EP1899648A2 - Molding compound for producing a refractory lining - Google Patents

Molding compound for producing a refractory lining

Info

Publication number
EP1899648A2
EP1899648A2 EP06763976A EP06763976A EP1899648A2 EP 1899648 A2 EP1899648 A2 EP 1899648A2 EP 06763976 A EP06763976 A EP 06763976A EP 06763976 A EP06763976 A EP 06763976A EP 1899648 A2 EP1899648 A2 EP 1899648A2
Authority
EP
European Patent Office
Prior art keywords
less
molding
refractory lining
molding compound
fired
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.)
Withdrawn
Application number
EP06763976A
Other languages
German (de)
French (fr)
Inventor
Holger Grote
Marc Tertilt
Wolfgang Kollenberg
Dieter Nikolay
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.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Priority to EP06763976A priority Critical patent/EP1899648A2/en
Publication of EP1899648A2 publication Critical patent/EP1899648A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped 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 aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase

Definitions

  • the invention relates to a molding compound for producing a refractory lining, in particular for a combustion chamber of a stationary gas turbine. Furthermore, the invention relates to a fired molded part, which has been produced on the basis of such a molding composition, an associated refractory lining and finally a method for
  • the walls of high-temperature reactors must be protected with suitable linings or shields, so that in particular underlying supporting structures are protected against hot gas attack.
  • a shield ceramic materials are generally better suited than metallic materials, because they are more temperature resistant and corrosion resistant and have a lower thermal conductivity.
  • the ceramic linings which are often also referred to as ceramic heat shields, have generally been produced by a sintering process in which the protective properties of the ceramics were then determined.
  • An object of the invention is to provide a molding material and a molded article molded therefrom for a refractory lining of the type mentioned, which can be processed with a comparatively low sintering temperature, for example, and thus opens up new possibilities in the development of high-temperature resistant composite components.
  • the molding compound must meet the requirements for ceramic components for use in stationary gas turbines in the hot gas path.
  • the object is achieved according to the invention with a molding compound for producing a refractory lining, which is formed with a weight fraction of more than approximately 50% aluminum oxide and a weight fraction of less than 50% aluminum silicate. Furthermore, the object is achieved with a fired shaped part for a refractory lining, which has a weight fraction of more than about 50% and less than about 90% aluminum oxide and / or a weight fraction of more than about 10% and less than about 50% aluminum silicate.
  • the object is also achieved according to the invention with a method for producing a fired molded part of a refractory lining, comprising the following steps: preparing a molding composition with at least the proportions of alumina and aluminum silicate with the addition of colloidal silica solution, casting the molding compound under vibration, leaps and bounds Lowering the temperature of the molding composition, as well as drying and firing the potted molding compound.
  • the molding composition may further contain less than about 30% by weight.
  • the molding compound composed according to the invention of said specific proportions by weight of aluminum oxide or aluminum silicate forms a base material which can be particularly advantageously solidified by addition of colloidal silica solution in a so-called sol-gel process and further processed by casting under vibration. That one- when initially present as sol or colloidal solution silica is converted by said abrupt lowering of the temperature in a gel and thus the molding material, which can also be referred to as a casting or vibrating mass, solidified.
  • the actual drying and sintering process can subsequently take place at comparatively low firing temperatures, as will be explained in more detail below.
  • mass in the inventive form ⁇ as corundum aluminum oxide, ie aluminum oxide in trigonal tional structure with the chemical formula Al 2 O 3, in particular in a proportion by weight of between about 50% and 90% is used.
  • the proportion by weight of the aluminum silicate used is particularly advantageously between about 10% and 50%, most preferably less than about 45%.
  • the aluminum silicate is advantageously mullite having the chemical formula 3Al 2 O 3 -2SiO 2 or 2Al 2 O 3 -ISiO 2 .
  • the molding composition according to the invention should advantageously be free of unbonded silicon oxide, SiO 2 or the proportion by weight of such silicon oxide should be at least less than approximately 5%. Finally, it is also advantageous if the molding material is free of calcium aluminates.
  • the proportion by weight of the colloidal silicic acid solution added according to the invention should advantageously be less than approximately 10%. Further, the colloidal silica solution should have a solids content of at least about 30 weight percent.
  • the molding composition should preferably be admixed with a liquid, in particular water, with a weight fraction of more than approximately 1% and less than approximately 10%.
  • the maximum grain size should typically be between about 20 and about 5 mm.
  • the weight fraction of this grain fraction should be less than about 25%.
  • the molding composition according to the invention should be supplemented with a weight fraction of less than approximately 30%, in particular less than approximately 25%, of reactive clay.
  • the molded part according to the invention should have proportions by weight in its composition which essentially correspond to those of the abovementioned molding compositions.
  • the open porosity of the fired molding should be greater than about 10%, more preferably greater than about 15%, and less than about 35%.
  • the inventively advantageously ange ⁇ targeted density of the fired molding is less than about 3.5 g / cm, in particular less than about 3.0 g / cm 3 .
  • the fired molding according to the invention should be adjusted to an average bending strength under normal conditions of more than about 7.0 MPa.
  • the specified mean bending strength is measured with a 3-point bending test.
  • the molded part thus produced from a molding composition according to the invention can be used particularly advantageously as a refractory lining in combustion chambers of stationary gas turbines.
  • the molding compound is vibrated by solidification on the
  • the ambient temperature of the molding material abruptly to a temperature of less than about O 0 C and lowered there, in particular over a period of more than about 15 min and held less than about 2.5 h.
  • a cooling temperature of the environment is particularly preferred.
  • the finished potted molding composition according to the invention preferably at a temperature of between about 1300 0 C and about 165O 0 C burned.
  • a fiber-reinforced ceramic is preferably fired at a temperature between about 1300 0 C and about 1400 0 C.
  • a firing temperature of between about 1300 0 C and about 1600 0 C is preferred.
  • the FIGURE shows a schematic flow diagram of a manufacturing process of a refractory lining including the preparation of the molding compound used.
  • a molded part provided as a refractory lining of a combustion chamber of a stationary gas turbine is produced according to the figure from a molding compound which is mixed together in a first step from essentially five constituents.
  • These five ingredients are specified in the Fig. With the reference numerals 10, 12, 14, 16 and 18 referred to in this order and include corundum (Al 2 O 3), mullite (2Al 2 O 3 -ISiO 2), silica ⁇ acid (Si (OH) 4 ), water (H 2 O), and reactive alumina.
  • the proportions by weight of these materials in alumina are between about 55% and 70% for aluminum oxide, between about 30% and 45% for mullite as aluminum silicate, and between about 4% and 7% for water.
  • the silica is as SoI or colloidal solution with a weight of between about 4% and 8% added.
  • the proportion of reactive clay is between about 15% and 30%.
  • the thus prepared casting mold is cooled temperature abruptly starting from Hauttem ⁇ , by exposure to an atmosphere having a temperature of about -25 0 C.
  • the silicic acid present therein as sol is solidified into a gel.
  • the molding material is solidified as a whole and prepared in a particularly advantageous manner for a designated last step 26 of drying and firing.
  • Sintering temperature of between about 1300 0 C and about 1600 0 C burned. Because of this comparatively low firing temperature employed can Faserver ⁇ are reinforcements in the form of mass, so that a fiber-reinforced ceramic can be produced as a whole.
  • the ceramic produced has particularly advantageous mecha ⁇ African properties with a particularly low tendency to form thermal cracks. This is based in particular on the fact that a special microcrack structure has been created in the ceramic by the mentioned sol-gel process and also due to the high proportion of aluminum oxide, which leads, inter alia, for example, to a considerable reduction in the crack lengths of edge cracks.
  • the casting compound as a whole is free of cement (ie essentially has no CaO) and, on account of the low sintering temperature, also results in cost advantages in the production process.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention relates to a molding compound for producing a refractory lining, especially for a combustion chamber of a stationary gas turbine. The inventive compound is especially characterized in that the molding compound comprises, in weight percent, more than approximately 50 % of aluminium oxide (10) and, in weight percent, less than approximately 50 % of aluminium silicate (12).

Description

Formmasse zum Herstellen einer feuerfesten AuskleidungMolding composition for producing a refractory lining
Die Erfindung betrifft eine Formmasse zum Herstellen einer feuerfesten Auskleidung, insbesondere für eine Brennkammer einer stationären Gasturbine. Ferner betrifft die Erfindung ein gebranntes Formteil, das auf der Grundlage einer derartigen Formmasse hergestellt worden ist, eine zugehörige feuer- feste Auskleidung sowie schließlich auch ein Verfahren zumThe invention relates to a molding compound for producing a refractory lining, in particular for a combustion chamber of a stationary gas turbine. Furthermore, the invention relates to a fired molded part, which has been produced on the basis of such a molding composition, an associated refractory lining and finally a method for
Herstellen eines gebrannten Formteils einer feuerfesten Auskleidung .Making a fired molding of a refractory lining.
Im Bereich der Brennkammertechnik müssen, wie beispielsweise bei Gasturbinen-Brennkammern, die Wände von Hochtemperaturreaktoren mit geeigneten Auskleidungen bzw. Abschirmungen geschützt werden, damit insbesondere sich dahinter befindende tragende Strukturen gegen Heißgasangriff geschützt sind. Als Abschirmung sind keramische Materialien in der Regel besser geeignet als metallische Werkstoffe, weil sie temperaturbeständiger sowie korrosionsbeständiger sind und eine niedrigere Wärmeleitfähigkeit aufweisen.In the field of combustion chamber technology, such as in gas turbine combustors, the walls of high-temperature reactors must be protected with suitable linings or shields, so that in particular underlying supporting structures are protected against hot gas attack. As a shield ceramic materials are generally better suited than metallic materials, because they are more temperature resistant and corrosion resistant and have a lower thermal conductivity.
Die keramischen Auskleidungen, welche oftmals auch als kera- mische Hitzeschilde bezeichnet werden, sind in der Regel durch einen Sinterungsprozess hergestellt worden, bei dem dann auch die schützenden Eigenschaften der Keramiken festgelegt wurden.The ceramic linings, which are often also referred to as ceramic heat shields, have generally been produced by a sintering process in which the protective properties of the ceramics were then determined.
An die keramischen Hitzeschilde werden ferner hohe Anforderungen hinsichtlich ihrer mechanischen Belastbarkeit gestellt und es wird verstärkt versucht hier Verbesserungen durch Herstellen von Composite-Bauteilen, wie beispielsweise mit faserverstärkten Bauteilen auf Basis CMC (ceramic matrix com- posites) , oder mit Strukturkeramik-Bauteilen oder gradierten Bauteilen besonders gute mechanische Eigenschaften zu erzielen . Eine Aufgabe der Erfindung ist es, eine Formmasse sowie ein daraus gebranntes Formteil für eine feuerfeste Auskleidung der eingangs genannten Art bereitzustellen, welche mit einer z.B. vergleichsweise geringen Sintertemperatur verarbeitet werden kann und dadurch neue Möglichkeiten bei der Entwicklung von hochtemperaturbeständigen Composite-Bauteilen eröffnet .Furthermore, high demands are placed on the ceramic heat shields with regard to their mechanical strength, and improvements are increasingly being made here by producing composite components, such as, for example, fiber-reinforced components based on CMC (ceramic matrix composites), or structured ceramic components or graded ones Components to achieve very good mechanical properties. An object of the invention is to provide a molding material and a molded article molded therefrom for a refractory lining of the type mentioned, which can be processed with a comparatively low sintering temperature, for example, and thus opens up new possibilities in the development of high-temperature resistant composite components.
Die Formmasse muss die Anforderungen an keramische Bauteile für den Einsatz in stationären Gasturbinen im Heißgaspfad erfüllen .The molding compound must meet the requirements for ceramic components for use in stationary gas turbines in the hot gas path.
Die Aufgabe ist erfindungsgemäß mit einer Formmasse zum Her¬ stellen einer feuerfesten Auskleidung gelöst, die mit einem Gewichtsanteil von mehr als zirka 50% Aluminiumoxid und einem Gewichtsanteil von weniger 50% Aluminiumsilikat gebildet ist. Ferner ist die Aufgabe mit einem gebrannten Formteil für eine feuerfeste Auskleidung gelöst, das einen Gewichtsanteil von mehr als zirka 50% und weniger als zirka 90% Aluminiumoxid und/oder einen Gewichtsanteil von mehr als zirka 10% und weniger als zirka 50% Aluminiumsilikat aufweist. Darüber hin¬ aus ist die Aufgabe auch erfindungsgemäß mit einem Verfahren zum Herstellen eines gebrannten Formteils einer feuerfesten Auskleidung gelöst, welches die folgenden Schritte umfasst: Herstellen einer Formmasse mit mindestens den Anteilen Aluminiumoxid und Aluminiumsilikat unter Zugabe kolloidaler Kieselsäurelösung, Vergießen der Formmasse unter Vibration, sprunghaftes Absenken der Temperatur der Formmasse, sowie Trocknen und Brennen der vergossenen Formmasse. Die Formmasse kann weiterhin einen Gewichtsanteil von weniger als zirka 30% enthalten .The object is achieved according to the invention with a molding compound for producing a refractory lining, which is formed with a weight fraction of more than approximately 50% aluminum oxide and a weight fraction of less than 50% aluminum silicate. Furthermore, the object is achieved with a fired shaped part for a refractory lining, which has a weight fraction of more than about 50% and less than about 90% aluminum oxide and / or a weight fraction of more than about 10% and less than about 50% aluminum silicate. In addition ¬ the object is also achieved according to the invention with a method for producing a fired molded part of a refractory lining, comprising the following steps: preparing a molding composition with at least the proportions of alumina and aluminum silicate with the addition of colloidal silica solution, casting the molding compound under vibration, leaps and bounds Lowering the temperature of the molding composition, as well as drying and firing the potted molding compound. The molding composition may further contain less than about 30% by weight.
Die erfindungsgemäß aus den genannten bestimmten Gewichtsanteilen von Aluminiumoxid bzw. Aluminiumsilikat zusammenge- setzte Formmasse bildet ein Grundmaterial, welches besonders vorteilhaft durch Zugabe von kolloidaler Kieselsäurelösung in einem so genannten Sol-Gel-Prozess verfestigt und ferner mittels Gießen unter Vibration verarbeitet werden kann. Die da- bei zunächst als SoI bzw. kolloidale Lösung vorliegende Kieselsäure wird durch das genannte sprunghafte Absenken der Temperatur in ein Gel überführt und damit die Formmasse, welche auch als Gießmasse oder Vibrationsmasse bezeichnet werden kann, verfestigt. Der eigentliche Trocknungs- und Sinterpro- zess kann nachfolgend bei vergleichsweise geringen Brenntemperaturen erfolgen, wie unten noch genauer erläutert werden wird.The molding compound composed according to the invention of said specific proportions by weight of aluminum oxide or aluminum silicate forms a base material which can be particularly advantageously solidified by addition of colloidal silica solution in a so-called sol-gel process and further processed by casting under vibration. That one- when initially present as sol or colloidal solution silica is converted by said abrupt lowering of the temperature in a gel and thus the molding material, which can also be referred to as a casting or vibrating mass, solidified. The actual drying and sintering process can subsequently take place at comparatively low firing temperatures, as will be explained in more detail below.
Besonders vorteilhaft wird bei der erfindungsgemäßen Form¬ masse als Aluminiumoxid Korund, d.h. Aluminiumoxid in trigo- naler Struktur mit der chemischen Formel Al2O3, insbesondere bei einem Gewichtsanteil zwischen zirka 50% und 90% verwendet.Particularly advantageous is mass in the inventive form ¬ as corundum aluminum oxide, ie aluminum oxide in trigonal tional structure with the chemical formula Al 2 O 3, in particular in a proportion by weight of between about 50% and 90% is used.
Der Gewichtsanteil des verwendeten Aluminiumsilikats beträgt besonders vorteilhaft zwischen zirka 10% und 50%, am Bevorzugtesten weniger als zirka 45%. Das Aluminiumsilikat ist dabei vorteilhaft Mullit mit der chemischen Formel 3Al2O3-2SiO2 oder 2Al2O3-ISiO2.The proportion by weight of the aluminum silicate used is particularly advantageously between about 10% and 50%, most preferably less than about 45%. The aluminum silicate is advantageously mullite having the chemical formula 3Al 2 O 3 -2SiO 2 or 2Al 2 O 3 -ISiO 2 .
Ferner sollte die erfindungsgemäße Formmasse vorteilhaft frei von ungebundenem Siliziumoxid, SiO2 sein oder der Gewichtsanteil von derartigem Siliziumoxid zumindest weniger als zirka 5% sein. Schließlich ist es auch von Vorteil, wenn die Formmasse frei von Calcium-Aluminaten ist.Furthermore, the molding composition according to the invention should advantageously be free of unbonded silicon oxide, SiO 2 or the proportion by weight of such silicon oxide should be at least less than approximately 5%. Finally, it is also advantageous if the molding material is free of calcium aluminates.
Der Gewichtsanteil der erfindungsgemäß zugefügten kolloidalen Kieselsäurelösung sollte vorteilhaft weniger als zirka 10% betragen. Ferner sollte die kolloidale Kieselsäurelösung einen Feststoffgehalt von mindestens zirka 30 Gewichtsprozent aufweisen .The proportion by weight of the colloidal silicic acid solution added according to the invention should advantageously be less than approximately 10%. Further, the colloidal silica solution should have a solids content of at least about 30 weight percent.
Um eine gute Verarbeitbarkeit zu erzielen sollte der Form- masse bevorzugt eine Flüssigkeit, insbesondere Wasser, mit einem Gewichtsanteil von mehr als zirka 1% und weniger als zirka 10% zugegeben sein. Die maximale Korngröße sollte typischerweise zwischen zirka 20 und zirka 5 mm liegen. Der Gewichtsanteil dieser Kornfraktion sollte weniger als zirka 25% sein.In order to achieve good processability, the molding composition should preferably be admixed with a liquid, in particular water, with a weight fraction of more than approximately 1% and less than approximately 10%. The maximum grain size should typically be between about 20 and about 5 mm. The weight fraction of this grain fraction should be less than about 25%.
Alternativ oder zusätzlich sollte die erfindungsgemäße Formmasse mit einem Gewichtsanteil von weniger als zirka 30%, insbesondere von weniger als zirka 25% reaktiver Tonerde ergänzt sein.Alternatively or additionally, the molding composition according to the invention should be supplemented with a weight fraction of less than approximately 30%, in particular less than approximately 25%, of reactive clay.
Das erfindungsgemäß gebrannte Formteil sollte in seiner Zusammensetzung Gewichtsanteile aufweisen, welche im Wesentlichen denen der oben genannten Formmassen entsprechen. Die offene Porosität des gebrannten Formteils sollte mehr als zirka 10%, insbesondere mehr als zirka 15% und weniger als zirka 35% betragen. Die erfindungsgemäß vorteilhaft ange¬ strebte Rohdichte des gebrannten Formteils beträgt weniger als zirka 3,5 g/cm , insbesondere weniger als zirka 3,0 g/cm3.The molded part according to the invention should have proportions by weight in its composition which essentially correspond to those of the abovementioned molding compositions. The open porosity of the fired molding should be greater than about 10%, more preferably greater than about 15%, and less than about 35%. The inventively advantageously ange¬ targeted density of the fired molding is less than about 3.5 g / cm, in particular less than about 3.0 g / cm 3 .
Hinsichtlich der gewünschten mechanischen Eigenschaften sollte das erfindungsgemäße gebrannte Formteil auf eine mittlere Biegefestigkeit bei Normalbedingungen von mehr als zirka 7,0 MPa eingestellt sein. Die angegebene mittlere Biegefestigkeit wird dabei mit einem 3-Punkt-Biegeversuch gemessen.With regard to the desired mechanical properties, the fired molding according to the invention should be adjusted to an average bending strength under normal conditions of more than about 7.0 MPa. The specified mean bending strength is measured with a 3-point bending test.
Das derart aus einer erfindungsgemäßen Formmasse hergestellte Formteil kann besonders vorteilhaft als feuerfeste Auskleidung bei Brennkammern von stationären Gasturbinen verwendet werden. Um es herzustellen, wird, wie oben bereits erwähnt, die Formmasse unter Vibration durch Verfestigung auf derThe molded part thus produced from a molding composition according to the invention can be used particularly advantageously as a refractory lining in combustion chambers of stationary gas turbines. To produce it, as already mentioned above, the molding compound is vibrated by solidification on the
Basis von kolloidaler Kieselsäurelösung hergestellt. Um diese Verfestigung zu erreichen wird erfindungsgemäß bevorzugt die Umgebungstemperatur der Formmasse sprunghaft auf eine Temperatur von weniger als zirka O0C abgesenkt und dort insbeson- dere über einen Zeitraum von mehr als zirka 15 min und weniger als zirka 2,5 h gehalten. Besonders bevorzugt wird eine Abkühltemperatur der Umgebung von zirka -2O0C bis zirka Die fertig vergossene Formmasse wird erfindungsgemäß bevorzugt bei einer Temperatur von zwischen zirka 13000C und zirka 165O0C gebrannt. Für das Brennen einer Monolith-Keramik wird innerhalb dieses Temperaturbereichs eine Temperatur von zwischen zirka 135O0C und zirka 165O0C bevorzugt. Eine faserverstärkte Keramik wird bevorzugt bei einer Temperatur zwischen zirka 13000C und zirka 14000C gebrannt. Für Strukturkeramik wird erfindungsgemäß eine Brenntemperatur von zwischen zirka 13000C und zirka 16000C bevorzugt.Base made of colloidal silicic acid solution. In order to achieve this hardening according to the invention preferably the ambient temperature of the molding material abruptly to a temperature of less than about O 0 C and lowered there, in particular over a period of more than about 15 min and held less than about 2.5 h. Particularly preferred is a cooling temperature of the environment of about -2O 0 C to about The finished potted molding composition according to the invention preferably at a temperature of between about 1300 0 C and about 165O 0 C burned. For the firing of a ceramic monolith to a temperature of between about 135o C and about 165o 0 0 C is preferred within this temperature range. A fiber-reinforced ceramic is preferably fired at a temperature between about 1300 0 C and about 1400 0 C. For structural ceramics according to the invention a firing temperature of between about 1300 0 C and about 1600 0 C is preferred.
Nachfolgend wird ein Ausführungsbeispiel einer erfindungsge¬ mäßen Formmasse, eines daraus hergestellten gebrannten Formteils, einer damit gebildeten feuerfesten Auskleidung sowie ein zugehöriges Verfahren zum Herstellen der Auskleidung anhand der beigefügten schematischen Zeichnungen näher erläutert.Hereinafter, an embodiment of a erfindungsge ¬ MAESSEN molding material, a fired molded part produced therefrom, a refractory lining formed therewith and an associated method for producing the lining will be explained in more detail with reference to the accompanying schematic drawings.
Die Fig. zeigt ein schematisches Ablaufdiagramm eines Her- Stellungsverfahrens einer feuerfesten Auskleidung inklusive der Vorbereitung der verwendeten Formmasse.The FIGURE shows a schematic flow diagram of a manufacturing process of a refractory lining including the preparation of the molding compound used.
Ein als feuerfeste Auskleidung einer Brennkammer einer stationären Gasturbine vorgesehenes Formteil wird gemäß der Fig. aus einer Formmasse hergestellt, welche in einem ersten Arbeitsschritt aus im Wesentlichen fünf Bestandteilen zusammengemischt wird.A molded part provided as a refractory lining of a combustion chamber of a stationary gas turbine is produced according to the figure from a molding compound which is mixed together in a first step from essentially five constituents.
Diese fünf Bestandteile sind in der Fig. mit den Bezugszei- chen 10, 12, 14, 16 und 18 bezeichnet und beinhalten in dieser Reihenfolge Korund (Al2O3), Mullit (2Al2O3-ISiO2), Kiesel¬ säure (Si(OH)4), Wasser (H2O) sowie reaktive Tonerde. Die Gewichtsanteile dieser Materialien betragen beim Korund als Aluminiumoxid zwischen zirka 55% und 70%, beim Mullit als Aluminiumsilikat zwischen zirka 30% und 45% und beim Wasser zwischen zirka 4% und 7%. Die Kieselsäure ist als SoI- bzw. kolloidale Lösung mit einem Gewichtanteil von zwischen zirka 4% und 8% zugegeben. Der Anteil an reaktiver Tonerde beträgt zwischen zirka 15% und 30%.These five ingredients are specified in the Fig. With the reference numerals 10, 12, 14, 16 and 18 referred to in this order and include corundum (Al 2 O 3), mullite (2Al 2 O 3 -ISiO 2), silica ¬ acid (Si (OH) 4 ), water (H 2 O), and reactive alumina. The proportions by weight of these materials in alumina are between about 55% and 70% for aluminum oxide, between about 30% and 45% for mullite as aluminum silicate, and between about 4% and 7% for water. The silica is as SoI or colloidal solution with a weight of between about 4% and 8% added. The proportion of reactive clay is between about 15% and 30%.
Die genannten Bestandteile werden in einem in der Fig. mit Bezugszeichen 20 beschrifteten Mischvorgang zu einer Form¬ masse zusammengefügt, welche nachfolgend in einem mit Bezugszeichen 22 bezeichneten Vergießvorgang unter Vibration in einer Gießform vergossen wird.The constituents mentioned are combined in a mixing process labeled 20 in the FIGURE to form a molding compound which is subsequently cast in a casting mold in a casting process designated by reference numeral 22 under vibration.
Die derart vorbereitete Gießform wird ausgehend von Raumtem¬ peratur sprunghaft abgekühlt, indem sie einer Atmosphäre mit einer Temperatur von zirka -250C ausgesetzt wird. Durch diese sprunghafte Abkühlung der sich in der Gießform befindenden Formmasse verfestigt sich die darin als SoI vorliegende Kie- seisäure zu einem Gel. Dabei wird auch die Formmasse insgesamt verfestigt und in besonders vorteilhafter Weise für einen mit Bezugszeichen 26 bezeichneten letzten Arbeitsschritt des Trocknens und Brennens vorbereitet.The thus prepared casting mold is cooled temperature abruptly starting from Raumtem ¬, by exposure to an atmosphere having a temperature of about -25 0 C. As a result of this abrupt cooling of the molding compound in the casting mold, the silicic acid present therein as sol is solidified into a gel. In this case, the molding material is solidified as a whole and prepared in a particularly advantageous manner for a designated last step 26 of drying and firing.
Bei diesem Arbeitsschritt 26 wird die Formmasse bei einerIn this step 26, the molding compound at a
Sintertemperatur von zwischen zirka 13000C und zirka 16000C gebrannt. Aufgrund dieser vergleichsweise niedrigen Brenntemperatur können sich in der Formmasse eingesetzte Faserver¬ stärkungen befinden, so dass insgesamt eine faserverstärkte Keramik hergestellt werden kann.Sintering temperature of between about 1300 0 C and about 1600 0 C burned. Because of this comparatively low firing temperature employed can Faserver ¬ are reinforcements in the form of mass, so that a fiber-reinforced ceramic can be produced as a whole.
Die hergestellte Keramik weist besonders vorteilhafte mecha¬ nische Eigenschaften mit besonders geringer Neigung zur Ausbildung von thermischen Rissen auf. Dies beruht insbesondere darauf, dass in der Keramik durch den genannten Sol-Gel-Pro- zess und auch aufgrund des hohen Aluminiumoxidanteils ein spezielles Mikrorissgefüge geschaffen worden ist, welches unter anderem beispielsweise zu einer starken Verminderung der Risslängen von Kantenrissen führt.The ceramic produced has particularly advantageous mecha ¬ African properties with a particularly low tendency to form thermal cracks. This is based in particular on the fact that a special microcrack structure has been created in the ceramic by the mentioned sol-gel process and also due to the high proportion of aluminum oxide, which leads, inter alia, for example, to a considerable reduction in the crack lengths of edge cracks.
Auf diese Weise kann mit dem erfindungsgemäßen Vorgehen das Verlustrisiko von keramischen Hitzeschildern an der Auskleidung reduziert und die Anzahl der Wartungs- und Austauschzyk- len der Hitzeschilder verringert werden. Insgesamt kann eine höhere Lebensdauer erreicht werden.In this way, with the procedure according to the invention, the risk of loss of ceramic heat shields on the lining can be reduced and the number of maintenance and replacement cycles can be reduced. len of the heat shields are reduced. Overall, a longer life can be achieved.
Darüber hinaus ist als besonderer Vorteil der Erfindung noch zu nennen, dass die Gießmasse insgesamt zementfrei ist (also im Wesentlichen kein CaO aufweist) und sich ferner aufgrund der niedrigen Sintertemperatur auch Kostenvorteile beim Her- stellungsprozess ergeben. In addition, it should be mentioned as a particular advantage of the invention that the casting compound as a whole is free of cement (ie essentially has no CaO) and, on account of the low sintering temperature, also results in cost advantages in the production process.

Claims

Patentansprüche claims
1. Formmasse zum Herstellen einer feuerfesten Auskleidung, insbesondere für eine Brennkammer einer stationären Gastur- bine, wobei die Formmasse mit einem Gewichtsanteil von mehr als zirka 50% Aluminiumoxid (10) und einem Gewichtsanteil von weniger als zirka 50% Aluminiumsilicat (12) gebildet ist.1. A molding composition for producing a refractory lining, in particular for a combustion chamber of a stationary gas turbine, the molding composition having a weight fraction of more than about 50% alumina (10) and a weight fraction of less than about 50% aluminum silicate (12) is formed ,
2. Formmasse nach Anspruch 1, mit einem Gewichtsanteil von weniger als zirka 10% kolloidaler Kieselsäurelösung (14).2. Molding composition according to claim 1, with a weight proportion of less than about 10% colloidal silica solution (14).
3. Formmasse nach Anspruch 2, bei der die kolloidale Kieselsäurelösung (14) einen Gewichtsanteil von mehr als zirka 30% Feststoff enthält.A molding composition according to claim 2, wherein the colloidal silica solution (14) contains more than about 30% solids by weight.
4. Formmasse nach einem der Ansprüche 1 bis 3, bei der eine Flüssigkeit, insbesondere Wasser (16), mit einem Gewichtsanteil von mehr als zirka 1% und weniger als zirka 10% zugegeben ist.4. Molding composition according to one of claims 1 to 3, wherein a liquid, in particular water (16), is added with a weight proportion of more than about 1% and less than about 10%.
5. Formmasse nach einem der Ansprüche 1 bis 4, mit einem Gewichtsanteil von weniger als zirka 30%, insbesondere von weniger als zirka 25% reaktiver Tonerde (18) .5. Molding composition according to one of claims 1 to 4, with a weight fraction of less than about 30%, in particular less than about 25% reactive alumina (18).
6. Gebranntes Formteil für eine feuerfeste Auskleidung, insbesondere einer Brennkammer einer stationären Gasturbine, mit einem Gewichtsanteil von mehr als zirka 50% und weniger als zirka 90% Aluminiumoxid (10).6. A burned molded part for a refractory lining, in particular a combustion chamber of a stationary gas turbine, with a weight proportion of more than about 50% and less than about 90% alumina (10).
7. Gebranntes Formteil für eine feuerfeste Auskleidung, insbesondere einer Brennkammer einer stationären Gasturbine, mit einem Gewichtsanteil von mehr als zirka 10% und weniger als zirka 50% Aluminiumsilicat (12). 7. A burned molded part for a refractory lining, in particular a combustion chamber of a stationary gas turbine, with a weight fraction of more than about 10% and less than about 50% aluminum silicate (12).
8. Gebranntes Formteil nach Anspruch 6 oder 7, mit einer offenen Porosität von mehr als zirka 10%, insbesondere von mehr als zirka 15% und weniger als zirka8. A fired molding according to claim 6 or 7, having an open porosity of more than about 10%, in particular more than about 15% and less than about
35%.35%.
9. Gebranntes Formteil nach einem der Ansprüche 6 bis 8, mit einer Rohdichte von weniger als zirka 3,5 g/cm3, insbesondere von weniger als zirka 3,0 g/cm3.9. A fired molding according to any one of claims 6 to 8, having a bulk density of less than about 3.5 g / cm 3 , in particular less than about 3.0 g / cm 3 .
10. Gebranntes Formteil nach einem der Ansprüche 6 bis 9, dessen mittlere Biegefestigkeit bei Normalbedingungen auf mehr als zirka 7,0 MPa eingestellt ist.10. A burned shaped article according to any one of claims 6 to 9, whose average bending strength is set at more than about 7.0 MPa under normal conditions.
11. Feuerfeste Auskleidung einer Brennkammer, insbesondere einer stationären Gasturbine, mit mindestens einem gebrannten Formteil nach einem der Ansprüche 6 bis 10.11. Refractory lining of a combustion chamber, in particular a stationary gas turbine, with at least one fired molded part according to one of claims 6 to 10.
12. Verfahren zum Herstellen eines gebrannten Formteils einer feuerfesten Auskleidung, insbesondere für eine Brennkammer einer stationären Gasturbine, mit den Schritten:12. A method for producing a fired shaped part of a refractory lining, in particular for a combustion chamber of a stationary gas turbine, comprising the steps of:
Herstellen (20) einer Formmasse mit mindestens den Anteilen Aluminiumoxid (10) und Aluminiumsilicat (12) unter Zugabe kolloidaler Kieselsäurelösung (14), Vergießen (22) der Formmasse unter Vibration, Sprunghaftes Absenken (24) der Temperatur der Formmasse, sowie Trocknen und Brennen (26) der vergossenen Formmasse.Producing (20) a molding compound having at least the proportions of aluminum oxide (10) and aluminum silicate (12) with the addition of colloidal silica solution (14), casting (22) the molding compound under vibration, rapidly lowering (24) the temperature of the molding compound, and drying and firing (26) the potted molding compound.
13. Verfahren nach Anspruch 12, bei dem in der Formmasse ein Gewichtsanteil von mehr als zirka 50% Aluminiumoxid (10) und ein Gewichtsanteil von weniger als zirka 50% Aluminiumsilicat (12) gemischt werden.13. The method of claim 12, wherein in the molding composition, a weight fraction of more than about 50% alumina (10) and a weight fraction of less than about 50% aluminum silicate (12) are mixed.
14. Verfahren nach Anspruch 12 oder 13, bei dem die Temperatur beim sprunghaften Absenken (24) auf weniger als zirka O0C gesenkt und dort insbesondere über einen Zeitraum von mehr als 15 min und weniger als zirka 2,5 h gehalten wird. 14. The method of claim 12 or 13, wherein the temperature in the sudden lowering (24) is lowered to less than about 0 0 C and held there in particular over a period of more than 15 minutes and less than about 2.5 hours.
15. Verfahren nach einem der Ansprüche 12 bis 14, bei dem die vergossene Formmasse bei einer Temperatur von zwischen zirka 13000C und zirka 165O0C gebrannt wird. 15. The method according to any one of claims 12 to 14, wherein the potted molding compound is fired at a temperature of between about 1300 0 C and about 165O 0 C.
EP06763976A 2005-07-01 2006-06-30 Molding compound for producing a refractory lining Withdrawn EP1899648A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06763976A EP1899648A2 (en) 2005-07-01 2006-06-30 Molding compound for producing a refractory lining

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP05014376A EP1739356A1 (en) 2005-07-01 2005-07-01 Moulding composition for making a refractory lining
PCT/EP2006/063717 WO2007003587A2 (en) 2005-07-01 2006-06-30 Molding compound for producing a refractory lining
EP06763976A EP1899648A2 (en) 2005-07-01 2006-06-30 Molding compound for producing a refractory lining

Publications (1)

Publication Number Publication Date
EP1899648A2 true EP1899648A2 (en) 2008-03-19

Family

ID=34937752

Family Applications (2)

Application Number Title Priority Date Filing Date
EP05014376A Withdrawn EP1739356A1 (en) 2004-12-01 2005-07-01 Moulding composition for making a refractory lining
EP06763976A Withdrawn EP1899648A2 (en) 2005-07-01 2006-06-30 Molding compound for producing a refractory lining

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP05014376A Withdrawn EP1739356A1 (en) 2004-12-01 2005-07-01 Moulding composition for making a refractory lining

Country Status (3)

Country Link
US (1) US20090221416A1 (en)
EP (2) EP1739356A1 (en)
WO (1) WO2007003587A2 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE469110T1 (en) * 2005-11-21 2010-06-15 Siemens Ag METHOD FOR PRODUCING A FIRED MOLD OF A FIREPROOF LINING
EP2169311A1 (en) 2008-09-29 2010-03-31 Siemens Aktiengesellschaft Material mixture for producing a fire-retardant material, fire-retardant moulding body and method for its manufacture
US8382436B2 (en) 2009-01-06 2013-02-26 General Electric Company Non-integral turbine blade platforms and systems
US8262345B2 (en) 2009-02-06 2012-09-11 General Electric Company Ceramic matrix composite turbine engine
US8347636B2 (en) 2010-09-24 2013-01-08 General Electric Company Turbomachine including a ceramic matrix composite (CMC) bridge

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS583998B2 (en) * 1975-02-15 1983-01-24 ニホンルツボ カブシキガイシヤ Futei Keitai Kazai
US4585485A (en) * 1983-01-24 1986-04-29 Hiroshi Shikano Refractory sliding nozzle plate
DE3419199A1 (en) * 1984-05-23 1985-12-19 Didier-Werke Ag, 6200 Wiesbaden FIRE RESISTANT BODIES OR MEASURES, ESPECIALLY FOR THE LINING OF OEFENS OR CASES FOR MELTED METALS
DE3842403C1 (en) * 1988-12-16 1990-01-18 Radex-Heraklith Industriebeteiligungs Ag, Wien, At
GB9124403D0 (en) * 1991-11-16 1992-01-08 Foseco Int Ceramic material
US5363995A (en) * 1993-12-14 1994-11-15 Indresco Inc. Slide gate plate and method
JPH09301780A (en) * 1996-05-09 1997-11-25 Toshiba Ceramics Co Ltd Lightweight monolithic refractory
DE19623425B4 (en) * 1996-06-12 2005-06-16 Deutsches Zentrum für Luft- und Raumfahrt e.V. Process for the preparation of reaction-bonded mullite-containing ceramic shaped bodies and their use
DE59901272D1 (en) * 1998-07-06 2002-05-23 Siemens Ag MOLDING MATERIAL FOR PRODUCING A FIRE-RESISTANT LINING, BURNED MOLDED PART, LINING AND METHOD FOR PRODUCING A MOLDED PART
JP2001220260A (en) * 2000-02-07 2001-08-14 Mitsui Mining & Smelting Co Ltd Alumina-based porous refractory sheet and method for producing the same
ZA200309168B (en) * 2002-12-10 2004-07-22 Magneco Metrel Inc Refractory system for glass melting furnaces.
DE102004060792A1 (en) * 2004-12-17 2006-06-29 BEGO Bremer Goldschlägerei Wilh. Herbst GmbH & Co. KG Process for producing a ceramic crucible

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007003587A2 *

Also Published As

Publication number Publication date
WO2007003587A2 (en) 2007-01-11
EP1739356A1 (en) 2007-01-03
US20090221416A1 (en) 2009-09-03
WO2007003587A3 (en) 2007-04-12

Similar Documents

Publication Publication Date Title
EP2329195B1 (en) Material mixture for producing a fire-retardant material, fire-retardant moulding body and method for its manufacture
DE69911202T3 (en) CONCRETE ORGANIC FIBERS DISPERSED IN A CEMENT MATRIX CONCRETE, CONCRETE CEMENT MATRIX AND PRE-MIXTURES
KR100217439B1 (en) Metal fiber concrete composition for casting a concrete element, elements obtained and method of thermal curing
EP2451596B1 (en) Mold wash for manufacturing mold coatings
DE102010009146B4 (en) Plastic refractory compound and refractory mortar and their use
EP1787967B1 (en) Process for the manufacture of a burnt shaped body for a refractory lining
EP2168935A1 (en) Material compound for producing a fire-retardant material and its application and fire-retardant moulding body and method for its manufacture
SK11382002A3 (en) Fire-resistant high performance concrete composition
CN107382346B (en) refractory wear-resistant pouring material and preparation method thereof
DE3829039C2 (en) Composite component, process for its preparation and its use
EP1899648A2 (en) Molding compound for producing a refractory lining
DE19623425A1 (en) Reaction bonded mullite-based ceramic article
DE69308830T2 (en) METHOD FOR PRODUCING FIBER COMPOSITES
DE2200002C3 (en) Unfired heterogeneous refractory mixture
DE2433698C3 (en) Process for producing a high-strength ceramic article for composite bodies with metals
DE19605149C2 (en) Process for the production of porous ceramic moldings, moldings made therefrom from titanium dioxide and their uses
EP1102730A1 (en) Moulding material for the production of a fire-resistant lining, fired formed part, lining and method for the production of a formed part
DE1471032C3 (en) Mixture for the production of a refractory body, mortar and the like
US4844848A (en) Method for preparing Al2 O3 powder and products
WO2012062913A1 (en) Lining material for gasification plants consisting of an alkali corrosion-resistant and thermal cycling-resistant chromium oxide- and carbon-free oxide ceramic material and use thereof
JP2515767B2 (en) Extruded building materials with excellent explosion resistance
AT502065A2 (en) FURNITURE CHIMNEY COVER PLATE
EP1072573A1 (en) Method of making a refractory body and ceramic combustion chamber stone
DE3511555A1 (en) ALUMINUM ALLOY COMPONENTS FOR INTERNAL COMBUSTION ENGINES
DE102008053231B4 (en) Thermally stable concrete-free composite material, process for its production and use of the composite material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20071228

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20091110

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20110322