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WO2007074970A1 - Procede de fabrication de brames d'acier inoxydable ferritiqie et acier inoxydable ferritique ainsi obtenu - Google Patents

Procede de fabrication de brames d'acier inoxydable ferritiqie et acier inoxydable ferritique ainsi obtenu Download PDF

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Publication number
WO2007074970A1
WO2007074970A1 PCT/KR2006/004673 KR2006004673W WO2007074970A1 WO 2007074970 A1 WO2007074970 A1 WO 2007074970A1 KR 2006004673 W KR2006004673 W KR 2006004673W WO 2007074970 A1 WO2007074970 A1 WO 2007074970A1
Authority
WO
WIPO (PCT)
Prior art keywords
molten steel
ferritic stainless
concentration
stainless steel
grain structures
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.)
Ceased
Application number
PCT/KR2006/004673
Other languages
English (en)
Inventor
Joo Hyun Park
Hyo Seok Song
Hee Ho Lee
Dong Sik Kim
Kyo Soo Lee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Posco Holdings Inc
Original Assignee
Posco Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Posco Co Ltd filed Critical Posco Co Ltd
Priority to EP06812508A priority Critical patent/EP1974063A4/fr
Priority to US12/158,515 priority patent/US20090223603A1/en
Priority to JP2008548373A priority patent/JP5221379B2/ja
Priority to CN2006800497022A priority patent/CN101351565B/zh
Publication of WO2007074970A1 publication Critical patent/WO2007074970A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/068—Decarburising
    • C21C7/0685—Decarburising of stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52—Manufacture of steel in electric furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum

Definitions

  • the present invention relates to a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures and the ferritic stainless steel manufactured by it, and more specifically to a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures and the ferritic stainless steel manufactured by it which control concentration of alumina inclusions in molten steel to maximize an available TiN generation effect serving as a non-uniform nucleating site of ferrite when solidifying it, thereby improving equiaxed crystal ratio.
  • TiN is formed by the following equation from a steel making process to a continuous casting process, wherein when its size and distribution are proper, it serves as a non-uniform nucleating site of ferrite in solidifying molten steel, thereby obtaining equiaxed grain structures.
  • European Patent No. 924313 has described that equiaxed crystal ratio in slab of 50% or more can be assured when satisfying [%Ti]x%N] ⁇ 0.14x [%A1] among the concentrations of Ti, Al and N.
  • European Patent No. 1491646 has described that slabs with equiaxed grain structures can be manufactured by adding Mg of 2 ⁇ 50ppm to the molten steel consisting of Cr:10 ⁇ 20%, C:0.001 ⁇ 0.01%, Si:0.01 ⁇ 0.3%, Mn:0.01 ⁇ 0.3%, N:0.001 ⁇ 0.02%, and Ti:0.05 ⁇ 0.3%.
  • Japanese Patent No. 2000-1602999 has described that when making vacuum oxygen decarburization refining, equiaxed crystal ratio in slab of 60% or more can be obtained by injecting CaO and Al to make basicity of CaO-Al O -based slag to be the range of 0.7-2.5 and making molten steel stirring for 5 minutes or more, and adding Ti to allow only TiN nitride to have area ratio of 0.01% or more.
  • the present invention is proposed to solve the problems in a prior art as described above. It is an object of the present invention to provide a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures and the ferritic stainless steel manufactured by it, which control concentration of the alumina inclusions in molten steel using composite deoxidation of Si/Mn/Al/Ti in vacuum oxygen decarburization refining process to maximize an available TiN generation effect serving as a non-uniform nucleating site of ferrite when solidifying it, thereby manufacturing ferritic stainless steel slab with high equiaxed crystal ratio and excellent formability, that is, low ridging defect.
  • a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures and the ferritic stainless steel manufactured by it according to the present invention as described above precisely controls components of molten steel, such as Si and Mn, etc., and concentration of alumina inclusions to effectively generate available TiN so that it can manufacture ferritic stainless steel slabs with equiaxed grain structures and high equiaxed crystal ratio while improving operating stability, thereby obtaining ferritic stainless steel slabs with equiaxed grain structures having excellent formability, that is, low ridging defect.
  • FlG. 1 is a flow chart illustrating a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures according to a preferred embodiment of the present invention
  • FlG. 2 is a graph illustrating a change in equiaxed crystal ratio in slabs according to the control of alumina inclusion concentration
  • FlG. 3 is a graph illustrating the result of FlG. 2 as distributed data
  • FlG. 4 is a graph illustrating the decrease of Al O and TiOx inclusions by a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures according to a preferred embodiment of the present invention, compared to the conventional example;
  • FlG. 5 is an electronmicroscope photograph illustrating the form of oxide-TiN composite inclusions distributed inside slabs with equiaxed grain structures by a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures according to a preferred embodiment of the present invention, compared to the conventional example.
  • a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures comprising the steps of: performing oxygen decarburization reaction by blowing oxygen from the upper part of the molten steel in a vacuum oxygen decarburization ladle; injecting Al in the molten steel to which the oxygen decarburization reaction is made for Cr O reduction; making composite deoxidation by injecting deoxidizer in the molten steel into which the Al is injected for the Cr O reduction; making alloying process by injecting alloying metal in the molten steel; first judging for judging whether Al concentration is in the range of a setting value by analyzing the Al concentration in the molten steel; if the Al concentration satisfies the setting value, stirring it using inert gas and second judging for judging whether alumina inclusion concentration in the final molten steel corresponds to a target value; and if the alumina inclusion concentration satisfies the target value, continuously casting the molten steel.
  • the deoxidizer in the composite deoxidating step, may be Si and Mn and in the allyoing step, the alloying metal may be Ti with 0.2-0.4 % by mass.
  • the alumina inclusion concentration in the molten steel satisfies the following condition.
  • the final composition of a refined slag in the vacuum oxygen decarburization refining ladle satisfies the following condition. [45] 1. l ⁇ (%CaO)/(% Al 2 O ) ⁇ 1.4
  • the molten steel is 80-85 ton.
  • the setting value of Al concentration in the first judging step is
  • the Al concentration is less than 0.05 % by mass, it further comprises the step of additionally injecting Al of 30 ⁇ 40kg relative to the molten steel of 80-85 ton and if the Al concentration is 0.12 % by mass or more, it further comprises the step of additionally injecting quicklime of 250 ⁇ 300kg relative to the molten steel of 80-85 ton.
  • the target value of the alumina inclusion concentration in the second judging is 70 ppm or less.
  • the ferritic stainless steel slabs with equiaxed grain structure of the present invention are manufactured according to a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures of the present invention, wherein it is characterized in that the alumina inclusion concentration is 70 ppm or less and equiaxed crystal ratio in slabs is 40% or more.
  • FIG. 1 a flow chart illustrating a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures according to a preferred embodiment of the present invention.
  • a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures comprises the steps of: performing (SlO) oxygen decarburization reaction by blowing oxygen from the upper part of the molten steel in a vacuum oxygen decarburization ladle; injecting Al in the molten steel to which the oxygen decarburization reaction is made for Cr O reduction (S20); making composite deoxidating (S30) by injecting deoxidizer in the molten steel into which the Al is injected for the Cr O reduction; making alloying process (S40) by injecting alloying metal in the molten steel; first judging (S50) for judging whether Al concentration is in the range of a setting value by analyzing the Al concentration in the molten steel; if the Al concentration satisfies the setting value, stirring (S60) it using inert gas and second judging (S70) for judging whether the alumina inclusion concentration in the final molten steel corresponds to a target value; and if
  • the deoxidizer is Si and Mn and in the allyoing step (S40), the alloying metal is Ti.
  • FlG. 2 is a graph illustrating a change in equiaxed crystal ratio in slabs according to the control of the alumina inclusion concentration and FlG. 3 is a graph illustrating the result of FlG. 2 as distributed data.
  • the equiaxed crystal ration in slabs is increased as the alumina inclusion concentration in the molten steel is decreased.
  • a proper concentration of the alumina inclusions can be set to be less than 70ppm.
  • the slabs with equiaxed crystal ratio of 40-100% can be obtained.
  • the alumina inclusion concentration exceeds 70ppm, the creation of available TiN is suppressed so that it is impossible to assure a targeted equiaxed crystal ratio.
  • the step of decreasing Cr O by injecting Al controls a targeted composition by making composite deoxidation by injecting Si and Mn and then injecting Ti.
  • the Al concentration is primarily analyzed. If the primary Al concentration is too low, Al is further injected and if too high, quicklime is further injected. Subsequently, they are stirred using inert gas in the bottom of the ladle so that the alumina inclusion concentration in the final molten steel is controlled to conform to the targeted range to make a continuous casting.
  • the present invention can obtain higher equiaxed crystal ratio of 40% or more, compared with the example of the prior art.
  • TiN is formed in the molten steel by the reaction of the equation 1 ; however, a point in time forming it varies depending on the composition and temperature of the molten steel. If TiN is formed in the ladle or a tundish prior to solidifying the molten steel, TiN may be generated through a uniform nucleating and growing by the reaction of Ti atom with N atom, however, it is advantageous that the nucleating is made at the third interface in terms of thermodynamics, for example, at the interface of oxidation-inclusions/molten steel, etc.
  • ⁇ A1203-TiN between Al 2 O 3 of a hexagonal structure and TiN of a fa centered cubic (FCC) structure is approximately 0.1, whereas ⁇ betw ⁇
  • MgO or MgAl O spinel of the same face-centered cubic and the TiN is approxin 0.0002.
  • the MgO-based inclusions will easily serves as the non-uniform nucleating site, rather than the Al O -based inclusions.
  • the TiN nucleating is degraded so that upon solidifying, it may be a factor to cause the non-uniform nucleating of ferrite to degrade.
  • TiO -based inclusions it is necessary to obtain a composite deoxidation effect by injecting Si/Mn.
  • FlG. 4 is a graph illustrating the decrease of Al O and TiOx inclusions by a method for manufacturing ferritic stainless steel slabs with equiaxed grain structures according to a preferred embodiment of the present invention, compared to the conventional example.
  • the [Al] concentration is primarily analyzed in the molten steel at a point in time elapsing about 5 minutes after the injection.
  • the Al concentration is less than 0.05%
  • the amount of Al added is 30-40 kg.
  • the amount of quicklime added is 250-300 kg.
  • the final composition of refined slag in the vacuum oxygen decarburization ladle is l.l ⁇ (%CaO)/(%Al O ) ⁇ 1.4 and 4 ⁇ (%TiO )/(% SiO ) ⁇ 6.
  • the ladle is moved to the vacuum oxygen decarburization refining stand in which a vacuum cover is put on it and oxygen gas is then supplied to it using a lance on the upper part of the molten steel.
  • the temperature of the molten steel is raised up to about 1670°C and the composition of the molten steel is analyzed as in the following table 2.
  • the ladle is transferred to a continuous casting process.
  • the component of the molten steel in the final tundish is analyzed as in the following table 3.
  • N concentration in the molten steel is about 110 ppm and reacts with 0.30% [Ti] to contribute the generation of available TiN as shown in FlG. 5, thereby obtain slabs with equiaxed grain structures.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Continuous Casting (AREA)

Abstract

Procédé de fabrication de brames d'acier inoxydable ferritique à structures à grains équiaxes (et l'acier inoxydable ferritique ainsi obtenu) permettant de maîtriser la concentration d'inclusions d'alumine dans l'acier en fusion et de maximiser l'effet de génération de TiN disponible en tant que site de nucléation non uniforme de la ferrite lors de la solidification, ce qui améliore le rapport cristallin équiaxe. Ce procédé se décompose comme suit : exécution d'une réaction de décarburation par oxygène par soufflage d'oxygène depuis le haut de l'acier en fusion dans une poche de coulée de décarburation sous vide par oxygène ; injection d'Al dans l'acier en fusion soumis à une réaction de décarburation par oxygène pour réduction du Cr2O3: exécution d'une désoxydation composite par injection d'un désoxydant dans l'acier en fusion dans lequel a lieu une injection d'Al pour réduction du Cr2O3; mise en oeuvre du processus d'alliage par injection du métal d'alliage dans l'acier en fusion; contrôle de la concentration d'Al afin de déterminer dans un premier temps si cette dernière se situe dans la plage d'une valeur de réglage par analyse de la concentration d'Al dans l'acier en fusion ; brassage de l'acier en fusion au moyen d'un gaz inerte afin de déterminer dans un second temps si la concentration d'inclusions d'alumine dans l'acier en fusion correspond à une valeur cible ; et, si tel est le cas, coulage en continu de l'acier en fusion.
PCT/KR2006/004673 2005-12-28 2006-11-09 Procede de fabrication de brames d'acier inoxydable ferritiqie et acier inoxydable ferritique ainsi obtenu Ceased WO2007074970A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP06812508A EP1974063A4 (fr) 2005-12-28 2006-11-09 Procede de fabrication de brames d'acier inoxydable ferritiqie et acier inoxydable ferritique ainsi obtenu
US12/158,515 US20090223603A1 (en) 2005-12-28 2006-11-09 Method for manufacturing ferritic stainless steel slabs with equiaxed grain structures and the ferritic stainless steel manufactured by it
JP2008548373A JP5221379B2 (ja) 2005-12-28 2006-11-09 凝固組織が微細なフェライト系ステンレス鋼の製造方法及びこれにより製造されるフェライト系ステンレス鋼
CN2006800497022A CN101351565B (zh) 2005-12-28 2006-11-09 具有等轴晶粒结构的铁素体不锈钢板坯的制造方法以及通过该方法制造的铁素体不锈钢

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2005-0131297 2005-12-28
KR1020050131297A KR100729934B1 (ko) 2005-12-28 2005-12-28 응고조직이 미세한 페라이트계 스테인리스강 제조방법 및이로써 제조된 페라이트계 스테인리스강

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WO2007074970A1 true WO2007074970A1 (fr) 2007-07-05

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PCT/KR2006/004673 Ceased WO2007074970A1 (fr) 2005-12-28 2006-11-09 Procede de fabrication de brames d'acier inoxydable ferritiqie et acier inoxydable ferritique ainsi obtenu

Country Status (6)

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US (1) US20090223603A1 (fr)
EP (1) EP1974063A4 (fr)
JP (1) JP5221379B2 (fr)
KR (1) KR100729934B1 (fr)
CN (1) CN101351565B (fr)
WO (1) WO2007074970A1 (fr)

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EP2047926A1 (fr) * 2007-10-10 2009-04-15 Ugine & Alz France Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé
CN102199688A (zh) * 2010-03-25 2011-09-28 宝山钢铁股份有限公司 一种高效精炼超纯铁素体不锈钢的方法
WO2012060397A1 (fr) 2010-11-05 2012-05-10 国立大学法人九州大学 Agent préventif ou thérapeutique de la douleur associée au zona en phase aiguë

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TWI412597B (zh) * 2010-05-28 2013-10-21 China Steel Corp Bearing steel refining method for improving fatigue life
KR101198589B1 (ko) 2010-12-27 2012-11-06 주식회사 포스코 고크롬 페라이트 스테인리스강 정련방법 및 정련장치
JP5687590B2 (ja) * 2011-09-27 2015-03-18 日本冶金工業株式会社 ボロン含有ステンレス鋼の製造方法
JP6306353B2 (ja) * 2014-01-21 2018-04-04 Ｊｆｅスチール株式会社 フェライト系ステンレス冷延鋼板用スラブの製造方法およびフェライト系ステンレス冷延鋼板の製造方法
DK3283608T3 (da) * 2015-04-17 2020-11-23 Univ Missouri Kornraffinering i jernbaserede materialer
KR101898165B1 (ko) * 2016-12-06 2018-09-13 주식회사 포스코 주조조직이 미세한 페라이트계 스테인리스강의 제조방법
KR101896340B1 (ko) * 2017-06-01 2018-09-07 주식회사 포스코 용강 제조 방법
CN107574385B (zh) * 2017-08-28 2019-07-12 北京科技大学 一种提高双稳定铁素体不锈钢连铸坯等轴晶率的工艺方法
CN113502376A (zh) * 2021-06-18 2021-10-15 鞍钢联众(广州)不锈钢有限公司 一种改善含钛不锈钢钢坯次表皮夹杂的方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2047926A1 (fr) * 2007-10-10 2009-04-15 Ugine & Alz France Procéde de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu à partir de ce procédé
WO2009074736A1 (fr) * 2007-10-10 2009-06-18 Arcelormittal-Stainless France Procede de fabrication d'aciers inoxydables comportant de fins carbonitrures, et produit obtenu a partir de ce procede
CN102199688A (zh) * 2010-03-25 2011-09-28 宝山钢铁股份有限公司 一种高效精炼超纯铁素体不锈钢的方法
WO2012060397A1 (fr) 2010-11-05 2012-05-10 国立大学法人九州大学 Agent préventif ou thérapeutique de la douleur associée au zona en phase aiguë
EP3132803A2 (fr) 2010-11-05 2017-02-22 Kyushu University Agent préventif ou thérapeutique de la douleur associée au zona en phase aiguë

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CN101351565A (zh) 2009-01-21
US20090223603A1 (en) 2009-09-10
JP5221379B2 (ja) 2013-06-26
CN101351565B (zh) 2011-02-02
EP1974063A4 (fr) 2010-07-21
EP1974063A1 (fr) 2008-10-01
JP2009521599A (ja) 2009-06-04
KR100729934B1 (ko) 2007-06-18

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