JPH0723250B2 - Refractory for continuous casting nozzle - Google Patents
Refractory for continuous casting nozzleInfo
- Publication number
- JPH0723250B2 JPH0723250B2 JP61146236A JP14623686A JPH0723250B2 JP H0723250 B2 JPH0723250 B2 JP H0723250B2 JP 61146236 A JP61146236 A JP 61146236A JP 14623686 A JP14623686 A JP 14623686A JP H0723250 B2 JPH0723250 B2 JP H0723250B2
- Authority
- JP
- Japan
- Prior art keywords
- continuous casting
- refractory
- casting nozzle
- graphite
- cao
- 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.)
- Expired - Lifetime
Links
- 238000009749 continuous casting Methods 0.000 title claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000011819 refractory material Substances 0.000 claims description 8
- 239000001506 calcium phosphate Substances 0.000 claims description 7
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 7
- 235000011010 calcium phosphates Nutrition 0.000 claims description 7
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229940043430 calcium compound Drugs 0.000 claims description 4
- 150000001674 calcium compounds Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910052845 zircon Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005350 fused silica glass Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は連続鋳造ノズル用耐火物に関し、特に連続鋳造
ノズルの長寿命化を図るものである。TECHNICAL FIELD The present invention relates to a refractory material for a continuous casting nozzle, and particularly, it is intended to extend the life of the continuous casting nozzle.
連続鋳造ノズル用耐火物としては、従来からアルミナ−
黒鉛質のものが知られている。このアルミナ−黒鉛質の
耐火物には、アルミナ及び黒鉛のほかに、黒鉛の酸化を
防止して長寿命化を図るために酸化防止剤が添加されて
いる。こうした酸化防止剤としては、金属シリコン、金
属アルミニウム、SiO、B4C、BN等から選択される少なく
とも１種が使用されている。As a refractory for continuous casting nozzles, conventionally, alumina-
Graphite materials are known. In addition to alumina and graphite, an antioxidant is added to the alumina-graphite refractory material in order to prevent oxidation of graphite and prolong the life of the graphite. As such an antioxidant, at least one selected from metallic silicon, metallic aluminum, SiO, B 4 C, BN and the like is used.
しかしながら、上述したいずれの酸化防止剤でも、長期
間にわたって黒鉛の酸化防止効果を維持することはでき
ず、連続鋳造ノズルを長寿命化するという目的が十分に
は達成できていなかった。However, none of the above-mentioned antioxidants can maintain the antioxidant effect of graphite for a long period of time, and the objective of extending the life of the continuous casting nozzle has not been sufficiently achieved.
すなわち、金属シリコンや炭化珪素が酸化されると、Si
O2が生成する。ところが、高温度下においてアルミナ−
黒鉛質の耐火物の内部はＣ−COの還元雰囲気となってお
り、生成したSiO2は還元され、SiOとなって蒸発揮散す
る。また、B4CやBNが酸化されると、低融点化合物であ
るB2O3等が生成して溶出してしまう。That is, when metallic silicon or silicon carbide is oxidized, Si
O 2 is generated. However, at high temperature, alumina-
The interior of the graphite refractory is in a reducing atmosphere of C-CO, and the produced SiO 2 is reduced and evaporated into SiO. Further, when B 4 C or BN is oxidized, B 2 O 3, which is a low melting point compound, is generated and eluted.
このような反応が起ると、連続鋳造ノズルの組織はポー
ラスとなり、しかも酸化防止剤が減少しているので、黒
鉛の酸化が促進され、結局連続鋳造ノズルの寿命が短く
なる。When such a reaction occurs, the structure of the continuous casting nozzle becomes porous, and since the antioxidant is reduced, the oxidation of graphite is promoted, which eventually shortens the life of the continuous casting nozzle.
本発明は上記問題点を解決するためになされたものであ
り、連続鋳造ノズルを長寿命化し得る耐火物を提供する
ことを目的とする。The present invention has been made to solve the above problems, and an object of the present invention is to provide a refractory that can extend the life of the continuous casting nozzle.
本発明の連続鋳造ノズル用耐火物は、アルミナ、黒鉛及
びシリカ源となる化合物を含有する連続鋳造ノズル用耐
火物において、CaOを0.1〜５重量％添加したことを特徴
とするものである。The refractory for a continuous casting nozzle of the present invention is characterized in that 0.1 to 5% by weight of CaO is added to the refractory for a continuous casting nozzle containing a compound serving as a source of alumina, graphite and silica.
なお、本発明において、主成分であるアルミナ、黒鉛及
びシリカ源となる化合物の組成は、アルミナ20〜60％、
黒鉛10〜40％、シリカ源となる化合物５〜30％であるこ
とが望ましい。すなわち、アルミナが20％未満では耐熱
温度の低下等により耐食性が劣り、一方60％を超えると
耐スポーリング性が低下する。また、黒鉛が10％未満で
は弾性率が大きくなって耐スポーリング性に劣り、一方
40％を超えると耐食性、耐酸化性が大幅に低下する。ま
た、シリカ源となる化合物が５％未満ではカルシウムシ
リケート等のガラスの生成量が少なく耐酸化性に劣り、
一方30％を超えると耐食性が低下する。In the present invention, the composition of the main component alumina, graphite and a compound serving as a silica source is 20 to 60% alumina,
It is desirable that the content of graphite is 10 to 40% and the compound serving as a silica source is 5 to 30%. That is, when the content of alumina is less than 20%, the corrosion resistance is poor due to a decrease in heat resistant temperature, and when it exceeds 60%, the spalling resistance is deteriorated. If the graphite content is less than 10%, the elastic modulus becomes large and the spalling resistance is poor.
If it exceeds 40%, the corrosion resistance and the oxidation resistance are significantly reduced. If the compound serving as a silica source is less than 5%, the amount of glass such as calcium silicate produced is small and the oxidation resistance is poor.
On the other hand, if it exceeds 30%, the corrosion resistance decreases.
このような連続鋳造ノズル用耐火物によれば、シリカ源
となる化合物が酸化されて生成したSiO2が更に耐火物内
部のＣ−CO雰囲気で還元されて生成したSiO（気相）
と、CaO（固相）とが反応してCaO−SiO2系のガラス成分
が生成する。このガラス成分はSiOの揮散によって気孔
が形成されたとしても、その気孔をただちに閉塞する作
用を有する。この結果、黒鉛の酸化を防止することがで
き、連続鋳造ノズルを長寿命化することができる。According to such a refractory for a continuous casting nozzle, SiO 2 produced by oxidizing a compound serving as a silica source is further reduced in a C-CO atmosphere inside the refractory and produced (gas phase).
Reacts with CaO (solid phase) to produce a CaO-SiO 2 -based glass component. Even if pores are formed by volatilization of SiO 2, this glass component has a function of immediately closing the pores. As a result, the oxidation of graphite can be prevented, and the life of the continuous casting nozzle can be extended.
本発明において、CaOの添加量を0.1〜５重量％としたの
は、0.1重量％未満では上述したガラス成分の生成によ
る黒鉛の酸化防止効果が得られず、一方５重量％を超え
ると耐熱性及び耐食性が低下するためである。In the present invention, the amount of CaO added is set to 0.1 to 5% by weight because when it is less than 0.1% by weight, the effect of preventing the oxidation of graphite due to the formation of the above glass components cannot be obtained, while when it exceeds 5% by weight, the heat resistance And the corrosion resistance is reduced.
本発明において、CaO源としては、所定量のCaOを含むよ
うな原料を用いてもよく、カルシウム化合物として添加
してもよい。このようなカルシウム化合物としては、リ
ン酸カルシウムを用いることが望ましい。これは、リン
酸カルシウム中のリンが黒鉛の表面活性を低下させる作
用を有し、より一層酸化防止効果を高めることができる
ためである。なお、リン酸カルシウムを用いた場合に
は、焼成中に次式 Ca3(PO4)2→3CaO＋P2O5 によりP2O5が蒸発してリン酸カルシウムに対して約54％
のCaOが生成する。In the present invention, as the CaO source, a raw material containing a predetermined amount of CaO may be used, or may be added as a calcium compound. It is desirable to use calcium phosphate as such a calcium compound. This is because phosphorus in calcium phosphate has a function of lowering the surface activity of graphite and can further enhance the antioxidant effect. When calcium phosphate is used, P 2 O 5 evaporates by the following formula Ca 3 (PO 4 ) 2 → 3CaO + P 2 O 5 during firing, and it is about 54% of calcium phosphate.
CaO is generated.
また、シリカ源となる化合物としては、電融シリカ、金
属シリコン、炭化珪素、ムライト、ジルコニアームライ
ト、カオリン、粘土又はジルコンサンドから選択される
少なくとも１種が用いられる。ただし、SiO2の還元によ
るSiOの揮散及びSiOとCaOとの反応によるガラス成分の
生成を長時間持続させて酸化防止効果を維持するため
に、シリカ源は多種類であることが望ましく、上記化合
物のうち２種以上を組合わせて用いるのが効果的であ
る。As the compound serving as the silica source, at least one selected from fused silica, metallic silicon, silicon carbide, mullite, zirconia nilite, kaolin, clay and zircon sand is used. However, in order to maintain the antioxidant effect by continuing the volatilization of SiO by the reduction of SiO 2 and the production of the glass component by the reaction of SiO and CaO for a long time, it is desirable that there are many kinds of silica sources. It is effective to use two or more of them in combination.
以下、本発明の実施例を説明する。 Examples of the present invention will be described below.
下記表に示す配合割合で原料を混合した後、焼成して実
施例１〜４及び比較例の連続鋳造ノズル用耐火物を製造
した。ここで、実施例１〜３ではCaO源としてリン酸カ
ルシウムを用い、実施例４ではCaO含有のジルコンサン
ドを用いた。なお、バインダーとしてはフェノールレジ
ン、ピッチを用いた。After mixing the raw materials in the mixing ratios shown in the following table, the raw materials were fired to manufacture refractory materials for continuous casting nozzles of Examples 1 to 4 and Comparative Example. Here, in Examples 1 to 3, calcium phosphate was used as the CaO source, and in Example 4, CaO-containing zircon sand was used. Phenolic resin and pitch were used as the binder.
これらの連続鋳造ノズル用耐火物について、見掛け気孔
率、カサ比重、圧縮強さ、曲げ強さ、灼熱減量及び酸化
抵抗性指数を調べた。これらの結果を下記表に併記す
る。なお、下記表中酸化抵抗性指数は、灼熱減量を100
として、表記の熱処理を行なったときの減少重量を指数
表示したものである。この値が小さいものほど酸化抵抗
性に優れている。For these refractory materials for continuous casting nozzles, the apparent porosity, bulk specific gravity, compressive strength, bending strength, ignition loss and oxidation resistance index were examined. The results are also shown in the table below. In addition, the oxidation resistance index in the table below is 100% for ignition loss.
Is the index of the weight loss when the above heat treatment is performed. The smaller this value, the better the oxidation resistance.
上記表から明らかなように、実施例１〜４の連続鋳造ノ
ズル用耐火物は、比較例の耐火物より800〜1400℃にお
ける酸化抵抗性指数が小さく、リン酸カルシウムによる
酸化防止効果が認められる。したがって、実施例１〜４
の耐火物を用いれば、連続鋳造ノズルを長寿命化するこ
とができる。 As is clear from the above table, the refractory materials for continuous casting nozzles of Examples 1 to 4 have a smaller oxidation resistance index at 800 to 1400 ° C. than the refractory materials of Comparative Examples, and the antioxidant effect of calcium phosphate is recognized. Therefore, Examples 1 to 4
If the refractory material of No. 1 is used, the life of the continuous casting nozzle can be extended.
以上詳述したように本発明によれば、連続鋳造ノズルを
長寿命化し得る耐火物を提供できるものである。As described in detail above, according to the present invention, it is possible to provide a refractory that can extend the life of the continuous casting nozzle.
Claims (4)
を含有する連続鋳造ノズル用耐火物において、CaOを0.1
〜５重量％添加したことを特徴とする連続鋳造ノズル用
耐火物。1. A refractory for a continuous casting nozzle containing alumina, graphite and a compound serving as a silica source, containing 0.1% of CaO.
A refractory material for a continuous casting nozzle, characterized by being added in an amount of up to 5% by weight.
ことを特徴とする特許請求の範囲第１項記載の連続鋳造
ノズル用耐火物。2. A refractory for a continuous casting nozzle according to claim 1, characterized in that CaO is added as a calcium compound.
ることを特徴とする特許請求の範囲第２項記載の連続鋳
造ノズル用耐火物。3. The refractory for a continuous casting nozzle according to claim 2, wherein the calcium compound is calcium phosphate.
シリコン、炭化珪素、ムライト、ジルコニアームライ
ト、カオリン、粘土又はジルコンサンドから選択される
少なくとも１種であることを特徴とする特許請求の範囲
第１項記載の連続鋳造ノズル用耐火物。4. A compound as a silica source is at least one selected from fused silica, metallic silicon, silicon carbide, mullite, zirconia nilite, kaolin, clay and zircon sand. Refractory for a continuous casting nozzle according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61146236A JPH0723250B2 (en) | 1986-06-24 | 1986-06-24 | Refractory for continuous casting nozzle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61146236A JPH0723250B2 (en) | 1986-06-24 | 1986-06-24 | Refractory for continuous casting nozzle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS632854A JPS632854A (en) | 1988-01-07 |
| JPH0723250B2 true JPH0723250B2 (en) | 1995-03-15 |
Family
ID=15403183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61146236A Expired - Lifetime JPH0723250B2 (en) | 1986-06-24 | 1986-06-24 | Refractory for continuous casting nozzle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0723250B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5370171B2 (en) * | 2010-01-19 | 2013-12-18 | 新日鐵住金株式会社 | Steel continuous casting method |
| KR102083536B1 (en) * | 2017-11-14 | 2020-03-02 | 주식회사 포스코 | Submerged nozzle and Method for treatment of molten steel |
-
1986
- 1986-06-24 JP JP61146236A patent/JPH0723250B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS632854A (en) | 1988-01-07 |
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