TWI676998B - Sintered body for forming rare earth magnets and rare earth sintered magnet - Google Patents
Sintered body for forming rare earth magnets and rare earth sintered magnet Download PDFInfo
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- TWI676998B TWI676998B TW105124165A TW105124165A TWI676998B TW I676998 B TWI676998 B TW I676998B TW 105124165 A TW105124165 A TW 105124165A TW 105124165 A TW105124165 A TW 105124165A TW I676998 B TWI676998 B TW I676998B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/08—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F7/00—Magnets
- H01F7/02—Permanent magnets [PM]
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Abstract
本發明係一種稀土類磁鐵形成用燒結體及稀土類燒結磁鐵,提供:在磁鐵剖面內之任意之微小區隔內,對於磁鐵材料粒子配向軸角度而言之各磁鐵材料粒子之磁化容易軸的配向角偏移,則呈加以維持為特定範圍內地加以構成之稀土類磁鐵形成用燒結體及稀土類燒結磁鐵者。稀土類磁鐵形成用燒結體係具有擁有長度方向之長度尺寸,和在直角於該長度方向之橫方向的剖面中,第1表面與第2表面之間的厚度方向之厚度尺寸,和對於該厚度方向而言正交之寬度方向的寬度尺寸之立體形狀。在位於包含厚度方向與寬度方向之面內的任意位置之4角形區隔內的各複數之磁鐵材料粒子之對於所預先設定之基準線的磁化容易軸之配向角之中,對於作為頻度最高之配向角所定義之配向軸角度而言,依據前述磁鐵材料粒子之各個磁化容易軸之配向角的差所訂定之配向角不均角度為9.0°以下。在一形態中,該區隔係將磁鐵材料粒子作為30個以上,例如包含200個或者300個之4角形區隔而加以訂定。4角形區隔係為正方形者為佳。在其他的形態中,該區隔係作為一邊為35μm之正方形區隔所訂定。 The present invention relates to a sintered body for forming a rare earth magnet and a rare earth sintered magnet, and provides: in an arbitrary minute segment in the cross section of the magnet, the magnetization of each magnetic material particle is easy to axis for the angle of the alignment axis of the magnetic material particle. The misalignment of the alignment angle is a sintered body for forming a rare-earth magnet and a sintered rare-earth magnet that are configured to be maintained within a specific range. The sintering system for forming a rare-earth magnet has a length dimension having a length direction, a thickness dimension in a thickness direction between a first surface and a second surface in a cross section perpendicular to the length direction of the transverse direction, and a thickness direction for the thickness direction. A three-dimensional shape with a width dimension orthogonal to the width direction. Among the alignment angles of the plurality of magnet material particles in a quadrangular segment located at arbitrary positions in the plane including the thickness direction and the width direction with respect to the easy-to-magnetize axis of the preset reference line, the most frequent Regarding the angle of the alignment axis defined by the alignment angle, the unevenness angle of the alignment angle determined based on the difference in the alignment angle of each of the easy-to-magnetize axes of the magnet material particles is 9.0 ° or less. In one aspect, the segmentation is determined by setting the magnet material particles as 30 or more, for example, quadrangular segments including 200 or 300. A quadrangular segment is preferably a square. In other forms, the segment is defined as a square segment with a side of 35 μm.
Description
本發明係有關為了形成稀土類燒結磁鐵的稀土類磁鐵形成用燒結體及經由磁化於該燒結體而得到之稀土類燒結磁鐵。特別是本發明係有關具有含有稀土類物質而各自具有磁化容易軸之多數的磁鐵材料粒子則一體地加以燒結之構成的稀土類磁鐵形成用燒結體及經由磁化於該燒結體而得到之稀土類燒結磁鐵。 The present invention relates to a sintered body for forming a rare earth magnet for forming a rare earth sintered magnet and a rare earth sintered magnet obtained by magnetizing the sintered body. In particular, the present invention relates to a sintered body for forming a rare-earth magnet having a structure in which a plurality of magnet material particles each containing a rare-earth substance and each having an easily magnetizable axis are integrally sintered, and a rare-earth material obtained by magnetizing the sintered body Sintered magnet.
稀土類燒結磁鐵係作為可期待高矯頑磁力及殘留磁通密度之高性能永久磁鐵而被注目,而加以實用化,為了更一層之高性能化而開發則進展。例如,記載於日本金屬學會誌第76輯第1號(2012)12頁至16頁之宇根康裕其他之「經由結晶微粒化之Nd-Fe-B焼結磁鐵的高矯頑磁力化」為題之論文(非專利文獻1)係依據了解到當細化磁鐵材料之粒徑時,矯頑磁力則增大情況,而為了Nd-Fe-B系焼結磁鐵的高矯頑磁力化,使用平均粉末粒徑為1μm之磁鐵形成用材料粒子而進行稀土類燒結磁鐵之製造的例則被加以記載。在此非專利文獻1所記載之稀土類燒 結磁鐵之製造方法中,加以記載有將混合磁鐵材料粒子與界面活性劑所成之潤滑劑的混合物,充填於碳製模型,再經由將該模型固定於空芯線圈內而施加脈衝磁場之時,使磁鐵材料粒子配向者。但在此方法中,磁鐵材料粒子之配向係因經由空芯線圈而加以施加之脈衝磁場而唯一確定之故,在磁鐵內之不同的位置,無法得到使磁鐵材料粒子配向於各不同所期望之方向的永久磁鐵者。另外,在此非專利文獻1中,對於經由脈衝磁場的施加而加以配向之磁鐵材料粒子的磁化容易軸,則對於所企圖之配向方向而言呈多少程度偏移的點,及其配向角度偏移則對於磁鐵的性能造成多少影響的點,係並未做任何研究。 Rare-earth sintered magnets have attracted attention as high-performance permanent magnets that can expect high coercive force and residual magnetic flux density, have been put into practical use, and development has been progressed for further high-performance. For example, the title "High Coercivity of Nd-Fe-B Junction Magnets Formed by Crystals and Micronization" described by Ugen Kangyu and others in Japanese Society of Metals, Vol. 76, No. 1 (2012), pages 12-16. The paper (Non-Patent Document 1) is based on the understanding that the coercive force increases when the particle size of the magnet material is refined. For the high coercive force of the Nd-Fe-B system sintered magnet, the average value is used. An example of manufacturing a rare earth sintered magnet with particles of a material for forming a magnet having a powder particle diameter of 1 μm is described. Rare earth burning described in Non-Patent Document 1 In the method for manufacturing a knotted magnet, a mixture of a lubricant made of mixed magnet material particles and a surfactant is filled in a carbon model, and a pulse magnetic field is applied by fixing the model in an air-core coil. To align the magnet material particles. However, in this method, the orientation of the magnetic material particles is uniquely determined by the pulsed magnetic field applied through the air-core coil. It is not possible to obtain the orientation of the magnetic material particles at different positions in the magnet. Permanent magnet for direction. In addition, in this Non-Patent Document 1, as for the axis of easy magnetization of the magnetic material particles aligned by the application of a pulsed magnetic field, the point of how much the direction of the intended alignment is deviated, and the alignment angle is deviated. The point that how much influence the performance of the magnet has on the system has not been studied.
日本特開平6-302417號公報(專利文獻1)係加以揭示也在將稀土類元素R與Fe及B作為基本構成元素之稀土類永久磁鐵的製造時,在接合磁鐵材料粒子之磁化容易軸則配向於各不同方向之複數之磁鐵體的狀態,保持為高溫加熱狀態,再經由接著磁鐵間之時,形成具有磁鐵材料粒子之磁化容易軸則配向於不同方向之複數的範圍之永久磁鐵的方法。如根據此專利文獻1所記載之永久磁鐵形成方法,可製造在各複數之範圍中,包含磁化容易軸則以任意且配向於不同方向之磁鐵材料粒子,複數之範圍所成之稀土類永久磁鐵者。但此專利文獻1係對於加以賦予於各個磁鐵體之磁鐵材料粒子的配向,則對於所企圖之配向方向而言呈多少程度偏移的點,未做任何敘述。 Japanese Unexamined Patent Publication No. 6-302417 (Patent Document 1) discloses that during the manufacture of a rare earth permanent magnet using the rare earth elements R, Fe, and B as basic constituent elements, the magnetization of the particles of the bonded magnetic material is easy to be performed. A method of maintaining a state of a plurality of magnet bodies aligned in different directions and maintaining a high-temperature heating state, and then passing between the magnets to form a permanent magnet having an easy-to-magnetize axis of the particles of the magnet material and then orienting a plurality of permanent magnets in different directions . According to the method for forming a permanent magnet described in this patent document 1, it is possible to produce rare-earth permanent magnets formed of a plurality of ranges, including magnetizable material particles that are arbitrarily and oriented in different directions, including the axis of easy magnetization. By. However, this patent document 1 does not describe the point to which the alignment of the magnet material particles given to the respective magnet bodies deviates to some extent from the intended alignment direction.
日本特開2006-222131號公報(專利文獻2)係 揭示將偶數個之永久磁鐵片配置於周方向,而連結之圓環狀的稀土類永久磁鐵的製造方法。在此專利文獻2中所揭示之稀土類永久磁鐵的製造方法係為了形成具有上下的扇形主面與一對的側面之扇形的永久磁鐵片,使用具有扇形之模孔之粉末衝壓裝置,於該扇形模孔內,充填稀土類合金粉末,經由具有配向線圈之上下的衝頭,施加配向磁場於該模孔內之稀土類合金粉末同時,衝壓成型該稀土類合金粉末。經由此工程,在各個主面之N極與S極之間,加以形成具有極異方性之永久磁鐵片。當詳細敘述時,加以形成具有自一方的主面與一方的側面所交差之角部,彎曲成弧狀於另一方的主面之方向,而於延伸於該一方的主面與另一方的側面所交差之角部之方向進行配向之磁化配向的永久磁鐵片。將如此作為所形成之極異方性永久磁鐵片的偶數個,呈成為鄰接之永久磁鐵片之對向的極性地連結成圓環狀,得到圓環狀永久磁鐵。 Japanese Patent Application Publication No. 2006-222131 (Patent Document 2) A method for manufacturing a ring-shaped rare earth permanent magnet in which an even number of permanent magnet pieces are arranged in the circumferential direction and connected to each other is disclosed. The manufacturing method of a rare earth permanent magnet disclosed in this patent document 2 is to form a fan-shaped permanent magnet piece having a fan-shaped main surface and a pair of side surfaces using a powder punching device having fan-shaped die holes. The fan-shaped die hole is filled with the rare-earth alloy powder, and the rare-earth alloy powder in the die-hole is applied with an alignment magnetic field through a punch having an alignment coil above and below, and the rare-earth alloy powder is punched and formed. After this process, a permanent magnet piece with extremely anisotropy is formed between the N pole and the S pole of each main surface. When described in detail, it is formed to have a corner portion that intersects from one principal surface and one lateral surface, is curved in an arc shape in the direction of the other principal surface, and extends to the principal surface of the other and the other side. Permanent magnet pieces with magnetized alignment aligned in the direction of the intersecting corners. An even number of the extremely anisotropic permanent magnet pieces thus formed are connected in a ring shape with the opposite polarities of the adjacent permanent magnet pieces to obtain a ring-shaped permanent magnet.
專利文獻2係另外,亦記載有加以連結成圓環狀之偶數個之扇狀永久磁鐵片之中,將隔一個加以配置之磁鐵片的磁化方向作為軸方向,而將呈成為此等軸方向配向地加以配置於所磁化之磁鐵片之間的磁鐵片之磁化方向作為徑方向之磁鐵片的配列。在此配置中,加以說明:加以磁化於隔一個加以配置之軸方向的磁鐵片的主面極性則成為相互異極,而加以配置於磁化於軸方向之磁鐵片之間的磁化於隔一個之徑方向的磁鐵片係經由作為呈同極則相互對向者之時,可使磁通集中於磁化於軸方向之一方的 磁鐵片之一方的主面之磁極,而使自該磁極之磁通,效率佳地聚集於磁化於軸方向之另一方的磁鐵片之一方的主面之磁極者。但此專利文獻2亦對於加以賦予於各個磁鐵材料粒子的配向,則對於所企圖之配向方向而言呈多少程度偏移的點,未做任何敘述。 Patent Document 2 also describes that among the even number of fan-shaped permanent magnet pieces connected in a ring shape, the magnetization direction of the magnet pieces arranged one by one is taken as the axial direction, and these axial directions are shown. The magnetization direction of the magnet pieces arranged between the magnetized magnet pieces is aligned as the arrangement of the magnet pieces in the radial direction. In this configuration, it is explained that the polarities of the major surfaces of the magnet pieces that are magnetized in the direction of the axis arranged one after the other become mutually different polarities, and the magnetization that is arranged between the magnet pieces that are magnetized in the axis direction is placed in the other one. When the magnet pieces in the radial direction are opposed to each other with the same poles, the magnetic flux can be concentrated in one of the axial directions. One of the main faces of the magnet pieces has a magnetic pole on the main surface, and the magnetic flux from the magnetic pole is efficiently collected on one of the main faces of the other magnet piece magnetized in the axial direction. However, this patent document 2 also does not describe the point to which the alignment given to each magnet material particle is shifted to some extent in the intended alignment direction.
日本特開2015-32669號公報(專利文獻3)及日本特開平6-244046號公報(專利文獻4)係揭示有:衝壓成形含有稀土類元素R與Fe及B之磁鐵材料粉末而形成平板狀的壓粉體,於此壓粉體施加平行磁場而進行磁場配向,再以燒結溫度進行燒結,形成燒結磁鐵,接著以不超過燒結溫度之溫度條件的基礎,經由使用按壓部為圓弧狀的鑄模而將該燒結磁鐵加壓成形為圓弧狀之時,形成放射狀配向之稀土類永久磁鐵的方向。此專利文獻3係為揭示可使用平行磁場而形成放射狀配向之磁鐵之方法者,但從平板形狀對於圓弧狀之彎曲成形則在磁鐵材料之燒結後加以進行之故,成形則為困難,進行大的變形或對於複雜的形狀之變形係為不可能。隨之,可經由此方法而製造之磁鐵係成為限定於該專利文獻4所記載之放射狀配向磁鐵者。更且,此專利文獻4亦對於加以賦予於各個磁鐵材料粒子的配向,則對於所企圖之配向方向而言呈多少程度偏移的點,未做任何敘述。 Japanese Unexamined Patent Publication No. 2015-32669 (Patent Document 3) and Japanese Unexamined Patent Publication No. 6-244046 (Patent Document 4) disclose that a magnetic material powder containing the rare earth elements R, Fe, and B is formed into a flat plate by press molding. The pressed powder body is applied with a parallel magnetic field to perform magnetic field alignment, and then sintered at a sintering temperature to form a sintered magnet. Then, based on a temperature condition that does not exceed the sintering temperature, the pressing portion is arc-shaped. When the sintered magnet is pressure-molded into a circular arc shape by a mold, the direction of the rare earth permanent magnet with radial alignment is formed. This Patent Document 3 discloses a method capable of forming a radially aligned magnet using a parallel magnetic field. However, the curved shape from a flat plate shape to a circular arc shape is performed after the magnet material is sintered, and the forming is difficult. It is impossible to perform large deformation or deformation of complicated shapes. Accordingly, the magnet system that can be manufactured by this method is limited to the radial alignment magnet described in Patent Document 4. Furthermore, this patent document 4 does not describe the point to which the alignment given to each magnet material particle is shifted to some extent in the intended alignment direction.
日本專利第5444630號公報(專利文獻5)係揭示有:使用於埋入磁鐵型馬達之平板形狀的永久磁鐵。此專利文獻5所揭示之永久磁鐵係在橫剖面內中,對於厚度 方向而言之磁化容易軸之傾斜角度,則作為自寬度方向兩端部朝向於寬度方向中央部而連續性地變化之放射狀配向。當具體地敘述時,磁鐵的磁化容易軸係呈聚集於自磁鐵的橫剖面內之寬度方向中央部延伸於厚度方向之假想線上之一點地,加以配向。作為具有如此磁化容易軸之放射狀配向的永久磁鐵之製造方法,在專利文獻5中,加以敘述有可以在成形時實現容易之磁場配向而形成,容易地製造者。在此專利文獻5中所揭示之方法係在磁鐵成形時,施加聚集於磁鐵外的一點之磁場者,在所形成之磁鐵的磁化容易軸之配向係限定為放射狀配向。隨之,例如,無法形成在橫剖面內之寬度方向中央範圍中係呈成為平行於厚度方向之配向,而在寬度方向兩端部之範圍中係呈成為斜配向地,加以配向磁化容易軸之永久磁鐵者。此專利文獻5亦對於加以賦予於各個磁鐵材料粒子的配向,則對於所企圖之配向方向而言呈多少程度偏移的點,未做任何敘述。 Japanese Patent No. 5444630 (Patent Document 5) discloses a flat-plate-shaped permanent magnet used in a buried-magnet-type motor. The permanent magnet disclosed in this patent document 5 In terms of direction, the inclination angle of the easy axis of magnetization is a radial alignment that continuously changes from both ends in the width direction toward the center in the width direction. When specifically described, the magnetization-easy shafting of the magnet is aligned at one point on an imaginary line extending from the central portion in the width direction in the cross section of the magnet to the thickness direction. As a method of manufacturing a permanent magnet having such a radial orientation of an easy-to-magnet shaft, Patent Document 5 describes that it can be formed by realizing easy magnetic field alignment during molding, and it is easy to manufacture. The method disclosed in this Patent Document 5 is a method in which a magnetic field concentrated on a point outside the magnet is applied during the formation of the magnet, and the orientation of the easily magnetized axis of the formed magnet is limited to a radial orientation. Accordingly, for example, in the widthwise central range that cannot be formed in the cross section, it is oriented parallel to the thickness direction, and in the range of both ends in the width direction, it is oriented obliquely. Permanent magnet. This patent document 5 also does not describe the point to which the alignment given to each magnet material particle is shifted to some extent in the intended alignment direction.
日本特開2005-44820號公報(專利文獻6)係揭示有:在組裝於馬達時,實質上未使頓轉扭矩產生之極異方性稀土類燒結環形磁鐵的製造方法。在此所揭示之稀土類燒結環形磁鐵係於具有間隔於周方向之複數的位置具有磁極,而磁化方向則在該磁極位置中呈成為法線方向,而在鄰接之磁極的中間位置中呈成為接線方向地加以磁化。此專利文獻6所記載之稀土類燒結環形磁鐵之製造方法係加以限定為極異方性之磁鐵製造,而在此製造方法 中,無法製造在單一的燒結磁鐵內,任意之複數的範圍內中,對於磁鐵材料粒子而言,賦予各不同方向之配向的磁鐵者。另外,此專利文獻6亦對於加以賦予於各個磁鐵材料粒子的配向,則對於所企圖之配向方向而言呈多少程度偏移的點,未做任何敘述。 Japanese Patent Application Laid-Open No. 2005-44820 (Patent Document 6) discloses a method for manufacturing an extremely anisotropic rare-earth sintered ring magnet that does not substantially generate cogging torque when assembled in a motor. The rare earth sintered ring magnet disclosed here has a magnetic pole at a plurality of positions spaced from the circumferential direction, and the magnetization direction becomes a normal direction at the magnetic pole position and becomes an intermediate position of the adjacent magnetic poles. Magnetize the wiring direction. The manufacturing method of the rare earth sintered ring magnet described in this patent document 6 is limited to the manufacturing of extremely anisotropic magnets, and the manufacturing method is here However, in a single sintered magnet, it is impossible to produce magnets in which the magnet material particles are provided with orientations in different directions within an arbitrary plural range. In addition, this patent document 6 does not describe the point to which the alignment given to each magnet material particle is shifted to some extent in the intended alignment direction.
日本特開2000-208322號公報(專利文獻7)係揭示有:具有在複數之範圍中,磁鐵材料粒子則加以配向於不同方向之構成,單一之板狀,扇形之永久磁鐵。在該專利文獻7中,加以形成複數的範圍於該永久磁鐵,在一方的範圍中,磁鐵材料粒子則加以配向為平行於厚度方向之圖案,而在鄰接於此之其他的範圍中,對於磁鐵材料粒子而言,加以賦予對於在該一方範圍之磁鐵材料粒子的配向方向而具有角度之配向。對於專利文獻7而言,係加以記載有:具有如此之磁鐵材料粒子的配向之永久磁鐵,則採用粉末冶金法,而在金屬模具內進行加壓成形時,可經由自配向構件施加適當方向之磁場之時而加以製造。但記載於此專利文獻7之永久磁鐵製造方法,亦僅可適用於具有特定配向之磁鐵的製造,而成為亦加以限定所製造之磁鐵的形狀者。另外,此專利文獻7亦對於加以賦予於各個磁鐵材料粒子的配向,則對於所企圖之配向方向而言呈多少程度偏移的點,未做任何敘述。 Japanese Patent Application Laid-Open No. 2000-208322 (Patent Document 7) discloses a structure in which a plurality of magnetic material particles are aligned in different directions, a single plate-shaped, sector-shaped permanent magnet. In Patent Document 7, a plurality of ranges are formed in the permanent magnet. In one range, the particles of the magnet material are aligned in a pattern parallel to the thickness direction, and in the other ranges adjacent to this, the magnet is formed. For the material particles, an orientation having an angle with respect to the alignment direction of the magnetic material particles in the one range is added. Patent Document 7 describes that a permanent magnet having such an orientation of magnetic material particles is powder metallurgy, and when pressure forming is performed in a metal mold, an appropriate orientation can be applied via a self-aligning member. Magnetic fields are created from time to time. However, the method for manufacturing a permanent magnet described in Patent Document 7 is also applicable only to the manufacture of a magnet having a specific orientation, and it is also limited to the shape of the manufactured magnet. In addition, this patent document 7 does not describe the point to which the alignment given to each magnet material particle is shifted to some extent in the intended alignment direction.
國際申請公開再公表公報WO2007/119393號(專利文獻8)係加以記載有:將含有稀土類元素的磁鐵材料粒子與結合劑之混合物形成為特定形狀,施加平行磁場 於此成形體而使平行於磁鐵材料粒子之配向產生,再經由使此成形體變形成另外的形狀之時,將磁鐵材料粒子的配向作為非平行之永久磁鐵的製造方法。此專利文獻8所揭示之磁鐵係具有經由樹脂組成物而加以接合磁鐵材料粒子的構成,所謂為黏合磁鐵,而非燒結磁鐵。黏合磁鐵係具有介入存在有樹脂組成物於磁鐵材料粒子之間的構造之故,與燒結磁鐵做比較,成為磁性特性則為劣化之構成,無法形成高性能之磁鐵者。 International Patent Application Publication No. WO2007 / 119393 (Patent Document 8) describes that a mixture of magnetic material particles containing rare earth elements and a binder is formed into a specific shape, and a parallel magnetic field is applied thereto. When the formed body has an orientation parallel to the magnet material particles, and when the formed body is deformed into another shape, the orientation of the magnet material particles is used as a method for manufacturing a non-parallel permanent magnet. The magnet system disclosed in this patent document 8 has a structure in which particles of a magnetic material are bonded via a resin composition, and is a so-called bonded magnet rather than a sintered magnet. The bonded magnet has a structure in which a resin composition is interposed between particles of the magnet material. Compared with a sintered magnet, the bonded magnet has a structure in which the magnetic characteristics are deteriorated, and a high-performance magnet cannot be formed.
日本特開2013-191612號公報(專利文獻9)係揭示有:形成將含有稀土類元素之磁鐵材料粒子,與樹脂結合劑混合之混合物,將此混合物成形為薄片狀而做成生坯薄片,經由施加磁場於此生坯薄片而進行磁場配向,對於所磁場配向之生坯薄片進行鍛燒處理而分解樹脂結合劑,使其噴散,接著以燒成溫度進行燒結,形成稀土類燒結磁鐵的方法。經由此專利文獻9所記載之方法而加以製造之磁鐵係磁化容易軸則加以配向於一方向之構成,而在此方法係無法製造在單一的燒結磁鐵內,任意之複數的範圍內中,對於磁鐵材料粒子而言,賦予各不同方向之配向的磁鐵者。另外,此專利文獻9亦對於加以賦予於各個磁鐵材料粒子的配向,則對於所企圖之配向方向而言呈多少程度偏移的點,未做任何敘述。 Japanese Unexamined Patent Publication No. 2013-191612 (Patent Document 9) discloses that a mixture of rare earth element-containing magnetic material particles and a resin binder is formed, and the mixture is formed into a sheet shape to form a green sheet. A method for magnetic field alignment by applying a magnetic field to the green sheet, and calcining the green sheet aligned with the magnetic field to decompose the resin binder, spray it, and then sinter it at the firing temperature to form a rare earth sintered magnet. . The magnetized easy-to-magnet shaft manufactured by the method described in Patent Document 9 is configured to be oriented in one direction. However, in this method, it cannot be manufactured in a single sintered magnet, and within an arbitrary plural range, As for the particles of the magnetic material, those having orientations in different directions are provided. In addition, this Patent Document 9 does not describe the point to which the alignment given to each magnet material particle is shifted to some extent in the intended alignment direction.
[專利文獻1]日本特開平6-302417號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 6-302417
[專利文獻2]日本特開2006-222131號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2006-222131
[專利文獻3]日本特開2015-32669號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2015-32669
[專利文獻4]日本特開平6-244046號公報 [Patent Document 4] Japanese Patent Laid-Open No. 6-244046
[專利文獻5]日本專利第5444630號公報 [Patent Document 5] Japanese Patent No. 5444630
[專利文獻6]日本特開2005-44820號公報 [Patent Document 6] Japanese Patent Laid-Open No. 2005-44820
[專利文獻7]日本特開2000-208322號公報 [Patent Document 7] Japanese Patent Laid-Open No. 2000-208322
[專利文獻8]國際申請公開再公表公報WO2007/119393號 [Patent Document 8] International Application Publication Re-publication Publication No. WO2007 / 119393
[專利文獻9]日本特開2013-191612號公報 [Patent Document 9] Japanese Patent Laid-Open No. 2013-191612
[專利文獻10]日本特開2001-210508號公報 [Patent Document 10] Japanese Patent Laid-Open No. 2001-210508
[非專利文獻1]日本金屬學會誌第76輯第1號(2012)12頁至16頁。 [Non-Patent Document 1] Journal of the Japanese Metal Society, Vol. 76, No. 1 (2012), pages 12 to 16.
如上述,關連於稀土類永久磁鐵的製造之專利文獻及非專利文獻之任一,均對於在磁鐵剖面內中,磁鐵材料粒子之磁化容易軸之配向不均係未做任何敘述。本發明者係在磁鐵內之不同位置,使磁鐵材料粒子配向於各不同之所期望的方向,在上述文獻記載之稀土類燒結磁鐵及現在實用化之稀土類燒結磁鐵中,驗證過依據後述定義 之配向角的不均,但均確認到配向角之不均角度係較9°為大者。但對於在磁鐵剖面內,含於微小區隔內之複數的磁鐵材料粒子之磁化容易軸的配向則自所企圖之配向方向偏移之情況,其偏移變越大,磁鐵的性能則降低。 As described above, any of the patent documents and non-patent documents related to the production of rare earth permanent magnets does not make any description about the uneven orientation of the axis of the magnetization particles of the magnet material in the cross section of the magnet. The inventors have aligned the magnet material particles in different desired directions at different positions in the magnet. The rare earth sintered magnets described in the above documents and the practically used rare earth sintered magnets have been verified based on the definitions described below. The unevenness of the alignment angle was confirmed, but it was confirmed that the unevenness of the alignment angle was larger than 9 °. However, in the cross section of the magnet, the orientation of the easy magnetization axis of the plurality of magnet material particles contained in the micro-segment is shifted from the intended alignment direction. The larger the shift, the lower the performance of the magnet.
隨之,本發明之主要目的係提供:在磁鐵剖面內之任意之微小區隔內,對於磁鐵材料粒子配向軸角度而言之各磁鐵材料粒子之磁化容易軸的配向角偏移,則呈加以維持為特定範圍內地加以構成之稀土類磁鐵形成用燒結體及稀土類燒結磁鐵者。換言之,本發明係提供:具有以往未存在之新穎的高精確度配向之稀土類燒結磁鐵,及為了形成如此之磁鐵的燒結體者。 Accordingly, the main object of the present invention is to provide: in an arbitrary minute segment in the cross section of the magnet, the orientation angle of the axis of each magnet material particle is easy to be shifted with respect to the angle of the orientation axis of the magnet material particle, and then the Those who maintain the sintered body for forming rare earth magnets and the rare earth based sintered magnets configured in a specific range. In other words, the present invention provides a rare-earth sintered magnet having a novel high-precision alignment that has not existed before, and a sintered body for forming such a magnet.
本發明係為了達成上述目的,而在一形態中,提供:具有含有稀土類物質而一體地加以燒結各自具有磁化容易軸之多數之磁鐵材料粒子的構成之稀土類磁鐵形成用燒結體。此稀土類磁鐵形成用燒結體係具有擁有長度方向之長度尺寸,和在直角於該長度方向之橫方向的剖面中,第1表面與第2表面之間的厚度方向之厚度尺寸,和對於該厚度方向而言正交之寬度方向的寬度尺寸之立體形狀。在位於包含厚度方向與寬度方向之面內的任意位置之4角形區隔內的各複數之磁鐵材料粒子之對於所預先設定之基準線的磁化容易軸之配向角之中,對於作為頻度最高之配向角所定義之配向軸角度而言,依據前述磁鐵材料 粒子之各個磁化容易軸之配向角的差所訂定之配向角不均角度為9.0°以下。在一形態中,該區隔係將磁鐵材料粒子作為30個以上,例如包含200個或者300個之4角形區隔而加以訂定。4角形區隔係為正方形者為佳。在其他的形態中,該區隔係作為一邊為35μm之正方形區隔所訂定。 In order to achieve the above-mentioned object, the present invention provides, in one aspect, a sintered body for forming a rare-earth magnet having a structure including a rare-earth substance and integrally sintering a plurality of magnet material particles each having an easy-to-magnetize axis. This sintering system for forming a rare-earth magnet has a length dimension having a length direction, a thickness dimension in a thickness direction between a first surface and a second surface in a cross section perpendicular to the lengthwise direction in the transverse direction, and a thickness for the thickness. The three-dimensional shape of the width dimension of the width direction orthogonal to the direction. Among the alignment angles of the plurality of magnet material particles in a quadrangular segment located at arbitrary positions in the plane including the thickness direction and the width direction with respect to the easy-to-magnetize axis of the preset reference line, the most frequent Regarding the angle of the alignment axis defined by the alignment angle, according to the aforementioned magnet material The misalignment angle of the alignment angle determined by the difference in the alignment angle of each easy-to-magnetize axis of the particles is 9.0 ° or less. In one aspect, the segmentation is determined by setting the magnet material particles as 30 or more, for example, quadrangular segments including 200 or 300. A quadrangular segment is preferably a square. In other forms, the segment is defined as a square segment with a side of 35 μm.
在本發明之上述形態中,磁鐵材料粒子之平均粒徑係為3μm以下者為佳。更且,在本發明之上述形態中,在各複數之該4角形區隔中之配向軸角度的差為10°以下者為佳。在更理想之形態中,此配向軸角度的差為5°以下。如此配向軸角度差為小之配向係可稱為平行配向者。 In the above aspect of the present invention, the average particle diameter of the magnetic material particles is preferably 3 μm or less. Furthermore, in the above aspect of the present invention, it is preferable that the difference in the angle of the alignment axes among the plural quadrangular segments is 10 ° or less. In a more desirable form, the difference in the angle of the alignment axis is 5 ° or less. An alignment system with such a small angular difference in the alignment axis can be referred to as a parallel alignment.
在本發明之另外的形態中,係加以提供:經由磁化於上述稀土類磁鐵形成用燒結體所形成之稀土類燒結磁鐵。 In another aspect of the present invention, there is provided a rare-earth sintered magnet formed by being magnetized to the above-mentioned sintered body for forming a rare-earth magnet.
具有上述構成之本發明之稀土類磁鐵形成用燒結體係為具有一體地加以燒結多數之磁鐵材料粒子之構成者之故,比較於例如專利文獻8所揭示之黏合磁鐵,磁鐵材料粒子之密度則大幅度地變高。隨之,經由磁化此稀土類磁鐵形成用燒結體之時而加以得到之稀土類燒結磁鐵,係呈現不能與黏合磁鐵相比程度之優越磁鐵性能。另外,該燒結體係因將磁鐵材料粒子作為30個以上,例如 包含200個或者300個之4角形區隔而加以訂定,或在作為一邊為35μm之正方形區隔所訂定之任意之4角形區隔內之複數的磁鐵材料粒子之磁化容易軸之配向角不均角度則作為呈收在9.0°之小範圍之高精確度的配向之故,經由磁化於該燒結體之時所得到之稀土類燒結磁鐵係比較於以往之稀土類燒結磁鐵而成為呈現優越之磁鐵性能者。 The sintering system for forming a rare-earth magnet according to the present invention having the above-mentioned structure is a structure having a large number of magnet material particles integrally sintered. Compared with the bonded magnet disclosed in Patent Document 8, for example, the density of the magnet material particles is larger. The amplitude becomes higher. Accordingly, the rare-earth sintered magnet obtained by magnetizing the rare-earth magnet forming sintered body exhibits superior magnetic performance that cannot be compared with a bonded magnet. In addition, the sintering system uses 30 or more particles of the magnetic material, for example, The orientation angle of the axis of the magnetization of the plurality of particles of the magnet material in the arbitrary quadrangular segment defined as a square segment with a side of 35 μm is determined by including 200 or 300 quadrangular segments. The average angle is used as a highly accurate alignment in a small range of 9.0 °. The rare earth sintered magnet obtained by magnetizing the sintered body is superior to the conventional rare earth sintered magnets. Magnetist.
1‧‧‧稀土類永久磁鐵形成用燒結體 1‧‧‧ Sintered body for forming rare earth permanent magnets
2‧‧‧上邊 2‧‧‧ top
3‧‧‧下邊 3‧‧‧ below
4,5‧‧‧端面 4,5‧‧‧face
6‧‧‧中央範圍 6‧‧‧ Central Range
7,8‧‧‧端部範圍 7,8‧‧‧end range
20‧‧‧電動馬達 20‧‧‧ Electric motor
21‧‧‧轉子鐵芯 21‧‧‧rotor core
21a‧‧‧周面 21a‧‧‧ weekly
22‧‧‧空氣間隙 22‧‧‧Air gap
23‧‧‧定子 23‧‧‧ stator
23a‧‧‧齒狀物 23a‧‧‧Tooth
23b‧‧‧磁場線圈 23b‧‧‧Magnetic coil
24‧‧‧磁鐵插入用槽 24‧‧‧Magnet insertion slot
24a‧‧‧直線狀中央部分 24a‧‧‧Straight central part
24b‧‧‧傾斜部分 24b‧‧‧ Inclined
30‧‧‧稀土類磁鐵 30‧‧‧ Rare Earth Magnet
117‧‧‧複合材料 117‧‧‧ Composite
118‧‧‧支持基材 118‧‧‧Support substrate
119‧‧‧生坯薄片 119‧‧‧Green sheet
120‧‧‧縫鑄模 120‧‧‧Seam Casting Mould
123‧‧‧加工用薄片 123‧‧‧ processing sheet
125‧‧‧燒結處理用薄片 125‧‧‧ Sintered sheet
C‧‧‧磁化容易軸 C‧‧‧ Easy to magnetize shaft
θ‧‧‧傾斜角 θ‧‧‧ tilt angle
圖1(a)係顯示配向角及配向軸角度之概略圖,顯示在稀土類磁鐵之磁鐵材料粒子的磁化容易軸之配向的一例之橫剖面圖。 FIG. 1 (a) is a schematic view showing the alignment angle and the angle of the alignment axis, and is a cross-sectional view showing an example of the orientation of the axis of the magnet material particles of the rare earth magnet that is easy to be magnetized.
圖1(b)係顯示配向角及配向軸角度之概略圖,顯示訂定各個磁鐵材料粒子的磁化容易軸之「配向角」及「配向軸角度」之步驟的概略擴大圖。 FIG. 1 (b) is a schematic enlarged view showing the alignment angle and the angle of the alignment axis, and is a schematic enlarged view showing a procedure for setting the "alignment angle" and the "alignment axis angle" of the magnetization-easy axis of each magnetic material particle.
圖2係顯示求得配向角不均角度的步驟之圖表。 FIG. 2 is a graph showing the steps for obtaining the misalignment angle of the alignment angle.
圖3(a)係顯示依據EBSD解析之配向角分布之顯示者,顯示稀土類磁鐵之軸的方向之斜視圖。 FIG. 3 (a) is a perspective view showing a display of an alignment angle distribution according to an EBSD analysis, showing a direction of an axis of a rare earth magnet.
圖3(b)係顯示依據EBSD解析之配向角分布之顯示者,顯示經由在該磁鐵之中央部與兩端部之EBSD解析而加以得到之極點圖的例。 FIG. 3 (b) shows an example of the display of the alignment angle distribution according to the EBSD analysis, showing an example of a pole figure obtained by EBSD analysis at the central portion and both end portions of the magnet.
圖3(c)係顯示依據EBSD解析之配向角分布之顯示者,顯示在(a)中之沿著A2軸之磁鐵的剖面之配向軸角度。 Fig. 3 (c) shows the display of the alignment angle distribution according to the EBSD analysis, and the alignment axis angle of the cross section of the magnet along the A2 axis shown in (a) is shown.
圖4係以橫剖面而顯示根據本發明之一實施形態之稀土類磁鐵形成用燒結體一例的剖面圖。 4 is a cross-sectional view showing an example of a sintered body for forming a rare-earth magnet according to an embodiment of the present invention in a cross-section.
圖5(a)係以橫剖面而顯示根據本發明之其他實施形態之稀土類磁鐵形成用燒結體一例的剖面圖,顯示全體之剖面圖。 5 (a) is a cross-sectional view showing an example of a sintered body for forming a rare-earth magnet according to another embodiment of the present invention in a cross-section, and shows a cross-sectional view of the whole.
圖5(b)係以橫剖面而顯示根據本發明之其他實施形態之稀土類磁鐵形成用燒結體一例的剖面圖,顯示端部之擴大圖。 5 (b) is a cross-sectional view showing an example of a sintered body for forming a rare earth magnet according to another embodiment of the present invention in a cross-section, and an enlarged view of an end portion is shown.
圖6係顯示加以設置於埋入有根據本發明之一實施形態之稀土類燒結磁鐵的電動馬達之轉子鐵芯的磁鐵插入用槽之一例的轉子部分之剖面圖。 6 is a cross-sectional view of a rotor portion showing an example of a magnet insertion groove provided in a rotor core of an electric motor in which a rare earth sintered magnet according to an embodiment of the present invention is embedded.
圖7係顯示加以埋入永久磁鐵於圖5所示之轉子鐵芯之狀態的轉子部分之端面圖。 FIG. 7 is an end view of a rotor portion showing a state where a permanent magnet is embedded in the rotor core shown in FIG. 5. FIG.
圖8係可適用本發明之永久磁鐵的電動馬達之橫剖面圖。 FIG. 8 is a cross-sectional view of an electric motor to which the permanent magnet of the present invention can be applied.
圖9係顯示在自經由圖5所示之實施形態之燒結體所形成之稀土類永久磁鐵的磁通密度之分布圖。 FIG. 9 is a diagram showing a magnetic flux density distribution of a rare earth permanent magnet formed from a sintered body according to the embodiment shown in FIG. 5.
圖10(a)係本發明之一實施形態,顯示圖1所示之永久磁鐵形成用燒結體之製造工程的概略圖,顯示至生坯薄片形成為止之各階段。 FIG. 10 (a) is an embodiment of the present invention, showing a schematic view of a manufacturing process of the sintered body for forming a permanent magnet shown in FIG. 1, and showing various stages up to the formation of a green sheet.
圖10(b)係本發明之一實施形態,顯示圖1所示之永久磁鐵形成用燒結體之製造工程的概略圖,顯示至生坯薄片形成為止之各階段。 FIG. 10 (b) is an embodiment of the present invention, showing a schematic view of a manufacturing process of the sintered body for forming a permanent magnet shown in FIG. 1, and showing various stages up to the formation of a green sheet.
圖10(c)係本發明之一實施形態,顯示圖1所示之永 久磁鐵形成用燒結體之製造工程的概略圖,顯示至生坯薄片形成為止之各階段。 FIG. 10 (c) is an embodiment of the present invention, showing A schematic view of a manufacturing process of a sintered body for forming a permanent magnet is shown at each stage until the green sheet is formed.
圖10(d)係本發明之一實施形態,顯示圖1所示之永久磁鐵形成用燒結體之製造工程的概略圖,顯示至生坯薄片形成為止之各階段。 FIG. 10 (d) is an embodiment of the present invention, showing a schematic view of a manufacturing process of the sintered body for forming a permanent magnet shown in FIG. 1, and showing various stages up to the formation of a green sheet.
圖11(a)係顯示在本實施形態之磁鐵材料粒子之磁化容易軸配向處理的加工用薄片之剖面圖,顯示磁場施加時之薄片的剖面形狀。 FIG. 11 (a) is a cross-sectional view showing a processing sheet in which the magnetization of the magnetic material particles in this embodiment is easy to be aligned with the axis, and shows the cross-sectional shape of the sheet when a magnetic field is applied.
圖11(b)係顯示在本實施形態之磁鐵材料粒子之磁化容易軸配向處理的加工用薄片之剖面圖,顯示在磁場施加後加以施以變形處理之燒結處理用薄片的剖面形狀。 FIG. 11 (b) is a cross-sectional view showing a processing sheet that is easy to align the magnetization axis of the magnet material particles in this embodiment, and shows a cross-sectional shape of a sintering process sheet that is subjected to a deformation process after a magnetic field is applied.
圖11(c)係顯示在本實施形態之磁鐵材料粒子之磁化容易軸配向處理的加工用薄片之剖面圖,顯示將第1成形體作成為第2成形體之彎曲變形加工工程。 Fig. 11 (c) is a cross-sectional view of a processing sheet showing the easy-to-axis alignment processing of the magnetized particles of the magnet material in this embodiment, and shows a bending deformation process in which a first formed body is made into a second formed body.
圖12係顯示在鍛燒處理中之理想昇溫速度的圖表。 FIG. 12 is a graph showing an ideal heating rate in the calcination process.
以下,將本發明之實施形態,依據圖面加以說明。先行於實施形態之說明,對於用語之定義及配向角的測定加以說明。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. Prior to the description of the embodiment, the definition of terms and the measurement of the alignment angle will be described.
配向角係意味對於預先所訂定之基準線而言之磁鐵材料粒子之磁化容易軸之方向的角度。 The alignment angle means an angle in a direction in which the magnetization of the magnetic material particles is easy to the axis for a predetermined reference line.
在磁鐵的特定面內,位於預先所訂定之區隔內之磁鐵形成材料粒子之配向角之中,頻度最高之配向角。在本發明中,訂定配向軸角度之區隔係作為含有30個以上磁鐵材料粒子之四角形區隔,或一邊為35μm之正方形區隔。 Among the specific angles of the magnet, among the alignment angles of the magnet-forming material particles located in a predetermined segment, the most frequent alignment angle. In the present invention, the segment defining the angle of the alignment axis is a quadrangular segment containing 30 or more magnet material particles, or a square segment with a side of 35 μm.
於圖1顯示配向角及配向軸角度。圖1(a)係顯示在稀土類磁鐵之磁鐵材料粒子的磁化容易軸之配向的一例之橫剖面圖,該稀土類磁鐵M係具有第1表面S-1,和位於自該第1表面S-1,具有僅厚度t間隔之位置的第2表面S-2,和寬度W,而對於寬度W方向之兩端部係加以形成端面E-1、E-2。在圖示例中,第1表面S-1與第2表面S-2係相互平行之平坦面,而在圖示之橫剖面中,此等第1表面S-1及第2表面S-2係以相互平行之2個直線所表示。端面E-1係成為對於第1表面S-1而言傾斜於上右方向之傾斜面,同樣地,端面E-2係成為對於第2表面S-2而言傾斜於上左方向之傾斜面。箭頭B-1係概略性地顯示在該稀土類磁鐵M之寬度方向中央範圍的磁鐵材料粒子之磁化容易軸之配向軸的方向。對此而言,箭頭B-2係概略性地顯示在鄰接於端面E-1之範圍的磁鐵材料粒子之磁化容易軸之配向軸的方向。同樣地,箭頭B-3係概略性地顯示在鄰接於端面E-2之範圍的磁鐵材料粒子之磁化容易軸之配向軸的方向。 The alignment angle and the alignment axis angle are shown in FIG. 1. FIG. 1 (a) is a cross-sectional view showing an example of the orientation of the axis of easy magnetization of the magnetic material particles of the rare earth magnet. The rare earth magnet M has a first surface S-1 and is located on the first surface S. -1, the second surface S-2 having a position separated only by the thickness t, and the width W, and both end portions in the width W direction are formed with end faces E-1, E-2. In the example of the figure, the first surface S-1 and the second surface S-2 are flat surfaces parallel to each other, and in the cross section shown in the figure, these first surface S-1 and second surface S-2 It is represented by two straight lines parallel to each other. The end surface E-1 is an inclined surface inclined to the upper right direction for the first surface S-1. Similarly, the end surface E-2 is an inclined surface inclined to the upper left direction for the second surface S-2. . The arrow B-1 schematically shows the direction of the alignment axis of the magnetization-easy axis of the magnet material particles in the center range in the width direction of the rare earth magnet M. In this regard, the arrow B-2 shows the direction of the orientation axis of the magnetization easy axis of the magnet material particles in a range adjacent to the end face E-1. Similarly, the arrow B-3 shows the direction of the orientation axis of the easy-to-magnetize axis of the magnet material particles in a range adjacent to the end surface E-2.
「配向軸角度」係由箭頭B-1、B-2、B-3所表示之配向軸,和一個基準線之間的角度。基準線係可任意地設定者,但如圖1(a)所示的例,對於以直線而表示第1表面S-1之剖面情況,將該第1表面S-1之剖面作為基準線者則為便利。圖1(b)係顯示訂定各個磁鐵材料粒子的磁化容易軸之「配向角」及「配向軸角度」之步驟的概略擴大圖。圖1(a)所示之稀土類磁鐵M之任意處,例如圖1(a)所示之4角形區隔R則加以擴大顯示於圖1(b)。對於此4角形區隔R,係包含有30個以上,例如200個乃至300個之多數的磁鐵材料粒子P。含於4角形區隔之磁鐵材料粒子的數量越多,測定精確度係越高,但即使為30個程度,亦可以充分的精確度而測定者。各磁鐵材料粒子P係具有磁化容易軸P-1。磁化容易軸P-1係通常未具有方向性,但成為經由加以磁化磁鐵材料粒子之時而具有方向性的向量。在圖1(b)中,考慮加以磁化之預定的極性,以賦予方向性於磁化容易軸之箭頭而顯示。 "Alignment axis angle" is the angle between the alignment axis indicated by arrows B-1, B-2, and B-3 and a reference line. The reference line can be set arbitrarily. However, as shown in the example of FIG. 1 (a), for the case where the cross section of the first surface S-1 is represented by a straight line, the cross section of the first surface S-1 is used as the reference line. For convenience. FIG. 1 (b) is a schematic enlarged view showing a step of setting the "alignment angle" and the "alignment axis angle" of the magnetization-easy axis of each magnetic material particle. Any place of the rare earth magnet M shown in Fig. 1 (a), for example, the quadrangular segment R shown in Fig. 1 (a) is enlarged and shown in Fig. 1 (b). The quadrangular segment R includes a plurality of magnet material particles P of more than 30, for example, 200 or 300. The larger the number of particles of the magnet material contained in the quadrangular segment, the higher the accuracy of the measurement, but even if it is 30 degrees, it can be measured with sufficient accuracy. Each magnet material particle P has an easy magnetization axis P-1. The easy-to-magnetize axis P-1 generally does not have a directivity, but becomes a vector having a directivity when the magnet material particles are added. In FIG. 1 (b), the magnetization is performed with a predetermined polarity in mind, and the arrow is shown to give directionality to the axis of easy magnetization.
如圖1(b)所示,各個磁鐵材料粒子P之磁化容易軸P-1係具有該磁化容易軸所指向之方向與基準線之間的角度之「配向角」。並且,圖1(b)所示之4角形區隔R內之磁鐵材料粒子P的磁化容易軸P-1之「配向角」之中,將頻度最高之配向角,作為「配向軸角度」B。 As shown in FIG. 1 (b), the easy-to-magnetize axis P-1 of each of the magnetic material particles P is a "alignment angle" having an angle between the direction in which the easy-to-magnetize axis points and the reference line. In addition, among the "alignment angles" of the easy-to-magnetize axis P-1 of the magnetic material particles P in the quadrangular segment R shown in FIG. 1 (b), the most frequent alignment angle is taken as the "alignment axis angle" B .
求取在任意之4角形區隔的配向軸角度,和 對於存在於該區隔內之磁鐵材料粒子之所有,其磁化容易軸之配向角的差,將經由在該配向角的差之分布之半值寬度而加以表示之角度的值,作為配向角不均角度。圖2係顯示求取配向角不均角度的步驟之圖表。在圖2中,對於磁化容易軸而言之各個磁鐵材料粒子之磁化容易軸的配向角的差△θ之分布,則經由曲線C而加以表示。將顯示於縱軸之累積頻度成為最大之位置,作為100%,而累積頻度成為50%之配向角差△θ的值則為半值寬度。 Find the angle of the alignment axis at any of the quadrangular segments, and For all the particles of the magnet material existing in the segment, the difference in the alignment angle of the easy-to-magnetize axis will be the value of the angle expressed by the half-value width of the distribution of the difference in the alignment angle as the alignment angle. Both angles. FIG. 2 is a graph showing the steps for obtaining the misalignment angle of the alignment angle. In FIG. 2, the distribution of the difference Δθ in the alignment angle of the magnetization easy axis of each magnet material particle for the magnetization easy axis is represented by a curve C. The position where the cumulative frequency displayed on the vertical axis becomes the maximum is taken as 100%, and the value of the alignment angle difference Δθ whose cumulative frequency becomes 50% is the half-value width.
在各個磁鐵材料粒子P之磁化容易軸P-1的配向角係可經由依據掃描電子顯微鏡(SEM)畫像之「電子背向散射繞射分析法」(EBSD解析法)而求取。作為為了此解析之裝置,係有著具備Oxford Instruments公司製之EBSD檢出器(AZtecHKL EBSD NordlysNano Integrated)之掃描電子顯微鏡,具備日本東京都昭島市所在之日本電子股份有限公司製JSM-70001F、或EDAX公司製之EBSD檢出器(Hikari High Speed EBSD Detector)之掃描電子顯微鏡,ZEISS公司製SUPRA40VP。另外,作為經由外部委託而進行EBSD解析之事業體,係有著日本東京都中央區日本橋所在之JFE Techno-Research股份有限公司及日本大阪府茨木市所在之股份有限公司日本日東分析中心。如根據EBSD解析,可求取存在於特定區隔內之磁鐵材料粒子之磁化容易軸的配向角及配向軸角度,依據此等的值, 而亦可取得配向角不均角度者。圖3係顯示經由EBSD解析法之磁化容易軸之配向顯示的一例,圖3(a)係顯示稀土類磁鐵的軸之方向的斜視圖,同(b)係顯示經由在中央部與兩端部之EBSD解析而加以得到之極點圖的例者。另外,於圖3(c)顯示沿著A2軸之磁鐵的剖面之配向軸角度。配向角係可將磁鐵材料粒子之磁化容易軸之配向向量,分為在包含A1軸與A2軸之平面之成分,和在包含A1軸與A3軸之平面之成分而表示。A2軸係寬度方向,而A1軸係厚度方向。圖3(b)之中央的圖係顯示在磁鐵的寬度方向中央,磁化容易軸之配向則略沿著A1軸之方向者。對此,圖3(b)之左的圖係顯示在磁鐵的寬度方向左端部之磁化容易軸之配向則自下方對於右上方向,沿著A1軸-A2軸的面而傾斜者。同樣地,圖3(b)之右的圖係顯示在磁鐵的寬度方向右端部之磁化容易軸之配向則自下方對於左上方向,沿著A1軸-A2軸的面而傾斜者。將如此之配向,作為配向向量,顯示於圖3(c)。 The alignment angle system at the easy-to-magnetize axis P-1 of each magnet material particle P can be obtained by the "electron backscatter diffraction analysis method" (EBSD analysis method) based on a scanning electron microscope (SEM) image. As a device for this analysis, a scanning electron microscope equipped with an EBSD detector (AZtecHKL EBSD NordlysNano Integrated) manufactured by Oxford Instruments, and JSM-70001F or EDAX manufactured by Japan Electronics Co., Ltd. located in Akishima, Tokyo, Japan. Scanning electron microscope of Hikari High Speed EBSD Detector manufactured by the company, SUPRA40VP manufactured by ZEISS. In addition, as an entity that conducts EBSD analysis through external commissions, there are JFE Techno-Research Co., Ltd., located in Nihonbashi, Chuo-ku, Tokyo, Japan, and Japan Nitto Analysis Center, located in Ibaraki, Osaka, Japan. According to the EBSD analysis, the orientation angle and orientation axis angle of the magnetization-easy axis of the magnetic material particles existing in a specific segment can be obtained. Based on these values, Those with uneven alignment angles can also be obtained. Fig. 3 shows an example of the orientation of the axis of easy magnetization by the EBSD analysis method. Fig. 3 (a) is a perspective view showing the direction of the axis of the rare earth magnet, and Fig. 3 (b) shows the center and both ends through the same. An example of a pole figure obtained by EBSD analysis. In addition, FIG. 3 (c) shows the alignment axis angle of the cross section of the magnet along the A2 axis. The alignment angle system can divide the alignment vector of the easy-to-magnetize axis of the magnet material particles into components on a plane including the A1 axis and the A2 axis, and components on a plane including the A1 axis and the A3 axis. The A2 axis is in the width direction and the A1 axis is in the thickness direction. The center of FIG. 3 (b) shows the center of the magnet in the width direction, and the orientation of the axis of easy magnetization is slightly along the direction of the A1 axis. In contrast, the left diagram in FIG. 3 (b) shows the orientation of the easy-to-magnetize axis at the left end of the magnet in the width direction, and the upper-right direction is tilted from below to the plane along the A1-A2 axis. Similarly, the graph on the right in FIG. 3 (b) shows the orientation of the easy-to-magnetize axis at the right end of the magnet in the width direction, and the one tilted along the plane of the A1-axis and A2-axis from the bottom to the top-left direction. Such an alignment is shown in FIG. 3 (c) as an alignment vector.
對於存在於任意之區隔內的各個磁鐵材料粒子,表示對於垂直於觀察面的軸而言之該磁鐵材料粒子之磁化容易軸的傾斜角的圖。此圖係可依據掃描電子顯微鏡(SEM)畫像而作成者。 For each magnet material particle existing in an arbitrary segment, a graph showing an inclination angle of the axis of easy magnetization of the magnet material particle with respect to the axis perpendicular to the observation surface. This image can be created based on a scanning electron microscope (SEM) image.
以下,將本發明之實施形態,依據圖面加以說明。圖4係顯示根據本發明之一實施形態之稀土類磁鐵形成用燒結體1的剖面圖,具有有著稱為第2表面之上邊2與有著稱為第1表面之下邊3,與正交於圖的紙面之方向的長度之長方體形狀。即,上邊2與下邊3係相互平行地延伸,此等上邊2與下邊3的間隔則成為厚度。在圖4中,沿著上邊2與下邊3之方向則為寬度方向,而兩端部4,5則訂定寬度尺寸。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 4 is a cross-sectional view showing a sintered body 1 for forming a rare earth magnet according to an embodiment of the present invention. The sintered body 1 has an upper side 2 called a second surface and an lower side 3 called a first surface, and is orthogonal to the figure. A rectangular parallelepiped shape with a length in the direction of the paper surface. That is, the upper side 2 and the lower side 3 extend parallel to each other, and the interval between the upper side 2 and the lower side 3 becomes a thickness. In FIG. 4, the direction along the upper side 2 and the lower side 3 is the width direction, and the two end portions 4 and 5 define the width dimension.
於圖5乃至圖8,顯示組裝根據本發明之其他實施形態之稀土類磁鐵形成用燒結體,和自燒結體所形成之永久磁鐵的電動馬達的一例。在圖5乃至圖8中,與圖4所顯示之實施形態之部分對應之部分係以和圖4同一的符號而顯示。在圖4所示之實施形態及圖5乃至圖8所示之實施形態之任一中,稀土類磁鐵形成用燒結體1係作為磁鐵材料,包含Nd-Fe-B系磁鐵材料。典型來說,Nd-Fe-B系磁鐵材料係以27乃至40wt%的比例而含有Nd,以0.8乃至2wt%的比例而含有B,以60乃至75wt%的比例而含有電解鐵的Fe。此磁鐵材料係將磁性特性提升作為目的,而含有少量Dy、Tb、Co、Cu、Al、Si、Ga、Nb、V、Pr、Mo、Zr、Ta、Ti、W、Ag、Bi、Zn、Mg等之其他元素亦可。 An example of an electric motor in which a sintered body for forming a rare earth magnet and a permanent magnet formed from the sintered body are assembled is shown in FIG. 5 to FIG. 8. In FIG. 5 to FIG. 8, parts corresponding to the parts of the embodiment shown in FIG. 4 are shown with the same symbols as in FIG. 4. In any of the embodiments shown in FIG. 4 and the embodiments shown in FIGS. 5 to 8, the sintered body 1 for forming a rare earth magnet is used as a magnet material, and includes a Nd—Fe—B based magnet material. Typically, Nd-Fe-B-based magnet materials contain Nd at a ratio of 27 to 40% by weight, B at a ratio of 0.8 to 2% by weight, and Fe of electrolytic iron at a ratio of 60 to 75% by weight. This magnet material is for the purpose of improving magnetic properties, and contains a small amount of Dy, Tb, Co, Cu, Al, Si, Ga, Nb, V, Pr, Mo, Zr, Ta, Ti, W, Ag, Bi, Zn, Other elements such as Mg are also possible.
在圖4所示之實施形態中,稀土類磁鐵形成用燒結體1係一體地燒結成形上述之磁鐵材料的細微粒子者,具有自下邊3朝向上邊2而指向之磁鐵材料粒子之磁 化容易軸的配向,而此磁化容易軸的配向係完全為相互平行之平行配向。 In the embodiment shown in FIG. 4, the sintered body 1 for forming a rare-earth magnet is integrally sintered to form the fine particles of the above-mentioned magnet material, and has the magnetism of the magnet material particles directed from the bottom 3 to the top 2 The orientation of the shaft is easily changed, and the orientation system of this magnetization is completely parallel to each other.
當參照圖5(a)時,經由此實施形態之磁鐵形成用燒結體1係一體地燒結成形上述之磁鐵材料的細微粒子者,具有相互平行之上邊2與下邊3,及左右兩端之端面4,5,該端面4,5係與圖4之實施形態不同,作為對於上邊2及下邊3而言傾斜之傾斜面而加以形成。上邊2係對應於第2表面的剖面的邊,而下邊3係對應於第1表面的剖面的邊。端面4,5之傾斜角係作為該端面4,5之延長線4a,5a與上邊2之間的角度θ而加以定義。在理想的形態中,傾斜角θ係45°乃至80°、而更理想為55°乃至80°。其結果,磁鐵形成用燒結體1係加以形成為具有上邊2則較下邊3為短之台形的寬度方向剖面的形狀。 When referring to FIG. 5 (a), the fine particles of the above-mentioned magnet material are integrally sintered through the sintered body 1 for forming a magnet in this embodiment, which has upper sides 2 and lower sides 3 parallel to each other, and end faces on the left and right ends. 4, 5, and the end faces 4, 5 are different from the embodiment of FIG. 4 and are formed as inclined surfaces inclined to the upper side 2 and the lower side 3. The upper side 2 is an edge corresponding to the cross section of the second surface, and the lower side 3 is an edge corresponding to the cross section of the first surface. The inclination angle of the end faces 4, 5 is defined as the angle θ between the extension lines 4a, 5a of the end faces 4, 5 and the upper side 2. In an ideal form, the inclination angle θ is 45 ° or even 80 °, and more preferably 55 ° or even 80 °. As a result, the sintered body 1 for magnet formation is formed in the shape which has the width | variety cross section of the mesa shape which has the upper side 2 and is shorter than the lower side 3.
磁鐵形成用燒結體1係於沿著上邊2及下邊3之寬度方向,具有區分為特定尺寸之中央範圍6,和兩端部側之端部範圍7,8之複數的範圍。在中央範圍6中,含於該範圍6之磁鐵材料粒子係成為其磁化容易軸則對於上邊2及下邊3而言實質上直角之平行地配向於厚度方向之平行配向。對此,在端部範圍7,8中,含於該範圍7,8之磁鐵材料粒子的磁化容易軸係對於厚度方向而言,自下朝向上,配向方向則傾斜於中央範圍6之方向,而其傾斜角係在鄰接於端面4,5之位置中為沿著該端面4,5之傾斜角θ的角度,而在鄰接於中央範圍6之位置中,對於該上邊2而言為略直角,伴隨著自鄰接於端面 4,5之位置接近於中央範圍6而漸次變大。將如此之磁化容易軸之配向,於圖5(a),對於中央範圍6之平行配向,以箭頭9,而對於端部範圍7,8之傾斜配向係以箭頭10而顯示。關於端部範圍7,8之傾斜配向,如作為另外的表現,含於此等範圍之磁鐵材料粒子之磁化容易軸係自上邊2與端面4,5所交叉之角部朝向中央部,呈聚集於對應於端部範圍7,8之寬度方向尺寸的特定之範圍之領域地加以配向。此配向的結果,在端部範圍7,8中,加以指向磁化容易軸於上邊2之磁鐵材料粒子的密度則成為較在中央範圍6為高。在本發明之理想形態中,對應於中央範圍6之上邊2的寬度方向之尺寸,即,平行長P,與上邊2之寬度方向尺寸L的比,即,平行率P/L則呈成為0.05乃至0.8、更理想為0.2乃至0.5地,加以訂定中央範圍6與端部範圍7,8之尺寸。 The sintered body 1 for magnet formation has a plurality of ranges of a central range 6 divided into a specific size and end ranges 7 and 8 on both end sides along the width direction of the upper side 2 and the lower side 3. In the central range 6, the magnetic material particles contained in the range 6 become the axis of easy magnetization, and the upper side 2 and the lower side 3 are aligned at substantially right angles in parallel and parallel in the thickness direction. In this regard, in the end range 7,8, the magnetization of the magnetic material particles contained in the range 7,8 is easy to magnetize. For the thickness direction, from bottom to top, the alignment direction is inclined to the direction of the central range 6, The inclination angle is an angle along the inclination angle θ of the end faces 4 and 5 in a position adjacent to the end faces 4 and 5, and a slightly right angle to the upper side 2 in a position adjacent to the central range 6. , Accompanied by self-adjacent to the end face The positions of 4, 5 are closer to the central range 6 and gradually become larger. Such an easy magnetization of the axis alignment is shown in FIG. 5 (a) by the arrow 9 for the parallel alignment of the center range 6 and the tilted alignment of the end ranges 7 and 8 by the arrow 10. Regarding the oblique alignment of the end ranges 7, 8 as another expression, the magnetization of the magnetic material particles contained in these ranges is easy to be axised from the intersection of the upper side 2 and the end faces 4, 5 toward the central portion, showing agglomeration. Orientation is performed in a specific range corresponding to the widthwise dimensions of the end ranges 7,8. As a result of this alignment, in the end ranges 7, 8 the density of the magnet material particles which are easily oriented to the axis of magnetization on the upper side 2 becomes higher than that in the center range 6. In an ideal form of the present invention, the ratio in the width direction of the upper side 2 of the central range 6, that is, the parallel length P, and the ratio L in the width direction of the upper side 2, that is, the parallelism ratio P / L becomes 0.05. It is even 0.8, more preferably 0.2 or 0.5, and the sizes of the central range 6 and the end ranges 7, 8 are determined.
將在上述之端部範圍7,8之磁鐵材料的磁化容易軸之配向,對於端部範圍7而誇大顯示於圖5(b)。在圖5(b)中,磁鐵材料粒子之各磁化容易軸C係在鄰接於端面4之部分中,略沿著該端面4,僅該端面4之傾斜角θ而傾斜加以配向。並且,該傾斜角係隨著自端部接近於中央部而漸次增加。即,磁鐵材料粒子之磁化容易軸C的配向係成為呈自下邊3側朝向於上邊2而聚集,而加以指向磁化容易軸C於上邊2之磁鐵材料粒子之密度係比較於平行配向的情況而變高。 The magnetization of the magnet material in the above-mentioned end range 7, 8 is easy to align the axis, and the end range 7 is exaggerated and shown in FIG. 5 (b). In FIG. 5 (b), each magnetization easy axis C of the magnet material particles is aligned in a portion adjacent to the end surface 4 along the end surface 4, and only the inclination angle θ of the end surface 4 is inclined. In addition, the tilt angle gradually increases as the end portion approaches the center portion. That is, the orientation system of the axis C of the magnetization particles of the magnetic material particles is aggregated from the lower side 3 toward the upper side 2, and the density of the magnet material particles directed to the magnetization axis C on the upper side 2 is compared to the case of parallel alignment. Becomes high.
圖6係擴大顯示適合於埋入經由使具有上述 之磁化容易軸的配向之磁鐵形成用燒結體1磁化之時而加以形成之稀土類磁鐵而使用電動馬達20之轉子鐵芯部分之剖面圖。轉子鐵芯21係其周面21a則藉由空氣間隙22而呈與定子23對向地,旋轉自由地加以配置於該定子23內。定子23係具備具有間隔於周方向而加以配設之複數的齒狀物23a,而卷繞有磁場線圈23b於此齒狀物23a。上述之空氣間隙22係成為加以形成於各齒狀物23a之端面與轉子鐵芯21之周面21a之間者。對於轉子鐵芯21係加以形成有磁鐵插入用槽24。此槽24係具有直線狀中央部分24a,和自該中央部分24a的兩端部傾斜延伸於轉子鐵芯21之周面21a的方向之一對之傾斜部分24b。從圖6了解到,傾斜部分24b係位於其末端部接近於轉子鐵芯21之周面21a的位置。 Figure 6 is an enlarged display suitable for embedding via A cross-sectional view of a rotor core portion of an electric motor 20 using a rare-earth magnet formed when the sintered body 1 for forming a magnet whose axis is easy to be magnetized is magnetized. The rotor core 21 is such that the peripheral surface 21 a of the rotor core 21 faces the stator 23 through the air gap 22 and is rotatably disposed in the stator 23. The stator 23 includes a plurality of teeth 23a arranged at intervals in the circumferential direction, and a magnetic field coil 23b is wound around the teeth 23a. The above-mentioned air gap 22 is formed between the end surface of each tooth 23 a and the peripheral surface 21 a of the rotor core 21. The rotor core 21 is formed with a magnet insertion groove 24. This groove 24 has a linear central portion 24a, and an inclined portion 24b opposite to the central portion 24a. The inclined portion 24b extends in one direction from the peripheral surface 21a of the rotor core 21. As can be understood from FIG. 6, the inclined portion 24 b is located at a position close to the peripheral surface 21 a of the rotor core 21 at the end portion.
將經有使具有上述磁化容易軸之配向的磁鐵形成用燒結體1磁化之時而加以形成之稀土類磁鐵30,插入於圖6顯示之轉子鐵芯21之磁鐵插入用槽24之狀態,示於圖7。如圖7所示,稀土類永久磁鐵30係其上邊2呈朝向於外側,即定子23側地,加以插入至形成於轉子鐵芯21之磁鐵插入用槽24的直線狀中央部分24a。對於較所插入之磁鐵30兩端為外側,係作為空隙部而加以殘留槽24之直線狀中央部分24a之一部分與傾斜部分24b。如此,將經由加以插入永久磁鐵於轉子鐵芯21的槽24而加以形成之電動馬達20的全體,以橫剖面圖而顯示於圖8。 A state in which a rare-earth magnet 30 formed by magnetizing a sintered body 1 for forming a magnet having the above-mentioned easy-to-magnet orientation is inserted into the magnet insertion groove 24 of the rotor core 21 shown in FIG. 6.于 图 7。 In Figure 7. As shown in FIG. 7, the rare-earth permanent magnet 30 is inserted into the linear central portion 24 a of the magnet insertion slot 24 formed in the rotor core 21 with its upper side 2 facing outward, that is, on the stator 23 side. The two sides of the inserted magnet 30 are outside, and a part of the linear central portion 24a and the inclined portion 24b of the remaining groove 24 are provided as a gap portion. In this way, the entire electric motor 20 formed by inserting a permanent magnet into the slot 24 of the rotor core 21 is shown in a cross-sectional view in FIG. 8.
圖9係顯示經由上述之實施形態而加以形成之稀土類永久磁鐵30之磁通密度的分布者。如圖9所示,在磁鐵30之兩側端部範圍7,8之磁通密度D係成為較在中央範圍6之磁通密度E為高。因此,將此磁鐵30埋入於電動馬達20之轉子鐵芯21而使其動作時,即使對於磁鐵30之端部產生有來自定子23之磁通,亦可加以抑制磁鐵30之端部的減磁,而對於磁鐵30之端部係減磁後亦成為殘留有充分的磁通者,而加以防止馬達20之輸出降低者。 FIG. 9 shows the distribution of the magnetic flux density of the rare-earth permanent magnet 30 formed by the above embodiment. As shown in FIG. 9, the magnetic flux density D of the range 7 and 8 at both end portions of the magnet 30 is higher than the magnetic flux density E of the central range 6. Therefore, when the magnet 30 is embedded in the rotor core 21 of the electric motor 20 and operated, even if a magnetic flux from the stator 23 is generated at the end of the magnet 30, the reduction of the end of the magnet 30 can be suppressed. It is magnetic, and the end of the magnet 30 becomes a person with sufficient magnetic flux remaining after demagnetization, and a decrease in the output of the motor 20 is prevented.
接著,對於為了製造經由圖4所示之實施形態及圖5乃至圖9所示之實施形態的稀土類磁鐵形成用燒結體1之經由本發明之一實施形態的製造方法,參照圖10而加以說明。圖10係顯示經由上述之2個實施形態之永久磁鐵形成用燒結體1之製造工程之概略圖。 Next, a manufacturing method for manufacturing a sintered body 1 for forming a rare earth magnet through the embodiment shown in FIG. 4 and the embodiments shown in FIG. 5 to FIG. 9 through one embodiment of the present invention will be described with reference to FIG. 10. Instructions. FIG. 10 is a schematic diagram showing a manufacturing process of the sintered body 1 for forming a permanent magnet through the above two embodiments.
首先,經由鑄造法而製造特定分率之Nd-Fe-B系合金所成之磁鐵材料之鑄錠。代表性來說,使用於釹磁鐵之Nd-Fe-B系合金係具有以30wt%之比例而含有Nd,以67wt%之比例而含有電解鐵者為佳之Fe,以1.0wt%之比例而含有B之組成。接著,將此鑄錠,使用搗碎機或粉碎機等之公知的手段而粗粉碎為粒徑200μm程度的大小。而對於取代性地,溶解鑄錠,經由片鑄造法而製作薄片,以氫解裂法而作粗粉化者亦可。經由此而得到粗粉碎 磁鐵材料粒子115(參照圖10(a))。 First, an ingot of a magnetic material made of a Nd-Fe-B alloy with a specific fraction is produced by a casting method. Typically, Nd-Fe-B alloys used in neodymium magnets contain Fe in an amount of 30% by weight, electrolytic iron in an amount of 67% by weight, and Fe in an amount of 1.0% by weight. The composition of B. Next, this ingot was coarsely pulverized to a size of about 200 μm using a known method such as a masher or a pulverizer. Alternatively, it is also possible to dissolve the ingot, make a flake through a sheet casting method, and make a coarse powder by a hydrogen decomposition method. Coarse crushed The magnetic material particles 115 (see FIG. 10 (a)).
接著,將粗粉碎磁鐵材料粒子115,經由使用根據珠磨機116之濕式法或噴射磨機之乾式法等而進行微粉碎。例如,在使用經由珠磨機116之濕式法的微粉碎中,在溶媒中,將粗粉碎磁鐵粒子115,特定範圍之粒徑例如呈0.1μm乃至5.0μm、理想係平均粒徑則呈成為3μm以下地進行微粉碎,做為成使磁鐵材料粒子分散於溶媒中之狀態(參照圖10(b))。之後,經由真空乾燥手段等之手段而使含於濕式粉碎後之溶媒的磁鐵粒子,取出乾燥之磁鐵粒子(未圖示)。在此,對於使用於粉碎之溶媒的種類係無特別限制,而可使用異丙醇,乙醇,甲醇等之醇類,乙酸乙酯等之酯類,戊烷,己烷等之低級碳化氫類,苯,甲苯,二甲苯等芳香族類,酮類,此等之混合物等之有機溶媒,或液化氬,液化氮,液化氦等之無機溶媒者。在此情況中,使用未含有氧原子於溶媒中之溶媒者為佳。 Next, the coarsely pulverized magnet material particles 115 are finely pulverized by a wet method using a bead mill 116 or a dry method using a jet mill. For example, in the fine pulverization using the wet method through the bead mill 116, the particle size of the coarsely pulverized magnet particles 115 in the solvent is, for example, 0.1 μm to 5.0 μm in a specific range, and the ideal average particle diameter is It is finely pulverized to 3 μm or less so that the magnet material particles are dispersed in a solvent (see FIG. 10 (b)). Thereafter, the magnet particles contained in the wet-pulverized solvent are taken out by means such as a vacuum drying method, and the dried magnet particles (not shown) are taken out. Here, the type of the solvent used for the pulverization is not particularly limited, and alcohols such as isopropanol, ethanol, and methanol, esters such as ethyl acetate, and lower hydrocarbons such as pentane and hexane can be used. , Organic solvents such as aromatics such as benzene, toluene, xylene, ketones, and mixtures thereof, or inorganic solvents such as liquefied argon, liquefied nitrogen, and liquefied helium. In this case, it is preferable to use a solvent that does not contain an oxygen atom in the solvent.
另一方面,在使用經由噴射磨機之乾式法的微粉碎中,作為將粗粉碎之磁鐵材料粒子115,在(a)氧含有量為0.5%以下、理想係實質上0%之氮氣,Ar氣體,He氣體等之非活性氣體所成之環境中,或(b)氧含有量為0.0001乃至0.5%之氮氣,Ar氣體,He氣體等之非活性氣體所成之環境中,經由噴射磨機而進行微粉碎,具有6.0μm以下、例如,0.7μm乃至5.0μm之特定範圍之平均粒徑的微粒子。在此,氧濃度實質上為0%係指未加以限定氧濃度完全為0%,而意味於微粉表面含有僅些微形成 氧化被膜程度的量的氧者亦可。 On the other hand, in the fine pulverization using the dry method via a jet mill, as the coarsely pulverized magnetic material particles 115, (a) the nitrogen content is 0.5% or less, and ideally substantially 0% nitrogen, Ar Gas, He gas and other inactive gases, or (b) Nitrogen with an oxygen content of 0.0001 or 0.5%, Ar gas, He gas and other inactive gases, through a jet mill The finely pulverized particles are fine particles having an average particle diameter in a specific range of 6.0 μm or less, for example, 0.7 μm to 5.0 μm. Here, the oxygen concentration of substantially 0% means that the oxygen concentration is completely 0% without limitation, and means that the surface of the fine powder contains only a small amount of It is also possible to oxidize the amount of oxygen of the coating level.
接著,將由珠磨機116等而加以微粉碎之磁鐵材料粒子,成形為所期望形狀。為了此磁鐵材料粒子之成形,準備混合如上述加以微粉碎之磁鐵材料粒子115與樹脂材料所成之接著劑的混合物,即,複合材料。作為接著劑所使用的樹脂係於構造中未含有氧原子,且有解聚合性之聚合物為佳。另外,如後述為了將磁鐵粒子與接著劑之複合材料,作為呈可再利用在形成為所期望形狀時產生的複合材料之殘餘物,且為了做為呈可在加熱複合材料而軟化的狀態,進行磁場配向,做為樹脂材料係使用熱可塑性樹脂者為佳。具體而言,最佳加以使用自以下一般式(1)所示之單體加以形成之1種或2種以上之聚合體或共聚合體所成之聚合物。 Next, the magnetic material particles finely pulverized by the bead mill 116 or the like are formed into a desired shape. For the formation of the magnetic material particles, a mixture of the magnetic material particles 115 and the adhesive made of the resin material, which are finely pulverized as described above, is prepared, that is, a composite material. The resin used as the adhesive is preferably a polymer that does not contain an oxygen atom in the structure and has a depolymerizable property. In addition, as described later, in order to make the composite material of the magnet particles and the adhesive as a remnant of the composite material generated when the composite material is formed into a desired shape and to be softened by heating the composite material, For magnetic field alignment, it is better to use thermoplastic resin as the resin material. Specifically, a polymer formed from one or more polymers or copolymers formed from a monomer represented by the following general formula (1) is preferably used.
作為符合於上述條件之聚合物,係例如有異丁烯之聚合體的聚異丁烯(PIB)、異戊二烯之聚合體的聚異戊二烯(異戊二烯橡膠,IR),1,3-丁二烯之聚合體的聚丁二烯(丁二烯橡膠,BR),苯乙烯之聚合體的聚苯乙烯,苯乙烯與異戊二烯之共聚合體的苯乙烯-異戊二烯段共聚 合體(SIS)、異丁烯與異戊二之共聚合體的丁基橡膠(IIR)、苯乙烯與丁二烯之共聚合體的苯乙烯-丁二烯段共聚合體(SBS)、苯乙烯與乙烯,丁二烯之共聚合體的苯乙烯-乙烯-丁二烯-苯乙烯共聚合體(SEBS)、苯乙烯與乙烯,丙烯之共聚合體的苯乙烯-乙烯-丙烯-苯乙烯共聚合體(SEPS)、乙烯與丙烯之共聚合體的乙烯-丙烯共聚合體(EPM)、與乙烯,丙烯同時使二烯單體共聚合之EPDM、2-甲基-1-戊烯之聚合體的2-甲基-1-戊烯聚合樹脂,2-甲基-1-丁烯之聚合體的2-甲基-1-丁烯聚合樹脂等。另外,作為使用於接著劑之樹脂,係作為含有少量包含氧原子,氮原子之單體的聚合體或共聚合體(例如,聚甲基丙烯酸丁酯或聚甲基丙烯酸甲酯等)之構成亦可。更且,未符合上述一般式(1)之單體則作為一部分共聚合亦可。在此情況,亦可達成本發明之目的者。 Polymers meeting the above conditions are, for example, polyisobutylene (PIB) having a polymer of isobutylene, and polyisoprene (isoprene rubber, IR) having a polymer of isoprene, 1,3- Polybutadiene (butadiene rubber, BR), a polymer of butadiene, polystyrene, a polymer of styrene, and a styrene-isoprene copolymer of a copolymer of styrene and isoprene (SIS), isobutylene and isoprene copolymer butyl rubber (IIR), styrene and butadiene copolymer styrene-butadiene segment copolymer (SBS), styrene and ethylene, butadiene Diene copolymers styrene-ethylene-butadiene-styrene copolymers (SEBS), styrene and ethylene, propylene copolymers styrene-ethylene-propylene-styrene copolymer (SEPS), ethylene and Ethylene-propylene copolymer (EPM) of propylene copolymer, 2-methyl-1-pentene of EPDM, 2-methyl-1-pentene copolymer of ethylene, propylene copolymerizing diene monomer at the same time Olefin polymer resin, 2-methyl-1-butene polymer resin of 2-methyl-1-butene polymer, and the like. In addition, the resin used for the adhesive is a polymer or copolymer (for example, polybutyl methacrylate or polymethyl methacrylate) containing a small amount of monomers containing oxygen and nitrogen atoms. can. In addition, a monomer that does not meet the general formula (1) may be copolymerized as a part. In this case, the object of the invention can also be achieved.
然而,作為使用於接著劑之樹脂,係為了適當地進行磁場配向而使用以250℃以下進行軟化之熱可塑性樹脂,更具體而言,係玻璃轉移點或流動開始溫度為250℃以下之熱可塑性樹脂者為佳。 However, as the resin used for the adhesive, a thermoplastic resin softened at 250 ° C or lower is used for proper magnetic field alignment, and more specifically, a thermoplastic having a glass transition point or a flow start temperature of 250 ° C or lower Resin is preferred.
為了使磁鐵材料粒子分散於熱可塑性樹脂中,適量添加分散劑(配向潤滑劑)者為佳。作為分散劑係醇,羧酸,酮,醚,酯,胺,亞胺,醯亞胺,醯胺,氰,磷系官能基,磺酸,具有二重結合或三重結合等之不飽和結合之化合物,及液狀飽和碳化氫化合物之中,添加至少一個者為佳。混合此等物質之複數而使用亦可。並且,如 後述,在對於磁鐵材料粒子與接著劑之混合物,即複合材料而言,施加磁場而磁場配向該磁鐵材料時,在加熱混合物而接著劑成分產生軟化之狀態,進行磁場配向處理。 In order to disperse the magnet material particles in the thermoplastic resin, an appropriate amount of a dispersant (alignment lubricant) is preferably added. As dispersant, alcohols, carboxylic acids, ketones, ethers, esters, amines, imines, amidines, amidines, cyanides, phosphorous functional groups, sulfonic acids, unsaturated bonds with double or triple bonds, etc. Of the compounds and the liquid saturated hydrocarbon compound, at least one is preferably added. A plurality of these substances may be mixed and used. And, as As will be described later, when a magnetic field is applied to a mixture of a magnet material particle and an adhesive, that is, a composite material, the magnetic material is aligned to the magnetic material, and the magnetic field alignment treatment is performed while the mixture is heated while the adhesive component is softened.
經由作為混合於磁鐵材料粒子之接著劑,而使用滿足上述條件之接著劑之時,成為可使殘存於燒結後之稀土類永久磁鐵形成用燒結體內之碳量及氧量者。具體而言,可將燒結後殘存於磁鐵形成用燒結體內之碳量,作為2000ppm以下、更理想為1000ppm以下者。另外,可將燒結後殘存於磁鐵形成用燒結體內之氧量,作為5000ppm以下、更理想為2000ppm以下者。 When an adhesive that satisfies the above conditions is used as an adhesive mixed with the magnetic material particles, it becomes the amount of carbon and oxygen that can remain in the sintered body for forming a rare earth permanent magnet after sintering. Specifically, the amount of carbon remaining in the sintered body for magnet formation after sintering can be 2,000 ppm or less, and more preferably 1,000 ppm or less. The amount of oxygen remaining in the sintered body for magnet formation after sintering can be 5,000 ppm or less, and more preferably 2000 ppm or less.
接著劑之添加量係在形成漿料或加熱熔融之複合材料之情況,作為成形之結果所得到之成形體的厚度精確度則呈上升地,作為可適當地充填在磁鐵材料粒子間的空隙的量。例如,對於磁鐵材料粒子與接著劑之合計量而言之接著劑的比率則作為1wt%乃至40wt%、更理想係2wt%乃至30wt%、又更理想係3wt%乃至20wt%。 The addition amount of the adhesive is in the case of forming a slurry or heating and melting a composite material. The thickness accuracy of the formed body obtained as a result of the molding is increased, and it is suitable for filling the gaps between the particles of the magnet material appropriately. the amount. For example, for the total amount of the magnetic material particles and the adhesive, the ratio of the adhesive is 1 wt% to 40 wt%, more preferably 2 wt% to 30 wt%, and still more preferably 3 wt% to 20 wt%.
在以下的實施形態中,對於在一旦將複合材料成形為製品形狀以外之形狀的成形體的狀態,施加平行磁場而進行在磁場之磁鐵材料粒子的配向,圖5乃至圖9所示之實施形態的情況,之後,更加地,將該成形體作為所期望之製品形狀,接著經由進行燒結處理之時,作為例如圖5(a)所示之台形形狀之所期望的製品形狀之燒結磁鐵。特別是在以下的實施形態中,將磁鐵材料粒子與接著劑所成之混合物,即複合材料117,一旦成形為薄片形狀 之生坯成形體(以下,稱為「生坯薄片」)之後,作為為了配向處理之成形體形狀。對於將複合材料特別成形為薄片形狀之情況,係可採用經由加熱例如磁鐵材料粒子與接著劑之混合物的複合材料117之後,成形為薄片形狀之熱熔塗工,或經由將磁鐵材料粒子與接著劑之混合物的複合材料117放入成形鑄模而進行加熱及加壓的方法,或者經由將含有磁鐵材料粒子與接著劑與有機溶媒之漿料塗工於基材上而成形為薄片狀之漿料塗工等之成形者。 In the following embodiments, in the state where the composite material is once formed into a shape other than the product shape, a parallel magnetic field is applied to align the magnetic material particles in the magnetic field. The embodiments shown in FIG. 5 to FIG. 9 In the case of this, the molded body is further formed into a desired product shape, and then subjected to a sintering treatment, and is used as, for example, a sintered magnet having a desired product shape in a mesa shape as shown in FIG. 5 (a). In particular, in the following embodiment, the composite material 117, which is a mixture of the particles of the magnetic material and the adhesive, is once formed into a sheet shape. The green compact (hereinafter referred to as "green sheet") is used as the shape of the green compact for alignment processing. In the case where the composite material is specifically formed into a sheet shape, a hot melt coater formed by heating the composite material 117, such as a mixture of magnet material particles and an adhesive, into a sheet shape, or A method of heating and pressing the composite material 117 of a mixture of agents into a molding mold, or forming a sheet-like slurry by coating a slurry containing magnet material particles, an adhesive, and an organic solvent on a substrate. Formers such as painters.
在以下中,特別對於使用熱熔塗工之生坯薄片成形加以說明,但本發明係未加以限定於如此之特定的成型法者。例如,將複合材料117放入至成形用鑄模,加熱為室溫~300℃同時,經由以0.1乃至100MPa之壓力而進行加壓之時,進行成形亦可。在此情況,更具體而言,係可採取將加熱為進行軟化之溫度之複合材料117,加上射出壓而壓入充填於金屬模具而形成之方法者。 Hereinafter, a green sheet molding using a hot melt coater will be described in particular, but the present invention is not limited to such a specific molding method. For example, when the composite material 117 is put into a molding mold and heated to room temperature to 300 ° C., and it is pressurized at a pressure of 0.1 to 100 MPa, the molding may be performed. In this case, more specifically, it is possible to adopt a method in which the composite material 117 heated to a temperature at which softening is performed, and the injection pressure is added to the mold to be filled.
如既已之敘述,經由混合接著劑於以珠磨機116等而加以微粉碎之磁鐵材料粒子之時,製作磁鐵材料粒子與接著劑所成之黏土狀的混合物,即複合材料117。在此,作為接著劑係可如上述使用樹脂及分散劑的混合物者。例如,作為樹脂材料係使用未含有氧原子於構造中,且有解聚合性之聚合物所成之熱可塑性樹脂者為佳,另一方面,作為分散劑係具有醇,羧酸,酮,醚,酯,胺,亞胺,醯亞胺,醯胺,氰,磷系官能基,磺酸,具有二重結合或三重結合等之不飽和結合之化合物之中,至少添加一 個者為佳。另外,接著劑之添加量係如上述對於添加後之複合材料117之磁鐵材料粒子與接著劑之合計量而言之接著劑的比率則作為呈成為1wt%乃至40wt%、更理想係2wt%乃至30wt%、又更理想係3wt%乃至20wt%。 As described above, when the magnetic material particles that are finely pulverized by a bead mill 116 or the like are mixed with the adhesive, a clay-like mixture of the magnetic material particles and the adhesive is produced, that is, a composite material 117. Here, as the adhesive, a mixture of a resin and a dispersant can be used as described above. For example, as the resin material, it is preferable to use a thermoplastic resin made of a polymer that does not contain oxygen atoms in the structure and has depolymerization properties. On the other hand, it has alcohol, carboxylic acid, ketone, and ether as a dispersant. , Esters, amines, imines, amines, amines, cyanamides, cyanide, phosphorus-based functional groups, sulfonic acids, compounds with unsaturated bonds such as double or triple bonds, at least one Individual is better. In addition, the amount of the adhesive is the ratio of the adhesive to the total amount of the magnetic material particles of the composite material 117 and the adhesive as described above. The ratio is 1 wt% to 40 wt%, more preferably 2 wt% or even 30 wt%, and more preferably 3 wt% or even 20 wt%.
在此,分散劑的添加量係因應磁鐵材料粒子之粒子徑而決定者為佳,而加以推薦磁鐵材料粒子之粒子徑越小,增加添加量者。作為具體的添加量係對於磁鐵材料粒子100重量份而言,作為0.1重量份乃至10重量份、而更理想為0.3重量份乃至8重量份。對於添加量少之情況係分散效果為小,而有配向性降低之虞。另外,添加量過多之情況係有污染磁鐵材料粒子之虞。加以添加於磁鐵材料粒子之分散劑係附著於磁鐵材料粒子的表面,使磁鐵材料粒子分散而賦予黏土狀混合物之同時,在後述之磁場的配向處理中,呈補助磁鐵材料粒子之迴轉地產生作用。其結果,可在施加磁場時容易地進行配向,而將磁鐵粒子之磁化容易軸方向一致於略同一方向,即,提高配向度者。特別是當混合接著劑於磁鐵材料粒子時,成為呈存在有接著劑於粒子表面之故,磁場配向處理時之摩擦力則變高,因此而有粒子之配向性降低之虞,而添加分散劑情況的效果則更高。 Here, the amount of the dispersant added is preferably determined according to the particle diameter of the magnetic material particles, and it is recommended that the smaller the particle diameter of the magnetic material particles, the larger the amount of the additive be added. The specific addition amount is 0.1 parts by weight to 10 parts by weight, and more preferably 0.3 parts by weight or 8 parts by weight, for 100 parts by weight of the magnet material particles. In the case where the amount of addition is small, the dispersion effect is small, and the alignment may be reduced. In addition, when the amount of addition is excessive, there is a concern that the particles of the magnetic material may be contaminated. The dispersant added to the magnet material particles adheres to the surface of the magnet material particles, disperses the magnet material particles to give a clay-like mixture, and acts to assist the rotation of the magnet material particles in an alignment process of a magnetic field described later. . As a result, alignment can be easily performed when a magnetic field is applied, and the axis direction of the magnetization of the magnet particles can be made to be almost the same, that is, the alignment degree can be improved. In particular, when the adhesive is mixed with the particles of the magnet material, the presence of the adhesive on the surface of the particles causes the frictional force during magnetic field alignment treatment to increase. Therefore, the alignment of the particles may be reduced, and a dispersant is added. The effect is even higher.
磁鐵材料粒子與接著劑之混合係在由氮氣,Ar氣體,He氣體等之非活性氣體所成之環境基礎進行者為佳。磁鐵材料粒子與接著劑之混合係例如將磁鐵材料粒子與接著劑,各投入置攪拌機,經由以攪拌機而攪拌者而 進行。在此情況中,為了促進捏和性而進行加熱攪拌亦可。更且,磁鐵材料粒子與接著劑之混合亦在由氮氣,Ar氣體,He氣體等之非活性氣體所成之環境進行者為佳。另外,特別對於以濕式法而粉碎磁鐵材料粒子之情況,係未自使用於粉碎之溶媒而取出磁鐵粒子,而將接著劑添加於溶媒中進行捏和,之後使溶媒揮發,而作為呈得到複合材料117亦可。 The mixing of the magnetic material particles and the adhesive is preferably performed on an environmental basis made of an inert gas such as nitrogen, Ar gas, He gas, or the like. The mixing of the magnetic material particles and the adhesive is, for example, putting the magnetic material particles and the adhesive into a mixer, and by mixing them with a mixer, get on. In this case, heating and stirring may be performed in order to promote kneadability. Furthermore, it is preferable that the mixing of the magnet material particles and the adhesive is performed in an environment made of an inert gas such as nitrogen, Ar gas, and He gas. In addition, particularly in the case of pulverizing the magnetic material particles by the wet method, the magnetic particles are not taken out from the solvent used for pulverization, and an adhesive is added to the solvent to knead it, and then the solvent is volatilized to obtain the obtained product. The composite material 117 may be used.
接著,經由將複合材料117成形為薄片狀之時,做成前述之生坯薄片。對於採用熱熔塗工之情況,係經由加熱複合材料117而熔融該複合材料117,而作成具有流動性之狀態之後,塗工於支持基材118上。之後,經由放熱而使複合材料117凝固,於支持基材118上形成長尺薄片狀之生坯薄片119(參照圖10(d))。在此情況中,加熱熔融複合材料117時之溫度係經由所使用之接著劑之種類或量而有差異,但通常係作為50℃乃至300℃。但有必要做為較所使用之接著劑之流動開始溫度為高之溫度。然而,對於使用漿料塗工之情況,係於多量之溶媒中使磁鐵材料粒子與接著劑,及隨為任意,但助長配向之添加劑分散,使漿料塗工於支持基材118上。之後,經由進行乾燥而使溶媒揮發之時,形成長尺薄片狀之生坯薄片119於支持基材118上。 Then, when the composite material 117 is formed into a sheet shape, the aforementioned green sheet is formed. In the case where a hot-melt coater is used, the composite material 117 is melted by heating the composite material 117 to form a fluid state, and then the coater is applied to the support base material 118. Thereafter, the composite material 117 is solidified by exothermic heat, and a long thin sheet-like green sheet 119 is formed on the support substrate 118 (see FIG. 10 (d)). In this case, the temperature when the molten composite material 117 is heated varies depending on the type or amount of the adhesive used, but it is usually 50 ° C to 300 ° C. However, it is necessary to make the temperature higher than the flow start temperature of the used adhesive. However, in the case of using a slurry coater, the magnet material particles and the adhesive are dispersed in a large amount of a solvent, and any optional additive that promotes the orientation is dispersed, so that the slurry coater is coated on the supporting substrate 118. Thereafter, when the solvent is volatilized by drying, a long thin sheet-like green sheet 119 is formed on the support substrate 118.
在此,進行熔融之複合材料117的塗工方式係使用縫鑄模方式或滾壓方式等之對於層厚控制性優越之方式者為佳。特別是對於為了實現高厚度精確度,特別是 使用對於層厚控制性優越,即可塗工高精確度之厚度的層於基材表面之方式之模塗佈方式或點塗工方式者為佳。例如,在縫鑄模方式中,經由齒輪幫浦而壓送做成加熱而具有流動性之狀態的複合材料117於模頭,經由自模頭吐出而進行塗工。另外,在滾壓方式中,於加熱之2支滾輪的輥隙間隙,以控制複合材料117的量而送入,使滾輪旋轉同時,於支持基材118上,塗工由以滾輪的熱熔融之複合材料117。作為支持基材118係例如使用聚矽氧處理聚酯膜者為佳。更且,經由使用消泡劑,或進行加熱真空脫泡之時,呈未殘留氣泡於加以塗工而所展開之複合材料117的層中地,充分地進行脫泡處理者為佳。或者,並非塗工於支持基材118上,而經由壓出成型或射出成形而將熔融之複合材料117成型為薄片狀之同時,壓出於於支持基材118上之時,亦可於支持基材118上成形生坯薄片119者。 Here, the coating method for melting the composite material 117 is preferably a method that is superior in layer thickness control, such as a seam casting method or a rolling method. Especially for achieving high thickness accuracy, especially It is better to use a die coating method or a spot coating method in which the layer thickness is excellent, and a layer with a high accuracy can be coated on the substrate surface. For example, in the seam casting method, the composite material 117 which is heated and has fluidity is pressure-fed via a gear pump to a die, and is sprayed out from the die to perform coating. In addition, in the rolling method, the nip gap of the two heated rollers is fed in to control the amount of the composite material 117, and the roller is rotated while the coating material is melted by the heat of the roller on the supporting substrate 118 The composite material 117. As the supporting substrate 118, for example, a silicone-treated polyester film is preferably used. Furthermore, when using a defoaming agent or heating and vacuum defoaming, it is preferable to perform a defoaming treatment sufficiently without leaving bubbles in the layer of the composite material 117 that is spread by coating. Alternatively, instead of coating on the supporting substrate 118, the molten composite material 117 is formed into a sheet shape by extrusion molding or injection molding, and at the same time it is pressed onto the supporting substrate 118, A green sheet 119 is formed on the base material 118.
在圖10所示之實施形態中,作為呈使用縫鑄模120而進行複合材料117之塗工。在經由此縫鑄模方式之生坯薄片119的形成工程中,實測塗工後之生坯薄片119的薄片厚度,經由依據此實測值之反饋控制之時,調節縫鑄模120與支持基材118之間的輥隙間隙者為佳。在此情況中,使供給至縫鑄模120之流動性複合材料117的量之變動極力降低者,例如抑制為±0.1%以下之變動,更且,亦使塗工速度的變動極力降低者,例如抑制為±0.1%以下之變動者為佳。經由如此之控制,可使生坯薄片119 厚度精確度提升者。然而,所形成之生坯薄片119之厚度精確度係對於例如1mm之設計值而言,作為±10%以內、更理想係作為±3%以內、又更理想係作為±1%以內者。在滾壓方式中,由同樣地依據實測值而反饋抑制者壓延條件者,可抑制加以轉印於支持基材118之複合材料117的膜厚者。 In the embodiment shown in FIG. 10, the coating of the composite material 117 is performed using a seam mold 120. In the process of forming the green sheet 119 through the seam casting method, the thickness of the green sheet 119 after the coating process is actually measured, and when the feedback control based on the measured value is adjusted, the thickness of the seam mold 120 and the supporting substrate 118 is adjusted. The nip gap is better. In this case, those who minimize the variation in the amount of the fluid composite material 117 supplied to the seam casting mold 120, for example, suppress the variation to ± 0.1% or less, and also minimize the variation in the coating speed, such as It is better to suppress the change below ± 0.1%. With such control, the green sheet 119 can be made Improved thickness accuracy. However, the thickness accuracy of the formed green sheet 119 is, for example, a design value of 1 mm, within ± 10%, more preferably within ± 3%, and more preferably within ± 1%. In the rolling method, a person who feeds back the suppressor's rolling condition based on the actual measured value similarly can suppress the thickness of the composite material 117 to be transferred to the supporting substrate 118.
生坯薄片119之厚度係設定為0.05mm乃至20mm之範圍者為佳。當將厚度作為較0.05mm為薄時,為了達成必要之磁鐵厚度,因必須做為多層積之故而成為生產性降低者。 The thickness of the green sheet 119 is preferably set to a range of 0.05 mm to 20 mm. When the thickness is made thinner than 0.05 mm, in order to achieve the necessary thickness of the magnet, it is necessary to make it a multilayer product and reduce productivity.
接著,自經由上述熱熔塗工而加以形成於支持基材118上之生坯薄片119,作成切出為對應於所期望之磁鐵尺寸之尺寸的加工用薄片123。此加工用薄片123係在圖4所示之實施形態中,對應於所期望之磁鐵的形狀者,但對於圖5乃至圖8所示之實施形態的情況係對應於第1成形體者,其形狀係與所期望之磁鐵的形狀不同。當詳細敘述時,在圖5乃至圖8所示之實施形態中,該第1成形體之加工用薄片123係加以施加平行磁場於該加工用薄片123,而含於該加工用薄片123之磁鐵材料粒子的磁化容易軸則呈成為平行地加以配向,之後,使該加工用薄片123變形而作為所期望之磁鐵形狀時,在具有其所期望之形狀的磁鐵中,加以成形為呈得到所期望之磁化容易軸配向之形狀。 Next, from the green sheet 119 formed on the support base material 118 through the above-mentioned hot-melt coating process, a processing sheet 123 cut out to a size corresponding to a desired magnet size is prepared. This processing sheet 123 corresponds to the shape of the desired magnet in the embodiment shown in FIG. 4. However, in the case of the embodiment shown in FIGS. 5 to 8, it corresponds to the first molded body. The shape is different from the shape of the desired magnet. When described in detail, in the embodiment shown in FIG. 5 to FIG. 8, the processing sheet 123 of the first formed body is applied with a parallel magnetic field to the processing sheet 123, and the magnets contained in the processing sheet 123 are included. The easy-to-magnetize axes of the material particles are aligned in parallel, and then, when the processing sheet 123 is deformed to have a desired magnet shape, the magnet having the desired shape is formed into a desired shape. Its magnetization is easy to align with the shape of the shaft.
在圖4所示之實施形態中,自生坯薄片119 所切出之加工用薄片係作為圖4所示之長方體形狀,所切出之實際尺寸係估計在後述之燒結工程之尺寸的縮小,而訂定為呈在燒結工程後得到特定之磁鐵尺寸。對此,在圖5乃至圖9所示之實施形態中,第1成形體之加工用薄片123係如圖11(a)所示,具有對應於在成為最終製品之台形剖面之稀土類永久磁鐵形成用燒結體1之中央範圍6的寬度方向長度之直線狀範圍6a,和連續於該直線狀範圍6a兩端之圓弧狀範圍7a、8a之剖面形狀。此加工用薄片123係於圖的紙面具有直角之方向的長度尺寸,剖面的尺寸及寬度尺寸係估計在後述之燒結工程的尺寸之縮小,而訂定為呈在燒結工程後得到特定之磁鐵尺寸。 In the embodiment shown in FIG. 4, the self-forming green sheet 119 The cut sheet for processing is a rectangular parallelepiped shape as shown in FIG. 4. The actual size of the cut sheet is estimated to be a reduction in the size of the sintering process described later, and is set to a specific magnet size obtained after the sintering process. In contrast, in the embodiment shown in FIG. 5 to FIG. 9, as shown in FIG. 11 (a), the processing sheet 123 of the first formed body has a rare-earth permanent magnet corresponding to the mesa-shaped cross section of the final product. The cross-sectional shape of the linear range 6a of the width direction length of the central range 6 of the sintered compact 1 for formation and the arc-shaped ranges 7a and 8a continuous at both ends of the linear range 6a. The sheet 123 for processing is based on the length dimension of the paper surface in the right angle direction. The size of the cross section and the width dimension are estimated to be reduced in the sintering process described later, and are set to have a specific magnet size obtained after the sintering process. .
對於圖4所示之實施形態之情況,係對於自生坯薄片119所切出之加工用薄片而言,自下邊3之外側對於該下邊3而言,於直角方向,加以施加平行外部磁場。經由此平行外部磁場之施加,存在於加工用薄片內之磁鐵材料粒子的磁化容易軸係如在圖4以箭頭9所示地,配向於直角於下邊3之方向。此配向係平行配向。如上述構成生坯薄片119,經由如後述加熱而進行磁場施加之時,成為可以高精確度使磁化容易軸作配向者。 In the case of the embodiment shown in FIG. 4, for the processing sheet cut out from the green sheet 119, a parallel external magnetic field is applied in a right-angle direction from the outer side of the lower side 3 to the lower side 3. As a result of the application of a parallel external magnetic field, the axis of magnetization of the magnetic material particles existing in the processing sheet is easily aligned as indicated by arrow 9 in FIG. This alignment is aligned in parallel. When the green sheet 119 is configured as described above, and when a magnetic field is applied by heating as described later, it becomes a person who can make the magnetization easy axis alignment with high accuracy.
對於圖11(a)所示之加工用薄片123而言,亦加以施加平行磁場121於成為直角於直線狀範圍6a表面之方向。經由此磁場施加之時,含於加工用薄片123之磁鐵材料粒子之磁化容易軸則如在圖11(a)以箭頭122所示,於磁場的方向,即厚度方向,平行地加以配向。 In the processing sheet 123 shown in FIG. 11 (a), a parallel magnetic field 121 is also applied in a direction that becomes a right angle on the surface of the linear range 6a. When the magnetic field is applied, the easy magnetization axis of the magnetic material particles contained in the processing sheet 123 is aligned in parallel with the direction of the magnetic field, that is, the thickness direction, as shown by arrow 122 in FIG. 11 (a).
在此工程中,在圖4所示之實施形態及圖5乃至圖9所示之實施形態之任一中,加工用薄片係加以收容於具有對應於該加工用薄片之形狀的模孔之磁場施加用鑄模內(未圖示),經由進行加熱而使含於加工用薄片之接著劑軟化。經由此等,磁鐵材料粒子係成為呈可在接著劑內迴轉,而可使其磁化容易軸,以高精確度而配向於沿著平行磁場121之方向者。 In this process, in any of the embodiments shown in FIG. 4 and the embodiments shown in FIGS. 5 to 9, the processing sheet is stored in a magnetic field having a die hole corresponding to the shape of the processing sheet. In the application mold (not shown), the adhesive contained in the processing sheet is softened by heating. As a result, the particles of the magnet material can be rotated in the adhesive, and can be easily magnetized, and can be aligned in a direction along the parallel magnetic field 121 with high accuracy.
在此,為了加熱加工用薄片之溫度及時間係經由所使用之接著劑的種類及量而有不同,但作為40乃至250℃,0.1乃至60分。無論如何,對於為了使加工用薄片內之接著劑軟化,加熱溫度係必須做為所使用之接著劑之玻璃轉移點或流動開始溫度以上之溫度。作為為了加熱加工用薄片之手段係例如有經由熱板之加熱,或將如矽油之熱媒體使用於熱源之方式。在磁場施加之磁場的強度係可作為5000[Oe]~150000[Oe]、而理想係作為10000[Oe]~120000[Oe]者。其結果,含於加工用薄片之磁鐵材料粒子的結晶之磁化容易軸則如在圖4以符號9所示,或在圖11(a)以符號122所示,於沿著平行磁場121之方向,平行地加以配向。在此磁場施加工程中,作為對於複數個之加工用薄片而言同時地施加磁場之構成者。為此,如使用具有複數個之模孔的鑄模,或者排列複數個的鑄模,同時施加平行磁場121即可。施加磁場於加工用薄片之工程係與加熱工程同時地進行亦可,而在進行加熱工程之後,於加工用薄片內之接著劑產生凝固之前進行亦 可。 Here, the temperature and time of the sheet for heating processing vary depending on the type and amount of the adhesive used, but they are 40 to 250 ° C and 0.1 to 60 minutes. In any case, in order to soften the adhesive in the processing sheet, the heating temperature must be a temperature above the glass transition point or flow start temperature of the adhesive used. The means for heating the sheet for processing are, for example, a method of heating via a hot plate, or a method of using a heat medium such as silicone oil as a heat source. The intensity of the magnetic field applied to the magnetic field can be 5,000 [Oe] ~ 150000 [Oe], and the ideal system can be 10000 [Oe] ~ 120000 [Oe]. As a result, the axis of easy magnetization of crystals of the magnetic material particles contained in the processing sheet is indicated by the symbol 9 in FIG. 4 or the symbol 122 in FIG. 11 (a) in the direction along the parallel magnetic field 121 , Aligned in parallel. In this magnetic field application process, it is a component which applies a magnetic field to several processing sheets simultaneously. For this purpose, for example, a mold having a plurality of mold holes may be used, or a plurality of molds may be arranged while applying a parallel magnetic field 121 at the same time. The process of applying a magnetic field to the processing sheet may be performed concurrently with the heating process. After the heating process is performed, the process may be performed before the adhesive in the processing sheet is solidified. can.
接著,對於圖4所示之實施形態之情況,加以施加外部磁場而加以平行配向磁鐵材料粒子之磁化容易軸的加工用薄片係直接加以送入至後述之鍛燒工程及燒結工程。對此,對於圖5乃至圖9之實施形態之情況,係將經由圖11(a)所示之磁場施加工程,如以箭頭122所示地加以平行配向磁鐵材料粒子之磁化容易軸的加工用薄片123,自磁場施加用的鑄模取出,轉移至具有圖11(b)(c)所示之細長長度方向尺寸之台形模孔124之最終成形用鑄模126內,經由具有對應於該模孔124之凸型形狀之公鑄模127,在模孔124內按壓該加工用薄片123,使加工用薄片123之兩端部的圓弧狀範圍7a、8a,呈連續為直線狀於中央的直線狀範圍6a地加以變形,成形於圖11(b)所示之燒結處理用薄片125。此燒結處理用薄片125則對應於第2成形體。 Next, in the case of the embodiment shown in FIG. 4, an external magnetic field is applied to parallelly align the magnetization particles of the magnetic material particles, and the processing sheet is directly fed to a calcination process and a sintering process described later. In this regard, in the case of the embodiment shown in FIG. 5 to FIG. 9, the magnetic field application process shown in FIG. 11 (a) is used to process the axis of easy magnetization of the magnet material particles in parallel as shown by arrow 122 as shown by arrow 122. The sheet 123 is taken out from the mold for applying a magnetic field, and transferred to the final molding mold 126 having a table-shaped mold hole 124 having a slender length dimension as shown in FIG. 11 (b) (c), and has a shape corresponding to the mold hole 124. The male mold 127 with a convex shape presses the processing sheet 123 in the die hole 124, so that the arc-shaped ranges 7a and 8a at both ends of the processing sheet 123 are continuous and linear in the center of the linear range. It is deformed at 6a and formed into a sintering treatment sheet 125 as shown in FIG. 11 (b). The sintering treatment sheet 125 corresponds to a second formed body.
經由此成形,加工用薄片123係兩端的圓弧狀範圍7a、8a則對於中央的直線狀範圍6a而言成為連續為直線狀之形狀,同時,對於兩端部係加以形成傾斜面125a,125b,而構成細長的台形狀。在經由此成形工程而加以形成之燒結處理用薄片125中,含於中央的直線狀範圍6a之磁鐵材料粒子之磁化容易軸係加以維持為平行地配向於厚度方向之平行配向狀態,但在兩端的範圍7a、8a中,朝上地凸的形狀則加以變形為連續於中央之直線狀範圍之直線形狀的結果,如圖11(b)所示,磁化容易軸係成 為聚集於在各對應之範圍的上邊之配向。 By this forming, the arc-shaped ranges 7a, 8a at both ends of the processing sheet 123 series are continuous linear shapes for the central linear range 6a, and inclined surfaces 125a, 125b are formed at both ends. , And form an elongated mesa shape. In the sintering processing sheet 125 formed through this forming process, the magnetization of the magnet material particles in the linear region 6a in the center is easily maintained, and the axis system is maintained in a parallel alignment state parallel to the thickness direction. In the end ranges 7a and 8a, the upwardly convex shape is deformed into a linear shape that is continuous with the linear range in the center. As shown in Fig. 11 (b), the magnetization is easy to form a shaft. It is an alignment gathered on each corresponding range.
如此作為而加以配向磁鐵材料粒子之磁化容易軸之配向後的燒結處理用薄片125係移送至鍛燒工程。在以下的說明中,在圖4所示之實施形態,亦包含歷經磁場配向工程而加以移送至鍛燒工程之加工法薄片,將進行鍛燒處理及燒結處理之薄片,稱為「燒結處理用薄片125」。在圖4所示之實施形態及圖5乃至圖9所示之實施形態之任一中,在鍛燒工程之鍛燒處理係在大氣壓,或者較大氣壓為高之壓力或低的壓力,例如,調節為0.1MPa乃至70MPa、理想係1.0Pa乃至1.0MPa之非氧化性環境,經由作為以接著劑分解溫度,進行數小時乃至數十小時,例如5小時保持而進行鍛燒處理。在此處理中,加以推薦使用氫環境或氫與非活性氣體的混合氣體環境者。對於在氫環境之基礎進行鍛燒處理之情況,鍛燒中之氫的供給量係例如作為5L/min。經由進行鍛燒處理之時,將含於接著劑之有機化合物,經由解聚合反應,其他的反應而分解成單體,而成為可使其噴散而除去者。即,成為進行使殘存於燒結處理用薄片125之碳的量降低之處理的脫碳處理者。另外,鍛燒處理係以將殘存於燒結處理用薄片125內之碳的量作為2000ppm以下、更理想係1000ppm以下之條件進行者為佳。經由此,成為可以之後的燒結處理而緻密地使燒結處理用薄片125全體燒結者,而成為可抑制殘留磁通密度及矯頑磁力降低者。然而,對於將進行上述之鍛燒處理時之加壓條件,作為較大氣壓為 高之壓力之情況,壓力係作為15MPa以下者為佳。在此,加壓條件係如作為較大氣壓為高之壓力,更具體而言係0.2MPa以上時,特別是可期待殘存碳量減輕之效果。 In this way, the sintering processing sheet 125 after the alignment of the easy-to-magnetize axis of the magnet material particles is transferred to the calcination process. In the following description, the embodiment shown in FIG. 4 also includes a processing method sheet which is transferred to a calcination process after undergoing magnetic field alignment process. The sheet subjected to the calcination process and the sintering process is referred to as "for sintering process" Sheet 125 ". In any of the embodiment shown in FIG. 4 and the embodiments shown in FIGS. 5 to 9, the calcination process in the calcination process is at atmospheric pressure, or the atmospheric pressure is high or low, for example, The non-oxidizing environment adjusted to 0.1 MPa to 70 MPa, ideally 1.0 Pa to 1.0 MPa, is subjected to a calcination treatment for several hours to several tens of hours, for example, 5 hours, by maintaining the decomposition temperature at the adhesive. In this process, it is recommended to use a hydrogen environment or a mixed gas environment of hydrogen and an inert gas. When the calcination process is performed on the basis of a hydrogen environment, the supply amount of hydrogen during the calcination is, for example, 5 L / min. When the calcination treatment is performed, the organic compound contained in the adhesive is decomposed into monomers through a depolymerization reaction and other reactions, and it can be dispersed and removed. That is, it becomes a decarburization processer who performs the process which reduces the amount of carbon which remains in the sintering process sheet 125. The calcination treatment is preferably performed under the condition that the amount of carbon remaining in the sintering treatment sheet 125 is 2000 ppm or less, and more preferably 1000 ppm or less. As a result, a person who can sinter the entire sintering treatment sheet 125 densely after the sintering treatment becomes a person who can suppress the reduction of the residual magnetic flux density and the coercive force. However, as for the pressure conditions when the above-mentioned calcination treatment is performed, the atmospheric pressure is In the case of high pressure, the pressure is preferably 15 MPa or less. Here, when the pressurization condition is a pressure that is high as the atmospheric pressure, and more specifically 0.2 MPa or more, the effect of reducing the amount of residual carbon is particularly expected.
接著劑分解溫度係經由接著劑之種類而有不同,但鍛燒處理之溫度係如作為200℃乃至900℃、更理想係300℃乃至500℃、例如450℃即可。 The decomposition temperature of the adhesive varies depending on the type of the adhesive, but the temperature of the calcination treatment may be 200 ° C or 900 ° C, more preferably 300 ° C or 500 ° C, for example, 450 ° C.
在上述之鍛燒處理中,與一般的稀土類磁鐵的燒結處理做比較,縮小昇溫速度者為佳。具體而言,經由將昇溫速度作為2℃/min以下、例如1.5℃/min之時,可得到理想的結果者。隨之,對於進行鍛燒處理之情況,係如圖12所示,以2℃/min以下之特定的昇溫速度進行昇溫,到達至預先所設定之設定溫度,即,接著劑分解溫度之後,經由以該設定溫度進行數小時乃至數十小時保持而進行鍛燒處理。如此,經由在鍛燒處理中縮小昇溫速度之時,因並非急遽地除去燒結處理用薄片125內的碳者,而成為呈階段性地加以除去之故,成為可至充分的位準為止使殘量碳減少,而使燒結後之永久磁鐵形成用燒結體的密度上昇者。即,經由使殘留碳量減少,而可使永久磁鐵中的空隙減少者。如上述,如使昇溫速度作為2℃/min程度時,可將燒結後之永久磁鐵形成用燒結體的密度作為98%以上、例如7.40g/cm3以上者,可期待在磁化後之磁鐵中達成高磁鐵特性者。 In the above-mentioned calcination treatment, it is better to reduce the temperature increase rate as compared with the sintering treatment of general rare earth magnets. Specifically, when a temperature increase rate is set to 2 ° C / min or less, for example, 1.5 ° C / min, a desired result can be obtained. Accordingly, in the case of the calcination process, as shown in FIG. 12, the temperature is raised at a specific heating rate of 2 ° C./min or less, and reaches a preset temperature, that is, the temperature at which the adhesive decomposes, This set temperature is maintained for several hours or even tens of hours to perform a calcination treatment. As described above, when the heating rate is reduced during the calcination process, the carbon in the sintering treatment sheet 125 is not removed in a hurry, but is removed stepwise, so that it can be left to a sufficient level. The amount of carbon decreases and the density of the sintered body for forming a permanent magnet after sintering increases. That is, by reducing the amount of residual carbon, the gap in the permanent magnet can be reduced. As described above, if the heating rate is about 2 ° C./min, the density of the sintered body for forming a permanent magnet after sintering can be 98% or more, for example, 7.40 g / cm 3 or more, and it can be expected to be used in magnetized magnets. Achieving high magnet characteristics.
接著,進行燒結經由鍛燒處理所鍛燒之燒結處理用薄片125之燒結處理。作為燒結處理係亦可使用在 真空中之無加壓燒結法者,在此所說明之實施形態中,係採用將燒結處理用薄片125,在一軸加壓於垂直於圖4或圖11之紙面的方向之燒結處理用薄片125之長度方向的狀態進行燒結之一軸加壓燒結法者為佳。在此方法中,對於圖4所示之實施形態之情況,於具有如圖4所示之長方形模孔之燒結用鑄模(未圖示)內,對於圖5乃至圖9所示之實施形態之情況,係於具有與在圖11(b)以符號「124」所示之構成相同台形形狀剖面的模孔之燒結用鑄模(未圖示)內,各裝填燒結處理用薄片125,封閉鑄模,加壓於垂直於圖4或圖11之紙面的方向之燒結處理用薄片125之長度方向同時,進行燒結。對於圖5乃至圖9所示之實施形態之情況,當特別詳細敘述時,加以使用將自燒結處理用薄片125所形成之稀土類永久磁鐵,收容於圖6所示之磁鐵插入用槽24時,於成為與轉子鐵芯21之軸方向同方向之方向,在將燒結處理用薄片125加壓於長度方向之狀態進行燒結之一軸加壓燒結。在任一之實施形態中,作為加壓燒結技術係例如,採用熱壓燒結,熱均壓(HIP)燒結,超高壓合成燒結,氣體加壓燒結,放電電漿(SPS)燒結等,公知之技術任一亦可。特別是使用可加壓於一軸方向之熱壓燒結者為佳。然而,對於以熱壓燒結進行燒結之情況,係將加壓壓力,作為例如0.01MPa~100MPa,在數Pa以下之真空環境,至900℃~1000℃、例如940℃為止,以3℃/分~30℃/分、例如10℃/分之昇溫速度,使溫度上昇,之後,加壓方向之每10秒之變化率則至成為0 為止而保持者為佳。此保持時間係通常為5分鐘程度。接著進行冷卻,再次昇溫至300℃~1000℃進行2小時,保持為其溫度之熱處理。如此之燒結處理之結果,自燒結處理用薄片125,加以製造本發明之稀土類永久磁鐵形成用燒結體1。如此,如根據在將燒結處理用薄片125加壓於長度方向之狀態進行燒結之一軸加壓燒結法,可抑制賦予於燒結處理用薄片125內之磁鐵材料粒子的磁化容易軸之配向紛亂者。在此燒結階段,燒結處理用薄片125內之樹脂材料係幾乎所有蒸散,而殘存樹脂量係即使存在亦成為非常微量的構成。 Next, a sintering process is performed to sinter the sintering processing sheet 125 which has been calcined through the calcination process. Can also be used as a sintering system In the vacuum-free sintering method, in the embodiment described here, the sintering processing sheet 125 is used to press the sintering processing sheet 125 on one axis in a direction perpendicular to the paper surface of FIG. 4 or FIG. 11. It is preferable to perform uniaxial pressure sintering in the state of the longitudinal direction. In this method, in the case of the embodiment shown in FIG. 4, in a sintering mold (not shown) having a rectangular die hole as shown in FIG. 4, for the embodiment shown in FIGS. 5 to 9 In this case, the sintering molds (not shown) each having a mold hole having the same mesa-shaped cross section as shown in FIG. 11 (b) with the symbol "124" are filled with sintering treatment sheets 125 and the mold is closed. The longitudinal direction of the sintering processing sheet 125 which is pressed in a direction perpendicular to the paper surface of FIG. 4 or FIG. 11 is simultaneously sintered. Regarding the case of the embodiment shown in FIG. 5 to FIG. 9, when a detailed description is given, a rare-earth permanent magnet formed by the self-sintering processing sheet 125 is used and stored in the magnet insertion groove 24 shown in FIG. 6. The sintering is performed in a direction that is the same direction as the axial direction of the rotor core 21, and the sintering treatment sheet 125 is pressed in the longitudinal direction to perform sintering. In any of the embodiments, as the pressure sintering technology, for example, a known technique such as hot-pressing sintering, hot-pressurization (HIP) sintering, ultra-high pressure synthetic sintering, gas pressure sintering, or discharge plasma (SPS) sintering is used. Either can be used. Particularly, it is preferable to use hot-pressing sintering that can be pressed in one axis direction. However, in the case of sintering by hot-press sintering, the pressurizing pressure is, for example, 0.01 MPa to 100 MPa, a vacuum environment of several Pa or less, to 900 ° C. to 1000 ° C., for example, 940 ° C., at 3 ° C./min. ~ 30 ° C / min, for example, a temperature increase rate of 10 ° C / min, to increase the temperature, and thereafter, the rate of change every 10 seconds in the direction of pressure becomes 0 It is better to keep it so far. This holding time is usually about 5 minutes. Then, it was cooled, and it heated up to 300 degreeC-1000 degreeC again for 2 hours, and maintained the heat processing of its temperature. As a result of the sintering process, the sintered body 1 for forming a rare earth permanent magnet of the present invention is produced from the sintering process sheet 125. As described above, if the uniaxial pressure sintering method is performed by sintering the sintering processing sheet 125 in the longitudinal direction, it is possible to suppress the misalignment of the axis of the magnet material particles easily imparted to the sintering processing sheet 125. At this sintering stage, almost all the resin material in the sintering processing sheet 125 is evapotranspiration, and the amount of residual resin is a very small amount structure even if it exists.
然而,經由燒結處理,加以蒸散樹脂狀態之前述磁鐵材料粒子則相互燒結而形成燒結體。典型來說,經由燒結處理,在前述磁鐵材料粒子中,稀土類濃度高之稀土類富有相則產生熔融,埋入存在於前述磁鐵材料粒子間之空隙同時,形成具有R2Fe14B組成(R係含有釔之稀土類元素)的主相與稀土類富有相所成之緻密的燒結體。 However, the sintered resin particles are sintered with each other to form a sintered body. Typically, after the sintering process, among the magnet material particles, the rare earth rich phase with a high rare earth concentration is melted, and the voids existing between the magnet material particles are buried, and at the same time, a R2Fe14B composition is formed (the R system contains yttrium) The rare earth element) is a dense sintered body formed by the rare earth-rich phase.
圖5乃至圖9所示之實施形態之情況,稀土類永久磁鐵形成用燒結體1係於圖2所示之轉子鐵芯21的磁鐵插入用槽24內,在未磁化之狀態加以插入。之後,對於加以插入至槽24內之稀土類永久磁鐵形成用燒結體1而言,沿著含於其中之磁鐵材料粒子之磁化容易軸,即C軸進行磁化。當具體敘述時,對於加以插入至轉子鐵芯21之複數的槽24之複數之稀土類永久磁鐵形成用燒結體1而言,沿著轉子鐵芯21的周方向,呈加以交互 地配置N極與S極地進行磁化。其結果,成為可製造永久磁鐵1者。然而,對於稀土類永久磁鐵形成用燒結體1之磁化,係例如亦可使用磁化線圈,磁化軛,電容式磁化電源裝置等之公知手段之任一。另外,稀土類永久磁鐵形成用燒結體1係作為呈在插入至槽24之前進行磁化,作為稀土類永久磁鐵,將此所磁化之磁鐵插入至槽24亦可。 In the case of the embodiment shown in FIGS. 5 to 9, the sintered body 1 for forming a rare-earth permanent magnet is inserted into the magnet insertion groove 24 of the rotor core 21 shown in FIG. 2 and is inserted in a non-magnetized state. Thereafter, the rare earth permanent magnet forming sintered body 1 inserted into the groove 24 is magnetized along the easy-to-magnetize axis of the magnetic material particles contained therein, that is, the C axis. Specifically, the sintered bodies 1 for forming a plurality of rare-earth permanent magnets that are inserted into the plurality of slots 24 of the rotor core 21 interact with each other along the circumferential direction of the rotor core 21. The ground is arranged with N pole and S pole for magnetization. As a result, a permanent magnet 1 can be manufactured. However, as for the magnetization of the sintered body 1 for forming a rare earth-based permanent magnet, any one of known means such as a magnetized coil, a magnetized yoke, or a capacitive magnetized power supply device can be used. The sintered body 1 for forming a rare-earth permanent magnet may be magnetized before being inserted into the groove 24. As the rare-earth permanent magnet, the magnetized magnet may be inserted into the groove 24.
如根據上述說明之稀土類永久磁鐵形成用燒結體之製造方法,形成混合磁鐵材料粒子與接著劑之混合物的複合材料,經由加熱至超過複合材料之軟化點之溫度同時,自外部施加平行磁場於加工用薄片之時,成為可以高精確度而使磁化容易軸配向於所期望之方向者。因此,亦可防止配向方向之不均,而可提高磁鐵的性能者。更且,因成形與接著劑之混合物之故,與使用壓粉成形等之情況做比較,未有在配向後磁鐵粒子產生迴轉者,而成為可更一層提升配向度者。如根據對於磁鐵材料粒子與接著劑之混合物的複合材料而言施加磁場,進行配向的方法時,可適宜增加通過為了磁場形成之電流的卷繞線之卷繞數之故,因可提高確保進行磁場配向時之磁場強度,且可在靜磁場施以長時間之磁場施加之故,成為可實現不均為少之高配向度者。並且,如圖5乃至圖9所示之實施形態,如作為呈在配向後補正配向方向時,成為可以高配向而確保不均為少之高配向度者。 According to the method for manufacturing a sintered body for forming a rare earth permanent magnet as described above, a composite material including a mixture of magnetic material particles and an adhesive is formed, and a parallel magnetic field is applied from the outside by heating to a temperature exceeding the softening point of the composite material. When processing a sheet, it becomes possible to align the axis of magnetization easily in a desired direction with high accuracy. Therefore, it is possible to prevent unevenness in the alignment direction and improve the performance of the magnet. In addition, because of the mixture of molding and adhesive, compared with the case of using powder molding, there is no one who rotates the magnet particles after the alignment, and it becomes a person who can improve the alignment. For example, when a magnetic field is applied to a composite material of a mixture of magnetic material particles and an adhesive, and the alignment method is performed, the number of windings of the winding wire through a current generated for the magnetic field can be appropriately increased. The strength of the magnetic field during magnetic field alignment and the application of a long-term magnetic field to the static magnetic field make it possible to achieve a high degree of alignment with few variations. In addition, as shown in FIG. 5 to FIG. 9, when the alignment direction is corrected after the alignment, it becomes a person who can achieve high alignment and ensure a high alignment degree with less unevenness.
如此,可實現不均為少之高配向度之情況係 連結於經由燒結之收縮的不均之降低。隨之,可確保燒結後之製品形狀的均一性者。其結果,加以減輕對於燒結後之外形加工的負擔,而可期待大大提升量產的安定性者。另外,在磁場配向之工程中,對於磁鐵粒子與接著劑之混合物的複合材料而言施加磁場之同時,對於圖5乃至圖9所示之實施形態的情況,係經由將磁場之所施加的複合材料變形成最終形狀之成形體而操作磁化容易軸之方向,加以進行磁場配向。隨之,經由變形一旦加以磁場配向之複合材料之時,成為可補正配向方向,呈朝向減磁對象範圍而使磁化容易軸適當地聚集地進行配向者。其結果,對於即使賦予複雜之配向,亦成為可以高精確度而達成不均為少之配向者。 In this way, it is possible to achieve a high degree of alignment with few variations. The reduction in unevenness associated with shrinkage through sintering. Accordingly, uniformity of the shape of the sintered product can be ensured. As a result, the burden on the external shape processing after sintering is reduced, and the stability of mass production can be expected to be greatly improved. In addition, in the process of magnetic field alignment, when a magnetic field is applied to a composite material of a mixture of magnet particles and an adhesive, in the case of the embodiment shown in FIG. 5 to FIG. The material is transformed into a final shape of the molded body, and the direction of the axis of easy magnetization is manipulated to perform magnetic field alignment. Accordingly, when the composite material is once subjected to magnetic field alignment through deformation, it becomes an alignment direction that can be corrected, and is oriented toward the range of the object to be demagnetized so that the axis of easy magnetization is appropriately gathered. As a result, even if a complicated alignment is provided, it becomes an alignment that can achieve a high degree of accuracy and achieve a small number of variations.
以下,說明本發明之方法的實施例。 Examples of the method of the present invention will be described below.
在以下記載之實施例中,使用下述表1所示之製造號碼的材料。 In the examples described below, materials having the manufacturing numbers shown in Table 1 below were used.
作為實施例1,由以下敘述的步驟而作成圖4所示之形狀的稀土類磁鐵形成用燒結體。 As Example 1, a sintered body for forming a rare-earth magnet having a shape shown in FIG. 4 was prepared by the steps described below.
將經由片鑄造法而加以得到之合金組成A(Nd:27.00wt%、Pr:4.60wt%、B:1.00wt%、Ga:0.10wt%、Nb:0.2wt%、Co:2.0wt%、Cu:0.10wt%、殘留部Fe、含有其他不可避不純物)之合金,以室溫吸著氫,以0.85MPa進行1日保持。之後,以液化Ar進行冷卻同時,經由以0.2MPa進行1日保持之時,進行氫粉碎。 The alloy composition A (Nd: 27.00wt%, Pr: 4.60wt%, B: 1.00wt%, Ga: 0.10wt%, Nb: 0.2wt%, Co: 2.0wt%, Cu) : 0.10% by weight, Fe in the residual portion, and other unavoidable impurities), hydrogen is absorbed at room temperature, and maintained at 0.85 MPa for one day. Then, while cooling with liquefied Ar, and pulverizing by hydrogen while maintaining at 0.2 MPa for one day.
對於加以粗粉碎之合金粗粉100重量份而言,混合己酸甲基1重量份之後,經由氦噴射磨粉碎裝置(裝置名:PJM-80HE、NPK製)而進行粉碎。粉碎之合金粒子的捕集係經由循環方式而進行分離回收,除去超微粉。將粉碎時之供給速度作為1kg/h,He氣體的導入壓力係0.6MPa、流量1.3m3/min、氧濃度1ppm以下、露點-75℃以下。所得到之磁鐵材料粒子的平均粒徑係1.1μm。 100 parts by weight of the coarsely pulverized alloy coarse powder was mixed with 1 part by weight of methyl hexanoate, and then pulverized by a helium jet mill pulverizer (device name: PJM-80HE, manufactured by NPK). The collection system of the pulverized alloy particles is separated and recovered through a circulation method to remove ultrafine powder. The feed rate during pulverization was taken as 1 kg / h, the introduction pressure of He gas was 0.6 MPa, the flow rate was 1.3 m 3 / min, the oxygen concentration was 1 ppm or less, and the dew point was -75 ° C or less. The average particle diameter of the obtained magnetic material particles was 1.1 μm.
對於粉碎後之合金粒子100重量份而言加上1-十八碳1.7重量份,1-十八烯4.3重量份,及加上62.5重量份聚異丁烯(PIB)B150之甲苯溶液(8重量%),經由攪 拌機(裝置名:TX-0.5、日本井上製作所製)而以60℃進行1小時加熱攪拌。甲苯蒸餾後,在真空下進行2小時捏和,製作黏土狀之複合材料。 For 100 parts by weight of the pulverized alloy particles, 1.7 parts by weight of 1-octadecene, 4.3 parts by weight of 1-octadecene, and toluene solution (8% by weight) of 62.5 parts by weight of polyisobutylene (PIB) B150 are added. ) The mixer (device name: TX-0.5, manufactured by Inoue Seisakusho) was heated and stirred at 60 ° C for 1 hour. After toluene distillation, kneading was performed under vacuum for 2 hours to prepare a clay-like composite material.
將此複合材料,充填於具有寬度50mm、長度37mm、厚度3mm之模孔的不鏽鋼製(SUS)製的鑄模而充填之後,經由超傳導螺管線圈(裝置名:JMTD-12T100、JASTEC製),自外部施加平行磁場而進行配向處理。配向係以外部磁場的強度7T,配向處理溫度80℃之條件基礎,進行10分鐘。外部磁場係對於模孔之厚度方向而言,呈成為平行地進行施加。維持保持為配向處理溫度,自螺管線圈取出,之後,施以脫磁處理。脫磁處理係自-0.2T至+0.18T,更且至-0.16T而使強度變化之同時,經由使其漸減為零磁場之時而進行。 This composite material was filled and filled with a stainless steel (SUS) mold having mold holes with a width of 50 mm, a length of 37 mm, and a thickness of 3 mm, and then passed through a superconducting solenoid coil (device name: JMTD-12T100, manufactured by JASTEC), An alignment process is performed by applying a parallel magnetic field from the outside. The alignment was performed for 10 minutes based on the conditions of an external magnetic field strength of 7T and an alignment processing temperature of 80 ° C. The external magnetic field is applied parallel to the thickness direction of the die hole. After maintaining the temperature at the alignment treatment, the coil was taken out from the solenoid coil, and then subjected to a demagnetization treatment. The demagnetization treatment is performed at a time when the intensity is changed from -0.2T to + 0.18T, and further to -0.16T, and is gradually reduced to a zero magnetic field.
對於配向處理後之複合材料而言,在0.8Mpa之氫加壓環境下,進行脫碳處理。在此處理中,自室溫至480℃為止,以0.95℃/min之昇溫速度進行昇溫,保持2小時為480℃。此時之氫流量係2~3L/min。 For the composite material after the alignment treatment, decarburization treatment is performed under a hydrogen pressure environment of 0.8Mpa. In this process, the temperature was raised from room temperature to 480 ° C at a temperature increase rate of 0.95 ° C / min, and the temperature was maintained at 480 ° C for 2 hours. The hydrogen flow rate at this time is 2 ~ 3L / min.
脫碳處理之後,在真空環境下,以昇溫速度8 ℃/min昇溫至980℃,經由保持2小時為此溫度之時,進行燒結。 After the decarburization treatment, under a vacuum environment, at a heating rate of 8 The temperature was raised to 980 ° C / min, and sintering was performed while maintaining the temperature for 2 hours.
將所得到之燒結體,自室溫至500℃花上0.5小時進行昇溫之後,以500℃進行保持1小時,之後,經由急冷而進行退火,得到稀土類磁鐵形成用燒結體。 The obtained sintered body was heated at room temperature to 500 ° C. for 0.5 hour, and then maintained at 500 ° C. for 1 hour, and then annealed by quenching to obtain a sintered body for forming a rare earth magnet.
除變更為表2~4所記載之條件者以外係進行與實施例1同樣的操作,得到稀土類磁鐵形成用燒結體。 Except changing the conditions described in Tables 2 to 4, the same operation as in Example 1 was performed to obtain a sintered body for forming a rare earth magnet.
在此,在加以記載有1-辛烯處理之實施例2中,在噴射磨粉碎之後,於將磁鐵材料粒子與接著劑組成混合之前,對於該磁鐵材料粒子100重量份而言,添加40重量份1-辛烯,經由攪拌機(裝置名:TX-0.5、日本井上製作所製)而以60℃進行1小時攪拌之後,由真空蒸餾1-辛烯與其反應物者,進行磁粉的脫氫處理。 Here, in Example 2 in which the 1-octene treatment is described, after pulverizing by a jet mill and before mixing the magnet material particles and the adhesive composition, 40 weight is added to 100 parts by weight of the magnet material particles. Parts of 1-octene were stirred at 60 ° C. for 1 hour via a mixer (device name: TX-0.5, manufactured by Inoue Seisakusho, Ltd.), and 1-octene and its reactants were vacuum-distilled to perform dehydrogenation treatment of magnetic powder.
所得到之稀土類磁鐵形成用燒結體之燒結粒子徑係將燒結體的表面,經由SiC紙研磨,拋光研磨,及碾磨而進行表面處理之後,經由具備EBSD檢出器(AZtecHKL EBSD NordlysNano Integrated、Oxford Instruments製)之SEM(裝置名:JSM-7001F、日本電子製)、或者具備EDAX公司製之EBSD檢出器(Hikari High Speed EBSD Detector)之掃描電子顕微鏡(ZEISS公司製SUPRA40VP)而進行分析。視野角係至少呈放入200個以上粒子個數地進行設定,間距係做成0.1~1μm。 The sintered particle diameter of the obtained sintered body for forming a rare earth magnet is obtained by surface-treating the surface of the sintered body through SiC paper grinding, polishing, and grinding, and then passing through an EBSD detector (AZtecHKL EBSD NordlysNano Integrated, An SEM (device name: JSM-7001F, manufactured by Japan Electronics Co., Ltd.), or a scanning electron micromirror (SUPRA40VP, manufactured by ZEISS Corporation) equipped with an EBSD detector (Hikari High Speed EBSD Detector) manufactured by EDAX, was analyzed. The viewing angle is set to at least 200 particles, and the pitch is set to 0.1 to 1 μm.
分析資料係經由Chanel5(Oxford Instruments 製)、或者、OIM解析軟體ver5.2(EDAX公司製)而進行解析,粒界之判斷係將結晶方位之偏移角度則成為2°以上之部分作為粒界層,進行資料處理。僅抽出主相,將其圓相當徑之個數平均值作成燒結粒子徑。 The analysis data is analyzed by Chanel5 (manufactured by Oxford Instruments) or OIM analysis software ver5.2 (manufactured by EDAX), and the grain boundary is determined as the grain boundary where the deviation angle of the crystal orientation is 2 ° or more Layer for data processing. Only the main phase is extracted, and the average value of the number of circles corresponding to the diameter is taken as the diameter of the sintered particles.
對於所得到之各燒結體而言進行研磨,使用BH追蹤器(TRF-5BH-25、日本東英工業製),測定殘留磁通密度(Br)、角型度(Hk/Hcj)、磁性能量積(BH)max。 Each of the obtained sintered bodies was ground, and a BH tracker (TRF-5BH-25, manufactured by Toyo Industries, Japan) was used to measure the residual magnetic flux density (Br), the angularity (H k / H cj ), Magnetic energy product (BH) max .
所得到之燒結體之配向角度係將燒結體的表面,經由SiC紙研磨,拋光研磨,及碾磨而進行表面處理之後,經由具備EBSD檢出器(AZtecHKL EBSD NordlysNano Integrated、Oxford Instruments製)之SEM(JSM-7001F、日本電子製)、或者具備EDAX公司製之EBSD檢出器(Hikari High Speed EBSD Detector)之掃描電子題微鏡(ZEISS公司製SUPRA40VP)而進行分析。然而,EBSD之分析係在35μm之視野角,以0.2μm間距進行。為了使分析精確度提升,而至少呈放入30個之燒結粒子地進行分析。 The orientation angle of the obtained sintered body was obtained by surface-treating the surface of the sintered body through SiC paper grinding, polishing, and grinding, and then passing through an SEM equipped with an EBSD detector (AZtecHKL EBSD Nordlys Nano Integrated, Oxford Instruments). (JSM-7001F, made by Japan Electronics), or a scanning electron microscopy (SUPRA40VP made by ZEISS) with an EBSD detector (Hikari High Speed EBSD Detector) made by EDAX. However, the analysis of EBSD was performed at a viewing angle of 35 μm with a pitch of 0.2 μm. In order to improve the accuracy of the analysis, at least 30 sintered particles were placed in the analysis.
經由EBSD分析而作成如圖3(b)之極點圖,在此極點圖中,將C軸(001)則以最高頻度所朝向之方向,作成在其分析點之配向向量。 An EBSD analysis is used to create a pole diagram as shown in Figure 3 (b). In this pole diagram, the C-axis (001) is oriented in the direction of the highest frequency to create an alignment vector at its analysis point.
經由根據解析軟體之Chanel5(Oxford Instruments製)之操作,作成上述配向向量則呈成為極點圖之中心(0°之方向)地進行補正之極點圖後,以畫素單位而算出自0°方向之C軸(001)的偏移角度,將該偏移角度之頻度自90°至0°進行積算之累積比率,繪製於成圖表, 累積比率則成為50%之角度作成「配向角不均角度(△θ之半值寬度)」。 Based on the operation of Chanel5 (manufactured by Oxford Instruments) of the analysis software, the above-mentioned alignment vector is prepared to be a pole figure that is corrected to become the center of the pole figure (in the direction of 0 °), and then calculated from the 0 ° direction in pixel units. C axis (001) offset angle, the cumulative ratio of the frequency of the offset angle from 90 ° to 0 °, is plotted on a chart, The cumulative ratio becomes an angle of 50% to make the "alignment angle unevenness angle (the half-value width of Δθ)".
作為比較例,調查非專利文獻1所記載之稀土類磁鐵(比較例1及2),及日本特開2001-210508號公報(專利文獻10)所記載之稀土類磁鐵(比較例3)之特性。將其結果示於表6。自此表6,加以確認到對於非專利文獻1所記載之磁鐵而言,係加上於殘留磁通密度Br,即使在最大磁性能量積(BH)max,作為磁性特性而亦有優位的差者。另外,對於申請專利範圍文獻10所記載之磁鐵而言,亦了解到在最大磁性能量積(BH)max,作為磁性特性而有優位的差者。然而,對於申請專利範圍文獻10係未記載有殘留磁通密度Br。 As comparative examples, the characteristics of the rare-earth magnets (Comparative Examples 1 and 2) described in Non-Patent Document 1 and the rare-earth magnets (Comparative Example 3) described in Japanese Patent Laid-Open No. 2001-210508 (Patent Document 10) were investigated. . The results are shown in Table 6. From Table 6, it was confirmed that the magnet described in Non-Patent Document 1 is added to the residual magnetic flux density Br. Even at the maximum magnetic energy product (BH) max , there is a difference in the superiority as a magnetic characteristic. By. In addition, the magnets described in Patent Application Document 10 also recognize that the maximum magnetic energy product (BH) max has a superiority as a magnetic characteristic. However, there is no description of the residual magnetic flux density Br in patent application range document 10 series.
在實施例1,2中,配向角不均角度之指標的△θ之半值寬度則為8°左右,得到配向角之不均非常小的稀土類燒結磁鐵。如此,抑制配向角不均角度之結果,殘留磁通密度Br則提昇,且可自磁鐵取出之能量的指標之(BH)max亦提升。順帶說明,記載於非專利文獻1之稀土類燒結磁鐵係Br則為1.43T、(BH)max則為49.0MGOe,而經由本發明而得到之磁鐵係可確認到具有較認為以往最高性能之磁鐵優越之特性者。 In Examples 1 and 2, the half-value width of Δθ, which is an index of the misalignment angle of the alignment angle, was about 8 °, and a rare-earth sintered magnet having a very small variation in the alignment angle was obtained. As a result, as a result of suppressing the uneven angle of the alignment angle, the residual magnetic flux density Br is increased, and (BH) max, which is an index of the energy that can be taken out of the magnet, is also increased. Incidentally, the rare-earth sintered magnet system Br described in Non-Patent Document 1 is 1.43T and (BH) max is 49.0MGOe, and the magnet system obtained through the present invention can be confirmed to have a magnet that is considered to have the highest performance in the past. Those with superior characteristics.
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