JPH0848586A - Laminated ceramic sintered compact and member for molten iron-based alloy - Google Patents
Laminated ceramic sintered compact and member for molten iron-based alloyInfo
- Publication number
- JPH0848586A JPH0848586A JP6187344A JP18734494A JPH0848586A JP H0848586 A JPH0848586 A JP H0848586A JP 6187344 A JP6187344 A JP 6187344A JP 18734494 A JP18734494 A JP 18734494A JP H0848586 A JPH0848586 A JP H0848586A
- Authority
- JP
- Japan
- Prior art keywords
- molten metal
- sintered body
- resistance
- boron nitride
- thermal shock
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5029—Magnesia
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
- C04B2111/00887—Ferrous metallurgy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Continuous Casting (AREA)
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
- Ceramic Products (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な複合セラミックス
焼結体に関し、実用上十分な耐熱衝撃性を備え、かつ溶
融金属に対する耐溶損性および難付着性に優れた複合セ
ラミックス焼結体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel composite ceramics sintered body, and more particularly to a composite ceramics sintered body which has a practically sufficient thermal shock resistance, and is excellent in melting loss resistance and difficult adhesion to molten metal.
【０００２】[0002]
【従来の技術】耐熱衝撃性に優れるセラミックスとして
は窒化硼素、窒化珪素、サイアロン焼結体が知られてい
る。しかし、窒化硼素は耐熱衝撃性に優れ、溶融金属に
対する耐溶損性に優れるが機械的強度や耐摩耗性に劣
り、窒化珪素やサイアロン焼結体は耐熱衝撃性、機械的
強度及び耐摩耗性に優れるが溶鋼に対する耐溶損性に劣
るという欠点を有していた。2. Description of the Related Art Boron nitride, silicon nitride and sialon sintered bodies are known as ceramics having excellent thermal shock resistance. However, boron nitride is excellent in thermal shock resistance and excellent in melting resistance against molten metal, but inferior in mechanical strength and wear resistance, and silicon nitride and sialon sintered bodies are excellent in thermal shock resistance, mechanical strength and wear resistance. Although it was excellent, it had a drawback that it was inferior in melt damage resistance to molten steel.
【０００３】このため窒化硼素と窒化珪素あるいは窒化
硼素とサイアロンを複合化し両者の欠点を補う努力がな
されている。窒化硼素と窒化珪素からなる複合セラミッ
クスとしては、特開昭５６−１２０５７５号公報、特開
平１−１３１０６２号公報、特開平４−２９４８４６号
公報および特開平５−７０２３４号公報が提案されてい
る。また、サイアロンと窒化硼素からなる複合セラミッ
クスとしては、特開昭６０−１４５９６３号公報、特開
平２−２５５２４７号公報、特開平２−２５５２４８号
公報および特開平３−１５３５７３号公報が提案されて
いる。しかし、窒化硼素と窒化珪素あるいは窒化硼素と
サイアロンからなる複合セラミックスは、Ｓｉ成分が複
合セラミックス中に存在するので、溶融金属の内、特に
溶鉄と接した場合、鉄とＳｉが選択的に反応し最終的に
溶損に至るという問題が残されていた。For this reason, efforts have been made to compound boron nitride and silicon nitride, or to compound boron nitride and sialon to compensate for the drawbacks of both. As composite ceramics composed of boron nitride and silicon nitride, Japanese Patent Application Laid-Open No. 56-120575, Japanese Patent Application Laid-Open No. 1-1131062, Japanese Patent Application Laid-Open No. 4-294846 and Japanese Patent Application Laid-Open No. 5-70234 have been proposed. Further, as composite ceramics composed of sialon and boron nitride, JP-A-60-145963, JP-A-2-255247, JP-A-2-255248 and JP-A-3-153573 have been proposed. . However, in the composite ceramics composed of boron nitride and silicon nitride or boron nitride and sialon, since the Si component is present in the composite ceramics, iron and Si selectively react with each other in the molten metal, especially when contacted with molten iron. There was a problem that it eventually melted.
【０００４】そこで、溶融金属中でも溶鋼に対し化学的
に安定な窒化アルミニウムを加えることにより耐溶損性
を改善した複合セラミックスが提案されている。例え
ば、窒化硼素と窒化アルミニウムと窒化珪素からなる複
合セラミックスとして特開昭５６−１２９６６６号公報
および特開昭６０−５１６６９号公報が提案されてい
る。しかしながらこれらも１０ｗｔ％以上の窒化珪素を
含んでいるため充分な耐溶損性は得られていない。Therefore, there has been proposed a composite ceramics which has improved corrosion resistance by adding aluminum nitride which is chemically stable to molten steel even in molten metal. For example, Japanese Patent Application Laid-Open Nos. 56-129666 and 60-51669 have been proposed as composite ceramics composed of boron nitride, aluminum nitride and silicon nitride. However, since these also contain 10 wt% or more of silicon nitride, sufficient erosion resistance is not obtained.
【０００５】そこで最近では、窒化珪素を含まず窒化硼
素と窒化アルミニウムからなる複合セラミックスが提案
されている。例えば、窒化硼素と窒化アルミニウムから
なる複合セラミックスとして特開平１−１３１０６９号
公報が、あるいは窒化硼素と窒化アルミニウムとＣａ系
化合物からなる複合セラミックスとして特開平１−２６
１２７９号公報が、窒化硼素と窒化アルミニウムとＣａ
及びＹ系化合物からなる複合セラミックスとして特開平
１−２５２５８４号公報、特開平１−３０５８６２号公
報が、窒化アルミニウムと窒化硼素と３ＣａＯ・Ａｌ2
Ｏ3からなる複合セラミックスとして特開平３−２５２
３６７号公報が提案されている。また、鉄基合金溶湯用
セラミックスとして特開平４−３３２８３１号公報や特
公平５−８１４１号公報に提案されるような窒化硼素と
窒化アルミニウムと酸化イットリウムからなる複合セラ
ミックスがある。Therefore, recently, a composite ceramic made of boron nitride and aluminum nitride without containing silicon nitride has been proposed. For example, Japanese Patent Application Laid-Open No. 1-131069 discloses a composite ceramic composed of boron nitride and aluminum nitride, or Japanese Patent Application Laid-Open No. 1-26 discloses a composite ceramic composed of boron nitride, aluminum nitride and a Ca compound.
1279 discloses boron nitride, aluminum nitride and Ca.
And Japanese Patent Laid-Open Nos. 1-252584 and 1-305862 disclose composite ceramics composed of a Y compound and aluminum nitride, boron nitride and 3CaO.Al 2.
O 3 Hei a composite ceramic composed of 3-252
Japanese Patent No. 367 has been proposed. Further, as a ceramic for molten iron-based alloy, there is a composite ceramic composed of boron nitride, aluminum nitride and yttrium oxide as proposed in JP-A-4-332831 and JP-B-5-8141.
【０００６】窒化アルミニウムは高熱伝導性材料として
良く知られているが、構造材料としてもアルミナと同程
度の硬さを持ち耐摩耗性に優れ、溶融金属に対する耐溶
損性が優れるため、窒化硼素と複合化することにより、
耐熱衝撃性、耐摩耗性に優れ、溶融金属に対する耐溶損
性が良好な材料となる。Aluminum nitride is well known as a material having high thermal conductivity, but as a structural material, it has the same hardness as alumina, has excellent wear resistance, and has excellent corrosion resistance against molten metal. By compounding,
It is a material that has excellent thermal shock resistance and wear resistance, and has good resistance to melting damage to molten metal.
【０００７】[0007]
【発明が解決しようとする課題】しかし、窒化硼素と窒
化アルミニウムからなる複合セラミックスは窒化硼素中
に含まれる酸化硼素や酸化イットリウム等の希土類酸化
物を焼結助剤として使用しているため溶融金属中に長時
間浸漬させると溶融金属とそれらの酸化物からなる複合
酸化物が濡れ、そこから溶融金属が浸食し溶損に至る
か、あるいは溶融金属中からセラミックスを取り出した
際、金属がセラミックスと付着し、その金属を剥離する
とセラミックスの方が破壊されるという問題をかかえて
いた。However, since the composite ceramics composed of boron nitride and aluminum nitride uses a rare earth oxide such as boron oxide or yttrium oxide contained in boron nitride as a sintering aid, it is a molten metal. If it is immersed in the molten metal for a long time, the molten metal and the complex oxide consisting of these oxides get wet, and the molten metal erodes from it, leading to melting loss, or when the ceramic is taken out from the molten metal, the metal becomes the ceramic. The problem was that if the metal adhered and the metal was peeled off, the ceramic would be destroyed.
【０００８】そこで溶融金属用構造部材として用いる場
合は耐溶損性に優れるだけでは十分ではなく、溶融金属
に対し難付着性が必要であり、付着しなければ溶損する
こともなくなり、特に溶融金属中へ浸漬して使用される
部材では有効である。溶融金属に対する難付着性とは、
セラミックスを溶融金属中に浸漬させた後、取り出した
時にセラミックス上に金属が付着していないこと、付着
していたとしてもセラミックスを破壊することなく容易
に剥離できることである。易付着性の場合や剥離が困難
な場合は、セラミックスが溶損するか、セラミックスが
破壊され、そのセラミックスが溶融金属中に混入し金属
の特性が劣化したり、セラミックスの繰り返し使用が困
難になるという問題がある。Therefore, when it is used as a structural member for molten metal, it is not enough to have excellent melting resistance, and it is necessary to have a poor adhesion property to the molten metal. It is effective for members used by being immersed in What is difficult adhesion to molten metal?
After the ceramic is dipped in the molten metal and then taken out, the metal is not adhered to the ceramic, and even if the metal is adhered, the ceramic can be easily peeled without breaking. In the case of easy adhesion or when peeling is difficult, the ceramic may be melted or destroyed, and the ceramic may mix into the molten metal to deteriorate the characteristics of the metal, or the repeated use of the ceramic becomes difficult. There's a problem.
【０００９】そこで、耐熱衝撃性および単に溶融金属に
対する耐溶損性に優れるだけでなく溶融金属に対し優れ
た難付着性を示す複合セラミックス焼結体の開発が強く
望まれていた。したがって、本発明は実用上十分な耐熱
衝撃性を備え、かつ溶融金属に対する耐溶損性および難
付着性に優れる複合セラミックス焼結体を提供すること
を目的とするものである。Therefore, there has been a strong demand for the development of a composite ceramics sintered body which is excellent not only in thermal shock resistance and erosion resistance to molten metal but also in excellent adhesion to molten metal. Therefore, it is an object of the present invention to provide a composite ceramics sintered body which has practically sufficient thermal shock resistance and is excellent in melting resistance and difficult adhesion to molten metal.
【００１０】[0010]
【問題を解決するための手段】本発明者等は、上記目的
を達成するため鋭意検討の結果、窒化アルミニウムと窒
化硼素と希土類酸化物および／またはアルカリ土類酸化
物からなる母材の表面にマグネシウム酸化物層を形成す
ることにより、金属溶湯中で用いてもクラックや割れが
発生せず実用上十分な耐熱衝撃性を備え、かつ溶融金属
に対する耐溶損性および難付着性に優れた複合セラミッ
クス焼結体が得られることを見い出した。Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that the surface of a base material composed of aluminum nitride, boron nitride, a rare earth oxide and / or an alkaline earth oxide is By forming a magnesium oxide layer, a composite ceramic that does not generate cracks or cracks even when used in molten metal, has practically sufficient thermal shock resistance, and is excellent in erosion resistance and difficult adhesion to molten metal. It was found that a sintered body was obtained.
【００１１】したがって、本発明は、窒化アルミニウム
３５〜８０ｗｔ％と窒化ホウ素１０〜６０ｗｔ％とＹを
含む希土類金属およびアルカリ土類金属の酸化物のうち
一種または二種以上を０．５〜２０ｗｔ％とからなる母
材の表面にマグネシウム酸化物からなる表面層を有する
複合セラミックス焼結体である。Ｙを含む希土類金属お
よびアルカリ土類金属の酸化物のうち一種または二種以
上のうち、酸化ディスプロシウムがより好ましい。ま
た、前記焼結体において酸化アルミニウムを２５ｗｔ％
以下含む焼結体としてもよい。Therefore, according to the present invention, 0.5 to 20 wt% of one or more oxides of rare earth metal and alkaline earth metal containing 35 to 80 wt% of aluminum nitride, 10 to 60 wt% of boron nitride and Y is contained. A composite ceramic sintered body having a surface layer made of magnesium oxide on the surface of a base material made of. Among the oxides of rare earth metals and alkaline earth metals containing Y, dysprosium oxide is more preferred among one or more oxides. Further, 25 wt% of aluminum oxide is contained in the sintered body.
It may be a sintered body containing the following.
【００１２】本発明の複合セラミックス焼結体は、融点
１０００℃以上の金属溶湯用部材として用いることがで
きる。金属溶湯用部材としては、測温用保護管、ブレー
クリング、浸漬ノズル等に適用することができる。ま
た、金属溶湯の中でも特に鉄系溶湯に対する難付着性に
優れるので鉄基合金溶湯用部材として用いることが望ま
しいが、Ｎｉ基合金、Ｃｏ基合金等の溶鋼用部材として
も用いることができる。The composite ceramics sintered body of the present invention can be used as a member for molten metal having a melting point of 1000 ° C. or higher. The metal melt member can be applied to a temperature measuring protective tube, a break ring, an immersion nozzle, or the like. Further, among metal melts, it is particularly preferable to use as a member for iron-based alloy melts because it has excellent adhesion to iron-based melts, but it can also be used as a member for molten steel such as Ni-base alloys and Co-base alloys.
【００１３】本発明の複合セラミックス焼結体の製造方
法は、従来から公知の方法でよく、例えば原料粉末をエ
タノールを分散媒としてボールミルにて混合し、得られ
たスラリーをスプレイドライヤーにて造粒し、その造粒
粉をＣＩＰあるいは一軸加圧による金型プレス等にて成
形し、窒素、アルゴン等の雰囲気中、１６００℃〜２０
００℃で０．５〜１０時間焼結することにより得ること
ができる。焼結は、常圧焼結、加圧焼結（ホットプレ
ス、ＨＩＰ等）のいづれでもよい。得られた焼結体は、
マグネシウム酸化物を分散させたスラリー中に浸漬する
かあるいはスラリーを塗布し、Ｎ2あるいはＡｒ雰囲気
中１４００〜２０００℃で０．５〜１時間焼結する。ま
た、成形体にマグネシウム酸化物層を形成した後、一体
焼結してもよい。The method for producing the composite ceramics sintered body of the present invention may be a conventionally known method. For example, raw material powders are mixed in a ball mill with ethanol as a dispersion medium, and the resulting slurry is granulated by a spray dryer. Then, the granulated powder is molded by a die press or the like by CIP or uniaxial pressurization, in an atmosphere of nitrogen, argon or the like, 1600 ° C to 20 ° C.
It can be obtained by sintering at 00 ° C. for 0.5 to 10 hours. The sintering may be either normal pressure sintering or pressure sintering (hot pressing, HIP, etc.). The obtained sintered body is
It is dipped in a slurry in which magnesium oxide is dispersed or coated with the slurry and sintered in an N 2 or Ar atmosphere at 1400 to 2000 ° C. for 0.5 to 1 hour. Alternatively, the magnesium oxide layer may be formed on the compact and then integrally sintered.
【００１４】[0014]
【作用】本発明は、窒化アルミニウムと窒化硼素と希土
類酸化物および／またはアルカリ土類酸化物からなる母
材により、耐熱衝撃性および溶融金属に対し優れた耐溶
損性を備え、かつ表面にマグネシウム酸化物層を形成す
ることにより、溶融金属に対し優れた難付着性を示す複
合セラミックス焼結体である。The present invention uses a base material composed of aluminum nitride, boron nitride, a rare earth oxide and / or an alkaline earth oxide, and has excellent thermal shock resistance and excellent erosion resistance against molten metal, and magnesium surface. By forming an oxide layer, it is a composite ceramic sintered body that exhibits excellent adhesion to molten metal.
【００１５】本発明において、マグネシウム酸化物層は
溶融金属に対する難付着性を得るために形成する。マネ
シウム酸化物としては、例えばＭｇＯやＭｇＡｌ2Ｏ4等
が含まれる。マグネシウム酸化物層は、１〜２００μｍ
の範囲で形成するのが望ましい。マグネシウム酸化物層
が１μｍ未満であると十分な難付着性が得られない。ま
た２００μｍを越えると緻密なマグネシウム酸化物層が
得られず、溶融金属が母材中に差し込み付着するとうい
う現象が生じる。In the present invention, the magnesium oxide layer is formed in order to obtain poor adhesion to molten metal. Examples of the manesium oxide include MgO and MgAl 2 O 4 . The magnesium oxide layer has a thickness of 1 to 200 μm.
It is desirable to form within the range. If the magnesium oxide layer is less than 1 μm, sufficient adhesion cannot be obtained. On the other hand, if it exceeds 200 μm, a dense magnesium oxide layer cannot be obtained, and a phenomenon that molten metal is inserted into the base material and adheres occurs.
【００１６】本発明複合セラミックス焼結体は、焼結体
表面のＭｇＡｌ2Ｏ4の存在によって、溶融金属に対する
難付着性を実現すると推測される。したがって、マグネ
シウム酸化物としてＭｇＡｌ2Ｏ4を用いることができ
る。また、マグネシウム酸化物としてＭｇＯを用いた場
合、焼結過程にＡｌ2Ｏ3と反応しＭｇＡｌ2Ｏ4が形成さ
れる。It is presumed that the composite ceramics sintered body of the present invention realizes difficult adhesion to molten metal due to the presence of MgAl 2 O 4 on the surface of the sintered body. Therefore, MgAl 2 O 4 can be used as the magnesium oxide. When MgO is used as the magnesium oxide, it reacts with Al 2 O 3 during the sintering process to form MgAl 2 O 4 .
【００１７】本発明の母材となる焼結体の組成限定理由
を以下に述べる。窒化アルミニウムは耐摩耗性及び耐溶
損性を得るために添加される。窒化アルミニウムが３５
ｗｔ％より少ないと耐摩耗性、耐溶損性が充分でなく、
８０ｗｔ％を越えると充分な耐熱衝撃性が得られない。
したがって、窒化アルミニウムは３５〜８０ｗｔ％とす
る。また、窒化アルミニウムが４０ｗｔ％以上であると
より耐摩耗性に優れる。さらに、６０ｗｔ％以下である
とより耐熱衝撃性に優れる。そのため４０〜６０ｗｔ％
の範囲で添加するのが最も望ましい。The reasons for limiting the composition of the sintered body as the base material of the present invention will be described below. Aluminum nitride is added to obtain wear resistance and erosion resistance. 35 aluminum nitride
If it is less than wt%, the wear resistance and melt resistance are not sufficient,
If it exceeds 80 wt%, sufficient thermal shock resistance cannot be obtained.
Therefore, the aluminum nitride content is 35-80 wt%. Further, when the aluminum nitride content is 40 wt% or more, the wear resistance is more excellent. Further, when it is 60 wt% or less, the thermal shock resistance is more excellent. Therefore, 40-60 wt%
It is most desirable to add in the range of.
【００１８】窒化硼素は耐熱衝撃性向上のために添加さ
れる。窒化硼素が１０ｗｔ％より少ないと充分な耐熱衝
撃性が得られず、さらには保護管のような内部が中空で
熱衝撃温度差が大きくなるような場合にはより充分な耐
熱衝撃性を得るために２０ｗｔ％以上の方がよい。６０
ｗｔ％を越えると窒化硼素が溶融金属と濡れ易くなり耐
溶損性が低下し、さらには特に耐摩耗性や強度が必要な
場合には４０ｗｔ％以下の方が良い。従って、窒化硼素
は１０〜６０ｗｔ％とし、さらに耐熱衝撃性を必要とす
る場合２０〜６０ｗｔ％、耐摩耗性や強度が必要な場合
１０〜４０ｗｔ％し、最も望ましいのは２０〜４０ｗｔ
％である。なお、窒化硼素は炭化硼素にて添加し、窒素
中雰囲気等の焼結により焼結体中に窒化硼素を形成させ
てもよい。また、窒化硼素中に微量の酸化硼素が含まれ
ていても、ＭｇＡｌ2Ｏ4が存在しない場合に比し、Ｍｇ
Ａｌ2Ｏ4が存在する場合の方が溶融金属に対する難付着
性が優れる。Boron nitride is added to improve thermal shock resistance. If the content of boron nitride is less than 10 wt%, sufficient thermal shock resistance cannot be obtained. Further, in the case where the inside of a protective tube is hollow and the thermal shock temperature difference becomes large, in order to obtain sufficient thermal shock resistance. It is better to be 20 wt% or more. 60
When the content is more than wt%, boron nitride is easily wetted with the molten metal to lower the melting resistance, and when the wear resistance and the strength are particularly required, the content is preferably 40 wt% or less. Therefore, the content of boron nitride is 10 to 60 wt%, 20 to 60 wt% when heat shock resistance is required, and 10 to 40 wt% when wear resistance and strength are required, and most preferably 20 to 40 wt%.
%. It should be noted that boron nitride may be added as boron carbide, and boron nitride may be formed in the sintered body by sintering in a nitrogen atmosphere or the like. Even if a small amount of boron oxide is contained in the boron nitride, the amount of Mg is less than that in the case where MgAl 2 O 4 is not present.
When Al 2 O 4 is present, it is more difficult to adhere to molten metal.
【００１９】前記複合セラミックス焼結体にＹを含む希
土類酸化物のうち一種または二種以上を０．５〜２０ｗ
ｔ％を添加した複合セラミックス焼結体としてもよい。
Ｙを含む希土類酸化物は焼結助剤であり、特に常圧焼結
する場合の緻密化に効果がある。０．５ｗｔ％では常圧
焼結により緻密な焼結体を得ることは困難で２０ｗｔ％
を越えると溶融金属と濡れ易くなり、難付着性が低下す
る。５ｗｔ％以上添加すれば常圧焼結による緻密化が更
に容易になる。また、難付着性低下を防止するために
は、添加量を１５ｗｔ％以下とすることが望ましい。0.5-20 w of one or more rare earth oxides containing Y is added to the composite ceramic sintered body.
A composite ceramics sintered body to which t% is added may be used.
The rare earth oxide containing Y is a sintering aid, and is particularly effective for densification when pressureless sintering is performed. At 0.5 wt%, it is difficult to obtain a dense sintered body by pressureless sintering, and 20 wt%
If it exceeds the range, it becomes easy to wet with the molten metal and the poor adhesion is deteriorated. If 5 wt% or more is added, densification by normal pressure sintering becomes easier. Further, in order to prevent the deterioration of the hard-to-adhere property, it is desirable that the addition amount be 15 wt% or less.
【００２０】Ｙを含む希土類酸化物としては焼結性、難
付着性の点から酸化ディスプロシウムが好ましい。ま
た、希土類酸化物の存在下においても、ＭｇＡｌ2Ｏ4が
存在しない場合に比し、ＭｇＡｌ2Ｏ4が存在する場合の
方が溶融金属に対する難付着性が優れる。As the rare earth oxide containing Y, dysprosium oxide is preferable from the viewpoints of sinterability and poor adhesion. Further, even in the presence of a rare earth oxide, compared to the case where MgAl 2 O 4 does not exist, towards the case of MgAl 2 O 4 are present excellent flame adhesion to the molten metal.
【００２１】本発明複合セラミックス焼結体は、酸化ア
ルミニウムを２５ｗｔ％以下添加することができる。酸
化アルミニウムは、焼結過程においてＭｇＯと反応して
ＭｇＡｌ2Ｏ4を生成する役割を果たすと共に、焼結助剤
としての役割を果たすが、２５ｗｔ％を越えて添加する
と耐熱衝撃性を低下させる。また酸化アルミニウムの添
加量を１０ｗｔ％以下とすれば、さらに良好な耐熱衝撃
性が得られる。酸化アルミニウムは窒化アルミニウムの
原料粉中に不可避的に含まれる酸素によってももたらさ
れる。焼結過程において酸素と窒化アルミニウムとから
生成された酸化アルミニウムは、添加した酸化アルミニ
ウムと同様の働きをしＭｇＡｌ2Ｏ4を生成するととも
に、焼結助剤としても働く。Aluminum oxide can be added to the composite ceramics sintered body of the present invention in an amount of 25 wt% or less. Aluminum oxide plays a role of reacting with MgO to form MgAl 2 O 4 in the sintering process and also plays a role of a sintering aid, but if added in excess of 25 wt%, the thermal shock resistance is lowered. Further, if the amount of aluminum oxide added is 10 wt% or less, even better thermal shock resistance can be obtained. Aluminum oxide is also provided by oxygen inevitably contained in the raw material powder of aluminum nitride. Aluminum oxide produced from oxygen and aluminum nitride in the sintering process acts like added aluminum oxide to produce MgAl 2 O 4 and also acts as a sintering aid.
【００２２】[0022]
【実施例】本発明を実施例をあげてさらに具体的に説明
するが、本発明はこれらの実施例に限定されるものでは
ない。 （実施例１）粒径０．２〜５μｍの窒化アルミニウム６
０ｗｔ％と粒径０．２〜１０μｍの窒化ホウ素３２ｗｔ
％と粒径０．２〜５μｍの酸化ディスプロシウム８ｗｔ
％を配合した原料粉末を、エタノールを分散媒としてボ
ールミルで混合し、スプレードライヤーにて作製した造
粒粉を一軸加圧プレスにて１ｔｏｎ／ｃｍ2で成形し、
得られた成形体にマグネシウム酸化物層を塗布した後、
焼結し、１５ （幅）×１００（長さ）×５（厚さ）ｍ
ｍの複合セラミックス焼結体を得た。焼結は窒素雰囲気
中、１８００℃×３ｈにて常圧焼結を行った。得られた
焼結体の耐熱衝撃性、耐溶損性および溶融金属に対する
難付着性について評価した。評価結果をマグネシウム酸
化物層の厚さと共に表１に示す。EXAMPLES The present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. (Example 1) Aluminum nitride 6 having a particle size of 0.2 to 5 μm
Boron nitride 32 wt% with 0 wt% and particle size 0.2-10 μm
% And dysprosium oxide with a particle size of 0.2-5 μm 8 wt
% Of the raw material powder mixed with ethanol as a dispersion medium in a ball mill, and the granulated powder produced by a spray dryer is molded at 1 ton / cm 2 by a uniaxial pressure press,
After applying a magnesium oxide layer to the obtained molded body,
Sintered, 15 (width) x 100 (length) x 5 (thickness) m
A composite ceramics sintered body of m was obtained. Sintering was carried out in a nitrogen atmosphere at 1800 ° C. for 3 hours under normal pressure. The resulting sintered body was evaluated for thermal shock resistance, melting resistance, and resistance to adhesion to molten metal. The evaluation results are shown in Table 1 together with the thickness of the magnesium oxide layer.
【００２３】耐熱衝撃性は、ＳＫＨ５１鋼を高周波溶解
炉中で溶解して１５２０℃の溶湯とした中に、作製した
焼結体を予熱無しにて直接浸漬し、１０分間浸漬後に取
りだした試料のクラックや破損の状況により評価した。
クラックや破損が無い試料が耐熱衝撃性に優れることを
示し、表には○と記す。Regarding the thermal shock resistance, the SKH51 steel was melted in a high-frequency melting furnace into a molten metal at 1520 ° C., and the produced sintered body was directly dipped without preheating, and after 10 minutes of dipping, a sample was taken out. It was evaluated based on the condition of cracks and damage.
Samples without cracks or damage show excellent thermal shock resistance, and are marked with "○" in the table.
【００２４】次に耐熱衝撃性評価においてクラックや破
損の無かった試料（耐熱衝撃性評価が○の試料）につい
て、耐溶損性および溶融金属に対する難付着性を評価し
た。高周波溶解炉中で溶解したＳＫＨ５１鋼を１５２０
℃に保持し、その溶湯中に試料を６０分間浸漬後に取り
出し、溶鉄やノロの付着を浸漬部分単位面積あたりの付
着量（mg/cm2）で評価することにより溶融金属に対する
難付着性を評価し、浸漬部分の浸漬前の体積に対する浸
漬後の溶損体積率（vol.%）を測定し耐溶損性を評価し
た。また、銅溶湯に対する難付着性を評価した。銅溶湯
中に試料を６０分間浸漬後に取り出し、銅の付着を浸漬
部分単位面積あたりの付着量（mg/cm2）を測定した。表
１において、難付着性は値の小さい試料が難付着性に優
れることを示し、耐溶損性は溶損率の小さい試料が耐溶
損性にすぐれることを示す。ＳＫＨ５１鋼に対する難付
着性を評価した試験片のうちＮｏ．３、６について試験
後の外観を図１（ａ）、（ｂ）に示す。Next, the samples that were not cracked or damaged in the thermal shock resistance evaluation (samples with a thermal shock resistance evaluation of ◯) were evaluated for melt damage resistance and poor adhesion to molten metal. 1520 SKH51 steel melted in a high frequency melting furnace
The sample is immersed in the molten metal for 60 minutes after being held at ℃, and the adhesion of molten iron or slag is evaluated by the adhesion amount per unit area of the immersion part (mg / cm 2 ) to evaluate the difficulty adhesion to molten metal. Then, the erosion resistance was evaluated by measuring the erosion volume ratio (vol.%) After the immersing part with respect to the volume before immersing. Further, the difficulty of adhering to the molten copper was evaluated. After the sample was immersed in the molten copper for 60 minutes, the sample was taken out, and the adhesion of copper was measured for the adhesion amount (mg / cm 2 ) per unit area of the immersed part. In Table 1, the sample having a small value of the poor adhesion property is excellent in the poor adhesion property, and the resistance to erosion is that the sample of the small erosion rate is excellent in the erosion resistance. No. out of the test pieces evaluated for poor adhesion to SKH51 steel. Appearances of the test pieces Nos. 3 and 6 after the test are shown in FIGS.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１より、本発明例および従来例共に耐熱
衝撃性に優れるが、従来例は付着量が本発明より多く、
また溶損率が大きくなっている。一方、本発明例である
試料ＮＯ．１〜４は付着量が少なく、また溶損率も０vo
l.%と溶損しておらず、溶融金属に対する難付着性およ
び耐溶損性に優れることがわかる。また、Ｎｏ．２の試
料をＸ線回折したところ、ＭｇＡｌ２ Ｏ4が表面層に
形成されていることが確認された。From Table 1, both the present invention example and the conventional example are excellent in thermal shock resistance, but the conventional example has a larger amount of adhesion than the present invention.
Also, the erosion rate is high. On the other hand, sample NO. 1 to 4 has a small amount of adhesion, and the melting loss rate is 0 vo
It can be seen that it is not melted as l.% and has excellent adhesion resistance to molten metal and excellent melt damage resistance. In addition, No. When the sample No. 2 was subjected to X-ray diffraction, it was confirmed that MgAl 2 O 4 was formed in the surface layer.
【００２７】（実施例２）粒径０．２〜５μｍの窒化ア
ルミニウムと粒径０．２〜１０μｍの窒化ホウ素と粒径
０．２〜５μｍの酸化ディスプロシウム（表２中にはRE
Oと記載）を配合した原料粉末を、エタノールを分散媒
としてボールミルで混合し、スプレードライヤーにて作
製した造粒粉を一軸加圧プレスにて１ｔｏｎ／ｃｍ2で
成形後、焼結し、１５ （幅）×１００（長さ）×５
（厚さ）ｍｍの複合セラミックス焼結体を得た。焼結は
窒素雰囲気中、１８００℃×３ｈにて常圧焼結を行っ
た。得られた焼結体の表面に粒径０．２〜１０μｍのＭ
ｇＯ・Ａｌ2Ｏ3ののスラリーを塗布して１６００℃×１
時間で焼結して厚さ１００μｍの表面層を有する複合セ
ラミックス焼結体を得、耐熱衝撃性、耐溶損性および溶
融金属に対する難付着性について実施例１と同様の方法
で評価した。評価結果を表２に示す。Example 2 Aluminum nitride having a particle size of 0.2 to 5 μm, boron nitride having a particle size of 0.2 to 10 μm, and dysprosium oxide having a particle size of 0.2 to 5 μm (in Table 2, RE
O)) was mixed with a ball mill using ethanol as a dispersion medium, and the granulated powder produced with a spray dryer was molded at 1 ton / cm 2 with a uniaxial pressure press and then sintered, 15 (Width) x 100 (length) x 5
A composite ceramics sintered body having a thickness of mm was obtained. Sintering was carried out in a nitrogen atmosphere at 1800 ° C. for 3 hours under normal pressure. On the surface of the obtained sintered body, M having a particle size of 0.2 to 10 μm
Apply a slurry of gO ・ Al 2 O 3 and apply 1600 ℃ × 1
A composite ceramics sintered body having a surface layer with a thickness of 100 μm was obtained by sintering for a period of time, and evaluated in the same manner as in Example 1 with respect to thermal shock resistance, erosion resistance and difficulty in adhering to molten metal. Table 2 shows the evaluation results.
【００２８】[0028]
【表２】 [Table 2]
【００２９】（実施例３）本発明複合セラミックス焼結
体を用いて図２に示す外寸１２０×１２０×２０ｍｍ、
内寸１００×１００×２０ｍｍのブレークリングを作製
した。本発明複合セラミックス焼結体は、３４wt.%窒化
ホウ素（粒径０．５〜１０μｍ）と７wt.%酸化ディスプ
ロシウム（粒径０．２〜５μｍ）と５９wt.%窒化アルミ
ニウム（粒径０．２〜５μｍ）とを配合した原料粉末
を、エタノールを分散媒としてボールミルで混合し、ス
プレードライヤーにて作製した造粒粉を静水圧プレスに
て１ｔｏｎ／ｃｍ2で 成形し、酸化マグネシウムを分散
させたスラリー中に浸漬した後、焼結した。焼結は窒素
雰囲気中、１８００℃×３ｈにて常圧焼結を行った。ま
た、表面層は３０μｍ形成した。得られたブレークリン
グを図３に示す水平連続鋳造機に適用し、１回９０分の
使用でＳＫＨ５１鋼の連続鋳造を行った。その結果、ブ
レークリングは鉄の付着もなく、得られた鋳片も良好で
あった。なお、図３は従来から一般的に用いられている
水平連続鋳造機の横断面図である。(Embodiment 3) Using the composite ceramic sintered body of the present invention, the outer dimensions shown in FIG. 2 are 120 × 120 × 20 mm,
A break ring having an inner size of 100 × 100 × 20 mm was produced. The composite ceramics sintered body of the present invention comprises 34 wt.% Boron nitride (particle size 0.5 to 10 μm), 7 wt.% Dysprosium oxide (particle size 0.2 to 5 μm), and 59 wt.% Aluminum nitride (particle size 0 2 to 5 μm) was mixed in a ball mill with ethanol as a dispersion medium, and a granulated powder produced by a spray dryer was molded at 1 ton / cm 2 by a hydrostatic press to disperse magnesium oxide. After being dipped in the prepared slurry, it was sintered. Sintering was carried out in a nitrogen atmosphere at 1800 ° C. for 3 hours under normal pressure. Further, the surface layer was formed with a thickness of 30 μm. The obtained break ring was applied to the horizontal continuous casting machine shown in FIG. 3, and continuous casting of SKH51 steel was performed by using it once for 90 minutes. As a result, the break ring was free of iron adhesion and the obtained slab was good. It should be noted that FIG. 3 is a cross-sectional view of a horizontal continuous casting machine which has been generally used conventionally.
【００３０】[0030]
【発明の効果】本発明により、実用上十分な耐熱衝撃性
を備え、かつ溶融金属に対する耐溶損性および難付着性
に優れる複合セラミックス焼結体が得られ、金属溶湯用
部材、特に鉄基合金溶湯用部材として最適な複合セラミ
ックス焼結体が得られた。EFFECTS OF THE INVENTION According to the present invention, a composite ceramics sintered body having practically sufficient thermal shock resistance, and excellent in melt damage resistance and poor adhesion to molten metal can be obtained. A composite ceramics sintered body most suitable as a member for molten metal was obtained.
【図１】（ａ）本発明複合セラミックス焼結体の浸漬試
験後の外観図である。 （ｂ）従来の複合セラミックス焼結体の浸漬試験後の外
観図である。FIG. 1 (a) is an external view of a composite ceramics sintered body of the present invention after an immersion test. (B) It is an external view of a conventional composite ceramics sintered body after an immersion test.
【図２】本発明複合セラミックス焼結体を用いたブレー
クリングの外観図である。FIG. 2 is an external view of a break ring using the composite ceramics sintered body of the present invention.
【図３】一般的な水平連続鋳造機を示す横断面図であ
る。FIG. 3 is a cross-sectional view showing a general horizontal continuous casting machine.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 35/583 35/581 Ｆ２７Ｄ 1/00 Ｎ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C04B 35/583 35/581 F27D 1/00 N
Claims (3)
化ホウ素１０〜６０ｗｔ％とＹを含む希土類酸化物のう
ち一種または二種以上を０．５〜２０ｗｔ％とからなる
母材の表面にマグネシウム酸化物からなる表面層を有す
ることを特徴とする複合セラミックス焼結体。1. Magnesium oxide on the surface of a base material composed of 35-80 wt% aluminum nitride, 10-60 wt% boron nitride, and 0.5-20 wt% of one or more rare earth oxides containing Y. A composite ceramics sintered body having a surface layer made of
下含む請求項１に記載の複合セラミックス焼結体。2. The composite ceramics sintered body according to claim 1, wherein the base material contains 25 wt% or less of aluminum oxide.
化ホウ素１０〜６０ｗｔ％とＹを含む希土類酸化物のう
ち一種または二種以上を０．５〜２０ｗｔ％とからなる
母材の表面にマグネシウム酸化物からなる表面層を有す
る複合セラミックス焼結体を用いたことを特徴とする鉄
基合金溶湯用部材。3. A magnesium oxide is formed on the surface of a base material comprising 35 to 80 wt% of aluminum nitride, 10 to 60 wt% of boron nitride, and 0.5 to 20 wt% of one or more rare earth oxides containing Y. A member for molten iron-based alloy characterized by using a composite ceramics sintered body having a surface layer made of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6187344A JPH0848586A (en) | 1994-08-09 | 1994-08-09 | Laminated ceramic sintered compact and member for molten iron-based alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6187344A JPH0848586A (en) | 1994-08-09 | 1994-08-09 | Laminated ceramic sintered compact and member for molten iron-based alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0848586A true JPH0848586A (en) | 1996-02-20 |
Family
ID=16204360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6187344A Pending JPH0848586A (en) | 1994-08-09 | 1994-08-09 | Laminated ceramic sintered compact and member for molten iron-based alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0848586A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010248054A (en) * | 2008-10-23 | 2010-11-04 | Ngk Insulators Ltd | Aluminum nitride-based composite material, method for manufacturing the same and member for semiconductor manufacturing apparatus |
-
1994
- 1994-08-09 JP JP6187344A patent/JPH0848586A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010248054A (en) * | 2008-10-23 | 2010-11-04 | Ngk Insulators Ltd | Aluminum nitride-based composite material, method for manufacturing the same and member for semiconductor manufacturing apparatus |
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