KR102045394B1 - Manufacturing method Of rare earth sintered magnet - Google Patents

Abstract

The method for preparing a rare earth permanent magnet according to the present invention comprises a rare earth alloy containing rare earth elements and iron, and preparing a raw material powder having a particle size range of 2 to 10 μm, and forming the raw material powder into a mold for molding. In the process of charging to, compressing and simultaneously applying a direct magnetic field of the low magnetic field to the pulse field after the pulse magnetic field application process, sintering process after the magnetic field forming, and heat treatment process performing heat treatment twice or more after the sintering process. Is done.

Description

Manufacturing method of rare earth permanent magnets {Manufacturing method Of rare earth sintered magnet}

The present invention fills a mold with a rare earth alloy containing rare earth elements and iron in a mold, and compresses and molds the magnetic field orientation of the rare earth alloy powder by applying a pulse magnetic field and a direct current magnetic field to magnetic field presses located on the left and right sides of the mold. The present invention relates to a method for producing a rare earth permanent magnet which is improved, sintered and heat treated multiple times.

Recently, the energy reduction and environmentally friendly green growth projects have emerged as a new issue, and the automobile industry is using hybrid cars using internal combustion engines using fossil raw materials in combination with motors or hydrogen, an environmentally friendly energy source, as alternative energy. Research on fuel cell vehicles that drive motors after generation of energy has been actively conducted.

Since these environmentally friendly cars are driven by electric energy, permanent magnet motors and generators are inevitably employed. In terms of magnetic materials, rare earth permanent motors exhibiting higher residual flux density and stable coercive force to further improve energy efficiency. The technical demand for magnets is increasing.

In addition, other aspects for improving fuel efficiency of automobiles should be realized in light weight and miniaturization of automotive parts. For example, in the case of motors, in order to realize light weight and miniaturization, permanent magnet materials are used in addition to the design of the motor. It is essential to replace magnets with rare earth permanent magnets that exhibit better magnetic performance.

Theoretically, if the residual magnetic flux density of permanent magnet is high, it can generate more magnetic force to the outside, which has the advantage to improve the efficiency and performance of the device in various applications such as motors, actuators and medical devices. In this case, the residual magnetic flux density increases in proportion to the saturation magnetic flux density of the main phase constituting the magnet, the degree of anisotropy of the powder or grains, or the density of the magnet.

As the composition of the alloy is determined in the process of manufacturing the real rare earth permanent magnet among the variables for improving the residual magnetic flux density, the saturation magnetic flux density of the columnar phase is fixed, and the density of the magnet is also easily obtained close to the theoretical value. By improving the manufacturing process of rare earth permanent magnets, the most important variable is to improve the magnetic orientation, which is anisotropic process of rare earth alloy powder or grains, and to sinter and heat-treat.

In general, a rare earth permanent magnet is manufactured by melting and casting an alloy made of rare earth-iron-boron-other metal, and preparing the alloy into a rare earth powder having a size of several μm using a milling method such as a ball mill or a jet mill. Pulverizing, charging the pulverized rare earth powder into a mold, applying magnetic field and simultaneously performing compression molding to orient the powder in one direction and sintering the magnetically oriented compressed molded body in vacuum or argon to produce a compact sintered body. It consists of steps.

According to the conventional magnetic field orientation technology, the rare earth powder is filled into the mold, and the direct magnetic field is oriented by the direct current magnetic field generated by applying a direct current magnetic field to the electromagnets located on the left and right sides of the mold, and at the same time, compression molding is performed. It goes through the process of manufacturing the molded body.

On the other hand, in the magnetic field forming process as described above, when the magnetic field is generated using a DC power source, since the applied current is generally limited to a current of several tens to several hundred amperes (A), it is difficult to generate the magnetic field strength of 2 Tesla or more. There is a technical problem that the improvement in magnetic field orientation is also limited.

In order to solve the above problems, Patent Document 1 applies a weak magnetic field of 1 to 2 Tesla to a powder compact to rotate and orient the particles, and instantaneously in a direction different from the direction of application of the weak magnetic field to which a strong magnetic field of 3 Tesla or more is first applied. It is a two-step process of increasing the bulk density by pressurizing the powder compact while applying a pulse magnetic field.

In Patent Document 1, the particle size of the powder compact is 2 μm or less, so the particle size is small, so that it is difficult to increase the degree of orientation upon application of a magnetic field, so that a weak magnetic field is first applied to act as a rotation moment for orientation. It is effective when the particle size is fine particles of 2 mu m or less.

Republic of Korea Patent Publication No. 10-2014-0052926 (published May 07, 2014) Republic of Korea Patent Publication No. 10-0543582 (January 09, 2006 registration) Republic of Korea Patent Publication No. 10-0524827 (October 21, 2005 registration)

In the present invention, in order to solve the problem that the improvement of the magnetic field orientation of the powder is limited as in the prior art, instead of using the conventional DC magnetic field or pulse magnetic field, the pulse magnetic field and the DC magnetic field generator are connected in series to the magnetic field press to pulse the magnetic field during forming. By using a mixture of magnetic and DC magnetic fields to improve the magnetic field orientation of the powder, and to sinter the molded body with improved magnetic field orientation degree, there is provided a method for producing a rare earth permanent magnet which is subsequently heat treated.

More specifically, the rare earth powder is filled into a mold, and a high magnetic field is generated by applying a pulse magnetic field to the electromagnets located on the left and right sides of the mold to completely orient the rare earth powder, and then applying a direct magnetic field of a low magnetic field rather than the pulse magnetic field. While maintaining the orientation of the rare earth powder already fully oriented by the direct current magnetic field is subjected to compression molding is carried out a process of producing a molded body.

By using such a magnetic field shaping method, the high magnetic field by the pulsed magnetic field can be used to overcome the limitations caused by the conventional direct-current magnetic field, thereby improving the magnetic orientation of the rare earth powder, and the final residual magnetic flux density is high and excellent quality is achieved. It is possible to produce a rare earth permanent magnet having.

The present invention provides a method for producing a rare earth permanent magnet that increases coercive force by stabilizing the structure and components of Nd-rich through sintering and multiple heat treatments after magnetic field molding using a pulse magnetic field and a direct current magnetic field.

In order to achieve the object as described above, the method for producing a rare earth permanent magnet according to the present invention is made of a rare earth alloy containing a rare earth element and iron, the preparation of preparing a raw material powder having a particle size range of 2 ~ 10㎛ And a pulse magnetic field applying step of applying a high magnetic pulse pulse field to the filled raw powder, and applying a direct magnetic field of a low magnetic field to the pulse magnetic field after the pulse magnetic field applying step. The compression molding process, the low-length molding sintering step, and the heat treatment step of the heat treatment two or more times after the sintering process, characterized in that it consists of.

Method for producing a rare earth permanent magnet according to the present invention is characterized in that the molding density of the raw material powder is in the range of 1.6 to 3.0 g / cc.

The method for producing a rare earth permanent magnet according to the present invention is characterized in that the pulse magnetic field is applied 1 to 10 times in the pulse magnetic field applying process.

The method for manufacturing a rare earth permanent magnet according to the present invention is characterized by alternately applying the direction of the pulse magnetic field applied in the pulse magnetic field applying process.

The method for preparing a rare earth permanent magnet according to the present invention comprises a rare earth alloy containing rare earth elements and iron, and preparing a raw material powder having a particle size range of 2 to 10 μm, and forming the raw material powder into a mold for molding. And a DC magnetic field applying step of applying a DC magnetic field of a low magnetic field to the filled raw material powder, and a process of simultaneously applying compression molding while applying a pulse magnetic field having a higher magnetic field than the DC magnetic field after the DC magnetic field applying process. do.

The rare earth permanent magnet manufacturing method according to the present invention is the rare earth alloy 27 ~ 36wt% RE-64 ~ 73wt% Fe-0 ~ 5wt% TM-0 ~ 2wt% B (where RE = rare earth element, TM = 3d transition Metal) composition.

Method for producing a rare earth permanent magnet according to the invention is characterized in that the applied magnetic field of the pulse magnetic field is 3 ~ 5 Tesla.

Method for producing a rare earth permanent magnet according to the invention is characterized in that the applied magnetic field of the direct current magnetic field is 1.5 ~ 2 Tesla.

The method for producing a rare earth permanent magnet according to the present invention is charged into a sintering furnace after the magnetic field orientation and molding process, and maintained at a temperature of 400 ° C. or lower in a vacuum atmosphere to completely remove the remaining solvent, and then to 900-1200 ° C. again. It sinters by heating up.

In the method for producing a rare earth permanent magnet according to the present invention, the heat treatment temperature of the heat treatment step is 400 to 900 ℃, the number of heat treatment is characterized in that 2 to 10 times.

According to the method for producing a rare earth permanent magnet according to the present invention, the rare earth powder is filled into a mold, and a high magnetic field is generated by applying a pulse magnetic field to an electromagnet positioned at the left and right sides of the mold to completely orient the rare earth powder, and then the pulse. By maintaining the direction of the rare earth powder that is already fully oriented by the direct current magnetic field generated by applying the direct magnetic field rather than the magnetic field, compression molding is carried out to manufacture a molded body, and thus the high magnetic field due to the pulse magnetic field of the high magnetic field can be used. Therefore, the magnetic field orientation of the rare earth powder can be improved by overcoming the limitations caused by the conventional direct current magnetic field, and then compression molding is performed while maintaining the direction of the rare earth powder already fully oriented by the direct current magnetic field generated by applying the direct current magnetic field. Process of manufacturing molded articles Through the effect that you can get a rare earth permanent magnet having a high residual magnetic flux density is the final quality.

In addition, according to the manufacturing method of the rare earth permanent magnet according to the present invention, the optimum coercive force can be obtained through a plurality of heat treatments for sintering and stabilizing the structure and components of the Nd-rich after the magnetic field forming using a pulse magnetic field and a direct current magnetic field.

1 is a composite magnetic field press of the pulse magnetic field and direct current magnetic field according to the present invention.
2A to 2E are examples of magnetic field application patterns of the press according to the present invention.
3A is a sintering graph showing a relationship between sintering temperature and time.
3B is a heat treatment graph illustrating a heat treatment performed a plurality of times.

Hereinafter, the present invention will be described in more detail. Hereinafter, "upward", "downward", "forward" and "rear" and other directional terms are defined based on the states shown in the figures.

[Manufacturing method]

[Preparation process]

As a starting powder, a powder made of a rare earth alloy is prepared. The rare earth alloy is at least one selected from RE = Y, La, Ce, Pr, Nd, Dy, Tb, and Sm, and at least one selected from Fe, TM = 3d transition metal, B, and RE-Fe. Alloys, or RE-Fe-TM alloys, RE-Fe-B alloys, and RE-Fe-TM-B alloys. More specifically, Nd-Fe-B alloy, Nd-Fe-Co alloy, Nd-Fe-Co-B alloy, etc. are mentioned. A powder made of a known rare earth alloy used for the rare earth sintered magnet can be used for the raw material powder.

The raw material powder is pulverized by a pulverizing apparatus such as a jet mill, an atrita mill, a ball mill, a vibration mill, or the like by melting a molten cast ingot made of an alloy of a desired composition or a thin body obtained by a quench solidification method. It can manufacture using the atomization method like the maize method. You may further grind | pulverize and use the powder obtained by the manufacturing method of a well-known powder, and the powder manufactured by the atomizing method. By changing grinding | pulverization conditions and manufacturing conditions suitably, the particle size distribution of a raw material powder and the shape of each particle which comprises a powder can be adjusted. Although the shape of particle | grains does not matter in particular, it is easy to densify as it becomes closer to a true spherical particle, and particle | grains tend to rotate by application of a magnetic field. By using the atomizing method, a powder having high sphericity can be obtained.

At this time, the process of producing the raw powder from the alloy ingot is preferably carried out in nitrogen or inert gas atmosphere in order to prevent the contamination of oxygen and magnetic properties.

A raw material powder is one of the characteristics characterized by containing the fine particle whose particle diameter is 2-10 micrometers. The particle size of the raw material powder is a value measured by a laser diffraction particle size distribution device.

The finer the raw material powder is, the easier it is to increase the packing density. Therefore, the maximum particle size is more preferably 10 µm or less.

A lubricant may be added to the raw material powder. When a mixture containing a lubricant is used, each particle constituting the raw material powder is easily rotated when the magnetic field is applied, and the orientation is easily increased. As the lubricant, various materials and forms (liquid and solid) that do not substantially react with the raw material powder may be used. Examples of the liquid lubricant include ethanol, machine oil, silicone oil, castor oil, and the like, and solid lubricants include metal salts such as zinc stearate, hexagonal boron nitride, and wax. The addition amount of a lubricating agent is 0.01 mass% or more and about 10 mass% or less with respect to 100 g of raw material powder with a liquid lubricant, and 0.01 mass% or more and 5 mass% or less with respect to the mass of a raw material powder are mentioned with a solid lubrication agent.

[Mold Filling Process]

The molding die of a desired shape and size is prepared so as to obtain a press-molded article of a desired shape and size. The molding die can be used in the manufacture of a compacted compact, which is conventionally used for a raw material of a sintered magnet, and typically, one having a die and a vertical punch. In addition, hydrostatic press (Cold Isostatic Press) can be used.

[Orientation process]

When the raw material powder is filled in the molding die, a pulse magnetic field is applied to the electromagnets positioned on the left and right sides of the molding die to generate a high magnetic field, thereby fully aligning the raw material powder, and then by the direct current magnetic field generated by applying the direct current magnetic field. At the same time, compression molding is performed while maintaining the orientation of the fully oriented raw material powder to prepare a molded article.

The pulse magnetic field applied in the present invention has a higher magnetic field strength than the direct current magnetic field, the magnetic field applying duration of the magnetic field is 0.01 ~ 0.1 seconds, the magnetic field or the duration is short, the direct current magnetic field is relative to the pulse current Low, and the duration of applying the magnetic field is about 5 to 20 seconds. This feature is relatively long compared to the magnetic field application time of the pulse magnetic field.

In order to increase the magnetic field orientation of the raw material powder, it is essential to increase the rotational magnetic moment of the raw material powder. In order to increase the rotational magnetic moment of the raw material powder, it is effective that the intensity of the applied magnetic field is high. It is also necessary to maintain a long duration for the magnetic field-oriented magnetic field.

In this way, in order to increase the magnetic field orientation of the raw material powder and increase the duration of application of the magnetic field applied to the magnetic field-oriented raw material powder, the magnetic field shaping is performed by using a combination of the pulse magnetic field and the direct current magnetic field.

At this time, in order to further improve the magnetic field orientation of the powder, in the method of using the pulse magnetic field and the direct current magnetic field, ① the filling density of the powder filled in the mold, ② the number of times each magnetic field is repeatedly applied, ③ the direction in which the magnetic field is applied Or ④ Change the combination of the order of applying the magnetic field, and perform the magnetic field shaping.

The reason for applying the pulse magnetic field and the direct current magnetic field as above is that the pulse magnetic field can generate a high magnetic field, while it is difficult to sustain the magnetic field application time, while the DC magnetic field, which is the static magnetic field, can maintain the magnetic field application time. However, there is a disadvantage in that high magnetic field cannot be applied. Thus, the magnetic field is more completely formed by applying a high magnetic field, which is an advantage of the pulsed magnetic field, to orient the permanent magnet, and then applying a static magnetic field, which is a direct-current magnetic field, to the oriented permanent magnet. Because you can.

(Pulse magnetic field application process)

In the pulsed magnetic field application process, a relatively large particle having a particle size of more than 2 μm, especially 5 μm or more, is sufficiently rotated, that is, a magnetic field of 3 to 5 Tesla is not applied without being pressurized to form a gap between the particles. The magnetic field application time is applied within 0.01 ~ 0.1 second.

The pulse magnetic field applying process may be applied 1 to 10 times. The frequency of application of the pulsed magnetic field depends on the particle diameter and shape of the raw material powder. When the particle size distribution of the particles constituting the raw material powder is high in proportion and the particle shape is not spherical but has crushed protrusions, it is difficult to align all the particles in the same direction by applying one magnetic field. Only a few particles rotate enough. Therefore, since only one authorization of the magnetic field is not sufficient, the number of times of application of the magnetic field must be increased. On the other hand, in the case where the ratio of the large particle size of the raw material powder is high and the particle shape is spherical, the application number of the magnetic field may be sufficient only once.

Since the fine particles are less likely to rotate than the coarse particles even when a magnetic field is applied, even if a plurality of magnetic fields are applied in the same direction, the particles rotated by the application of the first magnetic field are applied by subsequent application of the magnetic field. It does not rotate substantially, and this fine particle will be in the state which cannot fully rotate. Therefore, instead of applying the magnetic field in the same direction several times, at least two magnetic fields are applied in different directions. Further, the first of these two times is set to a direction different from the direction to be oriented. By doing in this way, since the particle | grains rotated by the application of the first magnetic field are originally rotating in the direction different from the direction to be oriented, it will also rotate by application of the second magnetic field. As a result, when the second magnetic field is applied, the number of rotating particles increases, i.e., a fine particle size of the same size as that of coarse particles existing around the fine particles or fine particles that did not rotate first. Since the particles can gather and rotate in a particle group, the particles can be easily rotated in the direction to be oriented.

Application of two or more magnetic fields or alternating magnetic fields in the pulsed magnetic field application step has an effect of increasing the number of particles to be rotated when the magnetic field is applied. A particle having a particle size of more than 2 μm and more than 5 μm, particularly 8 μm or more, can be rotated, so that a relatively small magnetic field such as 1 Tesla or more and 2 Tesla or less may be used. In addition, even when using a raw material powder having a large number of fine particles having a particle size of 3 μm or less, for example, a fine powder composed of substantially only fine particles, since the particles rotate by the magnetic field of 1 Tesla to 2 Tesla, When the magnetic field is applied, a large number of particles having a large rotation angle can be obtained. The larger the rotation angle, the greater the momentum of rotation, and therefore, it is less likely to be affected by friction or the like that inhibits rotation. Therefore, even when a raw material powder containing many fine particles is used, the structure is oriented by a plurality of excitations in different directions, alternately, so as to be oriented by a plurality of excitations in the case of orientation by one excitation or in the same direction. Higher orientation can be obtained than in the case.

The application of the magnetic field in the pulse magnetic field application step includes a magnet capable of applying a magnetic field of 3 Tesla to 5 Tesla, specifically, a phase conducting magnet having a phase conducting coil such as a copper wire coil, and a superconducting coil. Both superconducting magnets are available.

(DC field approval process)

The direct current magnetic field applying process is a process for more fully forming the magnetic field oriented in a molded body (hereinafter referred to as a precompact) that has undergone the pulse magnetic field applying process, and applies the magnetic field in the direction to be oriented in the pulse magnetic field applying process. do.

In the DC magnetic field applying process, a magnetic field of 1.5 Tesla to 2 Tesla is applied in the range of 5 to 20 seconds of the magnetic field application (excitation) time. Along with such a DC field application process, the raw material powder is uniformly charged, pressed and compressed in a packing density range of 1.6 to 3.0 g / cc.

The bulk density is set to the apparent density just before the pressurization and compression of the raw material powder (mass of the raw material powder filled in the molding die / volume of the molding region before pressing and compression in the molding die), and the packing density is pressurized. The apparent density after compression (volume of the molding powder after pressing and compression in the mass / molding mold of the raw material powder filled in the molding die (= volume of the powder compact)).

The magnitude | size of the pressurization pressure at the time of shaping | molding can be suitably selected according to packing density etc., for example, 0.5 ton / cm <2> -1.5 ton / cm <2> is mentioned. In the case where pressing and compression are performed by dividing into multiple layers as described later, the pressing pressure at the time of molding may be selected according to the packing density or the like.

[Sintered body]

The compacted green compact for magnet of the present invention was charged into a sintering furnace and sufficiently maintained in a vacuum atmosphere and at 400 ° C. or lower to completely remove the remaining solvent, and again the sintering conditions were temperatures: 900 ° C. to 1200 ° C. and holding time: 0.5 hours to 3 hours. Time and atmosphere: Sintering is carried out under conditions such as vacuum and argon. After sintering, heat treatment (for example, aging treatment) for adjusting the magnet characteristics can be appropriately performed. The heat treatment conditions include 2 to 10 times at a temperature of 500 ° C to 900 ° C, a holding time of 1 hour to 10 hours, and an atmosphere of vacuum and argon. The obtained sintered compact can be used suitably for a rare earth sintered magnet, typically a permanent magnet.

Hereinafter, more specific embodiment of this invention is described using a test example.

As shown in Fig. 1, the pulsed magnetic field supply device and the direct current magnetic field supply device were coaxially arranged, and a molding die was disposed on the inner circumference of the pulsed magnetic field supply device and the direct current magnetic field supply device. The molding die includes a columnar lower punch inserted into a mold having a through hole, and an upper punch disposed opposite to the lower punch and pressing and compressing the raw material powder together with the lower punch. A molding space is formed by a die die and a lower punch, a raw material powder is filled into the molding space, and pressed and compressed by an upper punch and a lower punch. At this time, by energizing each pulse magnetic field supply device and the direct current magnetic field supply device appropriately, a magnetic field can be formed and a magnetic field is applied to the molded object in a molding space.

Each prepared raw material powder is filled into a molding die (molding space: diameter φ 10 mm), a pulse magnetic field is applied, and a pressure is adjusted so as to have a packing density of 1.6 or more and 3.0 g / cc or less of the molding density while applying a direct magnetic field. Pressurize and compress.

Example 1

In this test, it is composed of an alloy of 32wt% RE-66wt% Fe-1wt% TM-1wt% B (where RE = rare earth element, TM = 3d transition metal), and the alloy is dissolved by a covalent heating method. In addition, an alloy ingot was manufactured by using a strip casting method. In order to improve the grinding performance of the prepared alloy ingot, a hydrogen atmosphere was absorbed in a hydrogen atmosphere and room temperature, followed by a process of removing hydrogen at vacuum and 600 ° C., followed by a jet mill. It was made into a uniform and fine powder of 3.5㎛ particle size by the grinding method using the technique. At this time, the process of producing a fine powder from the alloy ingot was carried out in a nitrogen or inert gas atmosphere in order to prevent the contamination of oxygen and magnetic properties. The pulverized rare earth powder is uniformly filled into the mold at a packing density range of 1.8 to 2.6 g / cc, and pulsed magnetic field is applied to the electromagnet positioned at the left / right side of the mold: 5 Tesla magnetic field is applied for 0.02 seconds to orient the powder in the magnetic field direction. Subsequently, the molded body was prepared by compression molding while applying a DC magnetic field: 2 Tesla magnetic fields for 15 seconds. The obtained molded object was sintered and the orientation and magnetic properties of the obtained sintered body were investigated.

The molded article obtained by the magnetic field molding technique by the pulse magnetic field + DC magnetic field mixing method is charged into the sintering furnace, sufficiently maintained in a vacuum atmosphere and below 400 ° C to completely remove the remaining solvent, and then heated up to the range of 1,060 ° C for 2 hours. The sinter compaction was completed by maintaining. The sintered body after the sintering was manufactured into a magnet by heat treatment at 500 ° C. for 2 hours.

As described above, the magnetic properties of the samples and the comparative samples carried out by the present invention were obtained by measuring each loop while applying up to a maximum magnetic field of 30 kOe using a B-H loop tracer, and the results are shown in Table 1.

In Examples 1-1-2 to 1-5-2 (5 times in total), a DC magnetic field was applied after applying a pulse magnetic field once, and in Comparative Examples 1-1-1 to 1-5-1 (total 5 times), the packing density was tested by increasing the packing density by 0.2 g / cc from 1.8 to 2.6 g / cc.

As a result of the test, the pulse magnetic field and the DC magnetic field were applied in the order of 0.13 ~ 0.3kG more than the residual magnetic flux density of the comparative example, compared with the case of applying only the DC magnetic field. 2.3% improvement.

Magnetic Property Changes According to Powder Packing Density in Mixed Magnetic Field Molding Technology Sample Packing density
(g / cc) Licensed field type Number of pulse magnetic fields applied Pulse magnetic field application direction Residual magnetic flux density
(kG) 1-1-1 (Comparative Example) 1.8 direct current 13.18 1-1-2 (Example) 1.8 Pulse + DC One N 13.31 1-2-1 (Comparative Example) 2.0 direct current 13.25 1-2-2 (Example) 2.0 Pulse + DC One N 13.38 1-3-1 (Comparative Example) 2.2 direct current 13.30 1-3-2 (Example) 2.2 Pulse + DC One N 13.45 1-4-1 (Comparative Example) 2.4 direct current 13.25 1-4-2 (Example) 2.4 Pulse + DC One N 13.52 1-5-1 (Comparative Example) 2.6 direct current 13.17 1-5-2 (Example) 2.6 Pulse + DC One N 13.47

Example 2

In this test, alloys of 32wt% RE-66wt% Fe-1wt% TM-1wt% B (where RE = rare earth element, TM = 3d transition metal) were dissolved by vacuum induction heating method and strip casting method was used. To prepare an alloy ingot.

In order to improve the grinding performance of the prepared alloy ingot, after the hydrogen atmosphere and absorbing hydrogen at room temperature and then removing the hydrogen at vacuum and 600 ℃, by the grinding method using jet mill technology, uniform and fine particle size of 3.5㎛ Prepared as a powder. At this time, the process of producing a fine powder from the alloy ingot was carried out in a nitrogen or inert gas atmosphere in order to prevent the contamination of oxygen and magnetic properties.

The pulverized rare earth powder is uniformly filled in the mold with a packing density range of 2.4 g / cc, and the pulse magnetic field is applied to the electromagnets located at the left and right sides of the mold. Orientation was performed, followed by compression molding while applying a direct current magnetic field: 2 Tesla magnetic field for 20 seconds to prepare a molded article.

The molded article obtained by the magnetic field molding technique by the pulse magnetic field + DC magnetic field mixing method is charged into the sintering furnace and sufficiently maintained in a vacuum atmosphere and below 400 ° C. to completely remove the remaining solvent, and the temperature is raised to 1,060 ° C. for 2 hours. The sinter compaction was completed by maintaining. The sintered body after the sintering was manufactured into a magnet by heat treatment at 500 ° C. for 2 hours.

As described above, the magnetic properties of the samples and the comparative samples carried out by the present invention were obtained by measuring each loop while applying up to a maximum magnetic field of 30 kOe using a B-H loop tracer, and the results are shown in Table 2.

In Examples 2-1 to 2-4 (four times in total), a DC magnetic field was applied after applying the pulse magnetic field 1 to 4 times, and Comparative Example 1-4-1 was compared. It was tested based on cc.

As a result of the test, the pulse magnetic field and the DC magnetic field were sequentially applied than the DC magnetic field alone, and the residual magnetic flux density was 0.27 ~ 0.3kG higher than that of the comparative example. 2.3% improvement.

Magnetic Property Variation with Pulsed Magnetic Field Number in Mixed Field Forming Technology Sample Packing density
(g / cc) Licensed field type Number of pulse magnetic fields applied Pulse magnetic field application direction Residual magnetic flux density
(kG) 1-4-1 (Comparative Example) 2.4 direct current 13.25 2-1 (Example) 2.4 Pulse + DC One N 13.52 2-2 (Example) 2.4 Pulse + DC 2 N-> N 13.53 2-3 (Example) 2.4 Pulse + DC 3 N-> N-> N 13.55 2-4 (Example) 2.4 Pulse + DC 4 N-> N-> N-> N 13.54

Example 3

32wt% RE-66wt% Fe-1wt% TM-1wt% B (where RE = rare earth element, TM = 3d transition metal) alloy is dissolved by vacuum induction heating method, and the alloy ingot is removed by strip casting method. Prepared.

In order to improve the grinding performance of the alloy ingot prepared by absorbing hydrogen in a hydrogen atmosphere and room temperature, followed by a process of removing hydrogen at vacuum and 600 ℃, uniform and fine 3.5㎛ particle size by grinding method using jet mill technology Prepared as a powder.

At this time, the process of producing a fine powder from the alloy ingot was carried out in a nitrogen or inert gas atmosphere in order to prevent the contamination of oxygen and magnetic properties.

Pulverized rare earth powder is uniformly filled in the mold with a packing density of 2.4 g / cc, and the pulse magnetic field is applied to the electromagnet located on the left / right side of the mold. Orientation, and the compression molding was performed while applying a direct current magnetic field: 2 Tesla magnetic field for 15 seconds to prepare a molded body. At this time, the direction of the DC power source was kept the same as the direction of the final pulse magnetic field.

The molded article obtained by the magnetic field molding technique by the pulse magnetic field + DC magnetic field mixing method is charged into the sintering furnace and sufficiently maintained in a vacuum atmosphere and below 400 ° C. to completely remove the remaining solvent, and the temperature is raised to 1,060 ° C. for 2 hours. The sinter compaction was completed by maintaining. The sintered body after the sintering was manufactured into a magnet by heat treatment at 500 ° C. for 2 hours.

As described above, the magnetic properties of the samples and the comparative samples carried out by the present invention were obtained by measuring each loop while applying up to a maximum magnetic field of 30 kOe using a B-H loop tracer, and the results are shown in Table 3.

In the case of Examples 3-1 to 3-3 (three times in total), the pulse magnetic field is applied four times, but in the case of Example 3-1, the DC magnetic field is applied after applying in the same direction, Example 3-2 alternately In the case of applying the DC magnetic field after applying the pulse magnetic field, Example 3-3 compares Comparative Example 1-4-1 when applying the DC magnetic field after applying the pulse magnetic field alternately to apply twice in the same direction, The packing density was tested based on 2.4 g / cc.

As a result of the test, the pulse magnetic field and the alternating magnetic field were applied 0.32 ~ 0.35kG more than the residual magnetic flux density of the comparative example, compared with the case of applying only the DC magnetic field. ˜2.6% improvement.

Magnetic Property Variation with Application of Pulsed Magnetic Field in Mixed Magnetic Field Molding Technology Sample Packing density
(g / cc) Licensed field type Number of pulse magnetic fields applied Pulse magnetic field application direction Residual magnetic flux density
(kG) 1-4-1 (Comparative Example) 2.4 direct current 13.25 3-1 (Example) 2.4 Pulse + DC 4 N-> N-> N-> N 13.54 3-2 (Example) 2.4 Pulse + DC 4 N-> S-> N-> S 13.60 3-3 (Example) 2.4 Pulse + DC 4 N-> N-> S-> S 13.57

Example 4

32wt% RE-66wt% Fe-1wt% TM-1wt% B (where RE = rare earth element, TM = 3d transition metal) alloy is dissolved by vacuum induction heating method, and the alloy ingot is removed by strip casting method. Prepared.

In order to improve the grinding performance of the alloy ingot prepared by absorbing hydrogen in a hydrogen atmosphere and room temperature, followed by a process of removing hydrogen at vacuum and 600 ℃, uniform and fine 3.5㎛ particle size by grinding method using jet mill technology Prepared as a powder.

At this time, the process of producing a fine powder from the alloy ingot was carried out in a nitrogen or inert gas atmosphere in order to prevent the contamination of oxygen and magnetic properties.

The pulverized rare earth powder is uniformly filled in a mold with a packing density range of 2.4 g / cc, and a pulse magnetic field is placed on an electromagnet positioned at the left and right sides of the mold; Orientating the powder in the magnetic field direction while alternating the direction of the 5 Tesla magnetic fields in 0.02 seconds, four times, followed by direct current magnetic field; 2 Tesla magnetic field was applied for 15 seconds while compression molding was carried out to prepare a molded body. At this time, the direction of the DC power source was kept the same as the direction of the final pulse magnetic field.

The molded article obtained by the magnetic field molding technique by the pulse magnetic field + DC magnetic field mixing method is charged into the sintering furnace, sufficiently maintained in a vacuum atmosphere and below 400 ° C to completely remove the remaining solvent, and then heated up to the range of 1,060 ° C for 2 hours. The sinter compaction was completed by maintaining. The sintered body after the sintering was manufactured into a magnet by heat treatment at 400-600 ° C. for 2 hours.

As described above, the magnetic properties of the samples and the comparative samples carried out by the present invention were obtained by measuring each loop while applying up to a maximum magnetic field of 30 kOe using a B-H loop tracer, and the results are shown in Table 4 below.

Examples 4-1 to 4-4 are specimens prepared by sintering at 1,060 ° C. and heat-treating at a range of 400-600 ° C. using a molded body formed by alternately applying a pulsed magnetic field four times.

As a result of the test, as the heat treatment temperature increases, Nd-rich's structure and components are stabilized and the coercivity increases, but it decreases again over a certain temperature, which indicates that there is an optimal heat treatment temperature range to stabilize the structure and components of Nd-rich. it means.

Magnetic Property Variation with Sintering Temperature in Mixed Magnetic Field Molding Technology Sample Packing density
(g / cc) Licensed field type Number of pulse magnetic fields applied Pulse magnetic field application direction Heat treatment temperature
(℃) Coercivity
(kG) 4-1 (Example) 2.4 Pulse + DC 4 N-> S-> N-> S 400 ℃ 16.0 4-2 (Example) 2.4 Pulse + DC 4 N-> S-> N-> S 450 ℃ 17.2 3-2 (Comparative Example) 2.4 Pulse + DC 4 N-> S-> N-> S 500 ℃ 17.5 4-3 (Example) 2.4 Pulse + DC 4 N-> S-> N-> S 550 ℃ 17.2 4-4 (Example) 2.4 Pulse + DC 4 N-> S-> N-> S 600 ℃ 17.0

The results of Example 4 show that there is a heat treatment temperature range showing an optimal coercive force when the compacted body manufactured by the magnetic field orientation method of mixing the pulse magnetic field and the direct current magnetic field is sintered at the optimum sintering temperature to densify the structure and then subjected to the heat treatment. Can be.

The results of Examples 1 to 4 show that the magnetic field alignment method of mixing the pulsed magnetic field and the DC magnetic field improves the residual magnetic flux density, compared to the conventional magnetic field alignment method applying only the direct current magnetic field. It can be seen that it is more effective to apply a direct current magnetic field after the.

In addition, after the sintering process, the optimum heat treatment temperature for stabilizing the structure and components of the Nd-rich was confirmed.

In addition, this invention is not limited to the aspect of embodiment mentioned above, It is possible to change suitably, without deviating from the summary of this invention. For example, the composition of the raw material powder, the shape and size of the molded body, the magnetic field application rate, the sintering conditions, and the like can be appropriately changed.

Claims (6)

In a manufacturing method for producing a sintered magnet using a raw material powder consisting of a rare earth alloy containing a rare earth element and iron,
Preparation process consisting of the rare earth alloy, preparing a raw material powder having a particle size range of 2 ~ 10㎛,
Filling the mold for molding the raw material powder,
The pulsed magnetic field of the high magnetic field is applied to the charged raw powder at the same peak, but the pulsed current is applied to the 5 Tesla magnetic field twice in the same polarity direction by 0.02 seconds and the 2 Tesla magnetic field to the opposite polarity direction by 0.02 seconds. Magnetic field approval process,
After the pulse magnetic field applying process, while applying the DC magnetic field of the low magnetic field than the pulse magnetic field in the same polarity direction as the last application direction of the pulse magnetic field and applying 2 Tesla magnetic fields for 15 seconds, compression molding at the same time,
Sintering process after the low tension molding,
Heat treatment two or more times after the sintering process, the heat treatment is made of a heat treatment process that is carried out two or more times to lower,
Sintering temperature of the sintering process is 1,000 ~ 1,100 ℃, heat treatment temperature of the heat treatment process is a manufacturing method of rare earth permanent magnets, characterized in that 400 ~ 600 ℃ The method of claim 1,
Molding density of the raw material powder is a method for producing a rare earth permanent magnet, characterized in that in the range of 1.6 to 3.0 g / cc delete delete delete delete

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