JPH06104108A - Nd-fe-co-b type sintered magnet - Google Patents
Nd-fe-co-b type sintered magnetInfo
- Publication number
- JPH06104108A JPH06104108A JP4249113A JP24911392A JPH06104108A JP H06104108 A JPH06104108 A JP H06104108A JP 4249113 A JP4249113 A JP 4249113A JP 24911392 A JP24911392 A JP 24911392A JP H06104108 A JPH06104108 A JP H06104108A
- Authority
- JP
- Japan
- Prior art keywords
- sintered magnet
- content
- coercive force
- type sintered
- max
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はネオジム（Ｎｄ）、鉄
（Ｆｅ）、コバルト（Ｃｏ）及びホウ素（Ｂ）を主成分
とする永久磁石に関し、特に優れた耐食性、耐熱性を有
するＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結永久磁石に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a permanent magnet containing neodymium (Nd), iron (Fe), cobalt (Co) and boron (B) as main components, and particularly Nd-Fe having excellent corrosion resistance and heat resistance. -Co-B type sintered permanent magnet.
【０００２】[0002]
【従来の技術】Ｎｄ−Ｆｅ−Ｂ型焼結磁石及びＮｄ−Ｆ
ｅ−Ｃｏ−Ｂ型焼結磁石は、ＳｍＣｏ5型焼結磁石或い
はＳｍ2Ｃｏ17型焼結磁石と比較して高いエネルギー積
（ＢＨ）ｍａｘを有するので、種々の用途に使用される
ようになっている。しかしながら、Ｎｄ−Ｆｅ−Ｂ型焼
結磁石及びＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石は、これら
Ｓｍ−Ｃｏ型焼結磁石に比較して熱安定性に劣るので、
その熱安定性を増す為に種々の試みが提案されている。
特開昭６４−７５０３号公報には、熱安定性の良好な永
久磁石として一般式： Ｒ（Ｆｅ1-x-y-zＣｏxＢyＧａz）A （但し、Ｒは希土類元素から選ばれた少なくとも１種で
あり、０≦ｘ≦０．７、０．０２≦ｙ≦０．３、０．０
０１≦ｚ≦０．１５、４．０≦Ａ≦７．５である。）、
及び、 Ｒ（Ｆｅ1-x-y-zＣｏxＢyＧａzＭu）A （但し、Ｒは希土類元素から選ばれた少なくとも１種で
あり、ＭはＮｂ，Ｗ，Ｖ，Ｔａ及びＭｏから選ばれた１
種または２種以上の元素であり、０≦ｘ≦０．７、０．
０２≦ｙ≦０．３、０．００１≦ｚ≦０．１５、ｕ≦
０．１、４．０≦Ａ≦７．５である。）により表される
ものを開示している。2. Description of the Related Art Nd-Fe-B type sintered magnet and Nd-F
The e-Co-B type sintered magnet has a high energy product (BH) max as compared with the SmCo 5 type sintered magnet or the Sm 2 Co 17 type sintered magnet, and therefore, it is used in various applications. Has become. However, since the Nd-Fe-B type sintered magnet and the Nd-Fe-Co-B type sintered magnet are inferior in thermal stability to these Sm-Co type sintered magnets,
Various attempts have been proposed to increase its thermal stability.
JP A 64-7503 discloses the general formula as a good permanent magnet thermal stability: R (Fe 1-xyz Co x B y Ga z) A ( provided that at least 1 R is selected from rare earth elements Seed, 0 ≦ x ≦ 0.7, 0.02 ≦ y ≦ 0.3, 0.0
01 ≦ z ≦ 0.15 and 4.0 ≦ A ≦ 7.5. ),
And, R (Fe 1-xyz Co x B y Ga z M u) A ( where, R is at least one selected from rare earth elements, M is selected Nb, W, V, Ta and Mo 1
Element or two or more elements, 0 ≦ x ≦ 0.7, 0.
02 ≦ y ≦ 0.3, 0.001 ≦ z ≦ 0.15, u ≦
0.1 and 4.0 ≦ A ≦ 7.5. ) Is disclosed.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、高耐食
性、高耐熱特性を有し、かつ同時に高い水準の保磁力ｉ
Ｈｃ、エネルギー積（ＢＨ）ｍａｘを兼ね備えたＮｄ−
Ｆｅ−Ｃｏ−Ｂ型異方性焼結磁石を安定的に生産しよう
とする場合には前記公知技術を超えて更に詳細な研究・
検討に基づいた成分組成範囲の限定、酸化物の限定等が
必要であることが分かった。本発明はこのような知見に
基づき、特に耐食性、耐熱性に優れたＮｄ−Ｆｅ−Ｃｏ
−Ｂ型焼結磁石を提供するものである。本発明は、Ｃ
ｏ、Ｄｙ、Ｎｂを有効に利用することによって耐食性を
著しく高め、Ｄｙ量、Ｇａ量を特定範囲とすることによ
り高耐熱性を付与し、同時に希土類Ｒ量を低め、かつ、
酸素量を限定することにより保磁力ｉＨｃが大きく、か
つエネルギー積（ＢＨ）ｍａｘの大きいＮｄ−Ｆｅ−Ｃ
ｏ−Ｂ型焼結磁石を安定的に提供するものである。However, it has high corrosion resistance and high heat resistance, and at the same time has a high level of coercive force i.
Nd- that has both Hc and energy product (BH) max
In order to stably produce an Fe—Co—B type anisotropic sintered magnet, a more detailed study beyond the above-mentioned known techniques
It has been found that it is necessary to limit the composition range of components and oxides based on the study. The present invention is based on such knowledge, and particularly Nd-Fe-Co excellent in corrosion resistance and heat resistance.
-A B-type sintered magnet is provided. The present invention is C
o, Dy and Nb are effectively used to remarkably enhance the corrosion resistance, and the Dy amount and the Ga amount are set within a specific range to impart high heat resistance, and at the same time, the rare earth R amount is lowered, and
Nd-Fe-C having a large coercive force iHc and a large energy product (BH) max by limiting the amount of oxygen
The present invention stably provides an o-B type sintered magnet.
【０００４】[0004]
【課題を解決するための手段】本発明は、２８〜３２ｗ
ｔ％のＲ（但し、ＲはＹ及び希土類元素から選ばれた少
なくとも１種であり、Ｒの内、３．０〜８．０ｗｔ％が
Ｄｙ，残りは、Ｎｄ又はＰｒの１種又は２種であり、Ｎ
ｄをＲの内に５０ａｔ％以上を含む）、５．０ｗｔ％の
以下のＣｏ（但し、Ｃｏは必ず含む）、０．１〜１．０
ｗｔ％のＡｌ、０．５〜２．０ｗｔ％のＢ、０．１〜
２．０ｗｔ％のＮｂ、０．０５〜１．０ｗｔ％のＧａ、
１０００ｐｐｍ〜６０００ｐｐｍの酸素、及び不可避的
不純物を含有し、残部が主としてＦｅからなり保磁力ｉ
Ｈｃが２０ｋＯｅ以上、最大磁気エネルギー積（ＢＨ）
ｍａｘが３０ＭＧＯｅ以上である耐食性、耐熱性に優れ
たＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石である。本発明の永
久磁石の組成の限定理由について、以下詳細に説明す
る。The present invention provides 28-32w
t% of R (provided that R is at least one selected from Y and rare earth elements, 3.0 to 8.0 wt% of R is Dy, and the rest is one or two of Nd or Pr) And N
d includes 50 at% or more of R), 5.0 wt% or less of Co (however, Co is always included), and 0.1 to 1.0.
wt% Al, 0.5-2.0 wt% B, 0.1
2.0 wt% Nb, 0.05 to 1.0 wt% Ga,
It contains oxygen of 1000 ppm to 6000 ppm and unavoidable impurities, and the balance is mainly Fe and has a coercive force i.
Hc is 20 kOe or more, maximum magnetic energy product (BH)
It is a Nd-Fe-Co-B type sintered magnet having a max of 30 MGOe or more and excellent in corrosion resistance and heat resistance. The reasons for limiting the composition of the permanent magnet of the present invention will be described in detail below.
【０００５】本発明においてＲは２８〜３２ｗｔ％の範
囲で含有される。後述の実施例４に示されるようにＲ量
が３２ｗｔ％以下と少ないほど（ＢＨ）ｍａｘ、および
耐食性の向上に有効である。しかし、２８ｗｔ％未満で
はインゴット中にα−Ｆｅが発生し易くなり（ＢＨ）ｍ
ａｘの増大は期待しにくい。よってＲ量は２８〜３２ｗ
ｔ％とする。ＲはＮｄを主体とするために、Ｒ成分の
内、５０ａｔ％以上のＮｄを含有するものとする。Ｒの
内には３．０〜８．０ｗｔ％のＤｙを含有するが、残部
はＮｄ単独又はＮｄとＰｒとの混合である。Ｐｒは保磁
力ｉＨｃの向上に効果がある。In the present invention, R is contained in the range of 28 to 32 wt%. As shown in Example 4 which will be described later, the smaller the R amount is 32 wt% or less, the more effective it is in improving (BH) max and corrosion resistance. However, if it is less than 28 wt%, α-Fe tends to be generated in the ingot (BH) m
It is difficult to expect an increase in ax. Therefore, the amount of R is 28-32w
t%. Since R is mainly composed of Nd, 50 at% or more of Nd is contained in the R component. Although 3.0 to 8.0 wt% of Dy is contained in R, the balance is Nd alone or a mixture of Nd and Pr. Pr is effective in improving the coercive force iHc.
【０００６】ＤｙをＲ成分として含有させることによっ
て、キュリー点Ｔｃが上昇するとともに異方性磁場（Ｈ
A）が増大して保磁力ｉＨｃが向上し、耐熱性を著しく
向上させる。また、Ｄｙは耐食性向上にも効果がある。
本発明において、Ｄｙの含有量が３．０ｗｔ％より少な
いと、熱安定性、耐食性を向上させるという本発明の目
的は達成されない。しかし、８．０ｗｔ％よりも含有量
が多くなると、残留磁束密度Ｂｒ及び最大エネルギー積
（ＢＨ）ｍａｘの低下による磁気特性の劣化が著しい。
したがって、Ｄｙの含有量は３．０〜８．０ｗｔ％とす
る。Ｄｙが５．０ｗｔ％よりも含有量が多いと、残留磁
束密度Ｂｒ及び最大エネルギー積（ＢＨ）ｍａｘの低下
はあるものの、２５ｋＯｅ以上の保磁力ｉＨｃを得るこ
とができる。よってより高保磁力特性を得ようとする場
合にはＤｙの含有量を５．０〜８．０ｗｔ％とする。逆
に大きな残留磁束密度Ｂｒ及び最大エネルギー積（Ｂ
Ｈ）ｍａｘを得ようとする場合にはＤｙの含有量を３．
０〜５．０ｗｔ％とすればよい。By including Dy as the R component, the Curie point Tc rises and the anisotropic magnetic field (H
A ) is increased, the coercive force iHc is improved, and the heat resistance is remarkably improved. Dy is also effective in improving the corrosion resistance.
In the present invention, when the content of Dy is less than 3.0 wt%, the object of the present invention of improving thermal stability and corrosion resistance cannot be achieved. However, when the content is more than 8.0 wt%, the magnetic properties are significantly deteriorated due to the reduction of the residual magnetic flux density Br and the maximum energy product (BH) max.
Therefore, the content of Dy is set to 3.0 to 8.0 wt%. When the content of Dy is more than 5.0 wt%, the coercive force iHc of 25 kOe or more can be obtained although the residual magnetic flux density Br and the maximum energy product (BH) max are reduced. Therefore, in order to obtain higher coercive force characteristics, the Dy content is set to 5.0 to 8.0 wt%. On the contrary, the large residual magnetic flux density Br and the maximum energy product (B
H) max is set to 3.
It may be 0 to 5.0 wt%.
【０００７】本発明においてＣｏは、残留磁束密度Ｂｒ
を殆ど低下させることなく磁石合金自身の耐食性を改善
するとともに耐食コーティングであるＮｉメッキの密着
性を向上することにより耐食性を向上させる効果があ
る。また、主相（Ｎｄ2Ｆｅ14Ｂ）中のＦｅ がＣｏに置
換されることによりキューリー点Ｔｃを上昇させる効果
もある。しかしながらＣｏの置換量を多くすると、焼結
時の異常粒成長を原因とする粗大結晶粒が発生し、保磁
力ｉＨｃ及びヒステリシスカーブの角型性が低下する。
したがってＣｏ含有量は５．０ｗｔ％以下とする。In the present invention, Co is the residual magnetic flux density Br.
The corrosion resistance of the magnet alloy itself is improved with almost no deterioration, and the corrosion resistance is improved by improving the adhesion of the Ni plating which is the corrosion resistant coating. Further, Fe in the main phase (Nd2Fe14B) is replaced with Co, which also has the effect of raising the Curie point Tc. However, when the substitution amount of Co is increased, coarse crystal grains are generated due to abnormal grain growth during sintering, and the coercive force iHc and the squareness of the hysteresis curve are deteriorated.
Therefore, the Co content is 5.0 wt% or less.
【０００８】本発明においてＡｌは、Ｃｏ添加材の熱処
理時の温度条件を緩和する効果がある。すなわち、Ｃｏ
を含有すると材料は熱処理温度の変動に対して磁気特性
や熱安定性の変動が大きい。そこに適量のＡｌを添加す
ると、熱処理条件が多少変動しても磁気特性や熱安定性
が変動しなくなる。これにより、永久磁石の生産管理が
容易となり、品質の安定した永久磁石を効率よく生産で
きるようになる。Ａｌの含有量が０．１ｗｔ％未満では
上記の効果は不十分である。一方、１．０ｗｔ％を超え
ると、残留磁束密度Ｂｒの低下が顕著になる。従ってＡ
ｌの含有量は０．１〜１．０ｗｔ％とする。Ｂは、０．
５ｗｔ％未満の場合には高保磁力が得られず、一方、
２．０ｗｔ％を越えると、Ｂに富む非磁性相が増加し、
残留磁束密度Ｂｒが低下する。そのため、０．５〜２．
０ｗｔ％とする。好ましいＢの含有量は０．８〜１．２
ｗｔ％である。In the present invention, Al has the effect of relaxing the temperature conditions during the heat treatment of the Co additive. That is, Co
When it contains, the material has large fluctuations in magnetic properties and thermal stability with respect to fluctuations in heat treatment temperature. If an appropriate amount of Al is added thereto, the magnetic characteristics and thermal stability will not change even if the heat treatment conditions change to some extent. As a result, the production management of the permanent magnets becomes easy, and the permanent magnets with stable quality can be efficiently produced. If the Al content is less than 0.1 wt%, the above effect is insufficient. On the other hand, when it exceeds 1.0 wt%, the decrease in the residual magnetic flux density Br becomes remarkable. Therefore A
The content of 1 is 0.1 to 1.0 wt%. B is 0.
If it is less than 5 wt%, a high coercive force cannot be obtained, while
If it exceeds 2.0 wt%, the B-rich non-magnetic phase increases,
The residual magnetic flux density Br decreases. Therefore, 0.5-2.
It is set to 0 wt%. The preferable B content is 0.8 to 1.2.
wt%.
【０００９】Ｇａは、残留磁束密度Ｂｒを殆ど低下させ
ず、保磁力ｉＨｃを向上する効果がある。Ｇａ含有量が
０．０５ｗｔ％未満の場合は保磁力ｉＨｃを向上する効
果が十分でない。Ｇａ含有量が１．０ｗｔ％を超える
と、残留磁束密度Ｂｒが低下し、所望の高エネルギー積
が得られない。よって、Ｇａ含有量は０．０５〜１．０
ｗｔ％とする。Ｇａ含有量が多いと磁石のヒステリシス
カーブの角形性が悪くなるので、高い角形性を付与する
ためにも好ましいＧａの含有量は０．０５〜０．８ｗｔ
％である。より好ましいＧａの含有量は０．１〜０．６
ｗｔ％である。更に好ましくは０．１〜０．４ｗｔ％で
ある。Ga has the effect of improving the coercive force iHc without substantially reducing the residual magnetic flux density Br. If the Ga content is less than 0.05 wt%, the effect of improving the coercive force iHc is not sufficient. If the Ga content exceeds 1.0 wt%, the residual magnetic flux density Br decreases and the desired high energy product cannot be obtained. Therefore, the Ga content is 0.05 to 1.0.
wt%. If the Ga content is high, the squareness of the hysteresis curve of the magnet is deteriorated. Therefore, the preferable Ga content for imparting high squareness is 0.05 to 0.8 wt.
%. The more preferable Ga content is 0.1 to 0.6.
wt%. More preferably, it is 0.1 to 0.4 wt%.
【００１０】本発明の永久磁石は、上記成分の他に０．
１〜２．０ｗｔ％のＮｂを含有する。Ｎｂは焼結時に結
晶粒が粗大化することを抑制する効果がある。この効果
により、保磁力ｉＨｃが向上し、ヒステリシスカーブの
角型性が良好になる。また、焼結体の結晶粒が微細にな
ることは磁石の良好な着磁性に大きく寄与し、さらに着
磁性の良好なＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石は優れた
耐熱性を有する。よって、耐熱性を有する磁石にＮｂは
有効な添加物である。Ｎｂの含有量が０．１ｗｔ％未満
の場合、粗大粒を抑制する効果が不十分である。一方、
Ｎｂの含有量が２．０ｗｔ％を超える場合には、Ｎｂも
しくはＮｂ−Ｆｅの非磁性ホウ化物が多く発生し、残留
磁束密度Ｂｒ及びキュリー点Ｔｃが著しく低下し好まし
くない。よって、Ｎｂの含有量は０．１〜２．０ｗｔ％
とする。好ましくは、０．１〜１．０ｗｔ％である。The permanent magnet of the present invention has a composition of 0.
It contains 1 to 2.0 wt% Nb. Nb has an effect of suppressing coarsening of crystal grains during sintering. This effect improves the coercive force iHc and improves the squareness of the hysteresis curve. Further, the fine crystal grains of the sintered body greatly contribute to good magnetizability of the magnet, and the Nd-Fe-Co-B type sintered magnet having good magnetizability has excellent heat resistance. Therefore, Nb is an effective additive for heat-resistant magnets. If the Nb content is less than 0.1 wt%, the effect of suppressing coarse particles is insufficient. on the other hand,
When the content of Nb exceeds 2.0 wt%, a large amount of nonmagnetic boride of Nb or Nb—Fe is generated, and the residual magnetic flux density Br and the Curie point Tc are remarkably lowered, which is not preferable. Therefore, the content of Nb is 0.1 to 2.0 wt%
And Preferably, it is 0.1 to 1.0 wt%.
【００１１】酸素含有量は、１０００ｐｐｍ〜６０００
ｐｐｍとする。酸素が１０００ｐｐｍより少ない場合に
は磁石粉、及びその圧密体が発火しやすく工業生産上危
険がある。一方、６０００ｐｐｍより多い場合には酸素
が希土類Ｒ成分と反応して希土類酸化物を形成し、高保
磁力及び高エネルギー積の磁石を得るのが困難になる。The oxygen content is 1000 ppm to 6000.
ppm. If the oxygen content is less than 1000 ppm, the magnet powder and its compacted body are likely to ignite, which is dangerous in industrial production. On the other hand, when the amount is more than 6000 ppm, oxygen reacts with the rare earth R component to form a rare earth oxide, and it becomes difficult to obtain a magnet with high coercive force and high energy product.
【００１２】本発明の焼結磁石は、次のようにして製造
することができる。即ち、一定の成分組成を有するイン
ゴットを真空溶解で製作し、次にこのインゴットを粗粉
砕することにより粒径５００μｍ程度の粗粉を得る。こ
の粗粉をジェットミルを用い、不活性ガス雰囲気で微粉
砕し平均粒径３．０〜６．０μｍ（Ｆ．Ｓ．Ｓ．Ｓ．）
の微粉を得る。次にこの微粉を配向磁場１５ｋＯｅ、成
形圧力１．５ｔｏｎ／ｃｍ2の条件下で磁場中プレス成
形後、１０００〜１１５０℃の温度範囲で焼結す る。
焼結後の熱処理は、次のように行なうことができる。成
形体を焼結して得た焼結体をいったん室温まで冷却す
る。焼結後の冷却速度は最終製品の保磁力ｉＨｃに殆ど
影響を与えない。次いで、８００〜１０００℃の温度に
加熱し、０．２〜５時間保持する。これを第１次熱処理
とする。加熱温度が８００℃未満または１０００℃を超
える場合、充分な高保磁力が得られない。加熱保持の後
で０．３〜５０℃／分の冷却速度で室温ないし６００℃
の温度まで冷却する。冷却速度が５０℃／分を超える場
合は、時効のために必要な平衡相が得られず、充分な高
保磁力が得られない。また、０．３℃／分未満の冷却速
度は熱処理に時間を要し、工業生産上経済的でない。好
ましくは、０．６〜２．０℃／分の冷却速度が選ばれ
る。冷却終了温度は室温が望ましいが、多少保磁力ｉＨ
ｃを犠牲にすれば６００℃までとし、その温度以下は急
冷してもよい。好ましくは、常温〜４００℃の温度まで
冷却する。熱処理は更に５００〜６５０℃の温度で０．
２〜３時間行う。これを第２次熱処理とする。組成によ
って異なるが、好ましくは５４０〜６４０℃での熱処理
が有効である。熱処理温度が５００℃未満の場合及び６
５０℃より高い場合は、高保磁力が得られても不可逆減
磁率の低下がおきる。熱処理後は第１次熱処理と同様、
０．３〜４００℃／分の冷却速度で冷却する。冷却は水
中、シリコンオイル中、アルゴン気流中等で行うことが
できる。冷却速度が４００℃／分を越える場合、急冷に
より試料に亀裂が入り、工業的に価値のある永久磁石材
料が得られない。また、０．３℃／分未満の場合、冷却
過程で保磁力ｉＨｃに好ましくない相が出現する。The sintered magnet of the present invention can be manufactured as follows. That is, an ingot having a constant composition is manufactured by vacuum melting, and then the ingot is roughly crushed to obtain a coarse powder having a particle size of about 500 μm. This coarse powder was finely pulverized in an inert gas atmosphere using a jet mill, and the average particle size was 3.0 to 6.0 μm (FSSS).
To get a fine powder of. Next, this fine powder is press-molded in a magnetic field under the conditions of an orientation magnetic field of 15 kOe and a molding pressure of 1.5 ton / cm 2 , and then sintered in a temperature range of 1000 to 1150 ° C.
The heat treatment after sintering can be performed as follows. The sintered body obtained by sintering the compact is once cooled to room temperature. The cooling rate after sintering has almost no effect on the coercive force iHc of the final product. Then, it is heated to a temperature of 800 to 1000 ° C. and held for 0.2 to 5 hours. This is the first heat treatment. If the heating temperature is lower than 800 ° C or higher than 1000 ° C, a sufficiently high coercive force cannot be obtained. Room temperature to 600 ° C at a cooling rate of 0.3 to 50 ° C / min after heating and holding
Cool to the temperature of. If the cooling rate exceeds 50 ° C./minute, the equilibrium phase required for aging cannot be obtained, and a sufficiently high coercive force cannot be obtained. Further, a cooling rate of less than 0.3 ° C./minute requires a long time for heat treatment, which is not economical in industrial production. Preferably, a cooling rate of 0.6 to 2.0 ° C./min is selected. Room temperature is desirable as the cooling end temperature, but some coercive force iH
If c is sacrificed, the temperature may be up to 600 ° C., and the temperature below that may be rapidly cooled. Preferably, the temperature is cooled to room temperature to 400 ° C. The heat treatment is further performed at a temperature of 500 to 650 ° C.
Do 2-3 hours. This is the secondary heat treatment. Although it depends on the composition, heat treatment at 540 to 640 ° C. is effective. When the heat treatment temperature is less than 500 ° C and 6
If the temperature is higher than 50 ° C., the irreversible demagnetization rate will decrease even if a high coercive force is obtained. After the heat treatment, like the first heat treatment,
Cool at a cooling rate of 0.3 to 400 ° C./min. Cooling can be performed in water, in silicone oil, in an argon stream, or the like. If the cooling rate exceeds 400 ° C./minute, the sample is cracked by the rapid cooling and an industrially valuable permanent magnet material cannot be obtained. Further, if it is less than 0.3 ° C./min, an unfavorable phase appears in the coercive force iHc during the cooling process.
【００１３】[0013]
【実施例】以下、実施例により本発明を更に詳細に説明
する。 （実施例１）金属Ｎｄ、金属Ｄｙ、Ｆｅ、Ｃｏ、ｆｅｒ
ｒｏ−Ｂ、ｆｅｒｒｏ−Ｎｂ、金属Ｇａを所定の重量秤
量し、これを真空溶解して重量１０ｋｇのインゴットを
作製した。このインゴットの成分分析を行なうと重量比
で以下のような組成であった。 Ｎｄ27.5−Ｄｙ3.
6−Ｂ1.03−Ｎｂ0.58−Ｇａ0.18−Ｃｏ2.02−Ａｌ0.35
−Ｆｅbal. （ｗｔ％） このインゴットをハンマーで解砕した後、さらに粗粉砕
機を用い不活性ガス雰囲気中での粗粉砕を行い５００μ
ｍ以下の粒度の粗粉を得た。この粗粉を同じくジェット
ミルを用い不活性ガス雰囲気中で微粉砕をして微粉を得
た。この微粉は平均粒径４．０μｍ（Ｆ．Ｓ．Ｓ．
Ｓ．）であり、含有酸素量が５５００ｐｐｍであった。
次に、この微粉を配向磁場強度１５ｋＯｅ、成形圧力
１．５ｔｏｎ／ｃｍ2の条件下で磁場中プレス成形し、
３０×２０×１５の成形体を作製した。この成形体は実
質的に真空の条件で１０８０℃×３ｈｒの焼結を行い、
得られた焼結体に９００℃×２ｈｒの第１次熱処理、次
いで５３０℃×２ｈｒの第２次熱処理を施した。得られ
た焼結体の密度は７．５５ｇ／ｃｃ、また含有酸素量は
４８００ｐｐｍであった。この試料の常温磁気特性を測
定したところ以下の様な値を得た。 Ｂｒ＝１２．６ｋＧ ｂＨｃ＝１１．６ｋＯｅ ｉＨｃ＝２１．８ｋＯｅ （ＢＨ）ｍａｘ＝３５．６ＭＧＯｅ 更にキュリー点Ｔｃとして３４０℃、２３℃から１２０
℃のＢｒとｉＨｃの温度係数α、βとして各々−０．１
０、−０．５２％／℃の値を得た。またパーミアンス係
数Ｐｃ＝１．０，２．０形状をした試料の１００℃での
不可逆減磁率は各々２．１，１．１％であり優れた耐熱
性を有している。EXAMPLES The present invention will be described in more detail below with reference to examples. (Example 1) Metal Nd, metal Dy, Fe, Co, fer
A predetermined weight of ro-B, ferro-Nb, and metallic Ga was weighed and melted in vacuum to prepare an ingot having a weight of 10 kg. When the composition of this ingot was analyzed, it had the following composition by weight ratio. Nd27.5-Dy3.
6-B1.03-Nb0.58-Ga0.18-Co2.02-Al0.35
-Febal. (Wt%) After crushing this ingot with a hammer, further coarse crushing was performed in an inert gas atmosphere using a coarse crusher to obtain 500μ.
A coarse powder having a particle size of m or less was obtained. This coarse powder was finely pulverized in the same inert gas atmosphere using a jet mill to obtain fine powder. This fine powder has an average particle size of 4.0 μm (FSS.
S. ), And the oxygen content was 5500 ppm.
Next, this fine powder is press-molded in a magnetic field under the conditions of an orientation magnetic field strength of 15 kOe and a molding pressure of 1.5 ton / cm 2 ,
A 30 × 20 × 15 molded body was produced. This compact was sintered at 1080 ° C. for 3 hours under substantially vacuum conditions,
The obtained sintered body was subjected to a first heat treatment at 900 ° C. × 2 hr and then a second heat treatment at 530 ° C. × 2 hr. The density of the obtained sintered body was 7.55 g / cc, and the oxygen content was 4800 ppm. When the room temperature magnetic characteristics of this sample were measured, the following values were obtained. Br = 12.6 kG bHc = 11.6 kOe iHc = 21.8 kOe (BH) max = 35.6 MGOe Further, the Curie point Tc is 340 ° C., 23 ° C. to 120.
-0.1 for Br and iHc temperature coefficients α and β
A value of 0, -0.52% / ° C was obtained. Further, the irreversible demagnetization factors at 100 ° C. of the samples having the permeance coefficient Pc = 1.0 and 2.0 are 2.1 and 1.1%, respectively, and have excellent heat resistance.
【００１４】（実施例２）実験条件を変えて、実施例１
と同様にして次の実験結果を得た。 組成 ： Ｎｄ25.5−Ｄｙ6.4−Ｂ1.04−Ｎｂ0.55−Ｇ
ａ0.22−Ｃｏ2.00−Ａｌ0.36−Ｆｅbal.（ｗｔ％） 焼結 ： １１００℃×２ｈｒ 第１次熱処理 ： ９００℃×２ｈｒ 第２次熱処理 ： ５３０℃×２ｈｒ 常温磁気特性 ： Ｂｒ ＝ １１．４ｋＧ ｂＨｃ ＝ １１．０ｋＯｅ ｉＨｃ ＝ ２７．８ｋＯｅ （ＢＨ）ｍａｘ ＝ ３１．３ＭＧＯｅ キュリー点 ： Ｔｃ ＝ ３４０℃ 不可逆減磁率 ［ａｔ １００℃］ ： Ｐｃ ＝
１．０ → １．８％ Ｐｃ ＝ ２．０ → ０．８％ Ｂｒ温度係数（α），ｉＨｃ温度係数（β） ［２３℃
〜１２０℃］： α＝ −０．０９％／℃ β＝ −０．５１％／℃ 焼結体含有酸素量 ： ５８００ｐｐｍ 実施例１同様、常温磁気特性と共に高温特性に優れてお
り、耐熱性に優れた磁石を得ることができる。(Embodiment 2) Embodiment 1 is changed by changing the experimental conditions.
The following experimental results were obtained in the same manner as. Composition: Nd25.5-Dy6.4-B1.04-Nb0.55-G
a0.22-Co2.00-Al0.36-Febal. (wt%) Sintering: 1100 ° C. × 2 hr Primary heat treatment: 900 ° C. × 2 hr Secondary heat treatment: 530 ° C. × 2 hr Room temperature magnetic properties: Br = 11 .4 kG bHc = 11.0 kOe iHc = 27.8 kOe (BH) max = 31.3 MGOe Curie point: Tc = 340 ° C Irreversible demagnetization rate [at 100 ° C]: Pc =
1.0 → 1.8% Pc = 2.0 → 0.8% Br temperature coefficient (α), iHc temperature coefficient (β) [23 ° C.
~ 120 ° C.]: α = −0.09% / ° C. β = −0.51% / ° C. Oxygen content in sintered body: 5800 ppm As in Example 1, excellent magnetic properties at room temperature as well as high temperature properties are excellent and heat resistance is high. An excellent magnet can be obtained.
【００１５】（実施例３）ジジムメタル（Ｎｄ７０ｗｔ
％−Ｐｒ３０ｗｔ％）を使用し、実施例１、２と同様に
して次の実験結果を得た。 組成 ： Ｎｄ18.9−Ｐｒ5.1−Ｄｙ7.3−Ｂ1.10−Ｎｂ
0.71−Ｇａ0.37−Ｃｏ4.72−Ａｌ0.33−Ｆｅbal.（ｗｔ
％） 焼結 ： １０８０℃×２ｈｒ 第１次熱処理 ： ９００℃×２ｈｒ 第２次熱処理 ： ５２０℃×２ｈｒ 常温磁気特性 ： Ｂｒ ＝ １１．５ｋＧ ｂＨｃ ＝ １０．９ｋＯｅ ｉＨｃ ＝ ３０．０ｋＯｅ （ＢＨ）ｍａｘ ＝ ３１．２ＭＧＯｅ キュリー点 ： Ｔｃ ＝ ３７５℃ 不可逆減磁率 ［ａｔ １００℃］ ： Ｐｃ ＝
１．０ → １．４％ Ｐｃ ＝ ２．０ → ０．５％ Ｂｒ温度係数（α），ｉＨｃ温度係数（β） ［２３℃
〜１２０℃］： α＝ −０．０９％／℃ β＝ −０．４８％／℃ 焼結体含有酸素量 ： ５４００ｐｐｍ ジジムメタルを用いた場合でも、実施例１、２と同様常
温磁気特性、高温特性、耐熱性に優れた磁石を得ること
ができる。Example 3 Didymium metal (Nd 70 wt)
% -Pr 30 wt%) was used and the following experimental results were obtained in the same manner as in Examples 1 and 2. Composition: Nd18.9-Pr5.1-Dy7.3-B1.10-Nb
0.71-Ga0.37-Co4.72-Al0.33-Febal. (Wt
%) Sintering: 1080 ° C. × 2 hr Primary heat treatment: 900 ° C. × 2 hr Secondary heat treatment: 520 ° C. × 2 hr Normal temperature magnetic property: Br = 11.5 kG bHc = 10.9 kOe iHc = 30.0 kOe (BH) max = 31.2 MGOe Curie point: Tc = 375 ° C Irreversible demagnetization rate [at 100 ° C]: Pc =
1.0 → 1.4% Pc = 2.0 → 0.5% Br temperature coefficient (α), iHc temperature coefficient (β) [23 ° C.
~ 120 ° C]: α = -0.09% / ° C β = -0.48% / ° C Sintered body oxygen content: 5400 ppm Even when didymium metal is used, the magnetic properties at room temperature and high temperature are the same as in Examples 1 and 2. It is possible to obtain a magnet having excellent characteristics and heat resistance.
【００１６】（実施例４）金属Ｎｄ、金属Ｄｙ、Ｆｅ、
Ｃｏ、ｆｅｒｒｏ−Ｂ、ｆｅｒｒｏ−Ｎｂ、金属Ｇａを
所定の重量秤量し、これを真空溶解して重量各１０ｋｇ
のインゴットを作製した。このインゴットの成分分析を
行なうと重量比で以下のような組成であった。 Ｎｄa−Ｄｙb−Ｂ1.05−Ｎｂ0.58−Ｇａ0.20 −Ｃｏ0.20−Ａｌ0.33−Ｆｅbal. （a+b＝ＴＲＥ，b＝3.7） （ｗｔ％） 各々のインゴットをハンマーで解砕した後、さらに粗粉
砕機を用い不活性ガス雰囲気中での粗粉砕を行い５００
μｍ以下の粒度の粗粉を得た。この粗粉を同じくジェッ
トミルを用い不活性ガス雰囲気中で微粉砕をして微粉を
得た。この微粉は平均粒径３．７μｍ（Ｆ．Ｓ．Ｓ．
Ｓ．）であり、含有酸素量は１５００〜５０００ｐｐｍ
であった。次に、この微粉を配向磁場強度１５ｋＯｅ、
成形圧力１．５ｔｏｎ／ｃｍ2の条件下で磁場中プレス
成形し、３０×２０×１５の成形体を 作製した。この
成形体は実質的に真空の条件で１０７０℃×２ｈｒの焼
結を行い、得られた焼結体に９００℃×２ｈｒの第１次
熱処理、次いで５４０℃×２ｈｒの第２次熱処理を施し
た。得られた焼結体の密度は７．５５〜７．５８ｇ／ｃ
ｃ、また含有酸素量は１０００〜４０００ｐｐｍであっ
た。この試料について、ＴＲＥ含有量に対して最大エネ
ルギー積（ＢＨ）ｍａｘ及び腐食減量がどのように変化
するかを測定し、図１に示すような結果を得た。腐食減
量は磁石を温度１２０℃，湿度９０％，気圧１．０ａｔ
ｍの環境中に１００時間暴露したときに得られたもので
ある。図１に示されるようにＴＲＥ量を少なくすること
によって（ＢＨ）ｍａｘを向上することができるが、２
８ｗｔ％未満とするとインゴット中にα−Ｆｅが発生し
易くなり（ＢＨ）ｍａｘの増大は期待しにくい。腐食減
量もやはりＴＲＥ量を少なくすることによって減少させ
ることができる。これは、ＴＲＥを少なくすることによ
って腐食しやすいＮｄ−ｒｉｃｈ相が減少する為であ
る。しかしながら、ＴＲＥ量を２８〜３２ｗｔ％という
低い値としても含有酸素量が６０００ｐｐｍを超えてし
まうと保磁力ｉＨｃの減少が著しくなるため、酸素量は
１０００〜６０００ｐｐｍとする。図２に焼結磁石中の
酸素含有量と磁気特性の関係を示す。(Example 4) Metal Nd, metal Dy, Fe,
Co, ferro-B, ferro-Nb, and metallic Ga are weighed to a predetermined weight, and these are vacuum melted to weigh 10 kg each.
The ingot of was produced. When the composition of this ingot was analyzed, it had the following composition by weight ratio. Nda-Dyb-B1.05-Nb0.58-Ga0.20-Co0.20-Al0.33-Febal. (A + b = TRE, b = 3.7) (wt%) Each ingot was crushed with a hammer. After that, coarse pulverization is further performed in an inert gas atmosphere by using a coarse pulverizer to 500
A coarse powder with a particle size of less than μm was obtained. This coarse powder was finely pulverized in the same inert gas atmosphere using a jet mill to obtain fine powder. This fine powder has an average particle size of 3.7 μm (FSS.
S. ), And the oxygen content is 1500 to 5000 ppm
Met. Next, this fine powder is applied with an orientation magnetic field strength of 15 kOe,
Press molding was performed in a magnetic field under a molding pressure of 1.5 ton / cm 2 to prepare a 30 × 20 × 15 compact. This compact was sintered at 1070 ° C. × 2 hr under a substantially vacuum condition, and the obtained sintered compact was subjected to a first heat treatment at 900 ° C. × 2 hr and then a second heat treatment at 540 ° C. × 2 hr. did. The density of the obtained sintered body was 7.55 to 7.58 g / c.
c, and the oxygen content was 1000 to 4000 ppm. With respect to this sample, how the maximum energy product (BH) max and the corrosion weight loss change with respect to the TRE content was measured, and the results shown in FIG. 1 were obtained. The weight loss of the magnet is 120 ℃, the humidity is 90%, and the atmospheric pressure is 1.0at.
It was obtained when exposed to the environment of m for 100 hours. As shown in FIG. 1, (BH) max can be improved by reducing the TRE amount.
If it is less than 8 wt%, α-Fe is likely to be generated in the ingot, and it is difficult to expect an increase in (BH) max. Corrosion weight loss can also be reduced by reducing the amount of TRE. This is because the Nd-rich phase, which is easily corroded, is reduced by reducing the TRE. However, even if the TRE amount is set to a low value of 28 to 32 wt%, if the oxygen content exceeds 6000 ppm, the coercive force iHc decreases remarkably, so the oxygen amount is set to 1000 to 6000 ppm. FIG. 2 shows the relationship between the oxygen content in the sintered magnet and the magnetic characteristics.
【００１７】（実施例５）金属Ｎｄ、金属Ｄｙ、Ｆｅ、
Ｃｏ、ｆｅｒｒｏ−Ｂ、ｆｅｒｒｏ−Ｎｂ、金属Ｇａを
所定の重量秤量し、これを真空溶解して重量各１０ｋｇ
のインゴットを作製した。このインゴットの成分分析を
行なうと重量比で以下のような組成であった。 Ｎｄ30.5-a−Ｄｙa−Ｂ1.03−Ｎｂ0.59−Ｇａb −Ｃｏ2.10−Ａｌ0.34−Ｆｅbal. （2.8≦a≦8.5，0≦b≦1.2） （ｗｔ％） 各々のインゴットをハンマーで解砕した後、さらに粗粉
砕機を用い不活性ガス雰囲気中での粗粉砕を行い５００
μｍ以下の粒度の粗粉を得た。この粗粉を同じくジェッ
トミルを用い不活性ガス雰囲気中で微粉砕をして微粉を
得た。この微粉は平均粒径３．８μｍ（Ｆ．Ｓ．Ｓ．
Ｓ．）であり、含有酸素量は５５００〜６４００ｐｐｍ
であった。次に、この微粉を配向磁場強度１５ｋＯｅ、
成形圧力１．５ｔｏｎ／ｃｍ2の条件下で磁場中プレス
成形し、３０×２０×１５の成形体を 作製した。この
成形体は実質的に真空の条件で１１００℃×２ｈｒの焼
結を行い、得られた焼結体に９００℃×２ｈｒの第１次
熱処理、次いで５８０℃×２ｈｒの第２次熱処理を施し
た。得られた焼結体の密度は７．５５〜７．５９ｇ／ｃ
ｃ、また含有酸素量は５０００〜５９００ｐｐｍであっ
た。これら試料について、常温磁気特性を測定し、図
３、図４及び図５に示すような結果を得た。図３はＤｙ
＝５．０ｗｔ％として測定した結果であるがＧａ含有量
が０．０５ｗｔ％未満では効果を発揮しにくいが、一
方、１．０ｗｔ％以上にしても最大エネルギー積（Ｂ
Ｈ）ｍａｘの減少が著しくなるだけで保磁力ｉＨｃの向
上はさほど期待できないので０．０５〜１．０ｗｔ％が
適量である。ＧａはＤｙに比較して（ＢＨ）ｍａｘを著
しく低下することなく保磁力ｉＨｃを向上させる効果が
大きいので０．０１〜１．０ｗｔ％の含有は本発明にお
いて必須となる。図４にはＧａ含有量を０．２０ｗｔ％
としてＤｙ含有量を変化させた結果を示す。Ｄｙ含有は
ｉＨｃの向上に大きく貢献するが一方で（ＢＨ）ｍａｘ
を著しく低下させるので含有量は３．６〜８．０ｗｔ％
が適量である。図５にはＤｙ含有量をパラメータとして
Ｇａ含有量を０〜０．６ｗｔ％まで変化させた場合の結
果を示すが、Ｄｙ含有量が８．０ｗｔ％を超えると（Ｂ
Ｈ）ｍａｘが著しく低下する。また、Ｄｙ含有量が３．
０ｗｔ％未満であると、２０ｋＯｅを越える高保磁力が
得にくい。(Example 5) Metal Nd, metal Dy, Fe,
Co, ferro-B, ferro-Nb, and metallic Ga are weighed to a predetermined weight, and these are vacuum melted to weigh 10 kg each.
The ingot of was produced. When the composition of this ingot was analyzed, it had the following composition by weight ratio. Nd30.5-a-Dya-B1.03-Nb0.59-Gab-Co2.10-Al0.34-Febal. (2.8≤a≤8.5, 0≤b≤1.2) (wt%) Hammer each ingot After crushing with, coarse crushing is further performed in an inert gas atmosphere using a coarse crusher and 500
A coarse powder with a particle size of less than μm was obtained. This coarse powder was finely pulverized in the same inert gas atmosphere using a jet mill to obtain fine powder. This fine powder has an average particle size of 3.8 μm (FSS.
S. ), And the oxygen content is 5500 to 6400 ppm
Met. Next, this fine powder is applied with an orientation magnetic field strength of 15 kOe,
Press molding was performed in a magnetic field under a molding pressure of 1.5 ton / cm 2 to prepare a 30 × 20 × 15 compact. This compact was sintered at 1100 ° C. × 2 hr under a substantially vacuum condition, and the resulting sintered compact was subjected to a first heat treatment at 900 ° C. × 2 hr and then a second heat treatment at 580 ° C. × 2 hr. did. The density of the obtained sintered body is 7.55 to 7.59 g / c.
c, and the oxygen content was 5000 to 5900 ppm. The ambient temperature magnetic characteristics of these samples were measured, and the results shown in FIGS. 3, 4 and 5 were obtained. Figure 3 is Dy
= 5.0 wt%, the Ga content is less than 0.05 wt%, but it is difficult to exert the effect. On the other hand, even if the Ga content is 1.0 wt% or more, the maximum energy product (B
Since the decrease of (H) max becomes remarkable and the improvement of coercive force iHc cannot be expected so much, 0.05 to 1.0 wt% is an appropriate amount. Ga has a large effect of improving the coercive force iHc without significantly lowering (BH) max as compared with Dy, so that the content of 0.01 to 1.0 wt% is essential in the present invention. In FIG. 4, the Ga content is 0.20 wt%
Shows the result of changing the Dy content. Dy content greatly contributes to the improvement of iHc, while (BH) max
Content is 3.6 to 8.0 wt%
Is an appropriate amount. FIG. 5 shows the results when the Ga content was changed from 0 to 0.6 wt% using the Dy content as a parameter, but when the Dy content exceeds 8.0 wt% (B
H) max is significantly reduced. Further, the Dy content is 3.
If it is less than 0 wt%, it is difficult to obtain a high coercive force exceeding 20 kOe.
【００１８】（実施例６）ジジムメタル（Ｎｄ７０ｗｔ
％−Ｐｒ３０ｗｔ％）、金属Ｄｙ、Ｆｅ、Ｃｏ、ｆｅｒ
ｒｏ−Ｂ、ｆｅｒｒｏ−Ｎｂ、金属Ｇａを所定の重量秤
量し、これを真空溶解して重量各１０ｋｇのインゴット
を作製した。このインゴットの成分分析を行なうと重量
比で以下のような組成であった。 （Ｎｄ＋Ｐｒ）28.1−Ｄｙ3.6−Ｂ1.03−Ｎｂ0.58−Ｇａb −Ｃｏ2.05−Ａｌ0.35−Ｆｅbal. （0≦b≦0.6）（ｗｔ％） 各々のインゴットをハンマーで解砕した後、さらに粗粉
砕機を用い不活性ガス雰囲気中での粗粉砕を行い５００
μｍ以下の粒度の粗粉を得た。この粗粉を同じくジェッ
トミルを用い不活性ガス雰囲気中で微粉砕をして微粉を
得た。この微粉は平均粒径３．７μｍ（Ｆ．Ｓ．Ｓ．
Ｓ．）であり、含有酸素量は５６００ｐｐｍであった。
次に、この微粉を配向磁場強度１５ｋＯｅ、成形圧力
１．５ｔｏｎ／ｃｍ2の条件下で磁場中プレス成形し、
３０×２０×１５の成形体を作製した。 この成形体は
実質的に真空の条件で１０８０℃×２．５ｈｒの焼結を
行い、得られた焼結体に８９０℃×２ｈｒの第１次熱処
理、次いで５３０℃×２ｈｒの第２次熱処理を施した。
得られた焼結体の密度は７．５５〜７．５８ｇ／ｃｃ、
また含有酸素量は２８００ｐｐｍであった。これら試料
について、常温磁気特性を測定し、図６に示すような結
果を得た。図６に示されるようにＧａを含有させること
によって保磁力ｉＨｃ及びＨｋの向上が認められるので
０．０５ｗｔ％以上の含有が必須となる。しかしなが
ら、Ｇａが０．４ｗｔ％を超えるとＨｋが低下しヒステ
リシスループの角形性が低下するので上限は１．０ｗｔ
％ではあるが、好ましくは０．８ｗｔ％、より好ましく
は０．６ｗｔ％、更に好ましくは０．４ｗｔ％である。Example 6 Didymium metal (Nd 70 wt)
% -Pr30wt%), metal Dy, Fe, Co, fer
A predetermined weight of ro-B, ferro-Nb, and metallic Ga was weighed, and this was vacuum-melted to produce ingots each weighing 10 kg. When the composition of this ingot was analyzed, it had the following composition by weight ratio. (Nd + Pr) 28.1-Dy3.6-B1.03-Nb0.58-Gab-Co2.05-Al0.35-Febal. (0≤b≤0.6) (wt%) After crushing each ingot with a hammer Further, coarse pulverization is performed in an inert gas atmosphere using a coarse pulverizer and 500
A coarse powder with a particle size of less than μm was obtained. This coarse powder was finely pulverized in the same inert gas atmosphere using a jet mill to obtain fine powder. This fine powder has an average particle size of 3.7 μm (FSS.
S. ), And the oxygen content was 5600 ppm.
Next, this fine powder is press-molded in a magnetic field under the conditions of an orientation magnetic field strength of 15 kOe and a molding pressure of 1.5 ton / cm 2 ,
A 30 × 20 × 15 molded body was produced. This compact was sintered at 1080 ° C. × 2.5 hr under a substantially vacuum condition, and the resulting sintered compact was subjected to a primary heat treatment at 890 ° C. × 2 hr and then a secondary heat treatment at 530 ° C. × 2 hr. Was applied.
The density of the obtained sintered body was 7.55 to 7.58 g / cc,
The oxygen content was 2800 ppm. The ambient temperature magnetic characteristics of these samples were measured, and the results shown in FIG. 6 were obtained. As shown in FIG. 6, since the coercive force iHc and Hk are improved by adding Ga, the content of 0.05 wt% or more is essential. However, when Ga exceeds 0.4 wt%, Hk decreases and the squareness of the hysteresis loop decreases, so the upper limit is 1.0 wt.
%, But is preferably 0.8 wt%, more preferably 0.6 wt%, and further preferably 0.4 wt%.
【００１９】（実施例７）ジジムメタル（Ｎｄ７０ｗｔ
％−Ｐｒ３０ｗｔ％）、金属Ｄｙ、Ｆｅ、Ｃｏ、ｆｅｒ
ｒｏ−Ｂ、ｆｅｒｒｏ−Ｎｂ、金属Ｇａを所定の重量秤
量し、これを真空溶解して重量各１０ｋｇのインゴット
を作製した。このインゴットの成分分析を行なうと重量
比で以下のような組成であった。 （Ｎｄ＋Ｐｒ）28.0−Ｄｙ4.0−Ｂ1.03−Ｎｂx−Ｇａ0.15 −Ｃｏ2.04−Ａｌ0.35−Ｆｅbal. （0≦x≦1.0）（ｗｔ％） 各々のインゴットをハンマーで解砕した後、さらに粗粉
砕機を用い不活性ガス雰囲気中での粗粉砕を行い５００
μｍ以下の粒度の粗粉を得た。この粗粉を同じくジェッ
トミルを用い不活性ガス雰囲気中で微粉砕をして微粉を
得た。この微粉は平均粒径３．８μｍ（Ｆ．Ｓ．Ｓ．
Ｓ．）であり、含有酸素量は４９００ｐｐｍであった。
次に、この微粉を配向磁場強度１５ｋＯｅ、成形圧力
１．５ｔｏｎ／ｃｍ2の条件下で磁場中プレス成形し、
３０×２０×１５の成形体を作製した。 この成形体は
実質的に真空の条件で１０８０℃×３ｈｒの焼結を行
い、得られた焼結体に９００℃×２ｈｒの第１次熱処
理、次いで５３０℃×２ｈｒの第２次熱処理を施した。
得られた焼結体の密度は７．５５〜７．５８ｇ／ｃｃ、
また含有酸素量は４４００ｐｐｍであった。これら試料
について、常温磁気特性、および平均粒径を測定し、図
７に示すような結果を得た。図７に示されるようにＮｂ
を含有させることにより焼結時の結晶粒成長を抑制で
き、その結果焼結体平均粒径を小さくできる。また、こ
の効果により保磁力ｉＨｃの向上を期待できる。２．０
ｗｔ％以上の含有によっても平均粒径の減少をさほど期
待出来ず、また最大エネルギ−積（ＢＨ）ｍａｘの低下
も大きくなるので０．４〜２．０ｗｔ％の添加が適量で
ある。Example 7 Didymium metal (Nd 70 wt)
% -Pr30wt%), metal Dy, Fe, Co, fer
A predetermined weight of ro-B, ferro-Nb, and metallic Ga was weighed, and this was vacuum-melted to produce ingots each weighing 10 kg. When the composition of this ingot was analyzed, it had the following composition by weight ratio. (Nd + Pr) 28.0-Dy4.0-B1.03-Nbx-Ga0.15-Co2.04-Al0.35-Febal. (0≤x≤1.0) (wt%) After crushing each ingot with a hammer Further, coarse pulverization is performed in an inert gas atmosphere using a coarse pulverizer and 500
A coarse powder with a particle size of less than μm was obtained. This coarse powder was finely pulverized in the same inert gas atmosphere using a jet mill to obtain fine powder. This fine powder has an average particle size of 3.8 μm (FSS.
S. ), And the oxygen content was 4900 ppm.
Next, this fine powder is press-molded in a magnetic field under the conditions of an orientation magnetic field strength of 15 kOe and a molding pressure of 1.5 ton / cm 2 ,
A 30 × 20 × 15 molded body was produced. This molded body was sintered at 1080 ° C. for 3 hours under substantially vacuum conditions, and the obtained sintered body was subjected to a first heat treatment at 900 ° C. for 2 hours and then a second heat treatment at 530 ° C. for 2 hours. did.
The density of the obtained sintered body was 7.55 to 7.58 g / cc,
The oxygen content was 4400 ppm. The magnetic properties at room temperature and the average particle size of these samples were measured, and the results shown in FIG. 7 were obtained. Nb as shown in FIG.
By including the above, crystal grain growth during sintering can be suppressed, and as a result, the average grain size of the sintered body can be reduced. Further, this effect can be expected to improve the coercive force iHc. 2.0
Even if the content is more than wt%, the average particle size cannot be expected to be reduced so much, and the maximum energy product (BH) max is also greatly reduced, so 0.4 to 2.0 wt% is an appropriate amount.
【００２０】（実施例８）金属Ｎｄ、金属Ｄｙ、Ｆｅ、
Ｃｏ、ｆｅｒｒｏ−Ｂ、ｆｅｒｒｏ−Ｎｂ、金属Ｇａを
所定の重量秤量し、これを真空溶解して重量１０ｋｇの
インゴットを作製した。このインゴットの成分分析を行
なうと重量比で以下のような組成であった。 Ｎｄ
27.5−Ｄｙ4.0−Ｂ1.04−Ｎｂ0.59−Ｇａ0.19−Ｃｏa−
Ａｌb−Ｆｅbal. a＝0 b＝0 a＝2.02 b＝0 a＝2.10 b＝0.34 （ｗｔ％） 各々のインゴットをハンマーで解砕した後、さらに粗粉
砕機を用い不活性ガス雰囲気中での粗粉砕を行い５００
μｍ以下の粒度の粗粉を得た。この粗粉を同じくジェッ
トミルを用い不活性ガス雰囲気中で微粉砕をして微粉を
得た。この微粉は平均粒径３．８μｍ（Ｆ．Ｓ．Ｓ．
Ｓ．）であり、含有酸素量は６０００〜６４００ｐｐｍ
であった。次に、この微粉を配向磁場強度１５ｋＯｅ、
成形圧力１．５ｔｏｎ／ｃｍ2の条件下で磁場中プレス
成形し、３０×２０×１５の成形体を 作製した。この
成形体は実質的に真空の条件で１１００℃×２ｈｒの焼
結を行い、得られた焼結体に９００℃×２ｈｒの第１次
熱処理、次いで５００〜６００℃×２ｈｒの第２次熱処
理を施した。得られた焼結体の密度は７．５６〜７．５
９ｇ／ｃｃ、また含有酸素量は５４００〜５９００ｐｐ
ｍであった。これら試料について常温磁気特性を測定
し、図８に示されるような結果を得た。図８に示される
ように、Ｃｏを単独で添加したものはＣｏ及びＡｌ無添
加のものと比較して第２次熱処理温度依存性が大きくな
る。これでは、工業生産上安定した特性の製品をつくる
ことが困難である。そこで、Ｃｏ及びＡｌを複合添加す
ると図のように第２次熱処理温度依存性を小さくするこ
とができ、この問題を回避することができる。次に前記
（Ｃｏ無添加）、（Ｃｏ添加）、（Ｃｏ，Ａｌ添
加）の組成を有する磁石にＮｉメッキを施して、その密
着性を評価した。Ｎｉメッキは、ワット浴による電解メ
ッキで膜厚１０μｍとした。メッキ処理後水洗いして１
００℃で５分間乾燥後メッキ密着性試験を行った。結果
は下記の通りであり、Ｃｏ添加材が優れたメッキ密着性
を有する。 材 質 密着強度（Ｋｇｆ／ｃｍ2） （Ｃｏ無添加） １８０ （Ｃｏ添加） ６８０ （Ｃｏ，Ａｌ添加） ７００Example 8 Metal Nd, metals Dy, Fe,
A predetermined weight of Co, ferro-B, ferro-Nb, and metallic Ga was weighed, and this was melted in vacuum to produce an ingot having a weight of 10 kg. When the composition of this ingot was analyzed, it had the following composition by weight ratio. Nd
27.5-Dy4.0-B1.04-Nb0.59-Ga0.19-Coa-
Alb-Febal. A = 0 b = 0 a = 2.02 b = 0 a = 2.10 b = 0.34 (wt%) After crushing each ingot with a hammer, further using a coarse crusher in an inert gas atmosphere Coarse crushing 500
A coarse powder with a particle size of less than μm was obtained. This coarse powder was finely pulverized in the same inert gas atmosphere using a jet mill to obtain fine powder. This fine powder has an average particle size of 3.8 μm (FSS.
S. ), And the oxygen content is 6000 to 6400 ppm
Met. Next, this fine powder is applied with an orientation magnetic field strength of 15 kOe,
Press molding was performed in a magnetic field under a molding pressure of 1.5 ton / cm 2 to prepare a 30 × 20 × 15 compact. This compact was sintered at 1100 ° C. × 2 hr under a substantially vacuum condition, and the obtained sintered compact was subjected to a first heat treatment at 900 ° C. × 2 hr and then a second heat treatment at 500 to 600 ° C. × 2 hr. Was applied. The density of the obtained sintered body is 7.56 to 7.5.
9g / cc, and oxygen content is 5400-5900pp
It was m. The ambient temperature magnetic characteristics of these samples were measured, and the results shown in FIG. 8 were obtained. As shown in FIG. 8, when Co is added alone, the temperature dependence of the secondary heat treatment becomes larger than when Co and Al are not added. In this case, it is difficult to produce a product having stable characteristics in industrial production. Therefore, when Co and Al are added together, the temperature dependence of the secondary heat treatment can be reduced as shown in the figure, and this problem can be avoided. Next, the magnets having the above-mentioned (Co-free), (Co-added), and (Co, Al-added) compositions were plated with Ni, and their adhesion was evaluated. The Ni plating was electrolytically plated with a watt bath to a film thickness of 10 μm. After plating, wash with water 1
After drying at 00 ° C for 5 minutes, a plating adhesion test was conducted. The results are as follows, and the Co additive has excellent plating adhesion. Material Adhesion strength (Kgf / cm 2 ) (Co not added) 180 (Co added) 680 (Co, Al added) 700
【００２１】[0021]
【発明の効果】以上、実施例に示したようにＮｄ−Ｆｅ
−Ｃｏ−Ｂ型焼結磁石にＧａ、Ａｌ、Ｎｂを複合添加
し、Ｄｙ量を適正範囲で添加することにより、高保磁力
かつ高エネルギ−積を有し、高耐熱性、高耐食性を有す
る磁石を安定的に得ることができる。INDUSTRIAL APPLICABILITY As described in the above examples, Nd-Fe
A magnet having high coercive force, high energy product, high heat resistance, and high corrosion resistance by adding Ga, Al, and Nb in combination to a Co-B type sintered magnet and adding Dy in an appropriate range. Can be stably obtained.
【図１】Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石の全希土類量
に対する最大エネルギ−積（ＢＨ）ｍａｘ、腐食減量の
変化を示したグラフ。FIG. 1 is a graph showing changes in maximum energy product (BH) max and corrosion weight loss with respect to the total amount of rare earth in a Nd-Fe-Co-B type sintered magnet.
【図２】Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石の含有酸素量
に対する最大エネルギ−積（ＢＨ）ｍａｘ、保磁力ｉＨ
ｃの変化を示したグラフ。FIG. 2 shows the maximum energy product (BH) max and the coercive force iH with respect to the oxygen content of a Nd-Fe-Co-B type sintered magnet.
The graph which showed the change of c.
【図３】Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石のＧａ含有量
（０〜１．２ｗｔ％）に対する最大エネルギ−積（Ｂ
Ｈ）ｍａｘ、保磁力ｉＨｃの変化を示したグラフ。FIG. 3 shows the maximum energy product (B) with respect to the Ga content (0 to 1.2 wt%) of the Nd-Fe-Co-B type sintered magnet.
H) max, a graph showing changes in coercive force iHc.
【図４】Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石のＧａ含有量
に対する最大エネルギ−積（ＢＨ）ｍａｘ、保磁力ｉＨ
ｃ、腐食減量の変化を示したグラフ。FIG. 4 shows the maximum energy product (BH) max and the coercive force iH with respect to the Ga content of the Nd-Fe-Co-B type sintered magnet.
c, a graph showing changes in corrosion weight loss.
【図５】Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石のＧａ含有量
（０〜０．６ｗｔ％）及びＤｙ含有量に対するする最大
エネルギ−積（ＢＨ）ｍａｘ、保磁力ｉＨｃの変化を示
したグラフ。FIG. 5 shows changes in maximum energy product (BH) max and coercive force iHc with respect to Ga content (0 to 0.6 wt%) and Dy content of an Nd-Fe-Co-B type sintered magnet. Graph.
【図６】Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石のＧａ含有量
（０〜０．６ｗｔ％）に対する最大エネルギ−積（Ｂ
Ｈ）ｍａｘ、保磁力ｉＨｃ、角型性の変化を示したグラ
フ。FIG. 6 shows the maximum energy product (B) with respect to the Ga content (0 to 0.6 wt%) of the Nd-Fe-Co-B type sintered magnet.
H) max, coercive force iHc, and a graph showing changes in squareness.
【図７】Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石のＮｂ含有量
に対する焼結体平均結晶粒径、最大エネルギ−積（Ｂ
Ｈ）ｍａｘの変化を示したグラフ。FIG. 7 is an average crystal grain size of the sintered body, a maximum energy product (B) with respect to the Nb content of the Nd-Fe-Co-B type sintered magnet.
H) A graph showing changes in max.
【図８】Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石のＣｏ、Ａｌ
添加による第２次熱処理温度依存性の変化を示したグラ
フ。FIG. 8 Co and Al of Nd-Fe-Co-B type sintered magnet
The graph which showed the change of the secondary heat treatment temperature dependence by addition.
Claims (8)
び希土類元素から選ばれた少なくとも１種であり、Ｒの
内、３．０〜８．０ｗｔ％がＤｙ，残りは、Ｎｄ又はＰ
ｒの１種又は２種であり、ＮｄをＲの内に５０ａｔ％以
上を含む）、５．０ｗｔ％以下のＣｏ（但し、Ｃｏは必
ず含む）、０．１〜１．０ｗｔ％のＡｌ、０．５〜２．
０ｗｔ％のＢ、０．１〜２．０ｗｔ％のＮｂ、０．０５
〜１．０ｗｔ％のＧａ、１０００ｐｐｍ〜６０００ｐｐ
ｍの酸素、及び不可避的不純物を含有し、残部が主とし
てＦｅからなり保磁力ｉＨｃが２０ｋＯｅ以上、最大磁
気エネルギー積（ＢＨ）ｍａｘが３０ＭＧＯｅ以上であ
る耐食性、耐熱性に優れたＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結
磁石。1. 28 to 32 wt% of R (provided that R is at least one selected from Y and rare earth elements, 3.0 to 8.0 wt% of R is Dy, and the rest is Nd or P
1 or 2 of r, and Nd contains 50 at% or more of R in R), 5.0 wt% or less of Co (however, Co is always included), 0.1 to 1.0 wt% of Al, 0.5-2.
0 wt% B, 0.1-2.0 wt% Nb, 0.05
~ 1.0wt% Ga, 1000ppm ~ 6000pp
Nd-Fe-Co excellent in corrosion resistance and heat resistance containing m of oxygen and unavoidable impurities, the balance mainly consisting of Fe, coercive force iHc of 20 kOe or more, and maximum magnetic energy product (BH) max of 30 MGOe or more. -B type sintered magnet.
ある請求項１記載のＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石。2. The Nd—Fe—Co—B type sintered magnet according to claim 1, wherein the Ga content is 0.05 to 0.8 wt%.
る請求項１記載のＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石。3. The Nd—Fe—Co—B type sintered magnet according to claim 1, which has a Ga content of 0.1 to 0.6 wt%.
る請求項１記載のＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石。4. The Nd—Fe—Co—B type sintered magnet according to claim 1, which has a Ga content of 0.1 to 0.4 wt%.
あり、最大磁気エネルギー積（ＢＨ）ｍａｘが３５ＭＧ
Ｏｅ以上である請求項１〜請求項４のいずれかに記載の
Ｎｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁石。5. 3.0 to 5.0 wt% of R is Dy, and the maximum magnetic energy product (BH) max is 35 MG.
It is Oe or more, The Nd-Fe-Co-B type | mold sintered magnet in any one of Claims 1-4.
あり、保磁力ｉＨｃが２５ｋＯｅ以上である請求項１〜
請求項４のいずれかに記載のＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼
結磁石。6. R to 5.0-8.0 wt% is Dy, and coercive force iHc is 25 kOe or more.
The Nd-Fe-Co-B type sintered magnet according to claim 4.
力ｉＨｃ各々の温度係数α，βが −０．１２≦α≦−０．０８％／℃ −０．６５≦β≦−０．４０％／℃ である請求項１記載のＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結磁
石。7. The room temperature magnetic characteristics are iHc ≧ 20 kOe, (BH) max ≧ 30 MGOe, and the temperature coefficient α, β of each of the residual magnetic flux density Br and the coercive force iHc from 23 ° C. to 120 ° C. is −0.12 ≦ α. The Nd-Fe-Co-B type sintered magnet according to claim 1, wherein ≤ -0.08% / ° C -0.65 ≤ β ≤ -0.40% / ° C.
求項７のいずれかに記載のＮｄ−Ｆｅ−Ｃｏ−Ｂ型焼結
磁石。8. The Nd—Fe—Co—B type sintered magnet according to claim 1, wherein the surface is plated with Ni.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04249113A JP3080275B2 (en) | 1992-09-18 | 1992-09-18 | R-Fe-Co-Al-Nb-Ga-B sintered magnet excellent in corrosion resistance and heat resistance and method for producing the same |
| DE4331563A DE4331563A1 (en) | 1992-09-18 | 1993-09-16 | Sintered permanent magnet with good thermal stability - containing defined percentages by weight of specified elements |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04249113A JP3080275B2 (en) | 1992-09-18 | 1992-09-18 | R-Fe-Co-Al-Nb-Ga-B sintered magnet excellent in corrosion resistance and heat resistance and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06104108A true JPH06104108A (en) | 1994-04-15 |
| JP3080275B2 JP3080275B2 (en) | 2000-08-21 |
Family
ID=17188151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04249113A Expired - Lifetime JP3080275B2 (en) | 1992-09-18 | 1992-09-18 | R-Fe-Co-Al-Nb-Ga-B sintered magnet excellent in corrosion resistance and heat resistance and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3080275B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06231921A (en) * | 1993-01-29 | 1994-08-19 | Hitachi Metals Ltd | Nd-fe-b type permanent magnet |
| US7534311B2 (en) | 2003-08-12 | 2009-05-19 | Hitachi Metals, Ltd. | R-t-b sintered magnet and rare earth alloy |
| CN102592775A (en) * | 2011-01-17 | 2012-07-18 | 三环瓦克华（北京）磁性器件有限公司 | High-performance neodymium iron boron sintered magnet and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019102707A (en) | 2017-12-05 | 2019-06-24 | Tdk株式会社 | R-t-b based permanent magnet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6399502A (en) * | 1986-06-12 | 1988-04-30 | Toshiba Corp | Permanent magnet and manufacture thereof |
| JPH04184901A (en) * | 1990-11-20 | 1992-07-01 | Shin Etsu Chem Co Ltd | Rare earth iron based permanent magnet and its manufacture |
-
1992
- 1992-09-18 JP JP04249113A patent/JP3080275B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6399502A (en) * | 1986-06-12 | 1988-04-30 | Toshiba Corp | Permanent magnet and manufacture thereof |
| JPH04184901A (en) * | 1990-11-20 | 1992-07-01 | Shin Etsu Chem Co Ltd | Rare earth iron based permanent magnet and its manufacture |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06231921A (en) * | 1993-01-29 | 1994-08-19 | Hitachi Metals Ltd | Nd-fe-b type permanent magnet |
| US7534311B2 (en) | 2003-08-12 | 2009-05-19 | Hitachi Metals, Ltd. | R-t-b sintered magnet and rare earth alloy |
| CN102592775A (en) * | 2011-01-17 | 2012-07-18 | 三环瓦克华（北京）磁性器件有限公司 | High-performance neodymium iron boron sintered magnet and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3080275B2 (en) | 2000-08-21 |
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