JPH05170514A - Highly antioxidizing carbon-containing refractory compounded with magnesium boride - Google Patents
Highly antioxidizing carbon-containing refractory compounded with magnesium borideInfo
- Publication number
- JPH05170514A JPH05170514A JP3339172A JP33917291A JPH05170514A JP H05170514 A JPH05170514 A JP H05170514A JP 3339172 A JP3339172 A JP 3339172A JP 33917291 A JP33917291 A JP 33917291A JP H05170514 A JPH05170514 A JP H05170514A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- refractory
- resistance
- magnesium boride
- oxidation
- 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.)
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- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、二次燃焼比率の高い転
炉，混銑車．溶融還元炉などの溶融金属容器の内張り、
連続鋳造設備等の溶融金属処理設備に好適に使用される
カーボン含有耐火物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a converter and a mixed pig car having a high secondary combustion ratio. Lining of molten metal container such as smelting reduction furnace,
The present invention relates to a carbon-containing refractory material suitably used for molten metal treatment equipment such as continuous casting equipment.
【０００２】[0002]
【従来の技術】溶融金属処理設備に適用される耐火物
は、一般的にいって、耐スポーリング性、耐スラグ侵食
性．耐摩耗性に優れていることが条件であり、この条件
を満たすために最近ではカーボンを含有した耐火性骨材
を主成分とする耐火物が主流となっている。例えば、製
鋼用転炉の内張り材としてはマグネシア・カーボン質耐
火物が、また、混銑車、溶融還元炉などではアルミナ・
ＳｉＣ・カーボン質、アルミナ・カーボン質耐火物が、
さらに、運続鋳造設備にはアルミナ・カーボン質耐火物
が広く使用されている。2. Description of the Related Art Refractories applied to molten metal processing equipment generally have spalling resistance and slag erosion resistance. It is a condition that it has excellent wear resistance, and in order to satisfy this condition, a refractory material containing carbon as a main component and a refractory aggregate has recently become mainstream. For example, magnesia-carbon refractory is used as a lining material for steelmaking converters, and alumina is used as a smelter and smelting reduction furnace.
SiC / carbon, alumina / carbon refractory
Furthermore, alumina-carbon refractories are widely used in continuous casting equipment.
【０００３】そして、最近の鋼の高級化に伴い、転炉，
混銑車などにおいて、精錬温度の上昇、二次燃焼比率の
上昇、また溶融還元やスクラップ溶解などの新しい操業
方法、及び取鍋・タンディッシュでの精錬法の採用など
によって、耐火物の使用条件を著しく過酷なものとして
いる。With the recent advancement of steel quality, converters,
For refining of refractory materials such as hot metal by increasing refining temperature, increasing secondary combustion ratio, new operating methods such as smelting reduction and scrap melting, and refining method for ladle and tundish. It is extremely harsh.
【０００４】カーボン含有耐火物の場合、このような条
件下においては、カーボンの酸化による耐火物の組織の
劣化に伴う特性の低下は避けられない。In the case of a refractory material containing carbon, under such conditions, deterioration of the properties due to deterioration of the structure of the refractory material due to oxidation of carbon is unavoidable.
【０００５】このカーボンの酸化を抑制する手段とし
て、Ａｌ，Ｍｇ，Ｃａ，Ｓｉなどの各種金属、ＳｉＣ，
Ｂ4 Ｃなどの炭化物、さらには、硼化金属化合物系を添
加することが効果があることが、特公昭６１−３０３号
公報，特公昭６１−５２１００号公報、特開昭６０−１
９５０６１号公報、特開昭６４−１４１７４号公報等に
開示されている。As means for suppressing the oxidation of carbon, various metals such as Al, Mg, Ca and Si, SiC,
The fact that the addition of a carbide such as B 4 C, and further a metal boride compound system is effective is disclosed in JP-B-61-303, JP-B-61-52100, and JP-A-60-1.
It is disclosed in Japanese Patent Laid-Open No. 95061 and Japanese Patent Laid-Open No. 64-14174.
【０００６】[0006]
【発明が解決しようとする課題】しかし、これらの添加
物では耐酸化性の向上には未だ不十分で、しかも、多量
の使用を必要とし、そのため、耐火物自体が有する耐ス
ポーリング性．耐食性などの特性を損なう場合も多い。
具体的には、Ａｌ，Ｓｉなどの各種金属の添加は耐酸化
性の付与効果が小さいため、強酸化性とするためには多
量の添加を必要とし、耐スポーリング性・耐食性を損な
うことになる。またＢ4 Ｃ，ＳｉＣなどの炭化物はその
分解により耐食性の低下や組織劣化を招き易い。さら
に、硼化金属化合物系の添加物を使用した材料は高温焼
成を必要とする焼結体であり、溶融金属精錬設備に付属
しての使用は特性面でも不適である。However, these additives are still insufficient for improving the oxidation resistance, and moreover, a large amount of them must be used. Therefore, the spalling resistance of the refractory itself must be improved. In many cases, properties such as corrosion resistance are impaired.
Specifically, addition of various metals such as Al and Si has a small effect of imparting oxidation resistance. Therefore, it is necessary to add a large amount in order to obtain strong oxidation, and spoiling spalling resistance and corrosion resistance. Become. Further, carbides such as B 4 C and SiC are apt to cause deterioration of corrosion resistance and deterioration of structure due to their decomposition. Furthermore, the material using the metal boride compound-based additive is a sintered body that requires high temperature firing, and its use as an accessory to a molten metal refining facility is unsuitable in terms of characteristics.
【０００７】本発明の目的は、比較的少量で耐酸化性・
耐食性の向上、耐火物の組織強化に有効な添加剤と、配
合組成を有する高耐酸化性カーボン含有耐火物を提供す
ることにある。The object of the present invention is to improve oxidation resistance and
An object of the present invention is to provide an additive effective for improving corrosion resistance and strengthening the structure of a refractory and a refractory containing carbon having a high oxidation resistance and having a composition.
【０００８】[0008]
【課題を解決するための手段】本発明の高耐酸化性カー
ボン含有耐火物は、黒鉛を主とするカーボン粉末３〜３
０重量％と、Ａｌ，Ｍｇ，Ｃａ，Ｓｉの中の一種または
二種以上あるいはそれらの合金を０．５〜７重量％と、
残部が耐火性骨材からなる配合物に、硼化マグネシウム
粉末を０．１〜２重量％含有することを特徴とする。The refractory material containing high oxidation resistant carbon according to the present invention comprises carbon powder 3 to 3 containing graphite as a main component.
0% by weight and 0.5 to 7% by weight of one or more of Al, Mg, Ca and Si or alloys thereof.
The composition is characterized in that 0.1 to 2% by weight of magnesium boride powder is contained in the composition whose balance is made of refractory aggregate.
【０００９】硼化マグネシウムはＭｇＢ2 、ＭｇＢ4 、
ＭｇＢ6 、ＭｇＢ12などの組成が存在し、いずれも使用
可能であるが、最も一般的なものはＭｇＢ2 である。こ
の硼化マグネシウム粉末は高純度で、反応性，均−分散
性の点から粒度は１００μｍ以下であることが望まし
く、添加量は０．１重量％より少ない場合、その機能が
十分に発揮されず、２重量％より多い場合、耐スポーリ
ング性が顕著に低下する。Magnesium boride includes MgB 2 , MgB 4 ,
There are compositions such as MgB 6 and MgB 12 , which can be used, but the most common one is MgB 2 . This magnesium boride powder is highly pure, and preferably has a particle size of 100 μm or less from the viewpoint of reactivity and uniform dispersibility. When the addition amount is less than 0.1% by weight, its function is not sufficiently exhibited. If it is more than 2% by weight, the spalling resistance is significantly reduced.
【００１０】併用される黒鉛を主とするカーボン粉末は
天然または人造黒鉛にコークス．カーボンブラック，メ
ソフェイズカーボンなどで、できるだけ高純度のものが
好ましいが、3 重量％より少ない場合、耐スポーリング
性と耐スラグ浸食性の低下が顕著となり、３０重量％よ
り多い場合、配合の充填性が極めて低下する。Carbon powder which is mainly used in combination with graphite is natural or artificial graphite. Carbon black, mesophase carbon, etc. with as high a purity as possible are preferable, but if it is less than 3% by weight, the deterioration of spalling resistance and slag erosion resistance becomes noticeable, and if it is more than 30% by weight, the composition is filled. Sex is extremely reduced.
【００１１】Ａｌなどの添加金属は０．５重量％より少
ない場合、強度面での効果が不十分で、７重量％より多
い場合、耐スポール性の低下が顕著となる。If the amount of the added metal such as Al is less than 0.5% by weight, the effect in terms of strength is insufficient, and if it is more than 7% by weight, the spall resistance is significantly deteriorated.
【００１２】使用する骨材はできるだけ高純度・高かさ
比重であることが好ましく、電融品，焼成品などが使用
可能である。The aggregate used is preferably as high in purity and bulk specific gravity as possible, and an electromelted product, a calcined product or the like can be used.
【００１３】本発明のカーボン含有耐火物は前述の整粒
したカーボン粉末，金属、耐火性骨材と硼化マグネシウ
ム粉末を所定量調整し、ピッチ、タール．フェノールレ
ジン，変性フエノ一ルレジン、シリコーンレジンなどの
バインダーを適量添加し、混練、成形、熱処理を施すこ
とにより得られる。The carbon-containing refractory of the present invention is prepared by adjusting a prescribed amount of the above-mentioned sized carbon powder, metal, refractory aggregate and magnesium boride powder to obtain pitch, tar. It is obtained by adding an appropriate amount of a binder such as phenol resin, modified phenol resin, silicone resin, and kneading, molding and heat treatment.
【００１４】熱処理の条件としては、不焼成カーボン含
有耐火物は１５０℃〜３００℃処理によって得られ、ま
た、５００℃〜１４００℃還元処理により焼成カーボン
含有耐火物が得られる。As the conditions of heat treatment, the unfired carbon-containing refractory material is obtained by treatment at 150 ° C. to 300 ° C., and the fired carbon-containing refractory material is obtained by reduction treatment at 500 ° C. to 1400 ° C.
【００１５】[0015]
【作用】カーボン含有耐火物中での硼化マグネシウムは
使用中に分解し、ボロン成分は外部、もしくはれんが内
部の酸素と反応しＢ2 Ｏ3 となり耐酸化性に寄与する。
特にＢ2 Ｏ3 は、耐火性骨材がＭｇＯの場合３ＭｇＯ−
Ｂ2 Ｏ3 や２ＭｇＯ−Ｂ2 Ｏ3 、またＡｌ2 Ｏ3 の場合
９Ａｌ2 Ｏ3 ・２Ｂ2 Ｏ3 のような高粘性生成物を形成
し、カーボンを含む他の原料を被覆し、耐酸化性を向上
させる。The magnesium boride in the carbon-containing refractory decomposes during use, and the boron component reacts with oxygen outside or inside the brick to form B 2 O 3 which contributes to oxidation resistance.
In particular, B 2 O 3 is 3MgO-when the refractory aggregate is MgO.
B 2 O 3 and 2MgO-B 2 O 3, also to form a highly viscous product, such as in the case of Al 2 O 3 9Al 2 O 3 · 2B 2 O 3, coating the another material containing carbon, acid Improve the chemical conversion.
【００１６】更に、酸素親和力の大きいマグネシウムは
速やかにＭｇＯが形成され、耐食性の向上と組織強化に
寄与する。また、大気中からの耐火物へ侵入してくる酸
素を耐火物表面近傍で捉え、いわゆる稼働表面部にＭｇ
Ｏ、あるいはスピネル層を形成し背後の耐火物組織を保
護する機能も有する。Furthermore, magnesium, which has a high oxygen affinity, forms MgO promptly, which contributes to the improvement of corrosion resistance and the strengthening of the structure. In addition, oxygen entering the refractory from the atmosphere is captured near the refractory surface, and Mg
It also has the function of forming O or a spinel layer to protect the refractory structure behind it.
【００１７】また、組織観察より加熱による焼結促進機
能も有していることが認められ、組織強化に一層寄与す
る。Further, from the observation of the structure, it is recognized that it also has a sintering promoting function by heating, which further contributes to the structure strengthening.
【００１８】これらの特性は硼化マグネシウムの比較的
少量の添加により顕著な効果が認められ、Ａｌなどの金
属、または／及び合金との併用により発揮される。These characteristics are recognized as a remarkable effect by adding a relatively small amount of magnesium boride, and are exhibited in combination with a metal such as Al and / or an alloy.
【００１９】[0019]
【実施例】以下、実施例に基づき硼化マグネシウム粉末
の効果について説明する。EXAMPLES The effects of the magnesium boride powder will be described below based on examples.
【００２０】ただし、本発明はこれらの実施例に限定さ
れるものではない。However, the present invention is not limited to these examples.
【００２１】実施例１ 本発明をマグネシア・カーボン質耐火物に適用し、これ
を転炉用内張り材として使用した実施例である。Example 1 This is an example in which the present invention is applied to a magnesia carbonaceous refractory and is used as a lining material for a converter.
【００２２】表１に示す原料組成にそれぞれ液状のフェ
ノール系バインダーを適量添加して、混練、真空フリク
ション成形，乾燥（９０℃×２４ｈｒ）、硬化処理（２
５０℃×１０ｈｒ）を施してマグネシア・カーボンれん
がを得た。An appropriate amount of liquid phenolic binder was added to each of the raw material compositions shown in Table 1, kneading, vacuum friction molding, drying (90 ° C. × 24 hr), and curing treatment (2
50 ° C. × 10 hr) was applied to obtain a magnesia carbon brick.
【００２３】原料組成中のマグネシアクリンカーは電融
マグネシアと焼結マグネシアを併用し、カーボンは純度
９８％の天然黒鉛を使用した。In the raw material composition, the magnesia clinker was a combination of fused magnesia and sintered magnesia, and the carbon was natural graphite having a purity of 98%.
【００２４】表１の比較例に示すように、硼化マグネシ
ウム粉末の添加量が規定量の範囲外であると、実施例に
比較して耐酸化性・耐食性・熱間強度・耐スポーリング
性いずれかに関して劣る。As shown in the comparative example of Table 1, when the addition amount of the magnesium boride powder is out of the specified range, the oxidation resistance, the corrosion resistance, the hot strength and the spalling resistance are higher than those of the examples. Inferior to either.
【００２５】[0025]
【表１】 実施例２ 本発明をアルミナ・ＳｉＣ・カーボン質耐火物に適用
し、混銑車用内張り材として使用した実施例を示す。[Table 1] Example 2 An example in which the present invention is applied to an alumina / SiC / carbon refractory and used as a lining material for a mixed pig car is shown.
【００２６】表２に示す原料組成にそれぞれ液状のフェ
ノール系バインダーを適量添加して、混練．真空フリク
ション成形，乾燥（９０℃×２４ｈｒ）、硬化処理（２
５０℃×１０ｈｒ）を施してアルミナ・ＳｉＣ・カーボ
ン質耐火物を得た。An appropriate amount of liquid phenolic binder was added to each of the raw material compositions shown in Table 2 and kneading. Vacuum friction molding, drying (90 ° C x 24hr), curing treatment (2
50 ° C. × 10 hours) to obtain an alumina / SiC / carbon refractory material.
【００２７】ここでアルミナクリンカーは電融アルミナ
を使用し、カーボンは純度９８％の天然黒鉛を使用し
た。Here, as the alumina clinker, fused alumina was used, and as the carbon, natural graphite having a purity of 98% was used.
【００２８】表２の比較例に示すように、硼化マグネシ
ウム粉末の添加量が規定量の範囲外であると、実施例に
比較して耐酸化性・耐食性・熱間強度・耐スポーリング
性いずれかに関して劣る。As shown in the comparative example in Table 2, when the addition amount of the magnesium boride powder is out of the specified range, the oxidation resistance, the corrosion resistance, the hot strength and the spalling resistance are higher than those of the examples. Inferior to either.
【００２９】[0029]
【表２】 実施例３ 本発明をアルミナ・カーボン質耐火物に適用し連続鋳造
設備の浸漬ノズルに使用した実施例を示す。[Table 2] Example 3 An example in which the present invention is applied to an alumina / carbon refractory and used as a dipping nozzle of a continuous casting facility will be described.
【００３０】表３に示す原料組成にそれぞれ液状のフェ
ノール系バインダーを適量使用して、成形用配合物を調
整して、アイソスタチックプレス、乾燥（９０℃×２４
ｈｒ）、還元熱処理（１０００℃×１０ｈｒ）を施し、
アルミナ・カーボン質浸潰ノズルを得た。An appropriate amount of a liquid phenolic binder was used for each of the raw material compositions shown in Table 3 to prepare a molding compound, which was isostatically pressed and dried (90 ° C. × 24).
hr), reduction heat treatment (1000 ° C. × 10 hr),
An alumina / carbon soaking nozzle was obtained.
【００３１】ここで骨材クリンカーは電融アルミナを使
用し、カーボンは純度９８％の天然黒鉛を使用した。Here, as the aggregate clinker, fused alumina was used, and as the carbon, natural graphite having a purity of 98% was used.
【００３２】表３の比較例に示すように、硼化マグネシ
ウム粉末の添加量が規定量の範囲外であると、実施例に
比較して耐酸化性・耐食性・熱間強度・耐スポーリング
性いずれかに関して劣る。As shown in the comparative example of Table 3, when the addition amount of the magnesium boride powder is out of the specified range, the oxidation resistance, corrosion resistance, hot strength and spalling resistance are higher than those of the examples. Inferior to either.
【００３３】[0033]
【表３】 以上、表１〜表３の実施例に示したカーボン含有耐火物
は総合的に耐酸化性・耐食性・熱間強度が向上する結果
が得られた。[Table 3] As described above, the carbon-containing refractory materials shown in the examples of Tables 1 to 3 were comprehensively improved in oxidation resistance, corrosion resistance and hot strength.
【００３４】[0034]
【発明の効果】カーボン含有耐火物を比較的少量の耐酸
化性付与剤の添加により、耐スポーリング性を何ら損な
うことなく、耐酸化性の向上と組織強化を同時に向上で
きる。By adding a relatively small amount of the oxidation resistance-imparting agent to the carbon-containing refractory, it is possible to simultaneously improve the oxidation resistance and the microstructure strengthening without impairing the spalling resistance.
Claims (1)
重量％と、Ａｌ，Ｍｇ，Ｃａ，Ｓｉの中の一種または二
種以上あるいはそれらの合金を０．５〜７重量％と、残
部が耐火性骨材とからなる配合物に、硼化マグネシウム
粉末を０．１〜２重量％含有せしめてなる高耐酸化性カ
ーボン含有耐火物。1. A carbon powder 3 to 30 mainly composed of graphite.
%, Al, Mg, Ca, Si, one or more kinds, or alloys thereof in an amount of 0.5 to 7% by weight, and the balance being refractory aggregate, magnesium boride powder. A refractory material containing carbon of 0.1 to 2% by weight, which has high oxidation resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3339172A JPH05170514A (en) | 1991-12-21 | 1991-12-21 | Highly antioxidizing carbon-containing refractory compounded with magnesium boride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3339172A JPH05170514A (en) | 1991-12-21 | 1991-12-21 | Highly antioxidizing carbon-containing refractory compounded with magnesium boride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05170514A true JPH05170514A (en) | 1993-07-09 |
Family
ID=18324923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3339172A Pending JPH05170514A (en) | 1991-12-21 | 1991-12-21 | Highly antioxidizing carbon-containing refractory compounded with magnesium boride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05170514A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118057A (en) * | 1993-10-22 | 1995-05-09 | Shinagawa Refract Co Ltd | Carbon-containing refractory |
-
1991
- 1991-12-21 JP JP3339172A patent/JPH05170514A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118057A (en) * | 1993-10-22 | 1995-05-09 | Shinagawa Refract Co Ltd | Carbon-containing refractory |
| JP2592219B2 (en) * | 1993-10-22 | 1997-03-19 | 品川白煉瓦株式会社 | Carbon containing refractories |
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