JPS59211559A - Permanent magnet material - Google Patents

Abstract

PURPOSE:To provide a permanent magnet material which consists of a sintered body having magnetic anisotropy and has an excellent magnetic characteristic by sintering alloy powder incorporated with a rare earth element including Y, Co, B and specific elements in Fe. CONSTITUTION:<50% Co by atomic per cent, 8-30% at least 1 kind among rare earth elements including Y, 2-28% B, and a specific amt. of one or >=2 kinds among Ti, Bi, Nb, Cr, W, Al, Ni, V, Ta, Mo, Mn, Sb, Ge, Zr, Sn and Hf at the atomic per cent of the max. value among these added elements or below or one or >=2 kinds among <3.5 Cu, <2.0 S, <4.0 C, and <3.5 P at the max. content among these or below are incorporated in Fe as compsn. Such iron alloy powder is sintered, and the permanent magnet material which consists of the sintered body having magnetic anisotropy and 1-100mum average grain size and has high residual magnetization, high coercive force and high energy product is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a FeBR-based sintered permanent magnet material, and particularly to one having a specific crystal grain size that can realize preferable magnetic properties. In the present invention, R represents a rare earth element containing Y.

With the recent advances in electronics technology, permanent magnets are being used in speakers, motors, and magnetic disks, making use of energy conversion between mechanical energy and electrical energy, and the principle of deflection of ion and electron beams by the Lorentz force. Drive device.

RLJ is widely used in devices such as seismograph generators and magnetrons, and is one of the industrially important materials.

Furthermore, alnico, hard ferrite, samarium cobalt (SmCo), etc. are well known as permanent magnet materials and are in practical use. Among these, alnico has a high residual magnetic flux density (hereinafter abbreviated as Br), but has a small coercive force (hereinafter abbreviated as Hc), and /
\-Doferrite has high He but low Br.

With advances in electronics technology, electrical components are becoming more highly integrated and smaller, and Alnico.

A magnetic circuit using hard ferrite must be larger in both weight and volume than other components. On the other hand, SmCo magnets have high Br and large Hc, so they meet the demands for miniaturization and high performance of magnetic circuits, but samarium used as a raw material is a rare resource, and cobalt is a limited resource. Supply is unstable because it is unevenly distributed in the region.

Therefore, it has been desired to develop a new permanent magnet material that does not have these problems.

However, in order for rare earth magnets to be used cheaply and in large quantities in a wide range of fields, expensive cobalt must not be included in the multi-needle, and it must be contained in large amounts in the rare earth metal binder - C1 ore. It is necessary that the main component be light rare earth elements. As one attempt to develop such a permanent magnet material, R
Fez-based compounds (wherein R is at least one rare earth metal) were investigated. Clark (A, E, C1ark
) is 4.2° for sputtered amorphous TbFe2.
K Te29.5MGOe (7) Has energy product, 3
When heat treated at 00~500'O, the holding power Hc at room temperature
=3.4KOe, maximum energy product (BH)max=7
It was found that MGOe was exhibited. Similar studies have shown that SmF
It was also conducted for e2, and it was reported that it showed 9.2 MGOe at 77°. However, all of these materials are thin films made by sputtering, and are not magnets used in general speakers or motors. Also, PrF
It has been reported that an ultra-quenched ribbon of an e-based alloy exhibits a high coercive force of Hc=2.8KOe.

Salani, Kuhn, etc. (Feb42 Bo, +g) o
, q Tbo, o5La (), kfj of o5 When the quenched amorphous ribbon is annealed at 627°C, Hc=
l] KOe (Br = 5K
G). However, in this case, due to the poor squareness of the magnetization curve (
BH) Wax is low (N, C, Koon et al., Appl.

Phys, Lett, 39(10), 1981.840
~842 pages).

Also, force/< core (L, Kabacoff:)′J
is (Fe 6.g B 0.2)1-xPrx(X=0
An ultra-quenched ribbon with a composition of ~0.3 atomic ratio) was prepared, and Fe
It has been reported that there is a -Pr binary system with Hc at the KOe level at room temperature.

These ultra-quenched ribbons or Spunthal films are not practical permanent magnets (bodies) that can be used as such, and practical permanent magnets cannot be obtained from these ribbons or films.

That is, the conventional Fe11B-R ultra-quenched ribbon or RFe
It is not possible to obtain a bulk permanent magnet body having an arbitrary shape and shape from a thin film based on Subanta.

The magnetization curves of Fe-B-R ribbons reported so far have poor squareness, and cannot be considered practical permanent magnet materials that can compete with conventional magnets. Furthermore, both the sputtered thin film and the ultra-quenched ribbon are essentially isokinetic, and it is virtually impossible to obtain a practical permanent magnet with magnetic anisotropy from them.

Therefore, the basic object of the present invention is to eliminate the above-mentioned drawbacks of the conventional method and to obtain a new practical permanent magnet body having magnetic properties of wind 1-8 comparable to those of conventional hard ferrite. More specifically, the present invention provides a practical permanent magnet that has good magnetic properties above room temperature, can be formed into any shape and practical size, has a highly square magnetization curve, and has magnetic anisotropy. The object of the present invention is to obtain an element in which light rare earth elements, which are abundant in resources, can be used effectively as R.

The present inventors previously discovered that samarium is not necessarily required, but is rich in resources and has little known use to date, such as Nd and light rare earths, and Fe, which is mainly composed of Fe.
A BR compound permanent magnet was developed and filed by the same applicant as the present application (Japanese Patent Application No. 145072/1982).

This FeBR-based magnet material has high Br and high energy product (hereinafter abbreviated as (BH)wax), and is a completely new industrial permanent magnet material that can replace conventional alnico, hard ferrite, and SmCo-based magnets.

The Curie point of this FemBaR permanent magnet material is generally around 300°C, and a maximum of 370°C. This single Curie point is considerably lower than the single Curie point of about 800°C for conventional alnico-based or 5IIICO-based permanent magnets. Therefore, compared to conventional alnico-based or 5raCo-based magnets, Fe.B-R permanent magnet materials have a greater dependence of magnetic properties on magnetic properties, resulting in a decrease in magnetic properties at high temperatures.

The basic purpose of the present invention is to provide a new permanent magnet material to replace these permanent magnet materials, and in particular, it does not necessarily require rare S+a etc. as R, and it is not necessarily necessary to use a large amount of CO. It is an object of the present invention to provide a permanent magnet material having magnetic properties equivalent to or higher than those of conventional ferrite, and also to provide a material having a sufficiently high Curie point (temperature property) for practical use. As a series of research results in accordance with this objective, the present inventors have developed a Fe*B*R permanent magnet, which improves the hot magnetic properties of the material and provides a range of sintered crystal grain sizes to obtain good magnetic properties. The purpose is to

In terms of atomic percentage, 8 to 30% R (where R is at least one rare earth element including Y), 2 to 28% (7) B,
50% or less (7) Go (excluding LCo 0%), F
One or more of the additive elements M in the specified percentage (however, M
In the case where two or more of the above-mentioned additive elements are included as M, excluding OX, the total amount of M is equal to or less than the atomic percentage of the one having the maximum value among the additive elements), and the balance consists of Fe,
A magnetically anisotropic sintered permanent magnet material having an average crystal grain size of 1-100 gm; Ti 4.5% or less, Ni 8.0% or less, Hi 5.0% or less, V 9.5 %below,
Nb 12.5% or less, Ta 10.5% or less, Cr 8.5% or less, No 9.5% or less, w 8.5x or less, Mn 8.0% or less/AI 9.5% or less, Sb 2.5%
Below, Ge 7.0% or less, Sn 3.5%
Below, Zr is 5.5% or less, and Hf is 5.5% or less.

Furthermore, the present invention allows the above-mentioned sintered permanent magnet composition to contain one or more of the following elements X (Cu, S, C, P) at a predetermined 2 or less: Cu
3.5% or less, 9 2.0% or less, C4, 0% or less, and P 3.5% or less (However, if two or more types of X are included, the content of X has the maximum value among the relevant elements. It is less than the atomic percentage of
The contents of M and X shall be equal to or less than the atomic percentage of the element having the maximum value among the elements. ) The present invention will be explained in detail below.

As disclosed in Japanese Patent Application No. 57-145072, FeBR alloy exhibits high magnetic properties as a sintered body and has a Curie point 3.
It is a completely new crystalline alloy having a temperature of about 00°C to about 370°C. The inventors of the present invention have discovered that by making this FeBR alloy into a sintered body through the processes of melting, casting, pulverizing, orientation forming in a magnetic field, and sintering, a permanent magnet with magnetic properties that could not be confirmed with this system in the past. However, in general, in the present invention, excellent temperature and conflict magnetic properties as a permanent magnet can be exhibited when the average crystal grain size of the sintered body is within a certain range. This fact has been clarified through extensive experiments, and a high-performance FeCoBRM-based sintered permanent magnet 1 can be stably produced industrially.

The FeCoBRM alloy has been found by measurements by the present inventors to have a high magnetocrystalline anisotropy constant Ku and an anisotropic magnetic field Ha comparable to that of the conventional SmCo alloy 1.

According to the theory of single-domain particles, magnetic materials with high Ha have the potential to become high-performance fine particle magnets, such as hard ferrite and Sn+Go magnets. From this point of view, the present inventor created sintered fine particle magnets in which FeBR-based magnets had a wide composition range and varied the crystal grain size after sintering, and measured the permanent magnet characteristics.

As a result, we found that the obtained magnetic properties are closely related to the average grain size after sintering.

In general, in single-domain fine particle magnets, if the particles are large, the particles will have a domain wall, so 1. Reversal of magnetization easily occurs due to movement of domain walls, and He is small. On the other hand, when the particles become smaller to a certain size or less, the particles no longer have domain walls, and the reversal of magnetization proceeds only by rotation, so that He becomes larger. The critical dimension of this single magnetic domain differs depending on each material, and in the case of iron it is 0.01
gm, hard ferrite is 1 lm, SmCo type is 4
#i, it is said to be ranked 111th.

Further, high values of Hc for each of these materials are obtained near this critical dimension. In the FeCoBRN permanent magnet of the present invention, HclKOe or higher is obtained when the average crystal grain size is in the range of 1"100 gm, preferably 1.1 to 7 Qpm.
Hc4KOe or higher can be obtained within this range. The permanent magnet of the present invention is obtained as a sintered body. Therefore, the size of crystal grains after sintering the sintered body is a problem. The Hc of the sintered body is l K
In order to achieve Oe or more, the average grain size after this sintering is 1
It was experimentally confirmed that gra or more is required.

In order to obtain a finer sintered body crystal grain size, it is necessary to create a fine powder before sintering. However, FeCoBRM
The Hc of the sintered body is significantly lower due to the fact that fine alloy powder is easily oxidized, the effect of strain on the fine particles becomes large, and when the particle size becomes extremely small, it becomes superparamagnetic rather than ferromagnetic. It is thought that f is low.

Further, when the crystal grain size becomes larger than 80 lm, the particles are no longer single-domain fine particles, but have a domain wall inside the particles, and magnetization reversal easily occurs, and Hc becomes small. In order to be less than Hc l KOe, it must be less than 1100p. Particularly preferably 2 to 40Ji,
11, He can be obtained with high properties of 4 KOe or more (see Figure JJ1 below).

The permanent magnet material of the present invention has substantially the same temperature characteristics as the conventional one by substituting a part of Fe in the Fe*B*R alloy with Co and containing 50% or less (atomic percentage) of Go in the magnet composition. This is an improvement comparable to that of alnico and Sv+Go magnets. Furthermore, by containing GO, light rare earths such as Nd and Pr, which are abundant in resources, are used as the rare earth element R to exhibit high magnetic properties. Therefore, Fe・CO of the present invention
The φB-RM magnet material is also advantageous in terms of resources and life cost compared to conventional SmCo magnets.

Generally, when Go is added to an Fe alloy, it is difficult to predict the effect of the addition, as in some cases the Curie point increases by -1- in proportion to the amount of Go added, while in others it increases by a certain amount.

In the present invention, it has become clear that the Curie point when a portion of Fe is replaced with Go gradually increases as the amount of Co replacement increases, as shown in FIG.

Even a small amount of CO substitution is effective in increasing the curio by one point, and as shown in Figure 1, the amount of CO is about 300 to about 750
An alloy with an arbitrary Curie point of °C is obtained.

When the CO content exceeds 25'X, (BH)wax gradually decreases, and when it exceeds 35%, a rapid decrease occurs. This is mainly due to a decrease in He in the magnet. Co arrogance is 50%
(BH) mat is 4MGO of hard ferrite.
It decreases to about e. Therefore, the limit for the amount of Co is 50%. It is preferable that the Co amount is 35% or less because (BH) wax is high and the raw material price is low. Also, CO is Fe
Since it has corrosion resistance compared to Go, it is also possible to impart corrosion resistance by containing Go.

The rare earth element R used in the permanent magnet of the present invention includes Y,
It is a rare earth element including light rare earths and heavy rare earths, and one or more of them is used. That is, this R is Nd,
Pr, La, Ce, Tb, Dy, Ho.

Er, Eu, Sm, Gd, Pa, Tm, Y
b, Lu and Y are included. As R, a light rare earth element is sufficient, and Nd and Pr are particularly preferable. Also usually H
One of these is sufficient, but in practice, two or more types of mixed grains (Mitushmetal, Zidim, etc.) can be used for reasons such as convenience of acquisition, Ss, Y, La, C.
E, Gd, etc. can be used as a mixture with other R, especially Nd, Pr, etc. Note that this R does not have to be a pure rare earth element, and can be achieved by industrially skilled labor u (within the production efficiency i).
j) It may contain unavoidable impurities.

As B (boron), pure poron or ferroporon can be used, and those containing AI, Si, C, etc. as impurities can also be used.

The permanent magnet of the present invention has an R12 to 28% R of 8 to 30% as described above.
%B, 50% or less cy) Go, M at a given z, balance Fe
(atomic percentage), it exhibits magnetic properties with a coercive force Hc≧IKOe, a residual magnetic flux density Br4KG or more, and a maximum energy product (BH)wax that is equal to or higher than that of hard ferrite (about 4MGOe).

When R is less than 8 atomic %, Hc becomes lower than lKOe. As R increases, Hc increases, but 30
When the atomic % is exceeded, the Br value of hard ferrite is approximately 4.
It becomes less than KG. B shows a similar tendency; below 2%, Hc becomes lower than l KOe, and above 28%, Br
becomes lower than 4KG.

Light rare earth is the main component of R (i.e. 50 atomic% or more of light rare earth in all R), 11-24$R13-27%B, 35%
The following composition of Co, M of predetermined 2, and balance Fe is the maximum energy m (BH) Peng a! ≧7 indicates MGOe, which is a preferable range.

Most preferably, the main component of R is a light rare earth, and 12 to 2
The composition is 0$R14'~241B, 30% or less of co, a predetermined 2 or less of M, and the balance is Fe, and the maximum energy product (BH
)wax≧10MGOe, and (BH)max reaches a maximum of 35MGOe or more.

The permanent magnet of the present invention is a Fe*Co・BR@M system, and exhibits better temperature characteristics than the FeeB fist R system magnet, Br is almost the same, iHc is the same or slightly lower, but the squareness is lower. Since the (OH) wax is improved, the wax is the same or higher. Further, as R, a light rare earth element which is abundant in resources can be used, and it is not necessarily necessary to use S or to use Sl as a main component, so the raw materials are abundant, inexpensive, and extremely useful.

In the permanent magnet of the present invention, most of M has the effect of increasing Hc. Increasing Hc by adding M increases the stability of the magnet and expands its uses. However, since M is a non-magnetic element (except for old), as the addition range increases, Br decreases, and as a result, (BH)Ilax decreases. (BH) Peng aX has high iHc even if it is a little lower
M
The alloy containing is for large cloth □, but (BH)+ax is 4M
It is useful in the range of GOe or higher.

Hereinafter, aspects and effects of the present invention will be explained according to examples. However, the present invention is not limited to the examples and described aspects.

Tables 1 to 3 show various Fe produced by the following steps.
-Characteristics of a permanent magnet made of a Co.B@RM compound are shown (things outside the scope of the present invention are also shown with a C symbol for comparison).

(1) The alloy was high-frequency melted and cast in a water-cooled copper mold. The starting materials were electrolytic iron with a purity of 913.9% as Fe, and a teferoporon alloy as B (19.38% B, 5.32% AI).

0.74XSi, 0.03%G, balance Fe), R
and L-r purity of 88.7% or higher (impurities are mainly other rare earth metals).

As Co, electrolytic Co with a purity of 99.9% was used.

Purity of M is 1313% (y) T + + N
o+Br+Mn+Sb.

Old, Ta, Ge, 98% (7) W, 99.9
% AI, Sn, 85% ノHf, ttriV tLte8
1.2% (7) Vt-containing ferrovanadium, Nb
ferroniobium containing 61.13% Cr and Zr.
Ferrozirconium containing 75.5% Zr was used as the material.

(2) Grinding: Coarsely pulverize to 35 mesh through using a stamp mill, then finely pulverize (3 to 10 pm) using a ball mill for 3 hours.

(3) Orientation and molding (1.5t) in a magnetic field (10KOe)
/ am').

(4) Sintering 1000-1200'0 1 hour Ar
Medium, left to cool after sintering.

Next, in the above method, (2) pulverization was carried out using a sub-sieve-sizer manufactured by Fisher.
) The grinding time was appropriately changed so that each particle had an average particle size measurement value of 0.5 to 100 gm, and samples with the respective compositions shown in Table 3 were prepared.

Comparative example: 1004ti! In order to have a crystal grain size of “-”,
After sintering, it was held for a long time in an Ar atmosphere at a temperature 5 to 20°C lower than the sintering temperature.

Magnetization of the samples having the respective compositions shown in Tables 1 to 4 thus obtained was examined, and the magnetic properties and average crystal grain size were measured. The results are shown in Tables 1-4. Here, the average crystal grain size is defined as: After polishing the sample surface and etching it, take a micrograph at a magnification of X100 to X100O using an optical microscope, and draw a circle with a known area.1. A straight line was drawn to divide the circle into eight equal parts, and the average number of particles within the diameter was counted and calculated. however,
Particles separated by the boundary lx (on the circumference) are counted as 1/2 (this method is known as Heyn's method).

The part of the hole is omitted from the calculation.

(1,000 4 "■) Table 1 Table 2 Table 3 In the magnet material of the present invention, as the amount of B increases, He rapidly increases. Along with this, (BH) wax is 7 to 30 MGOe.
, it reaches a maximum of 35 MGOe or more, and exhibits high characteristics that even surpass SmCo magnets, which are the highest grade permanent magnets currently known. Tables 1 and 2 mainly show the cases of Nd and Pr, but as shown in Table 3, FeeCo*Bφ
RM compounds exhibit good permanent magnetic properties. Fe@Co
*BsReM compounds exhibit good permanent magnetic properties in moderate and R acids. As B increases from 0 in the Fe5Co*B*R*M system, Hc increases. On the other hand, the residual magnetic flux density B increases monotonically at first, but reaches a peak around 10 atoms, and as the amount of B increases further, Br decreases monotonically.As a permanent magnet (material), at least 1 KOe In order to satisfy this requirement, the amount of B must be at least 2 atomic % or more.
2 (preferably 3 atomic % or more). The permanent magnet of the present invention is characterized by high Br,
It is often used in applications that require high magnetic flux density.

In order to make the Br of hard ferrite approximately 4KG or more,
In the FeeCoeBsReM compound, Bi must be present at 28 atomic % or less. In addition, 83 to 27 atomic%
, 4 to 24 atomic % is a preferable or optimal range for (BH)wax to be 7 MGOe or more and 1-111-110 or more, respectively.

Next, the optimum range of the R amount will be considered.

The larger the μ of R, the higher the l(c), which is desirable as a permanent magnet.As a permanent magnet material, as mentioned earlier, H
Since e is required to be greater than IKOe, RH
4l must be 8 atoms 2 or more. On the other hand, it is good to have a high Hc as the R content increases, but since R is easily oxidized, the powder of the high R alloy is easily flammable and difficult to handle. Therefore, in consideration of Mars productivity, it is desirable that the amount of R is 30 atoms 2 or less. If the amount of H is more than this, the powder becomes easily flammable and mass production becomes very difficult.

Further, since R is more expensive than Fe, it is desirable that R be as small as possible. In addition, R11-24 original J'-%, 1
The range of 2 to 20 atomic% is large'/(OH)wax 7
The preferable or optimal range is 1-, which is MGOe or more and 10MGOe or more.

Considering the additive element M, in order to confirm the effect of each addition of the additive element M on Br, Br was measured by varying the amount added, and the results are shown in FIGS. 2 to plS4.

Old, Mn, other additive elements M other than old (Ti, Zr
.

Hf, V, Ta, Nb, Or, w, No,
The upper limit of the addition amount of sb, Sn, Ge, AI) is approximately 4 Br of hard ferrite as shown in Figures 3 to 5.
It can be selected as a range equivalent to KG. Furthermore, the preferable range from the viewpoint of Br is 8.5.8. l0K
By dividing them into stages such as G, they can be clearly read from FIGS. 3 to 5, respectively.

From these figures, the level of hard ferrite (BH) w
The upper limit of the amount of the additive element M is set to be equal to or higher than about 4 KGOe.

Ti 4.5X or less, Ni 8. Below OX,
Hi 5.0% or less, V 9.5% or less, N
b 12.5 or less X, Ta 10.5% or less, Cr 8.5% or less, No 9.5% or less, W 8.5% or less, Mn 8. O$X or less Al 11.5 X or less, Sb' 2.5
X or less, Ge 7.0% or less, Sn 3
．． 5% or less, Zr 5.5% or less, and HP 5.5% or less.

When two or more of the above elements are contained, the intermediate value of the characteristic curves of each added element shown in Figures 2 to 4 is generally indicated, and the content of each element is within the above percentage range and the content is within the above percentage range. It is below the maximum value of the above percentage for each element.

Generally, Br decreases as the amount of M added increases, but on the other hand, He increases for most M (B
H) max becomes approximately the same value by adding M as when not adding M. Increasing the coercive force Hc contributes to stabilizing the magnetic properties, so that a permanent magnet that is extremely stable in practical use and has a high energy product (BH) wax can be obtained.

Does adding a large amount of Mn or Ni reduce He?
Since is a ferromagnetic element, Br does not decrease much. Therefore, the old upper limit was set at 8z from the viewpoint of Br, and from the viewpoint of Hc, Ni is preferably 4.5z or higher.

Although the addition of Mn has a greater effect on Br reduction than N1, it is not a drastic effect. One upper limit of Mn is 8z from the viewpoint of Br.
From the viewpoint of He, 3.5z or less is preferable.

Regarding Bi, since it is virtually impossible to produce an alloy in which the vapor pressure is extremely high and exceeds Bi5%, the amount added is set to 5% or less. In addition, in the case of alloys containing M of △ class or higher, Br
In order to satisfy the condition of 4KGOe or more, it is necessary that the amount of addition of each element described in L be equal to or less than Kidai's value (1).

Fig. 6 shows a representative example of the Fe11co-B/R-M magnet of the present invention and a Fe-0o/B/M-free magnet for comparison.
R [Demagnetization curve of a representative example of stone is shown. In the figure, 1 is a magnet that does not contain additive elements, and 2 is a Mo-added magnet (Table 1 No. 20
), 3 shows the demagnetization curve of the Nb-added magnet (No. 18 in Table 2). All exhibit squareness useful as permanent magnet materials.

In addition, 4 shows the demagnetization curve of average crystal grain size D=52u, m (same composition as 3).

(Table 4 (Symbol C indicates a comparative example.) In Table 4, those with the symbol C indicate comparative examples. In addition, CI-C:3 is It is out of scope.

In addition, if the crystal grain size is outside the range of this patent' from 04.05, H
It can be seen that e has decreased to less than 1 KOe.

Next, we conducted a detailed study on the relationship between the average grain size and Hc for composition No. 21.41 in Table 2.3,
The relationship shown in Figure 6 was obtained. From FIG. 6, it can be seen that Hc peaks when D is around 3 to 104m, and decreases rapidly when it is smaller than that, and gradually decreases when it is larger. Even if the composition changes within the composition range of this patent, the relationship between He and average grain size shows the same tendency. This means that
This shows that the FeCOBRM magnet is a single domain fine particle magnet.

The present inventors further obtained an alloy having the same composition as No. 20 in Table 1 by the method (1) described above (casting method), but the average crystal grain size of the cast alloy was 20 to 804 m. Despite this, only a low value of Hc, less than IKOe, was obtained.

From the results in Table 1 and Figure 5, the Br of the FeCoBRM magnet is approximately 4KG or more than that of hard ferrite, and the H
In order for c to be 1 KOe or more, the compositional force must be within the patent range and the average grain size must be 1~too gm, and in order to obtain high properties of roughly He 4 KOe or more, the number must be 1.5. ~50IL1m is shown.

FIG. 6 shows the demagnetization characteristic curve of a sample prepared in the same manner as the samples listed in Tables 1 to 3, with a typical average crystal grain size of Fe--Go--B--Nd. It can be seen that the magnet 1i having an average crystal grain size falling within the range of the present invention has a high Hc and excellent squareness.

The crystal grain size of the sintered body can be controlled with zero labor by controlling manufacturing conditions such as crushing, sintering, and heat treatment.

As mentioned above, the permanent magnet made of the FeGoBRM ternary magnetic anisotropic sintered body of the present invention has F, e, Go, B,
R.

Although the presence of impurities that are inevitable in the external industrial production of M can be tolerated, the following development is also possible, and the practicality can be further improved.

The permanent magnet material of the present invention can also contain small amounts of Cu, C, S, P, etc., making it possible to improve manufacturability and lower prices. That is, Gu3. H or less, 52.0% or more,
The content of C4, O% or more, P 3.5% or less (however, the content of the metal is below the maximum value of each element) is still more than the same level of Br (about 4KG) as nord ferrite, and is useful. It is. Cu, P may be mixed in from cheap raw materials, C may be mixed in from organic molding aids, etc., and S may be mixed in from the manufacturing process (No. 7).
(see figure).

As described above, the present invention realizes a magnetically anisotropic sintered permanent magnet having high residual magnetization, high coercive force, and high energy product using an inexpensive Fe-based alloy containing a relatively small amount of GO. It has extremely high value.

[Brief explanation of the drawing]

Fig. 1 is a graph showing the relationship between the CO content (horizontal axis) and one Curie point in an example of the present invention, and Figs. ) is a graph showing the relationship between Hc and average grain size D(
(horizontal axis, log scale), FIG. 6 is a graph showing the demagnetization curve of the embodiment of the present invention, and FIG.
The figure shows a graph showing the relationship between Cu, C, P, and S-containing acids (horizontal axis) and Br. Applicant Sumitomo Special Metals Co., Ltd. Agent Patent Attorney Asamichi Kato Figure 3 M Hara Chisuke I7T ratio x (%) Figure 4 M 1j A8 & Ratio X (%) Procedural amendment (voluntary) July 1, 1988 Mr. Kazuo Wakasugi, Commissioner of the Patent Office, 1, Indication of the Case 1984 Patent Application No. 084860 (1982)
(filed on May 14, 2017) Relationship to the case: 4 patent applicants, 6 attorneys, Number of inventions increased by amendment: None -+
4゜'\, ・ Hand #, written amendment (spontaneous) August 14, 1980 1 Indication of the case 1984 Patent Application No. 84860 (filed on May 14, 1988) 2 Name of the invention Permanent magnet Material 3 Relationship with the case of the person making the amendment Name of applicant Sumitomo Special Metals Co., Ltd. 5 Date of amendment order Voluntary 6 Number of inventions increased by amendment None 7 Column for detailed explanation of the invention in the specification to be amended ■, Specifications The detailed explanation of the invention in the book is supplemented as follows. (1) On page 9, line 11 of the specification, “nari” is replaced with “wood purchase nari”
Correct. (2) On page 14, line 10, add "(for example, 0.1% to 1%)" after "slightly". (3) Add the following sentence to the end of page 14, line 13. When rCo is 5% or more, the temperature coefficient of Br is 0.1%/° C. or less, and when it is 25% or less, it contributes to increasing Tc without substantially impairing other magnetic properties. (4) Page 15, line 8,
Correct "I will return with" to "It is preferable." (5) Before “wa” at the beginning of line 16 of the same page, [, especially Sm,
Add La, Er, and TmJ. (6) On the 16th line of the same page, add "(other rare earth elements, Ca, Mg, Fe, Ti, C, 0, etc.)" after "impurities". (7) Page 26, line 18, “approximately 4KGOeJ”
Corrected to "GOe". (8) Page 28, line 3, rB rcr)
Corrected to ``To make iHc 1 koe or more''. (8) Delete "de" in the fourth line of the same page. (10) On the 6th line of the same page, correct rBrJ to "same as rNi." (11) Delete "wa" in line 7 of the same page. (12) Page 28, line 11, change “r4KGOe” to “4kG
” is corrected. (13) Add the following sentence to the end of page 28, line 13. [Note that the amount of M added is determined by considering the effect of increasing iHc, the tendency to decrease Br1lt, and the influence on (B H) max.
0.1 to 3% is most desirable, and M is ■. Nb, Ta, Mo, W, Cr, and AI are preferred. The addition of M makes the rise of iHc steeper. Generally B, R
As the amount increases, Br decreases after reaching its maximum value, but an increase in iHc is obtained in the region of the highest Br. (14) Page 31, line 13, r F e COB RM
Correct J to rFecoBRMJ. (15) m Page 32, line 14, "rFeCoBRM ternary system" is corrected to "FeCoBRM quinary system". (16) Add European language to the end of line 7 on page 33. ``Typical impurities are Ca, Mg, each 4% or less, 02% or less, Si 5% or less, and a total of 5% or less is acceptable.

Claims (2)

[Claims] (1) 8 to 30% in atomic percentage (7) R (LR is at least one rare earth element including Y), 2 to 28
% (7) B, 50 or less cy) Go (excluding Go OX), one or more of the following specified percentage of the additive elements M (excluding M 0%, two or more of the above additions as M) In the case of containing an element, the M ratio is less than the atomic percentage of the element having the maximum value among the added elements), and the remainder Fe.
and the average crystal grain size of the sintered body is 1-100 km.
Magnetic anisotropic sintered permanent magnet material: Ti 4.5X or less, Ni 8.0% or less, Bi 5.0% or more -F, V 9.5
% below F, Nb 12.5X below, Ta
10.5% JJ, lower, Or 8.5% or less,
No 9.5X or less, W 9.5 or less,
Mn 8.0% or less, AI 9.5X or less,
Sb 2.5% or less, Ge 7.0% or less,
Sn 3.5% or less, Zr 5.5X or less,
and Hf 5.5% or less. (2) In terms of atomic percentage, 8 to 30% NoR (where LR is at least one kind of rare earth element including Y), 2 to 28% (
7) B, less than 50 cy) Go (excluding CoO%)
, one or more of the following additive elements M in a predetermined percentage (however, in cases where two or more of the above additive elements are included as M, excluding MO boxes, the total amount of M is the maximum value of the additive elements) atomic percentage) Ti 4.5% or less, Ni 8.0%
Below, Bi 5.0% or less, V 9.5% or less. Nb 12.5% or less, Ta 10.5% or less, Cr 8.5% or less, No, 9.5
% or less, W 9.5% or less, Mn 8. O
X or less, AI L5 or less, Sb 2.5 or less, Ge 1.0% or less, Sn 3.5
% or less, Zr 5.5% or less, and Hf 5.5% or less, and one or two types of element In this case, the total amount of X is less than the atomic percentage of the element having the maximum value among the elements) Cu 3.5% or less, S 2. Below OX, C
4.0% or less, and P 3.5% or less, provided that the content of M and 1-
100 pLm magnetically anisotropic sintered permanent magnet material.