JPH04371353A - Calcium zirconate-containing nozzle for continuous casting - Google Patents
Calcium zirconate-containing nozzle for continuous castingInfo
- Publication number
- JPH04371353A JPH04371353A JP3146249A JP14624991A JPH04371353A JP H04371353 A JPH04371353 A JP H04371353A JP 3146249 A JP3146249 A JP 3146249A JP 14624991 A JP14624991 A JP 14624991A JP H04371353 A JPH04371353 A JP H04371353A
- Authority
- JP
- Japan
- Prior art keywords
- nozzle
- weight
- calcium zirconate
- graphite
- impurities
- 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.)
- Granted
Links
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000009749 continuous casting Methods 0.000 title claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 11
- 229910002976 CaZrO3 Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 239000011819 refractory material Substances 0.000 abstract description 6
- 230000000737 periodic effect Effects 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 description 27
- 239000010959 steel Substances 0.000 description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 238000004901 spalling Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910018404 Al2 O3 Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 235000019621 digestibility Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、鋼、とくにアルミニウ
ムを含有し、アルミナによるノズル孔の閉塞を起こし易
い鋼種や高清浄鋼の連続鋳造用ノズルの耐火物組成に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a refractory composition for continuous casting nozzles for steel, particularly steel types that contain aluminum and which are prone to clogging of nozzle holes by alumina, and high-cleanliness steel.
【０００２】0002
【従来の技術】鋼の連続鋳造用ノズルとしては、取鍋−
タンディッシュ間を結ぶロングノズル、タンディッシュ
−モールド間を結ぶタンディッシュノズル、及び浸漬ノ
ズルがあり、この中で特に長尺のロングノズル、浸漬ノ
ズルにおいては、耐スポーリング性、耐摩耗性、耐食性
に対する要求が厳しい。[Prior Art] As a nozzle for continuous casting of steel, ladle-
There are long nozzles that connect between tundishes, tundish nozzles that connect between tundishes and molds, and immersed nozzles.Among these, the long nozzles and immersed nozzles have particularly good spalling resistance, abrasion resistance, and corrosion resistance. There are strict requirements for
【０００３】この要求を満足させるものとしては、現在
ではアルミナ−シリカ−黒鉛質や、アルミナ−黒鉛質、
ジルコニア−黒鉛質のノズルが使用されており、高強度
、高耐食性を有するアルミナやジルコニアの骨材粒と耐
スポーリング性に優れたシリカ粒や黒鉛を組合せること
により、耐スポーリング性，耐摩耗性，耐食性等の要求
を満たしたものである。At present, materials that satisfy this requirement include alumina-silica-graphite, alumina-graphite,
A zirconia-graphite nozzle is used, and by combining alumina and zirconia aggregate particles, which have high strength and high corrosion resistance, with silica particles and graphite, which have excellent spalling resistance, it has excellent spalling resistance and resistance. It satisfies requirements such as wear resistance and corrosion resistance.
【０００４】しかしながら、アルミニウムを含有する鋼
にこれらのノズルを適用すると、鋼中のアルミニウムが
酸化されて生成するアルミナがノズルの表面に析出、堆
積しノズルの流路を塞いでしまう、いわゆるノズル閉塞
が起こりやすい。また不純物の少ない高清浄鋼に使用す
る場合、ノズルを形成する耐火物中のＡｌ，Ｓｉ等は鋼
に対して不純物であり、好ましくない。However, when these nozzles are applied to steel containing aluminum, alumina produced by oxidation of aluminum in the steel precipitates and accumulates on the surface of the nozzle, blocking the flow path of the nozzle, resulting in so-called nozzle blockage. is likely to occur. Furthermore, when using highly clean steel with few impurities, Al, Si, etc. in the refractory forming the nozzle are impurities to the steel and are not preferred.
【０００５】この問題の解決手段として、特開昭５７−
７１８６０号公報に、ノズルを形成する耐火物にＣａＯ
を含有させることが優れたノズル閉塞防止効果を奏する
ことが開示されている。[0005] As a means of solving this problem, Japanese Patent Application Laid-Open No. 1987-
No. 71860 discloses that CaO is added to the refractory material forming the nozzle.
It has been disclosed that the inclusion of the compound has an excellent effect of preventing nozzle clogging.
【０００６】これは、鋼の凝固温度より相当に低い液相
生成温度のＣａＯとＡｌ２ Ｏ３ の化合物を形成し、
これが溶鋼の中では、低融物として存在するので、析出
，堆積することがないことによるとされている。また、
ＣａＯを含有する非金属介在物は溶鋼の中で容易に浮上
し、鋼の中に不純物として取り込まれることが少なく、
ＣａＯを含有するノズル耐火物の表面では、Ａｌ２ Ｏ
３ が析出，堆積することなくＣａＯ−Ａｌ２ Ｏ３
化合物として溶鋼中に溶解し、しかも鋼の中に不純物と
して残存することが少ない効果も奏することができると
されている。[0006] This forms a compound of CaO and Al2O3 whose liquid phase formation temperature is considerably lower than the solidification temperature of steel.
This is said to be because this exists as a low-melting substance in molten steel, so it does not precipitate or accumulate. Also,
Nonmetallic inclusions containing CaO easily float in molten steel and are less likely to be incorporated into steel as impurities.
On the surface of the nozzle refractory containing CaO, Al2O
3 is precipitated and deposited without CaO-Al2 O3
It is said that it can be dissolved in molten steel as a compound, and also has the effect of being less likely to remain as an impurity in the steel.
【０００７】また、本願の発明者は、このＣａＯ添加に
よる効果を生かしつつ、しかも、その欠点である高い熱
膨張性と水分との反応性すなわち消化性を解消するため
に、それぞれＺｒＯ２ との化合物であるＣａＺｒＯ３
（カルシウムジルコネート）を配合して低膨張化し、
更に、周期率表のＩＩＩ 族及びＩＶ族の酸化物を０．
５〜５重量％添加することを提案し、一定の成果を挙げ
ている。[0007] In addition, the inventor of the present application has developed a compound with ZrO2 in order to take advantage of the effect of CaO addition and also eliminate its disadvantages of high thermal expansion and reactivity with moisture, that is, digestibility. is CaZrO3
(calcium zirconate) is blended to reduce expansion,
Furthermore, oxides of groups III and IV of the periodic table were added to 0.
We have proposed adding 5 to 5% by weight, and have achieved certain results.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、ＳｉＯ
２ ，ＴｉＯ２ ，Ａｌ２ Ｏ３ 等の周期率表のＩＩ
Ｉ 族及びＩＶ族の酸化物は、一般の鋼では問題にされ
ないが、高純度の高清浄鋼においては不純物となり、精
錬工程で純度を極限まで高くした溶鋼を連続鋳造する際
に、ノズルを形成する耐火物からそれらの不純物が混入
し好ましくない。[Problem to be solved by the invention] However, SiO
II of the periodic table of 2, TiO2, Al2 O3, etc.
Group I and IV oxides are not a problem in general steel, but they become impurities in high-purity, highly clean steel, and are used to form nozzles during continuous casting of molten steel that has been made to the highest purity in the refining process. These impurities are mixed in from the refractories used, which is undesirable.
【０００９】またＳｉＯ２ ，ＴｉＯ２ ，Ａｌ２ Ｏ
３ 等が多く含有されたカルシウムジルコネートをノズ
ルの原料として使用すると、ＣａＯ−ＳｉＯ２ −Ａｌ
２ Ｏ３ 系の低融物が生成し、ノズル耐火物の耐火性
を損ない、長時間の使用が困難となる。[0009] Also, SiO2, TiO2, Al2O
When calcium zirconate containing a large amount of
2 O3-based low-melting substances are generated, impairing the fire resistance of the nozzle refractory, and making it difficult to use it for a long time.
【００１０】本発明において解決すべき課題は、微量の
周期率表のＩＩＩ 族及びＩＶ族の酸化物と共にカルシ
ウムジルコネートを含有した耐火物からなるノズルにお
ける問題を解消し、アルミニウムを含有する鋼種や、高
清浄鋼に適用でき、長時間の耐用が可能なノズル用に適
した耐火物組成を提供することにある。The problem to be solved by the present invention is to solve the problem with nozzles made of refractories containing calcium zirconate as well as trace amounts of oxides of groups III and IV of the periodic table, and The object of the present invention is to provide a refractory composition suitable for a nozzle that can be applied to high-purity steel and has a long service life.
【００１１】[0011]
【課題を解決するための手段】本発明において使用する
カルシウムジルコネート系クリンカーについて、市販の
試薬から、ＣａＯ：３１重量％、ＺｒＯ２ ：６９重量
％となるように調整したカルシウムジルコネート系クリ
ンカーを１６００℃で焼成したものの消化性を調査した
結果以下の知見を得た。[Means for Solving the Problems] Regarding the calcium zirconate clinker used in the present invention, 1600% of the calcium zirconate clinker was prepared from a commercially available reagent and adjusted to have CaO: 31% by weight and ZrO2: 69% by weight. As a result of investigating the digestibility of materials fired at ℃, the following findings were obtained.
【００１２】■ 一般に市販の試薬中の不純物はＳｉ
，Ａｌ，Ｔｉ，Ｆｅの酸化物がほとんどであり、周期率
表のＩＩＩ 族及びＩＶ族の元素であるＢ，Ｓｃ，Ｇａ
，Ｇｅ，Ｓｎ，Ｐｂ等はほとんど含まれていない。これ
は天然のバデライトや石灰石系原料についても同様であ
る。■ Generally, impurities in commercially available reagents include Si.
, Al, Ti, and Fe, and B, Sc, and Ga, which are elements of group III and IV of the periodic table.
, Ge, Sn, Pb, etc. are hardly included. This also applies to natural baddellite and limestone-based raw materials.
【００１３】■ 不純物としてＳｉＯ２ ，ＴｉＯ２
，Ａｌ２ Ｏ３ の合量で０．２％以上を含んだ焼結
体は消化現象を示さないが、不純物がそれより少ない場
合は消化現象が見られる。■ SiO2, TiO2 as impurities
, Al2 O3 in a total amount of 0.2% or more does not show the digestion phenomenon, but when the impurities are less than that, the digestion phenomenon is observed.
【００１４】これにより、微量の添加物により消化現象
のないカルシウムジルコネートを得ることが可能である
ことの知見を得た。しかし、試薬を原料として使用する
と非常にコストの高いノズルとなってしまう。このため
、カルシウムジルコネートを電融法により製造すること
を検討した。[0014] As a result, it was found that it is possible to obtain calcium zirconate without digestive phenomena by adding a small amount of additives. However, if reagents are used as raw materials, the cost of the nozzle will be very high. For this reason, we considered producing calcium zirconate by an electrofusion method.
【００１５】従来の電融法によるカルシウムジルコネー
トは天然のバデライトと石灰石系の原料を混合し電気溶
融している。しかし、通常市販されているバデライトや
石灰石系の原料は不純物としてＳｉＯ２ ，ＴｉＯ２
，Ａｌ２ Ｏ３ ，Ｆｅ２ Ｏ３ を含み、その合量は
０．５〜１．５％程度である。従って単純に電融した場
合には、カルシウムジルコネート中のＳｉＯ２ ，Ｔｉ
Ｏ２ ，Ａｌ２Ｏ３ の合量が０．５％以上となり、従
来の技術と同程度になってしまう。[0015] Calcium zirconate produced by the conventional electrofusion method is produced by mixing natural baddeleyite and limestone raw materials and electromelting the mixture. However, normally commercially available baddellite and limestone-based raw materials contain impurities such as SiO2 and TiO2.
, Al2O3, and Fe2O3, and the total amount thereof is about 0.5 to 1.5%. Therefore, when simply electromelting, SiO2, Ti in calcium zirconate
The total amount of O2 and Al2O3 is 0.5% or more, which is about the same as that of the conventional technology.
【００１６】このため、本発明者は電融方法を種々検討
した。[0016] For this reason, the inventors have investigated various electrofusion methods.
【００１７】それは電融する際に溶融時間を従来よりも
長くすることにより、ＳｉＯ２ ，ＴｉＯ２ 等の酸素
結合力の弱い酸化物を還元揮散させてしまう方法である
。電融過程で溶解物を分解し、ＳｉＯ２ ，ＴｉＯ２
が減少した後に電融作業を終了すると、不純物の少ない
カルシウムジルコネートが得られる。また、溶解時間が
短い場合は溶解物に成分の偏析が生じるためにフリーの
ＣａＯが残留し消化の原因となってしまうが、この新方
法は溶解時間を長くすることにより、溶解物を均質にす
ることが可能であり、フリーのＣａＯを減少させること
が可能である。[0017] This is a method of reducing and volatilizing oxides with weak oxygen bonding strength, such as SiO2 and TiO2, by increasing the melting time during electric melting compared to the conventional method. During the electromelting process, the melt is decomposed to form SiO2, TiO2
If the electromelting operation is terminated after the amount of calcium zirconate is reduced, calcium zirconate with less impurities will be obtained. In addition, if the dissolution time is short, components will segregate in the melt, resulting in free CaO remaining and causing digestion; however, this new method makes the melt homogeneous by increasing the dissolution time. It is possible to reduce free CaO.
【００１８】しかし、この電融方法を実施する場合に、
原料中のＦｅ酸化物の量が多い場合は、電極カーボンの
損耗が大きく、良好な電融作業が困難となる。種々検討
した結果、Ｆｅ酸化物の含有量は０．５％以下が好まし
く、特にバデライトは充分に脱鉄したものを使用する必
要がある。なお、石灰石系の原料に不可避的に含まれる
ＭｇＯは電融作業の阻害要因にはならない。However, when implementing this electrofusion method,
If the amount of Fe oxide in the raw material is large, the electrode carbon will be worn to a large extent, making it difficult to perform a good electromelting operation. As a result of various studies, the content of Fe oxide is preferably 0.5% or less, and in particular, it is necessary to use baddeleyite that has been sufficiently iron-free. Note that MgO, which is unavoidably included in limestone-based raw materials, does not become an impediment to electromelting work.
【００１９】以上の検討結果により比較的安いコストで
カルシウムジルコネートを得ることが可能であり、得ら
れた原料クリンカーはＣａＯを１６〜３５重量％、Ａｌ
２ Ｏ３ 及びＳｉＯ２ 及びＴｉＯ２ の合量で０．
５〜０．２重量％、Ｆｅの酸化物０〜０．５ 重量％を
含有し、鉱物組成としてＣａＺｒＯ３ を主成分とする
カルシウムジルコネート系クリンカーとして規定される
。As a result of the above study, it is possible to obtain calcium zirconate at a relatively low cost, and the obtained raw material clinker contains 16 to 35% by weight of CaO and Al.
2 O3 and the total amount of SiO2 and TiO2 is 0.
It is defined as a calcium zirconate clinker containing 5 to 0.2% by weight and 0 to 0.5% by weight of Fe oxide, and whose mineral composition is mainly CaZrO3.
【００２０】すなわち、本発明に係る鋳造用ノズルは、
ＣａＯを１６〜３５重量％、Ａｌ２ Ｏ３ 及びＳｉＯ
２ 及びＴｉＯ２ の合量で０．５〜０．２重量％、Ｆ
ｅの酸化物０〜０．５重量％を含有し、鉱物組成として
ＣａＺｒＯ３ を主成分とするカルシウムジルコネート
系クリンカーを１０〜９５重量％、黒鉛５〜４０重量％
、その他の耐火性原料０〜５０重量％、金属シリコン１
重量％以下からなる耐火物組成からなること特徴とする
。That is, the casting nozzle according to the present invention has the following features:
16-35% by weight of CaO, Al2O3 and SiO
2 and TiO2 in a total amount of 0.5 to 0.2% by weight, F
Contains 0 to 0.5% by weight of oxides of e, 10 to 95% by weight of calcium zirconate clinker whose mineral composition is mainly CaZrO3, and 5 to 40% by weight of graphite.
, other refractory raw materials 0-50% by weight, metal silicon 1
It is characterized by being composed of a refractory composition consisting of less than % by weight.
【００２１】その他の耐火性原料として、耐食性を向上
させるために、ジルコニア，マグネシア等の添加も可能
である。[0021] As other refractory raw materials, zirconia, magnesia, etc. can also be added in order to improve corrosion resistance.
【００２２】かかる耐火組成物は有機質バインダーを用
いて混練し、成形後、非酸化性雰囲気で焼成することに
よってノズルを製造する。[0022] Such a refractory composition is kneaded with an organic binder, molded, and then fired in a non-oxidizing atmosphere to produce a nozzle.
【００２３】[0023]
【作用】このクリンカーを使用したノズルはＣａＯを含
有することにより、鋼中から析出するＡｌ２ Ｏ３ と
ＣａＯがノズルの表面で反応し、ＣａＯ−Ａｌ２ Ｏ３
化合物として溶鋼中に溶解することにより、ノズル閉
塞を防止することが可能である。しかも、鋼に対する不
純物としてのＡｌ２ Ｏ３ 及びＳｉＯ２ 及びＴｉＯ
２ の含有量が従来のノズルに比べてはるかに少なく、
高純度鋼の鋳造に対して有利である。[Operation] Because the nozzle using this clinker contains CaO, Al2 O3 precipitated from the steel and CaO react on the nozzle surface, forming CaO-Al2 O3.
By dissolving it as a compound in molten steel, it is possible to prevent nozzle clogging. Moreover, Al2 O3, SiO2 and TiO as impurities in steel
2 content is much lower than that of conventional nozzles,
It is advantageous for casting high purity steel.
【００２４】ノズルとしてのカルシウムジルコネート系
クリンカーの含有量については、１０重量％未満では充
分なノズル閉塞防止効果が得られず、９５重量％を超え
ると黒鉛の含有量が少なくなるために、耐スポーリング
性が低下する。カルシウムジルコネート系クリンカーの
含有量は１０〜９５重量％が適当である。Regarding the content of the calcium zirconate clinker in the nozzle, if it is less than 10% by weight, a sufficient nozzle clogging prevention effect cannot be obtained, and if it exceeds 95% by weight, the graphite content will decrease, so the durability will be reduced. Spalling property decreases. The content of the calcium zirconate clinker is suitably 10 to 95% by weight.
【００２５】次に黒鉛についてみると、黒鉛は耐スポー
リング性、耐スラグ性を付与するために使用するが、５
重量％未満では耐スポーリング性に劣り、４０重量％を
超えると溶鋼への溶解や、黒鉛の柔らかい性質が支配的
となり、摩耗による損耗の問題が発生する。黒鉛の含有
量は５〜４０重量％が適当である。黒鉛の種類としては
、鱗状黒鉛，土状黒鉛，キッシュ黒鉛等が使用可能であ
るが、耐スポーリング性，耐食性の観点から、天然の鱗
状黒鉛を使用することが好ましい。また、不純物の少な
い鱗状黒鉛を選定することも重要である。Next, regarding graphite, graphite is used to impart spalling resistance and slag resistance, but 5
If it is less than 40% by weight, the spalling resistance will be poor, and if it exceeds 40% by weight, it will dissolve into molten steel and the soft nature of graphite will become dominant, causing problems of wear and tear. The appropriate content of graphite is 5 to 40% by weight. As the type of graphite, scaly graphite, earthy graphite, quiche graphite, etc. can be used, but from the viewpoint of spalling resistance and corrosion resistance, it is preferable to use natural scaly graphite. It is also important to select graphite scales with few impurities.
【００２６】金属シリコンは黒鉛の酸化防止及びノズル
の強度発現のための焼結剤として添加される。この金属
シリコンは少量でもその効果は大きく、逆に過剰添加す
ると耐スポーリング性が低下する。含有量は必要最低限
にするべきであり、本発明では０〜１重量％とした。Metallic silicon is added as a sintering agent to prevent graphite from oxidizing and to increase the strength of the nozzle. Even a small amount of this metal silicon has a large effect, and conversely, if it is added in excess, the spalling resistance decreases. The content should be kept to the minimum necessary, and in the present invention it is set to 0 to 1% by weight.
【００２７】[0027]
【実施例】表１に示す配合物を結合剤を用いて混合，成
形したものを非酸化性雰囲気で焼成し、ノズルを得た。
実施例１〜３の組成のものはいずれも良好な耐食性，Ａ
ｌ２ Ｏ３ 付着防止効果を示した。比較例に示す従来
のノズル耐火物の場合は本発明の場合と比較してその特
性は劣ることが判る。[Example] The compositions shown in Table 1 were mixed with a binder, molded, and fired in a non-oxidizing atmosphere to obtain a nozzle. All of the compositions of Examples 1 to 3 had good corrosion resistance, A
It showed an effect of preventing l2 O3 adhesion. It can be seen that the properties of the conventional nozzle refractories shown in the comparative examples are inferior to those of the present invention.
【００２８】表２に配合原料であるカルシウムジルコネ
ートを示す。カルシウムジルコネートＡは本発明の範囲
内のものであり、カルシウムジルコネートＢ，Ｃ及びＤ
は範囲外のものである。カルシウムジルコネートＡは不
純物の含有量が少なく、純度の高い溶鋼に対して良好な
結果が期待できる。Table 2 shows calcium zirconate, which is a raw material. Calcium zirconate A is within the scope of the invention, calcium zirconate B, C and D
is out of range. Calcium zirconate A has a low content of impurities and can be expected to produce good results for high-purity molten steel.
【００２９】[0029]
【表１】[Table 1]
【００３０】[0030]
【表２】[Table 2]
【００３１】図１の（ａ），（ｂ），（ｃ）は表１に示
す実施例１〜３の組成の耐火物を用いて形成したノズル
の例を示す。同図（ａ）のノズル１は、全体を表１の実
施例１の組成の耐火物により形成したタンディッシュ用
ノズルである。同図（ｂ）のノズル２は、ノズル孔内面
部２１，２２を表１の実施例２の組成の耐火物により形
成し、上部と下部の外面部２３，２４，２５をアルミナ
−黒鉛質、中央部の外面部２６をジルコニア−黒鉛質の
耐火物により形成した浸漬ノズルである。同図の（ｃ）
のノズル３は、下部３１，３２を表１の実施例３の組成
の耐火物により形成し、上部３３部をアルミナ−黒鉛質
、中央部３４をジルコニア−黒鉛質の耐火物により形成
した浸漬ノズルである。FIGS. 1A, 1B, and 1C show examples of nozzles formed using refractories having the compositions of Examples 1 to 3 shown in Table 1. The nozzle 1 shown in FIG. 2A is a tundish nozzle made entirely of a refractory having the composition of Example 1 in Table 1. In the nozzle 2 shown in FIG. 2B, the nozzle hole inner surfaces 21 and 22 are made of a refractory having the composition of Example 2 in Table 1, and the upper and lower outer surfaces 23, 24, 25 are made of alumina-graphite. This is a submerged nozzle in which the outer surface portion 26 of the central portion is formed of a zirconia-graphite refractory. (c) in the same figure
The nozzle 3 is an immersion nozzle in which the lower parts 31 and 32 are made of a refractory having the composition of Example 3 in Table 1, the upper part 33 is made of alumina-graphite, and the central part 34 is made of a zirconia-graphite refractory. It is.
【００３２】[0032]
【発明の効果】本発明のノズルは、ＣａＯを含有するこ
とにより、鋼中から析出するＡｌ２ Ｏ３ とＣａＯが
ノズルの表面で反応し、その反応化合物の溶鋼中への溶
解によってノズル閉塞を効果的に防止すると共に、鋼に
対する不純物としてのＡｌ２ Ｏ３ 及びＳｉＯ２ 及
びＴｉＯ２ の含有量が従来のノズルに比べてはるかに
少なく、高純度鋼の鋳造に対して有利である。Effects of the Invention: By containing CaO in the nozzle of the present invention, Al2O3 precipitated from the steel reacts with CaO on the surface of the nozzle, and the reaction compound is dissolved into the molten steel, thereby effectively clogging the nozzle. In addition, the content of Al2O3, SiO2, and TiO2 as impurities in the steel is much lower than in conventional nozzles, which is advantageous for casting high-purity steel.
【図１】本発明実施例のノズルを示す断面図である。FIG. 1 is a sectional view showing a nozzle according to an embodiment of the present invention.
１，２，３ ノズル ２１，２２ ノズル孔内面部 ２３，２４，２５，２６ 外面部 ３１，３２ 下部 ３３ 上部 ３４ 中央部 1, 2, 3 nozzle 21, 22 Nozzle hole inner surface 23, 24, 25, 26 External part 31, 32 Lower part 33 Upper part 34 Central part
Claims (1)
Ｏ３ 及びＳｉＯ２ 及びＴｉＯ２ の合量で０．５〜
０．２重量％、Ｆｅの酸化物０〜０．５重量％を含有し
、鉱物組成としてＣａＺｒＯ３ を主成分とするカルシ
ウムジルコネート系クリンカーを１０〜９５重量％、黒
鉛５〜４０重量％、その他の耐火性原料０〜５０重量％
、金属シリコン１重量％以下からなるカルシウムジルコ
ネート含有連続鋳造用ノズル。Claim 1: 16 to 35% by weight of CaO, Al2
The total amount of O3, SiO2 and TiO2 is 0.5~
0.2% by weight, 0 to 0.5% by weight of Fe oxide, 10 to 95% by weight of calcium zirconate clinker whose mineral composition is mainly CaZrO3, 5 to 40% by weight of graphite, etc. 0-50% by weight of refractory raw materials
, a continuous casting nozzle containing calcium zirconate containing 1% by weight or less of metallic silicon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3146249A JPH07102436B2 (en) | 1991-06-18 | 1991-06-18 | Nozzle for continuous casting containing calcium zirconate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3146249A JPH07102436B2 (en) | 1991-06-18 | 1991-06-18 | Nozzle for continuous casting containing calcium zirconate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04371353A true JPH04371353A (en) | 1992-12-24 |
| JPH07102436B2 JPH07102436B2 (en) | 1995-11-08 |
Family
ID=15403469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3146249A Expired - Fee Related JPH07102436B2 (en) | 1991-06-18 | 1991-06-18 | Nozzle for continuous casting containing calcium zirconate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07102436B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188464A (en) * | 1994-12-29 | 1996-07-23 | Shinagawa Refract Co Ltd | Refractory for continuous casting |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101597254B1 (en) * | 2014-10-31 | 2016-02-24 | 주식회사 포스코 | Submerged nozzle for continuous casting |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0223494A (en) * | 1988-07-12 | 1990-01-25 | Matsushita Electric Ind Co Ltd | Ic card reader-writer |
-
1991
- 1991-06-18 JP JP3146249A patent/JPH07102436B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0223494A (en) * | 1988-07-12 | 1990-01-25 | Matsushita Electric Ind Co Ltd | Ic card reader-writer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188464A (en) * | 1994-12-29 | 1996-07-23 | Shinagawa Refract Co Ltd | Refractory for continuous casting |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07102436B2 (en) | 1995-11-08 |
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