JPS6037868B2

JPS6037868B2 - Manganese-aluminum-carbon alloy magnet

Info

Publication number: JPS6037868B2
Application number: JP57183979A
Authority: JP
Inventors: 進佐内; 清司小嶋
Original assignee: Matsushita Electric Industrial Co Ltd
Current assignee: Panasonic Holdings Corp
Priority date: 1982-10-19
Filing date: 1982-10-19
Publication date: 1985-08-28
Also published as: JPS5974253A

Description

【発明の詳細な説明】産業上の利用分野本発明は、磁気特性を向上させたマンガンーアルミニウ
ム−炭素（Ｍｎ−ＡＩ−Ｃ）系合金磁石に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a manganese-aluminum-carbon (Mn-AI-C) alloy magnet with improved magnetic properties.

従来例の構成とその問題点近年Ｍｎ６８．０〜７３．の重量％（以下単に％で表示
する）、Ｃ（命。Conventional structure and its problems Recently, Mn68.0 to 73. % by weight (hereinafter simply expressed as %), C (life).

Ｍｎ−６６）〜（きＭｎ−２２‐２）％（ただし数式内
のＭｎはマンガン成分の重量％を表す）、残部ＡＩの組
成からなる磁気特性の優れた異方性Ｍｎ−山一Ｃ系合金
磁石が開発されている（特公昭５４一３１４４８号公報
）。またＭｎ−ＡＩ−Ｃ合金の磁気特性を向上させた合
金としてＭｎ一ＡＩ−Ｃ−Ｎｉ合金（特関昭５３−７３
４１１号公報）、Ｍｈ−Ｎ−Ｃ−Ｎｉ−Ｔｉ合金（特関
昭５４−８３６１３号公報）、Ｍｎ−ＡＩ−Ｃ−Ｐ合金
（特顔昭５７−３９１８）などが提案されている。この
Ｍｎ−Ｎ−Ｃ系合金磁石は、すでにスピーカ、電気機器
などに使用されているが、電動機や発電機など磁石に逆
磁界が加わる機器においては、磁石の保磁力がより大き
くなること、及びスピーカ、電気機器などでは小型化の
煩向のため磁石のエネルギー積（ＢＨ）ｍａｘがより大
きくなることが要求されている。Anisotropic Mn-Yamaichi C system with excellent magnetic properties, consisting of Mn-66) to (Mn-22-2)% (Mn in the formula represents the weight% of the manganese component), with the balance being AI. Alloy magnets have been developed (Japanese Patent Publication No. 54-31448). In addition, as an alloy with improved magnetic properties of Mn-AI-C alloy, Mn-AI-C-Ni alloy (Tokukan Sho 53-73
411), Mh-N-C-Ni-Ti alloy (Tokukan Sho 54-83613), Mn-AI-C-P alloy (Tokukan Sho 57-3918), etc. have been proposed. This Mn-N-C alloy magnet is already used in speakers, electrical equipment, etc., but in equipment such as motors and generators where the magnet is subjected to a reverse magnetic field, the coercive force of the magnet becomes larger and In order to reduce the size of speakers, electrical equipment, and the like, it is required that the energy product (BH) max of the magnet be increased.

発明の目的本発明は、Ｍｈ−ＡＩ−Ｃ系合金磁石の磁気特性を高め
ることを目的とする。OBJECT OF THE INVENTION The object of the present invention is to improve the magnetic properties of Mh-AI-C alloy magnets.

発明の構成本発明は、上記の目的を達成するため、Ｍｎ−Ｎ−Ｃ合
金にリン（Ｐ）、ニッケル（Ｎｉ）の双方を添加するこ
とを特徴とする。Structure of the Invention In order to achieve the above object, the present invention is characterized in that both phosphorus (P) and nickel (Ni) are added to the Mn--N--C alloy.

また本発明は、上記の目的を達成するため、Ｐ、Ｎｉと
更にチタン（Ｔｉ）の３元素を添加することを特徴とす
る。本発明によれば、Ｍｎ−ＡＩ−Ｃ系合金磁石の磁気
特性、特に保磁力とエネルギー積を高めることができる
。実施例の説明Ｍｎ−ＡＩ−Ｃ系合金磁石は、前記組成範囲内のＭｎ−
ＡＩ−Ｃ系合金を５３０〜８３び０の温度領域で押圧加
工や圧縮加工などの温間塑性加工することにより製造さ
れる。Further, the present invention is characterized in that three elements, P, Ni, and further titanium (Ti) are added to achieve the above object. According to the present invention, the magnetic properties of the Mn-AI-C alloy magnet, particularly the coercive force and the energy product, can be improved. Description of Examples The Mn-AI-C alloy magnet has Mn-
It is manufactured by subjecting an AI-C alloy to warm plastic working such as pressing or compression working in a temperature range of 530 to 83 degrees.

第１図〜第３図は代表的な実験データで、前記組成範囲
内のＭｎ−ＡＩ−Ｃ合金にＰ及びＮｉの双方を添加した
鋳造ビレットに、１１００℃で溶体化熱処理を施した後
、室温まで冷却し、次に温間塑性加工（押出比５）した
後の添加量（前記合金１００に対する割合と％で表す）
に対する保磁力（，Ｈｃ）及び（ＢＨ）ｍａｘの変化を
示す。Figures 1 to 3 show typical experimental data, in which a cast billet containing both P and Ni added to an Mn-AI-C alloy within the above composition range was subjected to solution heat treatment at 1100°C. Addition amount after cooling to room temperature and then warm plastic working (extrusion ratio 5) (expressed as a ratio and % to the alloy 100)
The changes in coercive force (, Hc) and (BH)max are shown.

ただしＩＨｃ、（ＢＨ）ｍａｘの値は同じ条件で作成し
たＭｎ−ＡＩ−Ｃ−Ｎｉ合金（Ｎｉ＝０．８％）の，Ｈ
ｃ、（ＢＨ）ｍａｘに対する比で表してある。第１〜３
図に示してあるように、Ｐ、Ｎｉ双方を添加することに
より、温間塑性加工後の，Ｈｃ、（ＢＨ）ｍａｘはＭｎ
−ＡＩ−Ｃ−Ｎｉ合金に比べて大幅に向上し、特に０．
０１ＳＰＳＯ．〇０．４ミＮｉＳ２．０の範囲で，Ｈｃ
は１５％以上向上する。However, the values of IHc and (BH)max are the values of H
c, expressed as a ratio to (BH)max. 1st to 3rd
As shown in the figure, by adding both P and Ni, Hc, (BH)max after warm plastic working increases with Mn
- Significantly improved compared to AI-C-Ni alloy, especially 0.
01SPSO. 〇In the range of 0.4mm NiS2.0, Hc
will improve by more than 15%.

（ＢＨ）ｍａｘは０．０３≦Ｐ≦０．２、０．４ＳＮｉ
ＳＩ．２の範囲で約１０％以上向上する。またＰ、Ｎｉ
の添加量についは、Ｐ添加量が０．６％を越えると熱処
理後合金中に非磁性のｒ相が多くなり、Ｎｉ添加量が２
．５％を越えると熱処理後合金中にｋ相（Ｍｎ一山一Ｎ
ｉ相）が多くなり、残留磁束密度が大幅に低下して（Ｂ
Ｈ）ｍａｘも低下する。またＰはごく微量添加で，Ｈｃ
が向上し、またＮｉは０．２％以上で磁気特性に及ぼす
効果が大きい。よってＰ、Ｎｉの最適添加量は０くＰＳ
Ｏ．〇０．２ミＮｊＳ２．５である。Ｐ、Ｎｉを添加
することによってＩＨｃが向上する原因はまだ明らかで
ない。(BH)max is 0.03≦P≦0.2, 0.4SNi
S.I. In the range of 2, the improvement is about 10% or more. Also P, Ni
Regarding the addition amount of
．． If it exceeds 5%, k phase (Mn one mountain one N) will form in the alloy after heat treatment.
i phase) increases, and the residual magnetic flux density decreases significantly (B
H) max also decreases. In addition, P is added in a very small amount, and Hc
Moreover, Ni has a large effect on magnetic properties when it is 0.2% or more. Therefore, the optimal addition amount of P and Ni is 0 PS
O. 〇 0.2 miNjS2.5. The reason why IHc is improved by adding P and Ni is not yet clear.

しかし熱処理のみによって得られる等万性磁石では、Ｐ
、Ｎｊを添加してもＩＨｃは向上しないが、温間塑性加
工後の異方性磁石で向上すると、及びＰ、Ｎｉが相状態
に及ぼす影響として、Ｐ添加量が多いとご相（高温相）
→７相（磁性相）の変態速度が遅くなり、Ｎｉ添加量が
多いと逆に速くなる現象がある。以上から推察すると、
Ｐ、Ｎｉは主要構成元素のＭｎやＡＩのエネルギー状態
等に大きな影響を与えていると考えられ、またこれらの
影響は結晶粒の紬粒化を引き起している温間塑性加工の
効果によって、より促進される。これらのことが，Ｈｃ
増大の方向に作用していると考えられる。第４図、第５
図は前記組成範囲内のＭｎ−Ｎ−Ｃ合金にＰ、Ｎｉ、Ｔ
ｉの３元素を添加した鍵造ビレットに１１００午○で溶
体化熱処理を施した後「室温まで風冷し、次に温間塑性
加工（押出比５）した後の添加量に対する，Ｈｃ、（Ｂ
Ｈ）ｍａｘの変化を示す。However, in isomerial magnets obtained only by heat treatment, P
, adding Nj does not improve IHc, but it improves with an anisotropic magnet after warm plastic working, and the influence of P and Ni on the phase state. )
→There is a phenomenon in which the transformation rate of the 7-phase (magnetic phase) becomes slow, and conversely becomes faster when the amount of Ni added is large. Judging from the above,
P and Ni are thought to have a large influence on the energy states of the main constituent elements Mn and AI, and these influences are due to the effect of warm plastic working that causes pongee grain formation. , more promoted. These things mean that Hc
It is thought that this is working in the direction of increase. Figures 4 and 5
The figure shows Mn-N-C alloys within the above composition range with P, Ni, and T.
After applying solution heat treatment to the key billet to which the three elements of i were added at 1,100 pm, it was air-cooled to room temperature and then warm plastic worked (extrusion ratio 5). B
H) Shows the change in max.

ただしＨｃ、（ＢＨ）ｍａｘの値は同じ条件で作製した
Ｍｎ−ＡＩ−Ｃ−Ｎｉ合金（Ｎｉ＝０．８％）の，Ｈｃ
、（ＢＨ）ｍａｘに対する比で表している。第４図より
，ＨｃはＴｉの添加量にかかわらず、Ｎｉ−Ｐ添加合金
の，Ｈｃとほぼ同じ大きな値を示す。第５図より０．０
１ＳＴｉＳＯ．５のＴｉ添加で（ＢＨ）ｍａｘが大幅に
向上するのがわかる。これらの合金について金属頭微境
で熱処理後の合金の組織を観察してみると、Ｐ一Ｎｉ−
Ｔｉ添加合金はＮｉ添加合金、Ｎｉ−Ｐ添加合金に比べ
て結晶粒が小さくなっており、（ＢＨ）ｍａｘの向上は
Ｔｉ添加による結晶粒の微細化によるものと推定される
。以上よりＰ、Ｎｉ、Ｔｉの最適添加量は０＜Ｐ≦０．
００．２ＳＮｉＳ２．与０．０１ＳＴｉＳＯ．５で
ある。更に本発明のＭｎ−山一Ｃ−Ｐ−Ｎｉ合金、及び
Ｍｈ−Ｎ−Ｃ−Ｐ−Ｎｉ−Ｔｉ合金に鉄（Ｆｅ）、ホウ
素（Ｂ）、銅（Ｃｕ）をそれぞれ単独又は複数で少量添
加して検討したところ、それらの磁気特性はそれぞれＦ
ｅ、Ｂ、Ｃｕを添加しない合金（Ｍｎ−ＡＩ−Ｃ−Ｐ−
Ｎｉ合金、Ｍｎ−ＡＩ−Ｃ−Ｐ−Ｎｉ−Ｔｉ合金）と比
較してほぼ同じかやや向上する煩向があった。However, the values of Hc and (BH)max are those of the Mn-AI-C-Ni alloy (Ni = 0.8%) produced under the same conditions.
, (BH) is expressed as a ratio to max. From FIG. 4, Hc shows almost the same large value as Hc in the Ni-P alloy, regardless of the amount of Ti added. From Figure 5, 0.0
1STiSO. It can be seen that (BH)max is significantly improved by adding Ti in No. 5. When we observed the structure of these alloys after heat treatment in the metal head microstructure, we found that P-Ni-
The Ti-added alloy has smaller crystal grains than the Ni-added alloy and the Ni-P-added alloy, and it is presumed that the improvement in (BH)max is due to the refinement of the crystal grains due to the addition of Ti. From the above, the optimal addition amount of P, Ni, and Ti is 0<P≦0.
0 0.2SNiS2. Given 0.01STiSO. It is 5. Further, a small amount of iron (Fe), boron (B), and copper (Cu) may be added to the Mn-Yamaichi C-P-Ni alloy and Mh-N-C-P-Ni-Ti alloy of the present invention, individually or in combination. When investigated by adding F
Alloy without adding e, B, Cu (Mn-AI-C-P-
Ni alloy, Mn-AI-C-P-Ni-Ti alloy), it was almost the same or slightly improved.

実施例１Ｍｎ７０．０％、ＡＩ２９．５％、ＣＯ．５％の組成の
ものにＰＯ．０５％、Ｎｉｏ．８％を添加した外径１８
脚の円柱状の合金ビレツトを溶解鋳造により作成し、ビ
レツトを１１００ｑｏで約１時間保持後炉冷した。Example 1 Mn70.0%, AI29.5%, CO. 5% composition of PO. 05%, Nio. Outer diameter 18 with 8% added
A cylindrical alloy billet for the legs was prepared by melting and casting, and the billet was held at 1100 qo for about 1 hour and then cooled in a furnace.

このビレットを７００ｏｏの温度で押出加工（押出比５
）した。押出加工後の合金の磁化優位方向における磁気
特性値を測定したところ、残留磁束密度Ｂｒ＝５９０の
、，Ｈｃｉ斑０のｅ、（ＢＨ）ｍａｘ＝６．２ＭＧ比で
あり、上記のＰ−Ｎｉ添加合金と同じ条件で製造したＭ
ｎ−Ｍ−Ｃ−Ｎｉ合金の磁気特性値と比較して，Ｈｃが
２５％、（ＢＨ）ｍａｘが１５％向上した。実施例２
Ｍｎ６９．５％、ＡＩ２９．４％、ＣＯ．６％の組成の
ものにＰＯ．１％、Ｎｉｏ．４％を添加した外径１８肌
の円柱状の合金ビレットを溶解鋳造により作製した。This billet was extruded at a temperature of 700 oo (extrusion ratio 5
)did. When we measured the magnetic property values of the alloy in the dominant magnetization direction after extrusion processing, we found that the residual magnetic flux density Br = 590, e of Hci spots 0, (BH)max = 6.2MG ratio, and the above P-Ni M manufactured under the same conditions as the additive alloy
Compared to the magnetic property values of the n-M-C-Ni alloy, Hc was improved by 25% and (BH)max was improved by 15%. Example 2
Mn69.5%, AI29.4%, CO. 6% composition of PO. 1%, Nio. A cylindrical alloy billet with an outer diameter of 18 mm and containing 4% was produced by melting and casting.

このビレツトを１１００℃で約１時間保持後空冷し、７
００００の温度で押出加工（押出比５）した。押出加工
後のＮｊ−Ｐ添加合金の磁化優位方向における磁気特性
値を測定したところ、Ｂｒ＝６００的、ＩＨｃ＝３６０
的、（ＢＨ）ｍａｘ＝７．血４Ｇ０ｅであった。上記の
Ｐ−Ｎｉ添加合金と同じ条件で製造したＭｎ一Ｎ−Ｃ−
Ｎｉ合金の磁気特・性値と比較してＩＨｃが２０％、（
ＢＨ）ｍａｘが１０％向上した。実施例３Ｍｎ７０．２％、ＡＩ２９．４％、ＣＯ．４％の組成の
ものにＰＯ．０７％、Ｎｉｏ．６％、Ｔｉｏ．１％を添
加した外径１８脚の円柱状の合金ピレツトを溶解鋳造に
より作成し、ビレットを１１００ｏｏで約１時間保持後
風冷した。This billet was held at 1100°C for about 1 hour and then air cooled.
Extrusion processing was carried out at a temperature of 0,000 °C (extrusion ratio: 5). When the magnetic property values of the Nj-P added alloy in the magnetization dominant direction after extrusion processing were measured, Br = 600, IHc = 360
target, (BH)max=7. Blood was 4G0e. Mn-N-C- produced under the same conditions as the above P-Ni alloy
Compared to the magnetic properties and properties of Ni alloy, IHc is 20%, (
BH)max improved by 10%. Example 3 Mn70.2%, AI29.4%, CO. 4% composition of PO. 07%, Nio. 6%, Tio. A cylindrical alloy pillar with an outer diameter of 18 rods containing 1% was prepared by melting and casting, and the billet was held at 1100 oo for about 1 hour and then air-cooled.

このビレットを７００００の温度で押出加工（押出比５
）した。押出加工後の合金の磁化優位方向における磁気
特性値を測定したところ、Ｂｒ＝６０５の、，Ｈｃ＝３
８５に、（ＢＨ）ｍａｘ＝７．４ＭＧＯｅであった。上
記Ｐ−Ｎｉ−Ｔｉ添加合金と同じ条件で製造したＭｎ−
山一Ｃ−Ｎｉ合金及びＭｎ一ＡＩ−Ｃ−Ｎｉ一Ｔｉ合金
を比較した。，ＨｃについてはＮｉ添加合合金、Ｎｉ−
Ｔｉ添加金と比較して２６％向上した。（ＢＨ）ｍａｘ
についてはＮｉ添加合金と比較して３０％、Ｎｉ−Ｔｉ
添加合金と比較して１２％向上した。発明の効果本発明は、従来のＭｎ−ＡＩ−Ｃ系合金磁石よりも保磁
力、（ＢＨ）ｍａｘを改良したＭｎ−ＡＩ−Ｃ−Ｐ−Ｎ
ｊ系合金磁石、及びＭｎ−ＡＩ−Ｃ−Ｐ−Ｎｉ−Ｔｉ系
合金磁石を提供するもので、この合金磁石はスピーカ、
電気機器などに適している。This billet was extruded at a temperature of 70,000 °C (extrusion ratio: 5
)did. When the magnetic property values of the alloy in the dominant magnetization direction after extrusion processing were measured, it was found that Br=605, , Hc=3
85, (BH)max=7.4MGOe. Mn- produced under the same conditions as the above P-Ni-Ti alloy
A Yamaichi C-Ni alloy and a Mn-AI-C-Ni-Ti alloy were compared. , Hc is Ni-added alloy, Ni-
This was improved by 26% compared to Ti-added gold. (BH)max
30% compared to Ni-added alloy, Ni-Ti
It was improved by 12% compared to the additive alloy. Effects of the Invention The present invention provides Mn-AI-C-P-N which has improved coercive force and (BH) max than conventional Mn-AI-C alloy magnets.
J-based alloy magnets and Mn-AI-C-P-Ni-Ti based alloy magnets, and these alloy magnets can be used for speakers,
Suitable for electrical equipment, etc.

[Brief explanation of drawings]

第１図〜第３図はＭｎ−ＡＩ−Ｃ合金にＰ、Ｎｉ双方を
添加した合金を温間塑性加工した後の添加量と保磁力（
ＩＨｃ）、（ＢＨ）ｍａｘとの関係を示す図、第４図及
び第５図はＭｎ−ＡＩ−Ｃ合金にＰ、Ｎｉ、Ｔｉを添加
した合金を溢間塑性加工した後の添加量と，Ｈｃ、（Ｂ
Ｈ）ｍａｘとの関係を示す図である。第１図第２図第３図第４図第５図Figures 1 to 3 show the amount of addition and coercive force (
Figures 4 and 5 show the relationship between IHc) and (BH)max, and Figures 4 and 5 show the amounts of addition after the alloy in which P, Ni, and Ti are added to the Mn-AI-C alloy are subjected to overflow plastic working, and Hc, (B
H) is a diagram showing the relationship with max. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5

Claims

[Claims] 1 68.0 to 73.0% by weight of manganese and carbon (1/(
10) For 100 parts by weight of an alloy consisting of Mn-6.6) to (1/3 Mn-22.2)% by weight, the balance being aluminum, 0.6% by weight or less of phosphorus and 0.2% by weight of nickel.
A manganese-aluminum-carbon alloy magnet characterized by adding 2.5 parts by weight. 2 Manganese 68.0-73.0% by weight, carbon (1/(1
0) Mn-6.6) to (1/3 Mn-22.2) weight%
, 0.6 parts by weight or less of phosphorus and 0.2 to 0.2 parts of nickel for 100 parts by weight of an alloy with the balance being aluminum.
A manganese-aluminum-carbon alloy magnet characterized by adding 2.5 parts by weight and 0.01 to 0.5 parts by weight of titanium.