JPS63241141A - Ferromagnetic alloy - Google Patents
Ferromagnetic alloyInfo
- Publication number
- JPS63241141A JPS63241141A JP62329640A JP32964087A JPS63241141A JP S63241141 A JPS63241141 A JP S63241141A JP 62329640 A JP62329640 A JP 62329640A JP 32964087 A JP32964087 A JP 32964087A JP S63241141 A JPS63241141 A JP S63241141A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- ferromagnetic alloy
- permanent magnet
- elements
- rare earth
- 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.)
- Granted
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 49
- 239000000956 alloy Substances 0.000 title claims abstract description 49
- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 33
- 239000000654 additive Substances 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 15
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 4
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 abstract description 38
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052796 boron Inorganic materials 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 abstract description 7
- 229910052804 chromium Inorganic materials 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229910052758 niobium Inorganic materials 0.000 abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000005291 magnetic effect Effects 0.000 description 23
- 229910001047 Hard ferrite Inorganic materials 0.000 description 12
- 230000005415 magnetization Effects 0.000 description 9
- 229910002058 ternary alloy Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000005347 demagnetization Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910000828 alnico Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910000592 Ferroniobium Inorganic materials 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 108091006629 SLC13A2 Proteins 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明はＦｅ、希土類元素を主体とする強磁性合金、特
にＦｅ−Ｂ−Ｒ系強磁性合金に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a ferromagnetic alloy mainly composed of Fe and rare earth elements, particularly to a Fe-BR-based ferromagnetic alloy.
従来から強磁性合金の一つとして永久磁石材料が知られ
ている。永久磁石材料は一般家庭の各種電気製品から、
大型コンピュータの周辺端末機まで２幅広い分野で使わ
れるきわめて重要な電気・電子材料の一つである。近年
の電気、電子機器の小型化、高効率化の要求にともない
、永久磁石材料はますます高性能化が求められるように
なった。Permanent magnet materials have been known as one of the ferromagnetic alloys. Permanent magnet materials are used in various household electrical appliances.
It is one of the extremely important electrical and electronic materials used in a wide range of fields, including peripheral terminals for large computers. With the recent demand for smaller size and higher efficiency of electrical and electronic equipment, permanent magnet materials are required to have even higher performance.
現在の代表的な永久磁石材料はアルニコ、ハードフェラ
イトおよび希土類コバルト系磁石材料である。最近のコ
バルトの原料事情の不安定化にともない、コバルトを２
０〜３０重は％含むアルニコ磁石材料の需要は減り、鉄
の酸化物を主成分とする安価なハードフェライトが磁石
材料の主流を占めるようになった。一方、希土類コバル
ト系磁石材料はコバルトを５０〜６５重量％も含むうえ
、希土類鉱石中にあまり含まれていないＳｍを使用する
ため大変高価であるが、他の磁石材料に比べて。Current typical permanent magnet materials are alnico, hard ferrite, and rare earth cobalt based magnet materials. Due to the recent instability in the raw material situation for cobalt,
The demand for alnico magnet materials containing 0 to 30% weight has decreased, and inexpensive hard ferrite, whose main component is iron oxide, has become the mainstream of magnet materials. On the other hand, rare earth cobalt-based magnet materials contain 50 to 65% by weight of cobalt and use Sm, which is not included in rare earth ores, so they are very expensive compared to other magnet materials.
磁気特性が格段に高いため、主として小型で、付加価値
の高い磁気回路に多く使われるようになった。Because of its extremely high magnetic properties, it has come to be used mainly in small, high-value-added magnetic circuits.
希」−類を用いた磁石材料がもっと広い分野で安価に、
かつ多ごに使イ〕れるようになるためには。Magnet materials using rare-type materials can be used in a wider range of fields at low cost.
In order to be able to use it for many purposes.
高価なコバルトを含まず、かつ希土類金属として、鉱石
中に多量に含まれている軽希土類を主成分とすることが
必要である。このような永久磁石材料の一つの試みとし
て、ＲＦ ｅ ２磁化合物（ただしＲは希土類元素を示
す記号）が検討された。It is necessary that it does not contain expensive cobalt and that the main component is a light rare earth metal, which is contained in large amounts in ores. As one attempt at such a permanent magnet material, an RF e 2 magnetic compound (where R is a symbol representing a rare earth element) was investigated.
フロート（Ｊ、 Ｊ、 Ｃｒｏａｔ）はＰｒ Ｆｅ
の超０．４ ０．１３
急冷リボンが２９５Ｋにてｌｉｅ −２，８ｋｏｅの保
磁力を示すことを報告している（Ｊ、 Ｊ、 Ｃｒｏａ
ｔ Ａｐｐｌ。Float (J, J, Croat) is Pr Fe
reported that a super-0.4 0.13 quenched ribbon exhibits a coercive force of lie -2.8 koe at 295 K (J, J, Croa
t Appl.
Ｐｈｙｓ、 Ｌｏｔｔ、 ３７ （１２） １５ Ｄｅ
ｃｅｒＡｂｅｒ １９８０．１０９８〜１０９８頁）。Phys, Lott, 37 (12) 15 De
cerAber 1980. pp. 1098-1098).
その後Ｎｄ Ｆｅ の超急冷リボ０．４ ０
．８
ンにおいても２９５Ｋにてｌｉｅ −７，４５ｋＯｃの
保磁力を示すことを報告している（Ｊ、 Ｊ、 Ｃｒｏ
ａｔ Ａｐｐｌ。After that, NdFe super-quenched ribo 0.40
．． It has been reported that a coercive force of -7.45 kOc is exhibited at 295 K even at 800 nm (J, J, Cro
at Appl.
Ｐｈｙｓ、 Ｌｃｔｔ、 ３９ （４） １５ Ａｕｇ
ｕｓｔ １９８１．３５７〜３５８頁）。しかし、これ
らの超急冷リボンは、いずれも（Ｂｌｌ）ｗａｘが低い
（４ＭＧＯｅ未満）。Phys, Lctt, 39 (4) 15 Aug
ust 1981. pp. 357-358). However, all of these ultra-quenched ribbons have low (Bll) wax (less than 4 MGOe).
さらに、クーン（Ｎ、 Ｃ，Ｋｏｏｎ）等は（Ｆ ｅ
ｏ、８２Ｌａ ） Ｔｂ Ｌａ の超
急冷アモル０．１８ ０．９ ０．０５ ０．０５
フアスリボンを６２７℃で焼鈍すると、 ｌｌｅ −９
ｋｏｅにも達することを見い出した（Ｂｒ−５ｋＧ）。Furthermore, Kuhn (N, C, Koon) et al.
o, 82La) Ultra-quenched amol of TbLa 0.18 0.9 0.05 0.05
When the fast ribbon is annealed at 627°C, lle -9
It was found that it reached even koe (Br-5kG).
但し、この場合、磁化曲線の角形性が悪いため（Ｂ Ｉ
ｆ ） ｍ ａ ｘは低い（Ｎ、 Ｃ，Ｋｏｏｎ他、
Ａｐｐｌ、 Ｐｈｙｓ。However, in this case, because the squareness of the magnetization curve is poor (BI
f) max is low (N, C, Koon et al.
Appl, Phys.
Ｌｅｔｔ、 ３９ （１０）、 １９８１．８４０〜８
４２頁）。Lett, 39 (10), 1981.840-8
(page 42).
また、カバコツ（Ｌ、 Ｋａｂａｃｏｆｒ）等は（Ｆ
ｅ ｏ、ｓＢ ） Ｐｒ （ｘ＝ｏ 〜
０．３原子比）の組０．２ １−ｘ ｘ
成の超急冷アモルファスリボンを作製し、その非晶質合
金が５０ｃ程度のＨｅを有することを報告している。（
Ｌ、 Ｋａｂａｋｏｆ’［’他： Ｊ、 Ａｐｐｌ、
Ｐｈｙｓ、 ５３ （３）Ｍａｒｃｂ １９８２．２
２５５〜２２５７頁）。In addition, Kabakotsu (L, Kabacofr) etc. are (F
e o, sB ) Pr (x=o ~
reported that an ultra-quenched amorphous ribbon with a composition of 0.2 1-x (
L, Kabakof'['et al.: J, Appl,
Phys, 53 (3) Marcb 1982.2
(pp. 255-2257).
以上に示す超急冷リボンのほとんどが希土類としては軽
希土類を主成分とするものであるが、いずれも従来から
慣用される永久磁石材料と比べて（Ｂｉｔ）ｍａｘが低
く、実用永久磁石材料として使用することは困難であっ
た。また、これらの超急冷リボンはそれ自体として一般
のスピーカやモータ等に使用可能な実用永久磁石（体）
ではなく、これらのリボンから１モ意の形状・寸法を有
する実用永久磁石を得ることができなかった。Most of the ultra-quenched ribbons shown above have light rare earths as their main components, but all of them have lower (Bit)max than conventional permanent magnet materials and cannot be used as practical permanent magnet materials. It was difficult to do so. In addition, these ultra-quenched ribbons themselves can be used as practical permanent magnets (body) that can be used in general speakers, motors, etc.
However, it has not been possible to obtain a practical permanent magnet having a desired shape and dimensions from these ribbons.
本発明は、このような要請に応えるべき新規な実用強磁
性合金、特に永久磁石材料として有用なものを提供する
ことを基本目的とする。特に。The basic object of the present invention is to provide a new practical ferromagnetic alloy that should meet such demands, particularly one useful as a permanent magnet material. especially.
Ｆｅを主体とし、Ｒとして資源的に豊富な軽希土類元素
を有効に使用できるものを得ることを目的とする。The purpose is to obtain a material mainly composed of Fe and in which resource-rich light rare earth elements can be effectively used as R.
このような強磁性合金として１本発明者は、先に、Ｎｄ
、Ｐｒを特徴とする特定の希土類元素とＦｅとＢとを特
定比をもって必須とする強磁性合金、特に磁気異方性な
いし磁界中配向能力を有する。全く新しい種類の実用強
磁性合金を開発し。As such a ferromagnetic alloy, the present inventor previously developed Nd
, a ferromagnetic alloy that essentially includes a specific rare earth element characterized by Pr, and Fe and B in a specific ratio, and particularly has magnetic anisotropy or the ability to orient in a magnetic field. Developed a completely new type of practical ferromagnetic alloy.
本願と同一出願人により出願した（特願昭５７−１４５
０７２の分割出願としての特願昭５９−２４８８９７）
。Filed by the same applicant as the present application (Japanese Patent Application No. 57-145
Patent application No. 59-248897 as a divisional application of No. 072)
.
尚、このＦｅ−Ｂ−Ｒ三元系合金においてボロン（Ｂ）
は、従来の１例えば非晶質合金作成時の非晶質促進元素
又は粉末冶金法における焼結促進元素として添加される
ものではなく、Ｆｅ−Ｂ−Ｒ三元系合金のベースとなる
室温以上で磁気的に安定で高い磁気異方性を有するＲ−
Ｆｅ−８三元化合物の必須構成元素である。この合金は
実用上十分に高いキュリ一温度（約３００℃以」−）を
有する。In this Fe-B-R ternary alloy, boron (B)
is not added as an amorphous promoting element in the production of an amorphous alloy or as a sintering promoting element in powder metallurgy, but is added at room temperature or above, which is the base of the Fe-B-R ternary alloy. R- is magnetically stable and has high magnetic anisotropy.
Fe-8 is an essential constituent element of the ternary compound. This alloy has a Curie temperature (approximately 300° C. or higher) that is sufficiently high for practical use.
上述のＦｅ−Ｂ−Ｒ三元系強磁性合金は必ずしもＣｏを
含む必要がなく、またＲとしては資源的に豊富なＮｄ、
Ｐｒを主体とする軽希土類を用いることができ、必ずし
もＳｍを必要とせず或いはＳｍを主体とする必要もない
ので原料が安価であり、きわめて有用である。しかも、
この強磁性合金を用いて得られるＦｅ−Ｂ−Ｒ系磁気異
方性焼結永久磁石の磁気特性はハードフェライト磁石以
上の特性を有しく保磁力ＩＨｃ≧１ ｋＯｅ 、残留磁
束密度Ｂ「≧４ ｋＧ、最大エネルギ積（ＢＨ）ｗａｘ
≧４ＭＧＯｃ）特に好ましい組成範囲においては希土類
コバルト磁石と同等以上の極めて高いエネルギ積を示す
ことができる。The above-mentioned Fe-B-R ternary ferromagnetic alloy does not necessarily need to contain Co, and as R, Nd, which is abundant in resources,
A light rare earth element mainly composed of Pr can be used, and since it does not necessarily require Sm or mainly Sm, the raw material is inexpensive and extremely useful. Moreover,
The magnetic properties of the Fe-B-R magnetically anisotropic sintered permanent magnet obtained using this ferromagnetic alloy are better than those of hard ferrite magnets, with coercive force IHc≧1 kOe and residual magnetic flux density B≧4. kG, maximum energy product (BH) wax
≧4MGOc) In a particularly preferable composition range, it can exhibit an extremely high energy product equal to or higher than that of rare earth cobalt magnets.
本発明は、かかるＦｅ−Ｂ−Ｒ三元系強磁性合金合金に
おいて、 Ｔｉ、 Ｎｉ、Ｂｉ、Ｖ、Ｎｂ。The present invention provides such a Fe-B-R ternary ferromagnetic alloy comprising Ti, Ni, Bi, V, and Nb.
Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、ＡＪ、Ｓｂ。Ta, Cr, Mo, W, Mn, AJ, Sb.
Ｇｅ、Ｓｎ、Ｚｒ、Ｈｆよりなる群から選択された特定
の添加元素Ｍ一種又は二種以上を所定％をもって加える
ことにより、先願（特願昭５９−２４６８９７）に係る
Ｆｅ−Ｂ−Ｒ三元系合金と同様に、前述した目的を達成
するものである。即ち。By adding one or more specific additive elements M selected from the group consisting of Ge, Sn, Zr, and Hf at a predetermined percentage, Fe-B-R three according to the earlier application (Japanese Patent Application No. 59-246897) can be obtained. Similar to the element-based alloys, it achieves the above-mentioned objectives. That is.
本発明の強磁性合金は次の通りである。The ferromagnetic alloy of the present invention is as follows.
本願の第１発明：原子百分比で、希土類元素Ｒ（ＲはＮ
ｄとＰｒの一種又は二種）８〜３０％。First invention of the present application: Rare earth element R (R is N
d and Pr) 8 to 30%.
８２〜２８％、下記所定％以下（０％を除く）の添加元
素Ｍの一種又は二種以上（但し添加元素Ｍが二種量Ｊ−
のときは２Ｍ合量は当該添加元素のうち最大所定％を有
するものの当該所定％以下）、及び残部実質的にＦｅか
ら成ることを特徴とする強磁性合金；
Ｔ ｉ ４．５９６． Ｎ ｉ ８ ％。82 to 28%, below the specified percentage (excluding 0%) of one or more of the additive elements M (however, if the additive elements M are two types J-
T i 4.596. ferromagnetic alloy characterized in that the total amount of 2M is the maximum predetermined % of the added elements but not more than the predetermined %), and the remainder substantially consists of Fe; T i 4.596. N i 8%.
Ｂ ｉ５ ９ＣＶ ９．５％。B i5 9CV 9.5%.
Ｎ ｂ １２．５％、 Ｔ ａ １０．５％。Nb 12.5%, Ta 10.5%.
Ｃｒ８．５％、 Ｍｏ９．５％。Cr8.5%, Mo9.5%.
Ｗ ９．５％、 Ｍｎ ８ ％。W 9.5%, Mn 8%.
Ａで ９．５％、 Ｓｂ２．５％。A: 9.5%, Sb: 2.5%.
Ｇｅ ７ ％、 Ｓｎ３．５％。Ge 7%, Sn 3.5%.
Ｚｒ５．５％、及びＨｆ５．５％。Zr5.5%, and Hf5.5%.
本願の第２発明：原子百分比で、Ｒ（ＲはＮｄ、Ｐｒ、
Ｄｙ、Ｈｏ、Ｔｂ、Ｌａ、Ｃｅ。Second invention of the present application: R (R is Nd, Pr,
Dy, Ho, Tb, La, Ce.
Ｇｄ、Ｙのうち少なくとも一種で、かつＲの５０％以に
はＮｄとＰｒの一種又は二種）８〜３０％、８２〜２８
％、所定％以下（０％を除く）の添加元素Ｍの一種又は
二種以上（但し添加元素Ｍが二種以上のときは１Ｍ合量
は当該添加元素のうち最大所定％を存するものの当該所
定％以下）、及び残部実質的にＦｅから成ることを特徴
とする強磁性合金（添加元素Ｍの所定％は第１発明にお
けるものと同じ）。At least one of Gd and Y, and 50% or more of R is one or two of Nd and Pr) 8-30%, 82-28
%, below a specified % (excluding 0%) of one or more types of additive elements M (however, when there are two or more types of additive elements M, the total amount of 1M is the specified amount of the maximum specified % of the added elements) % or less), and the remainder substantially consists of Fe (the predetermined % of the additive element M is the same as that in the first invention).
本発明者は、Ｆｅ−Ｂ−Ｒ系三元合金、特に８〜３０％
のＲ，２〜２８％のＢ、残部Ｆｅから成るＦｅ−Ｂ−Ｒ
三元合金をベースとして、前述の目的達成を目標として
、放射性元素等を除くほとんどの元素についてその微量
域（０，００５原子％、以下％は原子％を示す）から１
０数％に回る範囲において、その添加による保磁力その
他の磁気特性の変化を詳細に調べた。その結果前記添加
元素Ｍの添加によっても前述した要請に応え得る新規な
実用強磁性合金をＳｍ、Ｃｏ等を必須とせずに提供し得
ることを見出した。しかも、永久磁石材料として使用し
たときハードフェライト磁石材料と同等以上の優れた磁
気特性を有し、好ましい態様においてはＦｅ−Ｂ−Ｒ三
元系合金に比してもより高保磁力を付与する効果を有す
ることを見出した。The present inventor has developed an Fe-B-R ternary alloy, particularly 8 to 30%
Fe-B-R consisting of R, 2 to 28% B, and the balance Fe
Based on ternary alloys, with the aim of achieving the above-mentioned objectives, we aim to reduce the amount of most elements, excluding radioactive elements, from the trace amount range (0,005 atomic %, hereinafter % indicates atomic %) to 1.
Changes in coercive force and other magnetic properties due to its addition were investigated in detail in the range of about 0.0%. As a result, it has been found that by adding the additive element M, it is possible to provide a new practical ferromagnetic alloy that can meet the above-mentioned requirements without requiring Sm, Co, etc. Moreover, when used as a permanent magnet material, it has excellent magnetic properties equivalent to or better than hard ferrite magnet materials, and in a preferred embodiment, has the effect of imparting a higher coercive force than the Fe-B-R ternary alloy. It was found that
但し、これらの添加元素Ｍの添加は、夫々の態様におい
て、Ｆｅ−Ｂ−Ｒ三元系合金に比して永久磁石材料とし
て残留磁化Ｂｒの漸次の低下を招くことも明らかとなっ
た。従って、添加元素Ｍの含有量は、少くとも残留磁化
Ｂ「が、従来のハードフェライトの残留磁化Ｂ「と同等
以上の範囲で、かつ高保磁力を示すものが本発明の対象
として把握される。かくて本発明はＦｅ−Ｂ−Ｒ三元系
合金において更に特定の添加元素Ｍを含をすることによ
り、Ｆｅ−Ｂ−Ｒ化合物をベースとした新規なＦｅ−Ｂ
−Ｒ−Ｍ系強磁性合金を提供するものである。Ｆｅ−Ｂ
−Ｒ三元系合金と同様に本発明のＦｅ−Ｂ−Ｒ−Ｍ系合
金も高い異方性磁界を示し磁界中配向能力を有するので
、特に異方性磁石用材料として有用である。However, it has also become clear that the addition of these additive elements M, in each aspect, causes a gradual decrease in residual magnetization Br as a permanent magnet material compared to the Fe-B-R ternary alloy. Therefore, the content of the additive element M is understood to be one in which the residual magnetization B is at least equal to or higher than the residual magnetization B of conventional hard ferrite, and which exhibits a high coercive force. Thus, the present invention further includes a specific additive element M in the Fe-B-R ternary alloy, thereby creating a new Fe-B-R compound based on the Fe-B-R compound.
-RM type ferromagnetic alloy is provided. Fe-B
Like the -R ternary alloy, the Fe-BRM-based alloy of the present invention exhibits a high anisotropic magnetic field and has the ability to orient in a magnetic field, so it is particularly useful as a material for anisotropic magnets.
本発明によれば、従来ハードフェライトと同等以上の磁
気特性を有し、Ｓｍ−Ｃｏ磁石材料に代替可能な高性能
磁石材料をも包含する工業上極めて有用な新規な実用強
磁性合金を提供可能とする。According to the present invention, it is possible to provide a novel practical ferromagnetic alloy that is extremely useful industrially and includes a high-performance magnet material that has magnetic properties equivalent to or better than conventional hard ferrite and can be substituted for Sm-Co magnet materials. shall be.
本発明の強磁性合金はＦｅ−Ｂ−Ｒ−Ｍ系であり、必ず
しもＣＯを含む必′要がなく、またＲとしては資源的に
豊富なＮｄ、Ｐｒを主体とする軽希土類を用いることが
でき、必ずしもＳｍを必要とせず或いはＳｍを主体とす
る必要もないので原料が安価であり、きわめてａ用であ
る。実施例から明らかな通り１本発明の合金は磁界中配
向能力を有する。The ferromagnetic alloy of the present invention is Fe-BRM-based and does not necessarily need to contain CO, and as R, light rare earths mainly consisting of Nd and Pr, which are abundant in resources, can be used. Since it does not necessarily require Sm or does not need to be made mainly of Sm, the raw material is inexpensive, and it is extremely suitable for A. As is clear from the examples, one of the alloys of the present invention has the ability to orient in a magnetic field.
最近、永久磁石材料はますます苛酷な環境１例えば磁石
の薄型化にともなう強い反磁界、コイルや他の磁石によ
って加えられる強い逆磁界、これらに加えて機器の高速
化、高負荷化による高温度の環境にさらされることが多
くなり、多くの用途における。特性安定化のためには、
一層の高保磁力化が必要とされる（一般に永久磁石材料
の１ｌｌｃは温度上昇にともない低下する。そのため室
温における １１１ｃが小さければ、永久磁石材料が高
温度に晒されると減磁が起こる。しかし、室温における
ｌ１ｌｃが十分高ければ実質的ににこのような減磁は
起こらない）。従って、Ｆｅ−Ｂ−Ｒ系強磁性合金（特
に永久磁石材料）よりもさらに高い ｌＨｃを６する永
久磁石材料を提供し得るものを包含する本発明強磁性合
金はこうした苛酷な環境下で使用される永久磁石材料と
して特に好適である。Recently, permanent magnet materials have been exposed to increasingly harsh environments 1, such as strong demagnetizing fields due to thinner magnets, strong reverse magnetic fields applied by coils and other magnets, and high temperatures due to higher speeds and higher loads of equipment. in many applications. In order to stabilize the characteristics,
An even higher coercive force is required (generally, the 1llc of a permanent magnet material decreases as the temperature rises. Therefore, if 111c at room temperature is small, demagnetization will occur when the permanent magnet material is exposed to high temperatures. If l1lc at room temperature is sufficiently high, such demagnetization will not occur substantially). Therefore, the ferromagnetic alloys of the present invention, including those capable of providing permanent magnet materials with higher lHc than Fe-B-R ferromagnetic alloys (particularly permanent magnet materials), cannot be used in such harsh environments. It is particularly suitable as a permanent magnet material.
本発明の強磁性合金はその形態は問わず、鋳塊あるいは
粉体等の公知の形態の永久磁石用の素材の他、任意の形
態からなる永久磁石材料をも包含する。The ferromagnetic alloy of the present invention is not limited to its form, and includes not only materials for permanent magnets in known forms such as ingots or powders, but also permanent magnet materials in any form.
本発明の強磁性合金において希土類元素ＲはＹを包含し
、軽希土類及び重希土類を包含する希土類元素でありそ
のうち所定の一種以上を用いる。In the ferromagnetic alloy of the present invention, the rare earth element R includes Y, and is a rare earth element including light rare earths and heavy rare earths, and one or more of them is used.
即ちこのＲとしては、Ｎｄ、Ｐｒ、Ｌａ、Ｃｅ。That is, this R includes Nd, Pr, La, and Ce.
Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｅｕ、Ｓｍ、Ｇｄ。Tb, Dy, Ho, Er, Eu, Sm, Gd.
Ｐｍ、Ｔｍ、Ｙｂ、Ｌｕ及びＹが包含される。Ｒとして
は１通常Ｎｄ、Ｐｒの一種又は二種をもって足りるが、
これらＮｄ、ＰｒをＲの５０９６以上として他のＤｙ、
Ｈｏ、Ｔｂ、Ｌａ、Ｃｅ、Ｇｄ。Pm, Tm, Yb, Lu and Y are included. As R, one or both of Nd and Pr are usually sufficient.
These Nd and Pr are R5096 or more, and other Dy,
Ho, Tb, La, Ce, Gd.
Ｙのうち少なくとも一種を混合して用いることができる
。実用上は二種以上の混合物（ミツシュメタル、ジジム
等）を入手上の便宜等の理由により用いることができる
。なお、これらのＲは純希土類元索でなくともよく、工
業上入手可能な範囲で製造上不可避な不純物（他の希土
類元素、Ｃａ。At least one type of Y can be mixed and used. Practically speaking, a mixture of two or more types (Mitsuhmetal, Didim, etc.) can be used for reasons such as availability. Note that these R do not have to be pure rare earth elements, but may contain impurities (other rare earth elements, Ca, etc.) that are unavoidable during production within the industrially available range.
Ｍｇ、Ｆｅ、Ｔｉ、Ｃ，Ｏ等）を含有するもので差支え
ない。このようにＲとしては工業上入手し易いものを主
体として用いることができる点で本発明は極めて有利で
ある。Mg, Fe, Ti, C, O, etc.) may be used. As described above, the present invention is extremely advantageous in that R that is industrially easily available can be mainly used.
Ｂ（ホウ素）としては、純ボロン又はフェロボロンを用
いることができ、不純物としてＡＪ。Pure boron or ferroboron can be used as B (boron), and AJ as an impurity.
３１、Ｃ等を含むものも用いることができる。31, C, etc. can also be used.
本発明の強磁性合金の組成範囲の限定理由は後述する実
施例によって詳細に説明するが、特に本発明を最も効果
的に用いた場合、すなわち、磁気異方性焼結永久磁石と
して用いた場合にノ１−ドフェライトと同等以上の磁気
特性を得ることが可能な組成範囲を選定した。すなわち
本発明の強磁性合金は、８〜３０％Ｒ，２〜２８％Ｂ、
所定％以下Ｍ、残部Ｆｅ（原子百分率）において、保磁
力ＩＨｃ≧１ ｋｏｃ 、残留磁束密度Ｂ「≧４ ｋＧ
、最大エネルギ積（ＢＨ）ｗａｘはハードフェライト（
〜４ ＭＧＯｅ程度）と同等以上の異方性焼結磁石とす
ることができる。The reasons for limiting the composition range of the ferromagnetic alloy of the present invention will be explained in detail in the Examples described below, but especially when the present invention is used most effectively, that is, when used as a magnetically anisotropic sintered permanent magnet. A composition range was selected in which it was possible to obtain magnetic properties equivalent to or better than that of Nord ferrite. That is, the ferromagnetic alloy of the present invention has 8 to 30% R, 2 to 28% B,
At a predetermined % or less M, balance Fe (atomic percentage), coercive force IHc≧1 koc, residual magnetic flux density B “≧4 kG
, the maximum energy product (BH) wax is hard ferrite (
The anisotropic sintered magnet can be made into an anisotropic sintered magnet that is equivalent to or more than 4 MGOe.
本発明のＦｅ−Ｂ−Ｒ−Ｍ系強磁性合金において、Ｒ，
Ｂの組成範囲は、基本的にＦｅ−Ｂ−Ｒ三元系合金と同
様（８〜３０％Ｒ，２〜２８％Ｂ）である。即ち、異方
性焼結体磁石として、保磁力 １１１ｃ≧１ ｋｏｏを
満たすためＢは２％以上とし、ハードフェライトの残留
磁束密度Ｂ「約４ｋＧ以上とするためにＢは２８９６以
下とし、Ｒは保磁力を１ ｋｏｏ以上とするため８％以
上必要であり、また燃え易く工業的取扱、製造上の困難
のため（かつまた高価であるため） 、 ３０９６以下
とする。このＢ、Ｒ範囲において異方性焼結磁石の最大
エネルギ積（１３ｔｌ）ｍａｘはハードフェライト（〜
４ ＭＧＯｅ程度）と同等以上となる。In the Fe-BRM-based ferromagnetic alloy of the present invention, R,
The composition range of B is basically the same as that of the Fe-B-R ternary alloy (8 to 30% R, 2 to 28% B). That is, as an anisotropic sintered magnet, B is set to 2% or more to satisfy the coercive force 111c≧1koo, B is set to 2896 or less to make the residual magnetic flux density of hard ferrite B "approximately 4 kG or more, and R is set to 2% or more. In order to have a coercive force of 1 koo or more, 8% or more is required, and because it is easily flammable and difficult to handle and manufacture industrially (and is expensive), it is set to 3096 or less. The maximum energy product (13 tl) max of a directional sintered magnet is hard ferrite (~
4 MGOe level).
Ｎｄ、ＰｒをＲの主成分（即ち全Ｒ中Ｎｄ。Nd and Pr are the main components of R (i.e. Nd in all R).
Ｐｒの１種以上が５０％以上）とし、１１〜２４％Ｒ９
３〜２７％Ｂ、残部（Ｆｅ＋Ｍ）の組成は、異方性焼結
体としたとき最大エネルギ積（Ｂｌｌ）ｗａｘ≧７ＭＧ
Ｏｅとするために好ましい範囲である。50% or more of Pr) and 11 to 24% R9
The composition of 3 to 27% B and the balance (Fe+M) is the maximum energy product (Bll) wax≧7MG when made into an anisotropic sintered body.
This is a preferable range for achieving Oe.
さらに好ましくは、Ｎｄ、ＰｒをＲの主成分（同上）と
し、１２〜２０％Ｒ，４〜２４％Ｂ、残部（Ｆｅ＋Ｍ）
の組成であり、異方性焼結体としたとき最大エネルギ積
（Ｂ ｔｌ ） Ｉｌａ ｘ≧ｌＯＭＧＯｅを可能とし
、 （Ｂｌｌ）ｏ＋ａｘは最高３５ＭＧＯｃ以上に達す
る。なお所定の最大エネルギ積を得るための所望のＢ「
に対応するＭの範囲は第１図〜第３図を参照して定めら
れる。More preferably, Nd and Pr are the main components of R (same as above), 12 to 20% R, 4 to 24% B, and the balance (Fe + M).
When made into an anisotropic sintered body, the maximum energy product (B tl ) Ila x≧lOMGOe can be achieved, and (Bll)o+ax reaches a maximum of 35MGOc or more. Note that the desired B'' to obtain a predetermined maximum energy product is
The range of M corresponding to is determined with reference to FIGS. 1-3.
本発明の強磁性合金は、新規なＦ ’ｅ −Ｂ −Ｒ化
合物をベースとするＦｅ−Ｂ−Ｒ−Ｍ系合金であるが、
Ｆｅの一部をＣＯで置換することによりキュリ一温度Ｔ
ｃを上昇できる。また、Ｂの一部をＣ，Ｐ、Ｓｔ等によ
り置換することも可能であり、製造性改善、低価格化が
可能となる。なお。The ferromagnetic alloy of the present invention is a Fe-B-R-M alloy based on a novel F'e-B-R compound.
By replacing part of Fe with CO, the Curie temperature T
c can be increased. Furthermore, it is also possible to replace a part of B with C, P, St, etc., which makes it possible to improve manufacturability and reduce costs. In addition.
本発明の強磁性合金は、Ｆｅ、Ｂ、Ｒ，Ｍの外。The ferromagnetic alloy of the present invention is other than Fe, B, R, and M.
Ｃ，Ｓ、Ｐ、Ｃａ、Ｍｇ、０．Ｓｉ等工業的に製造上不
可避な不純物の存在を許容できる。これらの不純物は、
原料或いは製造工程から混入することが多く１合計５％
以下とすることが好ましい。C, S, P, Ca, Mg, 0. The presence of industrially unavoidable impurities such as Si can be tolerated. These impurities are
Often mixed in from raw materials or manufacturing processes 1 total 5%
The following is preferable.
なお２本発明のＦｅ−Ｂ−Ｒ−Ｍ系合金を用いて、先に
出願したＦｅ−Ｂ−Ｒ系合金と同様に実用永久磁石を製
造できる。例えば１合金を溶成。Note that using the Fe-B-R-M alloy of the present invention, practical permanent magnets can be manufactured in the same manner as the Fe-B-R alloy that was previously filed. For example, one alloy is melted.
冷却１例えば鋳造し生成合金を粉末化した後、成形焼結
することにより適当なミクロ組織を形成することによっ
て、最も効果的に実用高性能永久磁石を得ることができ
る。Cooling 1 For example, a practical high-performance permanent magnet can be obtained most effectively by forming an appropriate microstructure by casting, pulverizing the resulting alloy, and then shaping and sintering it.
〈実施例〉
以下本発明について、実験例及び実施例を引照しつつ詳
述する。<Example> The present invention will be described in detail below with reference to Experimental Examples and Examples.
種々の添加元素を含むＦｅ−Ｂ−Ｒ−Ｍ合金を次の方法
で作成した。Fe-BRM alloys containing various additive elements were created by the following method.
合金を高周波溶成し、水冷銅鋳型に鋳造出発原料はＦｅ
として純度９９．９％の電解鉄、Ｂとしてフェロボロン
合金及び９９％の純度のボロンを用い、Ｒとして純度９
９．７％以上のもの（不純物は主として他の希土類元素
）を使用、添加元素として、純度９９％のＴｉ、Ｍｏ、
Ｂｉ、Ｍｎ、Ｓｂ。The alloy is high-frequency melted and cast into a water-cooled copper mold.The starting material is Fe.
Electrolytic iron with a purity of 99.9% is used as B, ferroboron alloy and boron with a purity of 99% are used as R, and purity 9 is used as R.
Uses 9.7% or more (impurities are mainly other rare earth elements), and 99% purity Ti, Mo,
Bi, Mn, Sb.
Ｎｉ、Ｔａ、９８％のＷ、 ９９．９％のＡｉ！、９５
％のＨｆ 、 ９９．９９６のＧｅ、Ｓｎ、またＶとし
て８１．２％のＶを含むフェロバナジウム、Ｎｂとして
８７．６％のＮｂを含むフェロニオブ、Ｃｒとして６１
，９％のＣｒを含むフェロクロム、及びＺｒとして７５
．５％のＺｒを含むフェロジルコニウムを使用した（な
お純度は重Ｑ ９６で示す）
この合金を用いて永久磁石試料を次のように作成
（１）粉砕 スタンプミルにより３５メツシユスルーま
で粗粉砕し２次いでボールミルにより３時間磁界中配向
可能な結晶粒子に微粉砕（３〜１０μ”） ；（２）
磁界（１０ｋＯｃ）中配向・成形（１，５ｔｏｎ／ｃシ
にて加圧）；
（３）焼結 ｔｏｏｏ 〜１２００℃１時間Ａｒ中、焼
結後放冷。Ni, Ta, 98% W, 99.9% Ai! , 95
% Hf, 99.996 Ge, Sn, also ferrovanadium with 81.2% V as V, ferroniobium with 87.6% Nb as Nb, 61 as Cr
, ferrochrome containing 9% Cr, and 75 as Zr.
．． Ferrozirconium containing 5% Zr was used (purity is indicated by weight Q 96). A permanent magnet sample was prepared using this alloy as follows: Finely pulverized into crystal grains (3-10 μ”) that can be oriented in a magnetic field for 3 hours using a ball mill; (2)
Orientation and forming in a magnetic field (10 kOc) (pressurized at 1.5 ton/c); (3) Sintering ~1200°C for 1 hour in Ar, then allowed to cool.
上記試料について、 ｆｉｌｅ、 Ｂｒ、 （［３１
１）ｓａｘを夫々測定し、そのうちの代表的な試料につ
いての結果を第１表（１）〜（４）に示す。又上記と同
様な方法にて作成した本発明試料との比較例を第２表に
示す。なお、第２表の符号Ｃは比較例であることを示す
。また第１．２表中Ｆｅは数値を挙げていないが残部を
示す。なお前記永久磁石試料の作成工程において微粉砕
後の合金（粉末状態）での特性を調べたところ、 １
１１ｃｌｋＯｅ以上の高い値を示していた。For the above sample, file, Br, ([31
1) Sax was measured, and the results for representative samples are shown in Tables 1 (1) to (4). Comparative examples with samples of the present invention prepared in the same manner as above are shown in Table 2. Note that the code C in Table 2 indicates a comparative example. Further, although Fe in Table 1.2 does not have a numerical value, it shows the remainder. In addition, when we investigated the properties of the alloy (powder state) after fine pulverization in the process of creating the permanent magnet sample, we found that 1
It showed a high value of 11 clkOe or more.
上記の結果から１次のことが明らかとなった。The above results revealed the following.
第１表試料１〜３６及び試料４８〜５０は、希土類元素
として軽希土類の代表的なものであるＮｄを中心として
、 Ｆ ｅ −８Ｂ −１５Ｎ ｄ系（試料１〜２Ｂ
）。Samples 1 to 36 and 48 to 50 in Table 1 are composed of Fe-8B-15N d system (Samples 1-2B
).
Ｆ ｅ−１７Ｂ−１５Ｎ ｄ系（：ｉ料２７〜３Ｂ）及
びＦｅ−１２Ｂ −２ＯＮ ｄ系（試料４８〜５０）に
おける添加元素Ｍの効果を調べたものである。その結果
、第２表の試料Ｃ１のｌ１ｌｃ ７．３ｋＯｅに比べて
、上記全ての試料（Ｎα１〜３６及びＮｏ、４８〜５０
）についてより高い保磁力を示し、最大１５ｋＯｃ以上
に達している（ Ｎｏ。The effect of the additive element M in the Fe-17B-15N d system (i-materials 27 to 3B) and the Fe-12B-2ON d system (samples 48 to 50) was investigated. As a result, compared to the l1lc 7.3 kOe of sample C1 in Table 2, all the above samples (Nα1-36 and No. 48-50
) shows a higher coercive force, reaching a maximum of 15 kOc or more (No.
３１、３６） Ｏ一方、残留磁化ＢｒはＣＩの１２．１
ｋＧに比べて同等程度（Ｎｏ、１．４等）から添加元素
Ｍの増大に従い一般に徐々に低下を示している。しかし
上記いずれの本発明試料も従来のハードフェライトのレ
ベルの残留磁化的４ ｋＧよりも十分に高い。31, 36) O On the other hand, the residual magnetization Br is 12.1 of CI
Compared to kG, it generally shows a gradual decrease as the added element M increases from the same level (No, 1.4, etc.). However, the residual magnetization of any of the above-mentioned samples of the present invention is sufficiently higher than the level of conventional hard ferrite, which is 4 kG.
第１表試料３７〜３９．４１．５１．５２は希土類元素
として軽希土類であるＰｒを用いたＦｅ−Ｂ−Ｐｒ系に
おける添加元素Ｍの効果を調べたものである。第１表試
料４３．４４．５３〜５ｇ、 ８３．８４は希土類元素
としてＮｄを用いるとともに添加元素Ｍとして２種以上
のものを用いた場合、同じく第１表試料４０．４２．６
５は希土類元素としてＰ「を用いるとともに添加元素Ｍ
として２種以上のものを用いた場合を示し、いずれも良
好な結果が得られることを示している。さらに第１表試
料４５〜４７．５９〜６２は希土類元素として２種以上
のものを用いた場合の添加元素Ｍの効果を調べたもので
ある。これら第１表試料３７〜４７及び試料５１〜６５
も前記第１表試料１〜３Ｂ及び試料４８〜５０と同様、
添加元素Ｍによる良好な結果を得ることが可能である。Samples 37 to 39.41.51.52 in Table 1 were used to investigate the effect of the additive element M in the Fe-B-Pr system using Pr, a light rare earth element, as the rare earth element. Samples 43.44.53 to 5g and 83.84 in Table 1 use Nd as the rare earth element and two or more types of additive elements M, and the same samples 40.42.6 in Table 1
5 uses P as the rare earth element and also uses the additive element M.
The results show cases in which two or more types of compounds are used, and good results can be obtained in both cases. Furthermore, Samples 45 to 47 and 59 to 62 in Table 1 were used to investigate the effect of the additive element M when two or more rare earth elements were used. These Table 1 Samples 37-47 and Samples 51-65
Similarly to Samples 1 to 3B and Samples 48 to 50 in Table 1,
It is possible to obtain good results with the additive element M.
なお、比較例Ｃ５，Ｃ６の ｌ１ｌｃの値が１２．４゜
１３．９ｋＯＯと高いのは、Ｎｄの高含有量によるもの
であり、これらに対しては、試料４８〜５０．５３〜５
５及び試料８３．８４により夫々Ｍ添加の効果が明らか
である。Note that the high value of l1lc of Comparative Examples C5 and C6 of 12.4°13.9kOO is due to the high content of Nd.
The effect of M addition is evident in Samples 5 and 83.84, respectively.
試料Ｎａ５６はｌ１ｌｃ ４．３ｋＯｅであるが、比較
例Ｃ１１３（Ｉｌｌｃ ２．８ｋＯｅ）と、また試料Ｎ
ｏ、５９の １１１ｃ ７．３ｋＯｃはＣ７（ｉｌｌｃ
５．１ｋＯｅ）と比較すると１Ｍ添加の効果が認めら
れる。Sample Na56 has l1lc 4.3 kOe, but Comparative Example C113 (Illc 2.8 kOe) and sample N
o, 59 111c 7.3kOc is C7 (illc
5.1 kOe), the effect of 1M addition is recognized.
また試料１．４．２０の如く、高（Ｂｌｌ）ＩＩｌａｘ
を保持しつつ高保磁力化を実現することも可能である。Also, as in sample 1.4.20, high (Bll) II lax
It is also possible to achieve a high coercive force while maintaining the same.
（以下余白）
第 １ 表 （１）
第 １ 表 （２）
第 １ 表 （３）
第 １ 表 （４）
第 ２ 表
本発明の強磁性合金は、そのベースとなるＦｅ−Ｂ−Ｒ
三元系において、既述の８〜３０％Ｒ，２〜２８％Ｂ、
残部Ｆｅ（原子百分率）の全範囲において、添加元素Ｍ
のを幼性が認められており、このＦｅ−Ｂ−Ｒの各組成
範囲外では、有効ではない（比較例Ｃ１２，Ｃ１３，Ｃ
１７はＲ過少；Ｃ１４はＢ過多；Ｃ１５はＲ過多；Ｃ８
〜Ｃ１ｌはＢ不含有等参照）。(The following are blank spaces) Table 1 (1) Table 1 (2) Table 1 (3) Table 1 (4) Table 2 The ferromagnetic alloy of the present invention has a base material of Fe-B-R.
In the ternary system, the already mentioned 8 to 30% R, 2 to 28% B,
In the entire range of the remaining Fe (atomic percentage), the additive element M
It is recognized that Fe-B-R is immature and is not effective outside the respective composition ranges of Fe-B-R (Comparative Examples C12, C13, C
17 has too little R; C14 has too much B; C15 has too much R; C8
~C1l does not contain B, etc.).
次に添加元素Ｍの夫々の添加の効果を明らかにするため
その添加量を変化させて実験によりＢ「の変化を測定し
、その結果を第１図〜第３図に示す。Ｂｉ、Ｍｎ、Ｎｉ
を除く添加元素Ｍ（Ｔｉ。Next, in order to clarify the effects of adding each of the additive elements M, we measured the changes in B by experiment by changing the amount added, and the results are shown in Figures 1 to 3.Bi, Mn, Ni
Additional elements M (Ti.
Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｎｂ、Ｃｒ、Ｗ、Ｍｏ。Zr, Hf, V, Ta, Nb, Cr, W, Mo.
Ｓｂ、Ｓｎ、Ｇｅ、Ａｆ）の添加量の上限は、第１図〜
第３図に示す通り、異方性焼結体としたときハードフェ
ライトのＢ「約４ ｋＧと同等以上の範囲として定めら
れる。さらに、好ましい範囲は、Ｂ「を６． ８． ｌ
０ｋＧ等の段階をもって区画することにより夫々第１図
〜第３図から明らかに読むことができる。The upper limit of the addition amount of Sb, Sn, Ge, Af) is shown in Figure 1~
As shown in Fig. 3, when made into an anisotropic sintered body, the B value of hard ferrite is determined to be equal to or higher than approximately 4 kG.Furthermore, the preferable range is that B is approximately 6.8 kG.
By dividing it into stages such as 0 kG, it can be clearly read from FIGS. 1 to 3, respectively.
Ｍｎ、Ｎｉは多量に添加すると＋ ＩＨｃが減少する
。即ち、 １ｌｌｅを１ ｋｏｅ以上とするためＭ
ｎ 。When large amounts of Mn and Ni are added, +IHc decreases. That is, in order to make 1lle more than 1koe, M
n.
Ｎｉの上限は夫々８％とする。Ｍｎ３．５％、Ｎｉ４．
５％を夫々越えると、 ＩＨｃが無添加の場合よりも
低くなってしまうため、これをもって好ましい範囲の上
限とする。The upper limit of Ni is 8%. Mn3.5%, Ni4.
If each exceeds 5%, the IHc will be lower than that without the addition, so this is taken as the upper limit of the preferred range.
Ｂｉについては、その蒸気圧が極めて高くＢｉ５％を超
える合金の製造が、事実上不可能であり５％以下とする
。２種以上の添加元素Ｍを含む合金の場合、異方性焼結
体としたときＢ「が４ｋＧ以上の条件を満たすためには
、その含量が上述の各元素の添加量の上限のうち最大の
所定値（％）以下であることが必要である。As for Bi, its vapor pressure is extremely high, and it is virtually impossible to manufacture an alloy containing more than 5% Bi, so it is set at 5% or less. In the case of an alloy containing two or more types of additive elements M, in order to satisfy the condition that B is 4 kG or more when made into an anisotropic sintered body, the content must be the maximum of the upper limits of the amounts of each element added above. must be less than or equal to a predetermined value (%).
第１図〜第３図から明らかな通り、添加元素Ｍの添加は
その添加量の増大と共に、はとんどの場合Ｂｒが減少し
ており、また（Ｂｌｌ）ｍＢｘも第１表に示す通り一部
の範囲を除き基本的に減少する傾向を示す。しかし、保
磁力ＩＨＣの増大は、極めて強い逆磁場や、高温の苛酷
な環境にさらされる場合。As is clear from Figures 1 to 3, as the amount of addition of the additive element M increases, Br decreases in most cases, and (Bll)mBx also remains constant as shown in Table 1. It basically shows a decreasing trend except in the range of 1. However, the coercive force IHC increases when exposed to an extremely strong reverse magnetic field or a harsh high temperature environment.
永久磁石材料にとって重要な特性であり、高（ＩＩＩ）
ｗａｘ型の永久磁石と同様工業的に有用性が大である。This is an important property for permanent magnet materials, and high (III)
Like wax type permanent magnets, it is highly useful industrially.
Ｍとして２種以上含む場合には、夫々の添加元素の特性
曲線を合成したものとほぼ同様なり「曲線を示す。なお
Ｍの添加量はｌ１ｌｃの増大効果、 Ｂｒ減少傾向、
（１３１１）ｗａｘへの影響を考慮すると０．１〜３％
が最も望ましく、Ｍとしては第１図〜第３図から明らか
な様にＶ、Ｎｂ、Ｔａ、Ｍｏ。When two or more types of M are included, the curve is almost the same as that obtained by combining the characteristic curves of each additive element.The amount of M added has an increasing effect on l1lc, a decreasing tendency for Br,
(1311) 0.1-3% considering the impact on wax
The most desirable M is V, Nb, Ta, and Mo, as is clear from FIGS. 1 to 3.
Ｗ、 Ｃｒ、 Ａ ｌｌ、 Ｍｎ、 Ｎ ｉは比較的多
量に添加してもＢｒを著しく低下させることなく （例
えば８％添加してもＢ「は４ ｋＧ以上）、特にＭｎ、
ＮＬを除（Ｖ、Ｔａ、Ｎｂ、Ｃｒ、Ｗ、Ｍｏ、Ａ１は広
い範囲においてＩＨｃ向上に寄与する。Even if W, Cr, All, Mn, and Ni are added in relatively large amounts, they do not significantly reduce Br (for example, even when added at 8%, B' is 4 kG or more), and especially Mn,
Except for NL, (V, Ta, Nb, Cr, W, Mo, and A1 contribute to improving IHc in a wide range.
第４図に代表例として（１）７７Ｆｅ−８Ｂ −１５Ｎ
ｄ 、 （２） ７６Ｆ ｅ −８Ｂ −１５Ｎ ｄ
−Ｉ Ｎ ｂ 。Figure 4 shows a typical example (1) 77Fe-8B-15N
d, (2) 76F e -8B -15N d
-INb.
（３） ７５Ｆｅ−８Ｂ−１５Ｎｄ−２Ａ１の３種の合
金から成る焼結磁石の防磁化曲線及び減磁曲線（１〜３
）を示す。(3) Magnetization curve and demagnetization curve (1 to 3
) is shown.
試料（１）（曲線１）は比較例ＣＩ（第２表）と同じも
の、試料（２）（曲線２）は実施例試料ＦＪ０．５と同
じもの、試料（３）（曲線３）は実施例試料随２Ｉと同
じものについて測定したものである。曲線２．３とも永
久磁石材料として有用な高い角形性を示している。Sample (1) (Curve 1) is the same as Comparative Example CI (Table 2), Sample (2) (Curve 2) is the same as Example Sample FJ0.5, Sample (3) (Curve 3) is the same as Comparative Example CI (Table 2). This was measured on the same sample as Example Sample No. 2I. Both curves 2.3 show high squareness useful as a permanent magnet material.
以上詳述の通り１本発明は、新規なＦｅ−Ｂ−Ｒ−Ｍ系
強磁性合金、即ちＦｅを主体とじＣｏを必須とせず、ま
たＲとしても資源的に豊富であり工業上人手し晶い希土
類元素（Ｎｄ、Ｐｒ）を主体としたＦｅ−Ｂ−Ｒ化合物
をベースとした強磁性合金であり、特に永久磁石材料と
して有用である。これを用いることによりハードフェラ
イト以、にの磁気特性をりし、Ｓｍ−Ｃｏ系材料にも代
替し得るＦｅ−Ｂ−Ｒ−Ｍ系磁気異方性焼結体永久磁石
の提供も可能としたもので、工業的に極めて高い価値を
もつものである。特に永久磁石材料としての利点は、従
来のＳｍ−Ｃｏ系と対比するとその主成分元素の点で極
めて顕著になる。加えて、Ｆｅ−Ｂ−Ｒ三元系強磁性合
金と対比してみても、特定の添加元素Ｍの含有によって
焼結磁石の保磁力の増大も可能ならしめ、応用範囲を拡
げ実用的価値を高めることにも寄与し得る。As detailed above, the present invention is a novel Fe-BRM-based ferromagnetic alloy, that is, it mainly consists of Fe and does not require Co, and R is also abundant in resources and can be easily crystallized from an industrial perspective. It is a ferromagnetic alloy based on a Fe-B-R compound mainly containing rare earth elements (Nd, Pr), and is particularly useful as a permanent magnet material. By using this, it has become possible to improve the magnetic properties of hard ferrite and to provide Fe-BRM-based magnetically anisotropic sintered permanent magnets that can be substituted for Sm-Co-based materials. It has extremely high industrial value. In particular, its advantages as a permanent magnet material are extremely significant when compared with conventional Sm--Co based elements. In addition, when compared with the Fe-B-R ternary ferromagnetic alloy, it is possible to increase the coercive force of the sintered magnet by including a specific additive element M, which expands the range of applications and has practical value. It can also contribute to increasing
第１図〜第３図は２本発明の実施例（７７−ｘ）Ｆｅ−
８Ｂ−１５Ｎｄ−ｘＭ系の合金から成る異方性焼結磁石
について添加金属Ｍの量（ｘ％）と残留磁化Ｂｒ（ｋＧ
）との関係を示すグラフ。
第４図は代表的な実施例試料１’ｈ５（７６Ｆｅ −８
Ｂ−１５Ｎｄ −Ｉ Ｎｂ） 、 Ｎ［Ｌ２１ （７５
Ｆ ｅ −８Ｂ −１５Ｎ ｄ −２Ａ Ｊ ）につい
ての防磁化曲線及び減磁曲線を、試料ＮａＣ１（７７Ｆ
ｅ−８Ｂ−１５Ｎｄ）と共に示すグラフ（縦軸は磁化４
π１ （ｋＧ） 、横軸は磁界Ｈ（ｋＯＱ）） 、を夫
々示す。
出願人 住友特殊金属株式会社
代理人 弁理士 加 藤 朝 道
（他１名）Figures 1 to 3 show two embodiments of the present invention (77-x) Fe-
The amount of additive metal M (x%) and residual magnetization Br (kG
) is a graph showing the relationship between Figure 4 shows a typical example sample 1'h5 (76Fe-8
B-15Nd-I Nb), N[L21 (75
The demagnetization curve and demagnetization curve for sample NaC1 (77F
e-8B-15Nd) (vertical axis is magnetization 4
π1 (kG), and the horizontal axis represents the magnetic field H (kOQ)). Applicant Sumitomo Special Metals Co., Ltd. Agent Patent Attorney Asami Kato (1 other person)
Claims (2)
）８〜３０％、Ｂ２〜２８％、下記所定％以下（０％を
除く）の添加元素Ｍの一種又は二種以上（但し添加元素
Ｍが二種以上のときは、Ｍ合量は当該添加元素のうち最
大所定％を有するものの当該所定％以下）、及び残部実
質的にＦｅから成ることを特徴とする強磁性合金； Ｔｉ４．５％、Ｎｉ８％、 Ｂｉ５％、Ｖ９．５％、 Ｎｂ１２．５％、Ｔａ１０．５％、 Ｃｒ８．５％、Ｍｏ９．５％、 Ｗ９．５％、Ｍｎ８％、 Ａｌ９．５％、Ｓｂ２．５％、 Ｇｅ７％、Ｓｎ３．５％、 Ｚｒ５．５％、及びＨｆ５．５％。(1) In atomic percentage, R (R is one or two of Nd and Pr) 8-30%, B2-28%, and one or more additive elements M (excluding 0%) below the specified percentage below ( However, when there are two or more types of additive elements M, the total amount of M is the maximum predetermined percentage of the additive elements, but not more than the predetermined percentage), and the remainder substantially consists of Fe; Ti4.5%, Ni8%, Bi5%, V9.5%, Nb12.5%, Ta10.5%, Cr8.5%, Mo9.5%, W9.5%, Mn8%, Al9.5%, Sb2 .5%, Ge7%, Sn3.5%, Zr5.5%, and Hf5.5%.
Ｔｂ、Ｌａ、Ｃｅ、Ｇｄ、Ｙのうち少なくとも一種で、
かつＲの５０％以上はＮｄとＰｒの一種又は二種）８〜
３０％、Ｂ２〜２８％、下記所定％以下（０％を除く）
の添加元素Ｍの一種又は二種以上（但し添加元素Ｍが二
種以上のときは、Ｍ合量は当該添加元素のうち最大所定
％を有するものの当該所定％以下）、及び残部実質的に
Ｆｅから成ることを特徴とする強磁性合金； Ｔｉ４．５％、Ｎｉ８％、 Ｂｉ５％、Ｖ９．５％、 Ｎｂ１２．５％、Ｔａ１０．５％、 Ｃｒ８．５％、Ｍｏ９．５％、 Ｗ９．５％、Ｍｎ８％、 Ａｌ９．５％、Ｓｂ２．５％、 Ｇｅ７％、Ｓｎ３．５％、 Ｚｒ５．５％、及びＨｆ５．５％。(2) R in atomic percentage (R is Nd, Pr, Dy, Ho,
At least one of Tb, La, Ce, Gd, Y,
and 50% or more of R is one or two of Nd and Pr)8~
30%, B2-28%, below specified % (excluding 0%)
(However, when there are two or more types of additive elements M, the total amount of M is not more than the specified % of the maximum specified % of the added elements), and the remainder is substantially Fe. Ferromagnetic alloy characterized by consisting of; Ti4.5%, Ni8%, Bi5%, V9.5%, Nb12.5%, Ta10.5%, Cr8.5%, Mo9.5%, W9.5 %, Mn 8%, Al 9.5%, Sb 2.5%, Ge 7%, Sn 3.5%, Zr 5.5%, and Hf 5.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62329640A JPS63241141A (en) | 1987-12-28 | 1987-12-28 | Ferromagnetic alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62329640A JPS63241141A (en) | 1987-12-28 | 1987-12-28 | Ferromagnetic alloy |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57200204A Division JPS5989401A (en) | 1982-08-21 | 1982-11-15 | Permanent magnet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63241141A true JPS63241141A (en) | 1988-10-06 |
| JPH0535210B2 JPH0535210B2 (en) | 1993-05-26 |
Family
ID=18223600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62329640A Granted JPS63241141A (en) | 1987-12-28 | 1987-12-28 | Ferromagnetic alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63241141A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6319336B1 (en) | 1998-07-29 | 2001-11-20 | Dowa Mining Co., Ltd. | Permanent magnet alloy having improved heat resistance and process for production thereof |
| WO2007010860A1 (en) * | 2005-07-15 | 2007-01-25 | Neomax Co., Ltd. | Rare earth sintered magnet and method for production thereof |
| JP2007049010A (en) * | 2005-08-11 | 2007-02-22 | Neomax Co Ltd | Rear earth sintered magnet and manufacturing method thereof |
| JP2007134417A (en) * | 2005-11-08 | 2007-05-31 | Neomax Co Ltd | Manufacturing method of rare earth sintered magnet |
| JP2007154241A (en) * | 2005-12-02 | 2007-06-21 | Neomax Co Ltd | Rare-earth sintered magnet and producing method thereof |
| JP2010114371A (en) * | 2008-11-10 | 2010-05-20 | Shin-Etsu Chemical Co Ltd | Sm-R-T-B(-M)-BASED SINTERED MAGNET |
-
1987
- 1987-12-28 JP JP62329640A patent/JPS63241141A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6319336B1 (en) | 1998-07-29 | 2001-11-20 | Dowa Mining Co., Ltd. | Permanent magnet alloy having improved heat resistance and process for production thereof |
| WO2007010860A1 (en) * | 2005-07-15 | 2007-01-25 | Neomax Co., Ltd. | Rare earth sintered magnet and method for production thereof |
| US9551052B2 (en) | 2005-07-15 | 2017-01-24 | Hitachi Metals, Ltd. | Rare earth sintered magnet and method for production thereof |
| JP2007049010A (en) * | 2005-08-11 | 2007-02-22 | Neomax Co Ltd | Rear earth sintered magnet and manufacturing method thereof |
| JP2007134417A (en) * | 2005-11-08 | 2007-05-31 | Neomax Co Ltd | Manufacturing method of rare earth sintered magnet |
| JP4635832B2 (en) * | 2005-11-08 | 2011-02-23 | 日立金属株式会社 | Manufacturing method of rare earth sintered magnet |
| JP2007154241A (en) * | 2005-12-02 | 2007-06-21 | Neomax Co Ltd | Rare-earth sintered magnet and producing method thereof |
| JP2010114371A (en) * | 2008-11-10 | 2010-05-20 | Shin-Etsu Chemical Co Ltd | Sm-R-T-B(-M)-BASED SINTERED MAGNET |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0535210B2 (en) | 1993-05-26 |
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