JPH07201545A - Sintered magnet and its manufacture thereof - Google Patents

Abstract

PURPOSE:To dispense with a grinding process which is usually carried out following a sintering process and to obtain a thin-walled sintered magnet at a low cost by a method wherein an R-T-B (R is an element out of rare earth elements which include Y, T is Fe or Fe and Co) sintered magnet is kept high in dimensional stability at sintering. CONSTITUTION:A molded body which contains R2T14 magnetic powder and R oxide powder and is 5.5g/cm<3> or above in density is sintered so as to be as large in density change as 0.2g/cm<3> or above. Or, a molded body which includes R2T14B main phase mother alloy powder, grain boundary phase mother alloy powder which includes 70 to 97% by weight of R and the rest, that is substantially Fe and/or Co, and R oxide powder is sintered, whereby a sintered magnet which contains 3 to 15% by volume of closed voids and 0.5 to 10% by weight of R oxide can be manufactured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rare earth sintered magnet having a small shrinkage during sintering, and a method for producing the same.

[0002]

2. Description of the Related Art As a rare earth magnet having high performance, an Sm-Co type magnet manufactured by powder metallurgy has an energy product of 32M.
GOe's are in mass production. In recent years, Nd-Fe
R-T-B magnets such as -B magnets (T is Fe, or Fe
And Co) were developed, and a sintered magnet is disclosed in JP-A-59-46008. R-T-B magnets are cheaper in raw material than Sm-Co magnets. RT
A conventional Sm—Co powder metallurgical process (melting → casting → coarse crushing → fine crushing → molding → sintering → magnet) can be applied to the production of a —B sintered magnet.

In the R-T-B system magnet, in addition to the sintered magnet,
Bonded magnets in which magnet powder is bonded with a resin binder or a metal binder are also in practical use. Since the dimensions of the bonded magnet are almost maintained during molding, the dimensional accuracy is high and no shape processing is required after manufacturing. However, since the industrialized RTB-based bonded magnet uses polycrystalline particles made of fine crystals produced by a quenching method such as a single roll method, anisotropy due to molding in a magnetic field does not occur. Have difficulty. The crushed powder of the RTB sintered magnet cannot be used as the raw material powder of the bonded magnet because the coercive force is drastically reduced due to the distortion and the oxidation due to the crushing. In addition, the crushed powder of the R-T-B type alloy ingot is reacted with hydrogen to decompose it into a rare earth hydride, a boride of T, and T, and dehydrogenate at a predetermined temperature to crystallize in individual particles. Proposals have also been made to deposit fine crystals with uniform orientation. The polycrystalline particles obtained by this method can be magnetically oriented, and high coercive force can be obtained by fine crystals.
Since hydrogen is used, the process is complicated and has not been put to practical use.

On the other hand, in the R-T-B system sintered magnet, since the powder consisting of substantially single crystal particles is molded in a magnetic field, an anisotropic magnet can be easily obtained, and a binder is not used. High characteristics can be obtained. However, in the sintering method, the molded body significantly shrinks during the sintering reaction, and the shrinkage is non-uniform, so that it is difficult to maintain the dimensional accuracy of the molded body. This shrinkage varies depending on the degree of orientation of particles in the molded body, variations in density, and the like. In an anisotropic sintered magnet, the contraction rate differs between the direction of easy magnetization and the direction perpendicular to it. For example, when the density of the molded body is 4.3 g / cm ³ , about 22% in the direction of easy magnetization, and It becomes about 15% in the vertical direction, and the density after sintering reaches 7.55 g / cm ³ .

Such a dimensional change in the anisotropic sintered magnet is particularly problematic when the ring-shaped magnet or the plate-shaped magnet is thin. This is because if the shrinkage ratio of the thin magnet becomes uneven, warpage occurs. Therefore, when commercialized, the sintered body is ground to correct such dimensional changes. However, the grinding process has the following problems.

The amount of material loss of the sintered body during grinding becomes large. For example, if a warp of 1 mm occurs when manufacturing a thin plate magnet with a thickness of 1 mm, it is necessary to first manufacture a sintered body with a thickness of about 3 mm and then grind the upper and lower surfaces of the sintered body. 2/3 of the material is lost. In order to avoid such a loss, even when cutting multiple thin plate magnets to a thickness of 1 mm from a single thick base material, if the tooth width of the grinding cutter is 0.6 mm, it will be about 40%. There will be a loss.
Further, since the thin-walled sintered body has low mechanical strength, chipping or cracking is likely to occur at the time of processing impact or handling, resulting in low yield.

The magnetic characteristics are degraded. Nd ₂ Fe ₁₄ B
It has been reported in detail in various papers that the coercive force of the system sintered magnet depends on the existence of the Nd-rich phase in the grain boundary. When processing a sintered magnet of this system,
The stress causes cracks and the like in the crystal grain boundaries in the region close to the processed surface, and the coercive force is lost in the region from the processed surface to a depth of 0.1 to 0.2 mm. The loss of the magnet characteristics in the vicinity of the machined surface is negligible for the thick magnet, but has a large effect for the thin magnet, and the deterioration of the magnetic characteristics of the entire magnet becomes apparent. Although it is possible to remove the region where the coercive force disappears by processing by acid etching, the amount of loss of the sintered body further increases and the manufacturing cost also increases.

Under these circumstances, a thin anisotropic magnet having a longitudinal length / thickness of 10 or more is usually Sm-
Co-based bonded magnets are used, and high cost is a problem. Although there are RTB-based thin-walled sintered magnets, processing for size adjustment is indispensable, and the material yield at the time of processing is 20 to 30%, which also increases the cost. ing.

[0009]

DISCLOSURE OF THE INVENTION The present invention provides an RTB.
An object of the present invention is to provide an inexpensive thin-walled magnet by suppressing the dimensional change during sintering in the production of a system-based sintered magnet, thereby eliminating the need for grinding after sintering.

[0010]

Such an object is achieved by the present invention described in (1) to (16) below. (1) A sintered magnet containing R (R is at least one kind of rare earth element including Y), T (T is Fe, or Fe and Co) and B, and having a closed hole. Three
The sintered magnet is characterized by containing ˜15% by volume and 0.5 to 10% by weight of R oxide. (2) The sintered magnet according to (1) above, which has a density of 7.15 g / cm ³ or less. (3) The average projected cross-sectional area per closed hole is 1000-
The sintered magnet according to the above (1) or (2), which has a size of 30,000 μm ² . (4) The above (1) to which the ratio of open pores is 2% by volume or less.
The sintered magnet according to any one of (3). (5) The above (1) to (4), which contains 30 to 45% by weight of R, 0.5 to 3.5% by weight of B, and the balance is substantially T.
One of the sintered magnets. (6) A method for producing a sintered magnet containing R (R is at least one rare earth element including Y), T (T is Fe, or Fe and Co) and B. Molding a mixture containing magnet powder having crystal grains substantially composed of R ₂ T ₁₄ B and R oxide powder,
Density to obtain a shaped body is 5.5 g / cm ³ or more, the production of sintered magnets of the green density change is characterized by having a step of sintering so that 0.2 g / cm ³ or more Method. (7) The method for producing a sintered magnet according to the above (6), wherein the average particle diameter of the magnet powder is 30 to 350 μm. (8) A method for producing a sintered magnet containing R (R is at least one kind of rare earth element including Y), T (T is Fe, or Fe and Co) and B. , A powder of a master alloy for a main phase having crystal grains substantially composed of R ₂ T ₁₄ B, and a grain boundary phase in which R is 70 to 97% by weight and the balance is substantially Fe and / or Co A method for producing a sintered magnet, comprising a step of sintering a molded body obtained by molding a mixture containing a powder of a mother alloy and a powder of an R oxide. (9) Manufacture of the sintered magnet according to the above (8), wherein the density of the molded body is 5.5 g / cm ³ or more, and the molded body is sintered so that the density change is 0.2 g / cm ³ or more. Method. (10) The average particle size of the main phase master alloy powder is 30 to
The method for producing a sintered magnet according to the above (8) or (9), which has a size of 350 μm. (11) The sintered magnet according to any one of (8) to (10) above, wherein the grain boundary phase master alloy remains in a sieve having an opening of 38 μm or more and passes through a sieve having an opening of 500 μm or less. Production method. (12) The method for producing a sintered magnet according to any one of (8) to (11) above, wherein the proportion of the grain boundary phase master alloy in the mixture is 2 to 20% by weight. (13) The method for producing a sintered magnet according to any one of the above (6) to (12), wherein the ratio of the R oxide powder in the mixture is 0.5 to 10% by weight. (14) The average particle diameter of the R oxide powder is 0.5 to 2
The method for producing a sintered magnet according to any of (6) to (13) above, wherein the sintered magnet has a thickness of 0 μm. (15) The molding pressure is 8 t / cm ² or more (6) to
The method for manufacturing a sintered magnet according to any one of (14). (16) The method for producing a sintered magnet according to any one of (6) to (15), which produces the sintered magnet according to any one of (1) to (5).

[0011]

[Operation and effect] The density of the conventional molded body for Nd ₂ Fe ₁₄ B sintered magnet is about 55% of the density (theoretical density: about 7.6 g / cm ³ ) assuming that there are no pores. 4.2g /
cm ³ ) and contains about 45% of holes. Then, since it is densified to about 99% of the theoretical density by sintering, the volumetric shrinkage rate becomes large.

On the other hand, in the present invention, shrinkage is suppressed to a small level by forming closed holes in the magnet at a predetermined ratio during sintering. Since the closed holes do not communicate with the outside of the magnet,
Unlike the open pores (open pores) of the conventional semi-sintered magnet described later, the magnet is not corroded. By reducing the shrinkage ratio during sintering in this way, even when manufacturing ring-shaped or plate-shaped thin-walled anisotropic magnets, there is no need for processing to correct the shape, resulting in cost reduction and production. The improvement of sex is realized. Further, since the high-density molded body has high bending strength, it is easy to handle, and cracks and chips are less likely to occur between the molding step and the sintering step.

In the present invention, in order to form the closed pores, R oxide powder is added to magnet powder (main phase master alloy powder), and a mixture of these is compacted and then sintered. . The powder of the R oxide has an effect of inhibiting sintering, and since it is difficult to move particles during sintering in a high-density compact, closed pores are formed in the magnet after sintering. .

In a preferred embodiment of the invention, the two alloy method is used. The two-alloy method in the production of the RTB-based sintered magnet is
This is a method in which powders of two kinds of alloys having different compositions are mixed and sintered. In the present invention, in the two-alloy method, the main phase master alloy and the grain boundary phase master alloy are used. The main phase master alloy powder used in the present invention has the same composition as that used in the conventional two-alloy method, but preferably has a large particle size.
The grain boundary phase master alloy used in the present invention has a low melting point composition centered on Nd ₈₉ Fe ₁₁ (weight ratio). The powder of the master alloy for the grain boundary phase melts at the time of sintering, flows into a liquid phase having extremely good wettability with respect to the main phase of R ₂ T ₁₄ B, and coats the periphery of the powder of the master alloy for the main phase. Then, it becomes a grain boundary phase of the magnet to improve the coercive force. In the present invention, in addition to these, R oxide powder is added. Since the R-rich grain boundary phase master alloy improves the sinterability, the shrinkage rate during sintering becomes large. However, in the present invention, since the powder of the R oxide which inhibits the sintering is also added, the sintering reaction is suppressed and the shrinkage ratio is suppressed. Moreover, although the residual magnetic flux density is lowered by adding the R oxide, the coercive force is rather improved. When the R oxide is brought into contact with the R-rich grain boundary phase master alloy, it is reduced in accordance with chemical equilibrium and becomes a metal in an active state. The metal in the active state is more likely to react with the R ₂ T ₁₄ B main phase than the added grain boundary phase master alloy, so that the coercive force is improved. Further, since the master alloy powder for grain boundary phase melts and surrounds the R oxide, the R oxide does not come into direct contact with the main phase.

Further, in the present invention, since the R oxide powder is added to inhibit the sintering reaction, it becomes difficult for the master alloy powder for the grain boundary phase to be filled with the sintering reaction after being melted and flowed, and the formation of closed pores is prevented. It will be easy. In particular, when the compact has a high density to make it difficult to move particles, or when the powder of the grain boundary phase master alloy has a large diameter, large closed pores can be easily formed.

Also in the conventional two-alloy method, the R-rich powder which becomes the grain boundary phase after sintering is added, but the R-oxide powder is not added. In the first place, the reason why the R-rich powder is added by the conventional two-alloy method is to improve the coercive force and to accelerate the liquid phase sintering to increase the density of the magnet. In the two-alloy method of adding R-rich powder, no proposal has been made so far to reduce the density of the sintered body to reduce the shrinkage rate.

Although open pores exist near the surface of the sintered magnet of the present invention, if at least a part of the sintering step is performed in a vacuum or under a reduced pressure atmosphere, a liquid phase master alloy for grain boundary phases is obtained. Blocks the communication path to the outside of the open hole, so that the ratio of open holes is reduced and corrosion resistance is improved.

In the present invention, high density (5.5 g / cm ³ or more)
It is preferable to use the molded body of (1) and not completely sinter it (the density after sintering is 7.15 g / cm ³ or less). As a result, the shrinkage rate during sintering becomes even smaller.

The magnetic properties {(BH) max = about 17 to 25 MGOe} of the sintered magnet manufactured according to the present invention have a conventional RT-
Although it is lower than that of the B-based high-density sintered magnet, it is higher than that of the Sm-Co-based bonded magnet {(BH) max = about 15 MGOe}. The raw material of the RTB magnet is cheaper than that of the Sm-Co magnet. Therefore, the sintered magnet manufactured according to the present invention is the Sm-Co conventionally used for a thin magnet.
It is suitable as a substitute for the system bonded magnet.

As described below, it is known that R oxide powder is added to the magnet powder when manufacturing the R ₂ T ₁₄ B system sintered magnet. In addition, R ₂ T
₁₄ Various proposals have been made to manufacture B-based sintered magnets,
A method for producing a low-density porous sintered body without completely sintering the molded body is also known as shown below, but any of them is different from the present invention.

Japanese Unexamined Patent Publication (Kokai) No. 61-289605 discloses a method of mixing granular rare earth oxides in the production of rare earth-iron-boron permanent magnets. The publication describes that the coercive force can be improved by adding a rare earth oxide.
However, the publication does not describe closed pores, and neither the density of the molded body nor the density of the magnet is disclosed. In the example of the publication, a magnet powder having a small diameter of 5 to 10 μm is used, and the molding pressure is about 7 × 10 ⁷ Newton /
Since the pressure is as low as m ² (about 0.71 t / cm ² ), it is considered that the compact density is the same as the conventional one.

Japanese Unexamined Patent Publication No. 4-41652 discloses light rare earth oxides (La ₂ O ₃ , Ce ₂ O ₃ , Pr ₂ O ₃ , Nd _2).
A rare earth magnet alloy containing 0.1 to 1.0 wt% of O ₃ and Sm ₂ O ₃ ) is disclosed. According to the publication, the corrosion resistance is improved by including a light rare earth oxide in the rare earth magnet alloy. However, the publication does not describe closed pores, and neither the density of the molded body nor the density of the magnet is disclosed. In the examples of the publication, magnet particles having a small diameter of 3.2 μm or less are used, and the molding pressure is as low as 1.0 t / cm ² , so that the density of the compact is considered to be the same as the conventional one.

Japanese Unexamined Patent Publication (Kokai) No. 5-47528 discloses a method for manufacturing an anisotropic rare earth bonded magnet. In this method, first, a Nd-Fe-B magnet powder is mixed with a sintering inhibitor or a vaporizing agent, or the surface of the magnet powder is oxidized, and then the magnet powder is exposed to a magnetic field of 0.2 to 5 t / cm ^2.
Compress with the pressure of to make a green compact. Next, 50
It is fired at 0 to 1140 ° C. to make an anisotropic fired body having open pores, and heat-treated at 400 to 1000 ° C. Then
After impregnating the open pores with the resin, the resin is cured. In Tables 1 and 2 of the publication, various sintering inhibitors are added to 700 to 1
The density of the fired body (before resin impregnation) produced by firing at 060 ° C. is described, and all of them have a density of 6.9 g / cm ³ or less.

The sintering inhibitor described in the above publication is an oxide, a fluoride, a chloride or the like which is not melted during firing or only partially melted. In the same publication, these sintering inhibitors prevent the flow of the R-rich liquid phase generated during firing, so that the fired body does not contract significantly even when performing high temperature firing, and as a result, the firing temperature is higher than in the past. It is said that it will be possible to obtain a high coercive force. The vaporizing agent described in the publication is camphor, phosphorus, sulfur, tin, etc., which vaporize during firing to leave open pores.
The open pores are continuous pores that have a pore inlet on the surface of the fired body and are large enough to allow resin to enter.

In the method of the same publication, a low-density sintered magnet having a density of 6.9 g / cm ³ or less is obtained. However, the purpose of the method of the publication is to form open pores, unlike the present invention. The publication describes that firing is stopped before closed pores are formed, and that the higher the ratio of the volume of open pores to the total pore volume (effective porosity), the better. The technical idea of the present invention of increasing the ratio is not found. Since the sintered magnet described in the publication is mainly composed of open pores, resin impregnation is indispensable for ensuring corrosion resistance, and since it is necessary to make the resin reach into the open pores that extend deep into the magnet, The sex becomes extremely low. For example, in the example of the publication, the resin impregnation is carried out for 2 hours after evacuation, and the resin is cured for 2 hours after further pressurizing and impregnating for 2 hours.

The publication describes that the preferable average particle size of the Nd-Fe-B alloy is 2 to 20 μm, and in the examples, fine powder of 3.5 μm is used. The publication does not describe the density of the green compact before firing, but the pressure applied during the green compact is as low as 0.2 to 5 t / cm ² , and a high-density molded body has not been obtained. Conceivable. Therefore, in the method described in the publication, unlike the present invention, the open pores are considered to be the main component.

Further, in a preferred embodiment of the present invention, since the R-rich powder having a predetermined composition is added to form the closed pores, the coercive force is also improved. Since the open pores are formed by using a vaporizing agent or a vaporizing agent, the dispersion of R in the magnet becomes poor and the coercive force becomes insufficient. On the other hand, if the R content of the magnet is increased to improve the coercive force, the residual magnetic flux density becomes insufficient. The publication does not describe the size of the sintering inhibitor. In addition,
The publication describes that a metal powder of Tb or Dy may be added in order to improve the coercive force within a range in which the shrinkage of the fired body does not significantly increase. However, the melting point of metal Tb is 13
Since the melting point of the metal Dy is 57 ° C. and the melting point of the metal Dy is 1407 ° C., the same effect as that of the grain boundary phase master alloy powder having a low melting point used in the present invention cannot be obtained. Moreover, the publication does not disclose the particle diameter ranges of the metal Tb and the metal Dy, and there is no example in which these are added.

In Japanese Patent Laid-Open No. 63-114939, low melting point elements (Al, Zn, Sn, Cu, Pb, S, In,
At least one of Ga, Ge, Te) or a matrix material powder containing a high melting point element and a R ₂ T ₁₄ B-based magnetic powder are mixed to form a mixed powder, and the mixed powder is molded. A method for producing a composite-type magnet material is disclosed which includes a magnetizing step of magnetizing. As the magnetizing step, there is a step of molding and sintering the mixed powder, or a hot pressing step of applying hot pressing to the mixed powder to generate a molded body. Prior to hot pressing, preforming is preferably performed. The sintering temperature is higher than the melting point of the matrix material and lower than 1150 ° C., the hot pressing temperature is 300 to 1100 ° C., and the hot pressing pressure is 5 to 5.
It is 5000 kgf / cm ² . In this publication, the problem is to improve the dimensional yield, and the publication describes that the dimensional yield of the product can be improved by the hot forming method. However, in the examples of the publication, the densities after sintering or after hot pressing are all 7.1 g / cm ³ or more, and the density of the compact before sintering or before hot pressing. Is not disclosed. The average particle diameter of the R ₂ T ₁₄ B-based magnetic powder in the example of the publication is as small as 3 to 4 μm, and the particle diameter of the matrix material powder containing the low melting point element is at most 20 to 30 μm.
It has a small diameter of m. In the publication, there is a comparative example in which hot pressing is performed using Al having an average particle size of 100 μm as a matrix material. In this case, a dense magnet having a density of 7.5 g / cm ³ is obtained. . The pressure at the time of molding and the pressure at the time of preforming in the examples of the publication are both 1.5 t / cm ^2.
Below is small.

Japanese Patent Laid-Open No. 3-80508 discloses RFe.
In a method for producing a B-based magnet by a powder metallurgy method, magnet powder is press-molded and then made into a porous sintered body in a temperature range of 400 to 900 ° C., which is a molten alloy Nd _x Fe.
A method of immersing in _1-x (x = 0.65 to 0.85) for a certain period of time is disclosed. This method is intended to suppress the deformation after sintering due to the anisotropy of thermal contraction due to the magnetic field orientation. However, in this method, no R oxide powder is added and no R rich powder is used. The Nd ₂ Fe ₁₄ B magnet powder used in the examples of the publication has a small diameter of about 10 μm.
The density of the compact and the density of the porous sintered body after low temperature sintering are not described.

Japanese Unexamined Patent Publication No. 55-15224 discloses Sm.
A method of impregnating a molded product with liquid plastic after pre-sintering the molded product at 400 to 900 ° C. when manufacturing a 2-17 series magnet such as ₂ Co ₁₇ or Pr ₂ Co ₁₇ is disclosed. This method aims to improve the strength of the magnet. In the examples of the publication, the shrinkage ratio when the particles of 5 to 30 μm were formed and sintered at 800 ° C. was 7%, and the shrinkage ratio when completely sintered at 1150 ° C. was about 12 to 30 μm. It is described that it was 15%. Then, it is described that the density after the temporary sintered body was immersed in an epoxy resin to be solidified was 6.80 g / cm ³ . However, this method differs from the present invention in the type of magnet. In this publication, small-diameter particles of 5 to 30 μm are used, and the publication does not disclose the density of the compact before pre-sintering.

Japanese Unexamined Patent Publication (Kokai) No. 4-314307 discloses a method of manufacturing a bulk body for a bonded magnet by crushing an alloy containing a rare earth element, iron and boron as basic components, molding in a magnetic field, and then sintering. It is disclosed. In this method, by sintering at a temperature of 700 to 1000 ° C. for 3 hours or less,
A semi-sintered alloy bulk body having a density of 60-95% of theoretical density is produced. The semi-sintered alloy has a structure containing a large number of pores. The pores serve as nuclei for crack development and further for fracture, so that they can be easily crushed with a small stress. Therefore, the influence of mechanical strain during crushing is reduced. In the example of the publication, a fine powder having an average particle size of 3 μm is molded and then semi-sintered to manufacture a bulk body. In this example, neither the density of the molded body nor the shrinkage rate during semi-sintering is described. The invention described in the publication is different from the present invention in that a two-alloy method is not used and a bulk body of a semi-sintered alloy is crushed to manufacture a bonded magnet. The density of the bulk body of the semi-sintered alloy in the example of the publication is 5.6 g / cm ³ or less, which is about the same as the density of the compact in the present invention. Therefore, the bulk body of the semi-sintered alloy described in the publication cannot be used as a bulk magnet because the porosity is too high and the magnetic properties and strength are insufficient.
That is, pulverization and bond magnetization are essential. Therefore, the coercive force is deteriorated and the manufacturing cost is increased.

Further, in Japanese Unexamined Patent Publication No. 4-314315, a semi-sintered alloy bulk body described in Japanese Unexamined Patent Publication No. 4-314307 is molded in a magnetic field, and then the molded body is impregnated with a resin to manufacture a bonded magnet. A method is disclosed. The magnetic field molding in this method serves both to crush and mold the bulk body of the semi-sintered alloy. In the publication, the bending strength of the conventional sintered body is 2.5 t / cm ² or more, whereas the bending strength of the bulk body of the semi-sintered alloy is very small, less than 1 t / cm ^2, and it is crushed. It is described that it is easy. In the example of the publication, fine powder having an average particle diameter of 3 μm is molded and semi-sintered in the same manner as in JP-A-4-314307 to obtain a density of 5.2 g /
A bulk magnet having a size of cm ³ or less is manufactured, further compression molded and impregnated with a resin to manufacture a bonded magnet having a density of 5.9 to 6.0 g / cm ³ . Since the bulk body of the semi-sintered alloy described in the publication is lower in density than the semi-sintered alloy disclosed in JP-A-4-314307, it cannot be used as a bulk magnet without compression molding and resin impregnation. Is. Therefore, the coercive force is deteriorated and the manufacturing cost is increased.

In the conventional semi-sintered alloy as described above, S
Although there is an example in which a powder composed of particles of 30 μm is used in a 2-17 series magnet such as m ₂ Co _17, a magnet powder composed of small particles having an average particle size of about 3 μm is used in an R ₂ T ₁₄ B series magnet. Molded at a pressure of about 5 t / cm ² or less. For this reason, the density of the molded body cannot be increased as in the present invention. In the case of semi-sintering, it is necessary to perform heat treatment at a temperature lower than that in complete sintering, but in the low temperature region, the sintered body density changes greatly in response to changes in the holding temperature. That is, in order to manufacture a semi-sintered body having a predetermined density, strict temperature control is required, which increases manufacturing cost.

On the other hand, the present invention differs from the conventional method for producing a semi-sintered magnet in that the R oxide powder is added and the compact density is increased. In a compact with high density, it is difficult to move particles through the rare earth element-rich liquid phase.
Even if the holding temperature in the sintering step is high (for example, the conventional complete sintering temperature range), the sintering reaction does not proceed before complete sintering. For this reason, a predetermined low-density sintered body can be stably obtained in a wide temperature range, and the management of the sintering process becomes extremely easy. When the main phase master alloy powder having a large diameter is used, the compact density can be easily increased at a low pressure, and the suppressing action of the sintering reaction is also improved. Further, since particles having a large diameter do not easily agglomerate, they are easy to handle and particularly easy to fill in a mold during molding.

[0035]

Specific Structure The specific structure of the present invention will be described in detail below.

<Sintered Magnet> The sintered magnet of the present invention is R (R
Is at least one rare earth element including Y), T
(T is Fe, or Fe and Co) and B
Contains.

The magnet composition is not particularly limited, but usually R
Of 30 to 45% by weight, B to 0.5 to 3.5% by weight, and the balance being substantially T.

R is Y, lanthanide or actinide, and R is preferably at least one of Nd, Pr and Tb, particularly Nd, and more preferably Dy. Also, La, Ce, Gd, Er, Ho, Eu,
One or more of Pm, Tm, Yb and Y may be included.
A mixture of misch metal or the like can be used as the raw material of the rare earth element. If the R content is too low, a phase rich in iron precipitates and high coercive force cannot be obtained, and if the R content is too high, high residual magnetic flux density cannot be obtained.

If the B content is too small, a high coercive force cannot be obtained, and if the B content is too large, a high residual magnetic flux density cannot be obtained.

The amount of Co in T is preferably 30% by weight or less.

In order to improve the coercive force, Al, Cr, M
n, Mg, Si, Cu, C, Nb, Sn, W, V, Z
Elements such as r, Ti, and Mo may be added, but if the addition amount exceeds 6% by weight, the reduction of the residual magnetic flux density becomes a problem.

The sintered magnet of the present invention contains an R oxide. The content of the R oxide is 0.5 to 10% by weight, preferably 1 to 7% by weight. If the amount of R oxide is too small, the action of R oxide in the sintering step becomes insufficient and the sintering proceeds too much. If the amount of R oxide is too large, the residual magnetic flux density will be significantly reduced. The content of R oxide in the magnet is a value converted into the content (weight percentage) of Nd ₂ O ₃ . As described later, in the present invention, various R oxide powders may be added to the main phase master alloy powder, but it is difficult to confirm the added R oxide after sintering. Therefore, measure the amount of oxygen in the magnet,
The amount of R oxide in the magnet is calculated assuming that it exists as d ₂ O ₃ . The amount of oxygen in the magnet can be measured by gas analysis. In gas analysis, He is used as a carrier gas, the sample is heated to a high temperature in a carbon crucible, and the amount of CO gas generated is measured to determine the amount of oxygen in the sample. In the magnet, the R oxide phase is present wrapped in the R rich phase or faces the holes.
This state can be confirmed by EPMA (electron probe X-ray microanalyzer).

In addition to these elements, the magnet may contain carbon as an unavoidable impurity or trace additive.

The sintered magnet of the present invention has a main phase having a substantially tetragonal crystal structure, and an R-rich phase having a higher R ratio than R ₂ T ₁₄ B is present in the crystal grain boundaries. . The average crystal grain size of the magnet depends on the crystal grain size of the master alloy for the main phase and the sintering conditions described later.

The sintered magnet of the present invention includes closed holes. The closed holes are holes that do not communicate with the magnet surface. The closed pores are 3 to 15% by volume of the magnet, preferably 3 to 12% by volume. A magnet with too few closed holes contracts greatly during sintering, and good dimensional accuracy of the molded body is not maintained. A magnet having too many closed holes has insufficient magnet characteristics and insufficient strength. The total volume ratio of the closed holes in the magnet and the total volume ratio of the open holes described later can be calculated as follows.

Open hole total volume ratio K Formula I K = (WW- _W ) / V Closed hole total volume ratio H Formula II H = 1-K-W / (V · ρ) V: volume calculated from the sample geometry, W: sample weight, W _W: sample was immersed in water, after holding for 30 seconds and evacuated to 100 Torr, taking out, the sample weight after wiping off water on the sample surface, ρ: theoretical density of the magnet.

The shape and size of the closed holes are not particularly limited, but the average projected cross-sectional area per closed hole is 1000 to 1000.
It is preferably 30,000 μm ² . Even if a small closed hole is formed in the early stage of sintering, it disappears by the end of sintering, so the average projected cross-sectional area of the closed hole is generally 10 or less.
It is less likely to be less than 00 μm ² . That is, if an attempt is made to form closed pores having an average projected cross-sectional area of less than 1000 μm ² , the closed pores will not be formed and sintering will proceed too much, and the total volume of the closed pores will be small and the shrinkage rate will be small. I won't. Also, the coercive force of the crystal grains adjacent to the closed pores is small, but when the density of the magnet is the same and the average volume per closed pore is small, the crystal grains adjacent to the closed pores are large, so that the high coercive force is high. Hard to get. On the other hand, if the average projected sectional area is too large, the strength of the magnet becomes insufficient. In order to form closed pores with an average projected cross-sectional area of more than 30,000 μm ² , it is necessary to use a huge grain boundary phase master alloy in the two-alloy method, which makes it difficult to form a thin-walled magnet. Magnetic flux tends to be non-uniform. The cross-sectional area of the closed holes can be measured using a scanning electron micrograph of the magnet cross section. In the measurement, after cutting the magnet, the cut surface is polished, a gold sputtered film is further formed on the cut surface, and then a photograph is taken. Then, the cross-sectional area of any 100 or more closed holes per magnet is measured to obtain an average value, which is taken as the average projected cross-sectional area per closed hole.

The density of the sintered magnet of the present invention is 7.15 g / cm.
It is preferably ³ or less. By molding with high pressure using large particles of about 200 μm, the density of the molded body is 6.4.
Although it can be increased to about g / cm ^3, it is difficult to move particles during firing in such a molded body, so even if it is fired at a high temperature, it is not possible to obtain a density exceeding 7.15 g / cm ^3. Have difficulty. On the other hand, when a compact having a low density is formed by using small-diameter particles, if firing is performed until the density exceeds 7.15 g / cm ³ , the sintering proceeds excessively and the shrinkage rate increases.
Even if the density of the sintered magnet is in this range, if there are many open holes communicating with the surface of the magnet, the corrosion resistance of the magnet is extremely reduced, which is not preferable. The ratio of open pores is preferably 2% by volume or less. The ratio of open holes can be determined by the method described above.

The sintered magnet of the present invention is preferably manufactured by the following method. In the first method, a molded body of a mixture of main phase master alloy powder (magnet powder) and R oxide powder is manufactured in the molding step, and in the second method, a main phase master alloy powder is molded in the molding step. And a mixture of the powder of the master alloy for the grain boundary phase and the powder of the R oxide are produced.

<Main Phase Master Alloy> The composition of the main phase master alloy is
In the first method, it is determined according to the target magnet composition, and in the second method, it may be appropriately determined in consideration of the composition of the grain boundary phase master alloy and its mixing ratio. In the first method, R is 27 to 40% by weight and B is 0.5 to 4.
5% by weight and the balance is substantially T. In the second method, 26 to 35% by weight of R and 0.
It is preferable that the content is 5 to 3.5% by weight, and the balance is substantially T.

In the R ₂ T ₁₄ B-based magnet, the R-rich phase becomes a liquid phase and flows so that the sintering reaction proceeds. In the second method, the R-rich master alloy powder for the grain boundary phase is used. Since it is necessary to add and suppress the progress of the sintering reaction in order to suppress the shrinkage, it is preferable to reduce the R content of the master alloy for the main phase.

The main phase master alloy has the above-mentioned main phase and the above-mentioned R-rich phase. The average crystal grain size of the main phase master alloy powder is not particularly limited. In the present invention, since it is anisotropy by magnetic field orientation, it is preferable that the crystal grain size is such that it becomes a single crystal grain when the grain size described later is used, but even if it is a polycrystalline grain, it is crystallized within the grain. As long as the grains are oriented, the average crystal grain size can be selected from a wide range of, for example, about 3 to 600 μm.

The average particle size of the main phase master alloy powder is preferably 30 μm or more, more preferably 50 to 350 μm.
And If the average particle size is too small, the above-described effect of increasing the particle size becomes insufficient. On the other hand, if the average particle size is too large, it becomes difficult to orient the magnetic field in a thin molded body.
The average particle diameter of the main phase master alloy powder is the diameter when an average projected area per particle is calculated and converted into a circle. The method for measuring the projected area of the particles is not particularly limited. For example, a powder dispersion can be applied onto a glass plate so that the particles do not overlap with each other, a photograph is taken, and the projected area of the particles can be determined from this photograph. In addition, the projected area of the particles can be obtained by scanning the coated object with a light beam and detecting the change in reflectance.

The method of producing the powder of the master alloy for the main phase is not particularly limited, and any method such as a method of pulverizing the cast alloy by hydrogen absorption pulverization or a reduction diffusion method may be used. You may make it into a powder. By crushing a sintered magnet anisotropy by magnetic field orientation, it is possible to obtain large-sized polycrystalline particles composed of oriented small-sized crystal grains,
A magnet having a high residual magnetic flux density and a high coercive force can be obtained.

<R Oxide> The R oxide powder is added to suppress the sintering reaction. The R oxide powder used in the present invention is not particularly limited, and for example, the rare earth oxide powder described in the description of the magnet composition can be used,
Two or more kinds of oxide powders may be used, but N is preferable.
d ₂ O ₃ , Dy ₂ O ₃ , Pr ₆ O ₁₁ , Tb ₄ O ₇ , Y ₂
At least one of O ₃ and CeO ₂ is used. Among these, Pr showing a high magnetic anisotropy constant as R ₂ T ₁₄ B,
When at least one of the oxides of Tb and Dy is used, the oxide is reduced by the excess R of the master alloy for the main phase and the R of the master alloy for the grain boundary phase, so that at least 1 of Pr, Tb, and Dy is used. R ₂ T, which has a large magnetic anisotropy constant due to seed diffusion into the main phase
₁₄ B is produced, which gives a high coercive force. Among the above oxides, Nd ₂ O ₃ and CeO ₂ are inexpensive.

The average particle diameter of the R oxide powder is not particularly limited, but is preferably 0.5 to 20 μm. If the average particle size is too small, it may be caught in the mold of the mold and the punch during molding, and the particle size becomes too small compared to the master alloy for the main phase, making uniform mixing difficult. On the other hand, if it is too large, the dispersion in the mixture becomes poor.

The R oxide may be produced by oxidizing metal R, or commercially available R oxide particles may be used.

<Master Alloy for Grain Boundary Phase> The master alloy for the grain boundary phase used in the second method has an R content of 70 to 97% by weight, preferably 7%.
5 to 92% by weight, with the balance being essentially Fe and / or Co. As R contained in the grain boundary phase master alloy, N
d is preferable, it is more preferable that Nd occupies 50% or more of R, and it is further preferable to use substantially only Nd as R. When the amount of Nd in R is small and the amount of R is small, the melting point of the grain boundary phase master alloy does not decrease, and closed voids are less likely to be formed. The melting point of Nd ₈₉ Fe ₁₁ (weight ratio) eutectic alloy is 640 ° C., and the melting point of Nd ₈₁ Co ₁₉ (weight ratio) eutectic alloy is 566 ° C., but Dy ₈₈ Fe ₁₂ (weight ratio).
The melting point of the eutectic alloy is 890 ° C. The grain boundary phase master alloy used in the present invention does not contain B. B in the grain boundary phase master alloy
Does not contribute to the improvement of the magnet characteristics, nor does it contribute to the lowering of the melting point of the grain boundary phase master alloy.

The powder of the grain boundary phase master alloy used in the present invention is
Preferably, the aperture remains 38 μm or more, more preferably 53 μm or more, and the aperture preferably remains 50 μm or more.
It passes through a sieve having an opening of 0 μm or less, more preferably 250 μm or less. If the particle size of the powder of the master alloy for the grain boundary phase is small, the average projected cross-sectional area of the closed holes becomes small and the total volume of the closed holes tends to be insufficient. In addition, the powder of the grain boundary phase master alloy is easily oxidized. If the particle size of the grain boundary phase master alloy is too large, the pores become too large, and the surface magnetic flux tends to be non-uniform. If the size of the holes remaining in the magnet is too large with respect to the size of the magnet, sufficient magnet strength cannot be obtained.

The method for producing the grain boundary phase master alloy is not particularly limited, but a liquid quenching method is preferably used. As the liquid quenching method, a method of bringing the molten alloy into contact with a cooling substrate to cool it, for example, a single roll method, a twin roll method, a rotating disk method, or the like is preferable, and a gas atomizing method may be used. The molten alloy is cooled in a non-oxidizing atmosphere such as nitrogen or Ar or in vacuum. When the cooling rate is slow, the master alloy for the grain boundary phase having the above-mentioned composition mainly undergoes phase separation into Nd and Fe ₂ Nd. The melting point of these is as high as 1000 ° C. or higher, and Nd is extremely easily oxidized, so that it is difficult to form closed pores. The grain boundary phase master alloy produced by the liquid quenching method has an amorphous phase or a microcrystalline phase.

<Crushing Step and Mixing Step> In the first method and the second method, the method for producing the mixture is not particularly limited. For example, in the second method, a mixture may be produced by mixing both mother alloys, pulverizing them at the same time, and further adding an R oxide powder. Further, after crushing each mother alloy, both mother alloy powders and R oxide powder may be mixed, or the mixture of both mother alloy powders may be further finely crushed and then the R oxide powder may be added.

The ratio of the R oxide powder in the mixture is
Preferably 0.5 to 10% by weight, more preferably 1 to 7
Weight% If this ratio is too low, the effect of suppressing sintering will be insufficient, and it will be difficult to form sufficient closed holes in the magnet. If this ratio is too high, the residual magnetic flux density of the magnet will be low.

The ratio of the grain boundary phase master alloy in the mixture is preferably 2 to 20% by weight, more preferably 3 to 1%.
2% by weight. If this ratio is too low, it will be difficult to form sufficient closed holes in the magnet, and if this ratio is too high, it will be difficult to obtain a magnet with high characteristics.

The method of crushing each mother alloy is not particularly limited, and a mechanical crushing method, a hydrogen absorbing crushing method or the like may be appropriately selected, and crushing may be performed by combining these methods. However, it is preferable to carry out hydrogen storage pulverization because a magnet powder having a sharp particle size distribution can be obtained. For mechanical pulverization, it is preferable to use an air flow type pulverizer such as a jet mill because a sharp particle size distribution can be obtained.

<Molding Step> In the molding step, the mixture is molded in a magnetic field. In the first method, molding is performed so that the density of the molded product is 5.5 g / cm ³ or more, preferably 6.0 g / cm ³ or more, and in the second method, such a high-density molded product is obtained. Molding as required. In the case of a compact having a low density, if sufficient magnet characteristics are to be obtained, the shrinkage rate at the time of sintering becomes large, and if the shrinkage rate at the time of sintering is made small, the magnet characteristics become insufficient. There is no particular upper limit to the density of the molded product, but it is difficult to achieve a density exceeding 6.4 g / cm ³ . For example, since an ultrahigh pressure of 20 t / cm ² or more is required at the time of molding, the molding apparatus and the mold are expensive, and the shape of the molded body is limited to a simple shape. The use of a large amount of organic lubricant is also effective for improving the compact density, but it is difficult to remove the organic lubricant before sintering, and residual carbon in the magnet deteriorates the magnet characteristics. I will end up. The density of the molded product can be calculated from the dimensions of the molded product measured with a micrometer or the like.

The molded article having such a high density has a bending strength of 0.3 kgf / mm ² or more, further 0.5 kgf / cm ² or more, so that it is easy to handle, and cracks and chips are less likely to occur. Become.

The molding pressure is not particularly limited and may be appropriately determined so as to obtain a molded product having a desired density, but it is preferably 8 t / cm ² or more, more preferably 12 t / cm ² or more. The magnetic field strength during molding is usually 10 kOe or more, preferably 15 kOe or more.

The magnetic field applied during molding may be a DC magnetic field or a pulsed magnetic field, or may be a combination of these. The present invention can be applied to a so-called transverse magnetic field forming method in which a pressure applying direction and a magnetic field applying direction are substantially orthogonal to each other, and a so-called longitudinal magnetic field forming method in which a pressure applying direction and a magnetic field applying direction are substantially coincident with each other.

<Sintering Step> The molded body obtained as described above is sintered and magnetized.

In the present invention, it is preferable that the value obtained by subtracting the density of the compact from the density of the sintered body (the amount of change in density during sintering) is 0.2 g / cm ³ or more. If the density change in the sintering step is too small, the sintering will be insufficient and the magnet characteristics and mechanical strength will be insufficient. In order to reduce the shrinkage rate, the density change amount is preferably 1.5 g / cm ³ or less, more preferably 1.2 g / cm ³ or less.

There are no particular restrictions on various conditions during sintering, and it may be appropriately selected so that the density change during sintering has a desired value. In the second method, the holding temperature during sintering may be higher than the melting temperature of the grain boundary phase master alloy. As mentioned above,
In the present invention, since the high-density compact containing the R oxide powder is sintered, the holding temperature can be made higher than in the case of conventional so-called semi-sintering. Specifically, 900 to 1100 ° C
It is preferable to heat-treat for 0.5 to 10 hours to sinter and then quench. The sintering atmosphere is preferably a vacuum or an inert gas atmosphere such as Ar gas, and as described above, it is possible to reduce the ratio of open pores, and thus the vacuum or reduced pressure inert gas atmosphere. Is more preferable. It should be noted that only part of the sintering process may be in a vacuum or reduced pressure atmosphere.

<Others> After sintering, if necessary, an aging treatment is performed to improve the coercive force.

In order to improve the corrosion resistance of the magnet, it is preferable to close the open holes. For this purpose, for example, the magnet may be dipped in a solution in which a resin is dissolved in an organic solvent and then dried. After such processing,
A usual anticorrosion coating may be provided by electrodeposition coating of resin, electroless plating, or the like.

The present invention is suitable for manufacturing a thin-walled ring-shaped or plate-shaped magnet as described later, and particularly for manufacturing a thin-walled magnet having a thickness of 3 mm or less. If the magnet thickness is less than 0.5 mm, molding tends to be difficult.

<Dimensional Deviation> In the present invention, since a sintered magnet having an extremely small dimensional deviation can be obtained, it can be manufactured as a product without performing shape processing such as grinding after sintering.

That is, according to the present invention, there is a parallel portion, and the value obtained by dividing the maximum length of the parallel portion by the average thickness is 10
In the thin-walled sintered magnet as described above, the thickness deviation of the parallel portion can be 1.5% or less, and can easily be 1% or less, and the maximum length / average thickness is 15 or more. The thickness deviation of a thin magnet can be kept within such a range. The parallel part is a block sandwiched by two parallel surfaces facing each other, and the magnet having the parallel part is, for example, a plate magnet, a disk magnet, or a ring magnet. The thickness deviation of the parallel part is a value obtained by dividing the difference between the maximum value and the minimum value of the thickness of the parallel part by the maximum length of the parallel part. The thickness deviation of the parallel part is a value that is an index of the warp of the parallel part and the nonuniformity of the thickness, and in the case of the thin-walled sintered magnet having the above dimensional ratio, the warpage and the nonuniformity of the thickness are Since it becomes large, the thickness deviation is generally 2.5% or more.

Further, according to the present invention, in a thin-walled magnet having a cylindrical portion and a value obtained by dividing the average outer diameter of the cylindrical portion by the average wall thickness is 10 or more, the outer diameter deviation of the cylindrical portion and / or The inner diameter deviation can be 1.5% or less, and it is easy to set it to 1% or less. Even for a thin magnet having an average outer diameter / average wall thickness of 15 or more, the outer diameter deviation and / or the inner diameter deviation can be reduced. It is possible to fit within such a range. The cylindrical portion is a cylindrical block having an outer peripheral surface or an outer peripheral surface and an inner peripheral surface, and the magnet having the cylindrical portion is
For example, a ring-shaped magnet or a disc-shaped magnet, the outer diameter deviation and the inner diameter deviation in this case target a cylindrical portion having an outer peripheral surface and an inner peripheral surface. The outer diameter deviation of the cylindrical portion is a value obtained by dividing the difference between the maximum value and the minimum value of the outer diameter of the cylindrical portion by the average outer diameter, and the inner diameter deviation is the maximum value and the minimum value of the inner diameter of the cylindrical portion. Is the value obtained by dividing the difference of by the average inner diameter. The outer diameter deviation and the inner diameter deviation of the cylindrical portion are values that are an index of the warp and strain of the cylindrical portion and the nonuniformity of the wall thickness, and in the case of the thin-walled sintered magnet having the above dimensional ratio, the warp and strain, Since the unevenness of the wall thickness becomes large, conventionally, the outer diameter deviation and the inner diameter deviation are generally 3% or more.

Even in a thin-walled sintered magnet having a cylindrical portion having only an outer peripheral surface such as a disc magnet and having an average outer diameter / average thickness of 10 or more, further 15 or more, the outer diameter deviation of the cylindrical portion is large. Can be 1.5% or less, and can easily be 1% or less.

In the present specification, the thickness deviation of the parallel portion is measured as follows. First, the object to be measured is placed on the surface plate such that one surface forming the parallel portion is in contact with the surface plate. Then, the height from the surface plate surface of the other surface forming the parallel portion is measured at 20 points. Next, the object to be measured is turned over and placed on the surface plate so that the other surface is in contact with the surface of the surface plate, and the height is measured at 20 points in the same manner.
The measurement position divides the surface to be measured into 20 evenly,
It is set at the center point in each area. The difference (Tmax-Tmin) between the maximum value (Tmax) and the minimum value (Tmin) is determined from all the obtained measured values. This difference is the maximum value L of the lengths (lengths in the longitudinal direction) of the surfaces forming the parallel portion.
The value obtained by dividing by {(Tmax-Tmin) / L} is taken as the thickness deviation. The thickness deviation of a thin-walled magnet having two or more pairs of mutually parallel surfaces has a large value when both main surfaces are the one surface and the other surface. The average thickness in the description of the thin magnet may be the average of all the measured values obtained as described above.

The outer diameter deviation and the inner diameter deviation of the cylindrical portion are obtained as follows. First, the outer diameter or inner diameter of the cylindrical part,
The maximum value and the minimum value are obtained by continuously measuring in the axial direction of the cylindrical portion. At this time, the measured values in the range of 0.1 mm at both axial ends of the cylindrical portion are excluded. Next, after rotating the cylindrical portion by 15 ° about its axis, the same measurement is performed.
In this way, the measurement is repeated 12 times in total in the circumferential direction of 180 ° at 15 ° intervals. The maximum of the 12 maximums is φmax, and the minimum of the 12 minimums is φmi.
Let n be the value of φmax-φmin. Next, the average value φ ₀ of the average of 12 maximum values and the average of 12 minimum values is calculated, and φ
₀ is the average outer diameter or the average inner diameter. And {(φma
x −φ min) / φ ₀ } is the outer diameter deviation or the inner diameter deviation. The average outer diameter in the explanation of the dimension ratio of the thin magnet,
The above-mentioned φ ₀ may be used for the average inner diameter, and (average outer diameter−average inner diameter) / 2 may be used for the average wall thickness.

For measuring the dimensional deviation, a non-contact type measuring instrument such as an optical type may be used, and a contact type three-dimensional measuring instrument or a contact type measuring instrument such as a micrometer or an inner circumference micrometer. May be used.

[0082]

EXAMPLES The present invention will be described in more detail below by showing specific examples of the present invention.

Example 1 Sintered magnet samples shown in Table 1 were prepared by the method described below.

First, an ingot of a master alloy for main phase was manufactured by casting. The composition of the ingot is shown in Table 1. The balance of the composition is Fe. The average crystal grain size of these alloy ingots was 300 μm. Each alloy ingot was roughly crushed by utilizing the expansion / contraction of the volume due to the hydrogen storage / degas reaction, and then crushed by the disc mill to obtain a powder having the average particle size shown in Table 1. The average particle size of the powder was determined by the method described above from the optical micrograph of the powder coating film.

Next, the molten alloy was cooled in an Ar atmosphere by a single roll method to produce a grain boundary phase master alloy having the composition shown in Table 1. The balance of the composition shown in Table 1 is Fe. A Cu roll was used as the cooling roll. The master alloy for the grain boundary phase was a thin strip having a thickness of 0.15 mm, and as a result of X-ray diffraction, it was confirmed to be in an amorphous state. The mother alloy for each grain boundary phase was crushed by a pin mill, and the obtained alloy powder was classified by a sieve. Table 1 shows the sieves used for classification of each powder. The residual sieve shown in Table 1 is a sieve having a smaller opening that regulates the lower limit of the particle diameter. The passage sieve, which has a larger opening and regulates the upper limit of the particle diameter, has a opening of 425 μm.

As the R oxide powder, those shown in Table 1 were prepared. The average particle size of each powder was 3 to 8 μm.

Each of these powders was mixed as shown in Table 1. In Table 1, the addition amount of the mother alloy powder for the grain boundary phase is the ratio of the mixture, the content of R oxide, after sintering were measured oxygen content by gas analysis, oxygen and all Nd ₂
O ₃ is a Nd ₂ O ₃ content, assuming that is included as.

Each mixture was molded in a magnetic field to obtain a disk-shaped molded product having a diameter of 20 mm and a thickness of 1.5 mm. Magnetic field strength is 12 kOe
The magnetic field was applied so that the axis of easy magnetization was in the thickness direction of the molded body. The molding pressure and the density of the molded body are shown in Table 1.

Then, after sintering each compact in a vacuum,
Quenched. Table 1 shows the heat treatment temperature at the time of sintering and the time of keeping the temperature. After sintering, aging treatment was performed at 650 ° C. for 1 hour in Ar atmosphere to obtain a disc-shaped sintered magnet sample. Density of each sintered magnet sample, density change amount during sintering, residual magnetic flux density (Br), coercive force (Hcj)
Is shown in Table 1. In addition, for the measurement of Br and Hcj,
A sample for measuring magnetic properties, which was produced by sintering a molded body having a diameter of 15 mm and a thickness of 10 mm, was used. The manufacturing conditions of the samples for measuring magnetic properties were the same as those of the samples shown in Table 1 except for the size of the molded body. Further, the total volume ratio of open pores and the total volume ratio of closed pores of each sample were obtained by the method described above. The theoretical density of the magnet is 7.55 g / cm ³
Was calculated as The results are shown in Table 1.

[0090]

[Table 1]

Next, using a JIS class 1 surface plate, the thickness deviation of each sample was determined by the method described above. As a result,
In the sample of the present invention, the thickness deviation was as small as 0.2 to 0.8%, and the warpage due to the non-uniform shrinkage during sintering was extremely small. If the thickness deviation of the thin magnet having a thickness of 1.5 mm is small as described above, it is possible to commercialize the thin magnet without modifying the dimensions by grinding. Moreover, as shown in Table 1, sufficient magnet characteristics were obtained in the sample of the present invention, and in particular, in Sample No. 5 using the two-alloy method,
In Nos. 6 and 8, high coercive force is obtained. When calculating the thickness deviation, the diameter of the magnet was used as the maximum length of the parallel portion.

On the other hand, in Comparative Sample No. 7, a low-density sintered body was obtained, and the thickness deviation was small as 0.9%, but since R oxide powder was not added, closed pores were formed. The number of open pores is remarkably increased. And the coercive force is extremely low. In sample No. 9, since the R oxide powder was not added, sintering proceeded too much and the number of closed pores was reduced. In Comparative Sample No. 10, since the low-density compact formed by using the powder of the main phase master alloy having a small particle size was sintered, the sintering proceeded too much and the closed pores were reduced. Comparative samples Nos. 9 and 10 have thickness deviations of 2.9 to
It was as large as 6.3%, and it was found that a large warp was generated due to non-uniform shrinkage during sintering. With such a large thickness deviation, commercialization is impossible.

Next, after cutting each sample and polishing the cross-section, a gold sputtered film was formed on the cross-section and a scanning electron micrograph was taken to determine the average projected cross-sectional area per closed hole. . The number of closed holes measured was 100 for each sample. As a result, while the average projected cross-sectional area of the closed pores in the present invention sample was 1500～25000Myuemu ^2, only comparative sample No. 7 in 300 [mu] m ^2, No. 9 in 80 [mu] m ^2, No. 10 in 5 [mu] m ² There wasn't. In the sample of the present invention using the two-alloy method, closed pores formed by melting and flowing of the flake-shaped grain boundary phase master alloy powder were observed.

The molded product having a density of 5.5 g / cm ³ or more exhibited a sufficiently high bending strength of 0.45 kgf / mm ² or more. On the other hand, in the case of the molded product for manufacturing sample No. 10 (density 4.28 g / cm ³ ), the bending strength is 0.15 kgf / mm ²
Was low.

Example 2 Sintered magnet sample Nos. 105 and 110 were prepared in the same manner as Sample Nos. 5 and 10 of Example 1 except that the shape was a ring. The compact density is 5.75 in sample No. 105.
g / cm ^3, sample No. 110 in 4.27 g / cm ^3, and the became slightly smaller than the respective samples No. 5 and 10, respectively, the density variation due to sintering sample N
o. Same as 5 and 10. The dimensions of the molded body are 30 mm in outer diameter, 27 mm in inner diameter, 1.5 mm in wall thickness, and 7 in height.
The magnetic field was applied so that the easy axis of magnetization was in the radial direction during molding.

With respect to these ring-shaped sintered magnet samples, the outer diameter deviation and the inner diameter deviation were measured by the method described above. At the time of measurement, each sample was placed on a JIS class 1 surface plate so that the outer peripheral surfaces were in contact with each other, and the outer diameter deviation was measured by a contact type three-dimensional measuring instrument, and the inner diameter deviation was measured by an inner circumference micrometer. As a result, sample No. 105 according to the present invention had an outer diameter deviation of 0.30% and an inner diameter deviation of 0.32%, which were extremely small values, but a sample obtained by sintering a compact having a low density. In No. 110, the outer diameter deviation reached 4.5% and the inner diameter deviation reached 5.5%, making it impossible to commercialize.

From the results of the above examples, the effect of the present invention is clear.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location H01F 41/02 G

Claims (16)

[Claims] 1. A sintered magnet containing R (R is at least one rare earth element including Y), T (T is Fe, or Fe and Co) and B, wherein Includes 3 to 15% by volume of pores and 0.5 to 10 R oxide.
A sintered magnet, characterized in that the content thereof is contained in a weight percentage. 2. The sintered magnet according to claim 1, which has a density of 7.15 g / cm ³ or less. 3. The average projected cross-sectional area per closed hole is 1
The sintered magnet according to claim 1 or 2, having a diameter of 000 to 30,000 µm ² . 4. The sintered magnet according to claim 1, wherein the ratio of open pores is 2% by volume or less. 5. R is 30 to 45% by weight and B is 0.5 to 45% by weight.
3. Containing 3.5% by weight, the balance being substantially T.
A sintered magnet according to any one of 4 to 4. 6. A method for producing a sintered magnet containing R (R is at least one of rare earth elements including Y), T (T is Fe, or Fe and Co) and B. Then, a mixture containing magnet powder having crystal grains substantially composed of R ₂ T ₁₄ B and R oxide powder is molded to obtain a molded body having a density of 5.5 g / cm ³ or more. A method for producing a sintered magnet, which comprises a step of sintering the molded body so that a density change is 0.2 g / cm ³ or more. 7. The average particle diameter of the magnet powder is 30 to 35.
The method for producing a sintered magnet according to claim 6, wherein the diameter is 0 μm. 8. A method for producing a sintered magnet containing R (R is at least one rare earth element including Y), T (T is Fe, or Fe and Co) and B. And a powder of the master alloy for the main phase having crystal grains substantially composed of R ₂ T ₁₄ B, and a grain boundary in which R is 70 to 97% by weight and the balance is substantially Fe and / or Co. A method for producing a sintered magnet, comprising a step of sintering a molded body obtained by molding a mixture containing a powder of a master alloy for phase and a powder of R oxide. 9. The sintered magnet according to claim 8, wherein the density of the green body is 5.5 g / cm ³ or more, and the green body is sintered so that the density change is 0.2 g / cm ³ or more. Production method. 10. The method for producing a sintered magnet according to claim 8, wherein the powder of the master alloy for main phase has an average particle diameter of 30 to 350 μm. 11. The grain boundary phase master alloy has an opening of 38 μm.
The method for producing a sintered magnet according to any one of claims 8 to 10, wherein the sintered magnet remains in a sieve of m or more and passes through a sieve of 500 µm or less. 12. The method for producing a sintered magnet according to claim 8, wherein the proportion of the grain boundary master alloy in the mixture is 2 to 20% by weight. 13. The method for producing a sintered magnet according to claim 6, wherein the ratio of the R oxide powder in the mixture is 0.5 to 10% by weight. 14. The method for producing a sintered magnet according to claim 6, wherein the R oxide powder has an average particle diameter of 0.5 to 20 μm. 15. The method for producing a sintered magnet according to claim 6, wherein the molding pressure is 8 t / cm ² or more. 16. The method for producing a sintered magnet according to claim 6, which produces the sintered magnet according to any one of claims 1 to 5.