JPH07192907A - Permanent magnet material of high coercive-force pr-co alloy and permanent magnet material of thin-film and manufacture thereof - Google Patents
Permanent magnet material of high coercive-force pr-co alloy and permanent magnet material of thin-film and manufacture thereofInfo
- Publication number
- JPH07192907A JPH07192907A JP5332969A JP33296993A JPH07192907A JP H07192907 A JPH07192907 A JP H07192907A JP 5332969 A JP5332969 A JP 5332969A JP 33296993 A JP33296993 A JP 33296993A JP H07192907 A JPH07192907 A JP H07192907A
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- Prior art keywords
- atomic
- alloy
- coercive force
- permanent magnet
- magnet material
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- 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
-
- 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
- H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
- H01F1/0556—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together pressed
-
- 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
- H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
- H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
- H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
- H01F10/12—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being metals or alloys
- H01F10/126—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being metals or alloys containing rare earth metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はＰｒ及びＣｏを主成分と
し、不可避の不純物からなるもの、及びこれに副成分と
してＦｅ，Ｃｕ，Ｗ，Ｔｉ，Ｃｅ，Ｓｍのうち１種また
は２種以上を含む粉末を加圧成形あるいは射出成形した
のち加熱、焼結した合金及び薄膜の永久磁石材料及びそ
の製造方法に関するもので、その目的とするところは保
磁力が極めて大きく小型で強力な永久磁石材料を提供す
ることにある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention comprises Pr and Co as main components and inevitable impurities, and one or more of Fe, Cu, W, Ti, Ce and Sm as auxiliary components. The present invention relates to a permanent magnet material of an alloy and a thin film obtained by pressure-molding or injection-molding a powder containing Pt, and then sintering the powder, and a method for manufacturing the same. To provide.
【０００２】[0002]
【従来の技術】最近、高性能永久磁石材料としてＦｅ−
Ｐｔ系、Ｎｄ−Ｆｅ−Ｂ系、Ｓｍ−Ｆｅ−Ｎ系合金や化
合物等が発見され、目覚ましい進展がみられている。一
方、電子技術の発展によって、小型で高性能の電子機器
が次々と生産されるようになった。特に上述した高特性
を有する永久磁石材料及びマイクロ磁気デバイスの研究
が盛んに行われており、その優れた特性によって機器の
小型化及び精密化に著しく貢献している。本発明に係わ
る高保磁力を有する小型の永久磁石材料は磁気記録、微
少な電磁アクチュエータあるいは磁気抵抗ヘッドのバイ
アス磁場の素子としての応用も考えられている。2. Description of the Related Art Recently, Fe-- has been used as a high-performance permanent magnet material.
Pt-based, Nd-Fe-B-based, Sm-Fe-N-based alloys and compounds have been discovered, and remarkable progress has been made. On the other hand, with the development of electronic technology, small and high-performance electronic devices have been produced one after another. In particular, research on the above-mentioned permanent magnet material and micro magnetic device having high characteristics has been actively conducted, and the excellent characteristics have contributed significantly to downsizing and precision of equipment. The small permanent magnet material having a high coercive force according to the present invention is also considered to be applied as a magnetic recording element, a minute electromagnetic actuator, or a bias magnetic field element of a magnetoresistive head.
【０００３】[0003]
【発明が解決しようとする課題】しかし高価なため特殊
な用途に限られるＰｔ系磁石合金（日本金属学会誌56(1
992)1495）耐食性に難点のあるＮｄ−Ｆｅ−Ｂ（日本応
用磁気学会誌14(1990)189 ）あるいは高温に熱処理する
と窒素が分解し優れた特性が失われ、材料の製造法に限
界があるＳｍ−Ｆｅ−Ｎ化合物（日本応用磁気学会誌17
(1993)５）等それぞれにおいて大きな問題をかかえてい
る。However, Pt-based magnet alloys are limited to special applications because they are expensive (Journal of the Japan Institute of Metals 56 (1)
992) 1495) Nd-Fe-B (Journal of Japan Society for Applied Magnetics 14 (1990) 189), which has difficulty in corrosion resistance, or nitrogen is decomposed by heat treatment at high temperature and excellent properties are lost, and there is a limit to the manufacturing method of the material. Sm-Fe-N compound (Journal of Japan Applied Magnetics Society 17
(1993) 5) Each of them has major problems.
【０００４】ＰｒＣｏ5 系永久磁石材料は1970年代にＳ
ｍＣｏ5 系磁石材料とほぼ同時に見い出されたもので、
両者の結晶構造はＣａＣｕ5 （六方格子）型を有してい
る。後者のＳｍＣｏ5 化合物は優れた磁石特性を発揮し
て極めて有名であるが、ＰｒＣｏ5 化合物は飽和磁化が
高く有利な条件を持っているにもかかわらず保磁力は最
高590 ｋＡ／ｍで（J.Less-Common Metals 148(1989)6
7）で希土類磁石としては低く（J.MMM 94(1991)57）未
だに実用化されていない。従来の研究結果によれば、低
い保磁力の原因は、図１に示してあるＰｒ−Ｃｏ系合金
の平衡状態図からわかるようにＰｒＣｏ5 に隣接するＰ
ｒ5 Ｃｏ19の化合物（斜方晶）が軟磁性的特性を有し、
これが高保磁力化を妨げるものと考えられていた。PrCo 5 based permanent magnet materials were S in the 1970s.
It was found almost at the same time as the mCo 5 based magnet material,
Both crystal structures have a CaCu 5 (hexagonal lattice) type. The latter SmCo 5 compound is extremely famous for its excellent magnet properties, but the PrCo 5 compound has a high coercive force of up to 590 kA / m even though it has favorable conditions because of its high saturation magnetization (J .Less-Common Metals 148 (1989) 6
7) It is low as a rare earth magnet (J.MMM 94 (1991) 57) and has not yet been put to practical use. According to the results of conventional studies, the cause of the low coercive force is that the P adjacent to PrCo 5 is as shown in the equilibrium diagram of the Pr—Co alloy shown in FIG.
The compound of r 5 Co 19 (orthorhombic) has soft magnetic properties,
It was thought that this hinders the increase in coercive force.
【０００５】しかし本発明は、それ等の結果を確かめる
ためＰｒＣｏ5 の組成からＰｒ量が多いＰｒ5 Ｃｏ19，
Ｐｒ2 Ｃｏ7 及びＰｒＣｏ3 を含みしかも自発磁化の認
められるＰｒが約30原子％を含む広い組成領域にわたっ
て研究を行った。その結果、これら化合物はボールミル
によって１〜20μｍに微細化し、そのまま加圧成形ある
いは射出成形したもの、さらにそれらの成形物を熱処理
することによって従来の保磁力より２〜10倍にも及ぶ大
きな値が得られることを明らかにし（日本金属学会講演
概要（1993年)181）、それ等の結果からＰｒ−Ｃｏ系合
金の永久磁石特性と組成との関係を表１及び図２に示し
た。However, according to the present invention, in order to confirm the results, Pr 5 Co 19 , which has a large amount of Pr from the composition of PrCo 5 ,
The study was carried out over a wide composition range including Pr 2 Co 7 and PrCo 3 and about 30 atomic% of Pr in which spontaneous magnetization is recognized. As a result, these compounds were miniaturized to 1 to 20 μm by a ball mill, pressed or injection molded as they were, and by heat-treating these molded products, the coercive force was 2 to 10 times larger than the conventional value. It was clarified that it was obtained (Summary of presentation of the Japan Institute of Metals (1993) 181), and from these results, the relationship between the permanent magnet characteristics and the composition of Pr—Co alloys is shown in Table 1 and FIG.
【０００６】また本合金は薄膜化しても高い保磁力が得
られることを確かめるため、室温の基板に成膜後300 〜
800 ℃に加熱したものあるいは300 〜800 ℃に加熱され
た基板上に薄膜を作製することによって高保磁力が得ら
れることを明らかにすることができた。Further, in order to confirm that the present alloy can obtain a high coercive force even if it is made into a thin film, after forming a film on a substrate at room temperature,
It was clarified that a high coercive force can be obtained by forming a thin film on a substrate heated to 800 ℃ or a substrate heated to 300 to 800 ℃.
【０００７】[0007]
【表１】 [Table 1]
【０００８】[0008]
【課題を解決するための手段】本発明はＰｒＣｏ5 から
ＰｒＣｏ3 の組成合金の粉末を加圧成形あるいは射出成
形したのち加熱したもの及び同等の組成を有する薄膜を
基板上に成膜したものを加熱あるいは加熱された基板上
に成膜することによって1200ｋＡ／ｍ以上の超高保磁力
を有する永久磁石材料を提供することにある。According to the present invention, a powder of a composition alloy of PrCo 5 to PrCo 3 is pressure-molded or injection-molded and then heated, and a thin film having an equivalent composition is formed on a substrate. It is to provide a permanent magnet material having an ultrahigh coercive force of 1200 kA / m or more by forming a film on a heated or heated substrate.
【０００９】本発明は上述しておいたように従来得られ
なかった永久磁石材料を発揮させるためになされたもの
で、本発明の特徴は下記の通りである。As described above, the present invention has been made in order to bring out the permanent magnet material which has not been obtained conventionally, and the features of the present invention are as follows.
【００１０】本発明の目的とする所は、主成分としてＰ
ｒを19.5〜30原子％含有し、残部がＣｏ及び不可避の不
純物からなる合金で、保磁力が80ｋＡ／ｍ以上を有する
ことを特徴とする高保磁力Ｐｒ−Ｃｏ系合金の永久磁石
材料を提供するにある。The object of the present invention is to use P as the main component.
Provided is a permanent magnet material of a high coercive force Pr-Co alloy, which is an alloy containing 19.5 to 30 atomic% of r, the balance being Co and unavoidable impurities and having a coercive force of 80 kA / m or more. It is in.
【００１１】本発明の更に他の目的とする所は、主成分
としてＰｒを15〜30原子％含有し、残部がＣｏ及び不可
避の不純物からなり、これに副成分としてＦｅ，Ｃｕ，
Ｗが0.1 〜３原子％及びＴｉ，Ｃｅ，Ｓｍが0.1 〜５原
子％のうち１種または２種以上の元素からなる80ｋＡ／
ｍ以上の保磁力を有することを特徴とする高保磁力Ｐｒ
−Ｃｏ系合金の永久磁石材料を提供とするにある。Still another object of the present invention is to contain Pr as a main component in an amount of 15 to 30 atomic%, and the balance being Co and inevitable impurities.
W of 0.1 to 3 atomic% and Ti, Ce, and Sm of 0.1 to 5 atomic% 80 kA / one or more elements.
High coercive force Pr having a coercive force of m or more
-To provide a permanent magnet material of a Co-based alloy.
【００１２】本発明の更に他の目的とする所は、主成分
としてＰｒを15〜30原子％含有し、残部がＣｏ及び不可
避の不純物からなる合金の薄膜で保磁力が80ｋＡ／ｍ以
上を有することを特徴とする高保磁力Ｐｒ−Ｃｏ系薄膜
の永久磁石材料を提供するにある。Still another object of the present invention is to use an alloy thin film containing Pr as a main component in an amount of 15 to 30 atomic% and the balance being Co and inevitable impurities and having a coercive force of 80 kA / m or more. Another object of the present invention is to provide a permanent magnet material having a high coercive force Pr—Co based thin film.
【００１３】本発明の更に他の目的とする所は、主成分
としてＰｒを15〜30原子％含有し、残部がＣｏ及び不可
避の不純物からなり、これに副成分としてＦｅ，Ｃｕ，
Ｗが0.1 〜３原子％及びＴｉ，Ｃｅ，Ｓｍが0.1 〜５原
子％のうち１種または２種以上の元素からなる合金薄膜
で保磁力が80ｋＡ／ｍ以上を有することを特徴とする高
保磁力Ｐｒ− Ｃｏ系薄膜の薄膜磁石材料を提供するに
ある。Still another object of the present invention is to contain Pr as the main component in an amount of 15 to 30 atomic%, and the balance being Co and inevitable impurities.
A high coercive force characterized by having a coercive force of 80 kA / m or more in an alloy thin film consisting of one or more elements out of 0.1 to 3 atomic% W and 0.1 to 5 atomic% Ti, Ce, Sm. It is to provide a thin film magnet material of a Pr-Co based thin film.
【００１４】本発明の更に他の目的とする所は、主成分
としてＰｒを15〜30原子％含有し、残部がＣｏ及び不可
避の不純物からなる合金をボールミルに５〜30時間かけ
て１〜20μｍに微細化した粉末及び同等の合金成分の金
属粗粒をメカニカル・アロイングして微粉末とし、これ
を加圧成形または磁界中に加圧成形或いは射出成形した
ものを、さらに300 〜1180℃に熱処理あるいは焼結する
ことを特徴とする超高保磁力のＰｒ−Ｃｏ系合金粉末の
永久磁石材料の製造方法を提供するにある。Still another object of the present invention is to use an alloy containing Pr as a main component in an amount of 15 to 30 atom% and the balance being Co and inevitable impurities in a ball mill for 1 to 20 μm in an amount of 5 to 30 hours. Finely pulverized powder and coarse metal particles of an equivalent alloy component are mechanically alloyed into a fine powder, which is then pressure-molded or pressure-molded in a magnetic field or injection-molded, and further heat-treated at 300-1180 ° C. Another object is to provide a method for producing a permanent magnet material of an ultra-high coercive force Pr—Co alloy powder, which is characterized by sintering.
【００１５】本発明の更に他の目的とする所は、主成分
としてＰｒを15〜30原子％含有し、残部がＣｏ及び不可
避の不純物からなり、これに副成分としてＦｅ，Ｃｕ，
Ｗが0.1 〜３原子％及びＴｉ，Ｃｅ，Ｓｍが0.1 〜５原
子％のうち１種または２種以上の元素からなる合金をボ
ールミルに５〜30時間かけて１〜20μｍに微細化した粉
末及び同等の合金成分の金属粗粒をメカニカル・アロイ
ングして微粉末とし、これを加圧成形または磁界中に加
圧成形或いは射出成形したものを、さらに300〜1180℃
に熱処理あるいは焼結することを特徴とする高保磁力Ｐ
ｒ−Ｃｏ系合金の永久磁石材料の製造方法を提供するに
ある。Still another object of the present invention is to contain Pr as a main component in an amount of 15 to 30 atom%, and the balance being Co and inevitable impurities.
A powder obtained by refining an alloy consisting of one or more elements out of 0.1 to 3 atomic% of W and 0.1 to 5 atomic% of Ti, Ce and Sm into 1 to 20 μm in a ball mill for 5 to 30 hours, and Mechanically alloyed coarse metal particles of the same alloy composition into fine powder, and press-molded or pressure-molded or injection-molded this in the magnetic field, and further 300-1180 ℃
High coercive force P characterized by heat treatment or sintering
Another object of the present invention is to provide a method for producing a permanent magnet material of r-Co alloy.
【００１６】本発明の更に他の目的とする所は、主成分
としてＰｒを15〜30原子％含有し、残部がＣｏ及び不可
避の不純物からなる合金をアルゴン、クリプトン、キセ
ノンのうち少なくとも１種の不活性ガスの雰囲気中で、
室温の基板に成膜後、300 〜800 ℃に加熱したものある
いは300 〜800 ℃に加熱した基板上に成膜した薄膜で、
80ｋＡ／ｍ以上の保磁力を有するものを得ることを特徴
とする高保磁力Ｐｒ−Ｃｏ系合金の永久磁石材料の製造
方法を提供するにある。Still another object of the present invention is to use an alloy containing Pr as a main component in an amount of 15 to 30 atomic% and the balance being Co and inevitable impurities, and using at least one of argon, krypton and xenon. In an atmosphere of inert gas,
A thin film deposited on a substrate at room temperature and then heated to 300-800 ° C or a substrate heated to 300-800 ° C.
Another object of the present invention is to provide a method for producing a permanent magnet material of a high coercive force Pr-Co alloy, which is characterized by obtaining a material having a coercive force of 80 kA / m or more.
【００１７】本発明の更に他の目的とする所は、主成分
としてＰｒを15〜30原子％含有し、残部がＣｏ及び不可
避の不純物からなり、これに副成分としてＦｅ，Ｃｕ，
Ｗが0.1 〜３原子％及びＴｉ，Ｃｅ，Ｓｍが0.1 〜５原
子％のうち１種または２種以上の元素からなる合金をア
ルゴン、クリプトン、キセノンのうち少なくとも１種の
不活性ガスの雰囲気中で、室温の基板に成膜した薄膜
で、80ｋＡ／ｍ以上を有するものを得ることを特徴とす
る高保磁力Ｐｒ−Ｃｏ系薄膜永久磁石材料の製造方法を
提供するにある。Still another object of the present invention is to contain Pr as a main component in an amount of 15 to 30 atomic%, and the balance being Co and inevitable impurities, in which Fe, Cu, and
In an atmosphere of an inert gas containing at least one of argon, krypton, and xenon, an alloy of one or more elements selected from 0.1 to 3 atomic% W and 0.1 to 5 atomic% Ti, Ce, and Sm is used. Then, there is provided a method for producing a high coercive force Pr—Co based thin film permanent magnet material, which comprises obtaining a thin film having a film thickness of 80 kA / m or more on a substrate at room temperature.
【００１８】本発明において、メカニカル・アロイング
とはボールミルで長時間（30〜100時間）微粉砕すると
金属結晶質が非晶質或は他の結晶質に変わる現象を言
う。In the present invention, the mechanical alloying means a phenomenon in which a metal crystal is changed to an amorphous or other crystal when it is pulverized for a long time (30 to 100 hours) by a ball mill.
【００１９】1.本発明は19.5〜30原子％Ｐｒ、残部Ｃｏ
及び不可避の不純物を含むＰｒ−Ｃｏ系合金の粉末永久
磁石に係わるものであり、この組成には六方晶のＰｒＣ
ｏ5 あるいはＰｒ2 Ｃｏ7 の結晶構造を有する化合物が
主体となり、これに斜方晶のＰｒ5 Ｃｏ19，ＰｒＣｏ3
の相が少量加わっている。従来Ｐｒ5 Ｃｏ19がＰｒＣｏ
5 の相に少量混合することによってＰｒＣｏ5 （16.7原
子％Ｐｒ）は高保磁力が発揮されないものとされていた
が、本発明はＰｒ5 Ｃｏ19（20.8原子％Ｐｒ）の組成合
金を含む上記組成範囲において超高保磁力を得ることが
できる。さらにより大きな保磁力を発揮させたい場合に
はＰｒが15〜30原子％の組成において副成分としてＦ
ｅ，Ｃｕ，Ｗが0.1 〜３原子％及びＴｉ，Ｃｅ，Ｓｍが
0.1〜５原子％のうち１種または２種以上の元素を加え
ればよい。1. The present invention is 19.5 to 30 atomic% Pr, balance Co
And a powder permanent magnet of a Pr-Co alloy containing unavoidable impurities. This composition has hexagonal PrC.
A compound having a crystal structure of o 5 or Pr 2 Co 7 is mainly used, and an orthorhombic Pr 5 Co 19 , PrCo 3
Is added in a small amount. Conventional Pr 5 Co 19 is PrCo
Although it was said that PrCo 5 (16.7 atom% Pr) does not exhibit a high coercive force by being mixed in a small amount with the 5 phase, the present invention provides the above composition including a composition alloy of Pr 5 Co 19 (20.8 atom% Pr). Ultra high coercive force can be obtained in the range. When a larger coercive force is desired, F is added as an auxiliary component in a composition of Pr of 15 to 30 atom%.
e, Cu, W is 0.1 to 3 atomic% and Ti, Ce, Sm are
It suffices to add one or more elements of 0.1 to 5 atomic%.
【００２０】2.アーク溶解あるいは高周波溶解によって
作られたこれら合金を粗く粉砕した後ボールミルに５時
間以上粉砕して、約１〜20μｍの微粉末にしたもの、あ
るいは目的の合金組成に秤量したそれぞれの金属の粗い
粉末をメカニカル・アロイングした微粉末を１〜10ｔ／
cm2 の圧力で加圧成形又は400 ｋＡ／ｍ以上の磁場中で
加圧成形あるいは射出成形したもの、あるいはその後30
0 〜1180℃に10分から10時間加熱あるいは焼結すること
によって超高保磁力永久磁石材料が得られる。2. These alloys produced by arc melting or high frequency melting were roughly crushed and then crushed in a ball mill for 5 hours or more to obtain fine powder of about 1 to 20 μm, or weighed to a desired alloy composition. 1-10t / of fine powder obtained by mechanical alloying
Pressure molded at a pressure of cm 2 or pressure molded or injection molded in a magnetic field of 400 kA / m or more, or 30 afterwards
An ultra-high coercive force permanent magnet material can be obtained by heating or sintering at 0 to 1180 ° C for 10 minutes to 10 hours.
【００２１】3.本発明は材料の使用目的によって薄膜と
する場合にはＰｒが15〜30原子％及び不可避の不純物を
含む合金薄膜、及び副成分としてＦｅ，Ｃｕ，Ｗあるい
はＴｉ，Ｃｅ，Ｓｍのうち１種または２種以上の元素を
0.1 〜３原子％あるいは0.1 〜５原子％含有し、残部が
Ｃｏとなる合金薄膜を室温の石英又はガラスの基板上に
蒸着したのち300 〜800 ℃に加熱し、あるいは300 〜80
0 ℃に加熱されている基板上に蒸着すればよい。アルゴ
ン、クリプトン、キセノンのうち１種の不活性ガス雰囲
気中においてスパッタリングによって薄膜とすることに
よっても合金粉末と同等の超高保磁力を持つ薄膜の永久
磁石材料が得られる。3. In the present invention, when a thin film is formed depending on the purpose of use of the material, an alloy thin film containing Pr of 15 to 30 atomic% and inevitable impurities, and Fe, Cu, W or Ti, Ce, Sm as a sub-component. One or more of these elements
An alloy thin film containing 0.1 to 3 atomic% or 0.1 to 5 atomic% with the balance being Co is vapor-deposited on a quartz or glass substrate at room temperature and then heated to 300 to 800 ° C, or 300 to 80 ° C.
It may be vapor-deposited on the substrate heated to 0 ° C. By forming a thin film by sputtering in an inert gas atmosphere of one of argon, krypton, and xenon, a thin film permanent magnet material having an ultra-high coercive force equivalent to that of alloy powder can be obtained.
【００２２】[0022]
【実施例】次に本発明の実施例について述べる。 実施例１ 実施例では代表的な磁石（Ａ）Ｐｒが19.5原子％、残り
Ｃｏ及び磁石（Ｂ）Ｐｒが23原子％残りＣｏの２種類の
組成からなる永久磁石材料の熱処理効果を調べ図３に示
した。 (1)まず原料としては99.9％純度の電解Ｃｏ及び電解Ｐ
ｒを用いた。実験の試料を造るには全重量20ｇの原料を
目的の組成に秤量してアーク溶解を行った。試料は数回
にわたり回転させてアーク溶解を繰り返し均質な合金と
した。EXAMPLES Next, examples of the present invention will be described. Example 1 In Example 1, the heat treatment effect of a permanent magnet material composed of two kinds of compositions, a typical magnet (A) Pr was 19.5 atomic% and the remaining Co and magnet (B) Pr was 23 atomic% and the remaining Co was investigated. It was shown to. (1) First, as a raw material, electrolytic Co and electrolytic P having a purity of 99.9%
r was used. In order to prepare a sample for the experiment, a total weight of 20 g of the raw material was weighed to a desired composition and subjected to arc melting. The sample was rotated several times to repeat arc melting and form a homogeneous alloy.
【００２３】(2)これらは更に1080℃に１〜10時間加熱
して均質化処理を施した後粉砕して粗い粉末とし、これ
をボールミルに入れてアルゴンを封したのち微細化して
１〜20μｍの微粉末とし800 ｋＡ／ｍの磁場中に５ｔ／
cm2 の圧力で加圧成形した。なお、等方性の永久磁石材
料の場合には磁場をかけないで加圧する。測定は4000ｋ
Ａ／ｍのパルス磁場で磁化したのちＢＨ磁束計で行っ
た。(2) These are further heated at 1080 ° C. for 1 to 10 hours, homogenized and pulverized to obtain a coarse powder, which is put in a ball mill and sealed with argon and then micronized to 1 to 20 μm. Fine powder of 5 t / in a magnetic field of 800 kA / m
It was pressure molded at a pressure of cm 2 . In the case of an isotropic permanent magnet material, pressure is applied without applying a magnetic field. Measurement is 4000k
It was magnetized with a pulsed magnetic field of A / m and then measured with a BH magnetometer.
【００２４】(3)図３からわかるように加圧成形された
磁石（Ａ）はそのままで450 ｋＡ／ｍの高保磁力 iＨc
及び0.70Ｔの残留磁束密度Ｂｒを示すが、その後さらに
真空中あるいはアルゴン雰囲気中で700 〜950 ℃、１時
間に加熱して焼成すると最高1350ｋＡ／ｍ以上の超高保
磁力 iＨc と0.75ＴのＢｒが得られる。この傾向は磁石
（Ｂ）についても同様であり、1270ｋＡ／ｍ以上の超高
保磁力、0.64Ｔの残留磁束密度Ｂｒを示した。(3) As can be seen from FIG. 3, the pressure-molded magnet (A) remains as it is and has a high coercive force iHc of 450 kA / m.
And 0.70 T of residual magnetic flux density Br. After that, when further heated in a vacuum or an argon atmosphere at 700 to 950 ° C. for 1 hour and baked, an ultra-high coercive force iHc of 1350 kA / m or more and Br of 0.75 T are obtained. can get. This tendency is the same for the magnet (B) as well, showing an ultrahigh coercive force of 1270 kA / m or more and a residual magnetic flux density Br of 0.64 T.
【００２５】(4)また1000℃〜1100℃に加熱し焼結処理
を施すと保磁力 iＨc は減少するが、残留磁束密度Ｂｒ
は加熱温度の上昇とともに漸次増加する。(4) The coercive force iHc decreases when heated to 1000 ° C to 1100 ° C and subjected to a sintering treatment, but the residual magnetic flux density Br
Gradually increases as the heating temperature increases.
【００２６】これらの結果は図３に示した。またこのよ
うにして得られたＰｒ−Ｃｏ系永久磁石材料の代表例は
表１に示した。The results are shown in FIG. Table 1 shows typical examples of the Pr—Co based permanent magnet material thus obtained.
【００２７】実施例２ 本発明に述べた組成の永久磁石材料はメカニカル・アロ
イングによっても容易に得られ、この方法では溶解の必
要がない。ここでは磁石（Ｂ）のＰｒが23原子％−Ｃｏ
合金について実施した例を述べる。Example 2 The permanent magnet material having the composition described in the present invention can be easily obtained by mechanical alloying and does not require melting in this method. Here, Pr of the magnet (B) is 23 atomic% -Co
An example performed on the alloy will be described.
【００２８】(1)まず100 〜200 メッシュ程度の粗いＣ
ｏ粉末とヤスリで削ったＰｒを必要な組成に秤量し、こ
れらをボールミルに入れアルゴンガスを封入してメカニ
カル・アロイングを50時間行って微粉末とし、800 ｋＡ
／ｍの磁場中において５ ｔ／cm2 の圧力で加圧成形し
た。(1) First, a coarse C of about 100 to 200 mesh
o Powder and sanded Pr were weighed to the required composition, placed in a ball mill, filled with argon gas, and mechanically alloyed for 50 hours to obtain fine powder, 800 kA
In a magnetic field of / m, pressure molding was performed at a pressure of 5 t / cm 2 .
【００２９】(2)この成形物の保磁力 iＨc は低く12ｋ
Ａ／ｍ程度であったが、800 ℃の真空炉に入れ１時間加
熱すると1400ｋＡ／ｍ以上の超高保磁力及び0.65Ｔの残
留磁束密度Ｂｒが得られ、アーク溶解した場合と同等の
特性が得られる。(2) The coercive force iHc of this molded product is low and is 12k.
It was about A / m, but when placed in a vacuum furnace at 800 ° C and heated for 1 hour, an ultra-high coercive force of 1400 kA / m or more and a residual magnetic flux density Br of 0.65 T were obtained, and the same characteristics as when arc melting was obtained. To be
【００３０】実施例３ Ｐｒ−Ｃｏ２元系を主成分としてこれに副成分として代
表的なＰｒ18Ｔｉ2 −Ｃｏ80，Ｐｒ17Ｃｕ3 Ｃｏ80，Ｐ
ｒ17Ｃｅ3 Ｃｏ80合金をアーク溶解し、これらをボール
ミルに入れてアルゴン封入した後、10時間微細化して１
〜20μｍの微粉末としたのち800 〜900 ℃に１時間加熱
し、これを4000ｋＡ／ｍのパルス磁場にかけたのち測定
して得られた減磁曲線の結果をＰｒ19.5Ｃｏ80.3の結果
と比較して図４に示した。これから分かるようにＣｅ系
は保磁力 iＨc は変わらないが残留磁束密度Ｂｒが増加
する。Ｔｉ及びＣｕを添加した場合には保磁力 iＨc が
増加するがＢｒが減少している。なお、図５にはＰｒ
20-xＸx Ｃｏ80（ｘは副成分）として副成分の原子％と
保磁力と残留磁束密度との関係が示してある。Example 3 A Pr-Co binary system as a main component and Pr 18 Ti 2 -Co 80 , Pr 17 Cu 3 Co 80 , P, which are typical as subcomponents, were added.
The r 17 Ce 3 Co 80 alloy was arc-melted, placed in a ball mill and filled with argon, and then refined for 10 hours to 1
After making it into a fine powder of ~ 20μm, heating it at 800-900 ° C for 1 hour, applying it to a pulsed magnetic field of 4000kA / m, and measuring it, the result of the demagnetization curve was compared with that of Pr 19.5 Co 80.3. And shown in FIG. As can be seen from this, in the Ce system, the coercive force iHc does not change, but the residual magnetic flux density Br increases. When Ti and Cu are added, the coercive force iHc increases but Br decreases. In addition, in FIG.
20-x X x Co 80 ( x is subcomponent) are the relationship between the atomic% and the coercive force of the secondary components and residual magnetic flux density shown as.
【００３１】実施例４ 製造法の実施例としてＰｒが18.5原子％−Ｃｏ合金の場
合について述べる。 (1)本発明では上記の合金をアーク溶解しこれを1050℃
で均質化したのち粗粉砕した粉末を、さらにアルゴンを
封じたボールミルで10時間微粉砕して１〜20μｍの微粉
末を得て、これを800 ｋＡ／ｍの磁場で５ｔ／cm2 で加
圧成形するだけで既に455 ｋＡ／ｍの高保磁力 iＨc が
得られた。Example 4 As an example of the manufacturing method, a case where Pr is 18.5 atomic% -Co alloy will be described. (1) In the present invention, the above alloy is arc-melted and then melted at 1050 ° C.
The powder was homogenized and then coarsely pulverized with a ball mill containing argon for 10 hours to obtain a fine powder of 1 to 20 μm, which was pressed under a magnetic field of 800 kA / m at 5 t / cm 2. A high coercive force iHc of 455 kA / m was already obtained only by molding.
【００３２】(2)更に上記の合金を、750 〜900 ℃のう
ち、ここでは850 ℃に１時間加熱することによって1270
ｋＡ／ｍの超高保磁力 iＨc 、0.82Ｔの残留磁束密度
Ｂｒが得られる。(2) Further, by heating the above alloy to 850 ° C., here 850 ° C., for 1 hour among 750 to 900 ° C., 1270
An ultrahigh coercive force iHc of kA / m and a residual magnetic flux density Br of 0.82T can be obtained.
【００３３】(3)しかし上記の合金について、従来行わ
れていた４時間のボールミリングを行ったところ図３に
示したSchweizer らの値（IEEE Trans.Mag.Sept.(1971)
429 ）とほぼ等しく最高500 ｋＡ／ｍの値が得られる
が、この1100℃の温度では、本発明では既に保磁力が低
下の段階にある。また合金粉末の粒度が微細化されてい
るため850 ℃の加熱でほぼ焼結に近い結果が得られ、そ
のときの比重は合金の95％以上に達し、ビッカース硬度
は約500 であった。(3) However, when the above-mentioned alloy was subjected to conventional ball milling for 4 hours, the values of Schweizer et al. Shown in FIG. 3 (IEEE Trans.Mag.Sept. (1971))
429) and a maximum value of 500 kA / m can be obtained, but at this temperature of 1100 ° C., the coercive force of the present invention is already at the stage of decreasing. In addition, since the grain size of the alloy powder was made fine, a result close to sintering was obtained by heating at 850 ° C. At that time, the specific gravity reached 95% or more of the alloy, and the Vickers hardness was about 500.
【００３４】実施例５ 高周波マグネトロンスパッタ法によりＰｒ−Ｃｏ合金を
成膜した。ターゲットはＣｏ板上にＰｒチップを配置し
た複合型である。ここでは組成が Ｐｒ19.5Ｃｏ80.5と
なるようにＰｒのチップを変化させた。最初真空にした
後成膜中のアルゴンガス圧力５ｍＴｏｒｒ、投入電力10
0 Ｗのもとでスパッタを行った。基板としては石英（Ｓ
ｉＯ2 ）を用い、基板温度を650 〜700 ℃とした。これ
をマイクロマグネトメータで測定したところほとんど合
金粉末系磁石と同様1200ｋＡ／ｍ以上の超高保磁力が得
られた。Example 5 A Pr—Co alloy film was formed by a high frequency magnetron sputtering method. The target is a composite type in which a Pr chip is arranged on a Co plate. Here, the Pr tip was changed so that the composition was Pr 19.5 Co 80.5 . Argon gas pressure during film formation 5 mTorr, power input 10 after first vacuuming
Sputtering was performed under 0 W. Quartz (S
iO 2 ) was used and the substrate temperature was 650 to 700 ° C. When measured with a micro magnetometer, an ultra-high coercive force of 1200 kA / m or more was obtained almost like the alloy powder magnet.
【００３５】本発明において合金粉末、薄膜永久磁石材
料及び製造条件の限定理由を述べると次の通りである。 (1)Ｐｒ−Ｃｏ系合金において主成分としてＰｒを19.5
〜30原子％、保磁力が80ｋＡ／ｍとしたのは、Ｐｒが1
9.5原子％未満は既にＰｒＣｏ5 化合物として研究成果
が報告されているからであり、Ｐｒが30原子％以上は磁
化が認められず磁石材料にならないからである。The reasons for limiting the alloy powder, the thin film permanent magnet material and the manufacturing conditions in the present invention are as follows. (1) Pr-Co alloy containing Pr as a main component at 19.5
〜30 at.% And coercive force of 80 kA / m, Pr is 1
This is because research results have already been reported as PrCo 5 compounds when the content is less than 9.5 atomic%, and magnetization is not recognized and a magnetic material cannot be obtained when Pr is 30 atomic% or more.
【００３６】(2)合金の製造過程に精錬材として不可避
の不純物として混入されるＭｇ，Ｍｎ，Ｓｉ，Ｃ，Ｃａ
はこれが0.5 原子％を超えて残留すると永久磁石特性が
劣化するので、これら不純物は0.5 ％以下とするのが好
ましい。(2) Mg, Mn, Si, C, Ca mixed as unavoidable impurities as refining material in the manufacturing process of the alloy
If 0.5% by weight remains, the characteristics of the permanent magnet deteriorate. Therefore, it is preferable that these impurities be 0.5% or less.
【００３７】(3)副成分としてＴｉ，Ｆｅ，Ｃｕ，Ｗ，
Ｃｅ，Ｓｍのうち何れか１種または２種以上を0.1 〜５
原子％添加することは、合計添加量が0.1 原子％以下で
は効果がなく、また合計添加量が５原子％を超えると永
久磁石特性が劣化するのでそれらの合計添加量を0.1 〜
５原子％と限定した。(3) Ti, Fe, Cu, W, and
Any one or more of Ce and Sm is 0.1 to 5
Addition of at.% Is ineffective if the total addition amount is less than 0.1 at.%, And if the total addition amount exceeds 5 at.%, The permanent magnet characteristics deteriorate.
Limited to 5 atom%.
【００３８】(4)副成分として他元素を添加した合金及
び薄膜の永久磁石材料の主成分のＰｒを15〜30原子％、
保磁力が80ｋＡ／ｍ以上と限定したのは全く新規の材料
として発明したもので、これ以外の組成では永久磁石特
性が得られないからである。(4) Pr, which is the main component of the alloy and thin film permanent magnet material to which another element is added as a subcomponent, is 15 to 30 atomic%,
The coercive force was limited to 80 kA / m or more because it was invented as a completely new material and permanent magnet characteristics cannot be obtained with other compositions.
【００３９】(5)スパッタリングの雰囲気をきめたのは
大気中、又は真空中では薄膜の生成が極めて困難であり
成膜できなくなるが、アルゴン、クリプトン、キセノン
の１種の不活性ガスの雰囲気でスパッタリングを行うこ
とにより不純物の少ない良質の薄膜が得られるからであ
る。(5) The atmosphere for sputtering is determined in the air or in vacuum because it is extremely difficult to form a thin film and film formation cannot be performed. However, in an atmosphere of an inert gas of argon, krypton or xenon. This is because a good quality thin film with few impurities can be obtained by performing sputtering.
【００４０】[0040]
【発明の効果】本発明は従来永久磁石材料としてとらえ
られていなかったＰｒ−Ｃｏ系合金の１〜20μｍの微粉
末及びメカニカルアロイングにより作られた微粉末を加
圧成形、それを熱処理、焼結することならびに同等の成
分を有する合金薄膜を作ることによって超高保磁力を発
揮せしめ、性能を著しく改善させることができる工業上
大きな効果がある。INDUSTRIAL APPLICABILITY The present invention pressure-molds fine powder of Pr-Co alloy having a size of 1 to 20 μm and fine powder made by mechanical alloying, which has not been conventionally regarded as a permanent magnet material, and heat-treats and burns it. By binding and by forming an alloy thin film having the same composition, it is possible to exert an ultra-high coercive force and significantly improve the performance, which is a great industrial effect.
【図１】図１はＰｒ−Ｃｏ系合金の平衡状態図である。FIG. 1 is an equilibrium state diagram of a Pr—Co based alloy.
【図２】図２はＰｒ−Ｃｏ系合金の永久磁石特性、組成
及びＰｒＣｏ5 ，Ｐｒ5 Ｃｏ19，Ｐｒ2 Ｃｏ7 ，ＰｒＣ
ｏ3 化合物との関係を示す特性図である。FIG. 2 is a permanent magnet characteristic and composition of Pr—Co alloy and PrCo 5 , Pr 5 Co 19 , Pr 2 Co 7 , and PrC.
It is a characteristic view showing a relationship with o 3 compound.
【図３】図３は従来得られていた保磁力と熱処理との関
係及び本発明の比較を示す図である。FIG. 3 is a diagram showing a relationship between coercive force and heat treatment, which have been conventionally obtained, and a comparison of the present invention.
【図４】図４はＰｒ19.5Ｃｏ80.5及び副成分を添加した
合金の代表的なＰｒ15−Ｔｉ2Ｃｏ80，Ｐｒ17Ｃｕ3 Ｃ
ｏ80，Ｐｒ17Ｃｅ3 Ｃｏ80の永久磁石材料の減磁曲線の
比較を示す特性図である。FIG. 4 shows typical Pr 15 —Ti 2 Co 80 , Pr 17 Cu 3 C of Pr 19.5 Co 80.5 and alloys containing secondary components.
o 80, is a characteristic diagram showing a comparison of the demagnetization curve of a permanent magnet material of Pr 17 Ce 3 Co 80.
【図５】図４はＰｒ20-xＸx Ｃｏ20としたときの副成分
Ｘx と磁石特性との関係を示す特性図である。FIG. 5 is a characteristic diagram showing a relationship between a sub-component X x and a magnet characteristic when Pr 20-x X x Co 20 is used.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年１月２５日[Submission date] January 25, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項４[Name of item to be corrected] Claim 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】[0007]
【表１】 [Table 1]
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３０[Name of item to be corrected] 0030
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３０】実施例３ Ｐｒ−Ｃｏ２元系を主成分としてこれに副成分として代
表的なＰｒ18Ｔｉ2 −Ｃｏ80，Ｐｒ17Ｃｕ3 Ｃｏ80，Ｐ
ｒ17Ｃｅ3 Ｃｏ80合金をアーク溶解し、これらをボール
ミルに入れてアルゴン封入した後、10時間微細化して１
〜20μｍの微粉末としたのち800 〜900 ℃に１時間加熱
し、これを4000ｋＡ／ｍのパルス磁場にかけたのち測定
して得られた減磁曲線の結果をＰｒ19.5Ｃｏ80.5の結果
と比較して図４に示した。これから分かるようにＣｅ系
は保磁力 iＨc は変わらないが残留磁束密度Ｂｒが増加
する。Ｔｉ及びＣｕを添加した場合には保磁力 iＨc が
増加するがＢｒが減少している。なお、図５にはＰｒ
20-xＸx Ｃｏ80（ｘは副成分）として副成分の原子％と
保磁力と残留磁束密度との関係が示してある。Example 3 A Pr-Co binary system as a main component and Pr 18 Ti 2 -Co 80 , Pr 17 Cu 3 Co 80 , P, which are typical as subcomponents, were added.
The r 17 Ce 3 Co 80 alloy was arc-melted, placed in a ball mill and filled with argon, and then refined for 10 hours to 1
Fine powder of ~ 20μm was heated to 800-900 ° C for 1 hour, and this was subjected to a pulsed magnetic field of 4000kA / m, and the result of the demagnetization curve obtained by measurement was compared with the result of Pr 19.5 Co 80.5. And shown in FIG. As can be seen from this, in the Ce system, the coercive force iHc does not change, but the residual magnetic flux density Br increases. When Ti and Cu are added, the coercive force iHc increases but Br decreases. In addition, in FIG.
20-x X x Co 80 ( x is subcomponent) are the relationship between the atomic% and the coercive force of the secondary components and residual magnetic flux density shown as.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図４[Name of item to be corrected] Fig. 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図４】図４はＰｒ19.5Ｃｏ80.5及び副成分を添加した
合金の代表的なＰｒ18Ｔｉ2Ｃｏ80，Ｐｒ17Ｃｕ3 Ｃｏ
80，Ｐｒ17Ｃｅ3 Ｃｏ80の永久磁石材料の減磁曲線の比
較を示す特性図である。FIG. 4 shows typical Pr 18 Ti 2 Co 80 , Pr 17 Cu 3 Co alloys containing Pr 19.5 Co 80.5 and subcomponents.
80 is a characteristic diagram showing a comparison of the demagnetization curve of a permanent magnet material of Pr 17 Ce 3 Co 80.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図２[Name of item to be corrected] Figure 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図２】 [Fig. 2]
Claims (8)
し、残部がＣｏ及び不可避の不純物からなる合金で、保
磁力が80ｋＡ／ｍ以上を有することを特徴とする高保磁
力Ｐｒ−Ｃｏ系合金の永久磁石材料。1. A high coercive force Pr—Co system characterized by containing Pr as a main component in an amount of 19.5 to 30 atomic% and the balance being Co and unavoidable impurities and having a coercive force of 80 kA / m or more. Alloy permanent magnet material.
し、残部がＣｏ及び不可避の不純物からなり、これに副
成分としてＦｅ，Ｃｕ，Ｗが0.1 〜３原子％及びＴｉ，
Ｃｅ，Ｓｍが0.1 〜５原子％のうち１種または２種以上
の元素からなる80ｋＡ／ｍ以上の保磁力を有することを
特徴とする高保磁力Ｐｒ−Ｃｏ系合金の永久磁石材料。2. Pr as a main component is contained in an amount of 15 to 30 atomic%, and the balance is composed of Co and unavoidable impurities, and Fe, Cu and W are contained as auxiliary components in an amount of 0.1 to 3 atomic% and Ti,
A permanent magnet material of a high coercive force Pr-Co alloy, which has a coercive force of 80 kA / m or more consisting of one or more elements of Ce and Sm of 0.1 to 5 atomic%.
し、残部がＣｏ及び不可避の不純物からなる合金の薄膜
で保磁力が80ｋＡ／ｍ以上を有することを特徴とする高
保磁力Ｐｒ−Ｃｏ系薄膜の永久磁石材料。3. A high coercive force Pr-Co which is a thin film of an alloy containing Pr as a main component in an amount of 15 to 30 atomic% and the balance being Co and inevitable impurities and having a coercive force of 80 kA / m or more. System thin film permanent magnet material.
し、残部がＣｏ及び不可避の不純物からなり、これに副
成分としてＦｅ，Ｃｕ，Ｗが0.1 〜３原子％及びＴｉ，
Ｃｅ，Ｓｍが0.1 〜５原子％のうち１種または２種以上
の元素からなる合金薄膜で保磁力が80ｋＡ／ｍ以上を有
することを特徴とする高保磁力Ｐｒ−Ｃｏ系薄膜の薄膜
磁石材料。4. Pr of 15 to 30 atomic% is contained as a main component, the balance is Co and unavoidable impurities, and Fe, Cu and W are contained as 0.1 to 3 atomic% of Ti, Ti and Ti, inevitable impurities.
A thin film magnet material of a high coercive force Pr-Co type thin film, which is an alloy thin film composed of one or more elements of Ce and Sm of 0.1 to 5 atomic% and has a coercive force of 80 kA / m or more.
し、残部がＣｏ及び不可避の不純物からなる合金をボー
ルミルに５〜30時間かけて１〜20μｍに微細化した粉末
及び同等の合金成分の金属粗粒をメカニカル・アロイン
グして微粉末とし、これを加圧成形または磁界中に加圧
成形或いは射出成形したものを、さらに300 〜1180℃に
熱処理あるいは焼結することを特徴とする超高保磁力の
Ｐｒ−Ｃｏ系合金粉末の永久磁石材料の製造方法。5. A powder obtained by refining an alloy containing 15 to 30 atomic% of Pr as a main component and the balance consisting of Co and inevitable impurities into a ball mill for 1 to 20 μm in 5 to 30 hours, and an equivalent alloy component. Characterized by subjecting the metal coarse particles of the above to mechanically alloying to form fine powder, which is then pressure-molded or pressure-molded or injection-molded in a magnetic field and further heat-treated or sintered at 300 to 1180 ° C. A method for manufacturing a permanent magnet material of a high coercive force Pr-Co alloy powder.
し、残部がＣｏ及び不可避の不純物からなり、これに副
成分としてＦｅ，Ｃｕ，Ｗが0.1 〜３原子％及びＴｉ，
Ｃｅ，Ｓｍが0.1 〜５原子％のうち１種または２種以上
の元素からなる合金をボールミルに５〜30時間かけて１
〜20μｍに微細化した粉末及び同等の合金成分の金属粗
粒をメカニカル・アロイングして微粉末とし、これを加
圧成形または磁界中に加圧成形或いは射出成形したもの
を、さらに300 〜1180℃に熱処理あるいは焼結すること
を特徴とする高保磁力Ｐｒ−Ｃｏ系合金の永久磁石材料
の製造方法。6. Pr as a main component is contained in an amount of 15 to 30 atomic%, and the balance is composed of Co and unavoidable impurities, and Fe, Cu and W are contained as auxiliary components in an amount of 0.1 to 3 atomic% and Ti,
An alloy consisting of one or more elements of Ce and Sm in the range of 0.1 to 5 atomic% is placed in a ball mill for 5 to 30 hours for 1 hour.
Powder finely powdered to ~ 20μm and coarse metal particles of an equivalent alloy component are mechanically alloyed into fine powder, which is then pressure-molded or pressure-molded in a magnetic field or injection-molded, and further 300-1180 ℃ 1. A method for producing a permanent magnet material of a high coercive force Pr—Co alloy, which is characterized by heat treatment or sintering.
し、残部がＣｏ及び不可避の不純物からなる合金をアル
ゴン、クリプトン、キセノンのうち少なくとも１種の不
活性ガスの雰囲気中で、室温の基板に成膜後、300 〜80
0 ℃に加熱したものあるいは300 〜800 ℃に加熱した基
板上に成膜した薄膜で、80ｋＡ／ｍ以上の保磁力を有す
るものを得ることを特徴とする高保磁力Ｐｒ−Ｃｏ系合
金の永久磁石材料の製造方法。7. An alloy containing Pr as a main component in an amount of 15 to 30 atomic% and the balance being Co and inevitable impurities in an atmosphere of an inert gas of at least one of argon, krypton, and xenon at room temperature. After film formation on the substrate, 300-80
A permanent magnet of a high coercive force Pr-Co alloy characterized by obtaining a thin film formed on a substrate heated to 0 ° C or heated to 300 to 800 ° C and having a coercive force of 80 kA / m or more. Material manufacturing method.
し、残部がＣｏ及び不可避の不純物からなり、これに副
成分としてＦｅ，Ｃｕ，Ｗが0.1 〜３原子％及びＴｉ，
Ｃｅ，Ｓｍが0.1 〜５原子％のうち１種または２種以上
の元素からなる合金をアルゴン、クリプトン、キセノン
のうち少なくとも１種の不活性ガスの雰囲気中で、室温
の基板に成膜した薄膜で、80ｋＡ／ｍ以上を有するもの
を得ることを特徴とする高保磁力Ｐｒ−Ｃｏ系薄膜永久
磁石材料の製造方法。8. Pr as a main component is contained in an amount of 15 to 30 atomic%, and the balance is composed of Co and unavoidable impurities, and Fe, Cu and W are contained as auxiliary components in an amount of 0.1 to 3 atomic% and Ti,
A thin film formed by depositing an alloy composed of one or more elements of Ce and Sm in the range of 0.1 to 5 atomic% on a substrate at room temperature in an atmosphere of an inert gas of at least one of argon, krypton, and xenon. And a method of producing a high coercive force Pr-Co thin film permanent magnet material, characterized in that the material having 80 kA / m or more is obtained.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5332969A JPH07192907A (en) | 1993-12-27 | 1993-12-27 | Permanent magnet material of high coercive-force pr-co alloy and permanent magnet material of thin-film and manufacture thereof |
| EP94120423A EP0660338A1 (en) | 1993-12-27 | 1994-12-22 | Permanent magnet material of high coercive force Pr-Co alloy and permanent magnet material of thin film and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5332969A JPH07192907A (en) | 1993-12-27 | 1993-12-27 | Permanent magnet material of high coercive-force pr-co alloy and permanent magnet material of thin-film and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07192907A true JPH07192907A (en) | 1995-07-28 |
Family
ID=18260849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5332969A Withdrawn JPH07192907A (en) | 1993-12-27 | 1993-12-27 | Permanent magnet material of high coercive-force pr-co alloy and permanent magnet material of thin-film and manufacture thereof |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0660338A1 (en) |
| JP (1) | JPH07192907A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008251993A (en) * | 2007-03-30 | 2008-10-16 | Tdk Corp | Magnetic material and magnet using the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104575920B (en) * | 2013-10-16 | 2018-01-19 | 中国科学院宁波材料技术与工程研究所 | Rare-earth permanent magnet and preparation method thereof |
| CN107604211A (en) * | 2017-09-21 | 2018-01-19 | 桂林电子科技大学 | A kind of LaPrCo magnetic microwave absorbing material and preparation method thereof |
| CN113502452B (en) * | 2021-07-12 | 2023-03-24 | 深圳市阿尔法材料科技有限公司 | TaN-rare earth composite coating and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5633806A (en) * | 1979-08-29 | 1981-04-04 | Seiko Instr & Electronics Ltd | Preparation of rare-earth magnet |
| JPS60197843A (en) * | 1984-03-17 | 1985-10-07 | Namiki Precision Jewel Co Ltd | Permanent magnet alloy |
| JPH05156397A (en) * | 1991-12-05 | 1993-06-22 | Mitsubishi Materials Corp | Rare earth-cobalt 1-5 series permanent magnet alloy |
-
1993
- 1993-12-27 JP JP5332969A patent/JPH07192907A/en not_active Withdrawn
-
1994
- 1994-12-22 EP EP94120423A patent/EP0660338A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008251993A (en) * | 2007-03-30 | 2008-10-16 | Tdk Corp | Magnetic material and magnet using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0660338A1 (en) | 1995-06-28 |
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