JPH05238839A - Alumina-magnesia refractory for casting - Google Patents
Alumina-magnesia refractory for castingInfo
- Publication number
- JPH05238839A JPH05238839A JP4075769A JP7576992A JPH05238839A JP H05238839 A JPH05238839 A JP H05238839A JP 4075769 A JP4075769 A JP 4075769A JP 7576992 A JP7576992 A JP 7576992A JP H05238839 A JPH05238839 A JP H05238839A
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- Prior art keywords
- magnesia
- alumina
- resistance
- refractory
- corrosion resistance
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、耐用性に優れたアル
ミナ−マグネシア質流し込み耐火物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alumina-magnesia cast cast refractory having excellent durability.
【０００２】[0002]
【従来の技術】取鍋、真空脱ガス炉などの内張りあるい
は溶鋼処理ランスなどの保護耐火物として、アルミナを
主成分にした流し込み耐火物が使用されている。この耐
火物の損傷は、溶鋼・スラグによる溶損と、スラグ浸透
で組織変化した部位が加熱冷却を受けてスポーリング剥
離することで進行する。2. Description of the Related Art A cast refractory material containing alumina as a main component is used as a protective refractory material for a lining of a ladle, a vacuum degassing furnace, or a molten steel treatment lance. The damage of this refractory material progresses due to melting loss due to molten steel / slag and spalling peeling due to heating and cooling of the site whose structure has changed due to slag infiltration.
【０００３】そこで、このアルミナ質流し込み耐火物に
おいて、さらにマグネシアやスピネルを添加し、その材
質改善を図ることが提案されている。例えば特開昭６４
−８７５７７号公報の、アルミナ５０〜９０ｗｔ％、粒
径１ｍｍ以下のスピネル５〜４０ｗｔ％、アルミナセメ
ント３〜２５ｗｔ％よりなる材質、特開昭６３−２１８
５８６号公報の、マトリックス部にマグネシア微粉とア
ルミナ超微粉を配合する材質である。Therefore, it has been proposed to add magnesia and spinel to the alumina cast refractory to improve its material. For example, JP-A-64
No. 87577, a material composed of 50 to 90 wt% alumina, 5 to 40 wt% spinel having a particle diameter of 1 mm or less, and 3 to 25 wt% alumina cement, JP-A-63-218.
It is a material in which magnesia fine powder and ultrafine alumina powder are blended in the matrix portion of Japanese Patent No. 586.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
の改善においても１６００℃以上の高温雰囲気での使用
は稼働表面が焼結やスラグの浸透によってガラス化し、
十分な耐食性および耐スポーリング性が得られない。こ
の発明は、従来のアルミナ質流し込み耐火物の耐食性お
よび耐スポーリング性をさらに向上させることを目的と
する。However, even in these improvements, when used in a high temperature atmosphere of 1600 ° C. or higher, the operating surface is vitrified due to sintering or penetration of slag,
Sufficient corrosion resistance and spalling resistance cannot be obtained. An object of the present invention is to further improve the corrosion resistance and spalling resistance of conventional alumina cast refractories.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、アルミナ
質の流し込み耐火物に添加するマグネシアの粒度が耐ス
ラグ浸透性、耐食性、耐スポーリング性に与える影響に
ついて調査研究を重ねた。その結果、特定の組成と粒度
を有するマグネシアの使用が流し込み耐火物の材質改善
に効果があることを見出し、本発明を完成するに至った
ものである。Means for Solving the Problems The inventors of the present invention have conducted extensive research and studies on the effect of the particle size of magnesia added to an alumina cast refractory material on slag penetration resistance, corrosion resistance and spalling resistance. As a result, they have found that the use of magnesia having a specific composition and particle size is effective for improving the material quality of cast refractories, and have completed the present invention.
【０００６】本発明の特徴とするところは、ＭｇＯ純度
９７％ｗｔ以上で粒径０．１５ｍｍ以下のマグネシア２
〜１０ｗｔ％、ＭｇＯ純度９０ｗｔ％以上で粒径０．３
ｍｍ以上のマグネシア１〜３０ｗｔ％、残部がアルミナ
を主材としたアルミナ−マグネシア質流し込み耐火物で
ある。A feature of the present invention is that magnesia 2 having a MgO purity of 97% wt or more and a particle size of 0.15 mm or less.
-10 wt%, MgO purity 90 wt% or more, particle size 0.3
It is an alumina-magnesia pouring refractory having a magnesia of 1 mm to 30% by weight and a balance of alumina as a main material.
【０００７】本発明で使用するアルミナは、電融品、焼
結品のいずれでもよく、またそれらの併用でもよい。ア
ルミナの成分は不純物の少ないものがよく、Ａｌ2Ｏ3含
有量９７％以上のものが好ましい。The alumina used in the present invention may be either an electromelted product or a sintered product, or may be a combination thereof. Alumina preferably has a small amount of impurities, and preferably has an Al 2 O 3 content of 97% or more.
【０００８】マグネシアについても、電融品、焼結品の
いずれでもよく、またそれらの併用でもよい。その粒度
について、本発明では、粒径が０．１５ｍｍ以下のもの
と０．３ｍｍ以上のものを使用する。The magnesia may be either an electromelted product or a sintered product, or may be a combination thereof. Regarding the particle size, in the present invention, those having a particle size of 0.15 mm or less and 0.3 mm or more are used.
【０００９】０．１５ｍｍ以下のマグネシアは、マトリ
ックス部を構成する。このマグネシアのＭｇＯ純度は９
７ｗｔ％以上のものとする。不純物は主としてＳｉ
Ｏ2、ＣａＯ、Ｆｅ2Ｏ3である。ＭｇＯ純度を９７ｗｔ
％以上にする理由は、このマグネシアは粒径が小さく、
マトリックス部に存在するために、不純物が多いと耐火
物の耐火性が急激に低下するためである。Magnesia having a size of 0.15 mm or less constitutes the matrix portion. The MgO purity of this magnesia is 9
7 wt% or more. Impurities are mainly Si
O 2, CaO, is Fe 2 O 3. MgO purity of 97wt
% Is because the particle size of this magnesia is small,
This is because the presence of a large amount of impurities in the matrix portion causes a sharp decline in the fire resistance of the refractory material.
【００１０】また、この粒径０．１５ｍｍ以下のマグネ
シアは、微粉であることで比較的低温でアルミナと反応
し、スピネルを生成して、ＦｅＯを含有するスラグの浸
透を防止する。さらにこのスピネルを生成する際に体積
膨張し、収縮亀裂の防止に効果がある。この粒度が０．
１５ｍｍを超える場合は低温域ではスピネルが生成せ
ず、しかもスピネル生成速度が遅くなる結果、前記した
スラグ浸透および収縮亀裂を防止する効果が低下する。
その添加量は、２ｗｔ％未満ではスピネル生成量が少な
くなってスラグ浸透防止効果がなく、１０％ｗｔを超え
ると耐食性が低下する。Further, the magnesia having a particle size of 0.15 mm or less reacts with alumina at a relatively low temperature because it is a fine powder and produces spinel to prevent the penetration of the slag containing FeO. Furthermore, when this spinel is produced, it expands in volume and is effective in preventing shrinkage cracks. This grain size is 0.
If it exceeds 15 mm, spinel is not generated in the low temperature region, and the spinel generation rate becomes slower, so that the effect of preventing the above-mentioned slag permeation and shrinkage cracking decreases.
If the addition amount is less than 2 wt%, the amount of spinel produced is small and the effect of preventing slag penetration is not obtained, and if it exceeds 10 wt%, the corrosion resistance decreases.
【００１１】このように、粒径０．１５ｍｍ以下の微粉
のマグネシアは耐食性、耐スラグ浸透性に効果がある
が、反面、焼結性の促進による耐スポーリング性低下の
現象がが見られた。この改善手段として、本発明ではさ
らに粒径０．３ｍｍ以上のマグネシアを配合する。この
粗粒のマグネシアはアルミナと反応して外周にスピネル
を生成する。スピネルの生成の際の体積膨張で粗粒のマ
グネシアの周囲には微亀裂が発生し、これが加熱冷却時
の熱衝撃を分散吸収し、大きな亀裂の発生を抑制して耐
スポーリング性の低下を防止する。As described above, fine powder magnesia having a particle diameter of 0.15 mm or less is effective in corrosion resistance and slag penetration resistance, but on the other hand, a phenomenon of spalling resistance reduction due to accelerated sintering is observed. .. As a means for improving this, magnesia having a particle diameter of 0.3 mm or more is further compounded in the present invention. This coarse-grained magnesia reacts with alumina to form spinel on the outer periphery. Micro-cracks are generated around the coarse-grained magnesia due to volume expansion during spinel formation, which disperse and absorb the thermal shock during heating and cooling, suppressing the generation of large cracks and reducing the spalling resistance. To prevent.
【００１２】この粗粒のマグネシアについて、粒径が
０．３ｍｍ未満では反応性が高くなって耐スポーリング
性の効果がない。ＭｇＯ純度は９０ｗｔ％未満では反応
が早く、焼結が促進されて耐スポーリング性の効果がな
く、しかも低融物の生成で耐食性が低下する。また、そ
の割合は、１ｗｔ％未満では前記の効果がなく、３０ｗ
ｔ％を超えると耐食性が低下して好ましくない。With respect to this coarse-grained magnesia, if the grain size is less than 0.3 mm, the reactivity becomes high and the effect of spalling resistance is not obtained. If the MgO purity is less than 90 wt%, the reaction is fast, the sintering is promoted, the effect of spalling resistance is not obtained, and the corrosion resistance is lowered due to the formation of a low melt. If the ratio is less than 1 wt%, the above effect does not occur, and 30w
If it exceeds t%, the corrosion resistance decreases, which is not preferable.
【００１３】図１は、重量比でアルミナ：マグネシア＝
７５：２５のアルミナ−マグネシア質流し込み耐火物に
おいて、マグネシアの粒度と処理温度によるスピネルの
生成度を示したものである。微粉のマグネシアは比較的
低い温度でアルミナと反応してスピネルを生成する。粒
度の粗いマグネシアは生成速度が遅い。本発明はこのよ
うなマグネシアの粒度によるアルミナとの反応速度の差
を利用して材質の耐用改善を成したものである。すなわ
ち、前記でも示したように、微粉のマグネシアはスラグ
の浸透防止の効果を発揮し、粗粒のマグネシアは耐スポ
ーリング性の改善の役割を果たす。FIG. 1 shows a weight ratio of alumina: magnesia =
This is a graph showing the degree of spinel formation depending on the particle size of magnesia and the treatment temperature in a 75:25 alumina-magnesia cast refractory material. Finely divided magnesia reacts with alumina at relatively low temperatures to form spinels. Coarse-grained magnesia has a slow production rate. The present invention utilizes such a difference in reaction rate with alumina depending on the particle size of magnesia to improve the durability of the material. That is, as described above, fine powder magnesia exerts an effect of preventing slag penetration, and coarse magnesia plays a role of improving spalling resistance.
【００１４】図２は、粒径０．１５ｍｍ以下の微粉のマ
グネシアを配合したアルミナ−マグネシア質流し込み耐
火物において、マグネシア量と流し込み耐火物の耐食
性、耐スラグ浸透性の関係を示したグラフである。マグ
ネシアは２〜１０ｗｔ％で耐スラグ浸透性・耐食性に効
果的であることがわかる。FIG. 2 is a graph showing the relationship between the amount of magnesia and the corrosion resistance and slag permeation resistance of a cast refractory in an alumina-magnesia cast refractory containing a fine powder of magnesia having a particle size of 0.15 mm or less. .. It can be seen that magnesia is effective for slag penetration resistance and corrosion resistance at 2 to 10 wt%.
【００１５】図３は、粒径０．１５ｍｍ以下の微粉のマ
グネシアを配合したアルミナ−マグネシア質流し込み耐
火物において、マグネシアを６ｗｔ％配合したときのマ
グネシアのＭｇＯ純度と流し込み耐火物の耐食性・耐ス
ラグ浸透性の関係を示したグラフである。マグネシアの
ＭｇＯ純度が９７％未満になると耐食性の低下が大きい
ことがわかる。FIG. 3 shows the alumina-magnesia cast refractory containing fine powder of magnesia having a particle diameter of 0.15 mm or less. It is a graph which showed the permeability relationship. It can be seen that when the MgO purity of magnesia is less than 97%, the corrosion resistance is greatly reduced.
【００１６】図４は、粒径０．１５ｍｍ以下の微粉のマ
グネシアと粒径０．３ｍｍ以上の粗粒のマグネシアとを
配合したアルミナ−マグネシア質流し込み耐火物におい
て、粒径０．３ｍｍ以上の粗粒のマグネシアの配合割合
と流し込み耐火物の耐食性および耐スポーリング性の関
係を示したものである。このグラフから、粒径０．３ｍ
ｍ以上のマグネシアが１〜３０ｗｔ％の範囲において、
耐食性を低下させずに耐スポーリング性が改善されるこ
とが確認される。なお、図１〜４で示す耐スラグ浸透
性、耐食性、耐スポーリング性の試験は、後述の実施例
の欄で示した試験方法と同様に測定した。FIG. 4 shows an alumina-magnesia pouring refractory in which fine powder magnesia having a particle diameter of 0.15 mm or less and coarse magnesia having a particle diameter of 0.3 mm or more are mixed. It shows the relationship between the mixing ratio of magnesia in the grains and the corrosion resistance and spalling resistance of the cast refractory. From this graph, the particle size is 0.3m
In the range of 1 to 30 wt% of magnesia of m or more,
It is confirmed that the spalling resistance is improved without lowering the corrosion resistance. The tests of slag penetration resistance, corrosion resistance, and spalling resistance shown in FIGS. 1 to 4 were measured in the same manner as the test method shown in the section of Examples below.
【００１７】結合剤は従来の流し込み耐火物と同様のも
のを使用できる。たとえば、アルミナセメント、軽焼マ
グネシアなどの水和で硬化するもの、珪酸ソーダー、シ
リカゾル系などのゲル化で結合されるものなどである。
また、施工時の流動性を促進するための分散剤、解こう
剤など添加してもよいことも従来材質と同様である。さ
らに、本発明の効果を阻害しない範囲内で、ファイバー
類、金属粉、シリカ超微粉、アルミナ超微粉などを添加
してもよい。The binder may be the same as a conventional cast refractory material. For example, those which are hardened by hydration such as alumina cement and light burned magnesia, those which are bound by gelation such as sodium silicate, silica sol and the like.
In addition, it is also possible to add a dispersant, a deflocculant, etc. for promoting fluidity at the time of construction, similarly to the conventional material. Further, fibers, metal powder, ultrafine silica powder, ultrafine alumina powder, etc. may be added within a range that does not impair the effects of the present invention.
【００１８】施工は常法どおり、外掛けで４〜８ｗｔ％
程度の水分を添加し、型枠を用いて流し込み施工され
る。施工の際には充填性を向上させるため、一般には型
枠にバイブレーターを取付けるか、あるいは形耐火物中
に棒状バイブレーターを挿入する。[0018] The construction is carried out in the usual manner, and the outer coating is 4 to 8% by weight.
Water is added to some extent, and it is poured and constructed using a formwork. In order to improve the filling property at the time of construction, generally, a vibrator is attached to the form or a rod-shaped vibrator is inserted into the refractory.
【００１９】[0019]
【実施例】表１は、本発明実施例、比較例、従来例およ
びそれらの試験結果を示したものありる。各例は、いず
れも適量の施工水分を添加し、型枠内に振動鋳込み成形
し、２００℃×２４ｈｒで乾燥後、試験した。EXAMPLES Table 1 shows examples of the present invention, comparative examples, conventional examples and test results thereof. In each of the examples, an appropriate amount of construction water was added, vibration casting was performed in a mold, and the sample was dried at 200 ° C. for 24 hours and then tested.
【００２０】本発明実施例は、従来例および比較例と比
べて回転侵食試験における耐スラグ浸透性に優れ、ま
た、耐スポーリング性の改善にも有効である。The examples of the present invention are superior to the slag penetration resistance in the rotary erosion test as compared with the conventional examples and the comparative examples, and are also effective in improving the spalling resistance.
【００２１】試験方法は次のとおりである。 見掛比重・かさ比重・気孔率；ＪＩＳ−Ｒ２２０５に準
じる。 線変化率；ＪＩＳ−Ｒ２５５３に準じる。 耐スポーリング性；１６００℃の溶鋼中に５分間浸漬し
た後、大気中で空冷し、これをくり返し、剥落するまで
の耐用回数を求めた。 回転侵食試験；鋼片：転炉スラグ＝６０：４０（重量
比）を侵食剤とし、１７００℃×５時間の回転侵食試験
を行った。耐食性は、回転侵食後の溶損寸法を測定し
た。耐スラグ浸透性は、回転侵食後のスラグ浸透寸法を
測定した。The test method is as follows. Apparent specific gravity / bulk specific gravity / porosity; according to JIS-R2205. Line change rate: According to JIS-R2553. Spalling resistance: After dipping in molten steel at 1600 ° C. for 5 minutes, it was air-cooled in the atmosphere, and this was repeated, and the number of times of durability until peeling was determined. Rotational erosion test: Steel erosion: converter slag = 60:40 (weight ratio) was used as an erosion agent, and a rotational erosion test was performed at 1700 ° C for 5 hours. The corrosion resistance was measured by measuring the erosion size after rotary erosion. The slag penetration resistance was measured by measuring the slag penetration size after rotary erosion.
【００２２】ＲＨ式真空脱ガス装置の浸漬管の耐火物と
して、従来は従来例２の材質を使用して７０チャージの
寿命を得ていたが、本発明実施例２の材質に換えること
で、１３０チャージの寿命に延長した。As the refractory for the immersion pipe of the RH type vacuum degassing apparatus, the material of Conventional Example 2 has been conventionally used to obtain a life of 70 charges, but by changing to the material of Example 2 of the present invention, Extended to 130 charge life.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【発明の効果】このように、本発明のアルミナ−マグネ
シア質流し込み耐火物は、耐スラグ浸透性、耐食性およ
び耐スポーリング性に優れ、その結果、この耐火物が施
工される溶融金属容器や溶鋼処理装置の寿命延長に大き
く貢献することができる。As described above, the alumina-magnesia cast-in refractory material of the present invention is excellent in slag penetration resistance, corrosion resistance and spalling resistance, and as a result, a molten metal container or molten steel on which the refractory material is constructed. It can greatly contribute to the extension of the life of the processing device.
【図１】アルミナ−マグネシア質流し込み耐火物におい
て、マグネシアの粒度と処理温度によるスピネルの生成
度を示したグラフ。FIG. 1 is a graph showing the degree of spinel formation depending on the particle size of magnesia and the treatment temperature in an alumina-magnesia cast refractory material.
【図２】粒径０．１５ｍｍ以下の微粉のマグネシアを配
合したアルミナ−マグネシア質流し込み耐火物におい
て、マグネシア量と流し込み耐火物の耐食性、耐スラグ
浸透性の関係を示したグラフ。FIG. 2 is a graph showing the relationship between the amount of magnesia and the corrosion resistance and slag permeation resistance of a cast refractory in an alumina-magnesia cast refractory containing a fine powder of magnesia having a particle size of 0.15 mm or less.
【図３】粒径０．１５ｍｍ以下の微粉のマグネシアを配
合したアルミナ−マグネシア質流し込み耐火物におい
て、マグネシアを６ｗｔ％配合したときのマグネシアの
ＭｇＯ純度と流し込み耐火物の耐食性・耐スラグ浸透性
の関係を示したグラフ。[Fig. 3] In an alumina-magnesia cast refractory containing fine powder of magnesia having a particle diameter of 0.15 mm or less, the MgO purity of magnesia and the corrosion resistance and slag penetration resistance of the cast refractory when 6 wt% of magnesia is blended. A graph showing the relationship.
【図４】粒径０．１５ｍｍ以下の微粉のマグネシアと粒
径０．３ｍｍ以上の粗粒のマグネシアとを配合したアル
ミナ−マグネシア質流し込み耐火物において、粒径０．
３ｍｍ以上の粗粒のマグネシアの配合割合と流し込み耐
火物の耐食性および耐スポーリング性の関係を示したグ
ラフ。FIG. 4 shows an alumina-magnesia cast-in refractory material in which fine powder magnesia having a particle diameter of 0.15 mm or less and coarse-grained magnesia having a particle diameter of 0.3 mm or more are mixed.
The graph which showed the relationship of the corrosion resistance and spalling resistance of a casting refractory and the compounding ratio of coarse-grained magnesia of 3 mm or more.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西 浩一 兵庫県高砂市荒井町新浜１−３−１ ハリ マセラミック株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koichi Nishi 1-3-1 Niihama, Arai-cho, Takasago-shi, Hyogo Harima Ceramic Co., Ltd.
Claims (1)
５ｍｍ以下のマグネシア２〜１０ｗｔ％、ＭｇＯ純度９
０ｗｔ％以上で粒径０．３ｍｍ以上のマグネシア１〜３
０ｗｔ％、残部がアルミナを主材としたアルミナ−マグ
ネシア質流し込み耐火物。1. A MgO purity of 97 wt% or more and a particle size of 0.1.
Magnesia of 5 mm or less 2-10 wt%, MgO purity 9
Magnesia 1-3 with a particle size of 0.3 mm or more at 0 wt% or more
Alumina-magnesia cast refractory with 0 wt% and the balance being alumina as the main material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4075769A JP2552980B2 (en) | 1992-02-28 | 1992-02-28 | Alumina-magnesia cast refractory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4075769A JP2552980B2 (en) | 1992-02-28 | 1992-02-28 | Alumina-magnesia cast refractory |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05238839A true JPH05238839A (en) | 1993-09-17 |
| JP2552980B2 JP2552980B2 (en) | 1996-11-13 |
Family
ID=13585751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4075769A Expired - Lifetime JP2552980B2 (en) | 1992-02-28 | 1992-02-28 | Alumina-magnesia cast refractory |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2552980B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5720268A (en) * | 1980-07-11 | 1982-02-02 | Kouzou Kayama | Method of beautifying skin by rubbing |
| JPS5950081A (en) * | 1982-09-14 | 1984-03-22 | ハリマセラミック株式会社 | Castable refractories |
| JPS63218586A (en) * | 1987-03-05 | 1988-09-12 | 日本鋼管株式会社 | Monolithic refractories |
-
1992
- 1992-02-28 JP JP4075769A patent/JP2552980B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5720268A (en) * | 1980-07-11 | 1982-02-02 | Kouzou Kayama | Method of beautifying skin by rubbing |
| JPS5950081A (en) * | 1982-09-14 | 1984-03-22 | ハリマセラミック株式会社 | Castable refractories |
| JPS63218586A (en) * | 1987-03-05 | 1988-09-12 | 日本鋼管株式会社 | Monolithic refractories |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2552980B2 (en) | 1996-11-13 |
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