EP1097763A1 - Stranggiessdüse - Google Patents

Stranggiessdüse Download PDF

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Publication number
EP1097763A1
EP1097763A1 EP99912101A EP99912101A EP1097763A1 EP 1097763 A1 EP1097763 A1 EP 1097763A1 EP 99912101 A EP99912101 A EP 99912101A EP 99912101 A EP99912101 A EP 99912101A EP 1097763 A1 EP1097763 A1 EP 1097763A1
Authority
EP
European Patent Office
Prior art keywords
roseki
nozzle
molten steel
continuous casting
alumina
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
Application number
EP99912101A
Other languages
English (en)
French (fr)
Other versions
EP1097763B1 (de
EP1097763A4 (de
Inventor
Mituru Ando
Kazumi Oguri
Toshiyuki Muroi
Toshikazu Takasu
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.)
Akechi Ceramics Co Ltd
TYK Corp
Original Assignee
Akechi Ceramics Co Ltd
TYK Corp
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 Akechi Ceramics Co Ltd, TYK Corp filed Critical Akechi Ceramics Co Ltd
Publication of EP1097763A1 publication Critical patent/EP1097763A1/de
Publication of EP1097763A4 publication Critical patent/EP1097763A4/de
Application granted granted Critical
Publication of EP1097763B1 publication Critical patent/EP1097763B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
    • B22D41/52—Manufacturing or repairing thereof
    • B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor

Definitions

  • the present invention relates to a continuous casting nozzle, in particular, a continuous casting nozzle which permits effective prevention of narrowing and clogging of the inner bore thereof through which molten steel passes in performing continuous casting of the molten steel containing aluminum such as aluminum-killed steel.
  • a continuous casting nozzle for casting molten steel is used for the following purposes.
  • a continuous casting nozzle has a function of pouring molten steel from a tundish to a mold.
  • a continuous casting nozzle is used for such purposes as preventing the molten steel from being oxidized by contacting with the open air, preventing the molten steel from splashing when the molten steel is poured from a tundish to a mold, and rectifying the flow of the poured molten steel so as not entrap non-metallic inclusion and slag present near or on the mold surface into the cast steel strand.
  • a refractory material of a conventional continuous casting nozzle of molten steel comprises graphite, alumina, silica, silicon carbide or the like, for example.
  • aluminum which is added as a de-oxidizer reacts with oxygen existing in the molten steel to produce non-metallic inclusion such as alpha ( ⁇ )-alumina or the like.
  • the aluminum in the molten steel reacts with oxygen in the open air to further produce alumina.
  • the non-metallic inclusion such as ⁇ -alumina adheres and accumulates onto the surface of the inner bore of the continuous casting nozzle, so that the inner bore is narrowed or clogged up in the worst case so as to make the stable casting thereof difficult. Furthermore, the non-metallic inclusion such as ⁇ -alumina adhered or accumulated onto the surface of the inner bore peels off or falls down, and the non-metallic inclusion thus peeled off or fell down is entrapped into the cast steel strand, thus degrading the quality of the cast steel strand.
  • the nozzle which enable to uniformly eject the inert gas from the surface of the inner bore of the nozzle toward the molten steel flowing through the inner bore. Furthermore, when the casting is performed for a long period of time, it becomes gradually difficult to stably control the amount of ejected inert gas, since the refractory material of the continuous casting nozzle degrades. As a result, the non-metallic inclusion such as ⁇ -alumina adheres and accumulates onto the surface of the inner bore of the nozzle in such manner that the inner bore is narrowed or eventually clogged up.
  • a nozzle as a remedy to solve the above problem, in which a non-oxide raw material (SiC, Si 3 N 3 , BN, ZrB 2 , Sialon, etc.) that has a low reactivity with aluminum oxide is added to alumina-graphite refractory, or a nozzle consisting of the above non-oxide material itself (for example, refer to Japanese Patent Publication No. Sho 61-38152/1986).
  • a non-oxide raw material SiC, Si 3 N 3 , BN, ZrB 2 , Sialon, etc.
  • the nozzle consisting essentially of the non-oxide material is not suitable for practical use, since the material cost and manufacturing cost are expensive, while the substantial effect of preventing adhesion may be expected.
  • a nozzle the refractory thereof comprising graphite-oxide raw material containing CaO, in which an oxide raw material containing CaO (CaO ⁇ ZrO 2 , CaO ⁇ SiO 2 , 2CaO ⁇ SiO 2 , and the like) produces by a reaction of CaO with Al 2 O 3 a low-melting-point material which is easily separated from the molten steel (for example, refer to Japanese Patent Publication No. Sho 62-56101/1987).
  • the object of the present invention is to provide a continuous casting nozzle which may prevents alumina inclusion from adhering and accumulating on the inner surface of the nozzle, and prevents the inner bore of the nozzle from being narrowed and clogged so as to enable a stable casting, by means of forming a glass layer on the surface of the inner bore of the nozzle when the nozzle is used, thereby preventing air from being entrapped through refractory structure thus not to produce alumina, and in addition, smoothing the surface of the inner bore of the nozzle.
  • the first embodiment of the present invention is a continuous casting nozzle for casting molten steel, wherein at least a surface layer of an inner bore of said continuous casting nozzle contacting with a molten steel is formed of a refractory comprising:
  • the second embodiment of the present invention is a continuous casting nozzle for casting molten steel, wherein at least a surface layer of an inner bore of said continuous casting nozzle contacting with a molten steel is formed by a process in which binder is added to a refractory material comprising 15 to 60 wt.% of an aggregate consisting essentially of alumina (Al 2 O 3 ), or an aggregate comprising alumina (Al 2 O 3 ) as its main component and melting point thereof being at least 1800 °C and roseki as a balance, and then said refractory material with said binder added is kneaded, formed, and sintered in an anti-oxidizing atmosphere.
  • a refractory material comprising 15 to 60 wt.% of an aggregate consisting essentially of alumina (Al 2 O 3 ), or an aggregate comprising alumina (Al 2 O 3 ) as its main component and melting point thereof being at least 1800 °C and roseki as a balance
  • the third embodiment of the present invention is a continuous casting nozzle for casting molten steel, wherein a mixing weight ratio of roseki having average grain diameter of up to 250 ⁇ m is up to 60 wt.% relative to a total content of said roseki.
  • the fourth embodiment of the present invention is a continuous casting nozzle for casting molten steel, wherein said roseki comprises pyrophyllite (Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O) as its main component.
  • the fifth embodiment of the present invention is a continuous casting nozzle for casting molten steel, wherein said roseki comprising roseki which is calcinated at a temperature of at least 800° C so as to remove crystal water therein.
  • the sixth embodiment of the present invention is a continuous casting nozzle for casting molten steel, wherein said binder comprises a thermosetting resin.
  • the most important feature of the casting nozzle of the present invention resides in that roseki is used as its main ingredient of the refractory material of the nozzle and graphite which is often used in the conventional nozzle is not contained.
  • the silica in the nozzle is decomposed to produce SiO(g) and CO(g), which become an origin to supply oxygen to the molten steel, and thus supplied oxygen reacts with aluminum in the molten steel to produce Al 2 O 3 .
  • the particles of roseki does not decompose even if carbon coexists in the molten steel.
  • the SiO 2 contained in pyrophyllite (Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O) or the like which is the main mineral of the roseki is stable.
  • pyrophyllite Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O
  • the above-mentioned fact is acknowledged in the following manner: a briquette comprising the roseki, resin powders and carbon powders was formed and buried in a breeze, and heat-treated at a temperature of 1500°C for 24 hours, and then the thus treated briquett was investigated with a microscope to find that the particles did not decay and bubbles were not produced.
  • the conventional refractory material with 10 wt.% of graphite added has a thermal conductivity of 9.8 (kcal/m/hr/°C), whereas the refractory material of the invention which does not contain graphite has such a low thermal conductivity as 2.4 (kcal/m/hr/°C), and excellent heat resistance.
  • the refractory material of the invention shows effective prevention of metal from being adhered or non-metallic inclusion such as ⁇ -alumina (Al 2 O 3 ) from being precipitated.
  • the smoothness of the surface of the inner bore is lowered.
  • the molten steel flowing through the inner bore of the nozzle produces turbulence so as to cause the non-metallic inclusion such as ⁇ -alumina to accumulate on the inner surface of the nozzle.
  • the smoothness of the surface of the inner bore is not lowered. In other words, concave and convex portions are not formed on the inner surface of the nozzle of the invention, thus the non-metallic inclusion such as ⁇ -alumina is not accumulated on the inner surface of the nozzle of the invention.
  • the half-melting temperature of the roseki is around 1500°C, so that it melts at the surface of the inner bore of the nozzle contacting with the molten steel to form a glass coat in such manner that the structure of the surface of the inner bore becomes to be smooth and air is prevented from being entrapped through a refractory structure.
  • the refractory comprising alumina-roseki with graphite added is heat-treated at a temperature of 1500°C for 1 hour in the oxidizing atmosphere, and the permeability thereof was investigated to find out to be about 6.5x10 -4 darcy
  • the refractory comprising alumina-roseki without graphite was heat-treated at a temperature of 1500° C for 1 hour in the oxidizing atmosphere, and the permeability thereof was investigated to find out to be about 1.0x10 -4 darcy, thus the permeability is lowered.
  • the roseki is contained in the refractory of the surface layer of the inner bore of the nozzle of the invention as a balance, i.e., the remaining ingredient of the refractory.
  • a mixing weight ratio of the roseki in the surface layer of the inner bore of the nozzle is preferably at least 40 wt%. Also, it is preferable that the mixing weight ratio of the roseki in the surface layer is up to 85 wt%, because with the mixing weight ratio of the roseki over 85 wt%, degree of softening deformation is large, and corrosion resistance against molten steel is deteriorated.
  • the refractory of the surface layer of the bore of the nozzle comprises roseki and 15 to 60 wt.% of an aggregate consisting essentially of Al 2 O 3 or an aggregate comprising Al 2 O 3 as its main ingredient and melting point thereof being at least 1800 degree centigrade.
  • the aggregate comprising Al 2 O 3 as its main ingredient spinel (MgO. Al 2 O 3 ) is used which has a function to provide the surface layer of the inner bore of the nozzle with strength and corrosion resistance.
  • roseki Three kinds may be used as the above-mentioned roseki, that is pyrophyllite roseki, kaolin roseki, and sericite roseki.
  • the pyrophyllite roseki with refractoriness from SK29 to SK32 (SK is a Japanese Standard for refractoriness ) is the most suitable, because the roseki is half-molten when the surface layer of the inner bore contacts with the molten steel to form a glass layer and the erosion resistance thereof against the molten steel is excellent.
  • the kaolin roseki has a greater refractoriness from SK33 to SK36
  • the sericite roseki has a smaller refractoriness from SK26 to SK29, both of which are not preferable.
  • the roseki calcinated at a temperature at least 800°C to vanish (remove) crystal water.
  • the reason for using the above roseki is that when the nozzle containing not calcinated roseki is formed and sintered, the crystal water is released from the roseki at a temperature within a range of from 500 to 800°C in sintering thereof, and then, the formed body may cracks by virtue of an unusually large thermal expansion coefficient.
  • a mixing weight ratio of roseki having average grain diameter of up to 250 ⁇ m should be up to 60 wt.% relative to the total content of the roseki, because when a mixing weight ratio of roseki having average grain diameter of up to 250 ⁇ m is over 60 wt%, structural defects such as lamination are inclined to be produced in molding and softening deformation of roseki particles is inclined to happen when used in operation as a continuous casting nozzle.
  • Roseki comprising pyrophyllite (Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O) as its main component may be more preferably contained in the refractory within a range from 65 to 85 wt.%.
  • the refractory comprising an aggregate consisting essentially of alumina (Al 2 O 3 ), or an aggregate comprising alumina (Al 2 O 3 ) as its main ingredient and the melting point thereof being at least 1800 degree centigrade, for example, spinel within a range of from 15 to 60 wt.%, and roseki as the balance, roseki particles are not discomposed, so that oxygen is not supplied into the molten steel, contrary to SiO2.
  • the half-melting temperature of the roseki is about 1500°C which is almost the same temperature as the casting temperature of molten steel. Accordingly, the roseki melts at the surface of the inner bore of the nozzle contacting with the molten steel to form a glass coat in such manner that the structure of the surface of the inner bore is smoothed and air is prevented from being entrapped through a refractory structure, thus preventing alumina (Al 2 O 3 ) and metal from adhering thereon.
  • Thermosetting resin for example, phenol resin, furan resin or the like is added as a binder within a range of from 5 to 15 wt.% to the above-mentioned material comprising the roseki and the aggregate, and then, a formed body of a nozzle is prepared and sintered. It is preferable that the above-mentioned formed body is prepared by the CIP (Cold Isostatic Pressing) process, considering that the formed body is uniformly compressed through the CIP process.
  • the sintering temperature is preferably within a range of from 1000 to 1300 °C. Reduction atmosphere, namely the anti-oxidizing atmosphere is preferable than the oxidizing atmosphere as the sintering atmosphere because the added thermosetting resin is not oxidized in the reduction atmosphere.
  • Fig. 1 schematically shows a vertical sectional view of the immersion nozzle for continuous casting according to the present invention.
  • the continuous casting nozzle 10 is placed between a tundish and a mold, and used in operation as an immersion nozzle for pouring the molten steel from the tundish to the mold.
  • a surface layer 2 of the inner bore 1, through which the molten steel flows, of the immersion nozzle 10 is formed by a refractory having the chemical composition as described above.
  • the remaining part of the nozzle 3 is formed by a conventional alumina-gaphite refractory.
  • the dimensions of the nozzle are about 1m in total length, about 60mm in diameter of the inner bore, 160mm in outer diameter of the nozzle, and about 50mm in thickness.
  • the thickness of the surface layer of the inner bore made of the refractory in the present invention is from about 2 mm to about 15mm.
  • the above-mentioned dimensions are shown as the example, and the nozzle of the present invention is not limited to the above dimensions. More specifically, the dimensions vary in accordance with the composition of the molten steel to be cast, and the size of the cast strand.
  • FIG. 2 schematically shows a longitudinal cross section of a nozzle in which the surface layer of the bore of the nozzle and the lower part (a part immersed in the molten steel) of the nozzle is made of the refractory according to the present invention.
  • alumina which clogs the inner bore of the nozzle is collected at the inner bore in the lower part of the nozzle.
  • the non-metallic inclusion such as alumina or the like is prevented from adhering and accumulating on the surface layer portion 2 of the inner bore 1.
  • the present invention is described by the examples.
  • Phenol resin in the state of powder and liquid was added in an amount within a range of from 5 to 10 wt.% to each of nine pieces of mixed materials having a different chemical composition, and kneaded.
  • a first formed body (hereinafter referred to as the "formed body 1") with dimensions of 30mm x 30mm x 230mm for investigating an amount of adhesion of non-metallic inclusion such as alumina and corrosion resistance against the molten steel
  • a second formed body hereinafter referred to as the “formed body 2" with dimensions of 50mm ⁇ x 20mm for investigating permeability
  • a third formed body hereinafter referred to as the "formed body 3" with dimensions of 100mm in outer diameter, 60mm in inner diameter and 250mm in length for investigating spalling resistance, were respectively prepared, and then the respective bodies were sintered in reducing atmosphere at a temperature within a range from 1000 to 1200°C to prepare samples No. 1 to 9.
  • sample of the present invention have the chemical compositions within the scope of the present invention
  • samples No. 6 to 9 hereinafter referred to as “sample for comparison”
  • sample for comparison have the chemical compositions out of the scope of the present invention.
  • the samples of the present invention can prevent air from being entrapped through the refractory in practical use because of small permeability.
  • the amount of adhesion of alumina is remarkably large, because it contains simple alumina (Al 2 O 3 ) and simple silica (SiO 2 ), in which SiO 2 decomposes to supply oxygen into the steel.
  • the sample for comparison No. 8 is remarkably inferior in spalling resistance, has a high permeability and shows adhesion of large amount of non-metallic inclusion such as alumina, due to the small amount of roseki content and the large amount of alumina (Al 2 O 3 ), inspite of the mineral supplying oxygen into the molten steel is removed.
  • the amount of alumina adhesion is slightly large and the amount of metal adhesion is large when the temperature of the molten steel is as low as 1520 ⁇ 10°C due to the containing of graphite.
  • the continuous casting nozzle according to the present invention it is possible to perform stable casting without deterioration of the refractory structure, while preventing narrowing or clogging of the bore caused by the non-metallic inclusion such as alumina.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Led Devices (AREA)
EP99912101A 1999-04-05 1999-04-05 Stranggiessdüse Expired - Lifetime EP1097763B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1999/001787 WO2000059657A1 (en) 1997-10-08 1999-04-05 Continuous casting nozzle

Publications (3)

Publication Number Publication Date
EP1097763A1 true EP1097763A1 (de) 2001-05-09
EP1097763A4 EP1097763A4 (de) 2001-11-14
EP1097763B1 EP1097763B1 (de) 2004-09-29

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ID=14235397

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99912101A Expired - Lifetime EP1097763B1 (de) 1999-04-05 1999-04-05 Stranggiessdüse

Country Status (7)

Country Link
EP (1) EP1097763B1 (de)
KR (1) KR100367647B1 (de)
AT (1) ATE277704T1 (de)
AU (1) AU746450B2 (de)
CA (1) CA2312482C (de)
DE (1) DE69920709T2 (de)
WO (1) WO2000059657A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200420371A (en) * 2002-10-16 2004-10-16 Vesuvius Crucible Co Resin-bonded, gas purged nozzle

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1808778A1 (de) * 1968-07-31 1970-08-20 Yawata Iron & Steel Co Ausgiessduese fuer Metallschmelzen
GB2202218A (en) * 1987-02-19 1988-09-21 De Beers Ind Diamond Method of making an article from pyrophyllite
JPH02172859A (ja) * 1988-12-26 1990-07-04 Toshiba Ceramics Co Ltd 鋳造用ノズル
EP0846514A1 (de) * 1996-12-05 1998-06-10 Akechi Ceramics Kabushiki Kaisha Ausguss für den Einsatz im Stahl-Strangguss
EP0885674A1 (de) * 1996-11-18 1998-12-23 Shinagawa Refractories Co., Ltd. Düse für das stranggiessen von stahl

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59121146A (ja) * 1982-12-28 1984-07-13 新日本製鐵株式会社 中空状アルミナ含有不焼成耐火物の製造法
JPH0659533B2 (ja) * 1987-06-01 1994-08-10 日本鋼管株式会社 連続鋳造用浸漬ノズル
JP3164342B2 (ja) * 1996-12-05 2001-05-08 明智セラミックス株式会社 連続鋳造用ノズル
AU725529B2 (en) * 1996-10-16 2000-10-12 Akechi Ceramics Kabushiki Kaisha A continuous casting nozzle for casting molten steel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1808778A1 (de) * 1968-07-31 1970-08-20 Yawata Iron & Steel Co Ausgiessduese fuer Metallschmelzen
GB2202218A (en) * 1987-02-19 1988-09-21 De Beers Ind Diamond Method of making an article from pyrophyllite
JPH02172859A (ja) * 1988-12-26 1990-07-04 Toshiba Ceramics Co Ltd 鋳造用ノズル
EP0885674A1 (de) * 1996-11-18 1998-12-23 Shinagawa Refractories Co., Ltd. Düse für das stranggiessen von stahl
EP0846514A1 (de) * 1996-12-05 1998-06-10 Akechi Ceramics Kabushiki Kaisha Ausguss für den Einsatz im Stahl-Strangguss

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FALBE J ET AL: "ROEMPP CHEMIE LEXIKON, PASSAGE "PYROPHYLLIT"" , ROEMPP CHEMIE LEXIKON. PL -S, STUTTGART, THIEME VERLAG, DE, VOL. BD. 5, PAGE(S) 3708-3709 XP002048137 * page 3709, left-hand column, paragraph 1 * *
See also references of WO0059657A1 *

Also Published As

Publication number Publication date
CA2312482A1 (en) 2000-10-05
EP1097763B1 (de) 2004-09-29
AU746450B2 (en) 2002-05-02
CA2312482C (en) 2006-11-21
EP1097763A4 (de) 2001-11-14
KR100367647B1 (ko) 2003-01-10
KR20010040299A (ko) 2001-05-15
AU3055899A (en) 2000-10-23
DE69920709D1 (de) 2004-11-04
DE69920709T2 (de) 2006-02-09
ATE277704T1 (de) 2004-10-15
WO2000059657A1 (en) 2000-10-12

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