JPH04132655A - Mgo-cao-c-based refractory - Google Patents
Mgo-cao-c-based refractoryInfo
- Publication number
- JPH04132655A JPH04132655A JP2256473A JP25647390A JPH04132655A JP H04132655 A JPH04132655 A JP H04132655A JP 2256473 A JP2256473 A JP 2256473A JP 25647390 A JP25647390 A JP 25647390A JP H04132655 A JPH04132655 A JP H04132655A
- Authority
- JP
- Japan
- Prior art keywords
- cao
- clinker
- mgo
- weight
- slag
- 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000011819 refractory material Substances 0.000 claims description 4
- 235000012245 magnesium oxide Nutrition 0.000 abstract description 38
- 239000002893 slag Substances 0.000 abstract description 37
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000008022 sublimation Effects 0.000 abstract 2
- 238000000859 sublimation Methods 0.000 abstract 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 102
- 239000000292 calcium oxide Substances 0.000 description 58
- 235000012255 calcium oxide Nutrition 0.000 description 45
- 239000011449 brick Substances 0.000 description 33
- 229910052799 carbon Inorganic materials 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000029087 digestion Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000004901 spalling Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 102000006463 Talin Human genes 0.000 description 1
- 108010083809 Talin Proteins 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は高温度での低塩基度スラグに対する耐用性の
高いＭｇＯ−ＣａＯ−Ｃ系耐火物に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an MgO--CaO--C refractory having high resistance to low basicity slag at high temperatures.
〈従来の技術〉
近年、転炉をはじめ電気炉、取鍋、精錬鍋、ＲＨなどの
溶融金属容器の内張つれんがとしてＭｇ０−Ｃれんがが
広（使用されるようになってきた。<Prior Art> In recent years, Mg0-C bricks have come to be widely used as lining bricks for molten metal containers such as converters, electric furnaces, ladles, refining ladle, and RH.
また、最近では低塩基度スラグ下でのステンレスなどの
溶製用内張りれんがとしてＭｇＯ−ＣａＯ系れんがも一
部で使用されている。Recently, MgO--CaO bricks have also been used as lining bricks for melting stainless steel under low basicity slag.
〈発明が解決しようとする課題〉
このＭｇＯ−Ｃれんがもステンレス溶製の場合のように
超高温下での操業に加えて低塩基度スラグ下での操業が
加わると、スラグによる溶損、スラグや空気中の酸素に
よる酸化反応に加えて高温下においてマグネシアとカー
ボンとが反応し、その結果、還元されたマグネシウムが
気化飛散する現象（ＭｇＯ＋Ｃ−Ｃ０十ＭｇＴ ）が発
生（以下、マグネシア・カーボン反応という）し、組織
が劣化することが加わって激しく損耗するのである。<Problem to be solved by the invention> When this MgO-C brick is operated under low basicity slag in addition to ultra-high temperature operation as in the case of stainless steel melting, slag erosion and slag In addition to the oxidation reaction caused by oxygen in the air, magnesia and carbon react at high temperatures, and as a result, a phenomenon in which reduced magnesium vaporizes and scatters (MgO + C-C0 + MgT) occurs (hereinafter referred to as the magnesia-carbon reaction). ) and the tissue deteriorates, resulting in severe wear and tear.
このような苛酷な条件下での操業に対処するため、金属
粉末の添加（例えば、特開昭５５１０７７４９号公報な
ど）、高純度グラファイトの使用（例えば、特開昭５７
＝１８３３．５９号公報など）、電融マグネシアクリン
カ−の使用（例えば、特開昭５７−３４０７４号公報な
ど）などが行なわれている。しかし、このようなＭｇＯ
−、Ｃれんがの改良も、超高温下低塩基度スラグ下のよ
うな操業条件の苛酷化には十分ではなく、さらに高性能
なれんがの開発が強（望まれている。In order to cope with operations under such harsh conditions, the addition of metal powder (for example, Japanese Patent Application Laid-Open No. 55107749, etc.) and the use of high-purity graphite (for example, Japanese Patent Application Laid-Open No. 57-198)
1833.59, etc.), and the use of electrofused magnesia clinker (for example, Japanese Patent Laid-Open No. 57-34074, etc.). However, such MgO
Improvements in - and C bricks are not sufficient to cope with harsher operating conditions such as under ultra-high temperatures and low basicity slag, and there is a strong desire to develop bricks with even higher performance.
一方、特開昭６１−１４６７５５号公報に示される・よ
うなＭｇ０＝ＣａＯれんがは低塩基度スラグには強いが
、その反面耐消化性に弱く、かつスラグ中のＦｅ２０ａ
やＭ２Ｏ３成分の影響を受は易い欠点を有し、溶融金属
の操業方法によっては容器用内張りれんがとして使用に
は限界がある。On the other hand, Mg0=CaO bricks such as those shown in JP-A No. 61-146755 are strong against low basicity slag, but on the other hand, they have poor digestion resistance and Fe2a in the slag.
It has the disadvantage that it is easily influenced by molten metal and M2O3 components, and there are limits to its use as a container lining brick depending on the method of operating the molten metal.
〈課題を解決するための手段〉
このような溶融金属容器用内張りれんかに必要な条件と
しては、高温下で安定な材料であることに加えてスラグ
に対する耐食性の高い材料であることが必要であり、現
在のところやはりカーボンを含有したれんが以外には最
適な材料は見当たらない。特開昭６１−１４１６６３号
公報にはＭｇＯ−ＣａＯクリンカーとカーボンを組合わ
せたれんがが示されているが、このれんがでも高温下低
塩基度スラグに対する耐食性は十分ではない。<Means for solving the problem> The necessary conditions for such a lining brick for molten metal containers are that it is a material that is stable at high temperatures and has high corrosion resistance against slag. However, at present, there is no optimal material other than carbon-containing bricks. JP-A-61-141663 discloses a brick made of a combination of MgO--CaO clinker and carbon, but even this brick does not have sufficient corrosion resistance against low basicity slag at high temperatures.
そこで、本発明者らは低基度スラグに対する耐食性の高
い成分としてこのＣａＯに注目し、特定のＭｇＯ−Ｃａ
Ｏクリンカーとカーボンとを組合わせてこの発明を完成
させたものである。Therefore, the present inventors focused on this CaO as a component with high corrosion resistance against low-base slag, and
This invention was completed by combining O clinker and carbon.
即ち、この発明はＣａＯ含有量が１〜１０重量％で、ペ
リクレス結晶粒の大きさが１５０ａｍ以上であり、ペリ
クレス結晶粒界にＣａＯが分布した構造を有するＭｇＯ
−ＣａＯクリンカー３０〜７０重量％とマグネシアクリ
ンカ−７０〜３０重量％との混合物１００重量部に対し
て炭素材料３〜４０重量部を添加したＭｇＯ−ＣａＯ−
Ｃ系耐火物を提供するものである。That is, the present invention uses MgO having a CaO content of 1 to 10% by weight, a Pericles crystal grain size of 150 am or more, and a structure in which CaO is distributed at the Pericles grain boundaries.
-MgO-CaO- in which 3-40 parts by weight of carbon material is added to 100 parts by weight of a mixture of 30-70% by weight of CaO clinker and 70-30% by weight of magnesia clinker.
It provides C-based refractories.
〈作用〉
ＣａＯ成分を含有する材料としては、合成ドロマイトク
リンカ−１天然ドロマイトクリンカ−あるいはカルシア
クリンカ−等が知られているが、これらのクリンカー中
ではＣａＯ成分は粒として分布しており、スラグ中の［
’ｅ ２０３やＭ２Ｏ３などの成分と反応して低融点物
質を生成し溶損してしまう。<Function> Synthetic dolomite clinker, natural dolomite clinker, calcia clinker, etc. are known as materials containing CaO components, but in these clinkers, the CaO component is distributed as particles, and is not present in the slag. of[
'e Reacts with components such as 203 and M2O3 to produce low melting point substances, resulting in melting loss.
一方、マグネシアクリンカー中のＭｇＯは低塩基度スラ
グとはスラグ中の５ｉ０２成分と反応して、やはり低融
点物質を生成し溶損してしまうのである。この場合、特
にＭｇＯ粒界が溶損される。さらに、ＭｇＯと炭素質材
料とが共存すると、１８００℃以上の温度では酸化雰囲
気中であってもマグネシア・カーボン反応が顕著となり
損耗が加速される。On the other hand, MgO in the magnesia clinker reacts with the 5i02 component in the low basicity slag to produce a low melting point substance, resulting in melting loss. In this case, especially the MgO grain boundaries are eroded. Furthermore, when MgO and carbonaceous material coexist, the magnesia-carbon reaction becomes noticeable even in an oxidizing atmosphere at temperatures of 1800° C. or higher, accelerating wear.
この発明のＭｇＯ−ＣａＯクリンカーはペリクレス結晶
粒界にＣａＯを配し、ペリクレス結晶粒子なＣａＯの網
状の架橋構造によって結びつけた構造を持つものである
。ＣａＯがＭｇＯ粒界に存在するためスラグ中の５ｉｆ
２成分とＭｇＯとの反応およびカーボンとＭｇＯとの反
応を防止し、またＣａＯが網状の架橋構造を持つため、
スラグ中のＦｅ２Ｏ３や５ｉｏ２成分と反応しに（くな
ると同時にＣａＯはＳｉＯ□と先に反応し、侵入したス
ラグ中に溶は込むとスラグの粘性が大きくなり、クリン
カー粒界やれんが内部へのスラグの浸透を防止する。The MgO--CaO clinker of the present invention has a structure in which CaO is arranged at Pericles crystal grain boundaries and connected by a network-like crosslinking structure of CaO, which is Pericles crystal grains. 5if in the slag because CaO exists at the MgO grain boundaries.
It prevents the reaction between the two components and MgO and the reaction between carbon and MgO, and since CaO has a network-like crosslinked structure,
As soon as CaO reacts with Fe2O3 and 5io2 components in the slag, it reacts with SiO□ first, and when it melts into the slag, the viscosity of the slag increases, causing the slag to enter the clinker grain boundaries and inside the brick. prevent the penetration of
また、ペリクレス結晶粒界にＣａＯが存在し、ペリクレ
ス結晶粒同志が直接接触していないため、ＣａＯのクリ
ープ特性のためクリンカーのスポーリングをも防止する
ことができる。Further, since CaO exists at the Pericles grain boundaries and the Pericles grains are not in direct contact with each other, it is also possible to prevent clinker spalling due to the creep property of CaO.
さらに、ＣａＯが存在することによってれんが表面にお
けるスラグの粘性を上げ、しかも低塩基度スラグとはな
じみが良いので、れんが表面へのスラグコートが良好で
ある。これによって、れんが内部へのスラグ侵入の防止
と同時にれんがの気孔を閉塞するので空気の侵入をも防
止し、カーボンの酸化を防ぎ、更に、密閉された気孔内
部ではマグネシア・カーボン反応によって生じた一酸化
炭素の分圧が上り、マグネシア・カーボン反応の進行を
阻止する。Furthermore, the presence of CaO increases the viscosity of the slag on the brick surface, and since it is compatible with low basicity slag, the slag coating on the brick surface is good. This prevents slag from entering inside the brick, and at the same time closes the pores of the brick, preventing air from entering and preventing carbon oxidation. The partial pressure of carbon oxide increases and prevents the magnesia-carbon reaction from proceeding.
しかし、これによってＭｇＯの反応が完全に抑えられる
わけではない。このＭｇＯのスラグ成分やカーボンとの
反応はペリクレス結晶の粒径を大きくすることによって
、その反応速度を低下させ見掛上小さくすることができ
る。また、タリン力−がスラグと接触すると、結晶粒よ
り粒界の方がスラグとの反応が速いため、粒界にスラグ
成分が侵入しペリクレス結晶粒間の結合が弱くなり、ス
ラグ中にペリクレス粒が流出して溶損の場合より損耗が
速やかに進行してしまう。従って、クリンカーはペリク
レス結晶粒径が太き（て粒界の少ないものはどスラグに
対する侵食抵抗性が大きいことになる。However, this does not completely suppress the reaction of MgO. This reaction of MgO with slag components and carbon can be reduced in appearance by decreasing the reaction rate by increasing the particle size of the Pericles crystals. In addition, when the Tallin force comes into contact with slag, grain boundaries react faster with slag than crystal grains, so slag components invade the grain boundaries, weakening the bond between Pericles crystal grains, and causing Pericles grains in the slag. is leaked out and the wear progresses more quickly than in the case of melting damage. Therefore, clinker with large Pericles grain size (and fewer grain boundaries) has greater resistance to erosion by slag.
ところが、ＣａＯの存在はクリンカー製造時のペリクレ
ス結晶の粒成長を抑制する作用があって、ＭｇＯ−Ｃａ
Ｏクリンカーの中のペリクレス結晶の結晶粒径はＣａＯ
含有量の増大と共に小さくなるのである。However, the presence of CaO has the effect of suppressing the grain growth of Pericles crystals during clinker production, and MgO-Ca
The grain size of the Pericles crystal in the O clinker is CaO
It becomes smaller as the content increases.
従って、特開昭６１−１４１６６３号公報に示されるよ
うなＣａＯ含有量の多いＭｇＯ−ＣａＯクリンカーでは
それほど損耗は低下しないのである。即ち、ＣａＯの含
有量は該クリンカーをれんがとして使用する場合には最
適な含有量のあることが判明したのである。Therefore, with the MgO--CaO clinker with a high CaO content as shown in JP-A-61-141663, wear does not decrease significantly. That is, it has been found that the CaO content is optimal when the clinker is used as a brick.
このようにペリクレス結晶粒の大きいクリンカーを使用
すると、れんが表面のマトリックス部分が先行溶損して
タリン力−粒が露出してもクリンカーの損耗が小さいた
めマトリックスへの楔効果で、マトリックスの溶損を抑
えると同時にスラグコートが良好となり、この点からも
損耗が抑制され、好都合である。When clinker with large Pericles crystal grains is used in this way, the matrix portion on the surface of the brick is pre-eroded, and even if the grains are exposed, the clinker wear is small, so the wedging effect on the matrix prevents the melting of the matrix. At the same time, the slag coating becomes good, and from this point of view as well, wear and tear is suppressed, which is advantageous.
一方、ＣａＯはＭｇＯと比較した場合、消化速度は格段
に大きく、れんがが間欠操業などで低温になった際には
ＣａＯの消化によりれんが組織が崩壊する危険性がある
。このＣａＯの消化を考えた場合、ＣａＯがペリクレス
結晶粒界に存在するため、ＣａＯが粒で分布する場合よ
りさらに消化し易（なっている。そのため、この発明に
おいてＭｇＯＣａＯクリンカーをできるだけ粗粒および
中粒部に使用し、微粉部には該クリンカーを使用せず、
代りにマグネシアクリンカ−を使用することが望ましい
。On the other hand, the digestion rate of CaO is much higher than that of MgO, and when bricks are exposed to low temperatures due to intermittent operation, etc., there is a risk that the brick structure will collapse due to the digestion of CaO. Considering the digestion of this CaO, since CaO exists at the Pericles grain boundaries, it is easier to digest than when CaO is distributed in grains.Therefore, in this invention, the MgOCaO clinker is used as coarse and medium grains as possible. The clinker is used in the grain part, and the clinker is not used in the fine powder part.
It is preferable to use magnesia clinker instead.
微粉部にマグネシアクリンカ−を使用すると、スラグに
よる微粉部の先行溶損とマグネシア・カーボン反応が心
配されるが、骨材として使用されたＭｇＯ−ＣａＯクリ
ンカー中のＣａＯによるれんがの焼結を促進する作用と
、上述のスラグコートの促進により微粉部の先行溶損と
マグネシア・カーボン反応は防止でき、れんが自体の損
耗はＭｇ０Ｃれんがの場合より著しく改善される。If magnesia clinker is used in the fine powder part, there are concerns about preliminary erosion of the fine part by slag and magnesia-carbon reaction, but the CaO in the MgO-CaO clinker used as aggregate promotes sintering of the bricks. By this action and the above-mentioned promotion of slag coating, advance erosion of the fine powder part and magnesia carbon reaction can be prevented, and the wear and tear of the brick itself is significantly improved compared to the case of Mg0C bricks.
〈発明の構成〉
この発明に用いられるＭｇＯ−Ｃａ’０クリンカーはク
リンカー中のＣａＯ含有量が１〜１０重量％、好ましく
は３〜７重量％であり、ＣａＯはペリクレス結晶粒界に
分布し、ペリクレスの結晶粒子をＣａＯの網状の架橋組
織によって結びつけた構造を持つものである。また、ペ
リクレス結晶粒子の大きさは１５０ＩＩｍ以上、好まし
くは２００ μｍ以上を必要とする。ＣａＯ含有量が１
重量％未満ではペリクレス結晶粒界をＣａＯが囲みきれ
ず、クリンカーの耐スポーリング性が低下し、またマグ
ネシア・カーボン反応の阻止も不十分となり好ましくな
い。<Structure of the invention> The MgO-Ca'0 clinker used in this invention has a CaO content of 1 to 10% by weight, preferably 3 to 7% by weight, and CaO is distributed at the Pericles grain boundaries, It has a structure in which Pericles crystal particles are linked by a network-like crosslinked structure of CaO. Further, the size of the Pericles crystal grains needs to be 150 IIm or more, preferably 200 μm or more. CaO content is 1
If it is less than % by weight, CaO cannot completely surround the Pericles grain boundaries, the spalling resistance of the clinker will be reduced, and the magnesia-carbon reaction will not be sufficiently inhibited, which is not preferable.
ＣａＯ含有量が１０重量％を越えるとペリクレス結晶粒
径が小さくなる。ペリクレス結晶粒子の大きさは１５０
１１ｍ未満ではスラグに対する溶損やマグネシア・カー
ボン反応が増加する。更に、このクリンカーの純度はＭ
ｇＯ＋ＣａＯが９８重量％以上であることが好ましい。When the CaO content exceeds 10% by weight, the Pericles crystal grain size becomes small. The size of Pericles crystal grain is 150
If the length is less than 11 m, erosion of the slag and magnesia-carbon reaction will increase. Furthermore, the purity of this clinker is M
It is preferable that gO+CaO is 98% by weight or more.
このＭｇＯ−ＣａＯクリンカーには製造方法によって焼
結体と電融体があり、焼結体でも使用可能であるが、焼
結体ではＣａＯが粒状となりやす（、この発明の目的に
は電融体の方が好ましい。There are two types of MgO-CaO clinker depending on the manufacturing method: a sintered body and a molten body, and the sintered body can also be used, but CaO tends to become granular in the sintered body (for the purposes of this invention, the molten body is not suitable for the purposes of this invention). is preferable.
この発明のれんかにはこのＭｇＯ−ＣａＯクリンカーを
用いるが、その使用量は３０〜７０重量％であり、残部
にはマグネシアクリンカ−を混合して用いる。ＭｇＯ−
ＣａＯクリンカーはできるだけ粗粒および中粒部に重点
的に使用し、マグネシアクリンカ−は微粉部に主として
使用する。こうすることにより、ＭｇＯ−ＣａＯクリン
カー中のＣａＯの消化を防止することができる。ＭｇＯ
−ＣａＯクリンカーの使用量が３０重量％未満では該ク
リンカーの効用が発揮されず、また、７０重量％を超え
ると該クリンカーを微粉部にも多量に使用するようにな
り、耐消化性の点で好ましくない。マグネシアクリンカ
−は通常耐火物に用いられるものが使用できるが、でき
ればＭｇＯ含有量９８重量％以上の高純度マグネシアク
リンカ−が望ましく、焼結マグネシアでもよいが、でき
れば電融マグネシアが耐溶損性の点で好ましい。This MgO-CaO clinker is used in the brick of the present invention, and the amount used is 30 to 70% by weight, and the remainder is mixed with magnesia clinker. MgO-
CaO clinker is used mainly in coarse and medium grains, and magnesia clinker is mainly used in fine grains. By doing so, digestion of CaO in the MgO-CaO clinker can be prevented. MgO
-If the amount of CaO clinker used is less than 30% by weight, the effectiveness of the clinker will not be exhibited, and if it exceeds 70% by weight, a large amount of the clinker will be used in the fine powder part, resulting in poor digestion resistance. Undesirable. Magnesia clinker that is normally used for refractories can be used, but if possible, high-purity magnesia clinker with an MgO content of 98% by weight or more is preferable.Sintered magnesia may also be used, but if possible, fused magnesia is preferable because of its corrosion resistance. It is preferable.
炭素材料としては天然黒鉛、人造黒鉛、各種コークス、
カーボンブラックなどを使用するほか、加熱によって炭
素結合を生じる熱硬化性樹脂やピッチなどのバインダー
で兼用することもできる。その使用量はＣに換算して、
ＭｇＯ−ＣａＯクリンカーとマグネシアクリンカ−の含
量１００重量部に対し、３〜４０＠＠％、好ましくは１
０〜２５重量％である。この使用量が４０重量％を超え
ると溶融金属流による摩耗が顕著となり、３重量％未満
ではれんがのスポーリング現象が見られず、いずれも耐
用が低下する。Carbon materials include natural graphite, artificial graphite, various types of coke,
In addition to using carbon black, it is also possible to use a binder such as thermosetting resin or pitch that forms carbon bonds when heated. The amount used is converted into C,
3 to 40@@%, preferably 1% to 100 parts by weight of MgO-CaO clinker and magnesia clinker.
It is 0 to 25% by weight. If the amount used exceeds 40% by weight, wear due to the molten metal flow becomes noticeable, while if it is less than 3% by weight, no brick spalling phenomenon is observed, and in either case, the durability decreases.
この発明のれんがの製造法は、ＭｇＯ−ＣａＯクリンカ
ー、マグネシアクリンカ−１炭素材料等の原料に熱硬化
性樹脂やピッチなどのバインダーを添加し、常法に従っ
て混練、成形、熱処理して製造される、更に、れんがの
酸化防止として金属粉末などの既知の材料を添加するこ
とは好ましいことである。The method for manufacturing bricks of the present invention is to add a binder such as a thermosetting resin or pitch to raw materials such as MgO-CaO clinker and magnesia clinker-1 carbon material, and then knead, mold, and heat-treat the bricks according to conventional methods. Furthermore, it is advantageous to add known materials such as metal powders to prevent oxidation of the bricks.
また、この発明のれんがは転炉、電気炉、取鍋、精錬鍋
、タンデイツシュなどの各種の溶融金属容器の内張り用
として広い範囲に使用できるものである。Furthermore, the bricks of the present invention can be used in a wide range of applications as linings for various molten metal containers such as converters, electric furnaces, ladles, smelting pots, and tundishes.
〈実施例〉 以下、実施例によってこの発明をより詳細に説明する。<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.
以下の実施例で使用されるＣａＯ含有クリンカーは（Ａ
） Ｍｇ０９４重量％、ＣａＯ３重量％、その他の成分
１重量％の組成でＣａＯがＭｇＯ粒界において網状の架
橋構造を有した電融のＭｇＯ−ＣａＯクリンカーであっ
て、ペリクレス結晶粒径範囲２００〜３００ ｐｍのも
の、（Ｂ） ＭｇＯ５４重量％、Ｃａ０４５重量％、そ
の他の成分１重量％の組成でＣａＯがＭｇＯ粒界で網状
の架橋構造を有している電融ＭｇＯＣａＯタリン力−で
ペリクレス結晶粒径が５０〜１００ ａｍのもの、（Ｃ
） Ｍｇ０７５重量％、ＣａＯ２４重量％、その他１重
量％の組成の焼成ＭｇＯ−にａ。The CaO-containing clinker used in the following examples was (A
) An electrofused MgO-CaO clinker with a composition of 94% by weight of Mg0, 3% by weight of CaO, and 1% by weight of other components, in which CaO has a network crosslinked structure at the MgO grain boundaries, and has a Pericles crystal grain size range of 200 to 300. pm, (B) Pericles crystal grain size with talin force, in which CaO has a network-like crosslinked structure at the MgO grain boundaries with a composition of 54% by weight of MgO, 45% by weight of Ca0, and 1% by weight of other components. is 50 to 100 am, (C
) Calcined MgO- with a composition of 75% by weight of Mg0, 24% by weight of CaO, and 1% by weight of other a.
クリンカーであってペリクレス結晶粒径が１０〜２０＋
＋ｍのものである。また、マグネシアクリンカ−は何れ
もＭｇ０９８重量％以上の高純度クリンカーを使用した
。Clinker with Pericles grain size of 10-20+
+m. Further, as the magnesia clinker, high purity clinker containing Mg098% by weight or more was used in all cases.
第１表に示す配合のれんがを常法に従って混練成形した
後、３００℃で熱処理した後の物性、および塩基度（Ｃ
ａ Ｏ／ ＳｉＯ□）１．３の転炉スラグによるスラグ
テストを１９００℃で５ ｈｒｓ行なった。The physical properties and basicity (C
A slag test using converter slag with a O/SiO□) 1.3 was conducted at 1900° C. for 5 hrs.
その結果も第１表に示した。The results are also shown in Table 1.
また、１０００℃で２ ｈｒｓ熱処理を行ない、５０℃
で飽和水蒸気中に８日間放置した消化試験の結果も同じ
（第１表に示した。In addition, heat treatment was performed at 1000℃ for 2 hrs, and 50℃
The results of a digestion test in which the samples were left in saturated steam for 8 days were also the same (shown in Table 1).
〈発明の効果〉
この発明のＣａＯ含有量が従来品より少なく、ペリクレ
ス結晶粒径の大きなＭｇＯ−ＣａＯクリンカーを用いた
ＭｇＯ−ＣａＯ−Ｃ系耐火物に実施例１〜４にみられる
ように、何れも高温下での低塩基度スラブに対して大き
な耐食性の低下はなく、耐消化性もよいことがわかる。<Effects of the Invention> As seen in Examples 1 to 4, the MgO-CaO-C refractory using the MgO-CaO clinker having a smaller CaO content and a larger Pericles crystal grain size than conventional products of the present invention, It can be seen that there is no significant decrease in corrosion resistance compared to low basicity slabs under high temperatures, and the digestion resistance is also good.
方、ＣａＯ含有量が多（、従ってペリクレス結晶粒径の
小さいＭｇＯ−ＣａＯクリンカーを用いた耐火物（比較
例１）では耐食性および耐消化性に劣り、ＣａＯが粒状
で存在するドロマイトクリンカ−を用いたれんが（比較
例２）では何れも低塩基度スラグに対する耐食性に劣り
、また、この発明のクリンカーであっても微粉域まで使
用すると（比較例５）、特に耐消化性が低下し、高温下
での低塩基度スラグに対するこの発明のれんがの優秀さ
が示された。On the other hand, refractories using MgO-CaO clinker with high CaO content (and therefore small Pericles crystal grain size (Comparative Example 1) have poor corrosion resistance and digestion resistance, and dolomite clinker with CaO present in granular form is inferior in corrosion resistance and digestion resistance. All of the bricks (Comparative Example 2) have poor corrosion resistance against low basicity slag, and even the clinker of the present invention, when used in the fine powder range (Comparative Example 5), has particularly low digestibility and is difficult to resist under high temperature conditions. The superiority of the bricks of this invention for low basicity slags was demonstrated.
Claims (1)
の大きさが１５０μｍ以上であり、ペリクレス結晶粒界
にＣａＯが分布した構造を有するＭｇＯ−ＣａＯクリン
カー３０〜７０重量％とマグネシアクリンカー７０〜３
０重量％との混合物１００重量部に対して、炭素材料３
〜４０重量部を添加したことを特徴とするＭｇＯ−Ｃａ
Ｏ−Ｃ系耐火物。MgO-CaO clinker 30-70% by weight and magnesia clinker 70-3 having a CaO content of 1-10% by weight, a Pericles crystal grain size of 150 μm or more, and a structure in which CaO is distributed at the Pericles grain boundaries.
3 parts by weight of the carbon material for 100 parts by weight of the mixture with 0% by weight
MgO-Ca characterized by adding ~40 parts by weight
O-C type refractories.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2256473A JPH04132655A (en) | 1990-09-25 | 1990-09-25 | Mgo-cao-c-based refractory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2256473A JPH04132655A (en) | 1990-09-25 | 1990-09-25 | Mgo-cao-c-based refractory |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04132655A true JPH04132655A (en) | 1992-05-06 |
Family
ID=17293126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2256473A Pending JPH04132655A (en) | 1990-09-25 | 1990-09-25 | Mgo-cao-c-based refractory |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04132655A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060128A (en) * | 2003-08-19 | 2005-03-10 | Nippon Steel Corp | Refractory |
| JP2012062233A (en) * | 2010-09-17 | 2012-03-29 | Nippon Steel Corp | Mgo-c-based refractory |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5935062A (en) * | 1982-08-23 | 1984-02-25 | 九州耐火煉瓦株式会社 | Magnesia carbon brick |
| JPS6096571A (en) * | 1983-10-31 | 1985-05-30 | 新日本化学工業株式会社 | Magnesia clinker |
| JPS63277557A (en) * | 1987-05-07 | 1988-11-15 | Kyushu Refract Co Ltd | Brick for lining vessel for fused metal |
| JPS63303854A (en) * | 1987-05-30 | 1988-12-12 | Nisshin Steel Co Ltd | Magnesia and carbon double-layered brick |
-
1990
- 1990-09-25 JP JP2256473A patent/JPH04132655A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5935062A (en) * | 1982-08-23 | 1984-02-25 | 九州耐火煉瓦株式会社 | Magnesia carbon brick |
| JPS6096571A (en) * | 1983-10-31 | 1985-05-30 | 新日本化学工業株式会社 | Magnesia clinker |
| JPS63277557A (en) * | 1987-05-07 | 1988-11-15 | Kyushu Refract Co Ltd | Brick for lining vessel for fused metal |
| JPS63303854A (en) * | 1987-05-30 | 1988-12-12 | Nisshin Steel Co Ltd | Magnesia and carbon double-layered brick |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060128A (en) * | 2003-08-19 | 2005-03-10 | Nippon Steel Corp | Refractory |
| JP4580155B2 (en) * | 2003-08-19 | 2010-11-10 | 新日本製鐵株式会社 | Continuous casting nozzle |
| JP2012062233A (en) * | 2010-09-17 | 2012-03-29 | Nippon Steel Corp | Mgo-c-based refractory |
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