JPS5866305A - Permanent magnet - Google Patents

Abstract

PURPOSE:To obtain a high energy product by a method wherein phases having excessive Zr are made to exist in parallel with the C plane of an intermetallic compound crystal at predetermined intervals or less in a permanent magnet composing rare earth Co as a main body. CONSTITUTION:In a permanent magnet containing an intermetallic compound and composing rare earth Co as a main body, the intervals between phases having excessive Zr located in parallel with the C plane of the intermetallic compound crystal are maintained at 5,000Angstrom or less. The intermetallic compound contains Ce of 20-30%, Cu of 3-9%, Zr of 1-5%, and Fe of 10-30% by weight percent and the residual is composed of Co. In this way, a permanent magnet having high energy product and coercive force can be obtained.

Description

【発明の詳細な説明】 本発明は、希土類スパルト磁石に関するもので、ありさ
らに詳しく述べるならば、七すウムーコパルＦ金属間化
合物を主体とするＣ・−Ｃｏ−Ｃｕ−Ｆ・系及びＣＩ−
ａｌｌ−Ｃ・−Ｃｍ−Ｆ・系析出硬化型永久磁石の改嵐
に関するものである・　” 希土類としてセリウムを使用した析出硬化型希土類ブパ
ルト磁石は、従来の高価なすマリラム及びコバルトを大
量に使用しているＳｍＣｏｇ系磁石忙比べ、資源原料コ
ストの面からも優位で６９、工業的に注ｉ！されてきた
が、実用的な磁気特性としては不十分なものであった。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to rare earth spult magnets, and more specifically, the present invention relates to rare earth spult magnets, and more specifically, C.--Co--Cu--F. system and CI-
This article concerns the improvement of all-C/-Cm-F system precipitation-hardening permanent magnets.'' Precipitation-hardening rare earth Bupart magnets that use cerium as the rare earth element do not use conventional expensive marillam and cobalt in large quantities. Compared to other SmCog-based magnets, it is advantageous in terms of resource and raw material costs69, and has been noted industrially, but its magnetic properties are insufficient for practical use.

例えば、１９７７年６３「ムｐｐｌｉｓｄ　Ｐｈｙｓｌ
ｅｓ　Ｌ＠ｔｔ＠ｒｓ　Ｊ第３０巻、ム１２ｐ６１１９
〜ｏ６７０の記載あるいは特公昭５Ｇ−３９３７５の記
載によるとＣｏ−Ｃｏ−Ｃｍ−Ｆｅ系ではエネルギ積（
ＢＨ）工＠ｚ　１３１［ＧＯ＠且つ保磁力ＩＨｃ６，１
００〜６．９０００ｏ程度であシ、その組成は鋼９饅以
上且つ鉄１２チ以下を指向していた。For example, 1977 63 “Mupplisd Physl.
es L@tt@rs J Volume 30, Mu 12 p6119
According to the description in ~o670 or the description in Japanese Patent Publication No. 5G-39375, in the Co-Co-Cm-Fe system, the energy product (
BH) Engineering@z 131 [GO@and coercive force IHc6,1
It was about 0.00 to 6.9000 degrees, and its composition was oriented to more than 9 degrees of steel and less than 12 degrees of iron.

さらに、セリウムの一部をサマリウムで置換したＣ・−
ａｍ−Ｃ６−Ｃ１−ｐ・系析出硬化型永久磁石は例えば
１９７９年５月ｒ　Ｐｒ＠＠ｓｓｄｉｎｇ　ｏｆ　ｔｈ
＠Ｆｏｕｒｔｈ’　Ｉｎｔ＠ｒｎａｔｌｏｎａｌ　Ｗｏ
ｒｋｓｈｏｐ　ｏｎ　Ｒａｒ・＊ａｒｔｈ　−Ｃｏｂａ
ｌｔ　Ｐ＠ｒｍａｎｅｎｔ　Ｍａｇｎ＠ｔｓ　Ｊの記載
によるとＣＩ／Ｃ＠　＋１１ｍｍ　０．５近傍では、エ
ネルギ積（ＩＨ）ｗａｘ１９ＭＧＯ・保持力負Ｈ・、７
，００００・程度であシ、やは）銅９饅以上、鉄１２饅
以下を指向していた。Furthermore, C・− in which a part of cerium was replaced with samarium
For example, the am-C6-C1-p precipitation hardening type permanent magnet was published in May 1979 at Pr@@ssding of th
@Fourth' Int@rnatlonal Wo
rkshop on Rar・*arth-Coba
According to the description of lt P@rmanent Magn@ts J, in the vicinity of CI/C@+11mm 0.5, the energy product (IH) wax19MGO・Retention force negative H・,7
,0,000,000,000,000,000,000,000,000,000,000,000,000,000,000, or more)) He was aiming for more than 9 pieces of copper and less than 12 pieces of iron.

これらの析出硬化型磁石ては、鋼過剰な相が微細組織の
セル構造を呈し、保磁力を向上させるｔのである。また
これらの従来の永久磁石に−おいては、保持力維持の観
点から比較的高い鋼含有量及び低い含有量を指向してい
るのである。In these precipitation hardening magnets, the steel-rich phase exhibits a microstructural cell structure, which improves the coercive force. In addition, these conventional permanent magnets are directed toward relatively high and low steel contents from the viewpoint of maintaining coercive force.

本発明の目的とするところは従来のＣ・−Ｃ・−Ｃ１１
−Ｆ・系、及びＣ・−１ｉ１ｍ−Ｃｏ−Ｃ菟−ｒ・系永
久磁石よ〉着しく磁気特性を向上させると共に、特に低
い銅含有量の組成及び高い鉄含有量の組成に＄Ｐ％Ａて
もなおかつ高保持力を維持し、その結果、エネルギー積
（ｉｔａ　）ｍ□、保持力ｌ−等の磁気特性が極めて優
れてお〕、シかもセリウムの使用にょシ安価な永久磁石
を提供することにある。The object of the present invention is to use the conventional C・-C・-C11
-F-based and C-1i1m-Co-C菟-r-based permanent magnets, the magnetic properties are significantly improved, and $P% is especially applied to compositions with low copper content and compositions with high iron content. As a result, the magnetic properties such as energy product (ita)m and coercive force l- are extremely excellent, and the use of cerium also provides an inexpensive permanent magnet. It's about doing.

本発明の基本的思想は、従来の析出硬化型磁石の微細組
織に、）られるＣ−過剰相のセル構造の他忙、セリウム
を必須成分とする希土類コバルト金属間化合物結晶の０
面に平行にジルコニウム過剰相を析出させて、銅過剰相
であるセル境界による磁壁のピンニング効果のみならず
ジルコニウム過剰相による磁壁のピンニング効果を追加
し、低い鋼含有量、高い鉄含有量忙於いてもなおかつ高
保磁カ會維持し、同時に高エネルプー積を可能ならしめ
るものである０本発明は鋭意研究の結果、上記金属間化
合物の結晶のＣＩｉに平行なりルコニウ五過剰相を析出
させる一連の熱ＩＩ＆ｓＹｔ見出し且つジルコニウム過
刺相（面）間隔と磁気特性の因果関係を確証することに
よ）完成したものである。The basic idea of the present invention is that in the microstructure of conventional precipitation hardening magnets, there is a cell structure of a C-excess phase, which is formed in the microstructure of a conventional precipitation hardening magnet, and a zero-cell structure of a rare earth cobalt intermetallic compound crystal containing cerium as an essential component.
By precipitating the zirconium-excess phase parallel to the plane, the pinning effect of the domain wall due to the zirconium-excess phase is added as well as the domain wall pinning effect due to the cell boundary, which is the copper-excess phase. As a result of intensive research, the present invention has developed a series of heat waves parallel to the CIi of the crystals of the intermetallic compound to precipitate a luconium-5-excess phase. II&sYt and was completed by confirming the causal relationship between the zirconium superimposed phase (planar) spacing and magnetic properties.

すなわち、本発明は、重量百分率で、２ｏないし３０％
のセリウム、３ないし９−の銅、１ないし５饅のジルコ
ニウム及び１０ないし３０−の鉄を含有し、残［ｌがコ
バルトからなる希土類コバルトを主体とする金属間化合
物を含んでなる永久磁石において、該金属間化合物結晶
の０面に平行にジルコニウム過剰なる相が相互の間隔が
ｓｏｏ。That is, the present invention provides 2o to 30% in weight percentage.
In a permanent magnet comprising an intermetallic compound mainly containing rare earth cobalt, containing 3 to 9 parts of cerium, 3 to 9 parts of copper, 1 to 5 parts of zirconium, and 10 to 30 parts of iron, with the balance [l being cobalt] , the mutual spacing between the zirconium-excess phases parallel to the zero plane of the intermetallic compound crystal is so large.

ｌ以下にて存在し、エネルギ積及び保磁力が高いことを
特徴とする。It is characterized by a high energy product and coercive force.

本発明においては、従来のＣ・−Ｃ・−Ｃ１ｌ−ＦＩ系
及びＣ・−ａｍ−Ｃｏ−Ｃｕ−Ｆ・系祈出硬化製永久磁
石には存在しなかったジルコニウム過剰相を希土類コバ
ルト結晶の０面と実質的な意味で平行に析出させ、前者
の系では保磁力ｉＨｅ　４　Ｇ　００以上、好ましくは
７００００・以上、且つエネルギ積（紐）、、Ｘｌ　５
　ＭＧＯ＊以上、好ましく　Ｆｉ　１６　ＭＧＯ＠以上
を、また後者の系で社、重量百分率の含有量で、１ｉｔ
ｒｅ／Ｃ・十８ｍの比率が０．５の場合に、保磁力ｌＨ
ｅ１２００００・以上且つエネルギ積（ＢＨ）ｗａｘ　
２３ＭＧＯ・以上で代表される高い保磁力及びエネルギ
積を可能にしたものである。而して、ｃｍｔｃ平行な面
状のジルコニウム過剰相の間隔が５０００１を越えると
磁気特性が従来の上記析出硬化型永久磁石と大差ないの
で、５０００Ｘを上脹として限定している。なおこの好
ましい間隔は２０００１である。In the present invention, the zirconium-excess phase, which did not exist in conventional C・-C・-C1l-FI system and C・-am-Co-Cu-F system permanent magnets, is replaced with a rare earth cobalt crystal. In the former system, the coercive force iHe 4 G 00 or more, preferably 70000 or more, and the energy product (string), Xl 5
MGO* or more, preferably Fi 16 MGO@ or more, and in the latter system, the content in weight percentage is 1 it
When the ratio of re/C・18m is 0.5, the coercive force lH
e120000 or more and energy product (BH) wax
This enables a high coercive force and energy product represented by 23 MGO· or more. If the spacing between the cmtc-parallel plane zirconium-excessive phases exceeds 50,001, the magnetic properties are not much different from those of the conventional precipitation hardening type permanent magnet, so 5,000X is defined as the upper expansion. Note that this preferred interval is 20001.

本発明の永久磁石においてセリウムの含有量が２０１１
未満、鋼含有量が３ｇ１未満、または鉄含有量が３０４
ｆ越えると、保磁力及びエネルギ積が低下する。セリウ
ム含有量が３０１１を越え、銅含有量７ｂｊ９饅を越え
、または鉄含有量が１ｏチ未満であると、残留磁束密度
ｎｒまたは減磁曲線の角型性が低下し、さらにエネルギ
積（ＢＨ）、。も低下する。ジルコニウムの含有量が１
饅未満であると、後述の発明の熱処ｍを行なってもジル
コニウム過剰相の間隔が５ｏｏｏｌを越えその効果が期
待されず、一方５嘩を越えると残留磁束密度及びエネル
ギ積が低下する。上記組成において、セリウム２８饅未
満、また高い磁束密度をもたらす鉄１２饅以上が４１１
Ｋ好ましい。The content of cerium in the permanent magnet of the present invention is 2011
less than 3g, steel content less than 3g1, or iron content less than 304
If f is exceeded, the coercive force and energy product decrease. If the cerium content exceeds 3011, the copper content exceeds 7bj9, or the iron content is less than 1o, the residual magnetic flux density nr or the squareness of the demagnetization curve will decrease, and the energy product (BH) will decrease. ,. also decreases. Zirconium content is 1
If the spacing is less than 5mm, the spacing of the excess zirconium phase will exceed 5mm and no effect can be expected even if heat treatment according to the invention described below is performed, while if the spacing exceeds 5mm, the residual magnetic flux density and energy product will decrease. In the above composition, less than 28 pieces of cerium and 12 pieces or more of iron, which brings about high magnetic flux density, are 411
K is preferred.

本発明においては、ジルコニウムの他にハフニウム、チ
タン、バナジウム、ニオブ及びタンタルの少なくとも１
種をジルコニウムとの合計量でｌ〜５−（但しジルコニ
ウムの下＠１ｌｌ）添加しても、ジルコニウム単独添加
の場合と同様の効果を生じる。In the present invention, in addition to zirconium, at least one of hafnium, titanium, vanadium, niobium, and tantalum is used.
Even if the seeds are added in a total amount of 1 to 5 - (but below zirconium @ 1 1 l), the same effect as when zirconium is added alone is produced.

マタ、ハフニウム、チタン、バナジウム、ニオブ及びタ
ンタル単独添加の場合もジルコニウムの場合と同様に各
元素の過剰相が析出し、同様な効また、セリウムの８０
慢以下（０を含まず）會サマリウムで置換すること、す
なわちＯ（１！！ｍ（１６）／Ｓｍ（％）＋Ｃ・（饅）
≦８０優の関係でサマリウムを当該永久磁石に加えるこ
と、−可能である。上記比率が８０−を超えると、高価
なサマリウムが多くな夛、資源、原料コストの面からの
工業的価値が低下する。さらに鉄の一部ｔ−８０１６（
０１含まず）以下のマンガン、ニッケル及びクロムの一
種一以上で置換しても、同様な効果が得られる。置換量
が８０−を越えると残留磁束密度Ｂｒが低下し、エネギ
ル積（ｎｕ）ｍ。も低下する。Even when cerium, hafnium, titanium, vanadium, niobium, and tantalum are added alone, an excess phase of each element precipitates as in the case of zirconium, and the same effect is obtained.
Replacement with samarium (not including 0), that is, O(1!!m(16)/Sm(%)+C・(饅)
- It is possible to add samarium to the permanent magnet in the relationship ≦80 well. When the above ratio exceeds 80, the industrial value in terms of the cost of expensive samarium, resources, and raw materials decreases. Furthermore, some iron T-8016 (
The same effect can be obtained even if one or more of the following manganese, nickel, and chromium is substituted. When the amount of substitution exceeds 80-, the residual magnetic flux density Br decreases, and the energy product (nu)m decreases. also decreases.

本発ｌＩｌ！Ｏ永久磁石社従来のＣ・−Ｃｏ　−Ｃｓｓ
　−Ｆｅ系、又はＣＩ　−８ｍ　−Ｃｏ　−Ｃｕ　−Ｆ
ｅ　　系と比較して、磁束の可逆温度変化及び不可逆減
磁等析出硬化型永久磁石の温度特性も着しく教養されて
いる。This is the real deal! O Permanent Magnet Co., Ltd. Conventional C・-Co-Css
-Fe-based or CI -8m -Co -Cu -F
Compared to e-type magnets, the temperature characteristics of precipitation hardening permanent magnets, such as reversible temperature change in magnetic flux and irreversible demagnetization, have also been well studied.

本発明によるＣ・−Ｃ・−Ｃｍ−Ｆ・系及びＣ・−８■
−Ｃ・−Ｃｕ−Ｆ−系析出硬イｔＪＩｌ永久磁石の製造
方法は以下の通りである。ｔず、原料金属を所望の比率
に配合し、真空中又は非酸化性雰囲気中で高周波溶解を
行ない合金化する。この時、ジルコニウム勢の添加金属
はフェロアロイの状態で用いても何等差し支えない・さ
らに溶解は他の方法、例えば抵抗加熱炉、赤外線イメー
ジ炉、アーク溶解炉等によってもよい、所定組成のイン
ゴットは、スタングミル、ジョークラ、シャー等で粗粉
砕を行ない合金粉末にする。ζζまでの過程で、還元抗
散法等の処理で合金粉末を得ても差し支えない、得られ
た合金粉末は、さらに、／７！　ｙ　）ミル、アトライ
ター、？−ルきル等で約３〜６ＪＩのサイ、ｅ□粒子に
微粉砕する。その後、微粉末は〆イブレス、静水圧ブレ
ス等で所望の形状に磁場中で圧縮成形する。以上の工程
は従来の永久磁石製造方法と特に相違していない。C・-C・-Cm-F・system and C・-8■ according to the present invention
The manufacturing method of the -C.-Cu-F- based precipitation hard JIl permanent magnet is as follows. First, raw metals are blended in a desired ratio and alloyed by high-frequency melting in vacuum or in a non-oxidizing atmosphere. At this time, there is no problem even if the additive metal of the zirconium group is used in the state of ferroalloy.Furthermore, the melting may be done by other methods, such as a resistance heating furnace, an infrared image furnace, an arc melting furnace, etc.The ingot of the predetermined composition is Coarsely grind it using a stang mill, jaw mill, shear, etc. to make an alloy powder. In the process up to ζζ, there is no problem in obtaining alloy powder by treatment such as reduction anti-dispersion method, and the obtained alloy powder further has /7! y) Mill, attritor, ? - Pulverize to particles of about 3 to 6 JI with a grinder or the like. Thereafter, the fine powder is compressed into a desired shape in a magnetic field using a final press, a hydrostatic press, or the like. The above steps are not particularly different from conventional permanent magnet manufacturing methods.

以下、ジルコニウム過剰相を析出させる熱処理を行う。Hereinafter, heat treatment is performed to precipitate the zirconium-excess phase.

成形体は真空中、非酸化雰囲気中、又は還元雰囲気中勢
で１０００℃〜１１５０℃Ｏａｍで焼結と同時に溶体化
処理を行ない、次に９５０℃以下の温度例えば室温まで
に急冷する。溶体化処理された焼結体（上述の場合は焼
結と溶体化が一段階の操作で行なわれる）を、その後、
７５０”〜９００℃の温度で１５分間以上、等温時効を
行ない、次に２　ｔ、／ｍｌｎ　〜１０　Ｃ／ｗｉｎの
速度で６５０℃以下の温度まで冷却する。さらに５００
〜６５０℃の温度範囲から２℃／ｗｉｎ以下の冷却速度
で４００℃以下の温度まで連続的にまたは段階的に徐冷
する。The compact is sintered and simultaneously subjected to solution treatment at 1000 DEG C. to 1150 DEG C. Oam in a vacuum, non-oxidizing atmosphere, or reducing atmosphere, and then rapidly cooled to a temperature of 950 DEG C. or less, for example, room temperature. The solution-treated sintered body (in the case described above, sintering and solutionization are carried out in one step) is then
Isothermal aging is performed at a temperature of 750" to 900°C for 15 minutes or more, and then cooled to a temperature of 650°C or less at a rate of 2 t,/mln to 10 C/win. Further, 500"
Slow cooling is performed continuously or stepwise from a temperature range of ~650°C to a temperature of 400°C or less at a cooling rate of 2°C/win or less.

本発明の永久磁石は、時計、電動モーター、計器、通信
機、コンピュータ一端末器、スピーカー、ビデオディス
ク、その他各種部品に広く利用することができる。The permanent magnet of the present invention can be widely used in watches, electric motors, meters, communication devices, computer terminals, speakers, video discs, and various other parts.

寮施例１ 所定組成となるように原料金属を配合・混合し、この混
合金属をアルｆ　：／ｆ！ス中で高周波加熱によル溶解
し、インプットを得た。仁のインゴットをスタンクンル
で粗粉砕し、さらにジェット２ルで平均粒径４μ＠度に
微粉砕した。得られた微粉末を磁場中で圧縮成形し前述
の本発明の熱処理を以下の各組成について行な−）た。Dormitory Example 1 Raw metals are blended and mixed to have a predetermined composition, and this mixed metal is made into Alf:/f! The input was obtained by melting the mixture in a bath using high-frequency heating. The kernel ingot was coarsely pulverized with a Stankunlu, and further finely pulverized with a jet 2l to an average particle size of 4 μm. The obtained fine powder was compression molded in a magnetic field, and the heat treatment of the present invention described above was carried out for each of the following compositions.

各供試材の保磁力曙Ｃ１残留磁束密度１１ｒ及びエネル
ギ積（８１）□８をそれぞれの図面に示す。百分率Ｉ／
ｉ特記しない限シ重量百分率である。The coercive force Akebono C1 residual magnetic flux density 11r and energy product (81)□8 of each sample material are shown in each drawing. Percentage I/
i is a weight percentage unless otherwise specified.

（１）　　７１ｇＣｌ、１４％Ｆ・、２．４％Ｚｒ及び
１９〜３ｌ−１１Ｃ・の組成−第１図 第１図により分かるように、エネルギ積（ＢＨ−〇及び
保磁力ｌＨ＠は約２６ｓにて最大になり、また２ないし
３０１Ｇのセリクム含有量の範囲で、良好な磁気特性、
特にエネルギ積”Ｈ＞Ｗａ＆Ｘ及び保磁力１Ｈ−１が得
られる。(1) Composition of 71gCl, 14%F・, 2.4%Zr and 19~3l-11C・Figure 1 As can be seen from Figure 1, the energy product (BH-〇 and coercive force lH@ , and in the range of Sericum content from 2 to 301G, good magnetic properties,
In particular, the energy product "H>Wa&X" and the coercive force 1H-1 are obtained.

（２）　　２６１ＧＣ＠、１４１１ＧＦｅ、２．５１Ｇ
Ｚｒ及び２〜１０チＣｍの組成−第２図 第２図よシ３〜９％の銅含有量の範囲で良好なエネルギ
積（ＢＨ）！１ｍ、ｘ及び保磁力ＩＨｅが得られる。(2) 261GC@, 1411GFe, 2.51G
Composition of Zr and 2 to 10 cm - Figure 2 Figure 2 Good energy product (BH) in the copper content range of 3 to 9%! 1 m, x and coercive force IHe are obtained.

なお、第２図のエネルギ積（ＢＨ）。□Ｏグラフは、従
来の析出硬化型永久磁石でれ特性値が低下するといわれ
ている銅含有量範囲にて極大のエネルギ積（ＢＥ　）ｍ
、工が得られていることが注目される。In addition, the energy product (BH) in FIG. □The O graph shows the maximum energy product (BE) m in the copper content range where it is said that the wear characteristics of conventional precipitation hardening permanent magnets decrease.
It is noteworthy that the results obtained are as follows.

（３）　　２６ＳＣｅ、７％Ｃｕ、’２．６１ｓＺｒ及
び６〜３５−Ｆ・の組成−第３図 ９３図に見られるよ５がエネルｄｆ覆（８Ｈ）、□及び
保磁力ＩＨｃの傾向よシ本発明で杜、鉄含有量を１０な
いし３０チの範囲とした。なお、第３図で、エネルギ積
（ＢＨ）ｆｆｌａ！及び保磁力の極大値は従来の析出硬
化型永久磁石ではこれらの値が低下している高い鉄含有
量にて得られている。(3) Composition of 26SCe, 7% Cu, '2.61sZr and 6~35-F. - As seen in Figure 3, 5 shows the trend of energy df cover (8H), □ and coercive force IHc. In the present invention, the Du and Iron content is set in the range of 10 to 30 Ti. In addition, in FIG. 3, the energy product (BH) ffla! The maximum values of coercivity and coercive force are obtained at high iron contents, where these values are reduced in conventional precipitation hardening permanent magnets.

（４）２６＊Ｃ・、７．１チＣ１１，１４１Ｆ−及び０
．５〜６％Ｚｒ−第４図 エネルギ積（ａＨ）　　　、磁束密度Ｂｒ及び保磁力ｍ
＆Ｘ ｌＨｅが極大となる約３％ジルコニウムを中心として１
〜５−のジルコニウム含有量を本発明の範囲とした。(4) 26*C・, 7.1ch C11, 141F- and 0
．． 5-6% Zr - Figure 4 Energy product (aH), magnetic flux density Br and coercive force m
&X 1 centered on about 3% zirconium where lHe is maximum
The zirconium content of ~5- was defined as the range of the present invention.

実施例２ 第１に示す組成の供試材を実施例１と同様の手順により
調製した。なお、磁場中圧縮成形体を１０００〜１１５
０℃の温度で真空中１時間焼結・溶体化処理し、その談
アルプンガスにて室温まで急冷し、更に７５０〜９００
℃の温度範囲で１５分分間上＊ｍ時効を行表い、次に２
℃／分〜１０℃／分の速度で６００℃まで冷却、引き続
き１℃／分の冷却速度で３００″Ｃｔで徐冷した。この
ようにして得られた永久磁石の磁気特性を第１ＰＫ＊す
・　　　　　　　　　　　　　　　６４．下余白供試材
１〜３は希土類元素セリウムの例であシ、１５、０　Ｍ
ＧＯ・以上のエネルギ積（Ｂ”ＩＩＩ！及び４００００
６以上の保磁力ＩＨｃを示している。Example 2 A test material having the composition shown in the first example was prepared by the same procedure as in Example 1. In addition, the compression molded product in a magnetic field is 1000 to 115
Sintered and solution treated in vacuum for 1 hour at a temperature of 0℃, then rapidly cooled to room temperature with alponic gas, and further heated to 750~900℃.
Aging was performed for 15 minutes at a temperature range of °C, then 2 m
It was cooled to 600°C at a rate of 10°C/min to 10°C/min, and then slowly cooled to 300"Ct at a cooling rate of 1°C/min. The magnetic properties of the permanent magnet thus obtained were determined by the first PK*.・ 64. Lower margin test materials 1 to 3 are examples of rare earth element cerium, 15.0 M
Energy product of GO・(B”III! and 40000
It shows a coercive force IHc of 6 or more.

供試材４〜１０はジルコニウムに加えてハフニウム、チ
タン、ニオブ、タンタル又はパナゾウムを添加し且り／
又はセリウムの一部をサマリヮムで置き換えたものであ
る・これらの供試材も良好な磁気特性を示して込る。Sample materials 4 to 10 had hafnium, titanium, niobium, tantalum, or panazoum added in addition to zirconium and/
Or, some of the cerium was replaced with Samarimu.These test materials also show good magnetic properties.

実施例３ 所定組成となるように原料金属を配合し、この混合金属
を実施例２と同様の方法で、溶解、粉砕。Example 3 Raw metals were blended to have a predetermined composition, and the mixed metal was melted and pulverized in the same manner as in Example 2.

焼結、溶体化、熱処理を行ない第２表のような磁気特性
を得た。After sintering, solution treatment, and heat treatment, the magnetic properties shown in Table 2 were obtained.

以下余白 第２表の供試材は、鉄の一部を同表中のマンｆン、二、
ケル及びクロムで置換したものであり、歳好な磁気特性
を示している。The test materials in Table 2 in the margin below are a portion of the iron listed in the same table.
It is substituted with Kel and chromium and shows good magnetic properties.

実施例４ 走査型透過型電子顧黴鏡にエネルギ分散識Ｘ＠分光形を
附設して本発明の組成範囲のＣｌ−８ＥＷ−Ｃ（１−Ｆ
・系析出硬化截永久磁石における保磁力ＩＨｅの異なる
供試材の微細組織を観察し、ｚｒ過過剰管同定しその間
隔を測定した。観察面祉金属間化合物結晶の１面とした
。結果を第３表に示す。Example 4 A scanning transmission type electronic mirror was equipped with an energy dispersion type
・We observed the microstructures of specimens with different coercive forces IHe in precipitation-hardened cut permanent magnets, identified ZR excess tubes, and measured their intervals. The observation surface was taken as one surface of the intermetallic compound crystal. The results are shown in Table 3.

第３表 上記第３表より、ジルコニウム過剰相の平均間隔（ａ）
が小さくなるとともに保磁力ＩＨｃが高くなる関係がｄ
とｌＨｅ０間にあることが分かる。十分に高い保磁力Ｉ
Ｈ１！が得られるように、本発明ではｄを５０００１以
下、好１しくｎ２ｏｏｏＸ以下とした。Table 3 From Table 3 above, average spacing of zirconium-excess phase (a)
As d becomes smaller, the coercive force IHc increases.
It can be seen that it is between and lHe0. Sufficiently high coercive force I
H1! In the present invention, d is set to 50001 or less, preferably n2oooX or less so that the following can be obtained.

実施例５ 実施例１と同様の手順により、本発明の組成の供試材を
調製する際に、２６　Ｔｏ　Ｃｓ、？　Ｔｏ　Ｃｕ　、
１４チＦ−及び２．４％Ｚｒの組成につき各段階の熱処
理条件を変化させ保磁力ＩＨｅを測定した。Example 5 When preparing a test material having the composition of the present invention by the same procedure as in Example 1, 26 To Cs, ? To Cu,
The coercive force IHe was measured by changing the heat treatment conditions at each stage for compositions of 14% F- and 2.4% Zr.

（１）　　等温時効温度（７００，７５０，８５０゜９
００℃）及び時間−第５図 第５図より、等温時効温度が７００℃では、最終的に処
理された供試材の保磁力ＩＨｅが低く以降の熱ｊｉＪＩ
Ｉ１１を前述の如く行なってもジルコニウム過剰相は生
成されない。次に、岬温時効温度が７５０℃又は８５０
℃の場合は保磁力に二つのピークが発生するが、従来の
等温時効法では低温側のピークが処理温度として使用さ
れていた。本発明では高温側のピークを等温時効処理温
度として使用し、他の段階の適切な熱処理と相まってゾ
ル；ニウム過刹相を最終製品中に存在せしめる。(1) Isothermal aging temperature (700, 750, 850°9
00℃) and time - Figure 5 From Figure 5, when the isothermal aging temperature is 700℃, the coercive force IHe of the final treated specimen is low and the subsequent heat jiJI
Even if I11 is carried out as described above, no zirconium-rich phase is produced. Next, the Cape temperature aging temperature is 750℃ or 850℃.
In the case of ℃, two peaks occur in the coercive force, but in the conventional isothermal aging method, the peak on the low temperature side was used as the processing temperature. In the present invention, the peak on the high temperature side is used as the isothermal aging treatment temperature, and in combination with appropriate heat treatments in other stages, the sol;nium pertemporal phase is caused to exist in the final product.

（２）８５０℃、１００分の等温時効より０．１〜、　
　３０度／分の冷却速度で６００．６５０又は７００Ｃ
との温度まで冷却する熱処理−第６図第６図に見られる
ように、尋温時効温度からの冷却降下温度及び速度条件
は６００℃且つ５℃／分が最良であり、また６５０℃以
下の温度に２〜ｌＯ℃／分の冷却速度で冷却する条件に
より良好な保磁力ＩＨｅが得られることが分る。(2) From isothermal aging at 850°C for 100 minutes,
600.650 or 700C at a cooling rate of 30 degrees/min
Heat treatment for cooling to a temperature of It can be seen that a good coercive force IHe can be obtained under the conditions of cooling at a cooling rate of 2 to 10° C./min.

（３）　　４５０　、５００　、６００又は６５０℃か
ら３００℃までＯ，１〜ｂ −第７図 第７図に見られる熱処理が保磁力に及ぼす影響　　。(3) Effect of heat treatment on coercivity from 450, 500, 600 or 650°C to 300°C.

より、２℃／分以下の冷却速度及び５００〜６５０℃の
温度範囲を本発明の時効処理温度範囲とする。Therefore, the aging treatment temperature range of the present invention is a cooling rate of 2° C./min or less and a temperature range of 500 to 650° C.

実施例６ 本発明による永久磁石の微細組織写真（結晶の鼻面）の
−例を第８図に示す。Example 6 An example of a microstructure photograph (crystal nose surface) of a permanent magnet according to the present invention is shown in FIG.

ジルコニウム過剰相がＣ軸方向に直角にすなわち０面と
平行に多数存在している。上記微細組織にてジルコニウ
ム過剰相が存在していない部分のエネルギ分散Ｗｌｘｉ
ｓ分光測定結果を第１０図に示す。同図の実機はａｍ（
ＣｂＣｕ）ｓ、点線はＳｍ２（ＣｏＦ＠Ｃｕ）１７であ
ル、ジルコニウム過剰相が存在したいところからはジル
コニウムは検出されない。第１１図にはジルコニウム過
剰相が存在する部分の微細組織を示し、Ｓｍ２（ＣｏＦ
＊Ｃａ）１７相及びＳｍ２（ＣｏＦ＊Ｃ’ｕＺｒ）ｔｙ
相が検出される。A large number of zirconium-excess phases exist perpendicularly to the C-axis direction, that is, parallel to the 0-plane. Energy dispersion Wlxi in the part where the zirconium-excess phase does not exist in the above microstructure
The results of the s spectroscopic measurements are shown in FIG. The actual machine in the same figure is am (
CbCu)s, the dotted line is Sm2(CoF@Cu)17, and zirconium is not detected where a zirconium-excess phase is expected to exist. Figure 11 shows the microstructure of the part where the zirconium-excess phase exists.
*Ca)17 phase and Sm2(CoF*C'uZr)ty
phase is detected.

なお、比較のために１．５１ＧＺｒを含有する８ｍ　２
　（Ｃ’ｏ　Ｆｓ　Ｃｕ　）　１　ｙ型磁石を８５０℃
×１０分間の等温時効処理を行ない、その他の熱処理は
本発明の条件範囲内にて処理をした供試材の電子顕微鏡
組織を第１１図に示す。この組織では銅過剰相のセル構
造のみが存在しゾルコニウム過剰相は全くない。For comparison, 8m2 containing 1.51GZr
(C'o Fs Cu) 1 Y type magnet at 850℃
FIG. 11 shows an electron microscope structure of a sample material subjected to isothermal aging treatment for 10 minutes and other heat treatments within the range of conditions of the present invention. In this structure, only the cell structure of the copper-rich phase exists, and there is no zolconium-rich phase at all.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図ないし第４図扛それぞれセリウム、銅、鉄及びジ
ルコニウムの含有量を変化させた場合の磁気特性を示す
グラフ、 第５図ないし第７図はそれぞれ等温時効処理、勢温時効
からの冷却及び時効処理の条件を変化させた場合の保磁
力の変化を示すグラフ、第８図は本発明の永久磁石の走
査型電子顕微鏡写真、 第９図及び第１０図は永久磁石のセル構造内部及びジル
コニウム過剰相のエネルギ分散分光図、第１１図は従来
の永久磁石の電子顕微鏡写真である。 特許出願人 東京電気化学工業株式会社 特許出願代理人 弁理士　　育　木　　　朗 弁理±　　７！ｌ１ＩＩ　　和　之 弁理士　　尉　井　卓　雄 弁理士　　山　口　昭　之 第１回 Ｃｅ　（ｗｔ　＠１．） 第２図 Ｃｕ　（ｗｔ　”１０） 第３図 第４図 第５図 等温時効時間　（ＭＩＮ） 第６図 冷却速度（ＤＥＧ／ＭＩＮ　） 第７図 冷却速度（ＤＥＧ／ＭＩＮ） 固 粉 手続補正書（方式） 昭和５７年３月を日 特許庁長官　島　１）春樹殿 １、事件の表示 昭和５６年特許願　第１６４８２６号 ２、発明の名称 永久磁石 ３、補正をする者 事件との関係　　特許出願人 名　称　（３０６）東京電気化学工業株式会社４、代理
人 ＆　補正命令の日付 ６和５７年２月２３日（発送日） ６、補正の対象 明細書の「図面の簡単な説明」の欄 ？、　　［正の内容 ｔｌ＋　　第２０員、１行の「永久磁石の」の次にｒ金
属組織を表わすｊ會加入する。′ ｔ２＋　　［２０頁、第９行の「永久磁石の」の次にｒ
金属！ｌｌ織を表わす」を加入する。 なお、補正指令事項第２番目の「適正な図面」に関しま
しては、上記「図面の簡単な説明」の補正に伴い、その
不備は解消したものと思料致しますＯFigures 1 to 4 are graphs showing the magnetic properties when the contents of cerium, copper, iron, and zirconium are varied, respectively. Figures 5 to 7 are graphs showing isothermal aging treatment and cooling from hot aging, respectively. Figure 8 is a scanning electron micrograph of the permanent magnet of the present invention; Figures 9 and 10 are graphs showing the inside of the cell structure of the permanent magnet; The energy dispersion spectrogram of the zirconium-excess phase, FIG. 11, is an electron micrograph of a conventional permanent magnet. Patent applicant: Tokyo Denki Kagaku Kogyo Co., Ltd. Patent attorney: Akira Ikuki ± 7! l1II Kazuyuki, Patent Attorney, Takashi Yoshii, Patent Attorney, Akira Yamaguchi 1st Ce (wt @1.) Fig. 2 Cu (wt ”10) Fig. 3 Fig. 4 Fig. 5 Isothermal aging time (MIN) Fig. 6 Figure Cooling Rate (DEG/MIN) Figure 7 Cooling Rate (DEG/MIN) Solid Powder Procedure Amendment (Method) March 1980, Japan Patent Office Commissioner Shima 1) Haruki-dono 1, Indication of the Case 1988 Patent Application No. 164826 2, Name of the invention Permanent magnet 3, Relationship with the case of the person making the amendment Name of patent applicant (306) Tokyo Denki Kagaku Kogyo Co., Ltd. 4, Agent & Date of amendment order 6 February 23, 1957 Date (shipment date) 6. “Brief explanation of drawings” column of the specification subject to amendment? , [Positive content tl+ 20th member, after "of permanent magnet" in the 1st line, r joins the j group representing the metal structure. ′ t2+ [Page 20, line 9, after “permanent magnet”, r
metal! Add ``I represent the weave''. Regarding the second amendment directive, "appropriate drawings," we believe that the deficiencies have been resolved as a result of the amendment to the "brief explanation of the drawings" mentioned above.

Claims (1)

【特許請求の範囲】 １６　　重量百分率で、２０ないし３０％のセリウム、
３な′いし９９１の鋼、工ないし５チのジルコニウム及
び１０７１ｔｎＬ３０−の鉄を含有し、残部がコバルト
からなる希土類＝パル）ｌ主体とする余興間化合物を含
んでなる永久磁石において、該金属間化合物結晶の０面
に平行にジルコニウム過剰なる相が相互の間隔が５００
０１以下にて存在し、エネルギ積及び保磁力が高−こと
を特徴とする永久磁石。 ２　前′記ゾルコニウムの他にハフニウム、チタン、バ
ナジウム、ニオブ及びタンタルからなる群の少なくとも
１種を合計で１ないし５−を含有することを特徴とする
請求の範囲１１１項記載の永久磁石。 ３、前記セリウムの８０１以下をサマリウムで置換した
ことＹｔ特徴とする請求の範ＩＩ第１項又は第２項記載
の永久磁石。 ４、前記鉄の８０嘔以下をマンガレ、ニッケル及びクロ
ムからなる群め少なくとも１種で置換したことを特徴と
する特許請求“の範囲＄１項ないし“ｓ３項の込ずれか
に記載の永久磁石。[Claims] 16. 20 to 30% cerium by weight percentage;
In a permanent magnet comprising an entertainment compound mainly containing a rare earth element (pal)l, which contains steel of 3 to 991, zirconium of 1 to 5, and iron of 1071tnL30, the balance being cobalt, the intermetallic The phase with excess zirconium parallel to the zero plane of the compound crystal has a mutual spacing of 500
01 or less, and has a high energy product and coercive force. 2. The permanent magnet according to claim 111, further comprising 1 to 5 in total of at least one member of the group consisting of hafnium, titanium, vanadium, niobium, and tantalum in addition to the zorconium. 3. The permanent magnet according to claim II, item 1 or 2, characterized in that 801 or less of the cerium is replaced with samarium. 4. A permanent magnet according to any one of claims $1 to s3, characterized in that less than 80% of the iron is replaced with at least one member of the group consisting of mangale, nickel, and chromium. .