WO2004022267A1 - Buse a gaz purge - Google Patents

Buse a gaz purge Download PDF

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Publication number
WO2004022267A1
WO2004022267A1 PCT/US2003/027209 US0327209W WO2004022267A1 WO 2004022267 A1 WO2004022267 A1 WO 2004022267A1 US 0327209 W US0327209 W US 0327209W WO 2004022267 A1 WO2004022267 A1 WO 2004022267A1
Authority
WO
WIPO (PCT)
Prior art keywords
refractory
nozzle
composition
gas
permeable
Prior art date
Application number
PCT/US2003/027209
Other languages
English (en)
Inventor
Johan Richaud
Original Assignee
Vesuvius Crucible Company
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 Vesuvius Crucible Company filed Critical Vesuvius Crucible Company
Priority to CA002497298A priority Critical patent/CA2497298A1/fr
Priority to BR0313972-7A priority patent/BR0313972A/pt
Priority to EP03749254A priority patent/EP1536902A1/fr
Priority to US10/530,092 priority patent/US20060071041A1/en
Priority to MXPA05002446A priority patent/MXPA05002446A/es
Priority to AU2003268298A priority patent/AU2003268298A1/en
Publication of WO2004022267A1 publication Critical patent/WO2004022267A1/fr

Links

Classifications

    • 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
    • B22D41/58—Pouring-nozzles with gas injecting means
    • 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

  • This invention relates to a refractory nozzle for use in the casting of molten steel, and particularly to a nozzle that uses inert gas for reducing unwanted accumulation of alumina deposits at the steel/nozzle interface.
  • Refractory articles for controlling a flow of molten metal such as steel
  • Such articles include nozzles, slide gate plates, stopper rods and shrouds, and are often used in combination to modulate a flow of liquid steel during the casting of molten metal.
  • nozzles slide gate plates
  • stopper rods stopper rods and shrouds
  • alumina and other refractory compounds deposit and accumulate at the interface of the article and the molten steel. Interfaces include, for example, the bore and top surface of the nozzle. Such deposits can ultimately cause the complete blockage of the nozzle or prevent shut-off of flow of the molten steel.
  • Nozzle assemblies frequently include porous, gas-conducting refractory elements.
  • Gas delivery systems such as channels, grooves or devices, within or outside the nozzle can direct inert gas to the porous elements. Examples of such nozzles are U.S. Pat. Nos.4,360,190; 5,100,035, 5,137,189, and 5,723,055.
  • a pressurized inert gas such as argon, travels through the gas delivery system and percolates through the porous refractory elements.
  • the porous elements may define at least a portion of the bore surface or may be proximate to the bore surface so that inert gas may escape into the bore.
  • the porous element may be near or at the top surface of the nozzle.
  • the resulting flow of small argon bubbles through the sides of the bore or top surface of the nozzle can reduce the deposition of unwanted alumina in these areas.
  • the prior art decreased the partial pressure of oxygen available to cause clogging.
  • the prior art injected inert gas into the nozzle and subsequently into the stream of molten steel causing a reduction in oxygen concentration and corresponding reduction in unwanted deposits.
  • This solution is not entirely satisfactory because oxygen is still present to the molten steel because of, for example, leaks in the inert gas system, contamination of the inert gas, and preexisting oxygen in the system. Clogging can still occur.
  • Prior art articles still permit the diffusion of oxygen through the article and into the molten steel.
  • Metal cans have not proven completely acceptable because oxygen can still penetrate along the interface between the article and the can.
  • "canning" significantly adds to the expense of the product.
  • a nozzle would scavenge or scrub oxygen from the inert gas while imposing an impermeable barrier around the molten metal.
  • the present invention describes a refractory article for use in the casting of molten steel that reduces the accumulation of inclusions, particularly alumina, on surfaces exposed to a stream of molten steel.
  • Surfaces may include the bore or top surface of a nozzle.
  • the article includes a liner comprising a substantially gas- impermeable refractory composition and a gas-permeable ref actory composition surrounding the liner.
  • the impermeable composition inhibits oxygen diffusion to the molten metal.
  • the permeable composition is adapted to permit diffusion of inert gas, thereby shielding the impermeable composition and the molten metal from oxygen.
  • the impermeable composition is preferably a resin-bonded composition comprising a refractory aggregate, binder and oxygen getter.
  • the latter includes compounds that scrub oxygen from the gas entering the molten metal, and includes reactive metals.
  • the gas-permeable composition may comprise carbon-bonded, oxide-bonded, resin-bonded, or castable refractories.
  • the permeable composition permits the diffusion of inert gas so that inert gas substantially shields the impermeable composition and the molten metal from oxygen ingress.
  • the porosity of the permeable composition can control the diffusion of inert gas.
  • a gas delivery system such as channels, grooves or devices, may facilitate the delivery and diffusion of inert gas through the permeable material.
  • the method of the present invention includes lining a bore of a refractory article with a substantially gas impermeable composition, surrounding at least a portion of the impermeable composition with a gas-permeable composition, and flooding the permeable composition with inert gas.
  • an overpressure of inert gas shields the molten metal from oxygen.
  • the inert gas purges molten metal within a metallurgical vessel.
  • Figure 1 shows a cross-section of a refractory nozzle of the present invention.
  • Figure 2 shows an alternative embodiment that permits purging of molten metal in a metallurgical vessel.
  • the present invention concerns refractory articles used to control the flow of molten metal, specifically steel.
  • the present invention may include any refractory article for conducting a flow of molten metal, including nozzles, shrouds and slide gate plates.
  • nozzle shall mean any refractory article used to conduct a flow of molten metal.
  • Figure 1 shows one embodiment of the present invention.
  • the article 1 comprises a nozzle body 2 having an inner surface 3 defining a bore 4, a top surface 5 surrounding an inlet 6 of the bore 4, an outlet 7 fluidly connected to the inlet 6, and an outer surface 8.
  • the bore 4 is adapted to transfer the steel from the inlet 6 to the outlet 7.
  • the inner surface 3 includes a liner 9 comprising a substantially gas- impervious composition.
  • the liner 9 defines at least a portion, and preferably all, of the bore 4.
  • An outer portion 10 of the nozzle 2 surrounds the liner 9 and comprises a gas-permeable composition.
  • the nozzle 2 is adapted to receive a flow of inert gas.
  • a conduit 11 may deliver the gas to the nozzle 2 and, in combination with various channels, grooves or devices 12 V ⁇ thin or surrounding the nozzle 2, the gas permeates the outer portion 10 effectively shielding the molten metal in the bore 4 from the atmosphere.
  • the gas-impermeable composition must be substantially impermeable to gases.
  • One skilled in the art is aware of several methods to produce an impermeable material using a variety of chemical and mechanical means.
  • fluxes, glazes, particle size distribution, bonding system, composition of the refractory, and processing conditions can individually and in combination affect permeability. Fluxes lower the glass temperature and facilitate vitrification. Glazes produce an impervious coating on the surface of the refractory. Particle size distribution in a refractory aggregate can substantially affect porosity, and ultimately permeability, in a finished product. Processing conditions, such as firing temperature and pressing, have profound effects on permeability. Chemical compositions of the refractory and bonding system also substantially affect permeability.
  • the gas-impermeable composition may be formed from any type of material, including resin-bonded, carbon-bonded, oxide-bonded, and castable refractories.
  • Carbon-bonded refractories include mixtures of refractory aggregate, graphite and a binder that have been fired under reducing conditions. Firing means heating the composition at a temperature capable of forming metal carbides, particularly aluminum carbide. Such temperatures are typically above 800°C, but may be higher depending on the firing time.
  • Oxide-bonded compositions are sintered at elevated temperatures, often substantially higher than temperatures needed for carbon-bonding.
  • Resin-bonded refractories are cured at temperatures below about 800°C, and frequently below about 500°C. Unlike the previous materials, castable refractories do not typically need pressing and can be molded at near ambient temperature and pressure.
  • a castable material includes any of the refractory cement-like products commonly used in the industry.
  • the impermeable composition comprises a resin- bonded material.
  • resin- bonded compositions are cured at low temperatures, can comprise clog- resistant materials, and may contain oxygen getters that would not survive high temperature firing needed for carbon-bonded or oxide bonded materials.
  • Suitable resin-bonded compositions include at least one refractory aggregate, a curable resin binder and a reactive metal.
  • Refractory aggregate includes any refractory material suitable for steel casting, including but not limited to alumina, magnesia, calcia, zirconia, silica, compounds and mixtures thereof.
  • compounds that can produce volatile oxides at elevated temperatures such as silica and magnesia, should be avoided because volatile oxides are a means of oxygen transport to the molten metal, and oxygen ingress has been correlated with alumina deposition.
  • the curable resin binder should be present in an amount to achieve adequate green strength after pressing and curing. Curing commonly occurs at below around 300 °C.
  • the composition may be heat treated at a temperature preferably below about 800°C and most preferably below about 500°C.
  • the amount of binder will vary depending on, for example, the type of binder used and the desired green strength. A sufficient amount of binder will typically be from 1-10 wt.%.
  • the binder is organic and usually the binder is a carbon resin, such as, a carbonaceous binder derived from pitch or resin.
  • the binder may include other types of organic binders, such as, phenolic compounds, starch, or ligno-sulfinate.
  • the gas-impermeable composition may also comprise oxygen getter.
  • An oxygen getter reacts with oxygen that diffuses into or forms within the gas- impermeable composition, thereby making the oxygen unavailable to the molten steel.
  • Common oxygen getters include, for example, boron compounds, carbides, nitrides, and reactive metal powders such as aluminum, magnesium, silicon and mixtures and alloys thereof.
  • boron compounds reduce porosity and permeability, thereby creating a physical barrier to oxygen diffusion.
  • the needed quantity of oxygen getter depends on the particular use to which the refractory article will be placed. A miiiimum of 0.25 wt.% is believed necessary to show demonstrable improvement in oxidation-resistance. Alternatively, more than 15 wt.% is costly, typically unnecessary, and may even be hazardous such as when using reactive metal powders. Additionally, oxygen getters may decrease thermal shock-resistance of the fired shape and reduce erosion-resistance to steel.
  • a preferred oxygen getter comprise reactive metals, including aluminum, magnesium, silicon, titanium, and mixtures and alloys thereof.
  • reactive metals are added as powders, flakes and the like.
  • the reactive metal should be present in sufficient quantity so that, during casting of molten steel, the reactive metal scavenges any oxygen that may diffuse into or emanate from the refractory article.
  • Various factors affect the amount of reactive metal that will be sufficient to scavenge oxygen.
  • the inclusion of oxygen-releasing compounds, such as silica require higher levels of reactive metal in order to scavenge the released oxygen.
  • Limitations on the amount of reactive metal include cost and hazardousness.
  • Reactive metals are generally more expensive than refractory aggregates and, especially as powders, reactive metals can be explosive during processing.
  • a typical amount of reactive metal is from 0.5-10 wt.%.
  • the impermeable composition may include a resin-bonded composition comprising ⁇ 50-90 wt.% refractory aggregate, 1-10 wt.% binder, and 0.5-15 wt.% reactive metal. More preferably, the resin-bonded composition comprises 65-80 wt.% fused alumina, 2-30 wt.% calcined urnina, 1-10 wt% binder, 0.5-10 wt.% alurninum metal, up to 15 wt.% zirconia, and less than 3 wt.% silica.
  • the gas-permeable refractory composition may comprise any suitable refractory composition, including carbon-bonded, oxide-bonded, resin-bonded, or castable refractories, but preferably comprises carbon-bonded refractories or castable materials.
  • suitable carbon-bonded refractories are well known by one skilled in the art, and typically are thermal shock resistant.
  • Castable materials are commonly dry powders that are mixed with water to form a slurry.
  • the slurry can be molded around the impermeable composition without pressure or temperature extremes.
  • the permeable composition should surround at least a portion of the impermeable composition, and preferably it surrounds the entire impermeable composition. Desirable, but not necessary, features of the permeable composition include easy grindability and low thermal conductivity compared to the impermeable composition. Grindability permits easier machining of a refractory article to its finished dimension. Low conductivity insulates the molten steel and reduces the likelihood of steel freezing in the nozzle.
  • the permeable composition permits the diffusion of inert gas so that inert gas substantially shields the impermeable composition and the molten metal from oxygen ingress. Conveniently, the porosity of the permeable composition can control the diffusion of inert gas.
  • Fugitive additives such as waxes and volatile compounds, may also be used to increase porosity.
  • a gas delivery system such as channels, grooves or devices, may facilitate the delivery and diffusion of inert gas through the permeable material.
  • Porosity of the refractory largely controls permeability.
  • Total porosity of the gas-permeable composition should be at least about 15%.
  • the gas- permeable composition should have a porosity at least about 5% greater than the gas- impermeable composition. The difference in porosities is sufficient to channel gas through the permeable composition and away from the impermeable composition.
  • Contiguous, open-cell pores are particularly effective at increasing permeability. Gases can readily travel from pore to pore without impediment. Large pore size also facilitates gas transport. In contrast, small pore size requires greater pressure to infuse the permeable composition with gas. Large pores, of course, can decrease the strength of the material.
  • the average pore size of the gas- permeable refractory is at least about one micron and less than five millimeters.
  • Gas delivery systems can increase gas transport. Such systems comprise channels, grooves or devices within or on a surface of the refractory article.
  • Figure 1 shows a device 12 within the article. The device can be perforated to permit uniform distribution of gas along its length. Channels 13 on the interior of the nozzle 2 perform a similar function. Channels are frequently produced by burning out wax or other low melting point material that had been pressed or cast into the refractory article.
  • a metal can 14 may be used with the refractory article, especially when the article is a collector nozzle of a ladle or tundish.
  • a metal canl4 often improves physical integrity and creates a mechanical barrier to oxygen diffusion.
  • An added benefit is the ability to create a gas channel from a groove 15 on the outer surface 8 of the nozzle 2 and the metal can 14. Such grooves are often easier to manufacture than gas channels within the refractory article.
  • Figure 2 shows an alternative embodiment of the present invention.
  • a subentry nozzle 2 extends from an interior volume 21 of a tundish 20 to a mold 22.
  • the nozzle 2 comprises an impermeable liner 9 surrounded by a permeable composition 10.
  • the nozzle 2 includes a top surface 5 surrounding the inlet 6.
  • the permeable composition 10 extends to the top surface 5.
  • Forcing inert gas through the permeable composition 10 at a pressure higher than the ferrostatic head can force the gas to exit the top surface 5, thereby purging the molten metal within the tundish 20.
  • purging can also be accomplished with a well nozzle of appropriate construction.
  • the impermeable and permeable compositions should form a single refractory article.
  • the compositions may be co-pressed; one composition may be formed around or within the other composition; or pieces comprising first and second compositions may be joined together, such as by mortaring.
  • Co-pressing is useful when the first and second compositions are particulates, and is particularly useful when the compositions require similar processing, such as, curing cycles, for example, when both compositions are resin-bonded compositions. Pressing includes isostatic and standard, uniaxial pressing. Co-pressing is also possible when one composition is pressed with a preform piece of the other composition. For example, a material may be pressed and fired to form a permeable, carbon-bonded preform. A second material, which will form the impermeable composition, can then be pressed and cured with the permeable preform to form the refractory article.
  • an impermeable composition may be pressed and a permeable material may be molded in or cast around the second material.
  • a slide gate plate may have a liner comprising the impermealbe material and a porous castable material may comprise the remainder of the plate.
  • the method of the present invention includes lining a bore of a refractory article with a substantially gas impermeable composition, surrounding at least a portion of the impermeable composition with a gas-permeable composition, and flooding the permeable composition with inert gas.
  • an overpressure of inert gas shields the molten metal from oxygen.
  • the inert gas shields molten metal within the bore from oxygen and purges molten metal within a metallurgical vessel.

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

Abstract

La présente invention concerne une buse (1) permettant de distribuer un flux de métal liquide à partir d'un convertisseur métallurgique. Combinée à du gaz inerte, la buse peut protéger le flux de métal liquide de l'oxygène et, de plus, elle peut être utilisée pour purger le métal liquide résidant dans le convertisseur métallurgique. La buse comprend une chemise (9) sensiblement imperméable au gaz entourée d'une composition perméable (10). La chemise imperméable au gaz peut comprendre un matériau lié par la résine et la chemise perméable est de préférence un matériau réfractaire lié au carbone ou un matériau réfractaire coulable. Une enveloppe métallique (14) peut entourer la buse.
PCT/US2003/027209 2002-09-03 2003-09-02 Buse a gaz purge WO2004022267A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA002497298A CA2497298A1 (fr) 2002-09-03 2003-09-02 Buse a gaz purge
BR0313972-7A BR0313972A (pt) 2002-09-03 2003-09-02 Bocal refratário para uso no lingotamento de metal em fusão
EP03749254A EP1536902A1 (fr) 2002-09-03 2003-09-02 Buse a gaz purge
US10/530,092 US20060071041A1 (en) 2002-09-03 2003-09-02 Gas purged nozzle
MXPA05002446A MXPA05002446A (es) 2002-09-03 2003-09-02 Surtidor purgado con gas.
AU2003268298A AU2003268298A1 (en) 2002-09-03 2003-09-02 Gas purged nozzle

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40781502P 2002-09-03 2002-09-03
US60/407,815 2002-09-03

Publications (1)

Publication Number Publication Date
WO2004022267A1 true WO2004022267A1 (fr) 2004-03-18

Family

ID=31978518

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/027209 WO2004022267A1 (fr) 2002-09-03 2003-09-02 Buse a gaz purge

Country Status (11)

Country Link
US (1) US20060071041A1 (fr)
EP (1) EP1536902A1 (fr)
KR (1) KR20050057141A (fr)
CN (1) CN1694774A (fr)
AU (1) AU2003268298A1 (fr)
BR (1) BR0313972A (fr)
CA (1) CA2497298A1 (fr)
MX (1) MXPA05002446A (fr)
PL (1) PL375692A1 (fr)
RU (1) RU2005109547A (fr)
WO (1) WO2004022267A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101905319A (zh) * 2010-08-05 2010-12-08 宜兴市耐火材料有限公司 钢铁浇注方法及下水口砖
CN102380591A (zh) * 2011-11-16 2012-03-21 中钢集团洛阳耐火材料研究院有限公司 一种弥散狭缝型透气上水口的制备工艺
AT517239B1 (de) * 2015-05-28 2019-07-15 Sheffield Hi Tech Refractories Germany Gmbh Stopfen in einem Zusammenwirken mit einer Bodenausgussdüse in einem metallurgischen Gefäß
MX2022003124A (es) * 2019-10-10 2022-04-06 Refractory Intellectual Property Gmbh & Co Kg Producto prensado isostaticamente para su uso en el manejo de metales fundidos y metodo de produccion.
CN113102743B (zh) * 2021-04-15 2022-09-13 北京利尔高温材料股份有限公司 一种连铸用高可靠免预热长水口及其制作方法
CN113560559B (zh) * 2021-09-27 2022-01-07 日照利尔高温新材料有限公司 长寿命浸入式水口的制备方法及长寿命浸入式水口

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6120660A (ja) * 1984-07-09 1986-01-29 Toshiba Ceramics Co Ltd 溶融金属容器の上ノズル
US4779775A (en) * 1985-08-29 1988-10-25 Kurosaki Refractories Co., Ltd. Casting nozzle
EP0399407A1 (fr) * 1989-05-22 1990-11-28 Vesuvius France S.A. Revêtement imperméable pour matériau réfractaire, pièce revêtue de ce matériau et produit de revêtement
US5691061A (en) * 1994-06-15 1997-11-25 Vesuvius Crucible Company Refractory shape having an external layer capable of forming a layer impermeable to gases and process for its preparation
US5723055A (en) * 1995-10-10 1998-03-03 Vesuvius Crucible Company Nozzle assembly having inert gas distributor
WO2000078484A1 (fr) * 1999-06-22 2000-12-28 Foseco International Limited Article forme d'une matiere refractaire a liaison de carbone

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6475426B1 (en) * 2001-03-27 2002-11-05 Vesuvius Crucible Company Resin-bonded liner

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6120660A (ja) * 1984-07-09 1986-01-29 Toshiba Ceramics Co Ltd 溶融金属容器の上ノズル
US4779775A (en) * 1985-08-29 1988-10-25 Kurosaki Refractories Co., Ltd. Casting nozzle
EP0399407A1 (fr) * 1989-05-22 1990-11-28 Vesuvius France S.A. Revêtement imperméable pour matériau réfractaire, pièce revêtue de ce matériau et produit de revêtement
US5691061A (en) * 1994-06-15 1997-11-25 Vesuvius Crucible Company Refractory shape having an external layer capable of forming a layer impermeable to gases and process for its preparation
US5723055A (en) * 1995-10-10 1998-03-03 Vesuvius Crucible Company Nozzle assembly having inert gas distributor
WO2000078484A1 (fr) * 1999-06-22 2000-12-28 Foseco International Limited Article forme d'une matiere refractaire a liaison de carbone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 010, no. 171 (M - 489) 17 June 1986 (1986-06-17) *

Also Published As

Publication number Publication date
CA2497298A1 (fr) 2004-03-18
AU2003268298A1 (en) 2004-03-29
CN1694774A (zh) 2005-11-09
MXPA05002446A (es) 2005-05-27
BR0313972A (pt) 2005-07-19
RU2005109547A (ru) 2005-09-10
US20060071041A1 (en) 2006-04-06
EP1536902A1 (fr) 2005-06-08
KR20050057141A (ko) 2005-06-16
PL375692A1 (en) 2005-12-12

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