150
By melting, quenching, pulverizing, heat treating, molding, cooling in a magnetic field, and measuring the BH curve of the raw material weighed in an atomic ratio of <Z ≦ 0.5, FIG.
7 to 30, a permanent magnet having exchange magnetic anisotropy could be manufactured. Here, the experiment was conducted on the premise of the process of manufacturing an actual bonded magnet, but by cooling a mixture of the above raw materials uniformly in a magnetic field, exchange magnetic anisotropy is exhibited and a permanent magnet having good magnetic properties is obtained. Could be manufactured. The experimental results will be sequentially described in detail below with reference to FIGS. 27 to 30.

FIG. 27 shows an example of an experimental result of the present invention (part 5).
1) is shown. The result of this experiment is that in the case of Fe _0.93-X S _X Cu _0.07 , when X is changed within the range of 0.03 to 0.45 as shown in the figure.

In the example of the experimental result of FIG. 27, the amounts of Fe, S, and Cu corresponding to the value of X are melted in the high-frequency melting furnace according to S52 to S58 of FIG.
After the liquid is rapidly cooled at 5 m / s, it is ground to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The results obtained by measuring iHc and + iHc are the results shown in FIG.

When X is less than 0.05, Br, i
Hc becomes smaller. When X exceeds 0.4, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0.05 ≦ X ≦ 0.4. Preferably,
If 0.1 ≦ X ≦ 0.35, a larger value of Br and a larger value of iHc can be obtained.

FIG. 28 shows an example of experimental results of the present invention (part 5).
2) is shown. The results of this experiment are for Fe _0.8-Y S _0.2 Cu _Y when Y is changed within the range of 0 to 0.18 as shown in the figure.

In the example of the experimental result of FIG. 28, the amounts of Fe, S, and Cu corresponding to the value of Y are melted in the high-frequency melting furnace according to S52 to S58 of FIG.
After the liquid is rapidly cooled at 5 m / s, it is ground to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. Next, the powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the product obtained, Br,
The results obtained by measuring iHc and + iHc are shown in FIG.

When Y is less than 0.01, Br, i
Hc becomes smaller. When Y exceeds 0.15, Br decreases. Therefore, a large Br value and a large iHc value were obtained within the range of 0.01 ≦ Y ≦ 0.15. Preferably,
If 0.04 ≦ X ≦ 0.1, a larger Br value and a larger iHc value can be obtained.

FIG. 29 shows an example of experimental results of the present invention (part 5).
3) is shown. The result of this experiment is that in the case of Fe _0.73 S _0.2 γ _0.07 , when γ is changed as shown in the figure.

In the example of the experimental result of FIG. 29, the amounts of Fe, S and γ corresponding to γ are melted in the high frequency melting furnace according to S52 to S58 of FIG. 26, and the roll speed is 55 m / s in the liquid quenching device.
After the liquid is rapidly cooled with, it is pulverized to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. next,
The powder was cooled from 400 ° C. to room temperature in a magnetic field of 10 kOe. For the obtained product, Br, iHc, +
The iHc was measured, and the obtained results are the results shown in FIG.

Γ is Cu, Ag, In, Ga, Al,
High magnetic properties were obtained with one or more Be. FIG. 30 shows an example (54) of the experimental result of the present invention. The results of this experiment are for (Fe _1-Z Co _Z ) _0.73 S _0.2 Cu _0.07 when Z is changed within the range of 0 to 0.55 as shown in the figure.

In the example of the experimental result of FIG. 30, the amounts of Fe, Co, S and Cu corresponding to the value of Z are changed from S52 to S5 of FIG.
In accordance with No. 8, melting is performed in a high frequency melting furnace, liquid is rapidly cooled in a liquid quencher at a roll speed of 55 m / s, and then pulverized to 300 μm or less. This fine powder is heat-treated at 500 ° C. for 1 hour in Ar gas. Next, the powder is heated from 400 ° C to room temperature at 10 kO.
It cooled in the magnetic field of e. For this obtained product, B
r, iHc, + iHc were measured, and the obtained results are shown in FIG.
The results are shown in.

When a part of Fe is replaced by Co, iHc
Grows larger. However, when Z exceeds 0.5, Br becomes small. Therefore, a large Br and a large iHc were obtained in the range of 0 <Z ≦ 0.5. Preferably 0.05
If ≦ Z ≦ 0.4, a value in which Br is larger and iHc is larger can be obtained.

[0144]

As described above, according to the present invention,
(Fe-Co) -S, (Fe-M) -S, ((Fe-C
o) -M) -S, Fe- (S-α), (Fe-Co)-
(S-α), Fe-S-β, (Fe-Co) -S-β,
Fe-S-T, (Fe-Co) -S-T, Fe-S-
A material consisting of γ and (FE-Co) -S-γ is cooled in a magnetic field to exhibit exchange magnetic anisotropy, and therefore has excellent magnetic properties (large Br and iHc and is easily magnetized). I got a magnet. Here, M, α, β, T and γ are
As described above, it is as follows.

M: Cr, Mn, Ni .alpha .: Sn, Se, Te, Sb, As .beta .: Si, B, C, P, Ge. T: Ti, V, Zr, Nb, Mo, Hf, Ta, W.γ: Cu, Ag, In, Ga, Al, Be By realizing this permanent magnet with exchange magnetic anisotropy, (1) a permanent magnet containing no rare earth element was realized.

(2) The Br value was larger than that of the ferrite magnet. (3) iHc was higher than that of alnico magnets, and higher than that of ferrite magnets depending on the conditions.

(4) Since + iHc is asymmetrical and smaller than iHc (see the BH curve in FIG. 5), the magnetic force at the time of magnetizing the permanent magnet can be small and can be magnetized easily.

[Brief description of drawings]

FIG. 1 is a configuration explanatory diagram of an embodiment of the present invention.

FIG. 2 is an example (1) of the experimental result of the present invention.

FIG. 3 is an example (2) of the experimental result of the present invention.

FIG. 4 is an example (No. 3) of experimental results of the present invention.

FIG. 5 is an example of BH loop measurement according to the present invention.

FIG. 6 is a diagram showing the configuration of another embodiment of the present invention.

FIG. 7 is an example (part 11) of the experimental result of the present invention.

FIG. 8 is an example (12) of the experimental result of the present invention.

FIG. 9 is an example (13) of the experimental result of the present invention.

FIG. 10 is an example (14) of the experimental result of the present invention.

FIG. 11 is a diagram illustrating the configuration of another embodiment of the present invention.

FIG. 12 is an experimental result example (21) of the present invention.

FIG. 13 is an example (22) of the experimental result of the present invention.

FIG. 14 is an example (23) of the experimental result of the present invention.

FIG. 15 is an example (24) of the experimental result of the present invention.

FIG. 16 is a diagram showing the configuration of another embodiment of the present invention.

FIG. 17 is an example (31) of the experimental result of the present invention.

FIG. 18 is an example (32) of the experimental result of the present invention.

FIG. 19 is an example (No. 33) of the experimental result of the present invention.

FIG. 20 is an example (34) of the experimental result of the present invention.

FIG. 21 is a structural explanatory view of another embodiment of the present invention.

FIG. 22 is an example (No. 41) of the experimental result of the present invention.

FIG. 23 is an example (42) of the experimental result of the present invention.

FIG. 24 is an example (43) of the experimental result of the present invention.

FIG. 25 is an example (No. 44) of the experimental result of the present invention.

FIG. 26 is a diagram showing the configuration of another embodiment of the present invention.

FIG. 27 is an example (No. 51) of experimental results of the present invention.

FIG. 28 is an example (52) of the experimental result of the present invention.

FIG. 29 is an example (53) of the experimental result of the present invention.

FIG. 30 is an example of the experimental results of the present invention (No. 54).

[Explanation of symbols]

S1, S11, S21, S31, S41, S51: Weighing S7, S17, S27, S37, S47, S57: Cooling in magnetic field

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Matsui 5-36-11 Shinbashi, Minato-ku, Tokyo Fuji Electric Chemical Co., Ltd.

Claims (11)

[Claims] 1. An atomic ratio of (Fe _{1 -Y} Co _Y ) _1-X S _X 0.05≤X≤0.4 0.02≤Y≤0.5, which is obtained by cooling in a magnetic field and exchanging magnetism. A permanent magnet that exhibits anisotropy. 2. The atomic ratio of (Fe _{1 -Y} M _Y ) _1-X S _X M is one or more of Cr, Mn, and Ni 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ A permanent magnet consisting of 0.3 and exhibiting exchange magnetic anisotropy when cooled in a magnetic field. 3. An atomic ratio of ((Fe _{1 -Z} Co _Z ) _{1 -Y} M)
_Y ) _1-X S _X M is one or more of Cr, Mn, and Ni 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.3 0 <
A permanent magnet having Z ≦ 0.5 and being cooled in a magnetic field to exhibit exchange magnetic anisotropy. 4. Fe _1-X (S _1-Y α _Y ) _X α in terms of atomic ratio is _one or more of Sn, Se, Te, Sb, As 0.05 ≦ X ≦ 0.4. A permanent magnet having 02 ≦ Y ≦ 0.5 and being cooled in a magnetic field to exhibit exchange magnetic anisotropy. 5. The atomic ratio of (Fe _1-Z Co _Z ) _1-X (S
_1-Y α _Y ) _X α is one or more of Sn, Se, Te, Sb and As 0.05 ≦ X ≦ 0.4 0.02 ≦ Y ≦ 0.5 0 <
A permanent magnet having Z ≦ 0.5 and being cooled in a magnetic field to exhibit exchange magnetic anisotropy. 6. The atomic ratio of Fe _1-XY S _X β _Y β is one or more of Si, B, C, P and Ge 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0 .25, which is a permanent magnet cooled in a magnetic field to exhibit exchange magnetic anisotropy. 7. An atomic ratio of (Fe _1-Z Co _Z ) _1-XY S _X
β _Y β is one or more of Si, B, C, P and Ge 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.25 0
A permanent magnet consisting of <Z ≦ 0.5 and exhibiting exchange magnetic anisotropy by cooling in a magnetic field. 8. The atomic ratio of Fe _1-XY S _X T _Y T is one or more of Ti, V, Zr, Nb, Mo, Hf, Ta and W. 0.05 ≦ X ≦ 0.4 0 A permanent magnet of 0.01 .ltoreq.Y.ltoreq.0.2, which is cooled in a magnetic field to exhibit exchange anisotropy. 9. An atomic ratio of (Fe _1-Z Co _Z ) _1-XY S _X
T _Y T is one or more of Ti, V, Zr, Nb, Mo, Hf, Ta, W 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.2 0 <
A permanent magnet having Z ≦ 0.5 and being cooled in a magnetic field to exhibit exchange magnetic anisotropy. 10. An atomic ratio of Fe _1-XY S _X γ _Y γ is one or more of Cu, Ag, In, Ga, Al and Be 0.05 ≦ X ≦ 0.4 0.01 ≦ Y A permanent magnet consisting of ≦ 0.15, which exhibits exchange magnetic anisotropy when cooled in a magnetic field. 11. An atomic ratio of (Fe _1-Z Co _Z ) _1-XY S
_X γ _Y γ is one or more of Cu, Ag, In, Ga, Al and Be 0.05 ≦ X ≦ 0.4 0.01 ≦ Y ≦ 0.150
A permanent magnet consisting of <Z ≦ 0.5 and exhibiting exchange magnetic anisotropy by cooling in a magnetic field.