WO2011058811A1 - Plaque de buse coulissante - Google Patents

Plaque de buse coulissante Download PDF

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Publication number
WO2011058811A1
WO2011058811A1 PCT/JP2010/065283 JP2010065283W WO2011058811A1 WO 2011058811 A1 WO2011058811 A1 WO 2011058811A1 JP 2010065283 W JP2010065283 W JP 2010065283W WO 2011058811 A1 WO2011058811 A1 WO 2011058811A1
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WO
WIPO (PCT)
Prior art keywords
resistance
surface roughness
thermal expansion
plate
nozzle plate
Prior art date
Application number
PCT/JP2010/065283
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English (en)
Japanese (ja)
Inventor
経一郎 赤峰
勝美 森川
丈記 吉富
Original Assignee
黒崎播磨株式会社
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Application filed by 黒崎播磨株式会社 filed Critical 黒崎播磨株式会社
Publication of WO2011058811A1 publication Critical patent/WO2011058811A1/fr

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    • 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
    • B22D41/14—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
    • B22D41/28—Plates therefor
    • B22D41/30—Manufacturing or repairing thereof
    • B22D41/32—Manufacturing or repairing thereof characterised by the materials used therefor

Definitions

  • the present invention relates to a sliding nozzle plate (hereinafter referred to as “SN plate”) which is a plate brick used in a sliding nozzle device (hereinafter referred to as “SN device”) for controlling the flow rate of molten steel.
  • SN plate sliding nozzle plate
  • SN device sliding nozzle device
  • an SN device In steel production, an SN device is used to control the flow rate of molten steel discharged from a molten metal container such as a ladle or tundish.
  • a molten metal container such as a ladle or tundish.
  • an SN plate having two or three refractory nozzle holes is used. The SN plate is superposed under a restrained condition and is slid with a surface pressure applied, and the flow rate of the molten steel is adjusted by adjusting the opening of the nozzle hole.
  • the SN plate has mechanical strength that can withstand use under restraint conditions, resistance to spalling against thermal stress during casting, corrosion resistance to components and slag in molten steel, oxidation resistance, Characteristics such as “surface roughness resistance” against “surface roughness” in which the sliding surface serving as the working surface is worn are required.
  • an alumina carbon refractory is used for the SN plate.
  • a refractory raw material such as zirconia mullite or alumina zirconia having a low thermal expansion coefficient is used.
  • the use of high-purity and dense raw materials such as fused alumina that does not easily react with slag, and the optimization of the type and content of carbon are being studied.
  • techniques such as making the structure denser and strengthening by optimizing the particle size composition of the raw materials used, and further improving the polishing accuracy of the sliding surface are implemented.
  • antioxidants such as silicon carbide, boron carbide, and aluminum nitride, and metals such as silicon and aluminum are used as the sintered material.
  • Patent Document 1 3 to 40% by mass of a carbonaceous raw material and 0.5% of aluminum oxycarbide are used for the purpose of improving the oxidation resistance, corrosion resistance, and spalling resistance of an alumina carbon refractory. It is proposed to add up to 15% by mass.
  • Patent Document 2 discloses a refractory material containing an electro-fused refractory aggregate containing alumina-aluminum oxycarbide as a main component and containing 0.5 to 3.0% by mass of carbon. Yes.
  • the elements required for the SN plate include “surface roughness resistance” indicating resistance to sliding surface wear, so-called “surface roughness”, in addition to oxidation resistance, corrosion resistance, and spalling resistance. .
  • surface roughness resistance is not taken into consideration, and it has been difficult to obtain an SN plate having excellent “surface roughness resistance” based on the description of these documents.
  • the problem to be solved by the present invention is to provide an SN plate which is excellent in “surface roughness resistance” in addition to oxidation resistance, corrosion resistance and spalling resistance.
  • the SN plate of the present invention is characterized by containing 5 to 95% by mass of Al 4 O 4 C as a mineral phase.
  • the SN plate of the present invention contains a specific amount of Al 4 O 4 C which is aluminum oxycarbide.
  • Al 4 O 4 C Al 2 OC is known as the aluminum oxycarbide, but the present invention specifies Al 4 O 4 C among the aluminum oxycarbides. This is because Al 4 O 4 C can produce a more industrially stable quality than Al 2 OC, and the effect of stably improving the characteristics of the SN plate is high. is there.
  • Al 4 O 4 C reacts with CO gas generated by oxidation of carbon in the refractory with FeO or the like to precipitate alumina and carbon, thereby densifying the structure. Therefore, the effect of suppressing the oxidation of brick is known. Moreover, since Al 4 O 4 C reacts with carbon in the refractory as shown in formula (2) to produce aluminum gas, this aluminum gas reacts with CO gas as shown in formula (3). Then, it has the effect of precipitating alumina and carbon and densifying the structure. Further, in terms of operation, as shown in the formula (4), the aluminum gas reacts with FeO in the steel and precipitates alumina, so that an oxidation resistance effect is obtained similarly.
  • Al 4 O 4 C does not become a cavity like metallic aluminum, but precipitates alumina and carbon, as shown by formulas (1), (3), and (4). It is known that
  • the present inventors tried to evaluate “surface roughness resistance”, which is an important characteristic for the SN plate, by using the (oxidation resistance) evaluation method described in JP-A-2009-204594. That is, using the induction furnace shown in FIG. 1, the value obtained by indexing the thickness of the decarburized layer of the steel bath portion caused by the reaction between the molten steel and the sample refractory (with the base material as 100), and these refractories are actual machines The relationship with “surface roughness”, which is the wear of the sliding surface used and received, was investigated.
  • FIG. 2 shows the relationship between the decarburized layer thickness index of the steel bath and the stroke digestion speed, which is an index of “surface roughness resistance”.
  • the stroke digestion speed refers to the wear speed of damage to the sliding surface and “surface roughness”, and is an index representing “surface roughness resistance” of the SN plate. That is, the smaller the stroke digestion rate, the better the “surface roughness resistance”.
  • FIG. 2 there is a good correlation between the thickness of the decarburized layer in the steel bath and the “surface roughness resistance”. The smaller the decarburized layer thickness index of the steel bath, the smaller the stroke digestion rate and the “surface roughness resistance”. Can be confirmed to be good. From this, it can be understood that the evaluation method shown in FIG. 1 is effective as an evaluation method of “surface roughness resistance”.
  • the “surface roughness resistance” of the refractory to which Al 4 O 4 C was applied was evaluated by this evaluation method. As a result, it was confirmed that the refractory to which Al 4 O 4 C was applied formed a dense alumina layer, which is a thin decarburized layer, only on the working surface of the iron bath, and from this, application of Al 4 O 4 C was confirmed. It is estimated that is effective as a means for improving the “surface roughness resistance”.
  • alumina and carbon are precipitated by Formula (1) and Formulas (3) and (4) to provide oxidation resistance. It is considered that the dense alumina layer, which is a thin decarburized layer, is provided with sliding wear resistance against sliding and an effect on “surface roughness resistance” can be obtained. In addition, since the reaction of Al 4 O 4 C is very slight and maintained inside the working surface, the feature of low thermal expansion coefficient is also maintained, and the spalling resistance effect can be maintained.
  • Al 2 OC which is the same aluminum oxycarbide, but Al 2 OC is stable only at high temperatures as shown in the Al 2 O 3 -Al 4 C 3 phase diagram of FIG. At normal temperature, it exists as a normal stable phase. For this reason, it is difficult to stably produce an Al 2 OC composition by a melting method using an electric furnace in particular, and it is difficult to control the characteristics and quality of Al 2 OC. On the other hand, since Al 4 O 4 C exists as a stable phase at normal temperature, it is possible to industrially produce a raw material having a stable quality.
  • an SN plate having excellent surface roughness resistance in addition to oxidation resistance, corrosion resistance, and spalling resistance.
  • FIG. 3 is an Al 2 O 3 —Al 4 C 3 system phase diagram.
  • Al 4 O 4 C used in the present invention can be produced by a sintering method in which a carbonaceous raw material and an alumina raw material are heat-treated in a firing furnace, or a melting method in which melting is performed in an arc furnace.
  • a blend of a carbonaceous raw material having a mesh size of 50 mesh or less and an alumina raw material having a mesh size of 100 mesh or less is allowed to have a variation of C component within ⁇ 10%.
  • High purity Al 4 O 4 C can be produced by uniformly mixing the mixture and melting the mixture in an arc furnace.
  • the SN plate of the present invention is obtained by mixing and molding Al 4 O 4 C and other refractory raw materials at a predetermined ratio and then firing. You may impregnate pitch after baking as needed.
  • the SN plate of the present invention contains 5 to 95% by mass of Al 4 O 4 C as a mineral phase.
  • the content of Al 4 O 4 C is preferably 40 to 95% by mass, and more preferably 70 to 95% by mass.
  • the SN plate of the present invention preferably has a thermal expansion coefficient of 8 ⁇ 10 ⁇ 6 / K or less.
  • the thermal expansion coefficient exceeds 8 ⁇ 10 ⁇ 6 / K, wear due to thermal stress such as radial cracks from the nozzle holes and edge cracks in the nozzle holes increases.
  • the nozzle inner hole portion expands at a high temperature at the time of casting, so that not only edge chipping occurs, but also air enters between the SN plate surfaces and becomes a factor that promotes oxidation and wear of the sliding surface.
  • the thermal expansion coefficient is preferably 8 ⁇ 10 ⁇ 6 / K or less.
  • the SN plate of the present invention preferably has a bending strength at room temperature of 10 MPa or more and 60 MPa or less.
  • the SN plate is used under conditions of being attached to the SN device and restrained. For this reason, if it does not have sufficient strength with respect to the restraining force, a peculiar crack is generated and becomes a cause of trouble.
  • the spalling resistance was judged as good or bad from the state of cracks after being immersed in molten steel at 1600 ° C for 3 minutes.
  • ⁇ indicates that cracks are slight and good
  • ⁇ indicates that small cracks are generated
  • ⁇ indicates that large cracks are generated and defects are not achieved.
  • Thermal expansion coefficient is effective as an evaluation index for SN chip edge chipping. That is, the smaller the thermal expansion coefficient, the lower the thermal stress is because the expansion of the nozzle hole that becomes hot due to the molten steel flow is suppressed, and the edge chipping is less likely to occur.
  • the coefficient of thermal expansion was calculated from the coefficient of thermal expansion at 1500 ° C. measured according to JIS R2207.
  • the amount of erosion was evaluated by performing a erosion test at 1600 ° C. for 2 hours using molten iron and iron oxide powder in an induction furnace.
  • the amount of erosion of Comparative Example 1 is indexed as 100, and the smaller the index, the better the corrosion resistance.
  • Chemical components were subjected to chemical analysis by X-ray diffraction and refractory analysis methods defined in JIS R2212, 2216. Specifically, Al 4 O 4 C is first quantified from the X-ray diffraction result by the internal standard method, and Al 2 O 3 corresponding to the quantified Al 4 O 4 C amount is determined from the analysis results prescribed in JIS R2212, 2216. The ZrO 2 , Al 2 O 3 , and C contents of the remainder were calculated except for the amount and C amount. If the total of chemical components is less than 100%, the balance is a metal such as aluminum or silicon, or the reactants such as carbide, oxynitride, nitride, carbide, boride and other antioxidants. Ingredients included.
  • Table 1 shows the case where the content of Al 4 O 4 C is changed.
  • Examples 1 to 4 have an Al 4 O 4 C content within the range of the present invention, and are excellent in “surface roughness resistance” and spalling resistance. The coefficient of thermal expansion tends to decrease as the Al 4 O 4 C content increases.
  • Comparative Examples 1 and 2 have a content of Al 4 O 4 C that is less than the range of the present invention, and are inferior in “surface roughness resistance” and spalling resistance. The coefficient of thermal expansion is higher than that of the example, and the effect of improving edge chipping is small.
  • Comparative Example 3 since the content of Al 4 O 4 C was larger than the range of the present invention, cracks occurred due to the volume change of Al 4 O 4 C during firing.
  • the coefficient of thermal expansion is zirconia-based materials such as alumina zirconia and zirconia mullite, which are aggregate materials having a low coefficient of thermal expansion, SiO 2 -containing aggregates such as mullite and fused silica, silicon carbide and boron carbide, and silicon nitride and aluminum nitride. It is possible to adjust by the addition amount of carbides and nitrides such as carbon, addition amount of carbon, firing temperature, firing time and the like. In Table 2, the thermal expansion coefficient was changed by adjusting the Al 4 O 4 C and alumina zirconia raw materials that are low thermal expansion aggregates within the scope of the present invention, the amount of carbon added, and the firing temperature.
  • Example 5 the thermal expansion coefficient was as high as 8.1 ⁇ 10 ⁇ 6 / K, and the spalling resistance was evaluated by thermal expansion. This is inferior to Examples 6 to 9 having a coefficient of 8.0 ⁇ 10 ⁇ 6 / K or less. Therefore, when the thermal expansion coefficient is 8.0 ⁇ 10 ⁇ 6 / K or more, wear due to thermal stress may be a problem.
  • Table 3 shows the case where the bending strength at normal temperature is changed. Flexural strength at room temperature can be adjusted by adding metal as a sintered material such as aluminum and silicon, firing conditions such as firing temperature and firing time, filling density and particle size composition of mixed refractory raw material composition It is.
  • the bending strength at room temperature was changed by adjusting the metal addition amount and the particle size constitution within the scope of the present invention. In both cases, a sufficient effect has been obtained with respect to “surface roughness resistance”, but in Example 10, the bending strength at room temperature is 10 MPa or less and the strength is low. May occur.
  • Example 14 the bending strength at room temperature is as high as 60 Mpa or more, and in the spalling resistance test, it is inferior to Examples 11 to 13, and the thermal stress in the actual machine such as a nozzle hole edge defect. There is concern about wear and tear. In Examples 11 to 13, sufficient bending strength can be obtained, and “surface roughness resistance” is also good.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

La présente invention concerne une plaque de buse coulissante avec une résistance supérieure à rugosification de surface, outre une résistance à l'oxydation, à la corrosion, et au choc thermique. La plaque de buse coulissante comporte entre 5 et 95% en poids de Al4O4C sous forme de phase minérale, et présente un coefficient de dilatation thermique égal ou inférieur à 8×10-6/K et une résistance à la flexion à la température ambiante comprise entre 10 MPa et 60 MPa.
PCT/JP2010/065283 2009-11-12 2010-09-07 Plaque de buse coulissante WO2011058811A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009259063A JP2011104596A (ja) 2009-11-12 2009-11-12 スライディングノズルプレート
JP2009-259063 2009-11-12

Publications (1)

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WO2011058811A1 true WO2011058811A1 (fr) 2011-05-19

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TW (1) TW201125660A (fr)
WO (1) WO2011058811A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013031435A1 (fr) * 2011-09-02 2013-03-07 黒崎播磨株式会社 Composition d'oxycarbure d'aluminium, procédé de production correspondant, et matériau réfractaire
JP2015193512A (ja) * 2014-03-31 2015-11-05 黒崎播磨株式会社 鋳造用耐火物、並びにそれを使用した鋳造用ノズル及びスライディングノズル用プレート

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017154146A (ja) * 2016-02-29 2017-09-07 黒崎播磨株式会社 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
CA3037462C (fr) * 2016-09-27 2021-04-27 Krosakiharima Corporation Placage resistant au feu destine a une buse coulissante, et procede de fabrication dudit placage resistant au feu

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5560067A (en) * 1978-10-28 1980-05-06 Tsurumi Goseirozai Co Ltd Refractories
JPH02503423A (ja) * 1988-03-11 1990-10-18 ペシネ・エレクトロメタルルジ アルミナ及びアルミニウムオキシカーバイド及びオキシナイトライドをベースとする電気溶融多相材料
JPH09253835A (ja) * 1996-03-19 1997-09-30 Nisshin Steel Co Ltd スライディングゲート耐火物の固定方法
JPH09295857A (ja) * 1996-04-26 1997-11-18 Kyushu Refract Co Ltd アルミニウムオキシカ−バイドを含むカ−ボン含有れんが
JPH1157957A (ja) * 1997-08-19 1999-03-02 Kawasaki Refract Co Ltd スライディングノズルプレートおよびその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5560067A (en) * 1978-10-28 1980-05-06 Tsurumi Goseirozai Co Ltd Refractories
JPH02503423A (ja) * 1988-03-11 1990-10-18 ペシネ・エレクトロメタルルジ アルミナ及びアルミニウムオキシカーバイド及びオキシナイトライドをベースとする電気溶融多相材料
JPH09253835A (ja) * 1996-03-19 1997-09-30 Nisshin Steel Co Ltd スライディングゲート耐火物の固定方法
JPH09295857A (ja) * 1996-04-26 1997-11-18 Kyushu Refract Co Ltd アルミニウムオキシカ−バイドを含むカ−ボン含有れんが
JPH1157957A (ja) * 1997-08-19 1999-03-02 Kawasaki Refract Co Ltd スライディングノズルプレートおよびその製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013031435A1 (fr) * 2011-09-02 2013-03-07 黒崎播磨株式会社 Composition d'oxycarbure d'aluminium, procédé de production correspondant, et matériau réfractaire
JP2013053034A (ja) * 2011-09-02 2013-03-21 Kurosaki Harima Corp アルミニウムオキシカーバイド組成物及びその製造方法、並びに耐火物
CN103649009A (zh) * 2011-09-02 2014-03-19 黑崎播磨株式会社 铝氧碳化物组合物及其制造方法与耐火物
JP2015193512A (ja) * 2014-03-31 2015-11-05 黒崎播磨株式会社 鋳造用耐火物、並びにそれを使用した鋳造用ノズル及びスライディングノズル用プレート
US20170088469A1 (en) * 2014-03-31 2017-03-30 Krosakiharima Corporation Refractory for casting, nozzle for casting and sliding nozzle plate using same
US9815741B2 (en) * 2014-03-31 2017-11-14 Krosakiharima Corporation Refractory for casting, nozzle for casting and sliding nozzle plate using same

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JP2011104596A (ja) 2011-06-02
TW201125660A (en) 2011-08-01

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