JPH08229641A - Production of r-fe-b permanent magnet cast slab - Google Patents
Production of r-fe-b permanent magnet cast slabInfo
- Publication number
- JPH08229641A JPH08229641A JP7062087A JP6208795A JPH08229641A JP H08229641 A JPH08229641 A JP H08229641A JP 7062087 A JP7062087 A JP 7062087A JP 6208795 A JP6208795 A JP 6208795A JP H08229641 A JPH08229641 A JP H08229641A
- Authority
- JP
- Japan
- Prior art keywords
- roll
- nozzle
- permanent magnet
- slab
- magnet
- 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
- H01F1/0572—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 with a protective layer
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Continuous Casting (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、微細均質組織を有す
るＲ−Ｆｅ−Ｂ系永久磁石用鋳片の製造方法に係り、Ｒ
−Ｆｅ−Ｂ系合金溶湯を溶解炉にて溶解後、タンディッ
シュ先端部のノズルより、溶湯を特定の空隙長に配置さ
れ、且つ特定角度に配置された急冷片ロールに注湯して
急冷凝固して、Ｒリッチ相が微細に分散した均質組織を
有する特定厚の急冷鋳片を得ることを特徴とするＲ−Ｆ
ｅ−Ｂ系永久磁石用鋳片の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a slab for an R-Fe-B type permanent magnet having a fine homogeneous structure,
After melting the -Fe-B alloy melt in a melting furnace, the melt is poured from a nozzle at the tip of the tundish into a quench piece roll arranged at a specific gap length and at a specific angle, and rapidly solidified. Then, an R-F characterized by obtaining a quenched slab of a specific thickness having a homogeneous structure in which an R-rich phase is finely dispersed.
The present invention relates to a method for manufacturing a slab for an e-B system permanent magnet.
【０００２】[0002]
【従来の技術】高性能永久磁石として代表的なＲ−Ｆｅ
−Ｂ系永久磁石（特開昭５９−４６００８号）は、三元
系正方晶化合物の主相とＲリッチ相を有する組織にて高
い磁石特性が得られ、一般家庭の各種電器製品から大型
コンピューターの周辺機器まで幅広い分野で使用され、
用途に応じた種々の磁石特性を発揮するよう種々の組成
のＲ−Ｆｅ−Ｂ系永久磁石が提案されている。2. Description of the Related Art R-Fe, which is a typical high-performance permanent magnet
The B-type permanent magnet (Japanese Patent Laid-Open No. 59-46008) has high magnet characteristics due to the structure having the main phase of the ternary tetragonal compound and the R-rich phase. Used in a wide range of fields including
R-Fe-B based permanent magnets having various compositions have been proposed so as to exhibit various magnet characteristics according to applications.
【０００３】Ｒ−Ｆｅ−Ｂ系焼結磁石の残留磁束密度
（Ｂｒ）を高めるためには、１）強磁性相であり、主相
のＲ2Ｆｅ14Ｂ相の存在量を多くすること、２）焼結体
の密度を主相の理論密度まで高めること、３）さらに、
主相結晶粒の磁化容易軸方向の配向度を高めることが要
求される。In order to increase the residual magnetic flux density (Br) of the R-Fe-B system sintered magnet, 1) increase the abundance of the R 2 Fe 14 B phase, which is a ferromagnetic phase and is the main phase, 2) Increasing the density of the sintered body to the theoretical density of the main phase 3) Further,
It is required to increase the degree of orientation of the main phase crystal grains in the easy axis direction of magnetization.
【０００４】すなわち、前記１）項の達成のためには、
磁石の組成を上記Ｒ2Ｆｅ14Ｂの化学量論的組成に近づ
けることが重要であるが、上記組成の合金を溶解し、鋳
型に鋳造した合金塊を、出発原料としてＲ−Ｆｅ−Ｂ系
焼結磁石を作製しようとすると、合金塊に晶出したα−
Ｆｅや、Ｒ−ｒｉｃｈ相が局部的に遍在していることな
どから、特に微粉砕時に粉砕が困難となり、組成ずれを
生ずる等の問題があった。That is, in order to achieve the above item 1),
It is important to bring the composition of the magnet close to the stoichiometric composition of the above R 2 Fe 14 B, but the alloy ingot having the above composition melted and cast in a mold is used as a starting material in the R—Fe—B system. When trying to make a sintered magnet, α-
Since Fe and the R-rich phase are locally ubiquitous, it is difficult to pulverize especially during fine pulverization, and there is a problem that composition shift occurs.
【０００５】最近、鋳塊粉砕法によるＲ−Ｆｅ−Ｂ系合
金粉末の欠点たる結晶粒の粗大化、α−Ｆｅの残留、偏
析を防止するために、Ｒ−Ｆｅ−Ｂ系合金溶湯を双ロー
ル法により、特定板厚の鋳片となし、前記鋳片を通常の
粉末冶金法に従って、焼結磁石を製造する方法が提案
（特開昭６３−３１７６４３号公報）されている。Recently, in order to prevent coarsening of crystal grains, residual α-Fe, and segregation, which are defects of the R-Fe-B alloy powder by the ingot crushing method, a molten alloy of R-Fe-B alloy is used. A method has been proposed (Japanese Patent Laid-Open No. 63-317643) in which a slab having a specific plate thickness is formed by a roll method, and the slab is manufactured by a conventional powder metallurgy method.
【０００６】また、Ｒ−Ｆｅ−Ｂ系合金溶湯を片ロール
を用いて、横注ぎストリップキャスト法により永久磁石
用急冷鋳片を製造する方法として、タンディッシュ先端
部の水平方向に所要幅のノズルを設け、このノズルに隣
接させて片ロールを水平方向に軸支配置し、高周波溶解
炉にて溶解した溶湯をタンディッシュに収容後、該ノズ
ルから溶湯を水平配置されて連続回転する片ロール面に
注湯して、急冷凝固させて急冷鋳片を製造する方法が提
案（特開平５−２２２４８８号公報、特開平６−８４６
２４号公報）されている。Further, as a method for producing a quenching cast piece for a permanent magnet by a horizontal pouring strip casting method using a single roll of R-Fe-B alloy melt, a nozzle having a required width in the horizontal direction of the tip of the tundish. Is provided, and one roll is horizontally supported adjacent to this nozzle, and after the molten metal melted in the high-frequency melting furnace is accommodated in the tundish, the molten roll is horizontally arranged from the nozzle and continuously rolled. A method for producing a rapidly-quenched slab by pouring the molten metal into the molten steel and rapidly solidifying it is proposed (JP-A-5-222488 and JP-A-6-846).
No. 24).
【０００７】[0007]
【発明が解決しようとする課題】一般に、横注ぎストリ
ップキャスト法の場合、前記ノズルと片ロール間の空隙
より溶湯の漏洩流出を防止するため、前記空隙にはアル
ミナ、シリカ等の耐火物からなるクッション材を介在さ
せて、ノズル部を片ロールに押圧して使用していた。し
かし、前記クッション材が溶湯に接触しているため、凝
固した鋳片がクッション材に固着し、鋳片がクッション
材を徐々に引き裂きながら鋳造されるため、前記クッシ
ョン材が鋳片中に混入し、混入した耐火物は焼結時に磁
石合金の液相により還元され、例えば、耐火物がアルミ
ナの場合は、Ａｌ2Ｏ3が還元されてできたＡｌの回りに
希土類酸化物が集積した異常組織となり、焼結磁石の耐
食性を劣化する問題があった。Generally, in the horizontal pouring strip casting method, in order to prevent the molten metal from leaking out through the gap between the nozzle and one roll, the gap is made of a refractory material such as alumina or silica. The cushion part was used and the nozzle part was pressed against one roll and used. However, since the cushion material is in contact with the molten metal, the solidified slab adheres to the cushion material, and the slab is cast while gradually tearing the cushion material, so that the cushion material is mixed in the slab. The mixed refractory is reduced by the liquid phase of the magnet alloy during sintering. For example, when the refractory is alumina, an abnormal structure in which rare earth oxides are accumulated around Al formed by reducing Al 2 O 3. Therefore, there is a problem that the corrosion resistance of the sintered magnet is deteriorated.
【０００８】また、横注ぎストリップキャスト法の場合
は、溶湯温度や溶湯と片ロールの熱伝達係数等が一定で
あれば、ノズル部の湯面高さとロール周速度、すなわち
溶湯と片ロールの接触長とロール周速度により、鋳片の
板厚および結晶組織が決定されるが、操業上、湯面高さ
を一定にすることは難しく、板厚が変動するために結晶
組織は大小にばらつく問題がある。かかる結晶組織の短
軸方向の結晶粒径の大きさとそのバラツキは、磁石特
性、特に保磁力を変動させるため、安定した磁石特性が
得難い問題があった。さらに、鋳片と片ロールの接触時
間が短かいと、鋳片の冷却が不十分で、鋳片が片ロール
を離れた時の鋳片温度が高いため、結晶粒は成長して粗
大化するため、磁石特性、特に保磁力が低下する問題が
あった。In the case of the horizontal pouring strip casting method, if the molten metal temperature and the heat transfer coefficient between the molten metal and the one roll are constant, the height of the molten metal at the nozzle and the peripheral speed of the roll, that is, the contact between the molten metal and the one roll. The plate thickness and crystal structure of the slab are determined by the length and the peripheral speed of the roll, but it is difficult to keep the height of the molten metal surface constant during operation, and there is a problem that the crystal structure varies depending on the plate thickness. There is. The size of the crystal grain size in the minor axis direction of the crystal structure and the variation thereof change the magnet characteristics, especially the coercive force, so that there is a problem that it is difficult to obtain stable magnet characteristics. Furthermore, when the contact time between the slab and the one roll is short, the slab is insufficiently cooled, and the slab temperature when the slab leaves the one roll is high, so that the crystal grains grow and become coarse. Therefore, there is a problem in that the magnet characteristics, especially the coercive force is lowered.
【０００９】この発明は、横注ぎストリップキャスト法
における溶湯と片ロールとの問題点を解消し、Ｒ−Ｆｅ
−Ｂ系永久磁石の耐食性の劣化を防止でき、また、結晶
組織を安定的に微細化でき、保磁力などの磁石特性がす
ぐれかつ安定したＲ−Ｆｅ−Ｂ系永久磁石用鋳片の製造
方法の提供を目的としている。The present invention solves the problems of molten metal and single roll in the horizontal pouring strip casting method, and
A method for producing a slab for an R-Fe-B system permanent magnet, which can prevent deterioration of corrosion resistance of a B system permanent magnet, can stably refine a crystal structure, and has excellent and stable magnet characteristics such as coercive force. The purpose is to provide.
【００１０】[0010]
【課題を解決するための手段】この発明は、発明者は、
横注ぎストリップキャスト法のクッション材の問題を解
消するため、ノズルとロール間のクッション材をなくす
ることを目的に種々検討した結果、ノズルとロール間の
空隙長はロール周速度によって変化し、周速度が速い
程、空隙長を大きくすることができ、又鋳造時の急冷片
ロールの熱膨張により空隙長が変化することより、予め
急冷片ロールの材質、周速度等により、空隙長を所要長
さに調整する必要があり、前々空隙長を０．０１〜３．
０ｍｍに設定することが重要であることを知見した。The present invention is
As a result of various studies aimed at eliminating the cushioning material between the nozzle and the roll in order to solve the problem of the cushioning material in the horizontal pouring strip casting method, the air gap length between the nozzle and the roll changes depending on the peripheral speed of the roll. The faster the speed, the larger the void length.Also, the void length changes due to the thermal expansion of the quench strip roll during casting. It is necessary to adjust the gap length to 0.01-3.
It was found that setting to 0 mm is important.
【００１１】また、発明者は鋳片の厚みを０．０３ｍｍ
〜１０ｍｍにして、その組織を微細化するため、ノズル
とロールとの位置関係について種々検討した結果、急冷
片ロールの最上部と中心点を結ぶ線とノズルとのなす角
度が３０°〜９０°になるよう配置することにより、急
冷片ロールにより鋳造される鋳片の厚みを０．０３〜１
０ｍｍの所要厚みとなし、その組織を微細化できること
を知見し、この発明を完成した。The inventor has made the thickness of the cast piece 0.03 mm.
As a result of various studies on the positional relationship between the nozzle and the roll in order to make the structure finer by 10 mm to 10 mm, the angle formed by the nozzle and the line connecting the uppermost point of the quenching piece roll and the center point is 30 ° to 90 °. By arranging so that the thickness of the slab cast by the quenching piece roll is 0.03 to 1
The present invention has been completed by finding that the required thickness is 0 mm and the structure can be miniaturized.
【００１２】すなわち、この発明は、真空中又は不活性
雰囲気でＲ−Ｆｅ−Ｂ系合金溶湯をノズルより急冷片ロ
ールに注湯して急冷鋳片を得るＲ−Ｆｅ−Ｂ系永久磁石
用鋳片の製造方法において、前記合金溶湯を収容するタ
ンディッシュ先端部のノズルを、急冷片ロールの最上部
と中心点を結ぶ線に対して、３０°〜９０°の角度範囲
位置に臨ませて配置し、かつ急冷片ロール表面と前記ノ
ズル端間の空隙長を０．０１ｍｍ〜３．０ｍｍにしたこ
とを特徴とするＲ−Ｆｅ−Ｂ系永久磁石用鋳片の製造方
法である。That is, the present invention is a casting for an R-Fe-B system permanent magnet, in which a molten R-Fe-B system alloy is poured from a nozzle into a quenching piece roll in a vacuum or in an inert atmosphere to obtain a quenching cast piece. In the method for manufacturing a piece, the nozzle of the tip of the tundish containing the molten alloy is arranged so as to face an angle range of 30 ° to 90 ° with respect to a line connecting the uppermost part of the quenching piece roll and the center point. And the gap length between the surface of the quenched piece roll and the end of the nozzle is 0.01 mm to 3.0 mm, which is a method for producing a cast piece for an R-Fe-B system permanent magnet.
【００１３】以下にこの発明においてＲ−Ｆｅ−Ｂ系永
久磁石を製造する合金鋳片の好ましい合金組成を説明す
る。この発明の永久磁石鋳片に含有される希土類元素Ｒ
はイットリウム（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る。Ｒとしては、軽希土類を
もって足り、特にＮｄ，Ｐｒが好ましい。また通常Ｒの
うち１種もって足りるが、実用上は２種類以上の混合物
（ミッシュメタル、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、Ｓｍ，Ｙ，Ｌａ，Ｃｅ，Ｇｄ
等は他のＲ、特にＮｄ，Ｐｒ等との混合物として用いる
ことができる。なお、このＲは純希土類元素でなくても
よく、工業上入手可能な範囲で製造上不可避な不純物を
含有するものでも差し支えない。The preferred alloy composition of the alloy slab for producing the R-Fe-B system permanent magnet in the present invention will be described below. Rare earth element R contained in the permanent magnet slab of the present invention
Is a rare earth element including yttrium (Y) and including light rare earths and heavy rare earths. As R, a light rare earth element is sufficient, and Nd and Pr are particularly preferable. Usually, one kind of R is sufficient, but in practice, a mixture of two or more kinds (Misch metal, didymium, etc.) can be used for reasons such as convenience of availability, and Sm, Y, La, Ce, Gd.
Etc. can be used as a mixture with other R, especially Nd, Pr, etc. It should be noted that this R does not have to be a pure rare earth element, and may contain impurities that are unavoidable in production within the industrially available range.
【００１４】Ｒは、Ｒ−Ｆｅ−Ｂ系永久磁石を製造する
合金鋳片の必須元素であって、１０原子％未満では高磁
気特性、特に高保磁力が得られず、３０原子％を越える
と残留磁束密度（Ｂｒ）が低下して、すぐれた特性の永
久磁石が得られない。よって、Ｒは１０原子％〜３０原
子％の範囲とする。R is an essential element of the alloy slab for producing R-Fe-B system permanent magnets. If it is less than 10 atomic%, high magnetic properties, particularly high coercive force cannot be obtained, and if it exceeds 30 atomic%. The residual magnetic flux density (Br) decreases, and a permanent magnet with excellent characteristics cannot be obtained. Therefore, R is in the range of 10 atom% to 30 atom%.
【００１５】Ｂは、Ｒ−Ｆｅ−Ｂ系永久磁石を製造する
合金鋳片の必須元素であって、２原子％未満では高い保
磁力（ｉＨｃ）は得られず、２８％原子を越えると残留
磁束密度（Ｂｒ）が低下するため、すぐれた永久磁石が
得られない。よって、Ｂは２原子％〜２８原子％の範囲
とする。B is an essential element of an alloy slab for producing an R-Fe-B system permanent magnet. If it is less than 2 atom%, a high coercive force (iHc) cannot be obtained, and if it exceeds 28% atom, it remains. Since the magnetic flux density (Br) decreases, an excellent permanent magnet cannot be obtained. Therefore, B is in the range of 2 at% to 28 at%.
【００１６】Ｆｅは、Ｒ−Ｆｅ−Ｂ系永久磁石を製造す
る合金鋳片の必須元素であって、４２原子％未満では残
留磁束密度（Ｂｒ）が低下し、８８％原子を超えると高
い保磁力が得られないので、Ｆｅは４２原子％〜８８原
子％に限定する。また、Ｆｅの一部をＣｏ、Ｎｉの１種
又は２種で置換可能であり、これは永久磁石の温度特性
を向上させる効果及び耐食性を向上させる効果が得られ
るためであるが、Ｃｏ、Ｎｉの１種又は２種はＦｅの５
０％を越えると高い保磁力が得られず、すぐれた永久磁
石が得られない。よって、Ｃｏ、Ｎｉの１種又は２種の
置換量はＦｅの５０％を上限とする。Fe is an essential element of alloy slabs for producing R-Fe-B system permanent magnets. If it is less than 42 atomic%, the residual magnetic flux density (Br) is lowered, and if it exceeds 88% atomic level, it is high. Since no magnetic force can be obtained, Fe is limited to 42 atom% to 88 atom%. Further, a part of Fe can be replaced with one or two of Co and Ni. This is because the effect of improving the temperature characteristics of the permanent magnet and the effect of improving corrosion resistance can be obtained. 1 or 2 is Fe 5
If it exceeds 0%, a high coercive force cannot be obtained and an excellent permanent magnet cannot be obtained. Therefore, the upper limit of the substitution amount of one or two of Co and Ni is 50% of Fe.
【００１７】この発明による合金鋳片において、高い残
留磁束密度と高い保磁力を共に有するすぐれた永久磁石
を得るためには、Ｒ１２原子％〜１６原子％、Ｂ４原子
％〜１２原子％、Ｆｅ７２原子％〜８４原子％が好まし
い。、また、この発明による合金鋳片は、Ｒ、Ｂ、Ｆｅ
の他、酸素、Ｃ、Ｃａ、Ｍｇなどの工業的生産上不可避
的不純物の存在を許容できるが、Ｂの一部を４．０原子
％以下のＣ、３．５原子％以下のＰ、２．５原子％以下
のＳ、３．５原子％以下のＣｕのうち少なくとも１種、
合計量で４．０原子％以下で置換することにより、磁石
合金の製造性改善、低価格化が可能である。In order to obtain an excellent permanent magnet having both a high residual magnetic flux density and a high coercive force in the alloy slab according to the present invention, R12 atom% to 16 atom%, B4 atom% to 12 atom%, Fe72 atom % To 84 atom% is preferable. Further, the alloy slab according to the present invention is made of R, B, Fe.
In addition to the above, the presence of impurities such as oxygen, C, Ca, and Mg that are unavoidable in industrial production is acceptable, but part of B is 4.0 atomic% or less of C, 3.5 atomic% or less of P, 2 .5 atomic% or less of S, 3.5 atomic% or less of at least one of Cu,
By substituting the total amount by 4.0 atomic% or less, it is possible to improve the manufacturability of the magnet alloy and reduce the cost.
【００１８】さらに、前記Ｒ、Ｂ、Ｆｅ合金あるいはＣ
ｏを含有するＲ−Ｆｅ−Ｂ合金に、９．５原子％以下の
Ａｌ、４．５原子％以下のＴｉ、９．５原子％以下の
Ｖ、８．５原子％以下のＣｒ、８．０原子％以下のＭ
ｎ、５原子％以下のＢｉ、１２．５原子％以下のＮｂ、
１０．５原子％以下のＴａ、９．５原子％以下のＭｏ、
９．５原子％以下のＷ、２．５原子％以下のＳｂ、７原
子％以下のＧｅ、３５原子％以下のＳｎ、５．５原子％
以下のＺｒ、５．５原子％以下のＨｆのうち少なくとも
１種添加含有させることにより、永久磁石合金の高保磁
力が可能になる。この発明のＲ−Ｆｅ−Ｂ系永久磁石に
おいて、結晶相は主相が正方晶であることが不可欠であ
り、特に、微細で均一な合金粉末を得て、すぐれた磁気
特性を有する焼結永久磁石を作製するのに効果的であ
る。Further, the R, B, Fe alloy or C
8. O-containing R-Fe-B alloy, 9.5 atomic% or less Al, 4.5 atomic% or less Ti, 9.5 atomic% or less V, 8.5 atomic% or less Cr, 8. M of 0 atomic% or less
n, 5 atomic% or less Bi, 12.5 atomic% or less Nb,
10.5 atomic% or less Ta, 9.5 atomic% or less Mo,
W of 9.5 atomic% or less, Sb of 2.5 atomic% or less, Ge of 7 atomic% or less, Sn of 35 atomic% or less, 5.5 atomic%
A high coercive force of the permanent magnet alloy becomes possible by adding at least one of the following Zr and 5.5 at% or less of Hf. In the R-Fe-B system permanent magnet of the present invention, it is essential that the main phase of the crystal phase is a tetragonal crystal, and in particular, a fine and uniform alloy powder is obtained to obtain a sintered permanent having excellent magnetic properties. It is effective for making magnets.
【００１９】この発明において、Ｒリッチ相が微細に分
散した組織を有する磁石材料の鋳片の板厚を０．０３ｍ
ｍ〜１０ｍｍに限定した理由は、０．０３ｍｍ未満では
急冷効果が大となり、結晶粒径が３μｍより小となり、
粉末化した際に酸化しやすくなるため、磁気特性の劣化
を招来するとともに、微粉砕後の粒子が多結晶となり配
向度が低下しＢｒが低下するので好ましくなく、また１
０ｍｍを越えると、冷却速度が遅くなり、α−Ｆｅが晶
出しやすく、結晶粒径が大となり、Ｎｄリッチ相の遍在
も生じるため、磁気特性、特に保磁力が低下するので好
ましくないことによる。より好ましくは板厚０．０５ｍ
ｍ〜３ｍｍである。In the present invention, the plate thickness of the cast slab of the magnetic material having a structure in which the R-rich phase is finely dispersed is 0.03 m.
The reason for limiting the thickness to m to 10 mm is that if it is less than 0.03 mm, the quenching effect is large, and the crystal grain size is smaller than 3 μm.
Since it is easily oxidized when pulverized, the magnetic properties are deteriorated, and the finely pulverized particles become polycrystals, which lowers the degree of orientation and Br, which is not preferable.
If it exceeds 0 mm, the cooling rate becomes slow, α-Fe is easily crystallized, the crystal grain size becomes large, and the Nd-rich phase becomes ubiquitous. . More preferably the plate thickness is 0.05 m
It is m to 3 mm.
【００２０】この発明のストリップキャスティング法に
より得られた特定組成のＲ−Ｆｅ−Ｂ系合金の断面組織
は、主相のＲ2Ｆｅ14Ｂ結晶が従来の鋳型に鋳造して得
られた鋳塊のものに比べて、約１／１０以上も微細であ
り、例えば、その短軸方向の寸法は０．１μｍ〜５０μ
ｍ、長軸方向は５μｍ〜２００μｍの微細結晶であり、
かつその主相結晶粒を取り囲むようにＲリッチ相が微細
に分散されており、局部に遍在している領域において
も、その大きさは２０μｍ以下である。The cross-sectional structure of the R-Fe-B type alloy having a specific composition obtained by the strip casting method of the present invention is an ingot obtained by casting the R 2 Fe 14 B crystal of the main phase in a conventional mold. The size is about 1/10 or more finer than that of, for example, the dimension in the minor axis direction is 0.1 μm to 50 μm.
m, the long axis direction is a fine crystal of 5 μm to 200 μm,
In addition, the R-rich phase is finely dispersed so as to surround the main phase crystal grains, and the size is 20 μm or less even in the locally ubiquitous region.
【００２１】[0021]
【作用】この発明による製造方法の作用を図に基づいて
詳述する。図１はこの発明のストリップキャスティング
法に使用する装置の概略を示す説明図である。真空中も
しくは不活性雰囲気となした密閉室１内には、高周波溶
解炉２と先端部にノズル４を有するタンディッシュ３、
これに隣接配置する急冷用片ロール５、さらに急冷用片
ロール５面に接触させて設けるスクレパー６、並びに鋳
片回収容器７が配置、収容されている。急冷用片ロール
５は、水平方向に軸配置されて図示しない回転駆動装置
にて所定の回転数で水平回転する構成で、また、図示し
ない水冷装置で冷却されている。The operation of the manufacturing method according to the present invention will be described in detail with reference to the drawings. FIG. 1 is an explanatory view showing the outline of an apparatus used in the strip casting method of the present invention. A high frequency melting furnace 2 and a tundish 3 having a nozzle 4 at the tip end are provided in a closed chamber 1 in vacuum or in an inert atmosphere,
A quenching piece roll 5 disposed adjacent to this, a scraper 6 provided in contact with the surface of the quenching piece roll 5 and a cast piece collecting container 7 are arranged and housed. The quenching piece roll 5 is axially arranged in the horizontal direction and horizontally rotated at a predetermined rotation speed by a rotation driving device (not shown), and is cooled by a water cooling device (not shown).
【００２２】タンディッシュ３の先端部のノズル４は、
上記の急冷用片ロール５の最上部５ａと中心点５ｂを結
ぶ線に対して、θ＝３０°〜９０°の角度範囲位置に臨
むように配置され、かつ急冷用片ロール５表面より、空
隙長Ｔを０．０１ｍｍ〜３．０ｍｍに設定してある。溶
解炉２にて溶解したＲ−Ｆｅ−Ｂ系磁石組成の合金溶湯
８をタンディッシュ３内に傾注した後、タンディッシュ
３内の溶湯８は、急冷用片ロール５に対して所定の角度
範囲位置に所定の空隙長をもって配置されるノズル４よ
り、矢印方向に回転中の急冷用片ロール５面に注湯さ
れ、冷却されたロール面で急冷凝固して板厚０．０３ｍ
ｍ〜１０ｍｍの鋳片となり、次いでスクレパー６にて掻
きとられたのち鋳片回収容器７に収納される。The nozzle 4 at the tip of the tundish 3 is
With respect to the line connecting the uppermost part 5a of the quenching piece roll 5 and the central point 5b, it is arranged so as to face an angle range position of θ = 30 ° to 90 °, and a gap is formed from the surface of the quenching piece roll 5 The length T is set to 0.01 mm to 3.0 mm. After the molten alloy 8 of the R-Fe-B based magnet composition melted in the melting furnace 2 is poured into the tundish 3, the molten metal 8 in the tundish 3 has a predetermined angle range with respect to the quenching piece roll 5. From a nozzle 4 arranged with a predetermined gap length at a position, the melt is poured onto the surface of a single roll 5 for rapid cooling, which is rotating in the direction of the arrow, and rapidly cooled and solidified on the surface of the cooled roll to obtain a plate thickness of 0.03 m.
It becomes a slab of m to 10 mm, which is scraped by the scraper 6 and then stored in the slab collecting container 7.
【００２３】この発明において、急冷片ロールの最上部
と中心線を結ぶ線に対してノズルの位置を３０°〜９０
°に限定した理由は、３０°未満では鋳片とロールとの
接触時間が短く、鋳片の冷却が十分でなく、またノズル
部の湯面高さの変動による鋳片の板厚変動を生じ、鋳片
内組織の変化が大であり、所要の組織を得ることができ
ず、さらに９０°を越えると溶湯がロール面を滑りやす
く、ノズル部での溶湯の凝固によるノズルづまりを発生
し易くなり好ましくないことによる。より好ましい角度
範囲はは４５°〜８０°である。In the present invention, the position of the nozzle is 30 ° to 90 ° with respect to the line connecting the uppermost portion of the quenching piece roll and the center line.
The reason for limiting the temperature to 30 ° is that if it is less than 30 °, the contact time between the slab and the roll is short, the slab is not sufficiently cooled, and the plate thickness of the slab changes due to the change in the height of the molten metal at the nozzle. However, the change in the structure inside the slab is large, the required structure cannot be obtained, and if it exceeds 90 °, the molten metal tends to slip on the roll surface, and the nozzle clogging due to the solidification of the molten metal in the nozzle portion easily occurs. Because it is not preferable. A more preferable angle range is 45 ° to 80 °.
【００２４】又、この発明において、タンディッシュの
ノズル先端とロール面間の空隙長を０．０１ｍｍ 〜
３．０ｍｍに限定した理由は、０．０１ｍｍ未満では急
冷ロールとノズルが接触してロール表面に疵を生成した
り、ノズル先端部が欠ける恐れがあり好ましくなく、ま
た、３．０ｍｍを越えるとロール面とノズル間より湯洩
れを生ずるので好ましくない。好ましい空隙長は０．１
ｍｍ〜０．５ｍｍである。Further, in the present invention, the gap length between the tip of the tundish nozzle and the roll surface is 0.01 mm.
The reason for limiting the thickness to 3.0 mm is not preferable when the thickness is less than 0.01 mm because the quenching roll and the nozzle may come into contact with each other to form a flaw on the roll surface or the tip of the nozzle may be chipped, and when it exceeds 3.0 mm. It is not preferable because hot water leaks between the roll surface and the nozzle. The preferred void length is 0.1
mm to 0.5 mm.
【００２５】[0025]
実施例１ 図１に示す溶解炉、ノズルを有するタンディッシュ及び
急冷片ロールが収容される密閉室を真空となし、３１．
０Ｎｄ−１．０Ｄｙ−１．１Ｂ−３．０Ｃｏ−６３．９
Ｆｅ（ｗｔ％）磁石になる如く、溶解炉にて溶解した。
急冷片ロールには、径３００ｍｍ、回転数１３０ｒｐｍ
の水冷Ｃｕロールを用い、タンディッシュ先端部のノズ
ルは、水冷Ｃｕロール最上部と中心点を結ぶ線に対して
角度６０°並びに０．３ｍｍの空隙をもって配置され、
Ａｒ３００Ｔｏｒｒの雰囲気にした後、前記溶湯をタン
ディッシュ内に収容後、水冷Ｃｕロール上に溶湯をノズ
ル部の湯面高さ２０ｍｍでノズルより注湯して、幅１０
０ｍｍ、長さ１０〜３００ｍｍの急冷鋳片を得た。Example 1 The melting chamber shown in FIG. 1, a closed chamber accommodating a tundish having a nozzle and a quenching piece roll was evacuated, 31.
0Nd-1.0Dy-1.1B-3.0Co-63.9
It was melted in a melting furnace so that it became a Fe (wt%) magnet.
The quenching piece roll has a diameter of 300 mm and a rotation speed of 130 rpm.
Nozzle at the tip of the tundish is arranged with an angle of 60 ° and a gap of 0.3 mm with respect to the line connecting the top of the water-cooled Cu roll and the center point.
After making the atmosphere of Ar300 Torr, the molten metal is housed in a tundish, and then the molten metal is poured on a water-cooled Cu roll from the nozzle at a surface height of the nozzle portion of 20 mm, and the width is 10 mm.
Quenched slabs having a length of 0 mm and a length of 10 to 300 mm were obtained.
【００２６】鋳片３００枚を任意に選びその鋳片厚を測
定した結果、板厚０．２３〜０．３５ｍｍ、平均値０．
３１ｍｍであった。前記鋳片の結晶粒径は短軸方向の寸
法０．５μｍ〜１５μｍ、長軸方向寸法は１０μｍ〜２
５０μｍであり、Ｒリッチ相は主相を取囲むように１μ
ｍ以下に微細に分散して存在することを確認した。As a result of arbitrarily selecting 300 slabs and measuring the slab thickness, a plate thickness of 0.23 to 0.35 mm and an average value of 0.
It was 31 mm. The crystal grain size of the slab is 0.5 μm to 15 μm in the minor axis direction, and 10 μm to 2 in the major axis direction.
50 μm, the R-rich phase is 1 μm so as to surround the main phase
It was confirmed that the particles were finely dispersed in a size of m or less.
【００２７】前記鋳片を公知の方法で粗粉砕、微粉砕し
て、平均粒度３．５μｍ合金粉末を得た後、磁場強度１
５ｋＯｅ中で圧力１．０Ｔ／にて成型し、１０６０℃に
３時間の条件にて焼結後、６００℃に１時間の時効処理
を行い、永久磁石を得た。得られた永久磁石の磁石特性
及び耐食性試験結果を表１に示す。なお、耐食性試験は
焼結磁石を１５ｍｍ×１５ｍｍ×８ｍｍ寸法に加工後、
膜厚２５μｍのエポキシ樹脂塗装をした後、磁石１０個
を８０℃×９０％ＲＨの環境に２００時間保持した後、
その外観を検査する方法で行った。The slab was roughly pulverized and finely pulverized by a known method to obtain an alloy powder having an average particle size of 3.5 μm, and then the magnetic field strength was 1
After molding in 5 kOe at a pressure of 1.0 T /, sintering at 1060 ° C. for 3 hours, aging treatment at 600 ° C. for 1 hour was performed to obtain a permanent magnet. Table 1 shows the magnetic properties and corrosion resistance test results of the obtained permanent magnets. The corrosion resistance test is performed after processing the sintered magnet into a size of 15 mm × 15 mm × 8 mm,
After applying an epoxy resin coating with a film thickness of 25 μm, after holding 10 magnets in an environment of 80 ° C. × 90% RH for 200 hours,
The appearance was inspected.
【００２８】比較例１ 実施例１と同一の磁石組成を有する溶湯をタンディッシ
ュのノズルと急冷ロール間に厚み３ｍｍのアルミナのク
ッション材を介在させる以外は、実施例１と同一の鋳造
条件、製造条件にて磁石を得た。得られた鋳片の結晶粒
径は実施例の場合とほぼ同一であった。また、得られた
永久磁石の磁石特性及び実施例１と同一の耐食性試験結
果を表１に表す。耐食性試験結果は、表に示すごとく、
磁石１０個中６３の塗膜に直径０．５〜２ｍｍのフクレ
が認められた。Comparative Example 1 The same casting conditions and production as in Example 1 except that a molten metal having the same magnet composition as in Example 1 was interposed between a tundish nozzle and a quenching roll with a 3 mm thick alumina cushion material. A magnet was obtained under the conditions. The crystal grain size of the obtained slab was almost the same as that of the example. Table 1 shows the magnet characteristics of the obtained permanent magnet and the same corrosion resistance test results as in Example 1. The results of the corrosion resistance test are as shown in the table.
Blisters having a diameter of 0.5 to 2 mm were recognized in the coating film of 63 of the 10 magnets.
【００２９】上記のフクレ部の塗膜を除去してＥＰＭＡ
により調査した結果、Ａｌの周りにＮｄ酸化物が集積し
ていることが確認された。鋳片に混入したＡｌ2Ｏ3製の
クッション材が焼結時にＮｄリッチな液相により還元さ
れ、Ａｌの周りにＮｄ酸化物が集積するＮｄ酸化物は耐
食性がきわめて悪く、水分と反応してＮｄ（ＯＨ）3に
変化するため、塗膜がふくれることが確認された。The coating film on the blisters is removed to remove the EPMA
As a result of the investigation, it was confirmed that Nd oxide was accumulated around Al. The cushioning material made of Al 2 O 3 mixed in the slab is reduced by the Nd-rich liquid phase during sintering, and the Nd oxide that accumulates Nd oxide around Al has extremely poor corrosion resistance and reacts with moisture. It was confirmed that the coating film swelled because it changed to Nd (OH) 3 .
【００３０】比較例２ 実施例１と同一磁石組成を有する溶湯を、ノズルと水冷
Ｃｕロールの最上部と中心点を結ぶ線に対する角度が２
０°で、湯面高さ１１ｍｍで実施例１と同一の鋳造条
件、磁石化製造条件にて磁石を得た。得られた鋳片の寸
法は幅１００ｍｍ長さ１０〜３００ｍｍであり、鋳片３
００枚を任意に選び、厚みを測定した結果、板厚０．１
８〜０．４２ｍｍ平均値０．３２ｍｍであった。また、
この比較例の鋳片結晶粒径は短軸方向は寸法３μｍ〜３
０μｍ、長軸方向寸法は３０μｍ〜２００μｍであっ
た。得られた永久磁石の磁石特性及び耐食性試験結果を
第１表に表す。Comparative Example 2 A molten metal having the same magnet composition as in Example 1 was formed at an angle of 2 with respect to the line connecting the nozzle and the top of the water-cooled Cu roll with the center point.
A magnet was obtained under the same casting conditions and magnetizing production conditions as in Example 1 at 0 ° and a molten metal height of 11 mm. The size of the obtained slab is 100 mm in width and 10 to 300 mm in length.
As a result of arbitrarily selecting 00 sheets and measuring the thickness, the plate thickness is 0.1
The average value was 8 to 0.42 mm and 0.32 mm. Also,
The slab crystal grain size of this comparative example is 3 μm to 3 in the minor axis direction.
The dimension in the long axis direction was 0 μm and was 30 μm to 200 μm. Table 1 shows the magnetic properties and corrosion resistance test results of the obtained permanent magnets.
【００３１】比較例３ 実施例１と同一磁石組成を有する溶湯を、ノズルと水冷
Ｃｕロールの最上部と中心点を結ぶ線に対する角度が１
００°で湯面高さ１８ｍｍ以外は実施例１と同一の鋳造
条件で溶湯をノズルより注湯した。鋳造開始後１２秒で
ノズル部で溶湯が凝固し、ノズルづまりが発生し、鋳造
できなくなった。Comparative Example 3 A molten metal having the same magnet composition as in Example 1 was formed at an angle of 1 with respect to the line connecting the nozzle and the top of the water-cooled Cu roll and the center point.
Molten metal was poured from a nozzle under the same casting conditions as in Example 1 except that the height of the molten metal was 00 ° and the height of the molten metal was 18 mm. Twelve seconds after the start of casting, the molten metal solidified at the nozzle, nozzle clogging occurred, and casting could not be performed.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】この発明は、横注ぎストリップキャスト
法における溶湯と片ロールとの問題点を解消するため、
ノズルとロール間のクッション材をなくし、かつノズル
とロール間の空隙長並びにノズルとロールとの位置関係
を特定し最適化することにより、実施例に明らかなよう
にクッション材の混入によるＲ−Ｆｅ−Ｂ系永久磁石の
耐食性の劣化を防止でき、また、結晶組織を安定的に微
細化でき、保磁力などがすぐれかつ安定した磁石特性の
Ｒ−Ｆｅ−Ｂ系永久磁石を得ることが可能な同系磁石用
鋳片を安定的に製造できる。The present invention solves the problems of molten metal and single roll in the horizontal pouring strip casting method.
By eliminating the cushioning material between the nozzle and the roll and specifying and optimizing the gap length between the nozzle and the roll and the positional relationship between the nozzle and the roll, as is apparent from the examples, R-Fe due to the mixing of the cushioning material It is possible to prevent deterioration of the corrosion resistance of the -B system permanent magnet, to stably refine the crystal structure, to obtain an R-Fe-B system permanent magnet having excellent coercive force and stable magnet characteristics. A slab for similar magnets can be stably manufactured.
【図１】この発明のストリップキャスティング法に使用
する装置の概略を示す説明図である。FIG. 1 is an explanatory view showing an outline of an apparatus used for a strip casting method of the present invention.
１ 密閉室 ２ 高周波溶解炉 ３ タンディッシュ ４ ノズル ５ 急冷用片ロール ５ａ 最上部 ５ｂ 中心点 ６ スクレパー ７ 鋳片回収容器 ８ 合金溶湯 1 Closed Chamber 2 High Frequency Melting Furnace 3 Tundish 4 Nozzle 5 Piece Roll for Quenching 5a Top 5b Center Point 6 Scraper 7 Cast Piece Recovery Container 8 Alloy Molten Metal
フロントページの続き (72)発明者 植田 雅己 大阪府吹田市南吹田２丁目19番１号 住友 特殊金属株式会社吹田製作所内 (72)発明者 児嶋 尊 大阪府吹田市南吹田２丁目19番１号 住友 特殊金属株式会社吹田製作所内 (72)発明者 渡辺 幸良 大阪府吹田市南吹田２丁目19番１号 住友 特殊金属株式会社吹田製作所内Front page continuation (72) Inventor Masaki Ueda 2-19-1 Minamisuita, Suita-shi, Osaka Sumitomo Special Metals Co., Ltd. Suita Works (72) Inventor Takashi Kojima 2-1-1 Minamisuita, Suita, Osaka Sumitomo Special Metals Co., Ltd. Suita Works (72) Inventor Yuki Watanabe 2-19-1 Minami Suita, Suita City, Osaka Prefecture Sumitomo Special Metals Co., Ltd. Suita Works
Claims (1)
系合金溶湯をノズルより急冷片ロールに注湯して急冷鋳
片を得るＲ−Ｆｅ−Ｂ系永久磁石用鋳片の製造方法にお
いて、前記合金溶湯を収容するタンディッシュ先端部の
ノズルを、急冷片ロールの最上部と中心点を結ぶ線に対
して、３０°〜９０°の角度範囲位置に臨ませて配置
し、かつ急冷片ロール表面と前記ノズル端間の空隙長を
０．０１ｍｍ〜３．０ｍｍにしたことを特徴とするＲ−
Ｆｅ−Ｂ系永久磁石用鋳片の製造方法。1. R-Fe-B in vacuum or in an inert atmosphere
In a method for producing a slab for an R-Fe-B system permanent magnet, which comprises pouring a molten alloy into a quenching piece roll from a nozzle to obtain a quenched slab, a nozzle at a tip of a tundish containing the molten alloy is rapidly cooled. It is arranged so as to face an angle range position of 30 ° to 90 ° with respect to a line connecting the uppermost portion of the one roll and the center point, and the gap length between the surface of the rapidly cooled one roll and the nozzle end is 0.01 mm to 3 mm. R- characterized by being set to 0.0 mm
The manufacturing method of the cast piece for Fe-B type | system | group permanent magnets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06208795A JP3535253B2 (en) | 1995-02-23 | 1995-02-23 | Method for producing cast slab for R-Fe-B permanent magnet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06208795A JP3535253B2 (en) | 1995-02-23 | 1995-02-23 | Method for producing cast slab for R-Fe-B permanent magnet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08229641A true JPH08229641A (en) | 1996-09-10 |
| JP3535253B2 JP3535253B2 (en) | 2004-06-07 |
Family
ID=13189934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06208795A Expired - Lifetime JP3535253B2 (en) | 1995-02-23 | 1995-02-23 | Method for producing cast slab for R-Fe-B permanent magnet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3535253B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002030595A1 (en) * | 2000-10-06 | 2002-04-18 | Santoku Corporation | Process for producing, through strip casting, raw alloy for nanocomposite type permanent magnet |
| JP2003077717A (en) * | 2001-09-03 | 2003-03-14 | Showa Denko Kk | Rare-earth magnetic alloy agglomeration, its manufacturing method and sintered magnet |
| US7160398B2 (en) | 2002-08-08 | 2007-01-09 | Neomax Co., Ltd. | Method of making rapidly solidified alloy for magnet |
| CN100371106C (en) * | 2002-08-08 | 2008-02-27 | 株式会社新王磁材 | Method and producing device for making rapidly solidified alloy for magnet |
| JP2008264875A (en) * | 2007-04-16 | 2008-11-06 | Grirem Advanced Materials Co Ltd | Rare earth alloy cast sheet and method for producing the same |
| JP2010227993A (en) * | 2009-03-30 | 2010-10-14 | Hitachi Metals Ltd | Tundish and method for manufacturing r-t-b based alloy using tundish |
| CN102179493A (en) * | 2011-04-20 | 2011-09-14 | 钢铁研究总院 | Vacuum continuous casting apparatus for high-temperature alloy |
-
1995
- 1995-02-23 JP JP06208795A patent/JP3535253B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002030595A1 (en) * | 2000-10-06 | 2002-04-18 | Santoku Corporation | Process for producing, through strip casting, raw alloy for nanocomposite type permanent magnet |
| US7004228B2 (en) | 2000-10-06 | 2006-02-28 | Santoku Corporation | Process for producing, through strip casting, raw alloy for nanocomposite type permanent magnet |
| US7547365B2 (en) | 2000-10-06 | 2009-06-16 | Hitachi Metals, Ltd. | Process for producing, through strip casting, raw alloy for nanocomposite type permanent magnet |
| JP2003077717A (en) * | 2001-09-03 | 2003-03-14 | Showa Denko Kk | Rare-earth magnetic alloy agglomeration, its manufacturing method and sintered magnet |
| US7160398B2 (en) | 2002-08-08 | 2007-01-09 | Neomax Co., Ltd. | Method of making rapidly solidified alloy for magnet |
| CN100371106C (en) * | 2002-08-08 | 2008-02-27 | 株式会社新王磁材 | Method and producing device for making rapidly solidified alloy for magnet |
| JP2008264875A (en) * | 2007-04-16 | 2008-11-06 | Grirem Advanced Materials Co Ltd | Rare earth alloy cast sheet and method for producing the same |
| JP2010227993A (en) * | 2009-03-30 | 2010-10-14 | Hitachi Metals Ltd | Tundish and method for manufacturing r-t-b based alloy using tundish |
| CN102179493A (en) * | 2011-04-20 | 2011-09-14 | 钢铁研究总院 | Vacuum continuous casting apparatus for high-temperature alloy |
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| Publication number | Publication date |
|---|---|
| JP3535253B2 (en) | 2004-06-07 |
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