US3899341A - Refractory fired shaped element and process of its manufacture - Google Patents
Refractory fired shaped element and process of its manufacture Download PDFInfo
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- US3899341A US3899341A US458022A US45802274A US3899341A US 3899341 A US3899341 A US 3899341A US 458022 A US458022 A US 458022A US 45802274 A US45802274 A US 45802274A US 3899341 A US3899341 A US 3899341A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/14—Closures
- B22D41/16—Closures stopper-rod type, i.e. a stopper-rod being positioned downwardly through the vessel and the metal therein, for selective registry with the pouring opening
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/50—Pouring-nozzles
- B22D41/52—Manufacturing or repairing thereof
- B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor
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- 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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
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- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3248—Zirconates or hafnates, e.g. zircon
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- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
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- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6027—Slip casting
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- C—CHEMISTRY; METALLURGY
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/604—Pressing at temperatures other than sintering temperatures
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- 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
Definitions
- the closures are subjected torigorous requirements in regard to the resistance to wear, in relation to the steel, iron or metal flowing the rethrough high temperatures, and particularly in regard; to resistance to deterioration as a result steep changes of temperatures, since the pouring units providedwith the ties of employing nozzles of zirconium silicate are limited.
- the difficulties associated with zirconium silicate nozzles result during long casting periods and while casting rimmed or alloyed steels.
- the severe stress manifests itself in the noticeable widening of the cross section of the nozzle opening, which leads to an uncontrolled variation in the rate of pour.
- Previous attempts to remedy this problem included employment of closures made of zirconium oxide or dense aluminum oxide.
- wide application of such products is prevented by the price of the material, which is very high in comparison with the products of zirconium silicate, and, most importantly, by a high sensitivity to thermal shock, which is found in such products.
- the invention is based on the task of developing a reasonably priced, quality zirconium-based material for shaped elements to be inserted into closures in casting units for steel, iron and metal, which encompasses the advantages of a high resistance to wear and to a high resistance in regard to thermal shocks.
- the problem is solved by employing a composition comprising zirconium oxide at 10 50 by weight, preferably 35 by weight, zirconium silicate at 50 9O by weight, preferably 65 by weight. Moreover,
- the zirconium oxide is employed in a grain size of at most 0.1 mm, and preferably smaller than 0.06 mm, and the zirconium silicate is introduced in a grain size exceeding 02 mm, preferably 0.2 O.5 mm.
- zirconium oxide (grain size under 0.1 mm, preferably smaller than 0.06 mm) is based on the idea of introducing this valuable material only in an amount required for a good resistance to corrosion.
- this corrosion-resistant material forms the matrix, due to its fine grains, which matrix is resistant to slag corrosion.
- zirconium silicate in H -material, which'is more succep tibleto slag corrosion 20'" then zirconium oxide, is'made si'rnilar to that of zirconium oxide through its employment in theform of coarse grains (0.2 0.5 mm).
- silicate comprising an intermediate matrix of sintered ""zirc onium oxide. Since the known dissociation of the ZrSiO, at high temperatures zrsio, zro SiO proceeds from the inner surface, the fractionof silicic acid released through decomposition in the composition of the mixtureof the invention (ZrSiO, being in coarser grain) is smaller by a multiple than the fraction corresponding to the quantitative substitution of the ZrSiO in the mixture by ZrO This again leads to the fact that the matrix contains a smaller amount of lowmelting compounds and, consequently, is much more effective against the corrosive action at high temperature. Moreover, the ZrSiO framework confers a good stability in relation to the variation of temperature to the fired product.
- the shaped elements are manufactured both in accordance with the ceramic slurry casting process and also in accordance with the pressing process. ln order to avoid contamination of the starting material, a zirconium-oxide-containing slurry is used in the casting process. In the pressing process, this slurry or organic binding materials are employed as binders. In order to avoid contamination of the zirconium material through abrasion of foreign substances, the slurry is produced in a wet mill whose lining consists of shaped elements of zirconium oxide, which elements in suitable shape also perform the function of grinding elements.
- the steel-pouring nozzles produced in accordance with this process possess the following properties:
- a refractory fired shaped element for closures in casting units for metals comprising 10 to 50 by weight zirconium oxide and 50 to by weight zirconium silicate, 30 to 60 by weight of the total amount of zirconium oxide being present in stabilized form and 70 to 40 by weight of the total amount of zirconium oxide being present in unstabilized form.
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- Materials Engineering (AREA)
- Structural Engineering (AREA)
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- Compositions Of Oxide Ceramics (AREA)
Abstract
Novel refractory-fired, shaped elements for closures in pouring units for steel, iron and metal (nozzles, stoppers, spouts, slides) are provided. Said elements are based on zirconium oxide and zirconium silicate. The elements have advantageous thermal and mechanical properties and are economical to produce. A novel process for the production of these elements is also provided.
Description
United States Patent 1 Schwarz [451 Aug. 12,1975
[ REFRACTORY FIRED SHAPED ELEMENT AND PROCESS OF ITS MANUFACTURE [75] lnventor: Hans Georg Schwarz, Marktredwitz,
211 Appl. No.; 45am;
[30] Foreign Application Priority Data Apr. 30, 1973 Germany 2321810 [52] US. Cl, 106/57 [51] Int. Cl. C04B 35/48 [58] Field of Search 106/57 [56] References Cited UNITED STATES PATENTS 2,553,265 5/1951 Mochel 106/57 2,593,352 4/1952 Shaw et al. 106/57 2,624,097 l/1953 Kistler 106/57 3,175,919 3/1965 Smoot et a1 106/57 3,228,778 1/1966 Walther et al. 106/57 3,620,781 11/1971 Garvie 106/57 Primary Examiner-J. Poer Attorney, Agent, or F irm-Wenderoth, Lind & Ponack [5 7 ABSTRACT Novel refractory-fired, shaped elements for closures in pouring units for steel, iron and metal (nozzles, stoppers, spouts, slides) are provided. Said elements are based on zirconium oxide and zirconium silicate. The elements have advantageous thermal and mechanical properties and are economical to produce. A novel process for the production of these elements is also provided.
6 Claims, No Drawings 1 REFRACTORY FIRED SHAPED ELEMENT AND PROCESS OF ITS MANUFACTURE 60 by weight of the entire amount of zirconium oxide present must be in stabilized form and 70 4O Refractory closures are employed in connection with pouring the molten steel from ladles. Such closures are situated in or on the pouring unitsThe task of such refractory closures is to maintain, as constant as possible, the amount of steel flowing out therethrough per unit of time, in order to optimize the. subsequent solidification and cooling process. The amountof steel flowing out per unit of time is substantially a function of the level of the steel bath i'n'the casting'unit and of the cross section of the opening of the closure.
Accordingly, the closures are subjected torigorous requirements in regard to the resistance to wear, in relation to the steel, iron or metal flowing the rethrough high temperatures, and particularly in regard; to resistance to deterioration as a result steep changes of temperatures, since the pouring units providedwith the ties of employing nozzles of zirconium silicate are limited. The difficulties associated with zirconium silicate nozzles result during long casting periods and while casting rimmed or alloyed steels. The severe stress manifests itself in the noticeable widening of the cross section of the nozzle opening, which leads to an uncontrolled variation in the rate of pour. Previous attempts to remedy this problem included employment of closures made of zirconium oxide or dense aluminum oxide. However, wide application of such products is prevented by the price of the material, which is very high in comparison with the products of zirconium silicate, and, most importantly, by a high sensitivity to thermal shock, which is found in such products.
Experiments employing mixtures of zirconium oxide and zirconium silicate as starting material for refractory bricks have also been made. Thus, Harders- Kienow, in their book, Feuerfestkunde, pages 9067 1960), Springer-Verlag proposed to employ a mixture of 1000 g zirconium oxide and 500 g zirconium silicate (66.66 by weight ZrO and 33.34 by weight ZrSiO,) for making light refractory bricks. However, the employed brick is employed only for the purpose of insulation. Due to its high porosity, it cannot be employed as shaped element for closures of casting units which transmit the flow of fused steel. On the contrary, a shaped element for pouring purposes must be dense in order to resist effectively the corrosion.
The invention is based on the task of developing a reasonably priced, quality zirconium-based material for shaped elements to be inserted into closures in casting units for steel, iron and metal, which encompasses the advantages of a high resistance to wear and to a high resistance in regard to thermal shocks.
The problem is solved by employing a composition comprising zirconium oxide at 10 50 by weight, preferably 35 by weight, zirconium silicate at 50 9O by weight, preferably 65 by weight. Moreover,
by weight must be in a non-stabilized form. The zirconium oxide is employed in a grain size of at most 0.1 mm, and preferably smaller than 0.06 mm, and the zirconium silicate is introduced in a grain size exceeding 02 mm, preferably 0.2 O.5 mm.
The portion of zirconium oxide (grain size under 0.1 mm, preferably smaller than 0.06 mm) is based on the idea of introducing this valuable material only in an amount required for a good resistance to corrosion. In the completed brick, this corrosion-resistant material forms the matrix, due to its fine grains, which matrix is resistant to slag corrosion.
The employment of inexpensive zirconium silicate in H -material, which'is more succep tibleto slag corrosion 20'" then zirconium oxide, is'made si'rnilar to that of zirconium oxide through its employment in theform of coarse grains (0.2 0.5 mm).
silicate comprising an intermediate matrix of sintered ""zirc onium oxide. Since the known dissociation of the ZrSiO, at high temperatures zrsio, zro SiO proceeds from the inner surface, the fractionof silicic acid released through decomposition in the composition of the mixtureof the invention (ZrSiO, being in coarser grain) is smaller by a multiple than the fraction corresponding to the quantitative substitution of the ZrSiO in the mixture by ZrO This again leads to the fact that the matrix contains a smaller amount of lowmelting compounds and, consequently, is much more effective against the corrosive action at high temperature. Moreover, the ZrSiO framework confers a good stability in relation to the variation of temperature to the fired product.
The zirconium oxide to be added in accordance with the invention is a material that in its original modification, exhibits reversible changes of volume at increased temperature (above 1000C), which leads to cracks in the structure of a mass which contains this material in excess. This disadvantage is avoided by employing stabilized zirconium oxide. In order to avoid the introduction of fluxing materials into the matrix of zirconium oxide beyond a certain extent and the resulting detrimental effect exerted on its refractory properties, the addition of stabilized zirconium oxide, containing CaO as stabilizer (as is well known), is quantitatively limited.
The upper limit of the additive is situated at about 60 by weight of the entire zirconium-oxide material. On the other hand, there is required a minimum amount, in order to obtain the stabilizing effect in the mixture (minimum amount: 30 by weight of the amount of zirconium oxide).
The shaped elements are manufactured both in accordance with the ceramic slurry casting process and also in accordance with the pressing process. ln order to avoid contamination of the starting material, a zirconium-oxide-containing slurry is used in the casting process. In the pressing process, this slurry or organic binding materials are employed as binders. In order to avoid contamination of the zirconium material through abrasion of foreign substances, the slurry is produced in a wet mill whose lining consists of shaped elements of zirconium oxide, which elements in suitable shape also perform the function of grinding elements.
The invention is explained on the following exemplified embodiments:
a. Slurry-casting process A mixture of 83 kg. stabilized zirconium oxide, grain size less than 0.1 mm, and 83 kg. nonstabilized zirconium oxide, grain size less than 0.1 mm, with 34 liters water and 5 ml. aqueous solution of an alkali salt of a polycarboxylic acid, is ground for 200 hours in a wet mill charged with grinding elements of zirconium oxide, and provided with a lining of zirconium oxide bricks. After 200 hours, 60 parts by weight of zirconium silicate, grain size 0.2 0.5 mm, is added to 40 parts by weight of such a slurry and a mixture is made. The mixture is cast into gypsum molds, removed after 12 hours, dried and fired at 1620C.
b. Pressing process In a muller mixer, there are mixed 650 kg. zirconium silicate, grain size 0.2 0.5 mm, while adding 15 liter sulfite waste liquor (30B), with 175 kg. stabilized zirconium oxide, grain size smaller than 0.06 mm, and 175 kg. nonstabilized zirconium oxide, for about 10 minutes. The completed mass is pressed on a hydraulic press under 500 kg./cm pressure. The pressed blank is dried and then fired at 1620C.
The steel-pouring nozzles produced in accordance with this process possess the following properties:
Chemical analysis: ZrO- '71 by weight CaO 1.5 by weight SiO, 20 by weight Physical Properties: Gross density 4.0 g/cc Specific gravity (weight) 5.0 g/cc Total porosity 20 by volume When employed in steelworks, the nozzles of the invention withstood the tests of use with excellent results.
1 claim: I
l. A refractory fired shaped element for closures in casting units for metals, said element comprising 10 to 50 by weight zirconium oxide and 50 to by weight zirconium silicate, 30 to 60 by weight of the total amount of zirconium oxide being present in stabilized form and 70 to 40 by weight of the total amount of zirconium oxide being present in unstabilized form.
2. A refractory fired shaped element as in claim 1, characterized in that the zirconium oxide is employed in a grain size smaller than 0.1 mm.
3. A refractory fired shaped element as in claim 1, characterized in that the zirconium silicate is introduced in a grain size larger than 0.2 mm.
4. A refractory fired shaped element as claimed in claim 1 wherein the total stabilized and unstabilized zirconium oxide is present at about 35% by weight and the zirconium silicate is present at about 65% by weight.
5. A refractory fired shaped element as claimed in claim 1 wherein the zirconium oxide grain size is smaller than about-0.06 mm.
6. A refractory fired shaped element as claimed in claim 1 wherein the zirconium silicate grain size is about 0.2 0.5 mm.
Claims (6)
1. A REFRACTORY FIRED SHAPED ELEMENT FOR CLOSURES IN CASTING UNITS FOR METALS, SAID ELEMENT COMPRISING 10 TO 50% BY WEIGHT ZIRCONIUM OXIDE AND 50 TO 90% BY WEIGHT ZIRCONIUM SILICATE, 30 TO 60% BY WEIGHT OF THE TOTAL AMOUNT OF ZIRCONIUM OXIDE BEING PRESENT IN STABILIZED FROM 70 TO 40% BY WEIGHT OF THE TOTAL AMOUNT OF ZIRCONIUM OXIDE BEING PRESENT IN UNSTABILIZED FORM.
2. A refractory fired shaped element as in claim 1, characterized in that the zirconium oxide is employed in a grain size smaller than 0.1 mm.
3. A refractory fired shaped element as in claim 1, characterized in that the zirconium silicate is introduced in a grain size larger than 0.2 mm.
4. A refractory fired shaped element as claimed in claim 1 wherein the total stabilized and unstabilized zirconium oxide is present at about 35% by weight and the zirconium silicate is present at about 65% by weight.
5. A refractory fired shaped element as claimed in claim 1 wherein the zirconium oxide grain size is smaller than about 0.06 mm.
6. A refractory fired shaped element as claimed in claim 1 wherein the zirconium silicate grain size is about 0.2 -0.5 mm.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE19732321810 DE2321810C3 (en) | 1973-04-30 | Fireproof molded articles and processes for their manufacture |
Publications (1)
Publication Number | Publication Date |
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US3899341A true US3899341A (en) | 1975-08-12 |
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US458022A Expired - Lifetime US3899341A (en) | 1973-04-30 | 1974-04-04 | Refractory fired shaped element and process of its manufacture |
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US (1) | US3899341A (en) |
JP (1) | JPS5345212B2 (en) |
BE (1) | BE813411A (en) |
CA (1) | CA1020595A (en) |
ES (1) | ES425055A1 (en) |
FR (1) | FR2227243B1 (en) |
GB (1) | GB1464923A (en) |
IT (1) | IT1008467B (en) |
SE (1) | SE395880B (en) |
ZA (1) | ZA742505B (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4053320A (en) * | 1975-06-10 | 1977-10-11 | Keeling & Walker Limited | Production of refractory articles |
US4513089A (en) * | 1980-10-02 | 1985-04-23 | Dynamit Nobel Ag | Superrefractory dry ramming material based on zirconium oxide for the lining of induction-type crucible furnaces |
US4579829A (en) * | 1983-12-13 | 1986-04-01 | Garvie Ronald C | Zircon/zirconia refractories |
US5034358A (en) * | 1989-05-05 | 1991-07-23 | Kaman Sciences Corporation | Ceramic material and method for producing the same |
US20040102308A1 (en) * | 2002-11-06 | 2004-05-27 | Simpson Robert E. | Crucible material and crucible |
US20090111679A1 (en) * | 2007-10-31 | 2009-04-30 | Yanxia Lu | Low creep refractory ceramic and method of making |
EP2090554A1 (en) * | 2008-02-18 | 2009-08-19 | Refractory Intellectual Property GmbH & Co. KG | Refractory slag band |
US20100012484A1 (en) * | 2006-12-21 | 2010-01-21 | Saint-Gobain Centre De Recherches Et D'etudes | Doped sintered product based on zircon and zirconia |
US20100028665A1 (en) * | 2007-10-26 | 2010-02-04 | Yanxia Lu | Low-creep zircon material with nano-additives and method of making same |
US20100089098A1 (en) * | 2006-10-16 | 2010-04-15 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | SINTERED AND DOPED PRODUCT BASED ON ZIRCON + Nb2O5 or Ta2O5 |
CN102007089A (en) * | 2008-04-15 | 2011-04-06 | 法商圣高拜欧洲实验及研究中心 | Sintered product produced from a zircon-based charge |
US11634363B2 (en) | 2020-12-29 | 2023-04-25 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object and method of forming |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS584992A (en) * | 1981-07-01 | 1983-01-12 | Hitachi Ltd | Magnetism-electricity converting element |
US4791978A (en) * | 1987-11-25 | 1988-12-20 | Vesuvius Crucible Company | Gas permeable stopper rod |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2553265A (en) * | 1947-11-06 | 1951-05-15 | Corning Glass Works | Method of making zircon refractory |
US2593352A (en) * | 1945-08-23 | 1952-04-15 | Shaw | Production of zirconium silicate refractory |
US2624097A (en) * | 1951-01-09 | 1953-01-06 | Norton Co | Method of making dense, hard, abrasion resistant ceramic articles |
US3175919A (en) * | 1962-06-06 | 1965-03-30 | Harbison Walker Refractories | Zirconia refractory |
US3228778A (en) * | 1964-04-08 | 1966-01-11 | Harbison Walker Refractories | Glass furnace lining |
US3620781A (en) * | 1969-08-06 | 1971-11-16 | Corning Glass Works | Partially stabilized zirconia refractory |
-
1974
- 1974-04-04 US US458022A patent/US3899341A/en not_active Expired - Lifetime
- 1974-04-06 ES ES425055A patent/ES425055A1/en not_active Expired
- 1974-04-08 BE BE142935A patent/BE813411A/en not_active IP Right Cessation
- 1974-04-19 ZA ZA00742505A patent/ZA742505B/en unknown
- 1974-04-23 CA CA197,969A patent/CA1020595A/en not_active Expired
- 1974-04-23 IT IT7450573A patent/IT1008467B/en active
- 1974-04-29 SE SE7405725A patent/SE395880B/en unknown
- 1974-04-29 GB GB1868574A patent/GB1464923A/en not_active Expired
- 1974-04-29 FR FR7414806A patent/FR2227243B1/fr not_active Expired
- 1974-04-30 JP JP4865874A patent/JPS5345212B2/ja not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2593352A (en) * | 1945-08-23 | 1952-04-15 | Shaw | Production of zirconium silicate refractory |
US2553265A (en) * | 1947-11-06 | 1951-05-15 | Corning Glass Works | Method of making zircon refractory |
US2624097A (en) * | 1951-01-09 | 1953-01-06 | Norton Co | Method of making dense, hard, abrasion resistant ceramic articles |
US3175919A (en) * | 1962-06-06 | 1965-03-30 | Harbison Walker Refractories | Zirconia refractory |
US3228778A (en) * | 1964-04-08 | 1966-01-11 | Harbison Walker Refractories | Glass furnace lining |
US3620781A (en) * | 1969-08-06 | 1971-11-16 | Corning Glass Works | Partially stabilized zirconia refractory |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4053320A (en) * | 1975-06-10 | 1977-10-11 | Keeling & Walker Limited | Production of refractory articles |
US4513089A (en) * | 1980-10-02 | 1985-04-23 | Dynamit Nobel Ag | Superrefractory dry ramming material based on zirconium oxide for the lining of induction-type crucible furnaces |
US4579829A (en) * | 1983-12-13 | 1986-04-01 | Garvie Ronald C | Zircon/zirconia refractories |
US5034358A (en) * | 1989-05-05 | 1991-07-23 | Kaman Sciences Corporation | Ceramic material and method for producing the same |
US20040102308A1 (en) * | 2002-11-06 | 2004-05-27 | Simpson Robert E. | Crucible material and crucible |
US8236719B2 (en) | 2006-10-16 | 2012-08-07 | Saint-Gobain Centre De Recherches Et D'etudes European | Sintered and doped product based on zircon + Nb2O5 or Ta2O5 |
JP2012236766A (en) * | 2006-10-16 | 2012-12-06 | Saint-Gobain Centre De Recherches & D'etudes Europeen | SINTERED AND DOPED PRODUCT BASED ON ZIRCON + Nb2O5 OR Ta2O5 |
US20100089098A1 (en) * | 2006-10-16 | 2010-04-15 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | SINTERED AND DOPED PRODUCT BASED ON ZIRCON + Nb2O5 or Ta2O5 |
JP2011502918A (en) * | 2006-10-16 | 2011-01-27 | サン−ゴベン・セントル・ドゥ・レシェルシェ・エ・デチュード・ユーロペアン | Zircon + Nb2O5 or Ta2O5 based firing and dope products |
US9573850B2 (en) | 2006-12-21 | 2017-02-21 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Doped sintered product based on zircon and zirconia |
US20100012484A1 (en) * | 2006-12-21 | 2010-01-21 | Saint-Gobain Centre De Recherches Et D'etudes | Doped sintered product based on zircon and zirconia |
US20100028665A1 (en) * | 2007-10-26 | 2010-02-04 | Yanxia Lu | Low-creep zircon material with nano-additives and method of making same |
US20090111679A1 (en) * | 2007-10-31 | 2009-04-30 | Yanxia Lu | Low creep refractory ceramic and method of making |
US8986597B2 (en) | 2007-10-31 | 2015-03-24 | Corning Incorporated | Low creep refractory ceramic and method of making |
EA017317B1 (en) * | 2008-02-18 | 2012-11-30 | Рефректори Интеллекчуал Проперти Гмбх Унд Ко Кг | A refractory article for ladle as the ladle shroud, stopper rod, submerged entry nozzle or tube |
WO2009103949A1 (en) * | 2008-02-18 | 2009-08-27 | Refractory Intellectual Property Gmbh & Co Kg | Refractory slag band |
US8809214B2 (en) | 2008-02-18 | 2014-08-19 | Refractory Intellectual Property Gmbh & Co. Kg | Refractory slag band |
EP2090554A1 (en) * | 2008-02-18 | 2009-08-19 | Refractory Intellectual Property GmbH & Co. KG | Refractory slag band |
US20110107796A1 (en) * | 2008-04-15 | 2011-05-12 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Sintered product produced from a zircon-based charge |
CN102007089A (en) * | 2008-04-15 | 2011-04-06 | 法商圣高拜欧洲实验及研究中心 | Sintered product produced from a zircon-based charge |
US8258068B2 (en) | 2008-04-15 | 2012-09-04 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Sintered product produced from a zircon-based charge |
CN102007089B (en) * | 2008-04-15 | 2013-11-13 | 法商圣高拜欧洲实验及研究中心 | Sintered product produced from a zircon-based charge |
US11634363B2 (en) | 2020-12-29 | 2023-04-25 | Saint-Gobain Ceramics & Plastics, Inc. | Refractory object and method of forming |
Also Published As
Publication number | Publication date |
---|---|
GB1464923A (en) | 1977-02-16 |
FR2227243A1 (en) | 1974-11-22 |
BE813411A (en) | 1974-07-31 |
DE2321810A1 (en) | 1974-11-14 |
DE2321810B2 (en) | 1976-05-20 |
JPS5026814A (en) | 1975-03-19 |
FR2227243B1 (en) | 1978-08-04 |
ZA742505B (en) | 1975-04-30 |
SE395880B (en) | 1977-08-29 |
CA1020595A (en) | 1977-11-08 |
ES425055A1 (en) | 1976-11-16 |
IT1008467B (en) | 1976-11-10 |
JPS5345212B2 (en) | 1978-12-05 |
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