WO2004016568A1 - Refractory coating for ladles used in the stainless steel industry - Google Patents

Refractory coating for ladles used in the stainless steel industry Download PDF

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Publication number
WO2004016568A1
WO2004016568A1 PCT/ES2002/000397 ES0200397W WO2004016568A1 WO 2004016568 A1 WO2004016568 A1 WO 2004016568A1 ES 0200397 W ES0200397 W ES 0200397W WO 2004016568 A1 WO2004016568 A1 WO 2004016568A1
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Prior art keywords
stainless steel
percentage
weight
steel industry
thermal shock
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PCT/ES2002/000397
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Spanish (es)
French (fr)
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Pedro FAJARDO SOLÁ
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Fajardo Sola Pedro
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Application filed by Fajardo Sola Pedro filed Critical Fajardo Sola Pedro
Priority to AU2002367502A priority Critical patent/AU2002367502A1/en
Priority to PCT/ES2002/000397 priority patent/WO2004016568A1/en
Publication of WO2004016568A1 publication Critical patent/WO2004016568A1/en

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    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/02Linings
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    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/013Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics containing carbon
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    • C04B35/03Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/043Refractories from grain sized mixtures
    • C04B35/0435Refractories from grain sized mixtures containing refractory metal compounds other than chromium oxide or chrome ore
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    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00Casings; Linings; Walls; Roofs
    • F27D1/0003Linings or walls
    • F27D1/0006Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00Casings; Linings; Walls; Roofs
    • F27D1/16Making or repairing linings increasing the durability of linings or breaking away linings
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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Definitions

  • the invention that is protected in this Patent consists of a refractory coating for spoons of the stainless steel industry.
  • refractory materials are widely known in the stainless steel industry for the interior lining of the spoons that serve for the reception and transfer in the elaboration of said product in order to withstand the working temperatures, generally of the order of 1,650 degrees Celsius , and its consequent impacts on its reception and its physical-chemical reactions.
  • the various compositions of the refractory materials lead to varying degrees of hardness and resistance to cope with abrasion wear, chemical aggressions, operating time, thermal shock and working temperatures.
  • a refractory material of greater hardness and resistance to those already known about three times higher than conventional materials is achieved.
  • various refractory materials are known and used; but all of them have both operational and functional problems.
  • a combination of chemical elements is carried out due to their physical properties - magnesite (MgCO3), alumina (AI2O3), graphite, and improving additives and binding resins; whose structure has a low porosity and high refractory capacity.
  • This combination of crystalline solid compounds consisting mainly of magnesite-alumina-graphite is made with exact character in percentages by weight for each substance, in order to look for a high refractory capacity and an increase in the useful life of the interior lining refractory material of the transfer and pouring spoons of the stainless steel industry.
  • the coating material can be made and arranged as follows:
  • Magnesite (MgCO3) between 64-70%, preferably of a seawater magnesite, a weight percentage of alumina (AI2O3) between 12-18%, and 7-11% Graphite.
  • the graphite purity is preferably 94% crystalline and in flakes.
  • additives improving thermal shock and thermal resistance and oxidation (in a joint composition of aluminum powder, silicon metal, silicon carbide and clay) of between 7 - 9%.
  • phenolic resins between 3-4% by weight percentage.

Abstract

The invention relates to a refractory coating for ladles used in the stainless steel industry. The inventive coating is designed to provide resistance to thermal shock and physico-chemical reactions by means of a chemical composition comprising between 64 and 70 wt.- % magnesite (MgCO3), between 12 and 18 wt.- % alumina (Al2O3), between 7 and 11 % graphite and between 7 and 9 wt.- % of additives used to improve thermal shock, heat resistance and oxidation (in a combined composition of aluminium powder, silicon metal, silicon carbide and clay). Moreover, the invention comprises between 3 and 4 wt.- % phenolic resins by way of a binder, in relation to the total percentages referred to above.

Description

REVESTIMIENTO REFRACTARIO PARA CUCHARAS DE LA INDUSTRIA DEL ACERO INOXIDABLEREFRACTORY COATING FOR SPOONS IN THE STAINLESS STEEL INDUSTRY
DESCRIPCIÓNDESCRIPTION
La invención que se protege en esta Patente, consiste en un revestimiento refractario para cucharas de la industria del acero inoxidable.The invention that is protected in this Patent, consists of a refractory coating for spoons of the stainless steel industry.
Se trata, por tanto, de un material aplicable a los recubrimientos interiores de las cucharas de transferencia y de colada en los procedimientos de fabricación de acero inoxidable, en orden a su capacidad refractaria, y de resistencia a la agresión química, térmica, y a la abrasión.It is, therefore, a material applicable to the internal coatings of the transfer and pouring spoons in the stainless steel manufacturing processes, in order to their refractory capacity, and resistance to chemical, thermal aggression, and abrasion.
El uso de materiales refractarios es ampliamente conocido en la industria del acero inoxidable para el revestimiento interior de las cucharas que sirven para la recepción y trasvase en la elaboración de dicho producto con objeto de soportar las temperaturas de trabajo, generalmente del orden de 1.650 grados centígrados, y sus consiguientes impactos a su recepción y a sus reacciones físico-químicas. Sin embargo, las diversas composiciones de los materiales refractarios conllevan a la par distintos grados de dureza y resistencia para hacer frente al desgaste por abrasión, a las agresiones químicas, a su tiempo de operación, a su choque térmico y a las temperaturas de trabajo. A tal efecto, con la presente invención se logra un material refractario de mayor dureza y resistencia a los ya conocidos en torno a tres veces superior a los materiales convencionales. En la actualidad, se conocen, y son utilizados diversos materiales refractarios; pero todos ellos presentan inconvenientes tanto operativos como funcionales. Y muy especialmente con respecto al desgaste progresivo por las altas temperaturas del acero , como por su desconchado y resquebrajamiento, o bien por su rápido desgaste en la zona de recepción del acero a las temperaturas de trabajo; con lo cual el uso de los medios ya desarrollados presentan siempre ciertas limitaciones frente a la invención que se presenta, en base a sus ventajas técnicas y económicas.The use of refractory materials is widely known in the stainless steel industry for the interior lining of the spoons that serve for the reception and transfer in the elaboration of said product in order to withstand the working temperatures, generally of the order of 1,650 degrees Celsius , and its consequent impacts on its reception and its physical-chemical reactions. However, the various compositions of the refractory materials lead to varying degrees of hardness and resistance to cope with abrasion wear, chemical aggressions, operating time, thermal shock and working temperatures. For this purpose, with the present invention a refractory material of greater hardness and resistance to those already known about three times higher than conventional materials is achieved. At present, various refractory materials are known and used; but all of them have both operational and functional problems. And especially with regard to the progressive wear due to the high temperatures of the steel, such as its chipping and cracking, or because of its rapid wear in the steel receiving area at working temperatures; whereby the use of the means already developed always have certain limitations against the invention presented, based on its technical and economic advantages.
Así, son ya conocidos como materiales refractarios, los compuestos basados en la alúmina y el oxido de magnesio y que incorporan a otros elementos añadidos como la zirconia ( ZrO2 ), el cromo ( Cr2O3 ) o el carburo de silicio ( SiO2 ) entre otros y que se reflejan, respectivamente, en la patente coreana n° KR194333B1 de POSCO REFRACTORIES con alúmina-magnesia- carbono, la patente inglesa GB2101985 de AIKOH y NAMCO AIKOH comprendiendo la zirconia, la patente belga n° 858084 de MAGNESITAL- FEUERFES en relación al juego del cromo, la japonesa n° JP07330452 con el carburo de silicio de HARIMA CERAMIC y NIPPON STEEL; y todas ellas como anterioridades próximas a la invención que se presenta, pero con un amplio espectro de porcentajes de los distintos componentes aplicables a otros tipos de aceros que, en el caso específico que nos ocupa de aceros inoxidables, se da una relación de magnesia-alúmina indicada que, junto con el grafito, presentan un óptimo resultado que se reafirma con los aditivos que más adelante se detallan. Por tanto, resultan todas ellas, genéricas, imprecisas o alejadas con respecto a la misma y a su aplicación. Siendo invenciones todas de las que resultan composiciones químicas o formas, o bien no aplicadas a la especificidad de las cucharas de la fabricación de acero, o bien en porcentajes y/o composiciones de materiales de diferente naturaleza. Estas carencias se superan con la composición química de la invención - magnesita ( MgCO3 ) , alúmina ( AI2O3 ), grafito - , y aditivos mejoradores y resinas fenólicas -; la cual supera las limitaciones antes citadas y acrecienta su operatividad y rendimiento. Además presenta en su aplicación unos elementos que favorecen significativamente su uso en las cucharas de la industria del acero inoxidable.Thus, they are already known as refractory materials, compounds based on alumina and magnesium oxide and incorporating other added elements such as zirconia (ZrO2), chromium (Cr2O3) or silicon carbide (SiO2) among others and which are reflected, respectively, in the Korean Patent No. KR194333B1 of POSCO REFRACTORIES with alumina-magnesia-carbon, the English patent GB2101985 of AIKOH and NAMCO AIKOH comprising zirconia, the Belgian patent No. 858084 of MAGNESITAL-FEUERFES in relation to the game from chrome, the Japanese n ° JP07330452 with HARIMA CERAMIC silicon carbide and NIPPON STEEL; and all of them as prior to the invention presented, but with a wide spectrum of percentages of the different components applicable to other types of steels that, in the specific case that concerns us with stainless steels, a magnesia ratio is given. alumina indicated that, together with graphite, they have an optimal result that is reaffirmed with the additives detailed below. Therefore, they are all, generic, inaccurate or remote with respect to it and its application. Being inventions all of which result in chemical compositions or forms, or not applied to the specificity of the steel-making spoons, or in percentages and / or compositions of materials of different nature. These deficiencies are overcome with the chemical composition of the invention - magnesite (MgCO3), alumina (AI2O3), graphite -, and enhancement additives and phenolic resins -; which overcomes the aforementioned limitations and increases its operability and performance. It also presents in its application some elements that significantly favor its use in the spoons of the stainless steel industry.
Con referencia a la invención que se describe, se procede a una combinación de elementos químicos por razón de sus propiedades físicas - magnesita ( MgCO3 ) , alúmina ( AI2O3 ), grafito , y aditivos mejoradores y resinas ligantes ; cuyo estructura presenta una baja porosidad y alta capacidad refractaria.With reference to the invention described, a combination of chemical elements is carried out due to their physical properties - magnesite (MgCO3), alumina (AI2O3), graphite, and improving additives and binding resins; whose structure has a low porosity and high refractory capacity.
Esta combinación de compuestos sólidos cristalinos constituidos fundamentalmente por magnesita-alúmina-grafito es confeccionada con carácter exacto en porcentajes en peso por cada sustancia, con el fin de buscar una alta capacidad refractaria y un incremento de la vida útil del material refractario de revestimiento interior de las cucharas de transferencia y de colada de la industria del acero inoxidable.This combination of crystalline solid compounds consisting mainly of magnesite-alumina-graphite is made with exact character in percentages by weight for each substance, in order to look for a high refractory capacity and an increase in the useful life of the interior lining refractory material of the transfer and pouring spoons of the stainless steel industry.
En suma, el resultado obtenido por la combinación y porcentajes determinados de estos elementos permite lograr una ventaja técnica con un producto de mayor dureza y de mayor resistencia al desgaste por el calor del acero fundido y de su choque térmico y las consiguientes reacciones físico- químicas que sufre, y de la que derivan notables ventajas económicas; puesto que con la nueva invención se aumenta el número de los ciclos de utilización de las cucharas, así como también conlleva además de las mencionadas mejoras técnicas y económicas, a una ventaja en el proceso productivo. El material de revestimiento puede ser realizado y dispuesto de la siguiente manera :In sum, the result obtained by the combination and determined percentages of these elements allows to achieve a technical advantage with a product of greater hardness and greater resistance to heat wear of molten steel and its thermal shock and the consequent physicochemical reactions that suffers, and from which derive remarkable economic advantages; since with the new invention the number of the cycles of use of the spoons is increased, as well as also entails in addition to the mentioned technical and economic improvements, to an advantage in the productive process. The coating material can be made and arranged as follows:
En relación a los componentes químicos, un; porcentaje en peso deIn relation to chemical components, a; weight percentage of
Magnesita ( MgCO3 ) entre el 64 - 70 %, preferentemente de una magnesita de agua de mar, un porcentaje en peso de Alúmina ( AI2O3 ) entre un 12 - 18 %, y un 7 - 11 % de Grafito. Siendo la pureza del Grafito preferentemente de un 94 % cristalino y en escamas. Así como un porcentaje en peso de aditivos mejoradores del choque térmico y la resistencia térmica y la oxidación ( en una composición conjunta de aluminio en polvo, silicio metal, carburo de silicio y arcilla ) de entre un 7 - 9 %. Utilizándose como ligante sobre estos porcentajes totales a unas resinas fenólicas de entre un 3 - 4 % de porcentaje en peso.Magnesite (MgCO3) between 64-70%, preferably of a seawater magnesite, a weight percentage of alumina (AI2O3) between 12-18%, and 7-11% Graphite. The graphite purity is preferably 94% crystalline and in flakes. As well as a percentage by weight of additives improving thermal shock and thermal resistance and oxidation (in a joint composition of aluminum powder, silicon metal, silicon carbide and clay) of between 7 - 9%. Using as a binder over these total percentages to phenolic resins of between 3-4% by weight percentage.
Y en relación a su disposición en las cucharas, tanto en la de colada como la de transferencia, es preferente su utilización las zonas de impacto, pared y fondo y en los niveles de alcance de la escoria. And in relation to its arrangement in the spoons, both in the casting and transfer, the use of the impact, wall and bottom areas and in the slag reach levels is preferred.

Claims

REIVINDICACIONES
jL - Revestimiento refractario para cucharas de la industria del acero inoxidable para una resistencia al choque térmico y las reacciones físico -químicas caracterizado porque su composición química comprende la combinación de un porcentaje en peso mayor o igual un porcentaje en peso de Magnesita ( MgCO3 ) entre el 64 - 70 %, un porcentaje en peso de Alúmina ( AI2O3 ) entre un 12 - 18 %, y un 7 - 11 % de Grafito. Así como un porcentaje en peso de aditivos mejoradores del choque térmico y la resistencia térmica y la oxidación ( en una composición conjunta de aluminio en polvo, silicio metal, carburo de silicio y arcilla ) de entre un 7 - 9 %. Utilizándose como ligante sobre estos porcentajes totales a unas resinas fenólicas de entre un 3 - 4 % de porcentaje en peso. jL - Refractory coating for stainless steel industry spoons for resistance to thermal shock and physical-chemical reactions characterized in that its chemical composition comprises the combination of a percentage by weight greater than or equal to a percentage by weight of Magnesite (MgCO3) between 64-70%, a weight percentage of alumina (AI2O3) between 12-18%, and 7-11% graphite. As well as a percentage by weight of additives improving thermal shock and thermal resistance and oxidation (in a joint composition of aluminum powder, silicon metal, silicon carbide and clay) of between 7 - 9%. Using as a binder over these total percentages to phenolic resins of between 3-4% by weight percentage.
PCT/ES2002/000397 2002-08-08 2002-08-08 Refractory coating for ladles used in the stainless steel industry WO2004016568A1 (en)

Priority Applications (2)

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AU2002367502A AU2002367502A1 (en) 2002-08-08 2002-08-08 Refractory coating for ladles used in the stainless steel industry
PCT/ES2002/000397 WO2004016568A1 (en) 2002-08-08 2002-08-08 Refractory coating for ladles used in the stainless steel industry

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2002/000397 WO2004016568A1 (en) 2002-08-08 2002-08-08 Refractory coating for ladles used in the stainless steel industry

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007077267A2 (en) 2005-12-30 2007-07-12 Fajardo Sola Pedro Improved refractory coating for ladles used in the stainless steel industry
EP1984133A1 (en) * 2005-11-03 2008-10-29 North Cape Minerals AS Process for the production of a wear lining from a particulate refractory material for casting ladles and pouring boxes, together with the wear lining made in this way
WO2010094410A1 (en) * 2009-02-20 2010-08-26 Hexion Specialty Chemicals Gmbh Ceramic product

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES272636U (en) * 1981-05-08 1984-03-16 Quigley Company, Inc. Monolithic refractory layer for metallurgical vessels and method of application.
JPS5957968A (en) * 1982-09-28 1984-04-03 新日本製鐵株式会社 Blast furnace tap hole sealing material
ES8802123A1 (en) * 1985-04-20 1988-04-01 Foseco Trading Ag Pouring tubes.
ES2089526T3 (en) * 1991-03-27 1996-10-01 Minteq International Inc AGROMERATED REFRACTORY COMPOSITION WITH RESIN THAT FLUIDS BY VIBRATION.
EP1052233A1 (en) * 1998-01-28 2000-11-15 Krosaki Corporation Alumina-magnesia-graphite type refractory

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES272636U (en) * 1981-05-08 1984-03-16 Quigley Company, Inc. Monolithic refractory layer for metallurgical vessels and method of application.
JPS5957968A (en) * 1982-09-28 1984-04-03 新日本製鐵株式会社 Blast furnace tap hole sealing material
ES8802123A1 (en) * 1985-04-20 1988-04-01 Foseco Trading Ag Pouring tubes.
ES2089526T3 (en) * 1991-03-27 1996-10-01 Minteq International Inc AGROMERATED REFRACTORY COMPOSITION WITH RESIN THAT FLUIDS BY VIBRATION.
EP1052233A1 (en) * 1998-01-28 2000-11-15 Krosaki Corporation Alumina-magnesia-graphite type refractory

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1984133A1 (en) * 2005-11-03 2008-10-29 North Cape Minerals AS Process for the production of a wear lining from a particulate refractory material for casting ladles and pouring boxes, together with the wear lining made in this way
EP1984133A4 (en) * 2005-11-03 2009-11-25 North Cape Minerals As Process for the production of a wear lining from a particulate refractory material for casting ladles and pouring boxes, together with the wear lining made in this way
WO2007077267A2 (en) 2005-12-30 2007-07-12 Fajardo Sola Pedro Improved refractory coating for ladles used in the stainless steel industry
WO2007077267A3 (en) * 2005-12-30 2008-06-19 Sola Pedro Fajardo Improved refractory coating for ladles used in the stainless steel industry
WO2010094410A1 (en) * 2009-02-20 2010-08-26 Hexion Specialty Chemicals Gmbh Ceramic product
EP2230225A1 (en) * 2009-02-20 2010-09-22 Hexion Specialty Chemicals GmbH Ceramic product
CN102333740A (en) * 2009-02-20 2012-01-25 迈图特种化工有限公司 Ceramic product

Also Published As

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