Patent Grant
10176921
This application is a National Stage of International Application No. PCT/JP2013/071801, filed on Aug. 12, 2013 (which claims priority from Japanese Patent Application No. 2012-179192, filed on Aug. 13, 2012), the contents of which are incorporated herein by reference in their entirety.
The present invention relates to a method for producing a rare earth sintered magnet, and more particularly, to a method for producing a rare earth sintered magnet using a wet molding method, and a molding device therefor.
Rare earth sintered magnets, such as R-T-B-based sintered magnets (R means at least one of rare earth elements (concept including yttrium (Y)), T means iron (Fe) or a combination of iron and cobalt (Co), and B means boron) and Sm—Co-based sintered magnets (Sm may be partially substituted with other rare earth elements) are widely used because of excellent magnetic characteristics such as a residual magnetic flux density Br (hereinafter sometimes simply referred to as “Br”) and a coercive force Hcj (hereinafter sometimes simply referred to as “Hcj”).
Particularly, the R-T-B based sintered magnet has the highest magnetic energy product among various magnets hitherto known, and is relatively inexpensive. Thus, the R-T-B based sintered magnet has been used for various applications, including various motors, such as a voice coil motor for a hard disc drive, a motor for a hybrid vehicle, and a motor for an electric vehicle, and home electric appliances. In recent years, in order to achieve the reduction in size and weight or higher efficiency of products for various applications, the rare earth sintered magnets, such as the R-T-B based sintered magnet, are required to further improve its magnetic characteristics.
The production of most of the rare earth sintered magnets including an R-T-B-based sintered magnet includes the following steps of:
obtaining a raw material alloy cast with a desired composition, such as an ingot produced by melting (fusing) raw materials for examples metals, and casting the molten raw materials in a die to obtain an ingot, or strip produced by a strip cast method, and grinding the raw material alloy cast to produce alloy powder having a predetermined particle diameter; and
press molding the alloy powder (press molding the alloy powder in a magnetic field) to produce a molded body (green compact), and then sintering the molded body.
In the case of obtaining an alloy powder from a casting material, in many cases, steps to be used are two grinding steps of a coarsely grinding step of grinding into a coarse powder having a large particle diameter (coarsely ground powder) and a finely grinding step of further grinding the coarse powder into an alloy powder having a desired particle diameter.
The method of press molding (press molding in a magnetic field) is roughly classified into two methods. One is a dry molding method in which the obtained alloy powder is subjected to press molding in a dry state. The other one is a wet molding method mentioned, for example, in Patent Document 1, in which an alloy powder is dispersed in a dispersion medium such as oil to prepare a slurry, and the alloy powder is supplied in a cavity of a mold in a state of the slurry, followed by press molding.
Furthermore, the dry molding method and the wet molding method can be roughly classified into two methods, respectively, according to a relation between the pressing direction at the time of pressing in a magnetic field and the direction of the magnetic field. One is a perpendicular magnetic field molding method (also referred to as a “transverse magnetic field molding method”) in which the direction of compression performed by a press (pressing direction) is orthogonal to the direction of the magnetic field applied to an alloy powder. The other one is a parallel magnetic field molding method in which the pressing direction is in parallel with the direction of a magnetic field applied to an alloy powder (also referred to as a “longitudinal magnetic field molding method”).
There is a need for the wet molding method to perform supply of a slurry and removal of a dispersion medium, and thus the structure of a molding device becomes comparatively complicated. However, oxidation of the alloy powder and the molded body is suppressed by the dispersion medium, thus enabling reduction in the amount of oxygen of the molded body. The dispersion medium exists between alloy powders at the time of press molding in the magnetic field, leading to weak restriction due to a friction force. Thus, the alloy powder can rotate more easily in the magnetic field application direction. Therefore, higher orientation degree can be obtained. Thus, it is possible to obtain a rare earth sintered magnet which is more excellent in magnetic characteristics as compared with the dry molding method.
High orientation degree and excellent oxidation suppressing effect obtained using the wet molding method can be obtained in not only this R-T-B-based sintered magnet, but also other rare earth sintered magnets.
Among the wet molding methods, especially, the use of the parallel magnetic field molding method can achieve more excellent magnetic characteristics based on the following reasons.
In the wet molding method, when the slurry is charged in a cavity and press molding is performed in the magnetic field, there is a need for most of a dispersion medium (oil, etc.) in the slurry to be discharged out of the cavity. Usually, at least one of an upper punch and a lower punch is provided with a dispersion medium outlet and, when the volume of the cavity decreases by the movement of the upper punch and/or the lower punch to pressurize the slurry, the dispersion medium is discharged through the dispersion medium outlet. In this case, since the dispersion medium in the slurry is filtered and discharged from the portion close to the dispersion medium outlet, a layer called a “cake layer” having an increased concentration (high density) of the alloy powder is formed at the portion close to the dispersion medium outlet in an initial stage of press molding.
As the upper punch and/or the lower punch move(s) and press molding proceeds, much more dispersion medium is filtered and discharged, and thus an area of the cake layer spreads in the cavity. Finally, the cake layer having a high density of the alloy powder (low dispersion medium concentration) spreads all over the cavity, resulting in achieving bonding between the alloy powders (comparatively weak bonding) to obtain a molded body.
In the initial stage of press molding, when the cake layer is formed at the portion close to the dispersion medium outlet (upper portion and/or lower portion in the cavity), the direction of the magnetic field tends to be curved in the perpendicular magnetic field molding method.
The cake layer exhibits an increased magnetic permeability as compared with the portion other than the cake layer of the slurry (portion with less amount of the alloy powder per unit volume) because of high density of the alloy powder (large amount of the alloy powder per unit volume), thus causing focusing of the magnetic field in the cake layer. This means the fact that, even if the magnetic field is applied approximately perpendicularly to the cavity side surface outside the cavity, the magnetic field is curved toward the cake layer inside the cavity. Therefore, since the alloy powder is oriented along this curved magnetic field, the portion with curved orientation exists in the molded body after press molding, leading to a decrease in orientation degree in the single molded body, thus failing to obtain sufficient magnetic characteristics in the sintered magnet.
Meanwhile, in the parallel magnetic field molding method, since the magnetic field is applied to the direction parallel to the pressing direction, i.e. the direction parallel to the direction from the upper punch toward the lower punch, even if the cake layer is formed at the portion close to the dispersion medium outlet of the upper punch and/or the lower punch, the magnetic field travels straight toward the inside of the cake layer from the portion where the cake layer does not exist without being curved. Therefore, this does not cause the bending of the orientation of the magnetic field, unlike the perpendicular magnetic molding method.
Patent Document 1: JP 8-69908 A
Conventionally, the strength of the magnetic field applied in the parallel magnetic field molding method is 1.0 T or less. On the other hand, in recent years, in order to obtain more excellent magnetic characteristics, it is often necessary to perform a press molding in the magnetic field by applying a stronger magnetic field (more than 1.0 T) than before. However, when applying a magnetic field exceeding, for example, 1.0 T (for example, 1.1 T or more, and further 1.5 T or more) to the cavity, a slurry containing a magnetic powder is injected into the cavity through a slurry flow path, whereby the magnetic powder in the slurry is oriented through the slurry flow path, and tightly bonded together in the slurry flow path. In the parallel magnetic field molding method, the direction of the bonded magnetic powder is substantially orthogonal to the direction in which the slurry proceeds, so that the magnetic powder in the slurry itself serves as a resistance in the slurry flow path. The resistance of the magnetic powder in the slurry flow path due to the orientation of the magnetic field depends on the concentration of the magnetic powder in the slurry. When the concentration of the magnetic powder in the slurry becomes higher, the permeability of the slurry itself becomes larger. As a result, even under the same strength of the magnetic field, the resistance of the magnetic powder becomes larger. The resistance is not made uniform across the slurry flow path, which makes the injection rate or the injected amount of the slurry into the cavity non-uniform. This disadvantageously results in variations in weight of molded body (every shot) produced (hereinafter referred to as “unit weight variation” in some cases. Note that the term “unit weight” as used herein means the weight of one molded body).
Conventionally, in order to improve the productivity, a plurality of through holes are formed in a die for use in pressing under the magnetic field, and the upper punch and the lower punch are disposed at the respective through holes, so that a plurality of cavities is disposed in the magnetic field. The slurry is supplied to the respective cavities to perform press molding in each cavity (multi-cavity mold), whereby a plurality of molded bodies are conventionally produced. In the case of multi-cavity mold, however, unit weight variation occurs between the molded bodies molded at the same time for the same reason.
The unit weight variation leads to variations in size of the obtained molded body. In the case of a large variation in size, a target size needs to be set larger so that the small-sized molded body does not become a defective. As a result, a number of molded bodies each having a size that is larger than a necessary size thereof are fabricated. In some cases, it is necessary to reduce the size of the large-sized modified bodies fabricated, by cutting and/or polishing or the like, which leads to an increase in cost for material or processing. The large unit weight variation sometimes leads to variations in magnetic characteristics.
Therefore, the unit weight variation of the molded body is required to be reduced.
Accordingly, it is an object of the present invention to provide a method for producing a rare earth sintered magnet and a molding device therefor that can stably mold molded bodies with less variation in unit weight even though a large magnetic field, for example, exceeding 1.0 T (for example, 1.1 T or more, and further 1.5 T or more) is applied during press molding in the magnetic field.
A first aspect of the present invention is directed to a method for producing a rare earth sintered magnet, including the steps of:
1) preparing a slurry including an alloy powder and a dispersion medium, the alloy powder containing a rare earth element;
2) disposing an upper punch and a lower punch in respective through holes provided in a die, thereby preparing a plurality of cavities enclosed by the die, and the upper punch and the lower punch, at least one of the upper punch and the lower punch being movable toward and away from the other one, at least one of the upper punch and the lower punch including an outlet for discharging the dispersion medium of the slurry;
3) applying a magnetic field in each of the cavities by an electromagnet in a direction substantially parallel to a direction in which at least one of the upper punch and the lower punch is movable, and then supplying the slurry into the plurality of cavities via slurry flow paths connected to slurry supply paths extending from an outer peripheral side surface of the die to each of the cavities, wherein at least a part of a portion of the slurry flow path passing through a magnetic field formed by the electromagnet is covered by an external magnetic field shielding material being capable of shielding the magnetic field;
4) producing a molded body of the alloy powder in each of the cavities by press molding in the magnetic field, the upper punch and the lower punch coming closer to each other while applying the magnetic field; and
5) sintering the molded body.
A second aspect of the present invention is directed to the production method according to the first aspect, wherein the electromagnet includes:
a first electromagnet having a hollow portion; and
a second electromagnet opposed to and spaced from the first electromagnet and having another hollow portion.
A third aspect of the present invention is directed to the production method according to the second aspect, wherein the slurry is supplied into the cavities via the slurry flow path, at least a part of a portion of the slurry flow path passing through a magnetic field generated in the hollow portion of the first electromagnet, the hollow portion of the second electromagnet, a space for connecting between the hollow portion of the first electromagnet and the hollow portion of the second electromagnet, and an opposed space between the first and second electromagnets is covered by the external magnetic field shielding material being capable of shielding the magnetic field.
A fourth aspect of the present invention is directed to the production method according to the second aspect, wherein the slurry is supplied into each of the cavities via the slurry flow path, at least a part of a portion of the slurry flow path passing through a magnetic field generated in the hollow portion of the first electromagnet, the hollow portion of the second electromagnet, and the space for connecting between the hollow portion of the first electromagnet and the hollow portion of the second electromagnet is covered by the external magnetic field shielding material being capable of shielding the magnetic field.
A fifth aspect of the present invention is directed to the production method according to any one of the first to fourth aspects, wherein the external magnetic field shielding material allows the magnetic field to pass therethrough preferentially as compared to the slurry in the slurry flow path covered by the external magnetic field shielding material.
A sixth aspect of the present invention is directed to the production method according to any one of the first to fifth aspects, wherein the slurry supply path is not branched within the die.
A seventh aspect of the present invention is the production method according to any one of the first to sixth aspects, wherein the slurry supply path linearly extends from the outer peripheral side surface of the die toward the cavity.
An eighth aspect of the present invention is directed to the production method according to any one of the first to seventh aspects, wherein, in the step 3), the slurry is supplied into each of the cavities at a flow rate of 20 to 600 cm3/second.
A ninth aspect of the present invention is directed to the production method according to any one of the first to eighth aspects, wherein a magnetic field strength of the magnetic field is 1.5 T or more.
A tenth aspect of the present invention is directed to a molding device for a rare earth sintered magnet, including:
an upper punch and a lower punch, at least one of the upper punch and the lower punch being movable toward and away from the other one;
a die having at least one through hole, the die including a plurality of cavities, each of the plurality of cavities being enclosed by the upper punch and lower punch disposed in each through hole, and the through hole;
an electromagnet for applying a magnetic field in at least one cavity in a direction substantially parallel to a direction in which at least one of the upper and lower punches is movable;
a slurry supply path extending from an outer peripheral side surface of the die to each cavity, the slurry supply path being capable of supplying a slurry including an alloy powder and a dispersion medium to the cavity; and
a slurry flow path connected to the slurry supply path, wherein at least a part of a portion of the slurry flow path passing through a magnetic field formed by the electromagnet is covered by an external magnetic field shielding material being capable of shielding the magnetic field.
An eleventh aspect of the present invention is directed to the molding device according to the tenth aspect, wherein the electromagnet includes: a first electromagnet having a hollow portion; and a second electromagnet opposed to and spaced from the first electromagnet and having another hollow portion.
A twelfth aspect of the present invention is directed to the molding device according to the eleventh aspect, wherein at least a part of a portion of the slurry flow path passing through a magnetic field generated in the hollow portion of the first electromagnet, the hollow portion of the second electromagnet, a space for connecting between the hollow portion of the first electromagnet and the hollow portion of the second electromagnet, and an opposed space between the first and second electromagnets is covered by the external magnetic field shielding material being capable of shielding the magnetic field.
A thirteenth aspect of the present invention is directed to the molding device according to the eleventh aspect, wherein at least a part of a portion of the slurry flow path passing through a magnetic field generated in the hollow portion of the first electromagnet, the hollow portion of the second electromagnet, and the space for connecting between the hollow portion of the first electromagnet and the hollow portion of the second electromagnet is covered by the external magnetic field shielding material being capable of shielding the magnetic field.
A fourteenth aspect of the present invention is directed to the molding device according to any one of the tenth to thirteenth aspects, wherein the external magnetic field shielding material allows the magnetic field to pass therethrough preferentially as compared to the slurry in the slurry flow path covered by the external magnetic field shielding material.
A fifteenth aspect of the present invention is directed to the molding device according to any one of the tenth to fourteenth aspects, wherein the slurry supply path is not branched within the die.
A sixteenth aspect of the present invention is directed to the molding device according to any one of the tenth to fifteenth aspects, wherein the slurry supply path linearly extends from the outer peripheral side surface of the die toward the cavity.
The use of the production method or molding device according to the present invention can stably mold the molded bodies with little variation in unit weight even though the large magnetic field, for example, exceeding 1.0 T (for example, 1.1 T or more, and further 1.5 T or more) is applied during the press molding in the magnetic field. As a result, costs for material and processing can be reduced.
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the description below, if necessary, the terms indicative of the specific direction or position (for example, “upper”, “lower”, “right”, “left”, and other words including these words) are used for easy understanding of the present invention with reference to the drawings. The meanings of the terms do not limit the scope of the present invention in the present application. The same parts or members are designated by the same reference numerals throughout the drawings.
The inventors have intensively studied the reasons that when forming a molded body by press molding in a high magnetic field, for example, exceeding 1.0 T (for example, 1.1 T or more, further 1.5 T or more) by using a conventional method, a unit weight variation occurs between molded bodies in respective shots in the single-cavity mold, or between molded bodies in each shot in the multi-cavity mold.
As a result, as will be mentioned in detail later, in the conventional slurry supply method, for example, when a slurry containing a magnetic powder is injected into a cavity to which a large magnetic field exceeding 1.0 T is applied, the magnetic powder in the slurry is oriented while passing through the pipe, whereby the slurry has the resistance load together with the orientation of the magnetic field. That is, the magnetic powder is firmly bonded together in the pipe due to the orientation of the magnetic field, so that the magnetic powder itself in the slurry becomes the resistance in the pipe. Thus, it has been found that the resistance to the slurry is not equalized across the entire pipe, which makes the injecting rate or the injected amount of the slurry into the cavity non-uniform, resulting in variations in unit weight of the modified body.
Especially, a part of the slurry flow path that is more likely to be affected by the applied magnetic field and which is connected to a slurry supply path for charging the slurry into the cavity is covered by the external magnetic field shielding material being capable of shielding the magnetic field, and the slurry is supplied to the cavity via the slurry flow path. Thus, even though the large magnetic field exceeding 1.0 T is applied to the cavity, the magnetic field preferentially passes through the external magnetic field shielding material, which suppresses the orientation of the magnetic field in the slurry within the slurry flow path. Further, the magnetic powder contained in the slurry is less likely to be bonded together in the slurry flow path, which can decrease the possibility that the magnetic powder itself in the slurry becomes the resistance in the slurry flow path, thereby suppressing the unit weight variation of the modified bodies. In this way, the present invention has been made.
The production method and device according to the present invention will be described in detail below.
1. Press Molding Step in Magnetic Field
(1) Press Molding Device in Magnetic Field
The press molding device 100 in the magnetic field includes the first electromagnet 7a having a hollow portion 8a vertically penetrating therethrough (in the vertical direction shown in
In the embodiment shown in
In one preferred embodiment, in order to generate a uniform magnetic field therein, the hollow portion 8a serves as an air core (core portion) of a coil of the first electromagnet 7a, and the hollow portion 8b serves as an air core (core portion) of a coil of the second electromagnet 7b.
The die 5 has therein a cavity. An embodiment in which the die 5 includes four cavities 9a to 9d will be described below based on
In the embodiment shown in
Cavities 9a to 9d each are formed of four through holes vertically penetrating the die 5 (in the vertical direction shown in
Each of the cavities 9a to 9d has a length L0 along the molding direction. The term “molding direction” as used herein means a direction in which at least one of the upper and lower punches moves so as to get close to the other one (that is, in the pressing direction).
In the embodiment shown in
Broken lines M in
The reason for use of the terms “substantially parallel” and “substantially” is that for example, like the magnetic field in the air core of the coil, the magnetic field generated in the hollow portion provided within the electromagnet exhibits not a completely straight line, but a gentle curved line, and thus is not completely parallel to the straight molding direction. Note that based on understanding of these facts, a person skilled in the art sometimes expresses that the magnetic field on the gentle curved line is “parallel” to the longitudinal direction of the coil (vertical direction of
Referring to
The strength of the magnetic field of the inside of each of the cavities 9a to 9d preferably exceeds 1.0 T (for example, 1.1 T or more), and more preferably 1.5 T or more. This is because the magnetization direction of alloy powder in the slurry is surely oriented in the direction of the magnetic field upon supplying the slurry into the respective cavities 9a to 9d, which provides the high degree of orientation. The strength of the magnetic field in the cavity is 1.0 T or lower, which decreases the degree of orientation of the alloy powder, or can easily disturb the orientation of the alloy powder during the press molding. The strength of the magnetic field of the inside of the cavity 9 can be determined by measurement with a gaussmeter or analysis of the magnetic field.
Note that in the present invention, as will be mentioned later, when the magnetic field exceeding 1.0 T is applied in the cavities 9a to 9d, the significant effect is exhibited. However, also even when applying the magnetic field of 1.0 T or less, obviously, the molded bodies having little variation in unit weight can be stably molded.
The die 5 is preferably formed of non-magnetic material so as to form the magnetic field substantially parallel to the molding direction within each of the cavities 9a to 9d. Such a non-magnetic material can be a non-magnetic cemented carbide by way of example.
The upper punch 1 and the lower punches 3a to 3d are preferably made of magnetic material. In order to form the uniform parallel magnetic fields inside the cavities 9a to 9d, a non-magnetic material may be disposed on the lower end surface of the upper punch or the upper end surface of the lower punch.
The cavities 9a to 9d include slurry supply paths 15a to 15d, respectively (that is, each cavity includes the slurry supply path having a reference numeral with the same letter of the alphabet as that of a reference numeral showing the cavity). The slurry supply paths 15a to 15d formed to allow the slurry to pass therethrough extend from the outer peripheral side surface (outer periphery) of the die to the respective cavities 9a to 9d.
The slurry supply paths 15a to 15d are connected to the slurry flow path 17a or the slurry flow path 17b for supplying the slurry from the outside to the die 5 as will be mentioned later in detail. The slurry flow paths 17a and 17b have parts enclosed by an external magnetic field shielding material 30 (30a, 30b). In the embodiment shown in
The external magnetic field shielding material 30 is not specifically limited as long as the material 30 covers the slurry flow paths 17a and 17b to suppress the magnetic field from passing through the external magnetic field shielding material 30 and through the slurry flow paths 17a and 17b enclosed by the external magnetic field shielding material 30. For example, the external magnetic field shielding material 30 may be material such as a ferromagnetic material. Ferromagnetic material can be a soft magnetic material, and a hard magnetic material, and preferably a soft magnetic material. Soft magnetic material is preferably one having a high saturated magnetic flux density for allowing a magnetic field to pass therethrough when the magnetic field halting a large strength exceeding 1 T is applied thereto, and preferably one having a saturated magnetic flux density of about 1 to 2.5 T. Specifically, examples of the soft magnetic material preferably include a steel material, magnetic stainless steel, permalloy, permendur, iron and the like. Alternatively, examples of the external magnetic field shielding material may be a magnetic metal used as a material for a die, such as a tungsten carbide (WC) based cemented carbide, carbon steel or the like.
The slurry flow path 17a and the slurry flow path 17b may be formed of the external magnetic field shielding material itself (for example, by forming a hole in the external magnetic field shielding material and causing the hole to serve as the slurry flow). Alternatively, the slurry flow paths 17a and 17b may be formed by forming a slurry flow path in material other than the external magnetic field shielding material (for example, non-magnetic material or the like), and coating its outer periphery with an external magnetic field shielding material. As shown in
The slurry flow paths 17a and 17b have the shape formed by placing a Y shape on its side close to the die 5, as shown in
In the embodiment shown in
Like the embodiment shown in
As shown in
However, the inventors have found out that when applying a magnetic field exceeding 1.0 T in order to obtain the high magnetic characteristics, such a structure is more likely to have the unit weight variation of the molded bodies.
The reason for occurrence of the unit weight variation between the cavities that is considered by the inventors will be as follows. It is noted that this is not intended to restrict the scope of the present invention.
The alloy powder in the slurry supplied into the cavities 9a to 9d is oriented in parallel to the direction of the magnetic field by receiving the magnetic field applied. However, the orientation of the alloy powder in the magnetic field direction is not restricted to the inside of the cavity. The alloy powder existing in the slurry supply paths 115a to 115g is also oriented in the magnetic field direction.
That is, the alloy powder sometimes aggregate in the form of agglomerate by the magnetic field in the direction orthogonal to the traveling direction of the slurry in the slurry supply paths 115a to 115g. Such alloy powder in the form of agglomerate becomes the resistance to the slurry progressing in the traveling direction. Within the die 105, as the movement distance of the slurry becomes longer and the number of branch portions becomes greater, the slurry receives more resistance. When the magnetic field is relative small, e.g., 1.0 T or less, these variations in resistance due to the difference in moving distance of the slurry or the number of branch portions are not considered to be so problematic. When the applied magnetic field exceeds 1.0 T, however, the alloy powder is restrained by the strong magnetic field. In this case, variations in resistance due to the difference in movement distance of the slurry or the number of branch portions are not negligible.
Especially, the presence of the branch portion becomes a main cause for the unit weight variation of the molded body. When the branch point exists in the slurry supply path in the die, even though two slurry supply paths are geometrically branched in the same manner (for example, the slurry supply path 115b and slurry supply path 115c, and the slurry supply path 115a and slurry supply path 115d), the resistance to the slurry differs between two slurry supply paths depending on a difference in amount or shape of the alloy powder aggregating due to the magnetic field close to the branch portion, which often leads to large variations in unit weight between the cavities. As a result, this can be considered to assist in variations in magnetic characteristics of the thus-obtained rare earth sintered magnet.
Thus, for example, the presence of the branch portion in the die causes the unit weight variation of the molded bodies between the cavities, even though, like the embodiment shown in
In this way, the present invention can employ such an embodiment as that shown in
The slurry supply paths 15a to 15d preferably have the same length as each other (which is a length of a part of the slurry supply paths 15a to 15d included within the die 5). This is because the difference in resistance between the slurry supply paths can be more surely suppressed.
The slurry supply paths 15a to 15d preferably extend linearly (that is, have no curved part and no flexed part). Suppose that the slurry supply portion has the curved or flexed part with the magnetic field of above 1.0 T applied thereto, and the alloy powder oriented in the magnetic field direction aggregates in this part, such a part obviously becomes a large resistance to the fluidity of the slurry as compared to the formation of a straight linear part.
Referring to
When each of the cavities 9a to 9d has an optimal position for setting the cavity side end (slurry supply port) of each of the slurry supply paths 15a to 15d depending on the shape of a molded body to be obtained, the depth of the cavity and the like, the slurry supply paths 15a to 15d are not necessarily provided in the parts where a distance between each of the cavities 9a to 9d and the outer peripheral side surface of the die 5 is short. Even though the length of each of the slurry supply flow path 15a to 15d is slightly long, the slurry supply paths 15a to 15d preferably extend from the optimal positions.
The slurry supply paths 9a to 9d are connected to the slurry flow path 17a or 17b that is connected to a slurry supply device (not shown) (for example, a hydraulic device having a hydraulic cylinder), which allows the slurry from being supplied from the slurry supply device to the cavities 9a to 9d.
As shown in
Thus, as shown in
As shown in
The slurry flow path may be made of any material as long as the slurry flow path has a resistance to pressure of the slurry passing therethrough and has the resistance to corrosion or dissolution by a dispersion medium of the slurry. Preferably, the material for the slurry flow path is, for example, a copper pipe, or a stainless steel. The shape of the slurry flow path has any shape that has a small resistance upon flowing of the slurry and which hardly causes the retention of the slurry. A pipe or the formation of a hole penetrating a block-like member may form the slurry flow path.
In the above-mentioned preferable embodiment, the slurry flow paths 17a and 17b are disposed between the first electromagnet 7a and the second electromagnet 7b. However, the slurry flow paths 17a and 17b are not limited thereto, and may have any arrangement. For example, in use of a single electromagnet instead of the first electromagnet 7a and the second electromagnet 7b, the slurry flow path may be disposed to extend from the outside of the coil of the electromagnet to the air core through the coil.
The upper punch 1 preferably includes a dispersion medium outlet 11a that filters to discharge the dispersion medium in the slurry out of the cavity 9a. In a more preferable embodiment, the dispersion medium outlet 11a has a plurality of outlets.
Likewise, the upper punch 1 preferably has dispersion medium outlets 11b to 11d that filters to discharge the dispersion medium so as to filter to discharge the dispersion medium to the outside of the cavities 9b to 9d (note that the dispersion medium outlet 11c (for discharging the dispersion medium in the cavity 9c) and the dispersion medium discharge hole 11d (for discharging the dispersion medium in the cavity 9d) are not shown in the drawings).
In case the upper punch 1 includes the dispersion medium outlets 11a to 11d, the upper punch 1 preferably has a filter 13, e.g., a molding filter cloth, a molding filter paper, a porous filter, or a metal filter, so that the filter 13 covers the dispersion medium outlets 11a to 11d. This prevents the alloy powder from coming into the dispersion medium outlets 11a to 11d more securely (i.e. only the dispersion medium passes through the filter 13), thus making it possible to filter the dispersion medium in the slurry to discharge out of the cavities 9a to 9d.
Alternatively or in addition to providing the dispersion medium outlets 11a to 11d in the upper punch 1, the dispersion medium outlet 11a may be provided in the lower punch 3a, the dispersion medium outlet 11b may be provided in the lower punch 3b, the dispersion medium outlet 11c may be provided in the lower punch 3c, and the dispersion medium outlet 11d may be provided in the lower punch 3d.
In this way, even when the lower punches 3a to 3d are provided with the dispersion medium outlets 11a to 11d, the filters 13 are preferably disposed in the respective lower punches 3a to 3d to cover the dispersion medium outlets 11a to 11d, respectively.
(2) Press Molding Method
Supply of Slurry
The details of the step of press molding using the press molding device 100 in the magnetic field will be described below. As shown in
Then, the slurry is injected into the cavities 9a to 9d.
As mentioned above, the slurry is charged via a slurry supply device (not shown), the slurry flow paths 17a and 17b, and the slurry supply paths 9a to 9d.
The slurry 25 is preferably supplied into each of the cavities 9a to 9d at a flow rate of 20 to 600 cm3/second (in an amount of supply of the slurry). At the flow rate of less than 20 cm3/second, the magnetic field whose strength exceeds 1.0 T is applied, making it difficult to adjust the flow rate. Further, at the flow rate of less than 20 cm3/second, the slurry cannot be supplied into the cavity due to the resistance by the magnetic fields. On the other hand, when the flow rate exceeds 600 cm3/second, there occur variations in density of the thus-obtained molded body, which may generate cracks in the molded body when removing the molded body after the press molding, or generate cracks due to contraction thereof in sintering. When the flow rate exceeds 600 cm3/second, the disturbance of the orientation can be caused close to the slurry supply port. Particularly, when the dimension of the cavity in the magnetic field application direction (height of the cavity) exceeds 10 mm, the flow rate of the slurry is preferably in a range of 20 to 600 cm3/second.
The flow rate of the slurry is more preferably in a range of 20 to 400 cm3/second, and most preferably 20 to 200 cm3/second. By setting the flow rate of the slurry to the more preferable range and further the most preferable range, variations in density between respective parts of the molded body can be further reduced.
The flow rate of slurry can be controlled by adjusting a flow rate adjustment valve of the hydraulic device with the hydraulic cylinder serving as the slurry supply device to change the flow rate of oil to be fed to the hydraulic cylinder, thereby changing the speed of the hydraulic cylinder.
When a molded body is produced by supplying the slurry into the cavity at a flow rate of 20 cm3/second to 600 cm3/second while the magnetic field exceeding 1.0 T is applied in the cavity, the thus-obtained molded body can reduce variations in density of the respective parts of the molded body. As a result, the magnetic characteristics of respective parts of the rare earth sintered magnet obtained from the molded body have the uniform and high magnetic characteristics, which can further suppress variations in magnetic characteristics between the cavities.
The slurry is preferably supplied under a pressure of 1.96 MPa to 14.71 MPa (20 kgf/cm2 to 150 kgf/cm2).
The slurry supply paths 15a to 15d have any sectional shape (section orthogonal to the traveling direction of the slurry). One of the preferred shapes is substantially a circle, whose diameter is preferably in a range of 2 mm to 30 mm.
A magnetization direction of the alloy powder 21 of the slurry 25 supplied in cavities 9a to 9d becomes in parallel with the direction of the magnetic field, i.e., in parallel with the molding direction, due to the magnetic field of exceeding 1.0 T applied in the cavity. In
Press Molding
The press molding is performed after the cavities 9a to 9d are filled with the supplied slurry 25 in this way.
The press molding is performed so that at least one of the upper punch 1 and the lower punch 3 (lower punches 3a to 3d) is moved to cause the upper punch 1 and the lower punch 3 (lower punches 3a to 3d) to come close to each other, whereby, the each volume of the cavity 9 is reduced. In the embodiments as shown in
As shown in
In the press molding in magnetic field according to the invention of the present application, a ratio (L0/LF) between a length (L0) of the cavities 9a to 9d in the molding direction before the press molding is performed and a length (LF) of the obtained molded body in the molding direction is preferably within a range of 1.1 to 1.4. When the ratio L0/LF is 1.1 to 1.4, a risk that the alloy powder 21 having magnetization direction being oriented to a direction of the magnetic field rotates by a force applied when the alloy powder is subjected to the press molding, and thus the magnetization direction thereof deviates from a direction in parallel with the magnetic field can be reduced. This ensures achieving a further improvement in magnetic characteristics. To obtain the ratio L0/LF of 1.1 to 1.4, a method of increasing the concentration of the slurry to a high value (for example, concentration of 84% (by mass) or more) is exemplified.
In the embodiments shown in
A movable upper punch that can be inserted into the through hole of the upper punch die 5 (that is, like the lower punches 3a to 3d) may be used to fix the die 5, and move the movable upper punch downward and the lower punches 3a to 3d upward.
As a modified example of the embodiment shown in
2. Other Steps
Steps other than the molding step will be described below.
(1) Production of Slurry
Composition of Alloy Powder
An alloy powder may have the composition of a known rare earth sintered magnet including R-T-B-based sintered magnets (R means at least one of rare earth elements (concept including yttrium (Y)), T means iron (Fe) or a combination of iron and cobalt (Co), and B means boron) and Sm—Co-based sintered magnets (Sm may be partially substituted with other rare earth elements).
An R-T-B-based sintered magnet is preferable because of the highest magnetic energy product among various magnets and the affordable low price.
Preferable composition of the R-T-B-based sintered magnet is shown below.
R is selected from at least one of Nd, Pr, Dy and Tb. However, it is preferable that R contains either one of Nd and Pr. It is more preferable that a combination of the rare earth elements represented by Nd—Dy, Nd—Tb, Nd—Pr—Dy or Nd—Pr—Tb is used.
Among R, Dy and Tb particularly exert the effect of improving Hcj. The alloy powder may contain a small amount of another rare earth element, such as Ce or La. The element R is not necessarily a pure element (e.g. misch metal or didymium can be used) and may include inevitable impurities as long as it is available for industrial use. The content of the element R may be conventionally known content, and preferably can be within a range of 25 to 35% by mass. For the content of the element R of less than 25% by mass, the alloy powder cannot sometimes obtain the adequate magnetic characteristics, especially, the high Hcj. On the other hand, for the content of the element R exceeding 35% by mass, Br may be sometimes reduced.
The element T contains iron (including the case where T is substantially composed of iron), and may be substituted with cobalt (Co) by 50% by mass or less thereof (including the case where T is substantially composed of iron and cobalt). The element Co is effective for improving the temperature characteristics and corrosion resistance, and the alloy powder may contain 10% by mass or less of Co. The content of the element T occupies the balance of R and B, or R and B and below-mentioned M.
The content of the element B may be known content, and preferably may be within a range of 0.9 to 1.2% by mass. For the content of the element B of 0.9% by mass or less, the alloy powder cannot sometimes obtain the high Hcj. On the other hand, for the content of the element B of 1.2% by mass or more, Br may be sometimes reduced. A part of the elements B may be substituted with the element C (carbon). The substitution with the element C has the effect of improving the corrosion resistance of the magnet. In adding the elements B and C (including the case where both B and C are included), the total content of the elements B and C is preferably controlled so as to have the above preferable content of the element B by converting the number of substituent C atoms into the number of B atoms.
In addition to the above elements, the element M can be added for improving Hcj. The element M is at least one element selected from the group consisting of Al, Si, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Zr, Nb, Mo, In, Sn, Hf, Ta and W. The amount of addition of the element M is preferably 2.0% by mass or less. When the addition amount of the element M exceeds 5.0% by mass, Br may be sometimes reduced. Inevitable impurities can be permitted.
Method for Producing Alloy Powder
The alloy powder is obtained in the following manner, for example, an ingot or a flake of a raw material alloy for a rare earth sintered magnet having a desired composition is produced by a melting method, and hydrogen is absorbed (stored) in the ingot of the flake, thus performing hydrogen grinding to obtain a coarsely ground power.
Then, the coarsely ground power is further ground by a jet mill to obtain a fine powder (alloy powder).
A method for producing a raw material alloy for a rare earth sintered magnet will be exemplified below.
The alloy ingot is obtainable by an ingot casting method in which metal with finally required composition prepared in advance is melted and poured into a mold.
The alloy flake can be produced by a quenching method typified by a strip casting method or a centrifugal casting method in which a solidified alloy thinner than an alloy produced by an ingot casting method is quenched by bringing the molten metal into contact with a single roll, a twin roll, a rotation disk, or a rotating cylinder mold.
In the present invention, a material produced by either one of the ingot casting method or the quenching method can be used. However, a material produced by the quenching method is preferred.
The raw material alloy (quenched alloy) for a rare earth sintered magnet, produced by the quenching method, usually has a thickness within a range of 0.03 mm to 10 mm and has a flake shape. The molten alloy starts solidification from a surface in contact with a cooling roll (roll contact surface), and a crystal grain grows into a columnar shape in a thickness direction from the roll contact surface. The quenched alloy is cooled within a shorter period of time as compared with the alloy (ingot alloy) produced by a conventional ingot casting method (mold casting method), and thus the structure is refined, leading to a small crystal grain diameter. The quenched alloy has a wide grain boundary area. Since an R-rich phase expands largely within the grain boundary, the quenching method is excellent in dispersibility of the R-rich phase.
Therefore, the quenched alloy is likely to undergo grain boundary fracture by the hydrogen grinding method. The hydrogen grinding of the quenched alloy can control an average size of the hydrogen-ground powder (coarsely ground power) within a range of 1.0 mm or less.
The coarsely ground powder thus obtained is ground, for example, by a jet mill to obtain an alloy powder having a D50 grain size of 3 to 7 μm as measured by an airflow dispersion type laser analysis method.
The jet mill is preferably used in (a) atmosphere composed of a nitrogen gas and/or an argon gas (Ar gas) substantially having an oxygen content of 0% by mass, or (b) atmosphere composed of a nitrogen gas and/or an Ar gas having an oxygen content of 0.005 to 0.5% by mass.
In order to control the amount of nitrogen in the obtained sintered body, the atmosphere in the jet mill is replaced by an Ar gas atmosphere, and then a trace amount of a nitrogen gas is introduced thereinto to adjust the concentration of the nitrogen gas in the Ar gas.
Dispersion Medium
A dispersion medium is a liquid capable of obtaining a slurry by dispersing an alloy powder therein.
Examples of preferable dispersion medium to be used in the present invention include mineral oil and synthetic oil.
Although the kind of mineral oil or synthetic oil is not specified, when kinematic viscosity at normal temperature exceeds 10 cSt, the viscosity increases to enhance cohesion between alloy powders, and thus an adverse influence may be sometimes exerted on orientation property of the alloy powder when wet molding is performed in magnetism.
Therefore, the kinematic viscosity at the normal temperature of mineral oil or synthetic fluid is preferably 10 cSt or less. When a fractional distillation point of mineral oil or synthetic oil exceeds 400° C., it becomes difficult to perform deoiling after obtaining the molded body. As a result, the residual carbon amount in the sintered body may increase to cause deterioration of magnetic characteristics.
Therefore, the fractional distillation point of mineral oil or synthetic oil is preferably 400° C. or lower.
It is also possible to use vegetable oil as the dispersion medium. The vegetable oil means oil extracted from plants and is not limited to oil extracted from specific kinds of plants. Examples of the vegetable oil include soybean oil, rapeseed oil, corn oil, safflower oil, and sunflower oil.
Preparation of Slurry
Slurry can be obtained by mixing the obtained alloy powder with a dispersion medium.
There is no particular limitation on a mixing ratio of the alloy powder to the dispersion medium, and the concentration of the alloy powder in the slurry is preferably 70% or more (i.e., 70% by mass or more) in terms of a mass ratio. This is because, the alloy powder can be efficiently supplied in the cavity at a flow rate within a range of 20 to 600 cm3/second, and also excellent magnetic characteristics are obtained.
The concentration of the alloy powder in the slurry is preferably 90% or less in a mass ratio. This is because fluidity of the slurry is certainly ensured.
More preferably, the concentration of the alloy powder in the slurry is within a range of 75% to 88% in a mass ratio. This is because the alloy powder can be supplies more efficiently, and also fluidity of the slurry is ensured more certainly.
Still more preferably, the concentration of the alloy powder in the slurry is 84% or more in a mass ratio. As mentioned above, it is possible to adjust a ratio (L0/LF) of the length (L0) of the cavity 9 in molding direction to the length (LF) of the obtained molded body in the molding direction to a low value within a range of 1.1 to 1.4, thus enabling a further improvement in magnetic characteristics.
There is no particular limitation on the method for mixing the alloy powder with dispersion medium.
An alloy powder and a dispersion medium are separately prepared and, followed by weighing of predetermined amount of them to produce a mixture.
Alternatively, in the case of dry grinding of a coarsely ground powder by jet mill to obtain an alloy powder, a container accommodating a dispersion medium is disposed at an alloy powder discharging opening of a grinder such as a jet mill, and the alloy powder obtained by grinding is directly collected in the dispersion medium accommodated in the container to obtain a slurry. In this case, it is preferable that the container is also placed under atmosphere composed of a nitrogen gas and/or an argon gas, and then obtained alloy powder is directly collected into the container of dispersion medium without exposing the alloy powder to atmospheric air to prepare a slurry.
It is also possible that the coarsely ground powder kept in dispersion medium is wet-ground in a state of being held in the dispersion medium using a vibration mill, a ball mill, or an attritor to obtain a slurry composed of the alloy powder and the dispersion medium.
(2) Deoiling Treatment
A dispersion medium such as mineral oil or synthetic oil remains in the molded body obtained by the above mentioned wet molding method (longitudinal magnetic field forming method).
When the temperature of the molded body in this state is raised rapidly from normal temperature to, for example, 950 to 1,150° C., which is a sintering temperature, the inner temperature of the molded body rises rapidly, and thus the dispersion medium remaining in the molded body may react with a rare earth element of the molded body to produce rare earth carbide. In this way, when the rare earth carbide is produced, generation of a liquid phase sufficient for sintering is suppressed, thus failing to obtain a sintered body having sufficient density to cause deterioration of magnetic characteristics.
Therefore, before sintering, the molded body is preferably subjected to a deoiling treatment. The deoiling treatment is preferably performed under the conditions at 50 to 500° C., and more preferably 50 to 250° C., under a pressure of 13.3 Pa (10−1 Torr) or less for 30 minutes or more. This is because that the dispersion medium remaining in the molded body can be sufficiently removed.
A heating and holding temperature of the deoiling treatment is not limited to a single temperature as long as the heating and holding temperature is within a range of 50 to 500° C., and the deoiling treatment may be performed at two or more different temperatures. It is also possible to obtain the same effect as in the case of to the above mentioned preferable deoiling treatment by subjected to a deoiling treatment under the conditions of a pressure of 13.3 Pa (10−1 Torr) or less and a heating rate of from room temperature to 500° C. of 10° C./minuteute or less, more preferably 5° C./minuteute or less.
(3) Sintering
Sintering of the molded body is preferably performed under a pressure of 0.13 Pa (10−3 Torr) or less, and more preferably 0.07 Pa (5.0×10−4 Torr) or less, at a temperature within a range of 1,000° C. to 1,150° C. In order to avoid oxidation by sintering, it is preferable to replace the remaining gas of atmosphere by inert gas such as helium and argon.
(4) Heat Treatment
The obtained sintered body is preferably subjected to a heat treatment. By the heat treatment, the magnetic characteristics can be enhanced. Publicly known conditions can be employed for the heat treatment, e.g., temperature of the heat treatment and time for the heat treatment.
When a magnetic field of 1.50 T (in the direction indicated by the arrow in a broken line M of
As shown in Table 1, it is found that in each of Example 1, Comparative Example 1, and Comparative Example 2, the magnetic field strength of each of the positions (A, E, I) in the die was 1.50 T, while the magnetic field strength of each of the positions B, C and D in Example 1 (slurry flow paths 17a and 17b being covered by the external magnetic field shielding material 30 (30a, 30b)) was significantly reduced. Even by comparison with the magnetic field strength in each of the positions E, G and H of Comparative Example 1 (while the slurry flow paths 17a and 17b were not covered by the external magnetic field shielding material 30 (30a, 30b)) corresponding to the positions B, C and D of Example 1, the magnetic field strength of Example 1 was significantly reduced.
Further, it is found that the magnetic field strength in the position F of Comparative Example 1, that is, in a space for connecting between the hollow portion of the first electromagnet and the hollow portion of the second electromagnet was a large level (of 1.30 T) that was little different from that in the die (of 1.50 T). As can be seen from the result, the change from the structure of
An alloy molten metal was obtained by melting an alloy in a high-frequency melting furnace so as to have a composition (% by mass) of Nd20.7Pr5.5Dy5.5B1.0CO2.0Al0.1Cu0.1 and the balance of Fe. The thus-obtained alloy molten metal was quenched by a strip cast method, thereby producing a flaky alloy of 0.5 mm in thickness. The alloy was coarsely ground by a hydrogen grinding method, and then ground into fine particles by nitrogen gas containing an oxygen content of 10 ppm (0.001% by mass, that is, substantially 0% by mass) by a jet mill. A particle diameter D50 of the thus-obtained alloy powder was 4.7 μm. The alloy powder was immersed in mineral oil having a distillation point of 250° C. and a kinetic viscosity of 2 cSt at room temperature (manufactured by Idemitsu Kosan Co., Ltd., Trade name: MC OIL P-02) under nitrogen atmosphere, thereby providing a slurry in a concentration of 85% (% by mass).
The press molding was performed by using the press molding device in the magnetic field according to the present invention shown in
One time of the above step was defined as one shot. The molding process was carried out for forty shots to obtain one hundred and sixty molded bodies in total. Note that the depth of the cavity was adjusted such that the molded body after the sintering had a target weight of 100 g.
The thus-obtained molded body was heated at a rate of 1.5° C./minute from room temperature to 150° C. under vacuum, and then kept at that temperature for one hour. Thereafter, the molded body was heated again up to 500° C. at a rate of 1.5° C./minute, thereby removing the mineral oil from the molded body. Further, the molded body was heated at 20° C./minute from 500° C. to 1,100° C., and maintained at that temperature for 2 hours and sintered. The thus-obtained sintered body was subjected to heat treatment for one hour at 900° C., and then another heat treatment for one hour at 600° C. Variations in weight (unit weight) of the thus-obtained sintered body every shot were examined. The unit weight variation of each shot was defined by dividing a difference between the maximum weight and the minimum weight of four samples in each shot by an average weight of the four samples, and representing the thus-obtained value by percentage. Table 2 shows the minimum and maximum values of the unit weight variation for forty shots.
As can be seen from Table 2, the use of the press molding device in the magnetic field in the present invention (Example 2) drastically decreases the unit weight variation of the sintered compact as compared to the use of the press molding device in the magnetic field shown in
This application claims priority on Japanese Patent Application No. 2012-179192, the disclosure of which is incorporated by reference herein.
1 Upper punch
3
a, 3b, 3c, 3d Lower punch
5 Die
7
a First electromagnet
7
b Second electromagnet
8
a, 8b Hollow portion
9
a, 9b, 9c, 9d Cavity
11
a, 11b, 11c, 11d Dispersion medium outlet
13 Filter
15
a, 15b, 15c, 15d Slurry supply path
17
a, 17b Slurry flow path
21 Alloy powder
23 Dispersion medium
25 Slurry
27 Cake layer
| Number | Date | Country | Kind |
|---|---|---|---|
| 2012-179192 | Aug 2012 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2013/071801 | 8/12/2013 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2014/027641 | 2/20/2014 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2513242 | Inman | Jun 1950 | A |
| 3786857 | Sutherland | Jan 1974 | A |
| 5489343 | Uchida | Feb 1996 | A |
| 8066498 | Kurita | Nov 2011 | B2 |
| 20020185766 | Daihisa et al. | Dec 2002 | A1 |
| 20060219323 | Masuzawa et al. | Oct 2006 | A1 |
| 20070176329 | Saito | Aug 2007 | A1 |
| 20080230957 | Feigenblum et al. | Sep 2008 | A1 |
| 20090108970 | Ol | Apr 2009 | A1 |
| 20110205006 | Odaka | Aug 2011 | A1 |
| Number | Date | Country |
|---|---|---|
| 62-251109 | Oct 1987 | JP |
| 8-69908 | Mar 1996 | JP |
| 2010-215992 | Sep 2010 | JP |
| Entry |
|---|
| International Search Report for PCT/JP2013/071801 dated Sep. 3, 2013 [PCT/ISA/210]. |
| Communication dated Mar. 8, 2016 from the European Patent Office issued in corresponding Application No. 13879307.0. |
| International Preliminary Report on Patentability dated Feb. 26, 2015, issued by the International Bureau of WIPO in counterpart International application No. PCT/JP2013/071801. |
| Number | Date | Country | |
|---|---|---|---|
| 20150206656 A1 | Jul 2015 | US |
