JPH0931607A - High performance rare earth-iron-boron-carbon magnet material excellent in corrosion resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve corrosion resistance, orienting property, magnetic characteristics and the squarencess of a demagnetization curve by specifying a compsn. and regulating the grain diameter distribution and average grain diameter of tertragonal R2 TM14 (B1- XCX) as a principal phase. SOLUTION: This magnet material has a compsn. consisting of, by atom, 12-18% R, 2-6% B, <=4% C (4%<=B+C<=8%), 3% O2 , and the balance Fe, and Co and/or Ni may be substd. for part of the Fe. It has a structure consisting of >=85% tetragonal R2 TM14 (B1- XCX) as a principal phase, 0.5-10% grain boundary phase and <=5% R-C compd. phase, the grain diameter distribution of the principal phase is 0.05-30μm and the average grain diameter is 2.0-10μm. This magnet material is obtd. as follows; a molten alloy is cast into a strip, this strip is pulverized and the resultant powder is filled into a mold, oriented in a moment with a pulsating magnetic field, compacted, sintered and aged.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an R-Fe-B-C magnet material having excellent corrosion resistance and excellent magnetic properties, which contains R, Fe, B and C having a specific composition as main components. By a strip casting method such as a single-roll method or a twin-roll method, a molten alloy is obtained to obtain a slab having a homogeneous structure in which the R-rich phase is finely separated at a specific plate thickness, and the slab is coarsely crushed by the H ₂ storage collapse method, After adding and blending a lubricant, it becomes fine powder, which enables efficient fine pulverization, and the fine powder is molded in a magnetic field, sintered, and aged.
High performance R- with excellent corrosion resistance and orientation, excellent magnetic properties and squareness of demagnetization curve, and excellent corrosion resistance
It relates to an Fe-B-C based magnet material.

[0002]

2. Description of the Related Art Today, a typical high performance permanent magnet R
-Fe-B based permanent magnet (JP-A-59-46008)
Has high magnet characteristics due to the structure of the ternary tetragonal compound having the main phase and the R-rich phase, and is used in a wide range of fields from various household electrical appliances to large computer peripherals, depending on the application. R-Fe-B based permanent magnets of various compositions have been proposed so as to exhibit various magnet characteristics.

The R-Fe-B system permanent magnets have extremely excellent magnetic properties, but have problems in corrosion resistance and temperature characteristics. A method of coating the surface of the magnet with a corrosion resistant metal film or a resin film has been proposed (JP-A-60-54406 and JP-A-60-63901), and in order to improve the temperature characteristics of the magnetic characteristics of the magnet, the magnet has been proposed. Proposed to replace a part of Fe in the composition with Co (Japanese Patent Laid-Open No. 59-64733).
However, there is a problem that the cost is still insufficient and the cost of the magnet increases.

Recently, a part of B of the R-Fe-B system magnet is replaced with C
R-Fe-B- for improving the corrosion resistance and temperature characteristics by generating a boundary phase having excellent corrosion resistance by substitution with
A C-based magnet has been proposed (JP-A-3-82744). The R-Fe-BC system magnet has a B content of 2 at%.
It is characterized in that it is below and contains a large amount of C. That is, when a part of B is replaced by C, the main phase R ₂ Fe ₁₄ B tetragonal crystal is R ₂ F in which a part of B is replaced by C.
e ₁₄ (B _1-x C _x ) Tetragonal system, but the crystal structure is the same, and the grain boundary phase changes from R-rich phase to R-rich phase (R-Fe-C phase) with good corrosion resistance. , Part of Fe is Co
In substituted in the R-Fe-Co-B- C system magnets, main phase R ₂ in R ₂ Fe ₁₄ B tetragonal same crystal structure (Fe _1-x C
_{o x) 14 (B 1-} y C y) becomes tetragonal, also the grain boundary phase yet a good corrosion resistance of the R-rich phase R-rich phase (R-Fe-C
However, when a large amount of C is contained in the magnet, C reacts with R (rare earth element) to easily form R—C (rare earth carbide), which may cause a change in the raw alloy or a sintered magnet. R- in
C is generated.

In short, in the R-Fe-B-C type magnet, R reacts with C to become R-C, and R is consumed, so that R-Fe-B type magnet is required to obtain required magnetic characteristics. It requires a larger amount of R than a magnet. Therefore, since there are many R-Cs that do not contribute to the magnetic characteristics, the amount of the main phase present is reduced, and R-
Br is lower than that of the Fe-B system magnet, and a large amount of expensive R is required, which causes an increase in cost and
There has been a problem that the magnetic characteristics are deteriorated and vary with the increase of the oxygen content. Further, the R-Fe-B-
C-based magnets are made by casting molten alloy into a mold to produce an ingot,
The ingot is pulverized, powdered, molded, sintered, magnetized by a powder metallurgical method of aging treatment, or the ingot or the coarse powder after crushing the ingot is subjected to solution treatment and then pulverized, Although it was magnetized by the powder metallurgy method to improve the corrosion resistance and temperature characteristics, the magnetic characteristics of the R—Fe—B—C magnet were (BH) max of about 38 MGOe at most.
Further, the R-Fe-B-C type magnet has extremely poor squareness of the demagnetization curve, and is demagnetized with respect to temperature and reverse magnetic field as compared with the R-Fe-B type magnet having the same size and shape. There was an easy problem.

In order to prevent coarsening of crystal grains, residual α-Fe, and segregation, which are defects of the R-Fe-B alloy powder by the ingot crushing method, a molten R-Fe-B alloy is added. A slab with a plate thickness of 0.03 mm to 10 mm is formed by a roll method, and the slab is roughly crushed by a stamp mill / jaw crusher according to a usual powder metallurgical method, and then further disc mill, ball mill, attritor. Proposal of R-Fe-B based magnet materials with high performance by finely pulverizing the powder with an average particle size of 3 to 5 μm by a pulverizing method such as a jet mill and then pressing, sintering and aging in a magnetic field. (JP-A-63-
No. 317643).

[0007]

However, the R-F
There is a strong demand for cost reduction for e-B-C based permanent magnet materials, and it has become extremely important to efficiently manufacture high-performance permanent magnets having excellent corrosion resistance. For this reason, it is necessary to improve the metal structure in order to bring out characteristics close to the limit. In addition, today's electric and electronic devices are required to be smaller and lighter and to have higher functionality of (BH) max40MGOe or more, and the squareness of the demagnetization curve is excellent, and the improvement of corrosion resistance that does not require surface treatment is also improved. There is a demand for higher performance and cost reduction of R-Fe-B based permanent magnets.

Therefore, the applicant has previously made possible efficient pulverization, is excellent in oxidation resistance, and expresses a high iHc by refining the crystal grains of the magnet. For the purpose of providing a method for producing a high-performance R-Fe-B-based permanent magnet material by increasing the degree of orientation, an R-Fe-B-based alloy slab having a specific plate thickness obtained by the strip casting method is occluded with H ₂ The coarse powder obtained by the disintegration method was jet-milled in an inert gas stream and the fine powder obtained was filled into the mold at a specific packing density, and then a pulse magnetic field in a specific direction was momentarily applied. Then, a manufacturing method for obtaining a high-performance R-Fe-B based permanent magnet for molding, sintering and aging treatment after orientation was proposed (Japanese Patent Application No. 5-192886).

Further, in order to improve the performance of the R-Fe-B system permanent magnet, taking into consideration the improvement of the filling property into the mold, the improvement of the orientation, etc., for example, the fine powder obtained by the above method is used. Even if a lubricant is added and compounded before press molding, it is extremely difficult to uniformly coat the surface of the fine powder with lubricant, and defects such as weight variation and cracks per unit during press molding occur. I was afraid.

The present invention solves the problems of the conventional R-Fe-B-C based permanent magnet having excellent corrosion resistance and improved magnetic characteristics, and finely pulverized powder obtained by the above-mentioned strip casting method. With excellent press-filling property, by further increasing the degree of orientation of each crystal grain in the easy magnetization direction,
It is intended to provide a high-performance R-Fe-B-C based magnet material having a (BH) max of 40 MGOe or more and excellent in corrosion resistance and squareness of demagnetization curve.

[0011]

The inventors have found that R-Fe-
As a result of various studies on the relationship between the BC magnet structure and the magnetic properties of the sintered magnet, the composition was adjusted to a specific range, and the amounts of the main phase, grain boundary phase, and RC phase were suppressed to specific amounts, Further, by making the average crystal grain size fine and narrowing the crystal grain size distribution width, excellent corrosion resistance and magnetic properties, especially (BH) max of 40M are obtained.
High-performance R-F with superior demagnetization curve squareness above GOe
It was found that an e-B-C based magnet material can be obtained. That is, a molten alloy in which R, Fe, B, and C are adjusted to specific ranges is cast by a strip casting method to cast a slab having a specific plate thickness, and the slab is coarsely crushed by an H ₂ occlusion collapse method, and then the coarsely crushed powder is used. Add (BH) max to 40M by adding and blending lubricant to the product, pulverizing, and then forming in magnetic field and aging treatment.
High-performance R-F with superior demagnetization curve squareness above GOe
It was found that an e-B-C based magnet material can be obtained.

This invention is R12-18at%, B + C
= 6 to 10 at% (however, B: 2 to 6 at%, C: 4 to
8 at%), O ₂ 3 at% or less, balance Fe (however, F
(a part of e can be replaced by one or two of Co and Ni) as a main component, and the proportion of the phase in the whole structure is R ₂ TM ₁₄ (B _1-x C _x ) tetragonal crystal of the main phase. (However, TM: Fe, C
85% or more, 0.5% to 10% of the grain boundary phase, and 5% or less of the RC compound phase, and the crystal grain size distribution of the main phase is 0. High-performance R-Fe-B-C with excellent corrosion resistance and squareness of demagnetization curve, having an average crystal grain size of 2.0 μm to 10 μm
System magnet material.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION R-Fe-BC according to the present invention
Regarding the magnetic characteristics of the system permanent magnet, required magnetic characteristics can be obtained by appropriately selecting the composition, manufacturing conditions, and the like. Details will be described below. The cast slab of the magnetic material having the structure in which the R-rich phase of the specific composition is finely separated according to the present invention is manufactured by the alloy casting of the specific composition by the strip casting method by the single roll method or the twin roll method. The obtained slab is a thin plate material having a plate thickness of 0.03 mm to 10 mm.

The reason for limiting the plate thickness of the cast slab to 0.03 mm to 10 mm is that if it is less than 0.03 mm, the quenching effect becomes large, the crystal grain size becomes smaller than 3 μm, and it is easily oxidized when pulverized. It is not preferable because it causes deterioration of magnetic properties, and when it exceeds 10 mm, the cooling rate becomes slow, α-Fe is easily crystallized, and the crystal grain size becomes large.
This is because the Nd-rich phase is unevenly distributed, which deteriorates the magnetic properties, particularly the coercive force and the squareness of the demagnetization curve, which is not preferable.

The cross-sectional structure of the R-Fe-B-C type alloy having a specific composition obtained by the strip casting method of the present invention has the main phase R ₂ Fe ₁₄ (B _1-x C _x ) crystal as a conventional template. Compared to that of the ingot obtained by casting, it is about 1/10 or less finer, for example, the dimension in the minor axis direction is 0.1
The R-rich phase is finely dispersed so as to surround the main phase crystal grains, and the fine crystal has a size of μm to 50 μm and a long axis direction of 5 μm to 200 μm.

By finely separating the R-rich phase to 10 μm or less, volume expansion when the R-rich phase forms a hydride during the H ₂ occlusion treatment is uniformly generated and finely divided, and thus finely pulverized. As a result, the crystal grains of the main phase are subdivided to obtain fine powder having a uniform particle size distribution.

[0017] in H ₂ occlusion treatment, for example, charged slab of 0.03mm~10mm thickness broke predetermined size is inserted into the raw material case, in a vessel the material case be sealed by tightening the cap Then, the inside of the container is sufficiently evacuated, and then H ₂ gas having a pressure of 200 Torr to 50 kg / cm ² is supplied to occlude H ₂ in the slab. This H
_{(2) Since the} occlusion reaction is an exothermic reaction, a cooling pipe for supplying cooling water is provided around the outer periphery of the container to prevent the temperature inside the container from rising and to supply H ₂ gas at a predetermined pressure for a certain period of time. As a result, H ₂ gas is absorbed, and the slab is spontaneously disintegrated and pulverized.

The alloy powder pulverized by the H ₂ occlusion is subjected to the primary H ₂ degassing treatment in a vacuum. Further, the powdered alloy is heated to 100 ° C. to 750 ° C. in vacuum or argon gas.
By heating to 0 ° C. and subjecting to secondary de-H ₂ gas treatment for 0.5 hour or longer, oxidation of the powder or press-molded product due to long-term storage can be prevented, and deterioration of magnetic properties of the resulting permanent magnet can be prevented. Since the alloy powder of the above treatment has fine cracks in the grains, it can be finely pulverized in a short time by a ball mill, a jet mill or the like to obtain an alloy powder having a required grain size of 1 μm to 10 μm.

In the present invention, 0.02 to 5 wt% of a liquid lubricant or a solid lubricant is added to and mixed with the alloy powder obtained by the H ₂ occlusion / disintegration method, and then it is pulverized by a jet mill particularly in an inert gas stream. To obtain a fine powder having an average particle size of 1 to 10 μm. As the liquid lubricant in the present invention, a saturated or unsaturated fatty acid ester and a boric acid ester as an acid salt can be used, and they are dispersed in a petroleum solvent or an alcohol solvent. The amount of fatty acid ester in the liquid oil lubricant is 5 wt% to 50
wt% is preferred.

The saturated fatty acid ester is an ester represented by the general formula RCOOR 'R = C _n H _{2n + 2} (alkane), and the unsaturated fatty acid ester is represented by the general formula Indicated by

The solid lubricant is at least one kind of zinc stearate, copper stearate, aluminum stearate, ethylene vinylamide and the like, and when the average particle size of the solid lubricant is less than 1 μm, it is industrially produced. If it exceeds 50 μm, it is difficult to uniformly mix it with the coarsely pulverized powder, so that the average particle size is 1 μm.
˜50 μm is preferred.

In the present invention, if the addition amount of the liquid lubricant or the solid lubricant is less than 0.01 wt%, the powder particles are not uniformly coated, and the mold filling property and the crystal orientation property are improved and improved. If it exceeds 5% by weight, the non-volatile residue in the lubricant remains in the sintered body, resulting in a decrease in the sintered density and deterioration of the magnetic properties, which is not preferable. The amount is 0.01 wt% to 5 wt%.

In the present invention, it is preferable that the alloy powder before pulverization is coarsely pulverized to have an average particle size of 10 μm to 500 μm, and then a liquid lubricant or a solid lubricant is mixed and pulverized. The reason for limiting the average particle size of the coarsely pulverized powder is that it is not preferable that the average particle size is less than 10 μm because it is difficult to safely handle the raw material powder in the air, and the magnetic properties are deteriorated by the oxidation of the raw material powder. If it exceeds, it becomes difficult to supply the raw material powder to the jet mill pulverizer, and the pulverization efficiency is significantly reduced, which is not preferable,
The average particle size of the coarsely pulverized powder is 10 μm to 500 μm.

Next, for fine pulverization, an inert gas (for example, N 2
_2. Fine pulverize with a jet mill using Ar). Of course, it is also possible to use a ball mill using an organic solvent (for example, benzene, toluene, etc.) or attritor grinding. The average particle size of the finely pulverized powder according to the present invention is
If it is less than 1 μm, the powder becomes extremely active, and there is a risk of ignition in the process such as press molding, which is not preferable because the magnetic properties are deteriorated. If it exceeds 10 μm, the crystal grains of the permanent magnet obtained by sintering become large. Since the magnetization reversal easily occurs and the coercive force is lowered, which is not preferable, the average grain size is set to 1 μm to 10 μm. A preferable average particle size is 2.5 μm to 4 μm.

In the present invention, molding is performed under a pressing force of 0.5 t.
on / cm ² may be the magnetic field in the press of ~2.0ton / cm ^2. The strength of the magnetic field is preferably 10 kOe to 20 kOe, but in order to improve the magnetic properties and crystal orientation of the magnet material, it is desirable to perform cold isostatic pressing after applying the pulse magnetic field.

The following method is proposed for molding using a pulsed magnetic field. The finely pulverized powder is filled in a mold in an inert gas atmosphere. The mold may be made of non-magnetic metal, oxide, ceramics or the like, or may be an organic compound such as plastic or rubber. The packing density of the powder is
Resting bulk density of the powder (packing density 1.4 g / cm
³ ), the bulk density after tapping (filling density 3.5 g /
The range of cm ³ ) is preferred. Therefore, the packing density is 1.4 ~
Limited to 3.5 g / cm ³ .

To the finely pulverized powder filled in the mold, a pulsed magnetic field from an air-core coil or a condenser power source is applied to orient the powder. carry out. The higher the strength of the pulse magnetic field, the better, and at least 10 kOe or more is required. Preferred pulse magnetic field strength is 20 kOe
~ 60 kOe. In order to continuously perform the orientation and the pressing by the pulsed magnetic field, a coil for generating the pulsed magnetic field is embedded in the die, the orientation is performed by using the pulsed magnetic field, and then the ordinary magnetic field pressing method is used for molding. Is possible.

The pulsed magnetic field can be applied only once or repeatedly. When repeatedly applied, the magnetic field direction is not only the required direction, but it is possible to further improve the orientation by alternately inverting and applying the magnetic field direction. Furthermore, in addition to repeatedly applying the same magnetic field strength, The magnetic field strength can be gradually reduced and applied, and when the magnetic field direction is alternately inverted and applied, the strength can be gradually reduced to apparently deplete the molded body. Has the advantage of being easier. Pulse magnetic field time is 1 μsec to 1
0 sec is preferable, and further 5 μsec to 100 ms
ec is preferable, and the pulse magnetic field is applied 1 to 10 times,
Furthermore, it is preferably 1 to 5 times.

The molding of the powder after orientation is most preferably carried out by compression molding with a cold isostatic press. At this time, it is necessary to appropriately select the hardness and thickness of the plastic mold, and various types of molding are required. It is possible to manufacture large magnet materials including shaped products. The hydrostatic pressing conditions are as follows.
A pressing force of 0 ton / cm ^{2 to} 3.0 ton / cm ² is preferable, and the hardness of the mold is preferably Hs = 20 to 80.
In that case, the magnetic field strength of the static magnetic field is preferably 5 to 20 kOe. Further, the hydrostatic pressing can also be performed in a static magnetic field. For example, at the time of orientation, after repeatedly applying the magnetic field with the same magnetic field strength, the powder after orientation is subjected to hydrostatic pressing in a static magnetic field. , High-performance R-Fe
It is possible to obtain a -B-C based magnet material.

In the present invention, any known powder metallurgical means can be adopted as conditions and methods such as molding, sintering and heat treatment. The sintering of the molded product after orientation and the heat treatment condition after the sintering are appropriately selected according to the selected alloy composition.
Sintering process of holding 0 to 1180 ° C. and 1 to 6 hours, 450
An aging treatment step of holding at 950C for 1 to 8 hours is preferable.

The R-Fe-B in the present invention will be described below.
The reasons for limiting the composition of the C-based magnet material will be described. The rare earth element R contained in the magnet material of the present invention is a rare earth element including yttrium (Y) and including light rare earth and heavy rare earth. Usually, one kind of R is sufficient, but in practice, a mixture of two or more kinds (Missille metal, didymium, etc.) can be used for reasons such as convenience in obtaining, and Sm, Y, La, Ce, Gd, etc. Other R, especially N
It can be used as a mixture with d, Pr or the like. Note that R may not be a pure rare earth element, and may contain impurities that are unavoidable in production within the industrially available range.

R is an essential element of the R-Fe-B-C based magnet material. If it is less than 12 atomic%, high magnetic properties, particularly high coercive force cannot be obtained, and if it exceeds 18 atomic%, the residual magnetic flux density ( Br) decreases, and a permanent magnet with excellent characteristics cannot be obtained. Therefore, R is in the range of 12 atom% to 18 atom%. Preferably, R is 13 at% to 17 at%.

B and C are essential elements of the R-Fe-BC system magnet material, and when B + C is less than 6 atomic%, a high coercive force (iHc) cannot be obtained, and when more than 10 atomic%, they remain. Since the magnetic flux density (Br) decreases, an excellent permanent magnet cannot be obtained, and if B is less than 2 at%, the residual magnetic flux density decreases and the squareness of the demagnetization curve deteriorates, and B is 6a.
If it exceeds t%, the corrosion resistance is deteriorated, which is not preferable, and if C is less than 4 at%, the corrosion resistance is deteriorated, which is not preferable, and when C exceeds 8 at%, the amount of the RC phase is increased and the residual magnetic flux density Br is increased. And the squareness of the demagnetization curve deteriorates, which is not preferable. Therefore, B + C is 6
Atomic% -10 atomic% (however, B2-6 at%, C4-8
at%). The preferred range of B + C is 6 to 8
It is at%.

In the magnet material of the present invention, O ₂ is 3a
rare earth element is increased to be consumed as an oxide and exceeds t%, sinterability is lowered, not preferable because the residual density Br and the coercive force decreases with the sintering temperature is lowered, O ₂
Is 3 at% or less.

Fe is an essential element of the R-Fe-B-C based magnet material, and if it is less than 72 atomic%, the residual magnetic flux density (B
Since r) decreases and a high coercive force cannot be obtained when it exceeds 82 atom%, Fe is limited to 72 atom% to 82 atom%. The reason for substituting a part of Fe with one or two of Co and Ni is that the effect of improving the temperature characteristics of the permanent magnet and the effect of further improving the corrosion resistance can be obtained. When 1% or 2% exceeds 50% of Fe, a high coercive force cannot be obtained and an excellent permanent magnet cannot be obtained. Therefore, one or two substitutions of Co and Ni are Fe
50% of the upper limit.

In the magnetic material of the present invention, high residual magnetic flux density, high coercive force, and excellent squareness of demagnetization curve,
In order to obtain a high-performance magnet material that also has high corrosion resistance,
R13 atomic% to 17 atomic%, B + C = 6 to 8 atomic% (however, B2 to 4 atomic% and C4 to 6 atomic%), Fe75 atomic%
〜81 atomic% is preferable. Further, the magnetic material according to the present invention can tolerate the presence of impurities unavoidable in industrial production in addition to C, R, B and Fe, but a part of B + C is 3.5 atomic% or less of P, 2.5 or less. By substituting at least one of S in atomic% or less and Cu in 3.5 atomic% or less with a total amount of 4.0 atomic% or less, it is possible to improve the manufacturability and reduce the cost of the magnet alloy.

Further, in the R-Fe-B-C alloy containing R, B, C and Fe, 9.5 atomic% or less of Al,
4.5 atomic% or less Ti, 9.5 atomic% or less V, 8.
5 atomic% or less Cr, 8.0 atomic% or less Mn, 5 atomic% or less Bi, 12.5 atomic% or less Nb, 10.5 atomic% or less Ta, 9.5 atomic% or less Mo, W of 9.5 atomic% or less, Sb of 2.5 atomic% or less, Ge of 7 atomic% or less, Ga of 7 at% or less, Sn of 3.5 atomic% or less,
By adding at least one of Zr of 5.5 atomic% or less and Hf of 5.5 atomic% or less, a high coercive force of the magnet material becomes possible.

The proportion of the main phase, the grain boundary phase and the R—C compound phase in the entire structure is limited by the main phase R ₂ TM ₁₄ (B _1-x C
_x ) If the tetragonal crystal (however, one or more of TM: Fe, Co, and Ni) is less than 85% of the whole structure, a high residual magnetic flux density cannot be obtained, and the preferable main phase content is 90%.
That is all. If the amount of grain boundary phase is less than 0.5%, the sinterability is poor and the sintered density is lowered, and the coercive force is lowered, which is not preferable, and if it exceeds 10%, the residual magnetic flux density and the corrosion resistance are lowered. It is limited to 0.5% to 10%. Also, R
If the -C compound phase exceeds 5%, the amount of R that does not contribute to magnetism consumed as the R-C compound increases, the residual magnetic flux density and the coercive force decrease, and the squareness of the demagnetization curve decreases and the required amount. It is necessary to increase the amount of R in order to obtain the magnetic characteristics of No. 3, which is not preferable because it increases the magnet cost.
% Or less.

In the present invention, the reason why the crystal grain size distribution of the main phase is limited is that it is difficult to pulverize when the crystal grain size is less than 0.05 μm, and the oxygen content increases due to the refinement of the crystal grains. However, the coercive force decreases, which is not preferable,
When it exceeds 30 μm, the coercive force is lowered and the squareness of the demagnetization curve is lowered, which is not preferable, and the grain size distribution is set to be 0.
It is limited to 05 μm to 30 μm. More preferably 0.1
μm to 20 μm. The average crystal grain size is 2.0μ
If it is less than m, it is difficult to finely pulverize, and the content of oxygen increases and the coercive force decreases, which is not preferable, and if it exceeds 10 μm, the coercive force and the squareness of the demagnetization curve decrease.
It is limited to 2.0 μm to 10 μm.

According to the present invention, a strip-cast R-Fe-B-C type alloy having a specific composition with a specific plate thickness is coarsely pulverized by the H ₂ occluding and disintegrating method, and then a specific lubricant is added to the coarsely pulverized powder obtained. After the addition, by finely pulverizing with a jet mill, it becomes possible to subdivide the crystal grains of the main phase forming the alloy block, and it is possible to produce a powder with a uniform particle size distribution. When the lubricant is added to the alloy powder in which the phases are finely dispersed and the R ₂ Fe ₁₄ (B _1-x C _x ) phase is also refined and then finely pulverized, the pulverization ability is about twice that of the conventional one. Since the production efficiency is significantly improved, the mold filling property and the crystal orientation property are improved by instantaneously orienting the fine powder in the mold using a pulse magnetic field, followed by pressing and sintering. Improved corrosion resistance and magnetic properties and demagnetization High-performance R-Fe- excellent in the squareness
A BC magnet material is obtained.

[0041]

【Example】

Example 1 Using a twin roll type strip caster having two copper rolls with a diameter of 200 mm, the alloy melt obtained by melting in a high frequency vacuum melting furnace was used to obtain a thin plate-shaped slab with a plate thickness of about 0.3 mm. . The crystal grain size in the slab is 0.
The length is 5 μm to 15 μm, the dimension in the major axis direction is 5 μm to 80 μm, and the R-rich phase exists in a finely separated state of about 3 μm so as to surround the main phase. After breaking the slab to 50 mm square or less, 1000 g of the broken piece was housed in a closed container capable of sucking and exhausting air, and after evacuating the inside of the container to vacuum, 3 kg / cm ² of H ₂ gas was introduced into the container. After being supplied for 2 hours, the slab was naturally disintegrated by H ₂ occlusion, and then held at 500 ° C. for 6 hours in vacuum to remove H ₂ treatment, cooled to room temperature, and further roughly pulverized to 100 mesh.

Next, 800 collected from the coarsely crushed powder
g fatty acid ester as liquid lubricant (active ingredient 50%
After adding 1 wt% of cyclohexane (50%), the mixture was pulverized by a jet mill to obtain an alloy powder having an average particle size of 3.5 μm.
After filling the obtained powder in a mold, it was oriented in the magnetization of 15 kOe, molded at a pressure of 1.0 ton / cm2 in the direction perpendicular to the magnetic field, sintered at 1040 ° C. for 3 hours, and at 900 ° C. for 1 hour. Then, the permanent magnets (magnet Nos. 1 and 2) were obtained. Table 1 shows the composition of the obtained permanent magnet. The magnetic properties and the corrosion resistance test results of the obtained permanent magnet are shown in Table 2, and the main phase amount, the grain boundary phase amount, the RC compound phase amount, the crystal grain size distribution of the main phase, and the average crystal grain size are shown in Table 3. Shown in. The corrosion resistance test is represented by the increase in oxidation amount per unit area after being left under the condition of 80 ° C. × 90% RH × 500 hours. In Table 2, H
k is the strength of the reverse magnetic field when I becomes 0.9 × Br on the demagnetization curve.

Example 2 The fine alloy powder having an average particle size of 3.5 μm obtained in Example 1 was converted into a urethane rubber mold having an hardness of Hs = 40 (inner diameter φ25).
(Height 20 mm) to a packing density of 3.3 g / cm ³ , and then once with a pulsed magnetic field strength of 40 kOe,
After applying for 8/100 seconds for orientation, the oriented sample was cold isostatically pressed at a pressing pressure of 1.2 ton / cm ² to obtain a molded body. 1040 the molded body taken out from the mold
Sintering was performed under the conditions of 3 ° C. for 3 hours, and aging treatment was performed at 900 ° C. for 1 hour to obtain permanent magnets (magnet Nos. 3 and 4). Table 1 shows the composition of the obtained permanent magnet. The magnetic properties and corrosion resistance test results of the obtained permanent magnets are shown in Table 2, the main phase amount,
Grain boundary phase amount, R-C compound phase amount and crystal grain size distribution of main phase,
The average crystal grain size is shown in Table 3.

Example 3 The disintegrated alloy powder obtained by the H ₂ occlusion treatment in Example 1 was heated and held at 500 ° C. for 5 hours in vacuum to remove H ₂ and then solidified into 20 μm coarsely pulverized powder. After adding 0.1 wt% of zinc stearate as a lubricant, after adding 7kg / cm ² of A
Jet mill finely pulverized in r gas to obtain an average particle size of 3.2.
An alloy fine powder of μm was obtained. After being filled in a urethane rubber mold under the same conditions as in Example 2, a pulse magnetic field strength of 50 k was obtained.
After applying Oe and pulse magnetic field inversion repeatedly 4 times under the condition of one waveform of the pulse magnetic field for a time of 8 sec, cold isostatic pressing was performed at a pressing pressure of 1.0 ton / cm ² . The molded body taken out of the mold was sintered at 1040 ° C. for 3 hours and then subjected to an aging treatment at 900 ° C. for 1 hour to obtain permanent magnets (magnet Nos. 5 and 6). The composition of the obtained permanent magnet is shown in Table 1.
Shown in The magnetic properties and the corrosion resistance test results of the obtained permanent magnet are shown in Table 2, and the main phase amount, the grain boundary phase amount, the RC compound phase amount, the crystal grain size distribution of the main phase, and the average crystal grain size are shown in Table 3. Shown in.

Example 4 After the finely pulverized powder obtained in Example 1 was filled in a rubber mold, a repetitive repetitive pulsed magnetic field under the same conditions as in Example 3 was momentarily added, and then a static magnetic field of strength 12 kOe was applied. After cold isostatic pressing at a pressing pressure of 1.0 kg / cm ² to obtain a molded body, sintering and aging treatment under the same conditions as in Example 3 were performed to obtain permanent magnets (magnet Nos. 7 and 8). Obtained. Table 1 shows the composition of the obtained permanent magnet. The magnetic properties and the corrosion resistance test results of the obtained permanent magnet are shown in Table 2, and the main phase amount, grain boundary phase amount, R
Table 3 shows the amount of -C compound phase, the crystal grain size distribution of the main phase, and the average crystal grain size.

Comparative Example 1 A molten alloy having the same composition as in Example 1 was used to measure dimensions of 30 mm × 100.
50 mm of the ingot obtained by casting in a mm × 200 mm mold
After fractured to less than mm mm, the fractured pieces were subjected to H ₂ occlusion treatment and de-H ₂ treatment under the same conditions as in Example 1 and then subjected to the same conditions as in Example 1 without adding a lubricant. After crushing, pressing in a magnetic field, sintering, and aging treatment, a permanent magnet (magnet N
o. 9 and 10) were obtained. The crystal grain size of the ingot is 30 in the short axis direction.
μm, 300 μm in the major axis direction, and the R-rich phase was locally scattered in a size of about 60 μm. Table 1 shows the composition of the obtained permanent magnet. The magnetic properties and the corrosion resistance test results of the obtained permanent magnet are shown in Table 2, and the main phase amount, grain boundary phase amount, R-
Table 3 shows the amount of C compound phase, the crystal grain size distribution of the main phase, and the average crystal grain size.

Comparative Example 2 A sintered body (magnet N) was used under the same conditions as in Example 1 except that the coarsely pulverized powder obtained in Example 1 was pulverized to an average particle size of 2.2 μm.
o. 11, 12) was obtained. The composition of the obtained sintered body is shown in Table 1.
Shown in The obtained sintered body did not shrink and did not become a permanent magnet.

Comparative Example 3 Under the same conditions as in Example 1, the composition of No. 1 in Table 1 was used. A permanent magnet of No. 13 was obtained. The magnetic properties and the corrosion resistance test results of the obtained permanent magnet are shown in Table 2, and the main phase amount, the grain boundary phase amount, the RC compound phase amount, the crystal grain size distribution of the main phase, and the average crystal grain size are shown in Table 3. Shown in.

Comparative Example 4 A permanent magnet having a composition of 14 in Table 1 was obtained under the same conditions as in Example 1. The magnetic properties and the corrosion resistance test results of the obtained permanent magnet are shown in Table 2, and the main phase amount, the grain boundary phase amount, the RC compound phase amount, the crystal grain size distribution of the main phase, and the average crystal grain size are shown in Table 3. Shown in.

Comparative Example 5 A permanent magnet having a composition of 15 in Table 1 was obtained under the same conditions as in Example 1. The magnetic properties and the corrosion resistance test results of the obtained permanent magnet are shown in Table 2, and the main phase amount, the grain boundary phase amount, the RC compound phase amount, the crystal grain size distribution of the main phase, and the average crystal grain size are shown in Table 3. Shown in.

Comparative Example 6 Under the same conditions as in Example 1, a permanent magnet having a composition of 16 in Table 1 was obtained. The magnetic properties and the corrosion resistance test results of the obtained permanent magnet are shown in Table 2, and the main phase amount, the grain boundary phase amount, the RC compound phase amount, the crystal grain size distribution of the main phase, and the average crystal grain size are shown in Table 3. Shown in.

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[Table 1]

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[Table 2]

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[Table 3]

[0055]

The R-Fe-B-C type magnet material according to the present invention is formed by casting the molten R-Fe-B-C type alloy having a specific composition into strips having a specific plate thickness by strip casting. A specific amount of a lubricant is added to an alloy powder obtained by coarsely pulverizing the pieces by the H ₂ occlusion disintegration method and finely pulverized by a jet mill to subdivide the crystal grains of the main phase constituting the alloy lump. It was possible to produce a powder having a uniform particle size distribution, in which case the R-rich phase was finely dispersed and the R ₂ Fe ₁₄ (B _1-x C _x ) phase was also finely divided. When finely pulverized after adding a lubricant to alloy powder and pulverizing it, the pulverizing ability is improved about twice as much as the conventional one, so that the production efficiency is significantly improved and the fine powder is used in a mold by using a pulse magnetic field. Momentarily oriented, then pressed and sintered to mold Is Hama property and crystal orientation improving corrosion resistance and magnetic properties, high-performance R-Fe-B-C-based magnet material is obtained, particularly excellent in squareness of the demagnetization curve.

Claims (1)

[Claims] 1. R12-18 at%, B + C = 6-10
at% (B: 2 to 6 at%, C: 4 to 8 at)
%), O ₂ 3 at% or less, and the balance Fe (however, Fe of 1
Part can be replaced by one or two of Co and Ni), and the proportion of the phase in the whole structure is R ₂ TM of the main phase.
₁₄ (B _1-x C _x ) Tetragonal (provided that TM: Fe, Co, Ni
85% or more, and the grain boundary phase is 0.5
% -10%, RC compound phase 5% or less, main phase crystal grain size distribution is 0.05 μm to 30 μm, and average crystal grain size is 2.0 μm to 10 μm. -Fe-BC system magnet material.