DE102004014374C5 - Use of zirconium oxide and hafnium oxide-containing refractory material - Google Patents

Use of zirconium oxide and hafnium oxide-containing refractory material Download PDF

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DE102004014374C5
DE102004014374C5 DE200410014374 DE102004014374A DE102004014374C5 DE 102004014374 C5 DE102004014374 C5 DE 102004014374C5 DE 200410014374 DE200410014374 DE 200410014374 DE 102004014374 A DE102004014374 A DE 102004014374A DE 102004014374 C5 DE102004014374 C5 DE 102004014374C5
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refractory material
hafnium oxide
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glass
zirconium oxide
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Joachim Dr. Piroth
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Schott AG
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    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/481—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
    • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/484—Refractories by fusion casting
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C04B35/6455—Hot isostatic pressing
    • 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
    • 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
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics

Abstract

Verwendung eines Zirkoniumoxid- und Hafniumoxidhaitigen feuerfesten Materials zum Schmelzen von Glas, Glaskeramiken, Keramiken und zum Schmelzen und Züchten von Kristallen, wobei der Hafniumoxidgehalt mindestens 2 Gew.-% des Zirkoniumoxidgehalts beträgt, wobei Hafniumoxid zum feuerfesten Material zugegeben wurde.Use of a zirconia and hafnia-containing refractory material to melt glass, glass-ceramics, ceramics and to melt and grow crystals, wherein the hafnium oxide content is at least 2% by weight of the zirconia content, with hafnium oxide being added to the refractory material.

Description

Die Erfindung betrifft die Verwendung von Zirkoniumoxid- und Hafniumoxidhaltigem feuerfestem Material.The This invention relates to the use of zirconia and hafnia fireproof material.

In durch hohe Strömungsgeschwindigkeiten bei hohen Temperaturen besonders stark belasteten Bereichen von Schmelzwannen zur Herstellung von Gläsern und Glaskeramiken werden zur Verminderung des korrosiven Abtrags keramische Feuerfest-Werkstoffe (Materialien) auf ZrO2-Basis eingesetzt. Die typische chemische Zusammensetzung (in Gew.-%) solcher Materialien ist folgendermaßen: ZrO2 94, SiO2 4,5, Al2O3 0,8, Na2O 0,4, Fe2O3 0,05 und TiO2 0,05.In areas of melting furnaces which are particularly heavily loaded at high temperatures at high temperatures for the production of glasses and glass ceramics, ZrO 2 -based ceramic refractory materials are used to reduce corrosive erosion. The typical chemical composition (in% by weight) of such materials is as follows: ZrO 2 94, SiO 2 4.5, Al 2 O 3 0.8, Na 2 O 0.4, Fe 2 O 3 0.05, and TiO 2 2 0.05.

Schmelzgegossene feuerfeste Materialien, insbesondere zur Verwendung in der Glasindustrie sind aus den Schriften EP 0 431 445 und EP 0 403 387 bekannt.Melt-cast refractory materials, especially for use in the glass industry, are found in the documents EP 0 431 445 and EP 0 403 387 known.

Die Erfahrung in der Praxis zeigt jedoch, dass sogar solche an sich widerstandsfähigen Werkstoffe unter den oben genannten Einsatzbedingungen einem sehr hohen Verschleiß ausgesetzt sind. Dieser extreme Verschleiß an besonders kritischen Stellen, wie z. B. der Spülkante, kann wegen der Gefahr des unkontrollierten Austritts von Glasschmelze die Wannenlaufzeit begrenzen und eine vorzeitige Reparatur erforderlich machen. Lokal erhöhte Korrosion z. B. an Durchlässen birgt die Gefahr in sich, dass das Betriebsverhalten der Schmelzwanne hinsichtlich der Glasqualität im Verlauf der Betriebszeit einer Wanne schlechter wird.The However, experience in practice shows that even such in itself tough Materials under the above conditions of use a very exposed to high wear are. This extreme wear on particularly critical places, such as B. the flushing edge, because of the risk the uncontrolled discharge of glass melt the tub life limit and require early repair. Local increased Corrosion z. B. at passages entails the danger that the operating behavior of the melting tank in terms of glass quality becomes worse during the service life of a tub.

Unterschiedliche Maßnahmen, die das Material gegen übermäßige, die Laufzeit der Wanne limitierende Korrosionsverluste schützen, sind denkbar. Hierzu zählen etwa die Verlängerung der Standzeiten durch Vorhalten von Material an besonders gefährdeten Stellen wie z. B. Durchlass oder Spülfuge (theoretische Glaslinie) sowie das Bewehren mit (Edel-)Metallblechen.different Activities, the material against excessive, the Duration of the tub to protect limiting corrosion losses are conceivable. Which includes about the extension the lifetime by keeping material at particularly vulnerable Places such as B. passage or flush joint (theoretical glass line) as well as the reinforcement with (noble) metal sheets.

Aus der Schrift DE 692 27 107 T2 sind Zirkoniumoxid-Keramiken für Oberflächen bekannt, die einer oxidierenden Umgebung mit hoher Temperatur und Feuchte ausgesetzt sind. Diese Keramiken weisen einen ZrO2-Gehalt von 70 bis 100 Gew.-% auf und können 0 bis 10 Gew.-% HfO2 enthalten.From the Scriptures DE 692 27 107 T2 For example, zirconia ceramics are known for surfaces exposed to an oxidizing environment of high temperature and humidity. These ceramics have a ZrO 2 content of from 70 to 100% by weight and may contain from 0 to 10% by weight of HfO 2 .

Aufgabe der Erfindung, ein feuerfestes Material zu finden, das insbesondere zur Verwendung in der Herstellung von Glas, Glaskeramiken, Keramiken und Kristallen geeignet ist.task the invention of finding a refractory material, in particular for use in the manufacture of glass, glass ceramics, ceramics and Crystals is suitable.

Gelöst wird die Aufgabe gemäß Anspruch 1 durch die Verwendung eines Zirkoniumoxid- und Hafniumoxidhaltigen feuerfesten Materials, wobei der Hafniumoxidgehalt mindestens 2 Gew.-% des Zirkoniumoxidgehalts beträgt. Beträgt der Zirkoniumoxidgehalt beispielsweise 90 Gew.-%, so beträgt der Hafniumgehalt erfindungsgemäß mindestens 1,8 Gew.-%.Is solved the task according to claim 1 through the use of a zirconia and hafnium oxide containing refractory material, the hafnium oxide content being at least 2 Wt .-% of zirconium oxide content is. Is the zirconium oxide content For example, 90 wt .-%, the hafnium content according to the invention is at least 1.8% by weight.

Die wichtigsten Zirkoniumminerale sind Zirkon (ZrSiO4) und Baddeleyit (ZrO2), die stets Hafniumoxid enthalten, und zwar überwiegend in Mengen, die etwa 2% des Zirkoniumgehalts entsprechen. Es hat sich gezeigt, dass die Eigenschaften eines Zirkoniumoxidhaltigen feuerfesten Materials, insbesondere im Hinblick auf Korrosionsbeständigkeit, Standfestigkeit, Neigung zur Bildung von unerwünschten Gasblasen verbessert werden können, wenn der Hafniumoxidgehalt mindestens 2 Gew.-% des Zirkoniumoxidgehalts beträgt. Die übrigens Eigenschaften des feuerfesten Materials wie Herstellung und Verarbeitbarkeit werden durch den Hafniumoxidzusatz nicht oder nur unwesentlich verändert.The most important zirconium minerals are zircon (ZrSiO 4 ) and baddeleyite (ZrO 2 ), which always contain hafnium oxide, predominantly in amounts corresponding to about 2% of the zirconium content. It has been found that the properties of a zirconia-containing refractory material, in particular with regard to corrosion resistance, stability, tendency to form undesirable gas bubbles, can be improved if the hafnium oxide content is at least 2% by weight of the zirconium oxide content. The other properties of the refractory material such as production and processability are not or only slightly changed by the addition of hafnium oxide.

Allgemein gilt, dass eine Hafniumoxidzugabe, die Eigenschaften eines Zirkonoxidhaltigen feuerfesten Materials erhöht, insbesondere im Hinblick auf Korrosionsbeständigkeit gegenüber aggressiven Schmelzen, insbesondere Glas- und Keramikschmelzen, aber auch gegenüber Schmelzen, die zur Herstellung und Zucht von Einkristallen, wie CaF2 oder Al2O3, dienen. Die Hafniumoxidzugabe soll dabei über dem natürlichen Hafniumoxidgehalt des verwendeten Zirkonoxidrohstoffs liegen.In general, hafnium oxide addition increases the properties of a zirconia-containing refractory material, particularly with respect to corrosion resistance to aggressive melts, particularly glass and ceramic melts, but also to melts used to produce and grow single crystals such as CaF 2 or Al 2 O. 3 , serve. The hafnium oxide addition should be above the natural hafnium oxide content of the zirconium oxide raw material used.

Vorzugsweise beträgt der Hafniumoxidgehalt mindestens 2,5 Gew.-% des Zirkoniumoxidgehalts. Vorteile ergaben sich auch bei einem Hafniumoxidgehalt der mindestens 4 Gew.-%, insbesondere 6 Gew.-% des Zirkoniumoxidgehalts beträgt.Preferably is the hafnium oxide content is at least 2.5% by weight of the zirconium oxide content. advantages also resulted in a hafnium oxide content of at least 4% by weight, in particular 6% by weight of the zirconium oxide content.

Das feuerfeste Material ist vorzugsweise schmelzgegossen oder gesintert. Der Herstellungsprozess ist dabei endkonturnah oder aber das schmelzgegossene oder gesinterte Vorprodukt wird zur endgültigen Form und Kontur nachbearbeitet, z. B. zu Blöcken. Das feuerfeste Material kann zu sehr genau gearbeiteten Endprodukten, die eine sehr hohe Endkonturtreue und Ebenheit aufweisen, weiter verarbeitet werden (Fräsen, Polieren). Bei der Endkonturtreue und Ebenheit kommt es insbesondere auf den Einsatz des Materials an. Beim Einsatz in Unterdruckanlagen muss das Material insbesondere an den Kontaktflächen einzelner Bauteile, die aus dem erfindunsgemäßen Material bestehen, der art passgenau gearbeitet sein, dass ein Vakuum aufrecht erhalten werden kann. Vorzugsweise weist das feuerfeste Material eine geringe Porenzahl auf. Je kleiner die Porenzahl, desto geringer ist die Blasenbildung an der Grenzfläche beispielsweise zu einer Glasschmelze.The Refractory material is preferably melt cast or sintered. The manufacturing process is near net shape or the melt cast or sintered precursor is reworked to the final shape and contour, z. B. to blocks. The refractory material can be made into very precisely finished products, which have a very high final contour accuracy and flatness, further processed be (milling, Polishing). In the final contour accuracy and flatness it comes in particular the use of the material. When used in vacuum systems In particular, the material must be at the contact surfaces of individual components, the from the erfindunsgemäßen material The art must be made to fit perfectly, keeping a vacuum upright can be obtained. Preferably, the refractory material a low pore count. The smaller the pore number, the smaller For example, bubble formation at the interface is one Glass melt.

Das feuerfeste Material kann weitere Oxide, wie SiO2, Al2O3, B2O3, P2O5, TiO2, Fe2O3, Alkalioxide, Erdalkalioxide und/oder weitere Metall- oder Nichtmetalloxide, in veränderlichen Gewichtsanteilen enthalten. Vorzugsweise enthält das feuerfeste Material mindestens 90 Gew.-% Zirkoniumoxid und mindestens 1,8 Gew.-%, vorzugsweise mindestens 2,0 Gew.-% Hafniumoxid.The refractory material may contain other oxides, such as SiO 2 , Al 2 O 3 , B 2 O 3 , P 2 O 5 , TiO 2 , Fe 2 O 3 , alkali oxides, alkaline earth oxides and / or other metal or non-metal oxides, in varying proportions by weight. Preferably, the refractory material contains at least 90 weight percent zirconia and at least 1.8 weight percent, preferably at least 2.0 weight percent hafnium oxide.

Insbesondere Erdalkalioxide, wie CaO und MgO, dienen zur Stabilisierung von ZrO2/HfO2 über einen großen Temperaturbereich.In particular, alkaline earth oxides such as CaO and MgO serve to stabilize ZrO 2 / HfO 2 over a wide temperature range.

Erfindungsgemäß wird das feuerfeste Material zur Herstellung, insbesondere zum Schmelzen und Heißformgeben, von Glas, Glaskeramiken, Keramiken und zum Schmelzen und Züchten von Kristallen verwendet.According to the invention refractory material for the manufacture, in particular for melting and Hot forming, of glass, glass ceramics, ceramics and for melting and growing of Used crystals.

Ausführungsbeispiel:Embodiment:

Schmelzgegossenes feuerfestes Material (Angaben in Gew.-%): Beispiel Vergleichsbeispiel ZrO2 90–95 90–95 HfO2 > 2,0 - SiO2 3–7 3–7 Al2O3 0–3 0–3 Rest < 5,1 < 5,1 Melt-cast refractory (in% by weight): example Comparative example ZrO 2 90-95 90-95 HfO 2 > 2.0 - SiO 2 3-7 3-7 Al 2 O 3 0-3 0-3 rest <5.1 <5.1

Der quantitative Einfluss des HfO2-Anteils auf die Verschleißfestigkeit das erfindungsgemäßen Materials wurde durch systematische Tests im Labor zu ermittelt (Ausführungsbeispiel). Ein Gesamtanteil von größer 2,0 Gew.-% Hafniumoxid – bezogen auf den jeweiligen Zirkoniumoxidanteil – im schmelzgegossenen Feuerfestmaterial – hat sich als vorteilhaft bezüglich Korrosionsbeständigkeit gegenüber Glasschmelzen (SCHOTT Duran®, SCHOTT Fiolax®), Glaskeramikschmelzen SCHOTT Ceran®) oder in Kontakt mit Schmelzen, aus denen Korund-Einskristalle gezogen werden, erwiesen. Die Höhe des HfO2-Anteils ist dann nach Kosten-Nutzen-Analysen festzulegen, denn reines HfO2 ist teurer als ZrO2. Dabei ist zu berücksichtigen, dass beim Einsatz von Metall- oder Edelmetallbewehrungen aus Molybdän (Mo) oder Platin (Pt) nicht nur die reinen Kosten für das Metall, sondern auch die für die aufwändige Herstellung und Anbringung einer solchen Bewehrung anfallen. Solche Bewehrungs-Konstruktionen in Form von Umhüllungen u. ä. bergen zusätzlich das Risiko mechanischer Instabilität in sich, so dass auch ein hoher Hafniumoxidanteil durchaus wirtschaftlich ist.The quantitative influence of the HfO 2 content on the wear resistance of the material according to the invention was determined by systematic tests in the laboratory (exemplary embodiment). A total content of more than 2.0 wt .-% hafnium oxide - based on the respective proportion of zirconium oxide - in the fused cast refractory material - has proved to be advantageous in terms of corrosion resistance against molten glass (Schott Duran ®, SCHOTT Fiolax ®), glass ceramic melts SCHOTT Ceran ®) or in contact with Melt, from which corundum single crystals are pulled, proved. The amount of the HfO 2 share is then to be determined by cost-benefit analyzes, because pure HfO 2 is more expensive than ZrO 2 . It should be noted that when using metal or precious metal reinforcements made of molybdenum (Mo) or platinum (Pt) not only the pure cost of the metal, but also incurred for the complex production and attachment of such a reinforcement. Such reinforcing structures in the form of sheaths u. In addition, the risk of mechanical instability is inherent, so that even a high proportion of hafnium oxide is quite economical.

Claims (6)

Verwendung eines Zirkoniumoxid- und Hafniumoxidhaitigen feuerfesten Materials zum Schmelzen von Glas, Glaskeramiken, Keramiken und zum Schmelzen und Züchten von Kristallen, wobei der Hafniumoxidgehalt mindestens 2 Gew.-% des Zirkoniumoxidgehalts beträgt, wobei Hafniumoxid zum feuerfesten Material zugegeben wurde.Use of a zirconium oxide and hafnium oxide-containing refractory material for melting glass, glass ceramics, ceramics and for melting and breeding of crystals, the hafnium oxide content being at least 2% by weight of zirconium oxide content, wherein hafnium oxide was added to the refractory material. Verwendung des Materials nach Anspruch 1, wobei der Hafniumoxidgehalt mindestens 6 Gew.-% des Zirkoniumoxidgehalts beträgt.Use of the material according to claim 1, wherein the Hafnium oxide content is at least 6% by weight of the zirconium oxide content. Verwendung des Materials nach Anspruch 1 oder 2, wobei das feuerfeste Material schmelzgegossen ist.Use of the material according to claim 1 or 2, wherein the refractory material is melt-cast. Verwendung des Materials nach Anspruch 1 oder 2, wobei das feuerfeste Material gesintert ist.Use of the material according to claim 1 or 2, wherein the refractory material is sintered. Verwendung des Materials nach wenigstens einem der Ansprüche 1 bis 4, wobei das feuerfeste Material weitere Oxide, wie SiO2, Al2O3, B2O3, P2O5, TiO2, Fe2O3, Alkalioxide, Erdalkalioxide und/oder weitere Metall- oder Nichtmetalloxide, in veränderlichen Gewichtsanteilen enthält.Use of the material according to at least one of claims 1 to 4, wherein the refractory material further oxides such as SiO 2 , Al 2 O 3 , B 2 O 3 , P 2 O 5 , TiO 2 , Fe 2 O 3 , alkali oxides, alkaline earth oxides and / or further metal or non-metal oxides, contains in varying proportions by weight. Verwendung des Materials nach wenigstens einem der Ansprüche 1 bis 5, wobei das feuerfeste Material mindestens 90 Gew.-% Zirkoniumoxid und mindestens 1,8 Gew.-%, vorzugsweise mindestens 2,0 Gew.-% Hafniumoxid enthält.Use of the material according to at least one of claims 1 to 5, wherein the refractory material is at least 90% by weight zirconia and at least 1.8% by weight, preferably at least 2.0% by weight of hafnium oxide contains.
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB709882A (en) * 1952-01-05 1954-06-02 Norton Grinding Wheel Co Ltd Process for extracting zirconia from zircon ores
BE649595A (en) * 1963-06-27 1964-12-22
EP0195456A2 (en) * 1985-03-22 1986-09-24 CSELT Centro Studi e Laboratori Telecomunicazioni S.p.A. Method of surfacing the heater of a furnace for optical fibre drawing
DE3608854A1 (en) * 1986-03-17 1987-09-24 Leitz Ernst Gmbh USE OF AN OXIDE CERAMIC MATERIAL FOR PRESSING TOOLS FOR MOLDING COMPONENTS FROM GLASS OR A GLASS-CONTAINING CERAMIC HIGH SURFACE QUALITY AND MEASUREMENT ACCURACY
US4753902A (en) * 1986-11-24 1988-06-28 Corning Glass Works Transformation toughened zirconia-titania-yttria ceramic alloys
DE19730996A1 (en) * 1997-07-18 1999-01-21 Klaus Rennebeck Process for the production of ceramic fibers, the ceramic fibers produced thereafter and their use
DE69227107T2 (en) * 1991-04-09 1999-03-11 Modar Inc ZIRCONOXYDE CERAMICS FOR SURFACES SUBJECT TO AN OXIDIZING ENVIRONMENT WITH HIGH TEMPERATURE AND HUMIDITY
DE4042681C2 (en) * 1989-09-08 2002-01-03 Corhart Refractories Co Zircon refractory contg. uniform dispersion of unstabilised zirconia
DE10117776A1 (en) * 2001-04-09 2002-10-17 Morgan Crucible Co High temperature resistant fine ceramic sintered material, process for its production and its use
DE10133496A1 (en) * 2001-07-10 2003-01-23 Wojciech Muszynski Roller skate such as inline skate has wheels pivot mounted on rails, brake with lever, cable-pull, and fixtures
DE10315706A1 (en) * 2002-08-24 2004-03-04 FEE Forschungsinstitut für Mineralische und Metallische Werkstoffe Edelsteine/Edelmetalle GmbH Process for growing single crystals comprises holding the crystal at a temperature close to the melting temperature whilst the crystal material drawn from the melt and solidified is partially screened from heat losses

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB709882A (en) * 1952-01-05 1954-06-02 Norton Grinding Wheel Co Ltd Process for extracting zirconia from zircon ores
BE649595A (en) * 1963-06-27 1964-12-22
EP0195456A2 (en) * 1985-03-22 1986-09-24 CSELT Centro Studi e Laboratori Telecomunicazioni S.p.A. Method of surfacing the heater of a furnace for optical fibre drawing
DE3608854A1 (en) * 1986-03-17 1987-09-24 Leitz Ernst Gmbh USE OF AN OXIDE CERAMIC MATERIAL FOR PRESSING TOOLS FOR MOLDING COMPONENTS FROM GLASS OR A GLASS-CONTAINING CERAMIC HIGH SURFACE QUALITY AND MEASUREMENT ACCURACY
US4753902A (en) * 1986-11-24 1988-06-28 Corning Glass Works Transformation toughened zirconia-titania-yttria ceramic alloys
DE4042681C2 (en) * 1989-09-08 2002-01-03 Corhart Refractories Co Zircon refractory contg. uniform dispersion of unstabilised zirconia
DE69227107T2 (en) * 1991-04-09 1999-03-11 Modar Inc ZIRCONOXYDE CERAMICS FOR SURFACES SUBJECT TO AN OXIDIZING ENVIRONMENT WITH HIGH TEMPERATURE AND HUMIDITY
DE19730996A1 (en) * 1997-07-18 1999-01-21 Klaus Rennebeck Process for the production of ceramic fibers, the ceramic fibers produced thereafter and their use
DE10117776A1 (en) * 2001-04-09 2002-10-17 Morgan Crucible Co High temperature resistant fine ceramic sintered material, process for its production and its use
DE10133496A1 (en) * 2001-07-10 2003-01-23 Wojciech Muszynski Roller skate such as inline skate has wheels pivot mounted on rails, brake with lever, cable-pull, and fixtures
DE10315706A1 (en) * 2002-08-24 2004-03-04 FEE Forschungsinstitut für Mineralische und Metallische Werkstoffe Edelsteine/Edelmetalle GmbH Process for growing single crystals comprises holding the crystal at a temperature close to the melting temperature whilst the crystal material drawn from the melt and solidified is partially screened from heat losses

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CA 49: 5189i (1955) *
Hollemann Wiberg "Lehrbuch der anorganischen Chemie". 37.- 39. Aufl. 1956, S. 405 *
J. Wanderer "Zirkon - Rohstoff, Aufbereitung, metallurgische Gewinnung und Raffination von Zirkon" - EDV-Ausdruck-Dokumenten-Nr.: 05475 (2 Seiten) *
J.Am. Ceram. Soc. 1961, 44, S. 465 (CA 55:25189g (1961) *
Online-ausdruck vom 19. Juli 2006 zu "Zirkonium", www.wissenschaft-online.de *
W. Schulle "Feuerfeste Werkstoffe" 1. Aufl. , Leipzig, Deutscher Verlag für Grundstoffindustrie, 1990, S. 220 bis 226, 310 bis 316 *

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