JP4280608B2 - Manufacturing method of immersion nozzle for continuous casting - Google Patents
Manufacturing method of immersion nozzle for continuous casting Download PDFInfo
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- 238000007654 immersion Methods 0.000 title claims description 72
- 238000009749 continuous casting Methods 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000011819 refractory material Substances 0.000 claims description 94
- 229910000831 Steel Inorganic materials 0.000 claims description 49
- 239000010959 steel Substances 0.000 claims description 49
- 239000002994 raw material Substances 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052776 Thorium Inorganic materials 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052790 beryllium Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- -1 boride Chemical compound 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 239000010439 graphite Substances 0.000 description 20
- 229910002804 graphite Inorganic materials 0.000 description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000009826 distribution Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004901 spalling Methods 0.000 description 6
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- 230000007797 corrosion Effects 0.000 description 5
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- 229910004298 SiO 2 Inorganic materials 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000677 High-carbon steel Inorganic materials 0.000 description 2
- 229910000954 Medium-carbon steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 239000002436 steel type Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 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
- 239000004568 cement Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Description
本発明は、鋼の連続鋳造に用いられる浸漬ノズルの製造方法に関する。 The present invention relates to a manufacturing method of dipping Nozzle for use in continuous casting of steel.
鋼の連続鋳造に用いられる浸漬ノズルにおいて、溶鋼通過部及び浸漬部にＡｌ２Ｏ３−黒鉛質耐火材料が広く使用されているが、浸漬ノズル中のＡｌ２Ｏ３の脱落や溶鋼との反応に起因して、溶鋼中にＡｌ２Ｏ３介在物が発生する。そのため、Ａｌ２Ｏ３介在物が有害となる鋼種（例えば線材鋼）を鋳造する時は、溶鋼通過部及び浸漬部にＺｒＯ２−黒鉛質耐火材料が適用される場合がある。
In the immersion nozzle used in continuous casting of steel, molten steel passing portion and the
また、浸漬ノズルの閉塞を防止する目的で、特許文献１には、溶融金属流路となる内孔および吐出口部に、ジルコニア及び黒鉛を含有し、かつＢＮ、ＳｉＣ、Ｂ４Ｃを単独でまたは併用して添加した閉塞防止材料を配設したことを特徴とする連続鋳造用ノズルが開示されている。また、特許文献１には、ＣａＯ安定化ジルコニア７０質量％、黒鉛１０質量％、ＢＮ１０質量％、ＳｉＣ８質量％、Ｂ４Ｃ２質量％からなる耐火材料が開示されている。
Moreover, for the purpose of preventing the clogging of the immersion nozzle,
このようなＺｒＯ２−黒鉛質耐火材料に使用されているＺｒＯ原料は、通常４％程度のＣａＯを添加した電融のＣａＯ安定化ＺｒＯ２原料である。これは純粋なＺｒＯ２は高温で相転移して体積収縮するため、ＣａＯのような安定化剤を添加して高温での体積変化を抑制した安定化ＺｒＯ２原料の方が、高温での体積安定性に優れた耐火材料が得られるためである。ＺｒＯ２の安定化剤としては、ＣａＯ以外に、Ｙ２Ｏ３、ＣｅＯ２やＭｇＯなどが知られているが、Ｙ２Ｏ３及びＣｅＯ２安定化品は高価であること、ＭｇＯ安定化品は脱安定化し易いことからＣａＯ安定化品が使用されている。 The ZrO raw material used for such a ZrO 2 -graphite refractory material is an electromelted CaO-stabilized ZrO 2 raw material to which about 4% of CaO is usually added. This is because pure ZrO 2 undergoes phase transition at a high temperature and shrinks in volume. Therefore, a stabilized ZrO 2 raw material in which a volume change at high temperature is suppressed by adding a stabilizer such as CaO has a higher volume at high temperature. This is because a refractory material having excellent stability can be obtained. In addition to CaO, Y 2 O 3 , CeO 2 and MgO are known as stabilizers for ZrO 2 , but Y 2 O 3 and CeO 2 stabilized products are expensive, and MgO stabilized products. CaO stabilized product is used because it is easy to destabilize.
しかしながら、Ａｌ２Ｏ３−Ｃ質耐火材料の代わりに、上記ＺｒＯ２−黒鉛質耐火材料を浸漬ノズルに適用すると、溶鋼中のＡｌ２Ｏ３介在物を顕著に低減させることができるものの、ＺｒＯ２介在物が発生する。ＺｒＯ２介在物、特に大型のＺｒＯ２介在物は鋼品質にとって有害である。 However, when the above ZrO 2 -graphitic refractory material is applied to the immersion nozzle instead of the Al 2 O 3 -C quality refractory material, Al 2 O 3 inclusions in the molten steel can be remarkably reduced, but ZrO 2 Inclusions are generated. ZrO 2 inclusions, particularly large ZrO 2 inclusions, are detrimental to steel quality.
従って、本発明の目的は、耐スポーリング性を維持すると共に、溶鋼中にＺｒＯ２介在物を発生させることがない、耐摩耗性に優れたＺｒＯ２−ＭｇＯ−Ｃ質耐火材料で溶鋼通過部及び浸漬部を構成した連続鋳造用浸漬ノズルの製造方法を提供することにある。 Accordingly, the object of the present invention is to maintain the spalling resistance and not to generate ZrO 2 inclusions in the molten steel, which is a ZrO 2 —MgO—C quality refractory material having excellent wear resistance and passing through the molten steel. and to provide a manufacturing method of the continuous casting immersion nozzle configuring the submerged portion.
即ち、本発明の連続鋳造用浸漬ノズルの製造方法は、ノズル本体、スラグライン部、溶鋼通過部及び浸漬部から構成される連続鋳造用浸漬ノズルであって、少なくとも溶鋼通過部及び／または浸漬部が、ＭｇＯ：０．５〜１０質量％、ＺｒＯ２：５０〜９９質量％、ＣａＯ及びＹ２Ｏ３の合計量：０〜１０質量％及びＣ：０．５〜４０質量％の化学組成を有するＺｒＯ２−ＭｇＯ−Ｃ質耐火材料からなる連続鋳造用浸漬ノズルの製造方法において、前記ＺｒＯ ２ −ＭｇＯ−Ｃ質耐火材料が少なくともＭｇＯ含有原料、ＺｒＯ ２ 含有原料及びＣ含有原料から構成され、前記ＭｇＯ含有原料及び／またはＺｒＯ ２ 含有原料の一部または全量として、ＭｇＯの含有量が０．５〜１０質量％の範囲内にあるＭｇＯ含有ＺｒＯ ２ 原料を使用し、粒度が０．１ｍｍ以上のＺｒＯ ２ 含有原料を５〜８０質量％使用し、粒度が０．１ｍｍ以上のＺｒＯ ２ 含有原料中のＭｇＯ含有ＺｒＯ ２ 原料が２０質量％以上であり、且つ５００〜１３００℃の範囲内で焼成されることを特徴とする。 That is, the manufacturing method for the continuous casting immersion nozzle of the present invention, the nozzle body, the slag line portion, a immersion nozzle consists molten steel passing portion and submerged portion, at least the molten steel passing portion and / or the immersion unit but, MgO: 0.5 to 10 wt%, ZrO 2: 50 to 99 wt%, the total amount of CaO and Y 2 O 3: 0~10 wt%, and C: the chemical composition of 0.5 to 40 wt% in ZrO 2 -MgO-C protein production method of communicating immersion nozzle for connection cast from refractory material ing with the configuration from the ZrO 2 -MgO-C refractories material at least MgO-containing material, ZrO 2 containing feedstock and C-containing raw material is, as part or all of the MgO-containing raw material and / or ZrO 2 containing the raw material, the content of MgO is using MgO containing ZrO 2 raw material in the range of 0.5 to 10 mass%, Degrees is a more ZrO 2 containing feedstock 0.1mm using 5 to 80 wt%, a particle size is not more MgO containing ZrO 2 raw material in more than ZrO 2 containing feedstock 0.1mm 20% by mass or more, and 500 to 1300 fired at a range of ℃ characterized Rukoto.
更に、本発明の連続鋳造用浸漬ノズルの製造方法は、合計量として１０質量％以下の量でその他の成分を含有することを特徴とする。 Furthermore, the manufacturing method of the immersion nozzle for continuous casting according to the present invention is characterized by containing other components in a total amount of 10% by mass or less.
また、本発明の連続鋳造用浸漬ノズルの製造方法は、その他の成分は、Ａｌ、Ｓｉ、Ｗ、Ｔａ、Ｌａ、Ｈｆ、Ｔｈ、Ｃｅ、Ｍｏ、Ｂａ、Ｚｎ、Ｓｒ、Ｂｅ、Ｌｉ、Ｔｉ、Ｎｉ、Ｃｒ、Ｎｂ、Ｍｎ、Ｆｅ、Ｂ、Ｐｂからなる群から選択される１種または２種以上の元素の酸化物またはＺｒ、Ａｌ、Ｓｉ、Ｍｇ、Ｃａ、Ｗ、Ｔａ、Ｌａ、Ｈｆ、Ｔｈ、Ｃｅ、Ｍｏ、Ｂａ、Ｚｎ、Ｓｒ、Ｂｅ、Ｌｉ、Ｙ、Ｔｉ、Ｎｉ、Ｃｒ、Ｎｂ、Ｍｎ、Ｆｅ、Ｂ、Ｐｂからなる群から選択される１種または２種以上の元素の窒化物、炭化物、硫化物、ほう化物、塩化物、フッ化物、金属及び／または合金であることを特徴とする。 A manufacturing method for a continuous casting immersion nozzle of the present invention, other components, A l, Si, W, Ta, La, Hf, Th, Ce, Mo, Ba, Zn, Sr, Be, Li, T oxides of one or more elements selected from the group consisting of i, Ni, Cr, Nb, Mn, Fe, B, Pb, or Zr, Al, Si, Mg, Ca, W, Ta, La, One or more elements selected from the group consisting of Hf, Th, Ce, Mo, Ba, Zn, Sr, Be, Li, Y, Ti, Ni, Cr, Nb, Mn, Fe, B, and Pb nitrides, carbides, sulfides, borides, chlorides, fluorides, characterized in that it is a metal and / or alloy.
本発明の連続鋳造用浸漬ノズルの製造方法により得られた浸漬ノズルを使用することによって、浸漬ノズルの耐摩耗性が大幅に向上し、更に、鋼中のＺｒＯ２介在物が顕著に低減し、鋼の品質を向上させることができるという効果を奏する。 By using the immersion nozzle obtained by the method for manufacturing the immersion nozzle for continuous casting according to the present invention, the wear resistance of the immersion nozzle is greatly improved, and the ZrO 2 inclusions in the steel are significantly reduced. There is an effect that the quality of the steel can be improved.
本発明者らは、溶鋼とＺｒＯ２−黒鉛質耐火材料の反応について調査を行い、次のことが判った：
高温で、ＺｒＯ２−黒鉛質耐火材料の内部において、ＺｒＯ２粒と黒鉛が反応し、ＺｒＯ２粒の周囲にＺｒＣが生ずる。
High temperature, ZrO 2 - the interior of the graphite refractory materials, ZrO 2 grains and graphite reacts, ZrC occurs around the ZrO 2 grains.
上記の反応機構に基き、本発明者らは、ＺｒＯ２粒と黒鉛との反応によるＺｒＣ生成を抑制することで、ＺｒＯ２−黒鉛質耐火材料の耐摩耗性を向上させる方法を検討した。反応（１）は、ＺｒＯ２−黒鉛質耐火材料中のＣＯガス分圧に依存し、ＣＯガス分圧が低い程起こり易くなり、逆にＣＯガス分圧が高い程起こり難くなる。ＺｒＯ２−黒鉛質耐火材料中にＭｇＯを含有させると、少量の黒鉛が優先的にＭｇＯと反応（２）を起こして、ＺｒＯ２−黒鉛質耐火材料中のＣＯガス分圧を高くする：
また、反応（２）で生じたＭｇ（ガス）は、溶鋼とＺｒＯ２−黒鉛質耐火材料の界面へ拡散し、溶鋼中の酸素と反応してＺｒＯ２−黒鉛質耐火材料の表面付近における気孔にＭｇＯを生成させる。ＭｇＯの生成によって、ＺｒＯ２−黒鉛質耐火材料の組織が緻密となるため、内部のＣＯガスが外部へ拡散し難くなり、それによって高いＣＯガス分圧を維持することができる。この機構によっても、ＺｒＣが生成し難くなる。 Further, Mg (gas) generated in the reaction (2) diffuses to the interface between the molten steel and the ZrO 2 -graphitic refractory material and reacts with oxygen in the molten steel to cause pores near the surface of the ZrO 2 -graphitic refractory material. To produce MgO. Due to the formation of MgO, the structure of the ZrO 2 -graphitic refractory material becomes dense, so that it is difficult for the internal CO gas to diffuse outward, thereby maintaining a high CO gas partial pressure. This mechanism also makes it difficult to generate ZrC.
一方、反応（１）によるＺｒＣの生成量は、溶鋼中の炭素濃度（％Ｃ）にも依存する。溶鋼中の（％Ｃ）が低い程、ＺｒＯ２−黒鉛質耐火材料中でのＺｒＣ生成量は多くなる。高炭素鋼［（％Ｃ）０．２０以上］及び中炭素鋼［（％Ｃ）０．０８〜０．２０］の場合に比べて、低炭素鋼［（％Ｃ）０．０８以下］及び極低炭素鋼［（％Ｃ）０．０１以下］の場合はＺｒＣの生成量が特に多い。これは、低炭素鋼及び極低炭素鋼中の炭素濃度は低く、これらの鋼種と接しているＺｒＯ２−黒鉛質耐火材料中のＣＯガス分圧が低くなり、反応（１）が右方向へ反応し易いためである。従って、低炭素鋼及び極低炭素鋼を鋳造する場合には、ＺｒＯ２−黒鉛質耐火材料にＭｇＯを含有させる効果は、高炭素鋼及び中炭素鋼を鋳造する場合に比べて更に大きくなる。 On the other hand, the amount of ZrC produced by reaction (1) also depends on the carbon concentration (% C) in the molten steel. The lower the (% C) in the molten steel, the greater the amount of ZrC produced in the ZrO 2 -graphitic refractory material. Compared with high carbon steel [(% C) 0.20 or more] and medium carbon steel [(% C) 0.08 to 0.20], low carbon steel [(% C) 0.08 or less] and In the case of extremely low carbon steel [(% C) 0.01 or less], the amount of ZrC produced is particularly large. This is because the carbon concentration in the low carbon steel and the ultra low carbon steel is low, the CO gas partial pressure in the ZrO 2 -graphitic refractory material in contact with these steel types becomes low, and the reaction (1) moves to the right. It is because it is easy to react. Therefore, when casting low carbon steel and extremely low carbon steel, the effect of including MgO in the ZrO 2 -graphitic refractory material is even greater than when casting high carbon steel and medium carbon steel.
以上の研究結果から、本発明者らは、ノズル本体、スラグライン部、溶鋼通過部及び浸漬部から構成される連続鋳造用浸漬ノズルの溶鋼通過部及び浸漬部に使用されるＺｒＯ２−黒鉛質耐火材料の耐摩耗性を向上させるためには、ＺｒＣの生成を防止することが重要であり、そのため、ＺｒＯ２−黒鉛質耐火材料にＭｇＯを含有させることが有効であるとの知見に基づき、本発明の連続鋳造用浸漬ノズルの製造方法を開発したものである。 From the above research results, the present inventors have found that ZrO 2 -graphite used in the molten steel passage part and the immersion part of the continuous casting immersion nozzle composed of the nozzle body, the slag line part, the molten steel passage part and the immersion part. In order to improve the wear resistance of the refractory material, it is important to prevent the formation of ZrC. Therefore, based on the knowledge that it is effective to contain MgO in the ZrO 2 -graphitic refractory material, method for producing a continuous casting immersion nozzle Le of the present invention are those which developed.
このような構成を有する連続鋳造用浸漬ノズルの耐スポーリング性を維持しながら耐食性を向上させるために、浸漬ノズルを構成するノズル本体、スラグライン部、溶鋼通過部及び浸漬部のうち、少なくとも溶鋼通過部及び／または浸漬部を構成する耐火材料として、ＭｇＯ：０．５〜１０質量％、ＺｒＯ２：５０〜９９質量％、ＣａＯ及びＹ２Ｏ ３ の合計量：０〜１０質量％及びＣ：０．５〜４０質量％の化学組成を有するＺｒＯ２−ＭｇＯ−Ｃ質耐火材料を使用することが本発明の連続鋳造用浸漬ノズルの製造方法により得られた浸漬ノズルの特徴である。 In order to improve the corrosion resistance while maintaining the spalling resistance of the continuous casting immersion nozzle having such a configuration, at least molten steel among the nozzle body, the slag line portion, the molten steel passage portion and the immersion portion constituting the immersion nozzle. as the refractory material constituting the passage unit and / or the immersion unit, MgO: 0.5 to 10 wt%, ZrO 2: 50 to 99 wt%, the total amount of CaO and Y 2 O 3: 0~10 wt% and C The use of the ZrO 2 —MgO—C refractory material having a chemical composition of 0.5 to 40% by mass is a feature of the immersion nozzle obtained by the method for manufacturing an immersion nozzle for continuous casting according to the present invention.
上記ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料には、０．５〜４０質量％のＣの含有量を必要とする。Ｃ含有量が０．５質量％未満であると、連続鋳造用浸漬ノズルの溶鋼通過部、浸漬部の耐スポーリング性が不足するために好ましくない。また、Ｃ含有量が４０質量％を超えると、Ｃ含有量が多過ぎ、Ｃが溶鋼に溶解し易いため、浸漬ノズルの耐摩耗性が低下するために好ましくない。なお、Ｃのより好ましい含有量は、３〜３０質量％の範囲内である。また、Ｃ含有量を構成する成分としては、通常黒鉛が使用されるが、黒鉛の全量または一部を非結晶質カーボン（カーボンブラック）、ピッチなどの他のカーボン原料に置換しても良い。 The ZrO 2 —MgO—C quality refractory material requires a C content of 0.5 to 40% by mass. When the C content is less than 0.5% by mass, the spalling resistance of the molten steel passage part and the immersion part of the immersion nozzle for continuous casting is not preferable. Further, when the C-containing organic content exceeds 40 mass%, C content is excessive, C is liable to dissolve in the molten steel is not preferable because abrasion resistance of the immersion nozzle is reduced. In addition, more preferable content of C exists in the range of 3-30 mass%. As the component constituting the C content, graphite is usually used, but the whole or a part of the graphite may be replaced with other carbon raw materials such as amorphous carbon (carbon black) and pitch.
上記のＣ含有量において、ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料中のＺｒＣ生成を抑制するためのＣＯガスを発生させるためには、０．５質量％以上のＭｇＯ含有量を必要とする。ＭｇＯ含有量が０．５質量％未満であると、前述したＺｒＣ生成を抑制するＭｇＯの効果が小さく、ＺｒＣ生成量が多いため、充分な耐食性が得られないために好ましくない。一方、０．５〜４０質量％のＣ含有量を有する条件下で、ＭｇＯ含有量が１０質量％を超えると、ＭｇＯの揮発によって内部が多孔質の組織となり、強度不足により耐スポーリング性が低下するために好ましくない。なお、ＭｇＯ含有量は好ましくは１〜８質量％であり、更に好ましくは２〜６質量％の範囲内である。 In order to generate CO gas for suppressing ZrC generation in the ZrO 2 —MgO—C refractory material with the above C content, an MgO content of 0.5 mass% or more is required. If the MgO content is less than 0.5% by mass, the above-described effect of MgO that suppresses ZrC formation is small, and the amount of ZrC generation is large, so that sufficient corrosion resistance cannot be obtained. On the other hand, if the MgO content exceeds 10% by mass under a condition having a C content of 0.5 to 40% by mass, the inside becomes a porous structure due to volatilization of MgO, and the spalling resistance is reduced due to insufficient strength. Since it falls, it is not preferable. In addition, MgO content becomes like this. Preferably it is 1-8 mass%, More preferably, it exists in the range of 2-6 mass%.
また、上記ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料のＺｒＯ２含有量が５０質量％未満であると、ＺｒＯ２含有量が少な過ぎてＺｒＯ２−ＭｇＯ−Ｃ質耐火材料の耐摩耗性が低下するために好ましくない。また、ＺｒＯ２含有量が９９質量％を超えると、浸漬ノズルに必要とされる耐スポーリング性を確保することができないために好ましくない。なお、ＺｒＯ２含有量は、より好ましくは６５〜９５質量％の範囲内である。 Further, if the ZrO 2 content of the ZrO 2 —MgO—C refractory material is less than 50% by mass, the ZrO 2 content is too small and the wear resistance of the ZrO 2 —MgO—C refractory material is reduced. Therefore, it is not preferable. Also, undesirable because the ZrO 2 content exceeds 99 mass%, it is impossible to ensure the spalling resistance which is required for the immersion nozzle. The ZrO 2 content is more preferably in the range of 65 to 95% by mass.
更に、上記ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料は、ＣａＯ、Ｙ２Ｏ ３ 等のＺｒＯ２を安定化するために用いられるＺｒＯ２原料に起因する成分を含有することがある。なお、これらの成分の合計量は、０〜１０質量％、好ましくは０〜５質量％の範囲内である。即ち、これらの成分は不在であっても、１０質量％以下の量で存在していても良い。なお、これらの成分の合計量が１０質量％を超えると、ＭｇＯの添加効果が小さくなるために好ましくない。 Furthermore, the ZrO 2 —MgO—C refractory material may contain a component derived from a ZrO 2 raw material used to stabilize ZrO 2 such as CaO and Y 2 O 3 . In addition, the total amount of these components is 0-10 mass%, Preferably it exists in the range of 0-5 mass%. That is, these components may be absent or present in an amount of 10% by mass or less. In addition, since the addition effect of MgO will become small if the total amount of these components exceeds 10 mass%, it is not preferable.
更に、上記ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料は、その他の成分として、Ａｌ、Ｓｉ、Ｗ、Ｔａ、Ｌａ、Ｈｆ、Ｔｈ、Ｃｅ、Ｍｏ、Ｂａ、Ｚｎ、Ｓｒ、Ｂｅ、Ｌｉ、Ｔｉ、Ｎｉ、Ｃｒ、Ｎｂ、Ｍｎ、Ｆｅ、Ｂ、Ｐｂなどの元素の酸化物またはＺｒ、Ａｌ、Ｓｉ、Ｍｇ、Ｃａ、Ｗ、Ｔａ、Ｌａ、Ｈｆ、Ｔｈ、Ｃｅ、Ｍｏ、Ｂａ、Ｚｎ、Ｓｒ、Ｂｅ、Ｌｉ、Ｙ、Ｔｉ、Ｎｉ、Ｃｒ、Ｎｂ、Ｍｎ、Ｆｅ、Ｂ、Ｐｂなどの元素の窒化物、炭化物、硫化物、ほう化物、塩化物、フッ化物、金属（または合金）などの中の１種または２種以上を含有することができる。なお、その他の成分を含有する場合、その含有量は、１０質量％以下である。その他の成分の含有量が１０質量％を超えると、ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料の耐食性を低下させる恐れがあるために好ましくない。なお、耐火材料中で形成されたＺｒＣは、上述のように耐火材料に悪影響を及ぼすが、添加物としてＺｒＯ２−ＭｇＯ−Ｃ質耐火材料に最初から存在するＺｒＣは、ＺｒＯ２と黒鉛の反応により生成したＺｒＣの分布（ＺｒＯ２粒子の表面のＺｒＣコーティング層）とは異なるので、溶鋼の浸透を促進するような悪影響を及ぼすことはない。 Further, the ZrO 2 —MgO—C refractory material includes, as other components , Al, Si , W , Ta, La, Hf, Th, Ce, Mo, Ba, Zn, Sr, Be, Li , and Ti. , Ni, Cr, Nb, Mn, Fe, B, Pb or other oxides of elements or Zr, Al, Si, Mg, Ca, W, Ta, La, Hf, Th, Ce, Mo, Ba, Zn, Sr , Be, Li, Y, Ti, Ni, Cr, Nb, Mn, Fe, B, Pb, and other elements such as nitrides, carbides, sulfides, borides, chlorides, fluorides, metals (or alloys), etc. One or more of them can be contained. In addition, when it contains another component, the content is 10 mass% or less. If the content of other components exceeds 10% by mass, the corrosion resistance of the ZrO 2 —MgO—C refractory material may be reduced, which is not preferable. Incidentally, the ZrC formed in refractory material, adversely affects the refractory material as described above, ZrC is initially present in the ZrO 2 -MgO-C refractories material as an additive, ZrO 2 and graphite Since it differs from the distribution of ZrC produced by the reaction (ZrC coating layer on the surface of ZrO 2 particles), there is no adverse effect that promotes penetration of molten steel.
次に、本発明の連続鋳造用浸漬ノズルの製造方法により得られる浸漬ノズルの配材パターンを図を用いて説明する。
図１は、浸漬ノズルの溶鋼通過部（ノズル内管）にＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（３）を配設したものである。ここで、ノズル本体は、従来から公知のＡｌ２Ｏ３−Ｃ質耐火材料、Ａｌ２Ｏ３−ＳｉＯ２−Ｃ質耐火材料等（Ａｌ２Ｏ３−Ｃ質耐火材料等：１）で構成することができる。また、スラグライン部は、従来から公知のＺｒＯ２−Ｃ質耐火材料、ＺｒＯ２−ＣａＯ−Ｃ質耐火材料等（ＺｒＯ２−Ｃ質耐火材料等：２）で構成することができる。
図２は、浸漬ノズルの溶鋼通過部をＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（３）で構成し、浸漬部とノズル本体の一部をＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（４）で構成したものである。この実施態様においても、ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（３）とＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（４）は、同一組成ものであっても、異なる組成のものであっても良い。
図３は、浸漬ノズルのスラグライン部を除く部位を全てＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（４）で構成したものである。
図４は、浸漬ノズルのノズル本体、スラグライン部、溶鋼通過部及び浸漬部の全てをＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（４）で構成したものである。
Next, the distribution pattern of the immersion nozzle obtained by the method for manufacturing an immersion nozzle for continuous casting according to the present invention will be described with reference to the drawings.
FIG. 1 shows a case where a ZrO 2 —MgO—C refractory material (3) is disposed in a molten steel passage part (nozzle inner tube) of an immersion nozzle. Here, the nozzle body is composed of a conventionally known Al 2 O 3 —C quality refractory material, Al 2 O 3 —SiO 2 —C quality refractory material, etc. (Al 2 O 3 —C quality refractory material, etc .: 1). can do. Moreover, the slag line portion, known ZrO 2 -C refractories materials conventionally, ZrO 2 -CaO-C refractories materials (ZrO 2 -C refractories materials: 2) can be composed of.
FIG. 2 shows that the molten steel passage part of the immersion nozzle is composed of ZrO 2 —MgO—C refractory material (3), and the immersion part and part of the nozzle body are composed of ZrO 2 —MgO—C refractory material (4). It is a thing. Also in this embodiment, ZrO 2 -MgO-C refractories material (3) and ZrO 2 -MgO-C refractories material (4), even those same composition, may be of different compositions .
FIG. 3 shows a structure in which all portions of the immersion nozzle except the slag line portion are made of the ZrO 2 —MgO—C refractory material (4).
FIG. 4 shows that the nozzle body, slag line part, molten steel passage part and immersion part of the immersion nozzle are all made of a ZrO 2 —MgO—C refractory material (4).
なお、上記配材パターンに例示したノズル本体に用いられるＡｌ２Ｏ３−Ｃ質耐火材料としては、例えばＡｌ２Ｏ３３０〜９０質量％、ＳｉＯ２０〜３５質量％、黒鉛１０〜３５質量％の組成を有するものを挙げることができるが、これらに限定されるものではない。また、スラグライン部に用いられるＺｒＯ２−Ｃ質耐火材料としては、例えばＣａＯ安定化ＺｒＯ２８０〜９０質量％、黒鉛８〜１５質量％の組成を有するものを挙げることができるが、これらに限定されるものではない。
As the Al 2 O 3 -C refractories materials used in the illustrated nozzle body to the distribution material pattern, e.g., Al 2 O 3 30 to 90 wt%,
次に、本発明の連続鋳造用浸漬ノズルの製造方法について説明する。
本発明の連続鋳造用浸漬ノズルの製造方法において、上記ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料のＭｇＯ原料としては、ＭｇＯ単体原料を使用することができ、また、スピネルやドロマイトなどのＭｇＯ含有原料を使用することもできる。なお、ＭｇＯ成分を、ＭｇＯ安定化ＺｒＯ２原料などのＭｇＯ含有ＺｒＯ２原料として使用することがより望ましい。これは、ＺｒＯ２粒中ＭｇＯと黒鉛が反応（２）を起こして、ＺｒＯ２の周りにＺｒＣがより生成し難いためである。なお、ＭｇＯ含有ＺｒＯ２原料のＭｇＯ含有量は、０．５〜１０質量％、好ましくは２〜７質量％の範囲内である。ＭｇＯ含有量が０．５質量％未満であると、ＺｒＣ生成を抑制するＭｇＯの効果が不充分になるために好ましくなく、また、ＭｇＯ含有量が１０質量％を超えると、ＺｒＯ２粒中のＭｇＯと黒鉛の反応が激しくなり、ＺｒＯ２粒が崩壊してしまうことがあるために好ましくない。
Next, the manufacturing method of the immersion nozzle for continuous casting of this invention is demonstrated.
Te manufacturing method smell for continuous casting immersion nozzle of the present invention, the MgO raw material of the ZrO 2 -MgO-C refractories materials, can be used MgO single material, also, MgO-containing raw materials such as spinel or dolomite Can also be used. It is more desirable to use the MgO component as an MgO-containing ZrO 2 raw material such as an MgO-stabilized ZrO 2 raw material. This is because MgO and graphite in ZrO 2 grains cause a reaction (2), and ZrC is less likely to be generated around ZrO 2 . Incidentally, MgO content of MgO containing ZrO 2 raw material, 0.5 to 10 mass%, preferably in the range from 2 to 7 wt%. If the MgO content is less than 0.5 wt% is not preferable to become insufficient effect of suppressing MgO and ZrC generation, also, when the MgO content exceeds 10 wt%, ZrO 2 grains in the This is not preferable because the reaction between MgO and graphite becomes intense and the ZrO 2 grains may collapse.
本発明の連続鋳造用浸漬ノズルの製造方法において、上記ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料の効果を充分に発揮させるためには、ＺｒＯ２原料の粒度構成も重要となる。粒度が０．１ｍｍ以上のＺｒＯ２原料の配合量が５〜８０質量％であることが好ましく、より好ましくは１５〜７０質量％の範囲内である。粒度が０．１ｍｍ以上のＺｒＯ２原料が５質量％未満であると、全体の粒度が小さく、ＺｒＯ２粒の表面積が大き過ぎるため、ＺｒＯ２粒中のＭｇＯと黒鉛の反応が激しく、組織が脆化し、耐食性が低下するために好ましくない。また、粒度が０．１ｍｍ以上のＺｒＯ２原料の配合量が８０質量％を超えると、全体の粒度が大き過ぎて、ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料の成形性が悪化するために好ましくない。 In the method for producing an immersion nozzle for continuous casting according to the present invention, the particle size constitution of the ZrO 2 raw material is also important in order to sufficiently exhibit the effect of the ZrO 2 —MgO—C refractory material. The blending amount of the ZrO 2 raw material having a particle size of 0.1 mm or more is preferably 5 to 80% by mass, more preferably 15 to 70% by mass. When the particle size is 0.1mm or more ZrO 2 raw material is less than 5 wt%, small overall particle size, since the surface area of the ZrO 2 grain is excessively large, the reaction of MgO and graphite ZrO 2 grains in violently organizations It is not preferable because it becomes brittle and the corrosion resistance decreases. Further, if the blending amount of the ZrO 2 raw material having a particle size of 0.1 mm or more exceeds 80% by mass, the overall particle size is too large, and the moldability of the ZrO 2 —MgO—C refractory material is deteriorated. .
なお、粒度が０．１ｍｍ以上のＺｒＯ２原料の２０質量％以上、より好ましくは２５質量％以上は、ＭｇＯ含有ＺｒＯ２原料であることが好ましい。ＭｇＯ含有ＺｒＯ２原料の量が粒度０．１ｍｍ以上のＺｒＯ２原料の２０質量％未満であると、全体のＭｇＯ含有量を保持するため、粒度が０．１ｍｍ未満の小さなＺｒＯ２粒中のＭｇＯ含有量を増やさなければならず、小さなＺｒＯ２粒は表面積が大きいため、その粒中のＭｇＯ含有量を増やすと、ＭｇＯと黒鉛の反応が激し過ぎて、組織が脆化し、耐食性が低下する恐れがあるために好ましくない。 In addition, it is preferable that 20 mass% or more, more preferably 25 mass% or more of the ZrO 2 raw material having a particle size of 0.1 mm or more is the MgO-containing ZrO 2 raw material. When the amount of the MgO-containing ZrO 2 raw material is less than 20% by mass of the ZrO 2 raw material having a particle size of 0.1 mm or more, the entire MgO content is retained, so that the MgO in the small ZrO 2 particles having a particle size of less than 0.1 mm The content must be increased, and since the small ZrO 2 grains have a large surface area, if the MgO content in the grains is increased, the reaction between MgO and graphite becomes too intense, the structure becomes brittle and the corrosion resistance decreases. It is not preferable because of fear.
粒度が０．１ｍｍ以上のＺｒＯ２原料が鋳造時に溶鋼中に混入すると、大型介在物となり、鋳片欠陥や鋳片割れを生ずる原因となる場合がある。ＭｇＯ含有ＺｒＯ２原料は、通常ＺｒＯ２原料として耐火材料等に使用されているＣａＯ安定化ＺｒＯ２原料よりも溶鋼中で粒が崩壊し易いため、大型介在物を生じ難い。従って、ＭｇＯ含有ＺｒＯ２原料を用いて他のＺｒＯ２原料の比率を少なくすることは、鋳片品質の向上のためにも効果的である。 When a ZrO 2 raw material having a particle size of 0.1 mm or more is mixed in molten steel during casting, it may become a large inclusion, which may cause slab defects or slab cracks. MgO-containing ZrO 2 raw material liable to grains disintegrate in the molten steel than CaO stabilized ZrO 2 raw material used in the refractory material such as a normal ZrO 2 raw material hardly occurs a large inclusions. Therefore, using the MgO-containing ZrO 2 raw material to reduce the ratio of other ZrO 2 raw materials is also effective for improving the quality of the slab.
また、上記ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料には、Ａｌ、Ｓｉ、Ｗ、Ｔａ、Ｌａ、Ｈｆ、Ｔｈ、Ｃｅ、Ｍｏ、Ｂａ、Ｚｎ、Ｓｒ、Ｂｅ、Ｌｉ、Ｔｉ、Ｎｉ、Ｃｒ、Ｎｂ、Ｍｎ、Ｆｅ、Ｂ、Ｐｂなどの元素の酸化物またはＺｒ、Ａｌ、Ｓｉ、Ｍｇ、Ｃａ、Ｗ、Ｔａ、Ｌａ、Ｈｆ、Ｔｈ、Ｃｅ、Ｍｏ、Ｂａ、Ｚｎ、Ｓｒ、Ｂｅ、Ｌｉ、Ｙ、Ｔｉ、Ｎｉ、Ｃｒ、Ｎｂ、Ｍｎ、Ｆｅ、Ｂ、Ｐｂなどの元素の窒化物、炭化物、硫化物、ほう化物、塩化物、フッ化物、金属（または合金）などの中の１種または２種以上を適宜配合することもできる。 The aforementioned ZrO 2 -MgO-C refractories material, A l, Si, W, Ta, La, Hf, Th, Ce, Mo, Ba, Zn, Sr, Be, Li, T i, Ni, Cr , Oxides of elements such as Nb, Mn, Fe, B, and Pb or Zr, Al, Si, Mg, Ca, W, Ta, La, Hf, Th, Ce, Mo, Ba, Zn, Sr, Be, Li , Y, Ti, Ni, Cr, Nb, Mn, Fe, B, Pb, etc., one of the nitrides, carbides, sulfides, borides, chlorides, fluorides, metals (or alloys), etc. Or 2 or more types can also be mix | blended suitably.
更に、ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料の製造時に必要なバインダーとしては、フェノール樹脂や多糖類などのような有機バインダー及び、セメントや珪酸塩、リン酸塩のような無機バインダーの中の１種または２種以上を使用することができる。 Furthermore, as a binder required at the time of manufacture of a ZrO 2 —MgO—C refractory material, organic binders such as phenol resins and polysaccharides, and inorganic binders such as cement, silicate, and phosphate are used. Species or two or more can be used.
なお、上述の図１ないし４に示すような配材パターンを有する本発明の連続鋳造用浸漬ノズルを製造する際には、まず、浸漬ノズル成形時に、上述のＺｒＯ２−ＭｇＯ−Ｃ質耐火材料の練土をノズルの内孔や浸漬部に対応する枠の所定部位に装填し、ノズル本体及びスラグライン部を構成する練土を枠の他の部位に充填した後、同時に加圧成形する同時成形方法を使用することができる。また、予め作製されたノズル本体に、上述のＺｒＯ２−ＭｇＯ−Ｃ質耐火材料の練土を後から充填する２段階成形方法も使用することができる。 When the immersion nozzle for continuous casting of the present invention having the distribution pattern as shown in FIGS. 1 to 4 is manufactured, first, the above-described ZrO 2 —MgO—C refractory material is formed at the time of forming the immersion nozzle. Simultaneously press-molding at the same time after loading the kneaded clay in a predetermined part of the frame corresponding to the inner hole and the immersion part of the nozzle and filling the other part of the frame with the kneaded material constituting the nozzle body and slag line part A molding method can be used. Also, a two-stage molding method can be used in which a previously prepared nozzle body is filled later with the above-described ZrO 2 —MgO—C refractory material.
また、連続鋳造用浸漬ノズルを所定の形状に成形後、酸化防止のため、窒素、アルゴンまたはＣＯなどの非酸化の焼成雰囲気中で焼成する。なお、連続鋳造用浸漬ノズル中の揮発物質を充分に揮発させるため、焼成温度は、５００〜１３００℃、好ましくは８００〜１１００℃の範囲内である。焼成温度が５００℃未満であると、強度不足のために好ましくなく、また、１３００℃を超えると、強度低下のために好ましくない。 Further, after the continuous casting immersion nozzle is formed into a predetermined shape, it is fired in a non-oxidizing firing atmosphere such as nitrogen, argon or CO in order to prevent oxidation. In addition, in order to fully volatilize the volatile substance in the immersion nozzle for continuous casting, the firing temperature is in the range of 500 to 1300 ° C, preferably 800 to 1100 ° C. If the firing temperature is less than 500 ° C., it is not preferable because of insufficient strength, and if it exceeds 1300 ° C., it is not preferable because of strength reduction.
高周波炉にて８０ｋｇの鋼をアルゴン雰囲気で溶解し、１５６０℃に保持した。その後、以下の表１記載する組成を有する耐火材料の２０×２０×２５０ｍｍの供試体を溶鋼に１時間浸漬し、同時に１５０ｒｐｍの回転速度で供試体を回転させた。テスト後、供試体を観察し、亀裂の有無を確認した。また、供試体の損傷厚みを測定した。用いた鋼の成分は、Ｃ：０．５０質量％、Ｓｉ：０．２０質量％、Ｍｎ：０．５０質量％、Ｐ：０．０１質量％、Ｓ：０．００５質量％、Ａｌ：０．００２質量％の組成を有するものであった。得られた結果を表１に併記する。 In a high-frequency furnace, 80 kg of steel was melted in an argon atmosphere and maintained at 1560 ° C. Thereafter, a 20 × 20 × 250 mm specimen of a refractory material having the composition described in Table 1 below was immersed in the molten steel for 1 hour, and simultaneously the specimen was rotated at a rotational speed of 150 rpm. After the test, the specimen was observed to check for cracks. Moreover, the damage thickness of the specimen was measured. The steel components used were: C: 0.50 mass%, Si: 0.20 mass%, Mn: 0.50 mass%, P: 0.01 mass%, S: 0.005 mass%, Al: 0 It had a composition of 0.002% by mass. The obtained results are also shown in Table 1.
表中のＺｒＯ２−ＭｇＯ−Ｃ質耐火材料において、ＭｇＯ成分は、工業的不可避の不純物を除き、全てＺｒＯ２原料に含有されているＭｇＯに由来したものである。ＺｒＯ２原料に含有されているＭｇＯは、１〜９質量％の範囲である。粒度が０．１ｍｍ以上のＺｒＯ２原料が５０質量％であり、その全てはＭｇＯ含有ＺｒＯ２原料である。Ｃ原料には鱗状黒鉛を使用し、粒度が０．２ｍｍ以下、純度が９５質量％以上のものである。なお、耐火材料の供試体は、１０００℃の窒素（非酸化）雰囲気中で約８時間焼成したものであり、気孔率は１６〜１８質量％の範囲内であった。なお、バインダーとして全品フェノール樹脂を外掛で８質量％添加した。 In the ZrO 2 —MgO—C refractory material in the table, all MgO components are derived from MgO contained in the ZrO 2 raw material except for industrial unavoidable impurities. MgO contained in the ZrO 2 raw material is in the range of 1 to 9% by mass. The ZrO 2 raw material having a particle size of 0.1 mm or more is 50 mass%, and all of them are MgO-containing ZrO 2 raw materials. As the C raw material, scaly graphite is used, the particle size is 0.2 mm or less, and the purity is 95% by mass or more. The specimen of the refractory material was fired in a nitrogen (non-oxidizing) atmosphere at 1000 ° C. for about 8 hours, and the porosity was in the range of 16 to 18% by mass. In addition, 8 mass% of all phenolic resins were added as a binder.
また、比較用耐火材料については、ＣａＯ成分は、工業的不可避の不純物を除き、全てＺｒＯ２原料に含有されているＣａＯに由来したものである。ＺｒＯ２原料に含有されているＣａＯは、２〜８質量％の範囲である。粒度が０．１ｍｍ以上のＺｒＯ２原料が５０質量％であり、その全てはＣａＯ含有ＺｒＯ２原料である。Ｃ原料には、鱗状黒鉛を使用し、粒度が０．２ｍｍ以下、純度が９５質量％以上のものを使用した。なお、比較用耐火材料の供試体は、１０００℃の窒素（非酸化）雰囲気中で約８時間焼成したものであり、気孔率は１６〜１８質量％の範囲内であった。なお、バインダーとして全品フェノール樹脂を外掛で８質量％添加した。 In addition, as for the comparative refractory material, the CaO component is derived from CaO contained in the ZrO 2 raw material, except for industrial inevitable impurities. CaO contained in the ZrO 2 raw material is in the range of 2 to 8% by mass. The ZrO 2 raw material having a particle size of 0.1 mm or more is 50% by mass, all of which is a CaO-containing ZrO 2 raw material. As the C raw material, scaly graphite was used, with a particle size of 0.2 mm or less and a purity of 95% by mass or more. Note that the specimen of the comparative refractory material was fired in a nitrogen (non-oxidizing) atmosphere at 1000 ° C. for about 8 hours, and the porosity was in the range of 16 to 18% by mass. In addition, 8 mass% of all phenolic resins were added as a binder.
更に、表中の損傷指数は、（供試体の損傷厚み）／（比較用耐火材料８の供試体の損傷厚み）の値である。損傷指数が大きい程、供試体の損傷が大きくなる。損傷指数は、比較用耐火材料の供試体が０．６〜１．５であるのに対して、ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料の供試体は０．３〜０．４で、耐摩耗性が顕著に高いことが判る。
また、亀裂発生状況は、比較用耐火材料１の供試体のみ亀裂が発生しているが、その他の供試体はいずれも亀裂の発生はなかった。
Further, the damage index in the table is a value of (damage thickness of specimen) / (damage thickness of specimen of comparative refractory material 8). The greater the damage index, the greater the damage to the specimen. The damage index is 0.6 to 1.5 for the specimen of the comparative refractory material, while 0.3 to 0.4 for the specimen of the ZrO2-MgO-C refractory material, and wear resistance Is significantly higher.
Moreover, as for the crack generation situation, only the specimen of the comparative
次に、上記ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料を溶鋼通過部及び浸漬部に使用した連続鋳造用浸漬ノズルを用いて実機にて連続鋳造を実施した。使用した浸漬ノズルは、図２に示す配材パターンを有するもので、ノズル本体を構成するＡｌ２Ｏ３−Ｃ質耐火物等（１）として、Ａｌ２Ｏ３５８質量％、ＳｉＯ２１５質量％及びＣ２６質量％のＡｌ２Ｏ３−Ｃ質耐火材料を用い、スラグライン部を構成するＺｒＯ２−Ｃ質耐火材料等（２）として、ＣａＯ安定化ＺｒＯ２８７質量％及びＣ１３質量％のＺｒＯ２−Ｃ質耐火材料を使用し、溶鋼通過部を構成するＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（３）として、表中のＺｒＯ２−ＭｇＯ−Ｃ質耐火材料２を使用し、ノズル本体の一部及び浸漬部を構成するＺｒＯ２−ＭｇＯ−Ｃ質耐火材料（４）として、表中のＺｒＯ２−ＭｇＯ−Ｃ質耐火材料８を使用したものである。
また、比較用浸漬ノズルの配材パターンを図５に示す。図５に示す浸漬ノズルにおいて、ノズル本体を構成するＡｌ２Ｏ３−Ｃ質耐火物等（１）として、Ａｌ２Ｏ３５８質量％、ＳｉＯ２１５質量％及びＣ２６質量％のＡｌ２Ｏ３−Ｃ質耐火材料を用い、スラグライン部を構成するＺｒＯ２−Ｃ質耐火材料等（２）として、ＣａＯ安定化ＺｒＯ２８７質量％及びＣ１３質量％のＺｒＯ２−Ｃ質耐火材料を使用し、溶鋼通過部を構成する比較用耐火材料（５）として、表中の比較用耐火材料５を使用し、ノズル本体の一部及び浸漬部を構成する比較用耐火材料（４）として、表中の比較用耐火材料８を使用したものである。
Next, continuous casting was carried out with an actual machine using an immersion nozzle for continuous casting in which the ZrO 2 —MgO—C refractory material was used for the molten steel passage and immersion portions. The immersion nozzle used has the distribution pattern shown in FIG. 2, and Al 2 O 3 -C refractory and the like (1) constituting the nozzle body has 58% by mass of Al 2 O 3 and 15% by mass of SiO 2. % And C26% by mass of Al 2 O 3 —C quality refractory material, ZrO 2 —C quality refractory material etc. (2) constituting the slag line part, as CaO stabilized ZrO 2 87% by mass and C13% by mass using the ZrO 2 -C refractories materials, as ZrO 2 -MgO-C refractories materials constituting the molten steel passing portion (3), using a ZrO 2 -MgO-
Furthermore, Figure 5 shows the distribution material pattern of comparative immersion nozzle. In the immersion nozzle shown in FIG. 5 , Al 2 O 3 -C refractory or the like (1) constituting the nozzle body is 58% by mass of Al 2 O 3 , 15% by mass of SiO 2 , and 26% by mass of Al 2 O 3. -As a ZrO 2 -C quality refractory material etc. (2) constituting a slag line portion using a -C quality refractory material, using 87% by mass of CaO stabilized ZrO 2 and 13% by mass of ZrO 2 -C quality refractory material As a comparative refractory material (5) constituting the molten steel passage portion, the comparative
本発明品及び比較用の連続鋳造用浸漬ノズルは、いずれも同時成形方法で成形され、１０００℃の窒素（非酸化）雰囲気中で８時間焼成された。気孔率はいずれの部分でも１６〜１８％の範囲であった。 The product of the present invention and the immersion nozzle for continuous casting for comparison were both molded by the simultaneous molding method and fired in a nitrogen (non-oxidizing) atmosphere at 1000 ° C. for 8 hours. The porosity was in the range of 16-18% at any part.
連続鋳造に用いられた鋼は、Ｃ：０．０００５〜０．６５質量％、Ｓｉ：０．０３〜１．５質量％、Ｍｎ：０．２〜１．２質量％、Ｐ：０．００５〜０．０１５質量％、Ｓ：０．００２〜０．０２質量％、Ｔｉ：０．００５〜０．０５質量％、Ａｌ：０．００１〜０．０７質量％の範囲内であり、鋳造時間は１００〜５００分であった。
実機使用の結果、本発明品及び比較用浸漬ノズルともスポーリングの問題はなかった。また、使用後の浸漬ノズルの損傷厚みを測定した結果、比較用浸漬ノズルの最大損傷厚みを１とすると、本発明品の浸漬ノズルの最大損傷厚みは０．３〜０．４の範囲内であった。
また、鋳造された鋼中の単位体積当たりのＺｒＯ２介在物の個数を調べたところ、比較用浸漬ノズルを用いて鋳造した鋼中のＺｒＯ２介在物の個数を１とすると、本発明品の浸漬ノズルを用いて鋳造した鋼中のＺｒＯ２介在物の個数は０．２〜０．３の範囲内であった。
Steel used for continuous casting is C: 0.0005 to 0.65 mass%, Si: 0.03 to 1.5 mass%, Mn: 0.2 to 1.2 mass%, P: 0.005. ~ 0.015 mass%, S: 0.002 to 0.02 mass%, Ti: 0.005 to 0.05 mass%, Al: 0.001 to 0.07 mass%, and casting time Was 100-500 minutes.
As a result of using the actual machine, there was no problem of spalling in the product of the present invention and the comparative immersion nozzle. As a result of measuring the damage thickness of the immersion nozzle after use, assuming that the maximum damage thickness of the comparative immersion nozzle is 1, the maximum damage thickness of the immersion nozzle of the present invention is within the range of 0.3 to 0.4. there were.
We also examined the number of ZrO 2 inclusions per unit volume in the cast steel, equal to 1 the number of ZrO 2 inclusions in the steel which is cast using the comparative immersion nozzle, the present invention product The number of ZrO 2 inclusions in the steel cast using the immersion nozzle was in the range of 0.2 to 0.3.
本発明の連続鋳造用浸漬ノズルの製造方法により製造された浸漬ノズルは、各種鋼の連続鋳造用の浸漬ノズルに適用することができる。 The immersion nozzle manufactured by the method for manufacturing an immersion nozzle for continuous casting according to the present invention can be applied to an immersion nozzle for continuous casting of various steels.
１ Ａｌ２Ｏ３−Ｃ質耐火材料等
２ ＺｒＯ２−Ｃ質耐火材料等
３ ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料
４ ＺｒＯ２−ＭｇＯ−Ｃ質耐火材料
５ 比較用耐火材料
６ 比較用耐火材料
1 Al 2 O 3 -
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| JP2003394096A JP4280608B2 (en) | 2003-11-25 | 2003-11-25 | Manufacturing method of immersion nozzle for continuous casting |
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| JP2005152928A JP2005152928A (en) | 2005-06-16 |
| JP4280608B2 true JP4280608B2 (en) | 2009-06-17 |
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| JP2003394096A Expired - Lifetime JP4280608B2 (en) | 2003-11-25 | 2003-11-25 | Manufacturing method of immersion nozzle for continuous casting |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4734180B2 (en) * | 2006-06-06 | 2011-07-27 | 新日本製鐵株式会社 | Continuous casting method |
| JP4516937B2 (en) * | 2006-06-06 | 2010-08-04 | 新日本製鐵株式会社 | Immersion nozzle preheating device and continuous casting method. |
| PL2975010T3 (en) * | 2014-07-14 | 2017-01-31 | Refractory Intellectual Property Gmbh & Co. Kg | Zirconia, use of zirconia and method for manufacturing a refractory product |
| JP7071605B1 (en) * | 2022-03-02 | 2022-05-19 | 黒崎播磨株式会社 | Refractory and refractory members for continuous casting |
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