WO2010137333A1 - 鋼の連続鋳造方法及び鋼の連続鋳造で使用される耐火物 - Google Patents

鋼の連続鋳造方法及び鋼の連続鋳造で使用される耐火物 Download PDF

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WO2010137333A1
WO2010137333A1 PCT/JP2010/003574 JP2010003574W WO2010137333A1 WO 2010137333 A1 WO2010137333 A1 WO 2010137333A1 JP 2010003574 W JP2010003574 W JP 2010003574W WO 2010137333 A1 WO2010137333 A1 WO 2010137333A1
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mass
less
raw material
steel
nozzle
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PCT/JP2010/003574
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English (en)
French (fr)
Japanese (ja)
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伊藤智
松井剛
宮本健一郎
後藤潔
駿河俊博
脇田保
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新日本製鐵株式会社
黒崎播磨株式会社
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Application filed by 新日本製鐵株式会社, 黒崎播磨株式会社 filed Critical 新日本製鐵株式会社
Priority to CN201080018124.2A priority Critical patent/CN102413966B/zh
Priority to JP2011515905A priority patent/JP5564496B2/ja
Priority to KR1020117025062A priority patent/KR101333431B1/ko
Publication of WO2010137333A1 publication Critical patent/WO2010137333A1/ja

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    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/14—Closures
    • B22D41/22—Closures sliding-gate type, i.e. having a fixed plate and a movable plate in sliding contact with each other for selective registry of their openings
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    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
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    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
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Definitions

  • the present invention relates to a steel continuous casting method and a refractory used in continuous steel casting.
  • a molten steel passage hole is formed for the purpose of adjusting the flow rate of the molten steel.
  • a sliding nozzle is used. This sliding nozzle is configured by stacking a plurality of plate-like bodies on which passage holes are formed. By sliding this plate-like body, the opening degree of the passage hole of the molten steel is adjusted, and the flow rate of the molten steel is adjusted.
  • steel manufactured by the continuous casting method includes high oxygen steel, non-lead free cutting steel, high manganese steel, and the like. These steels, Mn and for improving the strength and free-cutting, B 4 C for improving the free-cutting is added.
  • Mg (g: gas), Al 2 O 3 (g), and CO (g) generated by decomposition of spinel at a high temperature of 1200 ° C. or higher in the vicinity of the operating surface are as follows.
  • a dense layer of spinel is generated by the reverse reaction shown in Formula (1).
  • Document 1 describes that the Mg (g) and Al 2 O 3 (g) cause a reaction represented by the following formula (2) with oxygen O in molten steel to form a dense spinel layer. ing.
  • Patent Document 1 Mg (g) + Al 2 O 3 (g) + 3O (g) ⁇ MgO ⁇ Al 2 O 3 (s) (2)
  • Patent Document 1 an attempt is made to prevent melting damage by suppressing the infiltration of slag by forming such a dense layer of spinel on the surface of the sliding nozzle.
  • Patent Document 1 cannot sufficiently form a spinel dense layer, and it is difficult to prevent melting damage.
  • the present invention relates to a continuous casting method of steel capable of reducing the erosion loss of a molten steel supply nozzle and stably performing continuous casting when producing high oxygen steel, non-lead free cutting steel, high manganese steel, and the like, and It aims at providing the refractory used for it.
  • the present invention employs the following configuration in order to solve the above-described problems.
  • the first aspect of the present invention is a steel continuous casting method, wherein Mn is 0.15% by mass or more and 3.0% by mass or less, 0.005% by mass or more, and 0.06% by mass or less.
  • the alumina raw material is 90% by mass to 100% by mass of alumina particles having a minimum particle size of 0.1 mm or more and a maximum particle size of 5 mm or less. The following may be included.
  • an upper nozzle is provided above the sliding nozzle, a lower nozzle is provided below the sliding nozzle, and the upper At least one of the nozzle and the lower nozzle may be obtained by kneading and molding the raw material by adding 2% by mass or more and 6% by mass or less of a binder to the raw material.
  • an immersion nozzle is further provided below the lower nozzle, and the immersion nozzle is 2% by mass or more on the raw material, It may be obtained by adding 6% by mass or less of binder and kneading and molding.
  • a supply nozzle for supplying molten steel from a ladle to the tundish is further provided below the lower nozzle, The supply nozzle may be obtained by adding 2% by mass to 6% by mass of a binder to the raw material and kneading and molding.
  • P 0.004 mass% or more, 0.5 mass% or less S, 0.0015 mass% or more, 0.02 mass% or less N, 0.001 mass% or more, 0.03 mass% or less B and a refractory used in a continuous casting method of steel using molten steel containing the balance containing Fe and inevitable impurities, and having a theoretical composition of 45% by mass to 94% by mass Raw material, 1% by mass or more and 50% by mass or less of alumina raw material, and 1% by mass or more, 7% by mass Lower metal Al, 0.5 mass% or more and 2 mass% or less of metal Si,
  • the present invention prevents melting damage of a sliding nozzle or a refractory by the following actions.
  • a sliding nozzle will be described as an example of a refractory.
  • the melting damage of the sliding nozzle progresses when an exogenous slag component reacts on the surface of the sliding nozzle, and the slag component and the component after the reaction infiltrate into the sliding nozzle. It is the pore state of the sliding nozzle, the aggregate component of the sliding nozzle, the extraneous slag component, and the like that limit the progress.
  • components of MnO and B 2 O 3 are contained in slag formed by collecting nonmetallic inclusions generated from molten steel. And when these inclusions adhere to the surface of the sliding nozzle containing Al 2 O 3 , MgO, ZrO 2, etc., a low-melting point substance is generated, and the sliding nozzle is greatly melted.
  • the present inventors use a sliding nozzle obtained by kneading and forming a raw material containing MgO.Al 2 O 3 (spinel) and Al 2 O 3 (alumina) as a sliding nozzle (1).
  • effect of MgO ⁇ Al 2 O 3 is immobilized as a solid solution of MnO in the slag, and (2) of Al 2 O 3 added penetration into the slag, attention is paid to the effect of improving the viscosity.
  • the present inventors have found that by using such a sliding nozzle, it is possible to slag from the surface in contact with the sliding nozzle molten steel to prevent the infiltration, increased erosion due to B 2 O 3 in the slag I found that I can cancel the minutes. As a result, the melting damage of the sliding nozzle can be greatly reduced, and the continuous casting can be stabilized.
  • a spinel material having a theoretical composition, an alumina material, a metal Al, a metal Si, a carbon material, B 4 C, and a material containing inevitable impurities are externally applied.
  • a sliding nozzle obtained by adding 2% by mass to 6% by mass of a binder and kneading and molding is used.
  • the raw material may contain unavoidable impurities of less than 1% by mass as unavoidable impurities, but it is preferable not to contain them as much as possible.
  • the spinel material having a theoretical composition includes MgO in an amount of 24% by mass or more and 30% by mass or less, Al 2 O 3 in an amount of 70% by mass or more and 76% by mass or less, and unavoidable impurities are 1.5% by mass or less. That's fine.
  • electrofused spinel, sintered spinel, etc. can be used as the spinel material.
  • the alumina raw material contains, for example, 95% by mass or more, desirably 98% by mass or more of Al 2 O 3 , and unavoidable impurities may be less than 5% by mass, desirably less than 2% by mass.
  • electrofused alumina or sintered alumina can be used as the alumina raw material.
  • the spinel raw material having a theoretical composition may be in the range of 45% by mass to 94% by mass, and the alumina raw material may be in the range of 1% by mass to 50% by mass.
  • the metal Al may be in the range of 1% by mass to 7% by mass.
  • metal Al is less than 1 mass%, there exists a tendency for corrosion resistance, oxidation resistance, and intensity
  • metal Al exceeds 7 mass%, there exists a tendency for corrosion resistance and spalling resistance to fall.
  • the content of metal Al is preferably 2% by mass or more and 6% by mass or less.
  • the metal Si may be in the range of 0.5% by mass or more and 2% by mass or less.
  • the corrosion resistance, oxidation resistance, and strength tend to decrease, and when it exceeds 2% by mass, the elastic modulus increases and the spalling resistance tends to decrease.
  • the carbon raw material may be in the range of 0.5% by mass or more and 4% by mass or less.
  • the spalling resistance tends to decrease, and when it exceeds 4% by mass, the oxidation resistance tends to decrease.
  • Carbon black, graphite, and pitch can be used as the carbon raw material.
  • the content of the carbon raw material is preferably 0.5% by mass or more and 3.0% by mass or less.
  • B 4 C may be in the range of 0.1% by mass to 1% by mass.
  • the above-mentioned sliding nozzle can be obtained by adding 2% by mass or more and 6% by mass or less of a binder to the raw material having the above-described composition and kneading and molding. If necessary, after molding, the molded body may be dried in an atmosphere of 150 ° C. or higher and 250 ° C. or lower, and then fired at a temperature of 800 ° C. or higher and 1400 ° C. or lower in a non-oxidizing atmosphere. Further, the molded body may be impregnated with tar or pitch. In addition to water, organic binders such as phenol resin, epoxy resin, silicone resin, and pitch can be used as the binder.
  • the above-mentioned sliding nozzle is attached to a molten steel supply port such as a ladle or tundish, and a continuous casting method of steel such as non-lead free-cutting steel is performed. Casting conditions in the continuous casting method of steel may be performed in accordance with conventional casting conditions corresponding to the steel raw material. Moreover, the sliding nozzle mentioned above may be attached to either the ladle or the molten steel supply port of the tundish. From the viewpoint of stabilization of continuous casting, it is preferable that the sliding nozzle is attached to both the ladle and the molten steel supply port of the tundish.
  • the alumina raw material in the raw material may mainly contain alumina particles having a minimum particle size of 0.1 mm or more, preferably 0.5 mm or more and a maximum particle size of 5 mm or less, preferably 3 mm or less.
  • the minimum particle size of the alumina particles of the alumina raw material is less than 0.1 mm, the specific surface area of the alumina raw material is increased and the alumina raw material is easily dissolved, so that the sliding nozzle (refractory) is greatly damaged. .
  • alumina raw material mainly containing alumina particles having a minimum particle size of 0.1 mm or more and a maximum particle size of 5 mm or less can pass through a 5 mm sieve but cannot pass through a 0.1 mm sieve. What is necessary is just the alumina raw material which contains an alumina grain 90 mass% or more and 100 mass% or less. Moreover, the minimum particle size and the maximum particle size here mean the minimum particle size and the maximum particle size in each alumina particle.
  • the sliding nozzle not only the sliding nozzle but also the upper nozzle provided on the upper side of the sliding nozzle and the lower nozzle provided on the lower side may be formed as the refractory using the above-described raw materials.
  • an immersion nozzle that is provided below the lower nozzle and injects molten steel from the tundish into the mold, and a so-called long nozzle (supply nozzle) that supplies molten steel from the ladle to the tundish may be formed. Since the molten steel flows on the inner surfaces of these nozzles, although not as much as the sliding nozzle, the melting loss due to MnO and B 2 O 3 in the molten steel still occurs. Therefore, by forming these nozzles with the raw material, melting damage of these nozzles can be reduced, and the continuous casting of steel can be further stabilized.
  • FIG. 1 shows a tundish 1 according to an embodiment of the present invention.
  • the tundish 1 is a container for supplying molten steel to the mold 2.
  • FIG. 2 which is a partially enlarged view of a portion surrounded by a circle in FIG. 1, an upper side of a sliding nozzle 3 provided at the molten steel supply port of the tundish 1 and provided at the lower surface of the molten steel supply port A nozzle 4 is provided, and a lower nozzle 5 is provided below the sliding nozzle 3.
  • An immersion nozzle 6 is further provided below the lower nozzle 5.
  • the sliding nozzle 3, the upper nozzle 4, the lower nozzle 5, and the immersion nozzle 6 are formed by forming a slurry-like refractory that is kneaded by adding 2% by mass or more and 6% by mass or less of a binder to the following raw materials. Depending on the case, it can be fired or impregnated with pitch or tar.
  • B 4 C 0.5% by weight of the total 100% by mass relative to the raw material phenolic resin as a binder was added at outer percentage 4 wt% can be preferably used.
  • the sliding nozzle 3 may be fired and impregnated, the upper nozzle 4 and the lower nozzle 5 may be unfired or fired, and the immersion nozzle and the long nozzle may be fired. Moreover, you may attach a hardware as needed.
  • a sliding nozzle 3, an upper nozzle 4, a lower nozzle 5, an immersion nozzle 6, and a long nozzle formed from the raw materials are attached to the ladle and the molten steel supply port of the tundish 1.
  • the molten steel M supplied to the tundish 1 is formed at the lower end of the immersion nozzle 6 while in contact with the inner wall of the upper nozzle 4, the inner peripheral edge of the sliding nozzle 3, the inner wall of the lower nozzle 5, and the inner wall of the immersion nozzle 6. It flows into the mold 2 (second container) from the discharged outlet.
  • the amount of the molten steel M supplied to the mold 2 can be adjusted by sliding a plate-like body having a hole on the lower side of the sliding nozzle 3 with a drive mechanism (not shown).
  • the conventional sliding nozzle causes melting damage due to MnO and B 2 O 3 in the molten steel M. It was.
  • MgO.Al 2 O 3 dissolves and fixes MnO in the slag and adds added Al 2 O.
  • the sliding nozzle 3 adjusts the amount of molten steel M supplied to the mold 2 by combining two plate-like bodies with holes and sliding the lower plate-like body.
  • the present invention may be applied to a sliding nozzle in which three perforated plate-like bodies are superposed.
  • Sample A sample was prepared as follows.
  • the alumina raw material was a sintered product having a purity of 99.5% by mass or more
  • the spinel was a sintered spinel having a theoretical composition
  • impurities other than Al 2 O 3 and MgO were 0.6% by mass or less.
  • the particle size of the alumina particles was 0.5 to 1.5 mm
  • the top size of the spinel was 5 mm
  • the particle size was adjusted so as to obtain the closest packing when combined with alumina.
  • Metal Al has a particle size of 250 to 74 ⁇ m and a purity of 99% by mass or more.
  • Metal Si has a particle size of 149 to 74 ⁇ m and a purity of 96% by mass or more.
  • B 4 C has a particle size of 44 ⁇ m or less and a purity of 95% by mass or more.
  • the particle size was 500 ⁇ m or less and the purity was 95% by mass or more.
  • a phenol resin was used as the binder, and the amount added was 4% by mass.
  • the erosion index is a value obtained by converting the erosion amounts of Experimental Examples 2 to 10 into relative values with the erosion amount of Experimental Example 1 being 100, and the larger the erosion index, the more the erosion loss is. Indicates big.
  • the erosion index decreases, that is, the erosion damage becomes difficult.
  • the erosion index is greater than that of Example 1 than that of Experimental Example 1 consisting only of spinel raw materials. From the above, compared with Experimental Example 1 consisting only of the spinel raw material of the theoretical composition, the range in which the sliding damage of the sliding nozzle can be prevented by adding the alumina raw material is 45% by mass or more and 94% by mass or less of the spinel raw material. It was confirmed that the alumina raw material was 1% by mass or more and 50% by mass or less.
  • metal Al is effective when the addition amount is 1% by mass or more, and is best at around 3% by mass. If it is up to 7% by mass, the erosion index is less than 100 and the effect of preventing erosion is exhibited. It was confirmed.
  • the addition of the carbon raw material is confirmed to be effective when the addition amount is 0.5% by mass, best at around 1% by mass, and confirmed to be effective up to 3% by mass. Thus, it was confirmed that the melting loss index was less than 100, and the effect of preventing the melting loss was exhibited.
  • a spinel material having a theoretical composition of 45% by mass or more and 94% by mass or less, an alumina material of 1% by mass or more and 50% by mass or less, 1% by mass or more and 7% by mass or less of metal Al, 0.5 mass% or more, and 2 mass% of a metal Si, 0.5 mass% or more, 4 mass% or less of the carbon material, 0.1 wt% or more, 4 and C 1 mass% of B, and
  • the sliding nozzle, upper nozzle, lower nozzle, and immersion nozzle are melted by forming the raw materials to be contained and manufacturing the sliding nozzle, upper nozzle, lower nozzle, and immersion nozzle, and performing the continuous casting method of non-lead free-cutting steel. It was confirmed that stabilization of continuous casting of steel can be achieved.
  • the present invention when producing high oxygen steel, non-lead free cutting steel, high manganese steel, etc., it is possible to reduce the melting damage of refractories such as nozzles and perform stable continuous casting.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Continuous Casting (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
PCT/JP2010/003574 2009-05-27 2010-05-27 鋼の連続鋳造方法及び鋼の連続鋳造で使用される耐火物 WO2010137333A1 (ja)

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CN201080018124.2A CN102413966B (zh) 2009-05-27 2010-05-27 钢的连续铸造方法及钢的连续铸造中使用的耐火材料
JP2011515905A JP5564496B2 (ja) 2009-05-27 2010-05-27 鋼の連続鋳造方法及び鋼の連続鋳造で使用される耐火物
KR1020117025062A KR101333431B1 (ko) 2009-05-27 2010-05-27 강의 연속 주조 방법 및 강의 연속 주조에서 사용되는 내화물

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JP7469667B2 (ja) 2020-09-18 2024-04-17 日本製鉄株式会社 真空脱ガス装置用スピネル－アルミナ－カーボン煉瓦及び真空脱ガス装置

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WO2015129745A1 (ja) * 2014-02-28 2015-09-03 黒崎播磨株式会社 鋼の鋳造用耐火物，及びスライディングノズル装置用のプレート，並びに鋼の鋳造用耐火物の製造方法

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JPH0692724A (ja) * 1992-09-08 1994-04-05 Harima Ceramic Co Ltd スピネル−アルミナ質焼成レンガの製造方法
JPH07308759A (ja) * 1994-05-16 1995-11-28 Tokyo Yogyo Co Ltd スライドゲート用プレートれんが
JP2006110614A (ja) * 2004-10-18 2006-04-27 Shinagawa Refract Co Ltd スライディングノズル用プレート耐火物
JP2008133503A (ja) * 2006-11-28 2008-06-12 Nippon Steel Corp Ｂを添加した低炭快削鋼の製造方法

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JP2002362969A (ja) * 2001-06-06 2002-12-18 Shinagawa Refract Co Ltd プレートれんが
JP2001353561A (ja) * 2001-11-29 2001-12-25 Shinagawa Refract Co Ltd 鋼の連続鋳造方法
WO2003064079A1 (fr) * 2002-01-28 2003-08-07 Jfe Steel Corporation Busette immergee pour une coulee continue de l'acier et procede de coulee continue de l'acier
JP4478137B2 (ja) * 2006-11-21 2010-06-09 新日本製鐵株式会社 Ｂ含有低炭非鉛快削鋼の製造方法

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JPH0692724A (ja) * 1992-09-08 1994-04-05 Harima Ceramic Co Ltd スピネル−アルミナ質焼成レンガの製造方法
JPH07308759A (ja) * 1994-05-16 1995-11-28 Tokyo Yogyo Co Ltd スライドゲート用プレートれんが
JP2006110614A (ja) * 2004-10-18 2006-04-27 Shinagawa Refract Co Ltd スライディングノズル用プレート耐火物
JP2008133503A (ja) * 2006-11-28 2008-06-12 Nippon Steel Corp Ｂを添加した低炭快削鋼の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7469667B2 (ja) 2020-09-18 2024-04-17 日本製鉄株式会社 真空脱ガス装置用スピネル－アルミナ－カーボン煉瓦及び真空脱ガス装置

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KR101333431B1 (ko) 2013-11-26
KR20120018121A (ko) 2012-02-29
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CN102413966B (zh) 2014-04-16
TW201107496A (en) 2011-03-01

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