JPS61159708A - Permanent magnet - Google Patents
Permanent magnetInfo
- Publication number
- JPS61159708A JPS61159708A JP59280125A JP28012584A JPS61159708A JP S61159708 A JPS61159708 A JP S61159708A JP 59280125 A JP59280125 A JP 59280125A JP 28012584 A JP28012584 A JP 28012584A JP S61159708 A JPS61159708 A JP S61159708A
- Authority
- JP
- Japan
- Prior art keywords
- coercive force
- permanent magnet
- rare earth
- composition
- ihc
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は希土類−鉄永久磁石に関するものである。[Detailed description of the invention] (Industrial application field) The present invention relates to rare earth-iron permanent magnets.
（従来の技術）
希土類−Ｆｅ−Ｂを基本成分とする永久磁石についての
研究が近年活発になされ、その結果が公開特許公報等に
よシ公表されるようにな郵つつある。(Prior Art) Research has been actively conducted in recent years on permanent magnets containing rare earth elements -Fe-B as a basic component, and the results are beginning to be published in published patent publications and the like.
特開昭５７−１４１９０１号公報によると、遷移裏金１
！（Ｔ）、メタロイド金１ｒＥ （Ｍ）、Ｙおよびラン
タニド元素Ｒの組み合わせからなる組成を非晶質化し、
次に非晶質組成を熱処理により結晶化することによって
保磁力を発生せしめる永久磁石粉末製法が記載されてい
る。この公報によると、ＴはＴｉ ｊＶ、Ｃｒ 、Ｍｎ
＊ＦＩ ＋Ｃｏ ＋Ｎｉ 、Ｃｕ 。According to Japanese Patent Application Laid-open No. 57-141901, transition back metal 1
! (T), metalloid gold 1rE (M), a composition consisting of a combination of Y and lanthanide element R is made amorphous,
Next, a permanent magnet powder manufacturing method is described in which a coercive force is generated by crystallizing an amorphous composition by heat treatment. According to this publication, T is Ti jV, Cr, Mn
*FI +Co +Ni,Cu.
Ｚｒ ｅ Ｎｂ ＠ Ｍｏ ｅ Ｈｆ ａ Ｔａ ＋Ｗ
よシ選ばれる１種もしくは２種以上の組合せであシ、ま
たＭはＢ。Zr e Nb @ Mo e Hf a Ta +W
One type or a combination of two or more types selected, and M is B.
ｓｔ、ｐ、ｃより選ばれる１種もしくは２種以上の組合
せ、ＲはＹおよびランタニド元素よシ選ばれるＩＮもし
くは２種以上の組合せ、であって、これらを（Ｔ、−１
Ｍｘ入Ｒ１−２なる関係式（但し、Ｏ≦ｘ≦０．３５．
０，３５≦ｚ≦０．９０）で含有させた永久磁石粉末に
ついての特許が請求されている。R is one or a combination of two or more selected from st, p, and c; R is IN or a combination of two or more selected from Y and a lanthanide element;
The relational expression Mx enters R1-2 (however, O≦x≦0.35.
A patent is claimed for a permanent magnet powder containing powder in the range of 0.35≦z≦0.90).
特開昭５８−１２３８５３号公報によると、Ｌａおよび
Ｐｒ含有材料が提案されており、その組成は、（”ｚＢ
ｆ−ｚ）ｙ（”ｚ”ｖ”１−ｚ−Ｗ）１−３”但し。According to JP-A-58-123853, a material containing La and Pr has been proposed, and its composition is ("zB
f-z)y("z"v"1-z-W)1-3"However.
ＲはＬ’ ＊ Ｐｒ以外の希土類金部、 ｘ ＝０．
７５〜０．８５゜）ｒ＝０．８５〜０．９５． ｚ ＝
０．４０Ｓ−０，７５，ｗ＝０．２５〜０．６０． ｚ
＋ｖ≦１．０である。この公報には、液体急冷法によ
シ非晶質化したＲ−Ｆ・−Ｂ含有合金を焼鈍して結晶化
させる際の保磁力増大を適切にするために、希土類元素
の種類および割合を上述の（Ｌａ ｚＰ ｒＪ １−
ｚ−ｖｒ）とする組成調節法が述べられている。R is L'* rare earth gold part other than Pr, x = 0.
75~0.85°) r=0.85~0.95. z =
0.40S-0.75, w=0.25~0.60. z
+v≦1.0. This publication describes the type and proportion of rare earth elements in order to appropriately increase the coercive force when annealing and crystallizing an R-F/-B-containing alloy that has been made amorphous by a liquid quenching method. (La zP rJ 1-
z-vr) is described.
特開昭５９−４６００８号公報には、８〜３０原子チの
Ｒ（但し、Ｒは希土類元素の少なくとも１種）、２〜２
８原子チのＢ、及び残部Ｆ・からなる磁気異方性焼結体
が提案されている。この会報で公開された発明は液体急
冷法によらず焼結法によって任意の形状の永久磁石体を
製造可能にすることをひとつの意図としている。また、
焼結体成分中のＲに関しては、Ｎｄ単独、Ｐｒ単独、
ＮｄとＰｒの組合せ、ＮｄとＣ・の組合せ、ＳｍとＰｒ
の組合せ、ＰｒとＹの組合せ、Ｎｄ 、 ＰｒとＬａの
組合せ、 Ｔｂ単独、ａｙ単独、Ｈｏ単独、ＥｒとＴｂ
の組合せ等についての焼結体の磁気特性が示されている
。JP-A No. 59-46008 discloses 8 to 30 atoms of R (wherein R is at least one rare earth element), 2 to 2
A magnetically anisotropic sintered body consisting of 8 atoms of B and the remainder F. has been proposed. One of the intentions of the invention disclosed in this newsletter is to make it possible to manufacture permanent magnets of arbitrary shapes by the sintering method rather than by the liquid quenching method. Also,
Regarding R in the sintered body components, Nd alone, Pr alone,
Combination of Nd and Pr, combination of Nd and C, Sm and Pr
combination of Pr and Y, Nd, combination of Pr and La, Tb alone, ay alone, Ho alone, Er and Tb
The magnetic properties of the sintered body are shown for combinations of.
上述の如き従来技術をまとめるとＲ−Ｆｅ−Ｂ（但し、
Ｒは希土類金属、以下同じ）系永久磁石においてＲがＮ
ｄまたはＰｒであるときに優れた磁石特性が得られてい
たことが分かる。To summarize the prior art as mentioned above, R-Fe-B (however,
R is a rare earth metal, the same applies hereafter) system permanent magnet, R is N
It can be seen that excellent magnetic properties were obtained when the magnet was d or Pr.
また、従来技術において、希土類元素としてＬａおよび
Ｃｅが使用可能であることを特許請求しているものもあ
るが、ＬａのみをＲとして使用するのではな（Ｌａの含
有量上限を制限していることにより多量のＬａによる磁
気特性低下が避けられている。In addition, some prior art patents claim that La and Ce can be used as rare earth elements, but it is not possible to use only La as R (the upper limit of the content of La is limited). This avoids deterioration of magnetic properties due to a large amount of La.
上記従来技術においてはＬａおよびＣ・を主体として希
土類成分を具体的に構成した永久磁石の例はない。In the above-mentioned prior art, there is no example of a permanent magnet having a specific rare earth component mainly composed of La and C.
第２図はＪ、Ａｐｐｌ 、Ｐｈｙｓ、Ｖｏｌ ５５ （
１９８４）第２０７９頁に掲載されているグラフを再掲
したＲ−Ｆ・−Ｂ系永久磁石合金の減磁曲線である。こ
のグラフよシも、Ｐｒ、ＮｄがＲ−Ｆｅ−Ｂ合金のＲ成
分として最も望ましく、ＬａまたはＣ・をＲ−Ｆ・−Ｂ
系合金のＲ成分とした合金は永久磁石としての特性をも
たなくなる仁とが分かる。このような点からして、上述
の従来技術は、Ｐｒ、Ｎｄ等の極〈一部をＬｍ 、 Ｃ
・で置換することを開示していても、Ｌ＆またはＣａを
主体としてＲ成分を構成したＲ−Ｆ・−Ｂ合金が永久磁
石になることは何ら開示していないと言えよう。Figure 2 is from J, Appl, Phys, Vol 55 (
1984) This is a demagnetization curve of the R-F·-B permanent magnet alloy, which is a reproduction of the graph published on page 2079. This graph also shows that Pr and Nd are the most desirable R components of the R-Fe-B alloy, and La or C.
It can be seen that the alloy with the R component of the system alloy no longer has the characteristics as a permanent magnet. From this point of view, the above-mentioned conventional technology uses poles such as Pr and Nd (parts of which are Lm, C
Even if it discloses that the R component is replaced by L& or Ca, it can be said that there is no disclosure that the R-F--B alloy in which the R component is mainly composed of L& or Ca becomes a permanent magnet.
最近の希土類−鉄永久磁石に関する注目すべき進展は、
１９８４年１０月のＭＭＭに発表されたｒｅ−（３２，
５〜３４．５１）Ｒ−（１〜１．６％）Ｂ。Recent notable developments in rare earth-iron permanent magnets include:
re-(32,
5-34.51) R-(1-1.6%)B.
（但しＲはジジム（Ｎｄ−１０％Ｐｒ）、５Ｃ・−ジジ
ム、または４０−Ｃ・ジジム）がＩＨｃ ＝ １０．２
にＧ。(where R is didymium (Nd-10%Pr), 5C・-didymium, or 40-C・didymium), IHc = 10.2
niG.
（ＢＨ）ｍ□＝ ４０ ＭＧＯ・を達成したことである
。(BH)m□=40 MGO• was achieved.
（ｒ ＤＩＤＹＭＩＵＭ−Ｆ・−Ｂ ｆ９ＩＮＴＥＲ
ＥＤ ＰＥＲＭＡＮＥＮＴＭＡＧＮＫＮ−ＴＳ Ｊ論文
Ｉが、この永久磁石でもＲ成分はＮｄが主体となってい
る。(r DIDYMIUM-F・-B f9INTER
ED PERMANENT MAGNKN-TS J Paper I shows that even in this permanent magnet, the R component is mainly Nd.
（発明が解決しようとする問題点）
Ｒ−Ｆｅ−８を基本成分とする永久磁石は磁気特性がす
ぐれているものの、そのひとつの問題点はすぐれた磁気
特性を得ようとするとＮｄ 、 Ｐｒを希土類金員の主
体とせざるを得す、このために永久磁石が高価になるこ
とでありた。よりて、上記ゾゾム含有永久磁石は、比較
的安価なジジムを使用してもＮｄ、Ｐｒと同等の磁気特
性を発揮できるので注目されているのである。(Problems to be Solved by the Invention) Permanent magnets containing R-Fe-8 as a basic component have excellent magnetic properties, but one problem is that in order to obtain excellent magnetic properties, Nd and Pr must be used. The permanent magnet had to be made mainly of rare earth metals, which made the permanent magnet expensive. Therefore, the zozom-containing permanent magnet is attracting attention because it can exhibit magnetic properties equivalent to those of Nd and Pr even when relatively inexpensive didymium is used.
Ｌ＆またはＣ・は他の希土類元素と比較して多量に産出
されそして安価であるために、これらを希土類金属の主
成分として使用可能になれば希土類−鉄永久磁石の大幅
なコストダウンが可能になる。Since L& or C is produced in large quantities and is inexpensive compared to other rare earth elements, if it were possible to use them as the main component of rare earth metals, it would be possible to significantly reduce the cost of rare earth-iron permanent magnets. Become.
だが、第２図から分かるようにＬａ、Ｃｏは磁気特性上
有害な元素である。Ｌａ、Ｃ・が磁気特性上有害である
理由は、希土類−鉄永久磁石の強磁性成分はＲ２Ｆｅ１
４Ｂ化合物であシ、そしてＲがＬａであると該化合物が
不安定になるかもしくは生成されず、ま九ＲがＣ・であ
る＋２（（Ｊ）、〒ｅ１４Ｂは保磁力が小さいためであ
る。However, as can be seen from FIG. 2, La and Co are elements harmful to magnetic properties. The reason why La and C are harmful in terms of magnetic properties is that the ferromagnetic component of rare earth-iron permanent magnets is R2Fe1
4B compound, and if R is La, the compound becomes unstable or is not produced, and R is C.+2 ((J), 〒e14B has a small coercive force. .
上述のように、従来技術はＬｍ、Ｃｅを希土類金属の主
成分として使用するに至っていない。As mentioned above, the prior art has not reached the point where Lm and Ce are used as main components of rare earth metals.
（問題点を暦法するための手Ｒ）
第１図は、液体急冷法で製造した板厚２０μｍ、板幅３
ｍｍのＦ・７７（Ｌ’１−ｘ Ｃ＠ｘ）１７Ｂ６合金の
保磁力を測定した結果を示すグラフである。(Method for calculating problems) Figure 1 shows a plate manufactured using the liquid quenching method with a thickness of 20 μm and a width of 3.
It is a graph which shows the result of measuring the coercive force of F*77 (L'1-x C@x)17B6 alloy of mm.
Ｆｅ２ Ｂ （Ｌａ、−ｘＣ＠ｘ ）、７８５なる組成
式において！＝１（すなわちＦ＊ ｙ ７Ｃ＠ 、７Ｂ
４ ）およびｘ＝０（すなわちＦ・７７”１７”Ａ
）のときの保磁力は第２図のそれぞれＣ・、Ｌａのデー
タとほぼ一致している。なお苔千の差は両図に保磁力が
示された合金の組成の差による。In the composition formula of Fe2 B (La, -xC@x), 785! = 1 (i.e. F* y 7C@ , 7B
4) and x=0 (i.e. F・77"17"A
), the coercive force almost coincides with the data for C. and La in FIG. 2, respectively. The difference in kosensen is due to the difference in the composition of the alloys whose coercive forces are shown in both figures.
第１図に示されているようにＬａとＣ・の両者が希土類
元素として用いられるとＬａまたはＣ・単独の場合より
も保磁力が格段に高められる。Ｉ値が約０．６５である
と保磁力（ｌＨｅ）は約７ｋＯ・となる。As shown in FIG. 1, when both La and C. are used as rare earth elements, the coercive force is much higher than when La or C. is used alone. When the I value is about 0.65, the coercive force (lHe) is about 7 kO·.
この保磁力はＰｒまたはＮｄｔ−Ｒの主体とする永久磁
石の保磁力の約袖であるが、ＬＡ、Ｃ・等のみからＲ成
分を構成できるようになると、かかる永久磁石はＰｒ、
Ｎｄ主体永久磁石と十分にコスト・性能の総合面から競
争できるようになる。This coercive force is about the same as that of a permanent magnet mainly composed of Pr or Ndt-R, but if the R component can be composed only of LA, C, etc., such a permanent magnet will become Pr,
It will be able to fully compete with Nd-based permanent magnets in terms of overall cost and performance.
本発明（以下、第１発明と称する）は第１図の如（Ｌａ
とＣ・の共すによって保磁力（ｉＨｃ ）が著しく高め
られるとの発明にもとづいて成立しているものであって
、その特徴とす、るところは。The present invention (hereinafter referred to as the first invention) is as shown in FIG.
It is based on the invention that the coercive force (iHc) can be significantly increased by the combination of C and C, and its characteristics are as follows.
（Ｃｓ ｘ Ｌａ、−ｘ入（Ｆ・１−ｖＢｖ）１−１但
し０．４≦Ｉ≦明において、Ｉが０．４未満もしくは０
．９を越えるとそれぞれＬａ単独またはＣ・単独の組成
と同等程度の保磁力しか得られないためＫ ｓ ｘ ＝
ｏ、 ４〜０．９とした。また２が０．０５未満である
と角型比および保磁力が低下し、２が０．３を越えると
残留磁束密度が低下するために、ｚ＝０．０５〜０．３
とした。さらに、マが０．０１未満であると保磁力が低
下し、またマが０．３を越えると残留磁束密度が低下す
るためマ＝０．０１〜０．３とした。さらに、よシ高い
保磁力を得るためには、０．６≦Ｉ≦０．８．０．０２
≦ｖ≦０．１５．０．１≦ｚ≦０．２の範囲であること
が好ましい。よシ好ましくは、０．０３≦ｖ≦０．１２
である。(Cs x La, -x included (F・1-vBv) 1-1 However, when 0.4≦I≦light, I is less than 0.4 or 0
．． If it exceeds 9, a coercive force comparable to that of La alone or C alone can be obtained, so K s x =
o, 4 to 0.9. Also, if 2 is less than 0.05, the squareness ratio and coercive force will decrease, and if 2 exceeds 0.3, the residual magnetic flux density will decrease, so z = 0.05 to 0.3.
And so. Further, if Ma is less than 0.01, the coercive force will decrease, and if Ma exceeds 0.3, the residual magnetic flux density will decrease, so Ma was set to 0.01 to 0.3. Furthermore, in order to obtain a higher coercive force, 0.6≦I≦0.8.0.02
It is preferable that the range is ≦v≦0.15.0.1≦z≦0.2. Preferably, 0.03≦v≦0.12
It is.
本発明において保磁力（ｉＨｃ ）を４ｋＯ・以上とし
九のは、４ｋＯ・の保磁力が達成されると、Ｃ・とＬａ
の顕著な相乗効果が認められるからであシ、また４ｋＯ
・以上の保磁力（ｔｉｃ ）を有するＦ・−Ｂ−（Ｌｍ
、Ｃｏ）系磁石は、市場において各種永久磁石に代替し
うる特性を有するからである。前者の点はＷＸ１図から
明らかであ〕、後者の点についてはＦ＠−Ｂという安価
な元素を用いかつ希土類金属中でも多量に産出されるＬ
ａ、Ｃ・を用いて、４ｋＯ・以上の保磁力を具備する本
発明の永久磁石は希土類コノ４ルト系およびＦ＊−Ｂ−
Ｐｒ（Ｎｄ）系？よび傾→Ｈ←会雫４袖フェライト系永
久磁石と十二分に対抗しうるものであるから、これらの
点から４ｋＯ・以上を本発明の構成要件とする。In the present invention, when the coercive force (iHc) is set to 4 kO. or more, and the coercive force of 4 kO. is achieved, C. and La
This is because a remarkable synergistic effect of 4kO is observed.
・F・-B−(Lm
, Co) type magnets have characteristics that allow them to be substituted for various permanent magnets on the market. The former point is clear from the WX1 diagram], and the latter point is based on L, which uses an inexpensive element called F@-B and is produced in large quantities among rare earth metals.
The permanent magnet of the present invention having a coercive force of 4 kO or more using a, C, and F*-B-
Pr(Nd) type? Since it can more than compete with the four-sleeve ferrite permanent magnet, from these points, 4 kO. or more is a constituent requirement of the present invention.
第３図および第４図は、それぞれ、”７５Ｍ１５Ｂ？。Figures 3 and 4 respectively show "75M15B?".
およびＦ・７８Ｍ１７Ｂ１．なる組成式の合金を液体急
冷法で、単ロールの周速（Ｖ）を変化させて薄帯化した
材料の保磁力（ＩＨｃ ）を示すグ２７である（図中−
急冷後、Ｏとして示す）、なお上記組成式中のＭは、約
３２９６ Ｌａ、約４８％Ｃｅ、約１５％Ｎｄ、約４．
５％のＰｒ、約０．３％Ｓｍ、残部Ｐａその他の不純物
からなるミヅシュメタルである。and F.78M17B1. Figure 27 shows the coercive force (IHc) of a material obtained by forming an alloy with the following composition formula into a thin ribbon by changing the circumferential speed (V) of a single roll using the liquid quenching method (-
After quenching, M in the above composition formula is approximately 3296 La, approximately 48% Ce, approximately 15% Nd, approximately 4.
It is a medium metal consisting of 5% Pr, about 0.3% Sm, and the balance Pa and other impurities.
第３図および第４図から分かるように、単ロールの周速
（Ｖ）が約３０３／ｓにおいて保磁力が最大の約８ｋＯ
・になっている。As can be seen from Figures 3 and 4, when the circumferential speed (V) of a single roll is approximately 303/s, the coercive force is at its maximum of approximately 8kO.
·It has become.
さらに、最大保磁力を達成する単ロールの周速以上の冷
却条件で得られた薄帯を５５０℃および６００℃で時効
した後の保磁力も第３図および第４図に示す。時効のデ
ータから、上記
Ｆ・７５Ｍｊ５”１゜およびＦ・７ＢＭ、７ＢＳなる組
成の合金は液体急冷状態では保磁力（ｉＨｃ）が低くと
も時効によ〕高保磁力化することが分かる。Furthermore, the coercivity after aging the ribbon at 550° C. and 600° C., which was obtained under cooling conditions at a circumferential speed of a single roll that achieves the maximum coercive force, is also shown in FIGS. 3 and 4. From the aging data, it can be seen that even though the coercive force (iHc) of the alloys having the compositions F.75Mj5''1°, F.7BM, and 7BS is low in the liquid quenched state, the coercive force increases with aging.
第３図および第４図を引用して上述した如きところから
（１）ＬａおよびＣ・以外の希土類元素が若干量存在し
ているときでもＬａおよびＣｓの相乗効果があり、（２
）このような相乗効果は液体急冷および時効処理等のプ
ロセスに依存性を有していす組成に起因するものである
ことが分かる。As mentioned above with reference to Figures 3 and 4, (1) even when rare earth elements other than La and C are present in small amounts, there is a synergistic effect of La and Cs;
) It can be seen that such a synergistic effect is dependent on processes such as liquid quenching and aging treatment and is caused by the chair composition.
本発明（以下、第２発明と称する）はこのような発見上
に成立しているものであって、その特徴とするところは
、
（（ｃｅｘＬａ、−ｘ）、Ｒ，−、）、（Ｆ・１−Ｖ
Ｂｖ）ｊ −ｚ、 但し、Ｒは少なくとも１種の希土類
金１ｍ！（Ｙを含む）、０．４≦ｘ≦０．９、ｏ、ｚ＜
ｙ＜ １．０．０．０５≦ｚ≦０．３，０．０１≦ｖ≦
０．０３であり、ＲはＣ・およびＬ１以外の少なくとも
１種の希土類元素である組成と、４ｋＯ・以上の保磁力
（ｉＨｃ ）とにある。第２発明におけるＸ、！、マの
限定理由および好ましい範囲は第１発明と同様である。The present invention (hereinafter referred to as the second invention) is based on such a discovery, and its characteristics are as follows: ((cexLa, -x), R, -,), (F・1-V
Bv) j −z, where R is 1 m of at least one rare earth metal! (including Y), 0.4≦x≦0.9, o, z<
y< 1.0.0.05≦z≦0.3, 0.01≦v≦
0.03, R has a composition of C. and at least one rare earth element other than L1, and a coercive force (iHc) of 4 kO. or more. X in the second invention! , Ma are the same as the first invention.
また、第２発明においてｙを０．２超えるように（ｙ＞
０．２）定めたのはＬａ、Ｃ・の量が０．２０以下では
希土類元素のコストが高くなるからである。またＦ （
１，０とし九のは、第１発明と第２発明の組成を区別す
るためである。好ましいｙの範囲は０．５≦７ ＜ １
．０である。In addition, in the second invention, y is set to exceed 0.2 (y>
0.2) is determined because the cost of rare earth elements increases if the amounts of La and C are less than 0.20. Also F (
The reason for the number 1,0 and 9 is to distinguish the compositions of the first invention and the second invention. The preferred range of y is 0.5≦7<1
．． It is 0.
第１発明および第２発明に係る合金には、Ａｔ。The alloys according to the first invention and the second invention include At.
ＴＩ 、Ｖ、 Ｃｒ 、Ｍｎ 、Ｚｒ 、Ｈｆ ＊Ｎ’
ｂ 、Ｔａ 、ＭＯ、Ｇ＠ 。TI, V, Cr, Mn, Zr, Hf *N'
b, Ta, MO, G@.
Ｓｂ 、 Ｓｏ 、 Ｂｌ 、 Ｎｉ 、
Ｗ、Ｃｕ 、 Ａｇ等の元素を添加することができ
る。これらの元素は保磁力をさらに改善する効果がある
。Sb, So, Bl, Ni,
Elements such as W, Cu, and Ag can be added. These elements have the effect of further improving coercive force.
さらに、第１発明および＠２発明のＢの一部を８１ 、
Ｃ，Ａｔ、 Ｐ、Ｎ、Ｇ・、Ｓ等で置換しても、Ｓｉ
等で置換されたＢはＢ単独と同様な効果を有する。Furthermore, part of B of the first invention and @2 invention is 81,
Even if replaced with C, At, P, N, G., S, etc., Si
B substituted with etc. has the same effect as B alone.
加えて、 Ｃｏを第１発明および第２発明に係る合金を
添加すると、キュリ一温度が上昇し、磁気的性質、特に
Ｂｒ、の温度特性が改善される。In addition, when Co is added to the alloys according to the first and second inventions, the Curie temperature increases and the magnetic properties, especially the temperature characteristics of Br, are improved.
（作用）
本発明に係る永久磁石の著しい特色は上述のように従来
の永久磁石と比較して組成上安価であるところにある。(Function) As mentioned above, the remarkable feature of the permanent magnet according to the present invention is that it is cheaper in terms of composition than conventional permanent magnets.
すなわち、従来はＦｅ−Ｂ−Ｒ系永久磁石の成分として
使用できないと考えられていたＬａ、Ｃ・を主体として
極めて安価な永久磁石を製造することが本発明の特色で
ある。而して、本発明においては、ＬａとＣ−の原子比
率が約０．３５対約０．６５において保磁力が最大にな
）、またかかる保磁力（ｉＨｃ ）はＬ＆単独のものに
比較して約３５倍、Ｃ・単独のものに比較して約３．５
倍となる。That is, the feature of the present invention is to manufacture an extremely inexpensive permanent magnet mainly using La and C, which were conventionally considered to be unusable as components of Fe-B-R permanent magnets. Therefore, in the present invention, the coercive force is maximum when the atomic ratio of La and C- is about 0.35 to about 0.65), and the coercive force (iHc) is compared to that of L & alone. approximately 35 times, approximately 3.5 times compared to C. alone.
It will be doubled.
本発明者等はかかるＬａとＣ・の共存による保磁力（ｉ
Ｈｃ ）の顕著な増大の原因を究明すべく、第１図で説
明した”７８（”１−ｘ”ｚ）１７ＢＳ の結晶構造を
Ｘ線で調べ、Ｒ２Ｆ・１４Ｂ型結晶の存在を確認した。The present inventors have discovered that the coercive force (i) due to the coexistence of La and C.
In order to investigate the cause of the remarkable increase in Hc), the crystal structure of "78("1-x"z)17BS explained in FIG. 1 was examined by X-rays, and the existence of R2F/14B type crystals was confirmed.
この結晶は従来Ｎｄ−Ｆ・−Ｂ系合金において検知され
ていたものと同じ結晶形を有するものであった。This crystal had the same crystal form as that conventionally detected in Nd-F.-B alloys.
従来、ＬａはＲ２Ｆ・１４Ｂ型結晶を作らないと考えら
れてお９．それ故ＬａはＲ−Ｆ・−Ｂ系永久磁石のＲ主
成分としては用いられていなかった。ところがＬａとＣ
ｍが共存する本発明の組成においてはＲ２Ｆｅ１４Ｂ
型結晶の存在が確認されたために、ＬｍとＣ・が共存
するとＲ２Ｆ・、４ＢＩＪ！結晶が生成されることが分
かりた。よって、この結晶が保磁力（ｌＨｃ）の向上に
寄与していると考えられる。Conventionally, it has been thought that La does not form R2F/14B type crystals.9. Therefore, La has not been used as the main R component of R-F.-B permanent magnets. However, La and C
In the composition of the present invention in which m coexists, R2Fe14B
Since the existence of a type crystal was confirmed, if Lm and C. coexist, R2F., 4BIJ! It was found that crystals were formed. Therefore, it is considered that this crystal contributes to the improvement of coercive force (lHc).
また、 Ｃｅ２Ｆ＊、４Ｂは格子定数１６ ＝Ｑ、ｇ
７７の正方晶結晶を作シ、その保磁力（ｌＨｅ ）はＬ
ＪＬ −Ｆ・−Ｂよシは格段に高いことが知られている
。ところが、本発明によると、Ｃ・とＬａを共存させる
ことによりて、Ｃ・２Ｆ・１４Ｂよ）もはるかに高い保
磁力（ｉＨｃ）が得られている。この点を考慮すると、
本発明によシ得られる高い保磁力（ｌＨｃ ）はＬａと
Ｃ・がＲ２Ｆ・１４Ｂ結晶中にある特定の割合で存在す
ることによる寄与もあると考えられる。このようなＬｌ
とＣ・が結晶構造にどのような影響を及ぼすかは解明さ
れていない。その結晶学的機構解明については今後の研
究を待たなければならない。Also, Ce2F*, 4B has a lattice constant of 16 = Q, g
77 tetragonal crystals were produced, and their coercive force (lHe) was L.
It is known that JL -F and -B values are significantly higher. However, according to the present invention, by making C. and La coexist, a much higher coercive force (iHc) can be obtained even for C.2F.14B. Considering this point,
It is believed that the high coercive force (lHc) obtained by the present invention is also due to the presence of La and C in a certain ratio in the R2F.14B crystal. Ll like this
It has not been elucidated how C and C affect the crystal structure. Elucidation of its crystallographic mechanism will have to wait for future research.
以下、単ロールを用いた液体急冷法によ）製造した本発
明の永久磁石の実施例を説明する。Examples of permanent magnets of the present invention manufactured by a liquid quenching method using a single roll will be described below.
なお１本発明に係る永久磁石は、液体急冷法のほかに、
液体急冷一時効法および焼結法によシ製造することがで
きる。これらの方法について述べると、液体急冷一時効
法は、熱処理によって保磁力（ＩＨｃ ）を高める方法
であシ、焼結法は所定組成の粉末を９００〜１１５０℃
で焼結することによシ任意の形状の永久磁石を製造する
方法である。In addition to the liquid quenching method, the permanent magnet according to the present invention can be produced by
It can be manufactured by a liquid quenching temporary effect method and a sintering method. Regarding these methods, the liquid quenching temporary effect method is a method to increase coercive force (IHc) by heat treatment, and the sintering method is a method in which powder of a predetermined composition is heated at 900 to 1150°C.
This is a method of manufacturing permanent magnets of any shape by sintering them.
さらに、粉末結合法は、液体急冷法によシ得たリボンま
たは粉末を必要ならばさらに時効処理および粉砕した後
に、樹脂等で結合してボンディッド磁石とする方法であ
る。Furthermore, the powder bonding method is a method in which the ribbon or powder obtained by the liquid quenching method is further subjected to aging treatment and pulverization if necessary, and then bonded with a resin or the like to form a bonded magnet.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
第１表に組成を示すインゴットを溶解法により製造し、
インゴットを小片に砕き、これを片ロールを用いた液体
急冷法によりロールの表面速度を変化させてリボン状の
試料を製造した。保磁力（ｉＨｃ）が最大となるロール
の表面速度において得られた試料の保磁力を次表に示す
。An ingot whose composition is shown in Table 1 is produced by a melting method,
The ingot was broken into small pieces, and ribbon-shaped samples were produced by liquid quenching using a single roll and varying the surface speed of the roll. The following table shows the coercive force of the sample obtained at the surface speed of the roll where the coercive force (iHc) is maximum.
以下ぐＺ臼
（発明の効果）
本発明に係る永久磁石は極めて安価であシまだ保磁力（
ｉＨｃ ）は満足すべき高い値を有するために各種用途
に使用されることが期待される。The following Z-mill (effects of the invention) The permanent magnet according to the present invention is extremely inexpensive and has a coercive force (
iHc) has a satisfactorily high value and is therefore expected to be used in various applications.
第１図はＦｓ ７７ （Ｌｍ １−、Ｃｏ ｘ） １７
Ｂ６のＸ値と保磁力（ｌＨｅ）の関係を示すグラフ、
第２図はＲＯ，１３５（”０．９３５８Ｇ、０６５ ）
０．１３６５の減磁界曲線、
第３図および第４図はＦ・７５Ｍ１５Ｂ１゜および２０
７８Ｍ１７ＢＳの単冷却ロールの周速（Ｖ）と保磁力（
ｉＨｃ ）の関係を示すグ″ｙ７である。Figure 1 shows Fs 77 (Lm 1-, Cox) 17
A graph showing the relationship between B6's X value and coercive force (lHe), Figure 2 is RO, 135 ("0.9358G, 065)"
0.1365 demagnetizing field curves, Figures 3 and 4 are for F.75M15B1° and 20
Circumferential speed (V) and coercive force (of 78M17BS single cooling roll)
This is a graph ``y7'' showing the relationship between iHc).
Claims (1)
＿ｖＢ＿ｖ）＿１＿−＿ｚ、−但し、０．４≦ｘ≦０．
９、 ０．０５≦ｚ≦０．３、 ０．０１≦ｖ≦０．３、−なる組成を有し、４ｋＯｅ以
上の保磁力（ｉＨｃ）を有することを特徴とする永久磁
石。 ２、〔（Ｃｅ＿ｘＬａ＿１＿−＿ｘ）＿ｙＲ＿１＿−＿
ｙ〕＿ｚ（Ｆｅ＿１＿−＿ｖＢ＿ｖ）＿１＿−＿ｚ、−
但し、ＲはＣｅ、Ｌａ以外の少なくとも１種の希土類金
属（Ｙを含む） ０．４≦ｘ≦０．９、 ０．２＜ｙ＜１．０、 ０．０５≦ｚ≦０．３、 ０．０１≦ｖ≦０．３−なる組成を有し、 ４ｋＯｅ以上の保磁力（ｉＨｃ）を有することを特徴と
する永久磁石。[Claims] 1, (Ce_xLa_1_-_x)_z(Fe_1_-
_vB_v)_1_-_z, -However, 0.4≦x≦0.
9. A permanent magnet having a composition of -0.05≦z≦0.3, 0.01≦v≦0.3, and having a coercive force (iHc) of 4 kOe or more. 2, [(Ce_xLa_1_-_x)_yR_1_-_
y]_z(Fe_1_-_vB_v)_1_-_z, -
However, R is at least one rare earth metal other than Ce and La (including Y) 0.4≦x≦0.9, 0.2<y<1.0, 0.05≦z≦0.3, A permanent magnet having a composition of 0.01≦v≦0.3 and having a coercive force (iHc) of 4 kOe or more.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59280125A JPH0630295B2 (en) | 1984-12-31 | 1984-12-31 | permanent magnet |
| US06/814,183 US4765848A (en) | 1984-12-31 | 1985-12-27 | Permanent magnent and method for producing same |
| DE8585309532T DE3582048D1 (en) | 1984-12-31 | 1985-12-30 | PERMANENT MAGNET AND METHOD FOR THE PRODUCTION THEREOF. |
| EP85309532A EP0187538B1 (en) | 1984-12-31 | 1985-12-30 | Permanent magnet and method for producing same |
| US07/572,568 USRE34838E (en) | 1984-12-31 | 1990-08-23 | Permanent magnet and method for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59280125A JPH0630295B2 (en) | 1984-12-31 | 1984-12-31 | permanent magnet |
Related Child Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60205005A Division JPS61159710A (en) | 1984-12-31 | 1985-09-17 | Permanent magnet |
| JP60205006A Division JP2513994B2 (en) | 1984-12-31 | 1985-09-17 | permanent magnet |
| JP60205004A Division JPH0624163B2 (en) | 1984-12-31 | 1985-09-17 | permanent magnet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61159708A true JPS61159708A (en) | 1986-07-19 |
| JPH0630295B2 JPH0630295B2 (en) | 1994-04-20 |
Family
ID=17620681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59280125A Expired - Fee Related JPH0630295B2 (en) | 1984-12-31 | 1984-12-31 | permanent magnet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0630295B2 (en) |
Cited By (8)
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|---|---|---|---|---|
| JPS63100155A (en) * | 1986-10-10 | 1988-05-02 | フィリップス エレクトロニクス ネムローゼ フェンノートシャップ | Magnetic material consisting of iron, boron and rare earth metal and its production |
| JP2018082177A (en) * | 2016-11-17 | 2018-05-24 | トヨタ自動車株式会社 | Rare earth magnet |
| JP2018110208A (en) * | 2016-12-28 | 2018-07-12 | トヨタ自動車株式会社 | Rare earth magnet and manufacturing method of the same |
| US10892076B2 (en) | 2016-12-28 | 2021-01-12 | Toyota Jidosha Kabushiki Kaisha | Rare earth magnet and method of producing the same |
| EP3919644A1 (en) | 2020-06-01 | 2021-12-08 | Toyota Jidosha Kabushiki Kaisha | Rare earth magnet and production method thereof |
| EP3989244A1 (en) | 2020-10-22 | 2022-04-27 | Toyota Jidosha Kabushiki Kaisha | Rare earth magnet and method for producing thereof |
| JP2023129176A (en) * | 2022-03-02 | 2023-09-14 | 浙江大学 | Method of increasing corrosion resistance of highly concentrated rare earth permanent magnet by high-temperature oxidation treatment |
| US11996219B2 (en) | 2020-09-25 | 2024-05-28 | Toyota Jidosha Kabushiki Kaisha | Magnetic material and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210125316A (en) | 2020-04-08 | 2021-10-18 | 현대자동차주식회사 | Rare-earth permanent magnet and method for manufacturing the same |
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| JPS59211549A (en) * | 1983-05-09 | 1984-11-30 | ゼネラル・モ−タ−ズ・コ−ポレ−シヨン | Adhered rare earth element-iron magnet |
| JPS60145357A (en) * | 1984-01-09 | 1985-07-31 | コルモーゲン コーポレイション | Magnetic alloy consisting of light rare earth elements, ironand boron with improved efficiency |
| JPS60221550A (en) * | 1984-04-18 | 1985-11-06 | Seiko Epson Corp | Rare earth permanent magnet |
| JPS60238448A (en) * | 1984-05-14 | 1985-11-27 | Seiko Epson Corp | Permanent magnet containing rare earth element |
| JPS6180805A (en) * | 1984-09-27 | 1986-04-24 | Daido Steel Co Ltd | Permanent magnet material |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63100155A (en) * | 1986-10-10 | 1988-05-02 | フィリップス エレクトロニクス ネムローゼ フェンノートシャップ | Magnetic material consisting of iron, boron and rare earth metal and its production |
| JP2018082177A (en) * | 2016-11-17 | 2018-05-24 | トヨタ自動車株式会社 | Rare earth magnet |
| JP2018110208A (en) * | 2016-12-28 | 2018-07-12 | トヨタ自動車株式会社 | Rare earth magnet and manufacturing method of the same |
| JP2020202383A (en) * | 2016-12-28 | 2020-12-17 | トヨタ自動車株式会社 | Rare earth magnet and manufacturing method of the same |
| US10892076B2 (en) | 2016-12-28 | 2021-01-12 | Toyota Jidosha Kabushiki Kaisha | Rare earth magnet and method of producing the same |
| EP3919644A1 (en) | 2020-06-01 | 2021-12-08 | Toyota Jidosha Kabushiki Kaisha | Rare earth magnet and production method thereof |
| US11996219B2 (en) | 2020-09-25 | 2024-05-28 | Toyota Jidosha Kabushiki Kaisha | Magnetic material and manufacturing method thereof |
| EP3989244A1 (en) | 2020-10-22 | 2022-04-27 | Toyota Jidosha Kabushiki Kaisha | Rare earth magnet and method for producing thereof |
| JP2023129176A (en) * | 2022-03-02 | 2023-09-14 | 浙江大学 | Method of increasing corrosion resistance of highly concentrated rare earth permanent magnet by high-temperature oxidation treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0630295B2 (en) | 1994-04-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |